Gravitational separation of major atmospheric components observed in the stratosphere over Syowa Station, Antarctica, Kiruna, Sweden and Sanriku, Japan.

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Shigeyuki Ishidoya

2010-12-01

Full Text Available To investigate the gravitational separation of atmospheric components in the stratosphere, air samples collected using an aircraft during the Arctic Airborne Measurement Program 2002 (AAMP02 were analyzed for the O_2 N_2 ratios (δ(O_2 N_2, δ^N of N_2, δ^O of O_2 and Ar N_2 ratio (δ(Ar N_2. The relationship between observed stratospheric δ^N of N_2, δ^O of O_2 and δ(Ar N_2 over the Svalbard Islands and Barrow showed mass-dependent fractionation of atmospheric components in the stratosphere, which suggested that gravitational separation could be observable in the lowermost stratosphere inside the polar vortex. By examining the rates of change in δ(O_2 Nv and δ^C of CO_2 relative to the CO_2 concentration, such observed correlations were bound to be mainly attributable to upward propagation of their seasonal cycles produced in the troposphere and height-dependent air age as well as gravitational separation in the stratosphere. Air samples collected over Syowa Station, Antarctica, Kiruna, Sweden and Sanriku, Japan using balloon-borne cryogenic air samplers were analyzed for δ^N of Nv and δ^O of O_2. Strength of the gravitational separation was a function of latitude, showing the largest separation inside the polar vortex over Kiruna. It is suggested that information on increase of gravitational separation with height is useful in understanding the vertical transport of air masses in the stratosphere. By comparing the gravitational separations, mean age of air and N_2O concentration at two height intervals with N_2O concentrations > 125 ppb and < 45 ppb, the effect of descending air was found to be more significant over Kiruna than over Syowa Station and Sanriku. The variation in the gravitational separation with height is found to be weaker in the region with N_2O concentrations between 45 and 125 ppb than in other regions, which might suggest that vertical mixing of air occurred in this region.

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

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Ana Fernández-Barquín

2016-05-01

Full Text Available 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.

Tropical troposphere to stratosphere transport of carbon monoxide and long-lived trace species in the Chemical Lagrangian Model of the Stratosphere (CLaMS

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R. Pommrich

2014-12-01

Full Text Available Variations in the mixing ratio of trace gases of tropospheric origin entering the stratosphere in the tropics are of interest for assessing both troposphere to stratosphere transport fluxes in the tropics and the impact of these transport fluxes on the composition of the tropical lower stratosphere. Anomaly patterns of carbon monoxide (CO and long-lived tracers in the lower tropical stratosphere allow conclusions about the rate and the variability of tropical upwelling to be drawn. Here, we present a simplified chemistry scheme for the Chemical Lagrangian Model of the Stratosphere (CLaMS for the simulation, at comparatively low numerical cost, of CO, ozone, and long-lived trace substances (CH4, N2O, CCl3F (CFC-11, CCl2F2 (CFC-12, and CO2 in the lower tropical stratosphere. For the long-lived trace substances, the boundary conditions at the surface are prescribed based on ground-based measurements in the lowest model level. The boundary condition for CO in the lower troposphere (below about 4 km is deduced from MOPITT measurements. Due to the lack of a specific representation of mixing and convective uplift in the troposphere in this model version, enhanced CO values, in particular those resulting from convective outflow are underestimated. However, in the tropical tropopause layer and the lower tropical stratosphere, there is relatively good agreement of simulated CO with in situ measurements (with the exception of the TROCCINOX campaign, where CO in the simulation is biased low ≈10–15 ppbv. Further, the model results (and therefore also the ERA-Interim winds, on which the transport in the model is based are of sufficient quality to describe large scale anomaly patterns of CO in the lower stratosphere. In particular, the zonally averaged tropical CO anomaly patterns (the so called "tape recorder" patterns simulated by this model version of CLaMS are in good agreement with observations, although the simulations show a too rapid upwelling

Effect of volcanic aerosol on stratospheric NO2 and N2O5 from 2002–2014 as measured by Odin-OSIRIS and Envisat-MIPAS

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C. Adams

2017-07-01

Full Text Available Following the large volcanic eruptions of Pinatubo in 1991 and El Chichón in 1982, decreases in stratospheric NO2 associated with enhanced aerosol were observed. The Optical Spectrograph and Infrared Imaging Spectrometer (OSIRIS measured the widespread enhancements of stratospheric aerosol following seven volcanic eruptions between 2002 and 2014, although the magnitudes of these eruptions were all much smaller than the Pinatubo and El Chichón eruptions. In order to isolate and quantify the relationship between volcanic aerosol and NO2, NO2 anomalies were calculated using measurements from OSIRIS and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS. In the tropics, variability due to the quasi-biennial oscillation was subtracted from the time series. OSIRIS profile measurements indicate that the strongest anticorrelations between NO2 and volcanic aerosol extinction were for the 5 km layer starting  ∼  3 km above the climatological mean tropopause at the given latitude. OSIRIS stratospheric NO2 partial columns in this layer were found to be smaller than background NO2 levels during these aerosol enhancements by up to  ∼  60 % with typical Pearson correlation coefficients of R ∼ −0. 7. MIPAS also observed decreases in NO2 partial columns during periods affected by volcanic aerosol, with percent differences of up to  ∼  25 % relative to background levels. An even stronger anticorrelation was observed between OSIRIS aerosol optical depth and MIPAS N2O5 partial columns, with R ∼ −0. 9, although no link with MIPAS HNO3 was observed. The variation in OSIRIS NO2 with increasing aerosol was found to be consistent with simulations from a photochemical box model within the estimated model uncertainty.

In situ trace gas and particle measurements in the summer lower stratosphere during STREAM II. Implications for O{sub 3} production

Energy Technology Data Exchange (ETDEWEB)

Bregman, A; Lelieveld, J; Scheeren, H A [Institute for Marine and Atmospheric Sciences, Utrecht (Netherlands); Arnold, F; Buerger, V; Schneider, J [Max-Planck-Inst. for Nuclear Physics, Heidelberg (Germany); Fischer, H; Waibel, A [Max-Planck-Inst. fuer Chemie, Mainz (Germany); Siegmund, P C; Wauben, W M.F. [Koninklijk Nederlands Meteorologisch Inst., De Bilt (Netherlands); Stroem, J [Stockholm Univ. (Sweden). Dept. of Meteorology

1998-12-31

In situ aircraft measurements of O{sub 3}, CO, HNO{sub 3}, and aerosol particles are presented, performed over the North Sea region in the summer lower stratosphere during the STREAM-II campaign (Stratosphere Troposphere Experiments by Aircraft Measurements). Elevated CO mixing ratios are attributed to mixing of polluted tropospheric air into the lowermost extra-tropical stratosphere. Model calculations illustrate that the O{sub 3} production efficiency of NO{sub x} is smaller than previously assumed, under conditions with relatively high HNO{sub 3} mixing ratios, as observed during STREAM-II. The model simulations further suggest a relatively high O{sub 3} production efficiency from CO oxidation, as a result of the relatively high ambient HNO{sub 3} and NO{sub x} concentrations, implying that upward transport of CO rich air enhances O{sub 3} production in the lowermost stratosphere. (author) 13 refs.

In situ trace gas and particle measurements in the summer lower stratosphere during STREAM II. Implications for O{sub 3} production

Energy Technology Data Exchange (ETDEWEB)

Bregman, A.; Lelieveld, J.; Scheeren, H.A. [Institute for Marine and Atmospheric Sciences, Utrecht (Netherlands); Arnold, F.; Buerger, V.; Schneider, J. [Max-Planck-Inst. for Nuclear Physics, Heidelberg (Germany); Fischer, H.; Waibel, A. [Max-Planck-Inst. fuer Chemie, Mainz (Germany); Siegmund, P.C.; Wauben, W.M.F. [Koninklijk Nederlands Meteorologisch Inst., De Bilt (Netherlands); Stroem, J. [Stockholm Univ. (Sweden). Dept. of Meteorology

1997-12-31

In situ aircraft measurements of O{sub 3}, CO, HNO{sub 3}, and aerosol particles are presented, performed over the North Sea region in the summer lower stratosphere during the STREAM-II campaign (Stratosphere Troposphere Experiments by Aircraft Measurements). Elevated CO mixing ratios are attributed to mixing of polluted tropospheric air into the lowermost extra-tropical stratosphere. Model calculations illustrate that the O{sub 3} production efficiency of NO{sub x} is smaller than previously assumed, under conditions with relatively high HNO{sub 3} mixing ratios, as observed during STREAM-II. The model simulations further suggest a relatively high O{sub 3} production efficiency from CO oxidation, as a result of the relatively high ambient HNO{sub 3} and NO{sub x} concentrations, implying that upward transport of CO rich air enhances O{sub 3} production in the lowermost stratosphere. (author) 13 refs.

Yield-scaled N2O emissions in a winter wheat - summer corn double-cropping system

NARCIS (Netherlands)

Qin, S.; Wang, Y.; Hu, C.; Oenema, O.; Li, X.; Zhang, Y.; Dong, W.

2012-01-01

Emissions of nitrous oxide (N2O) from agricultural soils contribute to global warming and stratospheric ozone depletion. Applications of fertilizer nitrogen (N) increase N2O emission, but also increase agricultural production. Here, we report on the responses of crop yield, N2O emission and

An Aircraft-Based Upper Troposphere Lower Stratosphere O3, CO, and H2O Climatology for the Northern Hemisphere

Science.gov (United States)

Tilmes, S.; Pan, L. L.; Hoor, P.; Atlas, E.; Avery, M. A.; Campos, T.; Christensen, L. E.; Diskin, G. S.; Gao, R.-S.; Herman, R. L.;

SPADE H2O measurements and the seasonal cycle of statospheric water vapor

Science.gov (United States)

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

1994-01-01

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

Sources and sinks of stratospheric water vapor

International Nuclear Information System (INIS)

Ellsaesser, H.W.

1979-11-01

A tutorial review of the understanding of stratospheric H 2 O and the processes controlling it is presented. Paradoxes posed by currently available observational data are cited and suggestions made as to how they might be resolved. Such resolution appears to require: that the bulk of our current data provides unrepresentative and misleading vertical and latitudinal H 2 O gradients immediately downstream from the tropical tropopause; and, that there exists within the troposphere a mechanism different from or in addition to the tropical tropopause cold trap for drying air to the mixing ratios found in the lower stratosphere. Satisfaction of these requirements will reconcile much heretofore puzzling observational data and will obviate the necessity for a stratospheric sink for H 2 O

Stratospheric BrONO2 observed by MIPAS

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H. Fischer

2009-03-01

Full Text Available The first measurements of stratospheric bromine nitrate (BrONO2 are reported. Bromine nitrate has been clearly identified in atmospheric infrared emission spectra recorded with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS aboard the European Envisat satellite, and stratospheric concentration profiles have been determined for different conditions (day and night, different latitudes. The BrONO2 concentrations show strong day/night variations, with much lower concentrations during the day. Maximum volume mixing ratios observed during night are 20 to 25 pptv. The observed concentration profiles are in agreement with estimations from photochemical models and show that the current understanding of stratospheric bromine chemistry is generally correct.

Retrieval of NO2 stratospheric profiles from ground-based zenith-sky uv-visible measurements at 60°N

Science.gov (United States)

Hendrick, F.; van Roozendael, M.; Lambert, J.-C.; Fayt, C.; Hermans, C.; de Mazière, M.

2003-04-01

Nitrogen dioxide (NO_2) plays an important role in controlling ozone abundances in the stratosphere, either directly through the NOx (NO+NO_2) catalytic cycle, either indirectly by reaction with the radical ClO to form the reservoir species ClONO_2. In this presentation, NO_2 stratospheric profiles are retrieved from ground-based UV-visible NO_2 slant column abundances measured since 1998 at the complementary NDSC station of Harestua (Norway, 60^oN). The retrieval algorithm is based on the Rodgers optimal estimation inversion method and a forward model consisting in the IASB-BIRA stacked box photochemical model PSCBOX coupled to the radiative transfer package UVspec/DISORT. This algorithm has been applied to a set of about 50 sunrises and sunsets for which spatially and temporally coincident NO_2 measurements made by the HALOE (Halogen Occultation Experiment) instrument on board the Upper Atmosphere Research Satellite (UARS) are available. The consistency between retrieved and HALOE profiles is discussed in term of the different seasonal conditions investigated which are spring with and without chlorine activation, summer, and fall.

Measurement of low-ppm mixing ratios of water vapor in the upper troposphere and lower stratosphere using chemical ionization mass spectrometry

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T. D. Thornberry

2013-06-01

Full Text Available A chemical ionization mass spectrometer (CIMS instrument has been developed for the fast, precise, and accurate measurement of water vapor (H2O at low mixing ratios in the upper troposphere and lower stratosphere (UT/LS. A low-pressure flow of sample air passes through an ionization volume containing an α-particle radiation source, resulting in a cascade of ion-molecule reactions that produce hydronium ions (H3O+ from ambient H2O. The production of H3O+ ions from ambient H2O depends on pressure and flow through the ion source, which were tightly controlled in order to maintain the measurement sensitivity independent of changes in the airborne sampling environment. The instrument was calibrated every 45 min in flight by introducing a series of H2O mixing ratios between 0.5 and 153 parts per million (ppm, 10−6 mol mol−1 generated by Pt-catalyzed oxidation of H2 standards while overflowing the inlet with dry synthetic air. The CIMS H2O instrument was deployed in an unpressurized payload area aboard the NASA WB-57F high-altitude research aircraft during the Mid-latitude Airborne Cirrus Properties Experiment (MACPEX mission in March and April 2011. The instrument performed successfully during seven flights, measuring H2O mixing ratios below 5 ppm in the lower stratosphere at altitudes up to 17.7 km, and as low as 3.5 ppm near the tropopause. Data were acquired at 10 Hz and reported as 1 s averages. In-flight calibrations demonstrated a typical sensitivity of 2000 Hz ppm−1 at 3 ppm with a signal to noise ratio (2 σ, 1 s greater than 32. The total measurement uncertainty was 9 to 11%, derived from the uncertainty in the in situ calibrations.

Evolution of stratospheric ozone during winter 2002/2003 as observed by a ground-based millimetre wave radiometer at Kiruna, Sweden

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U. Raffalski

2005-01-01

Full Text Available We present ozone measurements from the millimetre wave radiometer installed at the Swedish Institute of Space Physics (Institutet för rymdfysik, IRF in Kiruna (67.8° N, 20.4° E, 420 m asl. Nearly continuous operation in the winter of 2002/2003 allows us to give an overview of ozone evolution in the stratosphere between 15 and 55 km. In this study we present a detailed analysis of the Arctic winter 2002/2003. By means of a methodology using equivalent latitudes we investigate the meteorological processes in the stratosphere during the entire winter/spring period. During the course of the winter strong mixing into the vortex took place in the middle and upper stratosphere as a result of three minor and one major warming event, but no evidence was found for significant mixing in the lower stratosphere. Ozone depletion in the lower stratosphere during this winter was estimated by measurements on those days when Kiruna was well inside the Arctic polar vortex. The days were carefully chosen using a definition of the vortex edge based on equivalent latitudes. At the 475 K isentropic level a cumulative ozone loss of about 0.5 ppmv was found starting in January and lasting until mid-March. The early ozone loss is probably a result of the very cold temperatures in the lower stratosphere in December and the geographical extension of the vortex to lower latitudes where solar irradiation started photochemical ozone loss in the pre-processed air. In order to correct for dynamic effects of the ozone variation due to diabatic subsidence of air masses inside the vortex, we used N2O measurements from the Odin satellite for the same time period. The derived ozone loss in the lower stratosphere between mid-December and mid-March varies between 1.1±0.1 ppmv on the 150 ppbv N2O isopleth and 1.7±0.1 ppmv on the 50 ppbv N2O isopleth.

Coupled effects of atmospheric N/sub 2/O and O/sub 3/ on the earth's climate

Energy Technology Data Exchange (ETDEWEB)

Wang, W C; Sze, N D

1980-08-07

Increased application of nitrogen fertilizer could perturb the atmospheric nitrogen cycle and might lead to a possible increase in atmospheric N/sub 2/O. N/sub 2/O plays an important role in stratospheric chemistry as well as in the global radiation budget. Recent studies suggest that perturbation of local ozone could also significantly affect the global climate. Here we show that a doubling in the present day N/sub 2/O level might significantly perturb the distribution of O/sub 3/ and HNO/sub 3/, and that the associated climatic feedbacks from O/sub 3/ and HNO/sub 3/ perturbations could contribute as much as 0.23 K warming of the surface temperature, in addition to 0.44 K directly caused by N/sub 2/O doubling.

UV-induced N2O emission from plants

Science.gov (United States)

Bruhn, Dan; Albert, Kristian R.; Mikkelsen, Teis N.; Ambus, Per

2014-12-01

Nitrous oxide (N2O) is an important long-lived greenhouse gas and precursor of stratospheric ozone-depleting mono-nitrogen oxides. The atmospheric concentration of N2O is persistently increasing; however, large uncertainties are associated with the distinct source strengths. Here we investigate for the first time N2O emission from terrestrial vegetation in response to natural solar ultra violet radiation. We conducted field site measurements to investigate N2O atmosphere exchange from grass vegetation exposed to solar irradiance with and without UV-screening. Further laboratory tests were conducted with a range of species to study the controls and possible loci of UV-induced N2O emission from plants. Plants released N2O in response to natural sunlight at rates of c. 20-50 nmol m-2h-1, mostly due to the UV component. The emission response to UV-A is of the same magnitude as that to UV-B. Therefore, UV-A is more important than UV-B given the natural UV-spectrum at Earth's surface. Plants also emitted N2O in darkness, although at reduced rates. The emission rate is temperature dependent with a rather high activation energy indicative for an abiotic process. The prevailing zone for the N2O formation appears to be at the very surface of leaves. However, only c. 26% of the UV-induced N2O appears to originate from plant-N. Further, the process is dependent on atmospheric oxygen concentration. Our work demonstrates that ecosystem emission of the important greenhouse gas, N2O, may be up to c. 30% higher than hitherto assumed.

Mitigation of soil N2O emission by inoculation with a mixed culture of indigenous Bradyrhizobium diazoefficiens

Science.gov (United States)

Akiyama, Hiroko; Hoshino, Yuko Takada; Itakura, Manabu; Shimomura, Yumi; Wang, Yong; Yamamoto, Akinori; Tago, Kanako; Nakajima, Yasuhiro; Minamisawa, Kiwamu; Hayatsu, Masahito

2016-09-01

Agricultural soil is the largest source of nitrous oxide (N2O), a greenhouse gas. Soybean is an important leguminous crop worldwide. Soybean hosts symbiotic nitrogen-fixing soil bacteria (rhizobia) in root nodules. In soybean ecosystems, N2O emissions often increase during decomposition of the root nodules. Our previous study showed that N2O reductase can be used to mitigate N2O emission from soybean fields during nodule decomposition by inoculation with nosZ++ strains [mutants with increased N2O reductase (N2OR) activity] of Bradyrhizobium diazoefficiens. Here, we show that N2O emission can be reduced at the field scale by inoculation with a mixed culture of indigenous nosZ+ strains of B. diazoefficiens USDA110 group isolated from Japanese agricultural fields. Our results also suggested that nodule nitrogen is the main source of N2O production during nodule decomposition. Isolating nosZ+ strains from local soybean fields would be more applicable and feasible for many soybean-producing countries than generating mutants.

Comparison of CMAM simulations of carbon monoxide (CO, nitrous oxide (N2O, and methane (CH4 with observations from Odin/SMR, ACE-FTS, and Aura/MLS

Directory of Open Access Journals (Sweden)

B. Barret

2009-05-01

Full Text Available Simulations of CO, N2O and CH4 from a coupled chemistry-climate model (CMAM are compared with satellite measurements from Odin Sub-Millimeter Radiometer (Odin/SMR, Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS, and Aura Microwave Limb Sounder (Aura/MLS. Pressure-latitude cross-sections and seasonal time series demonstrate that CMAM reproduces the observed global CO, N2O, and CH4 distributions quite well. Generally, excellent agreement with measurements is found between CO simulations and observations in the stratosphere and mesosphere. Differences between the simulations and the ACE-FTS observations are generally within 30%, and the differences between CMAM results and SMR and MLS observations are slightly larger. These differences are comparable with the difference between the instruments in the upper stratosphere and mesosphere. Comparisons of N2O show that CMAM results are usually within 15% of the measurements in the lower and middle stratosphere, and the observations are close to each other. However, the standard version of CMAM has a low N2O bias in the upper stratosphere. The CMAM CH4 distribution also reproduces the observations in the lower stratosphere, but has a similar but smaller negative bias in the upper stratosphere. The negative bias may be due to that the gravity drag is not fully resolved in the model. The simulated polar CO evolution in the Arctic and Antarctic agrees with the ACE and MLS observations. CO measurements from 2006 show evidence of enhanced descent of air from the mesosphere into the stratosphere in the Arctic after strong stratospheric sudden warmings (SSWs. CMAM also shows strong descent of air after SSWs. In the tropics, CMAM captures the annual oscillation in the lower stratosphere and the semiannual oscillations at the stratopause and mesopause seen in Aura/MLS CO and N2O observations and in Odin/SMR N2O observations. The Odin/SMR and Aura/MLS N2O observations also show a quasi

Rapid meridional transport of tropical airmasses to the Arctic during the major stratospheric warming in January 2003

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A. Kleinböhl

2005-01-01

Full Text Available We present observations of unusually high values of ozone and N2O in the middle stratosphere that were observed by the airborne submillimeter radiometer ASUR in the Arctic. The observations took place in the meteorological situation of a major stratospheric warming that occurred in mid-January 2003 and was dominated by a wave 2 event. On 23 January 2003 the observed N2O and O3 mixing ratios around 69° N in the middle stratosphere reached maximum values of ~190 ppb and ~10 ppm, respectively. The similarities of these N2O profiles in a potential temperature range between 800 and 1200 K with N2O observations around 20° N on 1 March 2003 by the same instrument suggest that the observed Arctic airmasses were transported from the tropics quasi-isentropically. This is confirmed by 5-day back trajectory calculations which indicate that the airmasses between about 800 and 1000 K had been located around 20° N 3–5 days prior to the measurement in the Arctic. Calculations with a linearized ozone chemistry model along calculated as well as idealized trajectories, initialized with the low-latitude ASUR ozone measurements, give reasonable agreement with the Arctic ozone measurement by ASUR. PV distributions suggest that these airmasses did not stay confined in the Arctic region which makes it unlikely that this dynamical situation lead to the formation of dynamically caused pockets of low ozone.

Application of the NDHA model to describe N₂O dynamics in activated sludge mixed culture biomass

DEFF Research Database (Denmark)

Domingo-Felez, Carlos; Smets, Barth F.

A pseudo-mechanistic model describing three biological nitric oxide (NO) and nitrous oxide (N2O) production pathways was calibrated for an activated sludge mixed culture biomass treating municipal wastewater with laboratory-scale experiments. The model (NDHA) comprehensively describes N2O produci...

K‑Doped Co−Mn−Al Mixed Oxide Catalyst for N2O Abatement from\

Czech Academy of Sciences Publication Activity Database

Pacultová, K.; Karásková, K.; Kovanda, F.; Jirátová, Květa; Šrámek, J.; Kustrovski, P.; Kotarba, A.; Chromčáková, Ž.; Kočí, K.; Obalová, L.

2016-01-01

Roč. 55, č. 26 (2016), s. 7076-7084 ISSN 0888-5885 R&D Projects: GA ČR GA14-13750S; GA TA ČR TA01020336 Institutional support: RVO:67985858 Keywords : Co-Mn-Al mixed oxide * N2O decomposition * HNO3 pilot plant Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.843, year: 2016

Retrieval of stratospheric and tropospheric BrO profiles and columns using ground-based zenith-sky DOAS observations at Harestua, 60° N

Directory of Open Access Journals (Sweden)

J. A. Pyle

2007-09-01

Full Text Available A profiling algorithm based on the optimal estimation method is applied to ground-based zenith-sky UV-visible measurements from Harestua, Southern Norway (60° N, 11° E in order to retrieve BrO vertical profiles. The sensitivity of the zenith-sky observations to the tropospheric BrO detection is increased by using for the spectral analysis a fixed reference spectrum corresponding to clear-sky noon summer conditions. The information content and retrieval errors are characterized and it is shown that the retrieved stratospheric profiles and total columns are consistent with correlative balloon and satellite observations, respectively. Tropospheric BrO columns are derived from profiles retrieved at 80° solar zenith angle during sunrise and sunset for the 2000–2006 period. They show a marked seasonality with mean column value ranging from 1.52±0.62×1013 molec/cm² in late winter/early spring to 0.92±0.38×1013 molec/cm² in summer, which corresponds to 1.0±0.4 and 0.6±0.2 pptv, respectively, if we assume that BrO is uniformly mixed in the troposphere. These column values are also consistent with previous estimates made from balloon, satellite, and other ground-based observations. Daytime (10:30 LT tropospheric BrO columns are compared to the p-TOMCAT 3-D tropospheric chemical transport model (CTM for the 2002–2003 period. p-TOMCAT shows a good agreement with the retrieved columns except in late winter/early spring where an underestimation by the model is obtained. This finding could be explained by the non-inclusion of sea-ice bromine sources in the current version of p-TOMCAT. Therefore the model cannot reproduce the possible transport of air-masses with enhanced BrO concentration due to bromine explosion events from the polar region to Harestua. The daytime stratospheric BrO columns are compared to the SLIMCAT stratospheric 3-D-CTM. The model run used in this study, which assumes 21.2 pptv for the Bry loading (15 pptv for long

High-Temperature Corrosion of T92 Steel in N{sub 2}/H{sub 2}O/H{sub 2}S-Mixed Gas

Energy Technology Data Exchange (ETDEWEB)

Shi, Yuke; Kim, Min Jung; Park, Soon Yong; Abro, M. Ali; Yadav, Poonam; Lee, Dong Bok [Sungkyunkwan University, Suwon (Korea, Republic of)

2016-06-15

The ASTM T92 steel was corroded at 600 ℃ and 800 ℃ at 1 atm of N{sub 2}/3.1%H{sub 2}O/2.42%H{sub 2}S-mixed gas. The formed scales were thick and fragile. They consisted primarily of the outer FeS scale and the inner (FeS, FeCr{sub 2}S{sub 4})-mixed scale containing a small amount of the Cr{sub 2}O{sub 3} scale. This indicated that corrosion occurred mainly via sulfidation rather than oxidation due to the H{sub 2}S gas. Since FeS was present throughout the whole scale, T92 steel was non-protective, displaying high corrosion rates.

Budgetary and biogeochemical implications of N sub(2)O isotope signatures in the Arabian Sea

Digital Repository Service at National Institute of Oceanography (India)

Naqvi, S.W.A; Yoshinari, T.; Jayakumar, D.A; Altabet, M.A; Narvekar, P.V.; Devols, A; Brandes, J.A; Codispoti, L.A.

Nitrous oxide (N sub(2)O) is an important greenhouse gas that also plays a role in the chemistry of stratospheric ozone depletion, but its atmospheric budget has yet to be well-quantified sup(1-5). However, multi-isotope characterization of N sub(2...

Transport of mesospheric H2O during and after the stratospheric sudden warming of January 2010: observation and simulation

Directory of Open Access Journals (Sweden)

A. K. Smith

2012-06-01

Full Text Available The transportable ground based microwave radiometer MIAWARA-C monitored the upper stratospheric and lower mesospheric (USLM water vapor distribution over Sodankylä, Finland (67.4° N, 26.6° E from January to June 2010. At the end of January, approximately 2 weeks after MIAWARA-C's start of operation in Finland, a stratospheric sudden warming (SSW disturbed the circulation of the middle atmosphere. Shortly after the onset of the SSW water vapor rapidly increased at pressures between 1 and 0.01 hPa. Backward trajectory calculations show that this strong increase is due to the breakdown of the polar vortex and meridional advection of subtropical air to the Arctic USLM region. In addition, mesospheric upwelling in the course of the SSW led to an increase in observed water vapor between 0.1 and 0.03 hPa. After the SSW MIAWARA-C observed a decrease in mesospheric water vapor volume mixing ratio (VMR due to the subsidence of H2O poor air masses in the polar region. Backward trajectory analysis and the zonal mean water vapor distribution from the Microwave Limb Sounder on the Aura satellite (Aura/MLS indicate the occurrence of two regimes of circulation from 50° N to the North Pole: (1 regime of enhanced meridional mixing throughout February and (2 regime of an eastward circulation in the USLM region reestablished between early March and the equinox. The polar descent rate determined from MIAWARA-C's 5.2 parts per million volume (ppmv isopleth is 350 ± 40 m d−1 in the pressure range 0.6 to 0.06 hPa between early February and early March. For the same time interval the descent rate in the same pressure range was determined using Transformed Eulerian Mean (TEM wind fields simulated by means of the Whole Atmosphere Community Climate Model with Specified Dynamics (SD-WACCM. The average value of the SD-WACCM TEM vertical wind is 325 m d−1 while the along trajectory vertical displacement is 335 m d−1. The similar descent rates found indicate good

Is there any chlorine monoxide in the stratosphere?

Science.gov (United States)

Mumma, M. J.; Rogers, J. D.; Kostiuk, T.; Deming, D.; Hillman, J. J.; Zipoy, D.

1983-01-01

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3 x 10 to the 13th molecules/sq cm at the 95 percent confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought. Previously announced in STAR as N83-27518

Co-Mn-Al Mixed Oxides as Catalysts for Ammonia Oxidation to N2O.

Czech Academy of Sciences Publication Activity Database

Ludvíková, Jana; Jablońska, M.; Jirátová, Květa; Chmielarz, L.; Balabánová, Jana; Kovanda, F.; Obalová, L.

2016-01-01

Roč. 42, č. 3 (2016), s. 2669-2690 ISSN 0922-6168 R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : Co-Mn-Al mixed oxide s * catalytic ammonia oxidation * N2O production * mechanochemical production Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.369, year: 2016

Effects of mixing on resolved and unresolved scales on stratospheric age of air

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S. Dietmüller

2017-06-01

Full Text Available Mean age of air (AoA is a widely used metric to describe the transport along the Brewer–Dobson circulation. We seek to untangle the effects of different processes on the simulation of AoA, using the chemistry–climate model EMAC (ECHAM/MESSy Atmospheric Chemistry and the Chemical Lagrangian Model of the Stratosphere (CLaMS. Here, the effects of residual transport and two-way mixing on AoA are calculated. To do so, we calculate the residual circulation transit time (RCTT. The difference of AoA and RCTT is defined as aging by mixing. However, as diffusion is also included in this difference, we further use a method to directly calculate aging by mixing on resolved scales. Comparing these two methods of calculating aging by mixing allows for separating the effect of unresolved aging by mixing (which we term aging by diffusion in the following in EMAC and CLaMS. We find that diffusion impacts AoA by making air older, but its contribution plays a minor role (order of 10 % in all simulations. However, due to the different advection schemes of the two models, aging by diffusion has a larger effect on AoA and mixing efficiency in EMAC, compared to CLaMS. Regarding the trends in AoA, in CLaMS the AoA trend is negative throughout the stratosphere except in the Northern Hemisphere middle stratosphere, consistent with observations. This slight positive trend is neither reproduced in a free-running nor in a nudged simulation with EMAC – in both simulations the AoA trend is negative throughout the stratosphere. Trends in AoA are mainly driven by the contributions of RCTT and aging by mixing, whereas the contribution of aging by diffusion plays a minor role.

Diaqua-2κ2O-bis(μ-1-oxido-2-naphthoato-1:2κ3O1,O2:O2′;2:3κ3O2:O1,O2′-bis(1-oxido-2-naphthoato-1κ1O2,O2;3κ2O1,O2-hexapyridine-1κ2N,2κ2N,3κ2N-trimanganese(II/III pyridine disolvate dihydrate

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Daqi Wang

2008-12-01

Full Text Available The title complex, [Mn3(C11H6O34(C5H5N6(H2O2]·2H2O·2C5H5N, is a trinuclear mixed oxidation state complex of overline1 symmetry. The three Mn atoms are six-coordinated in the shape of distorted octahedra, each coordinated with an O4N2 set of donor atoms, where the ligands exhibit mono- and bidentate modes. However, the coordination of the MnII ion located on the inversion centre involves water molecules at two coordination sites, whereas that of the two symmetry-related MnIII ions involves an O4N2 set of donor atoms orginating from the organic ligands. Intramolecular C—H...π interactions between neighbouring pyridine ligands stabilize this arrangement. A two-dimensional network parallel to (001 is formed by intermolecular O—H...O hydrogen bonds.

Solid-State Photochemistry as a Formation Mechanism for Titan's Stratospheric C4N2 Ice Clouds

Science.gov (United States)

Anderson, C. M.; Samuelson, R. E.; Yung, Y. L.; McLain, J. L.

2016-01-01

We propose that C4N2 ice clouds observed in Titan's springtime polar stratosphere arise due to solid-state photochemistry occurring within extant ice cloud particles of HCN-HC3N mixtures. This formation process resembles the halogen-induced ice particle surface chemistry that leads to condensed nitric acid trihydrate (NAT) particles and ozone depletion in Earth's polar stratosphere. As our analysis of the Cassini Composite Infrared Spectrometer 478 per centimeter ice emission feature demonstrates, this solid-state photochemistry mechanism eliminates the need for the relatively high C4N2 saturation vapor pressures required (even though they are not observed) when the ice is produced through the usual procedure of direct condensation from the vapor.

[2-(Dimethylaminoethanol-κ2N,O][2-(dimethylaminoethanolato-κ2N,O]iodidocopper(II

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Elena A. Buvaylo

2012-04-01

Full Text Available The title compound, [Cu(C4H10NOI(C4H11NO], was obtained unintentionally as the product of an attempted synthesis of a Cu/Zn mixed-metal complex using zerovalent copper, zinc(II oxide and ammonium iodide in pure 2-(dimethylaminoethanol, in air. The molecular complex has no crystallographically imposed symmetry. The coordination geometry around the metal atom is distorted square-pyramidal. The equatorial coordination around copper involves donor atoms of the bidentate chelating 2-(dimethylaminoethanol ligand and the 2-(dimethylaminoethanolate group, which are mutually trans to each other, with four approximately equal short Cu—O/N bond distances. The axial Cu—I bond is substantially elongated. Intermolecular hydrogen-bonding interactions involving the –OH group of the neutral 2-(dimethylaminoethanol ligand to the O atom of the monodeprotonated 2-(dimethylaminoethanolate group of the molecule related by the n-glide plane, as indicated by the O...O distance of 2.482 (12 Å, form chains of molecules propagating along [101].

Solar UV irradiation-induced production of N2O from plant surfaces - low emissions rates but all over the world

DEFF Research Database (Denmark)

Mikkelsen, Teis Nørgaard; Bruhn, Dan; Ambus, Per

Nitrous oxide (N2O) is an important long-lived greenhouse gas and precursor of stratospheric ozone depleting mono-nitrogen oxides. The atmospheric concentration of N2O is persistently increasing; however, large uncertainties are associated with the distinct source strengths. Here we investigate f...

A consistent definition of the Arctic polar vortex breakup in both the lower and upper stratosphere

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Choi, W.; Seo, J.

2014-12-01

Breakup of the polar vortex is a dominant feature of the seasonal transition from winter to summer in the stratosphere, which significantly affects stratospheric O3 concentration and tropospheric weather. Previously several criteria for the vortex breakup have been suggested based on the potential vorticity (PV) and wind speed, however, those mainly have focused on the lower stratospheric vortex of which spatiotemporal evolution and decay are more continuous than those of the upper stratospheric vortex. To find a consistent criterion for the vortex breakup in both the lower and upper stratosphere, the present study defined a polar vortex breakup day as when PV gradient at the polar vortex edge becomes lower than that at the subtropical edge on the area equivalent latitude based on PV. With applying the new definition to the UK Met Office reanalysis data, the breakup days of the Arctic polar vortices on 18 isentropic levels from 450 K to 1300 K were calculated for the period of 1993-2005. In comparison with CH4, N2O and O3 measured by the ILAS and POAM II/III satellite instruments, the breakup days are well consistent with changes in the distribution of such tracers as well as their zonal standard deviations associated with the vortex structure breaking and irreversible mixing. The vortex breakup in the upper stratosphere occurs more or less a month prior to that in the middle and lower stratosphere while the stratospheric final warming events occurs simultaneously in the upper and lower stratosphere.

Investigation of dissolved N2O production processes during wastewater treatment system in Ulaanbaatar

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Tumendelger A

2017-02-01

Full Text Available Nitrous oxide (N2O is an increasing greenhouse gas in the troposphere and a potential destroyer of stratospheric ozone layer. Wastewater treatment plant (WWTP is one of the anthropogenic N2O sources because inorganic and organic nitrogen compounds are converted to nitrate (NO3-, in the case of standard system or N2 (in the case of advanced system by bacterial nitrification and denitrifcation processes in WWTP. These major processes can be distinguished by isotopocule analysis. In order to reveal production mechanisms of N2O in a standard wastewater treatment, we made water sampling at the central WWTP in Ulaanbaatar. The water samples collected from seven stations including biological reaction tanks were measured for concentration and isotopocule ratios of dissolved N2O and other inorganic nitrogen. Dissolved N2O concentration was extremely higher than that expected under atmospheric equilibrium (about 9 nmol/l at all stations, indicating that this system is a potential source of N2O. It showed a gradual increase with the progress of biological reaction and the highest concentration (335.7 nmol/l was observed at station N5-4 of the aeration tank when the DO was 5.7 mg/l. Nitrification by nitrifying bacteria could actively occur by the concentration of NH4+ decreased whereas NO2- and NO3- showed a temporal and monotonic increase, respectively, under high DO concentration. Although the reported values of site preference (SP of N2O, the difference in 15N/14N ratio between central (α and terminal (β nitrogen, produced via NO2- reduction (SP(ND, including both nitrifier and denitrifier denitrification, and NH2OH oxidation (SP(HO ranged from -10.7‰ to 0‰ and 31.4‰ to 36.3‰, respectively, the observed SP at aeration tank was close to SP(ND rather than SP(HO. It was ranged from 0.4‰ to 13.3‰ when N2O concentration was high, implying that the NO2- reduction made a greater contribution to N2O production. Slightly elevated SP (13.3‰ only at

Potential use of the non-random distribution of N2 and N2O mole masses in the atmosphere as a tool for tracing atmospheric mixing and isotope fractionation processes

International Nuclear Information System (INIS)

Well, R.; Langel, R.; Reineking, A.

2002-01-01

The variation in the natural abundance of 15 N in atmospheric gas species is often used to determine the mixing of trace gases from different sources. With conventional budget calculations one unknown quantity can be determined if the remaining quantities are known. From 15 N tracer studies in soils with highly enriched 15 N-nitrate a procedure is known to calculate the mixing of atmospheric and soil derived N 2 based on the measurement of the 30/28 and 29/28 ratios in gas samples collected from soil covers. Because of the non-random distribution of the mole masses 30 N 2 , 29 N 2 and 28 N 2 in the mixing gas it is possible to calculate two quantities simultaneously, i.e. the mixing ratio of atmospheric and soil derived N 2 , and the isotopic signature of the soil derived N 2 . Routine standard measurements of laboratory air had suggested a non-random distribution of N 2 -mole masses. The objective of this study was to investigate and explain the existence of non-random distributions of 15 N 15 N, 14 N 15 N and 14 N 14 N in N 2 and N 2 O in environmental samples. The calculation of theoretical isotope data resulting from hypothetical mixing of two sources differing in 15 N natural abundance demonstrated, that the deviation from an ideal random distribution of mole masses is not detectable with the current precision of mass spectrometry. 15 N-analysis of N 2 or N 2 O was conducted with randomised and non-randomised replicate samples of different origin. 15 N abundance as calculated from 29/28 ratios were generally higher in randomised samples. The differences between the treatments ranged between 0.05 and 0.17 δper mille 15 N. It was concluded that the observed randomisation effect is probably caused by 15 N 15 N fractionation during environmental processes. (author)

Stratospheric Influence on Summer Monsoon and Associated Planetary Wave Breaking and Mixing in the Subtropical Tropopause Region

Science.gov (United States)

Lubis, S. W.; Nakamura, N.

2017-12-01

Previous studies have shown that the monsoonal circulation plays an important role in planetary wave breaking (PWB). The highest frequency of breaking events occurs just downstream (east) of the monsoon region in summer. PWB induces mixing of potential vorticity (PV) and hence, alter the horizontal mixing in the atmosphere. Here, the authors hypothesize that the stratospheric easterlies in the boreal summer also play a significant role in the PWB and mixing associated with the summer monsoon. If the stratospheric winds were westerly in boreal summer, the frequency of PWB would be decreased due to more waves penetrating in the stratosphere, resulting in less horizontal PWB and thus reduced mixing in the subtropical tropopause region. The hypothesis is examined by using a set of idealized moist GFDL simulations. The monsoon circulation is produced by adding a land-sea contrast with a Gaussian-shaped mountains positioned in the midlatitudes. Other key ingredients for the monsoon, including albedo, oceanic warm pool, and Q-flux, were also ideally imposed in all simulations. Our control simulation produces a summer monsoon-like circulation similar to the observation. In particular, the thermally forced monsoonal circulation forms a prominent closed upper-level anticyclone that dominates the summertime upper-level flow. Associated with this circulation is an upward-bulging tropopause that forms a large reservoir of anomalously low PV. Consistent with previous studies, the well-defined tropospheric jet lies just poleward of the upper-level anticyclone, and acts as a dynamical barrier between the low-PV reservoir over the monsoonal region and the high-PV reservoir in the extratropics. This barrier disappears just northeast of the monsoon area in the jet exit region, allowing more quasi-planetary waves to break in this region. Repetitive wave breaking further weakens the PV gradient, leading to the formation of the surf zone and stronger mixing in this region. To quantify

Stratospheric ozone - Impact of human activity

Science.gov (United States)

Mcelroy, Michael B.; Salawitch, Ross J.

1989-01-01

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Monitoring N2O Production Using a cNOR Modeled Active Site

Science.gov (United States)

Griffiths, Z. G.; Hegg, E. L.; Finders, C.; Haslun, J. A.

2017-12-01

Nitrous oxide (N2O) is a potent greenhouse gas with a 100-year global warming potential 265-296 times greater than carbon dioxide (CO2). It is the leading contributor to ozone depletion and can persist in the stratosphere for approximately 114 years. Hence, understanding the sources of atmospheric N2O emissions is critical to remediating the effects of climate change. Agricultural activities are the largest contributor to N2O emissions in the U.S. with microbial nitrification and denitrification as the dominating soil processes. The enzyme cytochrome c nitric oxide reductase (cNOR) is involved in bacterial denitrification. It is often difficult to study the enzymes involved in biotic N2O production, hence, model enzymes are a useful tool. The enzyme I107EFeBMb, a sperm whale myoglobin derivative, models the active site of cNOR and was used to simulate the anaerobic reduction of NO to N2O by cNOR. Dithionite was used to induce the catalytic activity of I107EFeBMb by reducing the enzyme. However, dithionite is a strong reductant that is capable of reducing NO to N2O directly. Therefore, the dithionite-enzyme mixture was passed through a size-exclusion column to isolate the reduced enzyme. This reduced and purified enzyme was then utilized to investigate N2O production from NO. This project will provide both an enzymatic and abiotic model to study N2O production.

Respiratory transformation of nitrous oxide (N2O) to dinitrogen by Bacteria and Archaea.

Science.gov (United States)

Zumft, Walter G; Kroneck, Peter M H

2007-01-01

N2O is a potent greenhouse gas and stratospheric reactant that has been steadily on the rise since the beginning of industrialization. It is an obligatory inorganic metabolite of denitrifying bacteria, and some production of N2O is also found in nitrifying and methanotrophic bacteria. We focus this review on the respiratory aspect of N2O transformation catalysed by the multicopper enzyme nitrous oxide reductase (N2OR) that provides the bacterial cell with an electron sink for anaerobic growth. Two types of Cu centres discovered in N2OR were both novel structures among the Cu proteins: the mixed-valent dinuclear Cu(A) species at the electron entry site of the enzyme, and the tetranuclear Cu(Z) centre as the first catalytically active Cu-sulfur complex known. Several accessory proteins function as Cu chaperone and ABC transporter systems for the biogenesis of the catalytic centre. We describe here the paradigm of Z-type N2OR, whose characteristics have been studied in most detail in the genera Pseudomonas and Paracoccus. Sequenced bacterial genomes now provide an invaluable additional source of information. New strains harbouring nos genes and capability of N2O utilization are being uncovered. This reveals previously unknown relationships and allows pattern recognition and predictions. The core nos genes, nosZDFYL, share a common phylogeny. Most principal taxonomic lineages follow the same biochemical and genetic pattern and share the Z-type enzyme. A modified N2OR is found in Wolinella succinogenes, and circumstantial evidence also indicates for certain Archaea another type of N2OR. The current picture supports the view of evolution of N2O respiration prior to the separation of the domains Bacteria and Archaea. Lateral nos gene transfer from an epsilon-proteobacterium as donor is suggested for Magnetospirillum magnetotacticum and Dechloromonas aromatica. In a few cases, nos gene clusters are plasmid borne. Inorganic N2O metabolism is associated with a diversity of

Atomic layer deposition and properties of mixed Ta2O5 and ZrO2 films

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Kaupo Kukli

2017-02-01

Full Text Available Thin solid films consisting of ZrO2 and Ta2O5 were grown by atomic layer deposition at 300 °C. Ta2O5 films doped with ZrO2, TaZr2.75O8 ternary phase, or ZrO2 doped with Ta2O5 were grown to thickness and composition depending on the number and ratio of alternating ZrO2 and Ta2O5 deposition cycles. All the films grown exhibited resistive switching characteristics between TiN and Pt electrodes, expressed by repetitive current-voltage loops. The most reliable windows between high and low resistive states were observed in Ta2O5 films mixed with relatively low amounts of ZrO2, providing Zr to Ta cation ratio of 0.2.

Methane as a Diagnostic Tracer of Changes in the Brewer-Dobson Circulation of the Stratosphere

Science.gov (United States)

Remsberg, E. E.

2015-01-01

This study makes use of time series of methane (CH4/ data from the Halogen Occultation Experiment (HALOE) to detect whether there were any statistically significant changes of the Brewer-Dobson circulation (BDC) within the stratosphere during 1992-2005. The HALOE CH4 profiles are in terms of mixing ratio versus pressure altitude and are binned into latitude zones within the Southern Hemisphere and the Northern Hemisphere. Their separate time series are then analyzed using multiple linear regression (MLR) techniques. The CH4 trend terms for the Northern Hemisphere are significant and positive at 10 N from 50 to 7 hPa and larger than the tropospheric CH4 trends of about 3%decade(exp -1) from 20 to 7 hPa. At 60 N the trends are clearly negative from 20 to 7 hPa. Their combined trends indicate an acceleration of the BDC in the middle stratosphere of the Northern Hemisphere during those years, most likely due to changes from the effects of wave activity. No similar significant BDC acceleration is found for the Southern Hemisphere. Trends from HALOE H2O are analyzed for consistency. Their mutual trends with CH4 are anti-correlated qualitatively in the middle and upper stratosphere, where CH4 is chemically oxidized to H2O. Conversely, their mutual trends in the lower stratosphere are dominated by their trends upon entry to the tropical stratosphere. Time series residuals for CH4 in the lower mesosphere also exhibit structures that are anti-correlated in some instances with those of the tracer-like species HCl. Their occasional aperiodic structures indicate the effects of transport following episodic, wintertime wave activity. It is concluded that observed multi-year, zonally averaged distributions of CH4 can be used to diagnose major instances of wave-induced transport in the middle atmosphere and to detect changes in the stratospheric BDC.

Improving estimates of N2O emissions for western and central Europe using a Bayesian inversion approach

Science.gov (United States)

Thompson, R. L.; Gerbig, C.; Roedenbeck, C.; Heimann, M.

2009-04-01

The nitrous oxide (N2O) mixing ratio has been increasing in the atmosphere since the industrial revolution, from 270 ppb in 1750 to 320 ppb in 2007 with a steady growth rate of around 0.26% since the early 1980's. The increase in N2O is worrisome for two main reasons. First, it is a greenhouse gas; this means that its atmospheric increase translates to an enhancement in radiative forcing of 0.16 ± 0.02 Wm-2 making it currently the fourth most important long-lived greenhouse gas and is predicted to soon overtake CFC's to become the third most important. Second, it plays an important role in stratospheric ozone chemistry. Human activities are the primary cause of the atmospheric N2O increase. The largest anthropogenic source of N2O is from the use of N-fertilizers in agriculture but fossil fuel combustion and industrial processes, such as adipic and nitric acid production, are also important. We present a Bayesian inversion approach for estimating N2O fluxes over central and western Europe using high frequency in-situ concentration data from the Ochsenkopf tall tower (50 °01′N, 11 °48′, 1022 masl). For the inversion, we employ a Lagrangian-type transport model, STILT, which provides source-receptor relationships at 10 km using ECMWF meteorological data. The a priori flux estimates used were from IER, for anthropogenic, and GEIA, for natural fluxes. N2O fluxes were retrieved monthly at 2 x 2 degree spatial resolution for 2007. The retrieved N2O fluxes showed significantly more spatial heterogeneity than in the a priori field and considerable seasonal variability. The timing of peak emissions was different for different regions but in general the months with the strongest emissions were May and August. Overall, the retrieved flux (anthropogenic and natural) was lower than in the a priori field.

Stratospheric ozone: an introduction to its study

International Nuclear Information System (INIS)

Nicolet, M.

1975-01-01

An analysis is made of the various reactions in which ozone and atomic oxygen are involved in the stratosphere. At the present time, hydrogen, nitrogen, and chlorine compounds in the ranges parts per million, parts per billion, and parts per trillion may have significant chemical effects. In the upper stratosphere, above the ozone peak, where there is no strong departure from photochemical equilibrium conditions, the action of hydroxyl and hydroperoxyl radicals of nitrogen dioxide and chlorine monoxide on atomic oxygen and of atomic chlorine on ozone can be introduced. A precise determination of their exact effects requires knowledge of the vertical distribution of the H 2 O, CH 4 , and H 2 dissociation by reaction of these molecules with electronically excited oxygen atom O( 1 D); the ratio of the OH and HO 2 concentrations and their absolute values, which depend on insufficiently known rate coefficients; the various origins of nitric oxide production, with their vertical distributions related to latitude and season; and the various sources giving different chlorine compounds that may be dissociated in the stratosphere. In the lower stratosphere, below the ozone peak, there is no important photochemical production of O 3 , but there exist various possibilities of transport. The predictability of the action of chemical reactions depends strongly on important interactions between OH and HO 2 radicals with CO and NO, respectively, which affect the ratio n(OH)/n(HO 2 ) at the tropopause level; between OH and NO 2 , which lead to the formation of nitric acid with its downward transport toward the troposphere; between NO and HO 2 , which lead to NO 2 and its subsequent photodissociation; between ClO and NO, which also lead to NO 2 and become more important than the reaction of ClO with O; and between Cl and various molecules, such as CH 4 and H 2 , which lead to HCl with its downward transportation toward the troposphere

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

Science.gov (United States)

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.

Frictional properties of CeO$_{2}$-Al$_{2}$O$_{3}$-ZrO$_{2}$ plasma-sprayed film under mixed and boundary lubricating conditions

CERN Document Server

Kita, H; Osumi, K; 10.2109/jcersj.112.615

2004-01-01

In order to find a counterpart for reducing the frictional coefficient of Al/sub 2/O/sub 3/-ZrO/sub 2/-CeO/sub 2/ plasma-sprayed film, the sliding properties in mixed and boundary lubricating conditions was investigated. It was found that combination of a CrN- coated cast iron pin and an Al/sub 2/O/sub 3/-ZrO/sub 2/-CeO/sub 2/ plasma sprayed plate provided the lowest frictional coefficient among several combinations chosen from practical materials. The coefficient of friction was much lower than that of the materials combination widely used for piston ring and cylinder liner. It was inferred that the combination of a pin made of hard materials with high density, a smooth surface such as CrN-coated cast iron and a porous plate can reduce the frictional coefficient because less sliding resistance is implemented and porosity retains oil.

Polar-night O3, NO2 and NO3 distributions during sudden stratospheric warmings in 2003–2008 as seen by GOMOS/Envisat

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E. Kyrölä

2012-01-01

Full Text Available Sudden stratospheric warmings (SSW are large-scale transient events, which have a profound effect on the Northern Hemisphere stratospheric circulation in winter. During the SSW events the temperature in stratosphere increases by several tens of Kelvins and zonal winds decelerate or reverse in direction. Changes in temperature and dynamics significantly affect the chemical composition of the middle atmosphere. In this paper, the response of the middle-atmosphere trace gases during several sudden stratospheric warmings in 2003–2008 is investigated using measurements from the GOMOS (Global Ozone Monitoring by Occultation of Stars instrument on board the Envisat satellite. We have analyzed spatial and temporal changes of NO2 and NO3 in the stratosphere, and of ozone in the whole middle atmosphere. To facilitate our analyses, we have used the temperature profiles data from the MLS (Microwave Limb Sounder instrument on board the Aura satellite, as well as simulations by the FinROSE chemistry-transport model and the Sodankylä Ion and Neutral Chemistry model (SIC. NO3 observations in the polar winter stratosphere during SSWs are reported for the first time. Changes in chemical composition are found not to be restricted to the stratosphere, but to extend to mesosphere and lower thermosphere. They often exhibit a complicated structure, because the distribution of trace gases is affected by changes in both chemistry and dynamics. The tertiary ozone maximum in the mesosphere often disappears with the onset of SSW, probably because of strong mixing processes. The strong horizontal mixing with outside-vortex air is well observed also in NO2 data, especially in cases of enhanced NO2 inside the polar vortex before SSW. Almost in all of the considered events, ozone near the secondary maximum decreases with onset of SSW. In both experimental data and FinROSE modelling, ozone changes are positively correlated with temperature changes in the lower stratosphere

Inter-comparison of stratospheric mean-meridional circulation and eddy mixing among six reanalysis data sets

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K. Miyazaki

2016-05-01

Full Text Available The stratospheric mean-meridional circulation (MMC and eddy mixing are compared among six meteorological reanalysis data sets: NCEP-NCAR, NCEP-CFSR, ERA-40, ERA-Interim, JRA-25, and JRA-55 for the period 1979–2012. The reanalysis data sets produced using advanced systems (i.e., NCEP-CFSR, ERA-Interim, and JRA-55 generally reveal a weaker MMC in the Northern Hemisphere (NH compared with those produced using older systems (i.e., NCEP/NCAR, ERA-40, and JRA-25. The mean mixing strength differs largely among the data products. In the NH lower stratosphere, the contribution of planetary-scale mixing is larger in the new data sets than in the old data sets, whereas that of small-scale mixing is weaker in the new data sets. Conventional data assimilation techniques introduce analysis increments without maintaining physical balance, which may have caused an overly strong MMC and spurious small-scale eddies in the old data sets. At the NH mid-latitudes, only ERA-Interim reveals a weakening MMC trend in the deep branch of the Brewer–Dobson circulation (BDC. The relative importance of the eddy mixing compared with the mean-meridional transport in the subtropical lower stratosphere shows increasing trends in ERA-Interim and JRA-55; this together with the weakened MMC in the deep branch may imply an increasing age-of-air (AoA in the NH middle stratosphere in ERA-Interim. Overall, discrepancies between the different variables and trends therein as derived from the different reanalyses are still relatively large, suggesting that more investments in these products are needed in order to obtain a consolidated picture of observed changes in the BDC and the mechanisms that drive them.

Spatial Variations in N2O Concentration and Isotopomer Composition off the Peru Coast

Science.gov (United States)

Bourbonnais, A.; Letscher, R. T.; Kock, A.; Bange, H. W.; Altabet, M. A.

2016-02-01

Nitrous oxide (N2O) is a potent greenhouse gas and stratospheric ozone depleting substance. The ocean is an important source of N2O to the atmosphere, accounting for up to about 30% of total emissions. However, the factors controlling N2O production and consumption in oceanic environments are still not understood nor constrained. N2O is a by-product of aerobic nitrification, and is formed by two different pathways: 1) the decomposition of hydroxylamine, an intermediate during ammonium oxidation to nitrite, or 2) the reduction of nitrite to N2O (nitrifier-denitrification). N2O is also an intermediate during denitrification under anoxic conditions. In this study, we measured N2O concentrations and isotopomer ratios, as well as O2, nutrient and biogenic N2 concentrations and the isotopic compositions of nitrate, nitrite and biogenic N2 at several coastal stations during two cruises off the Peru coast (6-14°S, 75-81°W) in December 2012 and January 2013. [N2O] varied from below equilibrium values in the OMZ to up to 238 nmol L-1 at 11 m depth at one of the shallowest stations. The isotopic composition of N2O (bulk δ15N: -5 to 30‰, δ18O: 41 to 95‰, and Site Preference: -3 to 65‰) also varied widely, with important differences between stations. Our results show a strong spatial heterogeneity in the mechanisms controlling N2O production and consumption in coastal upwelling regions, which should be taken into account in oceanic N2O models. We will discuss the contributions from different N2O production processes responsible for the observed extreme N2O accumulations.

N2O emission from plant surfaces - light stimulated and a global phenomenon.

Science.gov (United States)

Mikkelsen, Teis; Bruhn, Dan; Ambus, Per

2017-04-01

Nitrous oxide (N2O) is an important long-lived greenhouse gas and precursor of stratospheric ozone depleting mono-nitrogen oxides. The atmospheric concentration of N2O is persistently increasing; however, large uncertainties are associated with the distinct source strengths. Here we investigate for the first time N2O emission from terrestrial vegetation in response to natural solar ultra violet radiation. We conducted field site measurements to investigate N2O atmosphere exchange from grass vegetation exposed to solar irradiance with and without UV-screening. Further laboratory tests were conducted with a range of species to study the controls and possible loci of UV-induced N2O emission from plants. Plants released N2O in response to natural sunlight at rates of c. 20-50 nmol m-2 h-1, mostly due to the UV component. The emission rate is temperature dependent with a rather high activation energy indicative for an abiotic process. The prevailing zone for the N2O formation appears to be at the very surface of leaves. However, only c. 26% of the UV-induced N2O appears to originate from plant-N. Further, the process is dependent on atmospheric oxygen concentration. Our work demonstrates that ecosystem emission of the important greenhouse gas, N2O, may be up to c. 30% higher than hitherto assumed. Literature: Mikkelsen TN, Bruhn D & Ambus P. (2016). Solar UV Irradiation-Induced Production of Greenhouse Gases from Plant Surfaces: From Leaf to Earth. Progress in Botany, DOI 10.1007/124_2016_10. Bruhn D, Albert KR, Mikkelsen TN & Ambus P. (2014). UV-induced N2O emission from plants. Atmospheric Environment 99, 206-214.

Stretching Diagnostics and Mixing Properties In The Stratosphere

Science.gov (United States)

Legras, B.; Shuckburgh, E.

The "finite size Lyapunov exponent" and the "effective diffusivity" are two diagnos- tics of mixing which have been recently introduced to investigate atmospheric flows. Both have been used to successfully identify the barriers to transport, for instance at the edge of the stratospheric polar vortex. Here we compare the two diagnostics in detail. The equivalent length has the advantage of arising as a mixing quantification from a rigid theoretical framework, however it has the disadvantage of being an aver- age quantity (the average around a tracer contour). The finite size Lyapunov exponent may be defined at any point in the flow, and quantifies the stretching properties expe- rienced by a fluid parcel both in its past and future evolution. In particular, the lines of maximum stretching at any time delineate the building blocks of the chaotic stirring. However the interpretation of the finite size Lyapunov exponent as a mixing time is less direct and depends on the alignment of tracer contours with the stretching lines.

Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO2, PrO2, and TbO2.

Science.gov (United States)

Minasian, Stefan G; Batista, Enrique R; Booth, Corwin H; Clark, David L; Keith, Jason M; Kozimor, Stosh A; Lukens, Wayne W; Martin, Richard L; Shuh, David K; Stieber, S Chantal E; Tylisczcak, Tolek; Wen, Xiao-Dong

2017-12-13

Understanding the nature of covalent (band-like) vs ionic (atomic-like) electrons in metal oxides continues to be at the forefront of research in the physical sciences. In particular, the development of a coherent and quantitative model of bonding and electronic structure for the lanthanide dioxides, LnO 2 (Ln = Ce, Pr, and Tb), has remained a considerable challenge for both experiment and theory. Herein, relative changes in mixing between the O 2p orbitals and the Ln 4f and 5d orbitals in LnO 2 are evaluated quantitatively using O K-edge X-ray absorption spectroscopy (XAS) obtained with a scanning transmission X-ray microscope and density functional theory (DFT) calculations. For each LnO 2 , the results reveal significant amounts of Ln 5d and O 2p mixing in the orbitals of t 2g (σ-bonding) and e g (π-bonding) symmetry. The remarkable agreement between experiment and theory also shows that significant mixing with the O 2p orbitals occurs in a band derived from the 4f orbitals of a 2u symmetry (σ-bonding) for each compound. However, a large increase in orbital mixing is observed for PrO 2 that is ascribed to a unique interaction derived from the 4f orbitals of t 1u symmetry (σ- and π-bonding). O K-edge XAS and DFT results are compared with complementary L 3 -edge and M 5,4 -edge XAS measurements and configuration interaction calculations, which shows that each spectroscopic approach provides evidence for ground state O 2p and Ln 4f orbital mixing despite inducing very different core-hole potentials in the final state.

On the cryogenic removal of NOy from the Antarctic polar stratosphere

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S. Smyshlyaev

2003-06-01

Full Text Available We review current knowledge about the annual cycle of transport of nitrogen oxides to, and removal from, the polar stratosphere, with particular attention to Antarctica where the annual winter denitrifi cation process is both regular in occurrence and severe in effect. Evidence for a large downward fl ux of NOy from the mesosphere to the stratosphere, fi rst seen briefl y in the Limb Infrared Monitor of the Stratosphere (LIMS data from the Arctic winter of 1978-1979, has been found during the 1990s in both satellite and ground-based observations, though this still seems to be omitted from many atmospheric models. When incorporated in the Stony Brook- St. Petersburg two dimensional (2D transport and chemistry model, more realistic treatment of the NOy fl ux, along with sulfate transport from the mesosphere, sulfate aerosol formation where temperature is favorable, and the inclusion of a simple ion-cluster reaction, leads to good agreement with observed HNO3 formation in the mid-winter middle to upper stratosphere. To further emphasize the importance of large fl uxes of thermospheric and mesospheric NOy into the polar stratosphere, we have used observations, supplemented with model calculations, to defi ne new altitude dependent correlation curves between N2O and NOy. These are more suitable than those previously used in the literature to represent conditions within the Antarctic vortex region prior to and during denitrifi cation by Polar Stratospheric Cloud (PSC particles. Our NOy -N2O curves lead to a 40% increase in the average amount of NOy removed during the Antarctic winter with respect to estimates calculated using NOy-N2O curves from the Atmospheric Trace Molecule Spectroscopy (ATMOS/ATLAS-3 data set.

Satellite observations and modeling of transport in the upper troposphere through the lower mesosphere during the 2006 major stratospheric sudden warming

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W. H. Daffer

2009-07-01

Full Text Available An unusually strong and prolonged stratospheric sudden warming (SSW in January 2006 was the first major SSW for which globally distributed long-lived trace gas data are available covering the upper troposphere through the lower mesosphere. We use Aura Microwave Limb Sounder (MLS, Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS data, the SLIMCAT Chemistry Transport Model (CTM, and assimilated meteorological analyses to provide a comprehensive picture of transport during this event. The upper tropospheric ridge that triggered the SSW was associated with an elevated tropopause and layering in trace gas profiles in conjunction with stratospheric and tropospheric intrusions. Anomalous poleward transport (with corresponding quasi-isentropic troposphere-to-stratosphere exchange at the lowest levels studied in the region over the ridge extended well into the lower stratosphere. In the middle and upper stratosphere, the breakdown of the polar vortex transport barrier was seen in a signature of rapid, widespread mixing in trace gases, including CO, H₂O, CH₄ and N₂O. The vortex broke down slightly later and more slowly in the lower than in the middle stratosphere. In the middle and lower stratosphere, small remnants with trace gas values characteristic of the pre-SSW vortex lingered through the weak and slow recovery of the vortex. The upper stratospheric vortex quickly reformed, and, as enhanced diabatic descent set in, CO descended into this strong vortex, echoing the fall vortex development. Trace gas evolution in the SLIMCAT CTM agrees well with that in the satellite trace gas data from the upper troposphere through the middle stratosphere. In the upper stratosphere and lower mesosphere, the SLIMCAT simulation does not capture the strong descent of mesospheric CO and H₂O values into the reformed vortex; this poor CTM performance in the upper stratosphere and lower mesosphere results

A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO2, CH4, N2O, SF6 and CO

NARCIS (Netherlands)

van der Laan, S.; Neubert, R. E. M.; Meijer, H. A. J.; Simpson, W.R.

2009-01-01

We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured

Effect of Preparation Method on Catalytic Properties of Co-Mn-Al Mixed Oxides for N2O Decomposition.

Czech Academy of Sciences Publication Activity Database

Klyushina, A.; Pacultová, K.; Karásková, K.; Jirátová, Květa; Ritz, M.; Fridrichová, D.; Volodorskaja, A.; Obalová, L.

2016-01-01

Roč. 425, DEC 15 (2016), s. 237-247 ISSN 1381-1169 R&D Projects: GA ČR GA14-13750S Institutional support: RVO:67985858 Keywords : Co-Mn-Al mixed oxide * N2O decomposition * preparation methods Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.211, year: 2016

Nitrogen loss from high N-input vegetable fields - a) direct N2O emissions b) Spatiotemporal variability of N species (N2O, NH4+, NO3-) in soils

Science.gov (United States)

Pfab, H.; Ruser, R.; Palmer, I.; Fiedler, S.

2009-04-01

Nitrous oxide is a climate relevant trace gas. It contributes 7.9 % to the total anthropogenic greenhouse gas emission and it is also involved in stratospheric ozone depletion. Approximately 85 % of the anthropogenic N2O emissions result from agricultural activities, more than 50 % are produced during microbial N-turnover processes in soils. Especially soils with high N-input (N-fertilizer and high amount of N in plant residues) like vegetable cropped soils are assumed to cause high N2O losses. The aims of the study presented were (i) to quantify the N2O loss from a vegetable field (lettuce-cauliflower crop rotation), (ii) to calculate an emission factor for the study site in Southwest Germany and to compare this factor with the default value provided by the IPCC (2006) and (iii) to test the emission reduction potential (Ammonium Sulfate Nitrate fertilizer, ASN either by reduced N-fertilization) in comparison with common N doses used for good agricultural practice or by the use of a nitrification inhibitor (DMPP), a banded N-application (lettuce) or a depot fertilization measure (pseudo-CULTAN in order to suppress nitrification). N2O fluxes determined with the closed chamber method were highly variable in time with strongly increased flux rates after N-fertilization in combination with rainfall or irrigation measures and after the incorporation of cauliflower crop residues. Using the mean soil nitrate contents of the top soil of our investigated treatments (0-25 cm depth), we could explain approximately 60 % of the variability of the cumulative N2O losses during the vegetation period of lettuce and cauliflower. The cumulative N2O emissions ranged between 0,99 kg N2O-N ha-1 from the unfertilized control plots (vegetation period) and 6,81 kg N2O-N ha-1 from the plots with the highest N-dose. Based on the guidelines of the IPCC (2006), we calculated an emission factor around 0,9 % for the cropping season. This value is in good agreement with the default value of the

MLS/Aura Near-Real-Time L2 Nitrous Oxide (N2O) Mixing Ratio V003

Data.gov (United States)

National Aeronautics and Space Administration — ML2N2O_NRT is the EOS Aura Microwave Limb Sounder (MLS) Near-Real-Time (NRT) product for nitrous oxide (N2O). This product contains daily N2O profiles taken from the...

High Resolution Measurements of Nitrous Oxide (N2O in the Elbe Estuary

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Lisa Brase

2017-05-01

Full Text Available Nitrous oxide (N2O is one of the most important greenhouse gases and a major sink for stratospheric ozone. Estuaries are sites of intense biological production and N2O emissions. We aimed to identify hot spots of N2O production and potential pathways contributing to N2O concentrations in the surface water of the tidal Elbe estuary. During two research cruises in April and June 2015, surface water N2O concentrations were measured along the salinity gradient of the Elbe estuary by using a laser-based on-line analyzer coupled to an equilibrator. Based on these high-resolution N2O profiles, N2O saturations, and fluxes across the surface water/atmosphere interface were calculated. Additional measurements of DIN concentrations, oxygen concentration, and salinity were performed. Highest N2O concentrations were determined in the Hamburg port region reaching maximum values of 32.3 nM in April 2015 and 52.2 nM in June 2015. These results identify the Hamburg port region as a significant hot spot of N2O production, where linear correlations of AOU-N2Oxs indicate nitrification as an important contributor to N2O production in the freshwater part. However, in the region with lowest oxygen saturation, sediment denitrification obviously affected water column N2O saturation. The average N2O saturation over the entire estuary was 201% (SD: ±94%, with an average estuarine N2O flux density of 48 μmol m−2 d−1 and an overall emission of 0.18 Gg N2O y−1. In comparison to previous studies, our data indicate that N2O production pathways over the whole estuarine freshwater part have changed from predominant denitrification in the 1980s toward significant production from nitrification in the present estuary. Despite a significant reduction in N2O saturation compared to the 1980s, N2O concentrations nowadays remain on a high level, comparable to the mid-90s, although a steady decrease of DIN inputs occurred over the last decades. Hence, the Elbe estuary still

UV Absorption Cross Sections of Nitrous Oxide (N2O) and Carbon Tetrachloride (CCl4) Between 210 and 350 K and the Atmospheric Implications

Science.gov (United States)

Carlon, Nabilah Rontu; Papanastasiou, Dimitrios K.; Fleming, Eric L.; Jackman, Charles H.; Newman, Paul A.; Burkholder, James B.

2010-01-01

Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at 27 temperatures in the range 210-350 K. In addition, UV absorption spectra of CCl4 are reported between 200-235 nm as a function of temperature (225-350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5-7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in 37 atmospheric model calculations is presented.

Upper limits for stratospheric H2O2 and HOCl from high resolution balloon-borne infrared solar absorption spectra

Science.gov (United States)

Larsen, J. C.; Rinsland, C. P.; Goldman, A.; Murcray, D. G.; Murcray, F. J.

1985-01-01

Solar absorption spectra from two stratospheric balloon flights have been analyzed for the presence of H2O2 and HOCl absorption in the 1230.0 to 1255.0 per cm region. The data were recorded at 0.02 per cm resolution during sunset with the University of Denver interferometer system on October 27, 1978 and March 23, 1981. Selected spectral regions were analyzed with the technique of nonlinear least squares spectral curve fitting. Upper limits of 0.33 ppbv for H2O2 and 0.36 ppbv for HOCl near 28 km are derived from the 1978 flight data while upper limits of 0.44 ppbv for H2O2 and 0.43 ppbv for HOCl at 29.5 km are obtained from the 1981 flight data.

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

Science.gov (United States)

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

Measurement from sun-synchronous orbit of a reaction rate controlling the diurnal NOx cycle in the stratosphere

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A. Dudhia

2011-05-01

Full Text Available A reaction rate associated with the nighttime formation of an important diurnally varying species, N2O5, is determined from MIPAS-ENVISAT. During the day, photolysis of N2O5 in the stratosphere contributes to nitrogen-catalysed ozone destruction. However, at night concentrations of N2O5 increase, temporarily sequestering reactive NOx NO and NO2 in a natural cycle which regulates the majority of stratospheric ozone. In this paper, the reaction rate controlling the formation of N2O5 is determined from this instrument for the first time. The observed reaction rate is compared to the currently accepted rate determined from laboratory measurements. Good agreement is obtained between the observed and accepted experimental reaction rates within the error bars.

Impacts of Stratospheric Sulfate Geoengineering on PM2.5

Science.gov (United States)

Robock, A.; Xia, L.; Tilmes, S.; Mills, M. J.; Richter, J.; Kravitz, B.; MacMartin, D.

2017-12-01

Particulate matter (PM) includes sulfate, nitrate, organic carbon, elemental carbon, soil dust, and sea salt. The first four components are mostly present near the ground as fine particulate matter with a diameter less than 2.5 µm (PM2.5), and these are of the most concern for human health. PM is efficiently scavenged by precipitation, which is its main atmospheric sink. Here we examine the impact of stratospheric climate engineering on this important pollutant and health risk, taking advantage of two sets of climate model simulations conducted at the National Center for Atmospheric Research. We use the full tropospheric and stratospheric chemistry version of the Community Earth System Model - Community Atmospheric Model 4 (CESM CAM4-chem) with a horizontal resolution of 0.9° x 1.25° lat-lon to simulate a stratospheric sulfate injection climate intervention of 8 Tg SO2 yr-1 combined with an RCP6.0 global warming forcing, the G4 Specified Stratospheric Aerosol (G4SSA) scenario. We also analyze the output from a 20-member ensemble of Community Earth System Model, version 1 with the Whole Atmosphere Community Climate Model as its atmospheric component (CESM1(WACCM)) simulations, also at 0.9° x 1.25° lat-lon resolution, with sulfur dioxide injection at 15°N, 15°S, 30°N, and 30°S varying in time to balance RCP8.5 forcing. While the CESM CAM4-chem model has full tropospheric and stratospheric chemistry, CESM1(WACCM) has an internally generated quasi-biennial oscillation and a comprehensive tropospheric and stratospheric sulfate aerosol treatment, but only stratospheric chemistry. For G4SSA, there are a global temperature reduction of 0.8 K and global averaged precipitation decrease of 3% relative to RCP6.0. The global averaged surface PM2.5 reduces about 1% compared with RCP6.0, mainly over Eurasian and East Asian regions in Northern Hemisphere winter. The PM2.5 concentration change is a combination of effects from tropospheric chemistry and precipitation

Swift heavy-ion induced trap generation and mixing at Si/SiO{sub 2} interface in depletion n-MOS

Energy Technology Data Exchange (ETDEWEB)

Shinde, N. [Ecotopia Science Institute, Division of Energy Science, Nagoya University, Nagoya 464-8603 (Japan) and Department of Physics, University of Pune, Pune 411 007 (India)]. E-mail: nss@nucl.nagoya-u.ac.jp; Bhoraskar, V.N. [Department of Physics, University of Pune, Pune 411 007 (India); Dhole, S.D. [Department of Physics, University of Pune, Pune 411 007 (India)

2006-01-15

Large channel depletion n-channel MOSFET (Metal oxide semiconductor field effect transistor) is a basic Si-SiO{sub 2} structure to understand irradiation-induced modifications. The contribution of interface and oxide states denoted as {delta}N {sub IT} and {delta}N {sub OT}, respectively, was separated out by using I {sub D}-V {sub DS}, I {sub D}-V {sub GS} measurements. The threshold voltage shift {delta}V {sub T} (V {sub T-irrad} - V {sub T-virgin}) increased for all ions (50 MeV Li, B, F, P and Ni) over the fluence of 2 x 10{sup 11}-2 x 10{sup 13} ions/cm{sup 2}. The increase in {delta}N {sub IT} was associated to trap generation at Si-SiO{sub 2} interface, but a small change in {delta}N {sub OT} indicate less charge trapping in oxide. The electronic energy loss S {sub e} induced increase in {delta}N {sub IT} is not adequate to explain the large shift in threshold voltage. A rough estimate shows that the channel width, W should decrease by 40% for a large increase in {delta}N {sub IT}. Thus, the possible factor affecting reduction of W may be ion beam mixing induced broadening of Si-SiO{sub 2} interface.

Long-term trends in stratospheric ozone, temperature, and water vapor over the Indian region

Science.gov (United States)

Thankamani Akhil Raj, Sivan; Venkat Ratnam, Madineni; Narayana Rao, Daggumati; Venkata Krishna Murthy, Boddam

2018-01-01

We have investigated the long-term trends in and variabilities of stratospheric ozone, water vapor and temperature over the Indian monsoon region using the long-term data constructed from multi-satellite (Upper Atmosphere Research Satellite (UARS MLS and HALOE, 1993-2005), Aura Microwave Limb Sounder (MLS, 2004-2015), Sounding of the Atmosphere using Broadband Emission Radiometry (SABER, 2002-2015) on board TIMED (Thermosphere Ionosphere Mesosphere Energetics Dynamics)) observations covering the period 1993-2015. We have selected two locations, namely, Trivandrum (8.4° N, 76.9° E) and New Delhi (28° N, 77° E), covering northern and southern parts of the Indian region. We also used observations from another station, Gadanki (13.5° N, 79.2° E), for comparison. A decreasing trend in ozone associated with NOx chemistry in the tropical middle stratosphere is found, and the trend turned to positive in the upper stratosphere. Temperature shows a cooling trend in the stratosphere, with a maximum around 37 km over Trivandrum (-1.71 ± 0.49 K decade-1) and New Delhi (-1.15 ± 0.55 K decade-1). The observed cooling trend in the stratosphere over Trivandrum and New Delhi is consistent with Gadanki lidar observations during 1998-2011. The water vapor shows a decreasing trend in the lower stratosphere and an increasing trend in the middle and upper stratosphere. A good correlation between N2O and O3 is found in the middle stratosphere (˜ 10 hPa) and poor correlation in the lower stratosphere. There is not much regional difference in the water vapor and temperature trends. However, upper stratospheric ozone trends over Trivandrum and New Delhi are different. The trend analysis carried out by varying the initial year has shown significant changes in the estimated trend.

The major stratospheric final warming in 2016: dispersal of vortex air and termination of Arctic chemical ozone loss

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G. L. Manney

2016-12-01

Full Text Available The 2015/16 Northern Hemisphere winter stratosphere appeared to have the greatest potential yet seen for record Arctic ozone loss. Temperatures in the Arctic lower stratosphere were at record lows from December 2015 through early February 2016, with an unprecedented period of temperatures below ice polar stratospheric cloud thresholds. Trace gas measurements from the Aura Microwave Limb Sounder (MLS show that exceptional denitrification and dehydration, as well as extensive chlorine activation, occurred throughout the polar vortex. Ozone decreases in 2015/16 began earlier and proceeded more rapidly than those in 2010/11, a winter that saw unprecedented Arctic ozone loss. However, on 5–6 March 2016 a major final sudden stratospheric warming ("major final warming", MFW began. By mid-March, the mid-stratospheric vortex split after being displaced far off the pole. The resulting offspring vortices decayed rapidly preceding the full breakdown of the vortex by early April. In the lower stratosphere, the period of temperatures low enough for chlorine activation ended nearly a month earlier than that in 2011 because of the MFW. Ozone loss rates were thus kept in check because there was less sunlight during the cold period. Although the winter mean volume of air in which chemical ozone loss could occur was as large as that in 2010/11, observed ozone values did not drop to the persistently low values reached in 2011.We use MLS trace gas measurements, as well as mixing and polar vortex diagnostics based on meteorological fields, to show how the timing and intensity of the MFW and its impact on transport and mixing halted chemical ozone loss. Our detailed characterization of the polar vortex breakdown includes investigations of individual offspring vortices and the origins and fate of air within them. Comparisons of mixing diagnostics with lower-stratospheric N2O and middle-stratospheric CO from MLS (long-lived tracers show rapid vortex erosion and

Simulating the Snowball Stratosphere and Its Influence On CO2 Inference

Science.gov (United States)

Graham, R. J.; Shaw, T.; Abbot, D. S.

2017-12-01

According to the snowball Earth hypothesis, a large quantity of CO2 must build up during an event in order to cause eventual deglaciation. One prediction of this model is a depletion in atmospheric oxygen-17 as a result of stratospheric chemical reactions, which has been observed in preserved barite minerals. This represents one of the most dramatic and compelling pieces of evidence in support of the snowball Earth hypothesis. The inference of anomalous atmospheric oxygen-17 based on measurements of barite minerals, however, was made by assuming that the stratosphere-troposphere mass exchange rate and mixing within the stratosphere were the same as the present. In this contribution we test these assumptions with simulations of modern and snowball atmospheric conditions using the global climate model ECHAM5. Our simulations are still running, but we will have results to report by December.

Co-composting of municipal solid waste mixed with matured sewage sludge: The relationship between N2O emissions and denitrifying gene abundance.

Science.gov (United States)

Bian, Rongxing; Sun, Yingjie; Li, Weihua; Ma, Qiang; Chai, Xiaoli

2017-12-01

Aerobic composting is an alternative measure to the disposal of municipal solid waste (MSW). However, it produces nitrous oxide (N 2 O), a highly potent greenhouse via microbial nitrification and denitrification. In this study, the effects of matured sewage sludge (MSS) amendment on N 2 O emissions and the inter-relationships between N 2 O emissions and the abundance of denitrifying bacteria were investigated during aerobic composting of MSW. The results demonstrated that MSW composting with MSS amendments (C1, and C2, with a MSW to MSS ratio of 2:1 and 4:1, (v/v), respectively) significantly increased N 2 O emissions during the initial stage, yet contributed to the mitigation of N 2 O emissions during the cooling and maturation stage. MSS amended composting emitted a total of 18.4%-25.7% less N 2 O than the control treatment without MSS amendment (CK). Matured sewage sludge amendment also significantly altered the abundance of denitrifying bacteria. The quantification of denitrifying functional genes revealed that the N 2 O emission rate had a significant positive correlation with the abundance of the nirS, nirK genes in both treatments with MSS amendment. The nosZ/(nirS + nirK) ratio could be a good indicator for predicting N 2 O emissions. The higher N 2 O emission rate during the initial stage of composting mixed with MSS was characterized by lower nosZ/(nirS + nirK) ratios, compared to CK treatment. Higher ratios of nosZ/(nirS + nirK) were measured during the cooling and maturation stage in treatments with MSS which resulted in a reduction of the N 2 O emissions. These results demonstrated that MSS amendment could be a valid strategy for mitigating N 2 O emissions during MSW composting. Copyright © 2017 Elsevier Ltd. All rights reserved.

Airborne Arctic Stratospheric Expedition II: An overview

Science.gov (United States)

Anderson, James G.; Toon, Owen B.

1993-11-01

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), staged from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromine radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the Antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O.In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-I), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NOx and to some degree NOy were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, ClO was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of ClO and its dimer ClOOCl.This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-II): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30°N in the winter/spring northern hemisphere reported in satellite observations?

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

Science.gov (United States)

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

A single gas chromatograph for accurate atmospheric mixing ratio measurements of CO2, CH4, N2O, SF6 and CO

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H. A. J. Meijer

2009-09-01

Full Text Available We present an adapted gas chromatograph capable of measuring simultaneously and semi-continuously the atmospheric mixing ratios of the greenhouse gases CO2, CH4, N2O and SF6 and the trace gas CO with high precision and long-term stability. The novelty of our design is that all species are measured with only one device, making it a very cost-efficient system. No time lags are introduced between the measured mixing ratios. The system is designed to operate fully autonomously which makes it ideal for measurements at remote and unmanned stations. Only a small amount of sample air is needed, which makes this system also highly suitable for flask air measurements. In principle, only two reference cylinders are needed for daily operation and only one calibration per year against international WMO standards is sufficient to obtain high measurement precision and accuracy. The system described in this paper is in use since May 2006 at our atmospheric measurement site Lutjewad near Groningen, The Netherlands at 6°21´ E, 53°24´N, 1 m a.s.l. Results show the long-term stability of the system. Observed measurement precisions at our remote research station Lutjewad were: ±0.04 ppm for CO2, ±0.8 ppb for CH4, ±0.8 ppb for CO, ±0.3 ppb for N2O, and ±0.1 ppt for SF6. The ambient mixing ratios of all measured species as observed at station Lutjewad for the period of May 2007 to August 2008 are presented as well.

Study of a Mixed Alkaline–Earth Effect on Some Properties of Glasses of the CaO-MgO-Al2O3-SiO2 System

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Valle-Fuentes, J. F.

2007-06-01

Full Text Available In the present work, we studied a “Mixed Alkaline–Earth Effect”, i.e. the non-linear behaviour showed by the glass transition temperature as well as by the compressive strength of glasses of the CaO-MgO-Al2O3-SiO2 system, when a part of the CaO contained in them was substituted by a BaO/SrO mixture, in variable molar proportions. An important factor for the occurrence of this phenomenon was the difference in atomic weight, ionic radii and field strength of the Ba2+ and Sr2+ ions in comparison with those corresponding to the Ca2+ ion. Another factor considered was the likely occurrence of a microphase separation caused by the addition of BaO and/or SrO, together with the presence of F- and Mg2+ in the glasses. Other glass properties studied as a function of the CaO substitution level were density, glass molar volume, oxygen molar volume, packing fraction, and chemical resistance in neutral, basic and acidic aqueous media. In general, the structural reinforcement of the glass network caused by the partial substitution of CaO by a BaO/SrO mixture was accompanied by an improvement in the alkaline resistance of the materials, which were found to be suitable for applications in corrosive environments, especially in basic media. Keywords: Mixed alkaline–earth effect; CaO-MgO-Al2O3-SiO2 system; glass properties.En el presente trabajo, se estudia el comportamiento no lineal mostrado por la temperatura de transición vítrea y por la resistencia a la compresión de vidrios del sistema CaO-MgO-Al2O3-SiO2, cuando una parte del CaO contenido en los mismos es sustituido por una mezcla de BaO/SrO, en relación molar variable. Factores importantes para que se de este comportamiento son la diferencia entre pesos atómicos, radios iónicos e intensidad de campo de los iones Ba2+ y Sr2+ y los del propio ión Ca2+. Otro factor considerado ha sido la probable existencia de una separación de microfases originada por la adición de BaO y/o SrO, junto con la

Isotope signatures of N2O emitted from vegetable soil: Ammonia oxidation drives N2O production in NH4(+)-fertilized soil of North China.

Science.gov (United States)

Zhang, Wei; Li, Yuzhong; Xu, Chunying; Li, Qiaozhen; Lin, Wei

2016-07-08

Nitrous oxide (N2O) is a potent greenhouse gas. In North China, vegetable fields are amended with high levels of N fertilizer and irrigation water, which causes massive N2O flux. The aim of this study was to determine the contribution of microbial processes to N2O production and characterize isotopic signature effects on N2O source partitioning. We conducted a microcosm study that combined naturally abundant isotopologues and gas inhibitor techniques to analyze N2O flux and its isotopomer signatures [δ(15)N(bulk), δ(18)O, and SP (intramolecular (15)N site preference)] that emitted from vegetable soil after the addition of NH4(+) fertilizers. The results show that ammonia oxidation is the predominant process under high water content (70% water-filled pore space), and nitrifier denitrification contribution increases with increasing N content. δ(15)N(bulk) and δ(18)O of N2O may not provide information about microbial processes due to great shifts in precursor signatures and atom exchange, especially for soil treated with NH4(+) fertilizer. SP and associated two end-member mixing model are useful to distinguish N2O source and contribution. Further work is needed to explore isotopomer signature stability to improve N2O microbial process identification.

Impact of future nitrous oxide and carbon dioxide emissions on the stratospheric ozone layer

International Nuclear Information System (INIS)

Stolarski, Richard S; Waugh, Darryn W; Douglass, Anne R; Oman, Luke D

2015-01-01

The atmospheric levels of human-produced chlorocarbons and bromocarbons are projected to make only small contributions to ozone depletion by 2100. Increases in carbon dioxide (CO 2 ) and nitrous oxide (N 2 O) will become increasingly important in determining the future of the ozone layer. N 2 O increases lead to increased production of nitrogen oxides (NO x ), contributing to ozone depletion. CO 2 increases cool the stratosphere and affect ozone levels in several ways. Cooling decreases the rate of many photochemical reactions, thus slowing ozone loss rates. Cooling also increases the chemical destruction of nitrogen oxides, thereby moderating the effect of increased N 2 O on ozone depletion. The stratospheric ozone level projected for the end of this century therefore depends on future emissions of both CO 2 and N 2 O. We use a two-dimensional chemical transport model to explore a wide range of values for the boundary conditions for CO 2 and N 2 O, and find that all of the current scenarios for growth of greenhouse gases project the global average ozone to be larger in 2100 than in 1960. (letter)

Ab initio studies of O-2(-) (H2O)(n) and O-3(-) (H2O)(n) anionic molecular clusters, n

DEFF Research Database (Denmark)

Bork, Nicolai Christian; Kurten, T.; Enghoff, Martin Andreas Bødker

2011-01-01

that anionic O-2(-)(H2O)n and O-3(-)(H2O)n clusters are thermally stabilized at typical atmospheric conditions for at least n = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H2O is due to normal hydrogen bonding....... Although clustering up to 12 H2O, we find that the O-2 and O-3 anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O-2(-) and O-3(-) speicies are thus accessible for further reactions. We consider the distributions of cluster sizes as function of altitude before...

Long-term trends in stratospheric ozone, temperature, and water vapor over the Indian region

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S. T. Akhil Raj

2018-01-01

Full Text Available We have investigated the long-term trends in and variabilities of stratospheric ozone, water vapor and temperature over the Indian monsoon region using the long-term data constructed from multi-satellite (Upper Atmosphere Research Satellite (UARS MLS and HALOE, 1993–2005, Aura Microwave Limb Sounder (MLS, 2004–2015, Sounding of the Atmosphere using Broadband Emission Radiometry (SABER, 2002–2015 on board TIMED (Thermosphere Ionosphere Mesosphere Energetics Dynamics observations covering the period 1993–2015. We have selected two locations, namely, Trivandrum (8.4° N, 76.9° E and New Delhi (28° N, 77° E, covering northern and southern parts of the Indian region. We also used observations from another station, Gadanki (13.5° N, 79.2° E, for comparison. A decreasing trend in ozone associated with NOx chemistry in the tropical middle stratosphere is found, and the trend turned to positive in the upper stratosphere. Temperature shows a cooling trend in the stratosphere, with a maximum around 37 km over Trivandrum (−1.71 ± 0.49 K decade−1 and New Delhi (−1.15 ± 0.55 K decade−1. The observed cooling trend in the stratosphere over Trivandrum and New Delhi is consistent with Gadanki lidar observations during 1998–2011. The water vapor shows a decreasing trend in the lower stratosphere and an increasing trend in the middle and upper stratosphere. A good correlation between N2O and O3 is found in the middle stratosphere (∼ 10 hPa and poor correlation in the lower stratosphere. There is not much regional difference in the water vapor and temperature trends. However, upper stratospheric ozone trends over Trivandrum and New Delhi are different. The trend analysis carried out by varying the initial year has shown significant changes in the estimated trend.

20 Years of ClO Measurements in the Antarctic Lower Stratosphere

Science.gov (United States)

Nedoluha, Gerald E.; Connor, Brian J.; Mooney, Thomas; Barrett, James W.; Parrish, Alan; Gomez, R. Michael; Boyd, Ian; Allen, Douglas R.; Kotkamp, Michael; Kremser, Stefanie;

Photocatalytic decomposition of N{sub 2}O over TiO{sub 2}/g-C{sub 3}N{sub 4} photocatalysts heterojunction

Energy Technology Data Exchange (ETDEWEB)

Kočí, K., E-mail: kamila.koci@vsb.cz [Institute of Environmental technologies, VŠB Technical University of Ostrava 17. listopadu 15/2172, 708 00 Ostrava (Czech Republic); Reli, M.; Troppová, I.; Šihor, M. [Institute of Environmental technologies, VŠB Technical University of Ostrava 17. listopadu 15/2172, 708 00 Ostrava (Czech Republic); Kupková, J. [Nanotechnology center, VŠB Technical University of Ostrava 17. listopadu 15/2172, 708 00 Ostrava (Czech Republic); Kustrowski, P. [Faculty of Chemistry, Jagiellonian University in Kraków, ul. Ingardena 3, 30-060 Kraków (Poland); Praus, P. [Institute of Environmental technologies, VŠB Technical University of Ostrava 17. listopadu 15/2172, 708 00 Ostrava (Czech Republic); Department of Chemistry, VŠB Technical University of Ostrava 17. listopadu 15/2172, 708 00 Ostrava (Czech Republic)

2017-02-28

Highlights: • TiO{sub 2}/g-C{sub 3}N{sub 4} photocatalysts with the various TiO{sub 2}/g-C{sub 3}N{sub 4} weight ratios. • N{sub 2}O photocatalytic decomposition under UVC and UVA irradiation. • Heterojunction on the TiO{sub 2}/g-C{sub 3}N{sub 4} interface play an important role. • Optimal ratio of TiO{sub 2}:g-C{sub 3}N{sub 4} was 1:2 for the highest activity at UVA irradiation. - Abstract: TiO{sub 2}/g-C{sub 3}N{sub 4} photocatalysts with the various TiO{sub 2}/g-C{sub 3}N{sub 4} weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO{sub 2} was prepared by thermal hydrolysis and pure g-C{sub 3}N{sub 4} 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 TiO{sub 2} and g-C{sub 3}N{sub 4} 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 TiO{sub 2}/g-C{sub 3}N{sub 4} nanocomposites showed moderate improvement compared to pure g-C{sub 3}N{sub 4} but pure TiO{sub 2} proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO{sub 2}/g-C{sub 3}N{sub 4} (1:2) nanocomposite exhibited an increase compared to pure TiO{sub 2}. Nevertheless, further increase of g-C{sub 3}N{sub 4} amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO{sub 2} and g-C{sub 3}N{sub 4} have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C{sub 3}N{sub 4}. This is

Signals of El Niño Modoki in the tropical tropopause layer and stratosphere

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F. Xie

2012-06-01

Full Text Available The effects of El Niño Modoki events on the tropical tropopause layer (TTL and on the stratosphere were investigated using European Center for Medium Range Weather Forecasting (ECMWF reanalysis data, oceanic El Niño indices, and general climate model outputs. El Niño Modoki events tend to depress convective activities in the western and eastern Pacific but enhance convective activities in the central and northern Pacific. Consequently, during El Niño Modoki events, negative water vapor anomalies occur in the western and eastern Pacific upper troposphere, whereas there are positive anomalies in the central and northern Pacific upper troposphere. The spatial patterns of the outgoing longwave radiation (OLR and upper tropospheric water vapor anomalies exhibit a tripolar form. The empirical orthogonal function (EOF analysis of the OLR and upper tropospheric water vapor anomalies reveals that canonical El Niño events are associated with the leading mode of the EOF, while El Niño Modoki events correspond to the second mode. The composite analysis based on ERA-interim data indicate that El Niño Modoki events have a reverse effect on middle-high latitudes stratosphere, as compared with the effect of typical El Niño events, i.e., the northern polar vortex is stronger and colder but the southern polar vortex is weaker and warmer during El Niño Modoki events. According to the simulation' results, we found that the reverse effect on the middle-high latitudes stratosphere is resulted from a complicated interaction between quasi-biennial oscillation (QBO signal of east phase and El Niño Modoki signal. This interaction is not a simply linear overlay of QBO signal and El Niño Modoki signal in the stratosphere, it is El Niño Modoki that leads to different tropospheric zonal wind anomalies with QBO forcing from that caused by typical El Niño, thus, the planetary wave propagation from troposphere to the stratosphere during El Niño Modoki events is

ATMOS Stratospheric Deuterated Water and Implications for Tropospheric-Stratospheric Transport

Science.gov (United States)

Moyer, Elisabeth J.; Irion, Fredrick W.; Yung, Yuk L.; Gunson, Michael R.

1996-01-01

Measurements of the isotopic composition of stratospheric water by the ATMOS instrument are used to infer the convective history of stratospheric air. The average water vapor entering the stratosphere is found to be highly depleted of deuterium, with delta-D(sub w) of -670 +/- 80 (67% deuterium loss). Model calculations predict, however, that under conditions of thermodynamic equilibrium, dehydration to stratospheric mixing ratios should produce stronger depletion to delta-D(sub w) of -800 to 900 (80-90% deuterium loss). Deuterium enrichment of water vapor in ascending parcels can occur only in conditions of rapid convection; enrichments persisting into the stratosphere require that those conditions continue to near-tropopause altitudes. We conclude that either the predominant source of water vapor to the uppermost troposphere is enriched convective water, most likely evaporated cloud ice, or troposphere-stratosphere transport occurs closely associated with tropical deep convection.

Mixed Alkali Effect in (40-x)K2O-xLi2O-10Na2O-50B2O3 Glasses - Physical and Optical Absorption Studies

Science.gov (United States)

Samee, M. A.; Ahmmad, Shaikh Kareem; Taqiullah, Sair. Md.; Edukondalu, A.; Bale, Shashidhar; Rahman, Syed

So far only a handful of publications have been concerned with the study of the mixed alkali effect in borate glasses containing three types of alkali ions. In the present work, the mixed alkali effect (MAE) has been investigated in the glass system (40-x) K2O-x Li2O -10Na2O-50B2O3.(0≤x≤40 mol%) through density and modulated DSC studies. The density and glass transition temperature of the present glasses varies non-linearly exhibiting mixed alkali effect. We report the mixed alkali effect in the present glasses through optical properties. From the absorption edge studies, the various values of optical band gap (Eo) and Urbach energy (ΔE) have been evaluated. The values of Eo and ΔE show non-linear behavior with compositional parameter showing the mixed alkali effect. The band gap energy based average electronic polarizability of oxide ions αO2-(Eo), optical basicity A(Eo), and Yamashita-Kurosawa’s interaction parameter A(Eo) have been examined to check the correlations among them and bonding character. Based on good correlation among electronic polarizability of oxide ions, optical basicity and interaction parameter, the present K2O- Li2O-Na2O-B2O3 glasses are classified as normal ionic (basic) oxides.

Mixed oxides forming in CdO-OsO2 and PbO-OsO2 systems

International Nuclear Information System (INIS)

Shaplygin, I.S.; Lazarev, V.B.

1978-01-01

The formation of mixed oxides in systems CdO-OsO 2 and PbO-OsO 2 was studied by derivatography, X-ray phase analysis, and IR spectroscopy. It was established that in the system CdO-OsO 2 cubic phases of Cdsub(2)Ossub(2)Osub(6.7) and Cdsub(2)Ossub(2)Osub(7.2) with a pyrochlor-type structure, as well as new compounds with the structure of rhombic perovskite CdOsO 3 and Cd(Cdsub(0.5)Ossub(0.5))Osub(3) containing osmium in the formal degree of oxidation +4 and +6, respectively, are formed. The thermal stability of the compounds obtained was studied and their electrical properties determined

MLS/Aura Level 2 Nitrous Oxide (N2O) Mixing Ratio V004

Data.gov (United States)

National Aeronautics and Space Administration — ML2N2O is the EOS Aura Microwave Limb Sounder (MLS) standard product for nitrous oxide derived from radiances measured primarily by the 640 GHz radiometer (Band 12)...

Band-gap narrowing of TiO2 films induced by N-doping

International Nuclear Information System (INIS)

Nakano, Y.; Morikawa, T.; Ohwaki, T.; Taga, Y.

2006-01-01

N-doped TiO 2 films were deposited on n + -GaN/Al 2 O 3 substrates by reactive magnetron sputtering and subsequently crystallized by annealing at 550 o C in flowing N 2 gas. The N-doping concentration was ∼8.8%, as determined from X-ray photoelectron spectroscopy measurements. Deep-level optical spectroscopy measurements revealed two characteristic deep levels located at 1.18 and 2.48 eV below the conduction band. The 1.18 eV level is probably attributable to the O vacancy state and can be active as an efficient generation-recombination center. Additionally, the 2.48 eV band is newly introduced by the N-doping and contributes to band-gap narrowing by mixing with the O 2p valence band

Fourier transform infrared studies of the N2-O2 binary system

International Nuclear Information System (INIS)

Minenko, M.; Jodi, H.-J.

2006-01-01

Solid solutions (N 2 ) x (O 2 ) 1-x have been investigated by infrared absorption measurements mainly in the O 2 and N 2 stretching regions, between 60-10 K, completing former similar studies by Raman scattering. We produced thermodynamically stable samples by a careful thermal treatment, followed by cooling/heating cycles over weeks, during which we took spectra. From fingerprints in the infrared spectra we deduce phase-transition and solubility lines and suggest a refined, improved T-x % phase diagram in respect to the inconsistencies between those in the literature. The spectra of N 2 -O 2 mixtures are pretty complex, but by referring to known spectra of the pure systems N 2 or O 2 we were able to assign and interpret broad (∼100 cm - 1 ) phonon side bands to fundamentals and an electronic transition (O 2 ), depending on actual temperature and concentration. Narrow features in the spectra ( -1 ) were attributed to the vibron DOS of N 2 or O 2 , whose bandwidth, band shape, and intensity are different and characteristic for each phase. Differences between pure and mixed systems are pointed out. The matrix isolation technique (2 ppm of CO) was used to probe our mixture

Poly[(μ3-benzene-1,3,5-tricarboxylato-κ3O1:O3:O5(μ2-2-methylimidazolato-κ2N:N′tris(2-methylimidazole-κNdizinc(II

Directory of Open Access Journals (Sweden)

Palanikumar Maniam

2011-06-01

Full Text Available Hydrothermal reaction involving zinc nitrate hexahydrate, trisodium benzene-1,3,5-tricarboxylate (Na3BTC and 2-methylimidazole (2-MeImH yielded the title compound, [Zn2(C9H3O6(C4H5N2(C4H6N23]. In this mixed-ligand metal-organic compound, Zn2+ ions are coordinated by N atoms from 2-MeImH molecules and (2-MeIm− ions, as well as by O atoms from (BTC3− ions. This results in two different distorted tetrahedra, viz. ZnN3O and ZnN2O2. These tetrahedra are interconnected via (BTC3− ions and N:N′-bridging (2-MeIm− ions, thus forming a layered structure in the bc plane. Hydrogen bonds between the O atoms of carboxylate ions and NH groups of 2-MeImH ligands link the layers into a three-dimensional structure.

Condensed Acids In Antartic Stratospheric Clouds

Science.gov (United States)

Pueschel, R. F.; Snetsinger, K. G.; Toon, O. B.; Ferry, G. V.; Starr, W. L.; Oberbeck, V. R.; Chan, K. R.; Goodman, J. K.; Livingston, J. M.; Verma, S.;

In-situ observation of Asian pollution transported into the Arctic lowermost stratosphere

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A. Roiger

2011-11-01

Full Text Available On a research flight on 10 July 2008, the German research aircraft Falcon sampled an air mass with unusually high carbon monoxide (CO, peroxyacetyl nitrate (PAN and water vapour (H₂O mixing ratios in the Arctic lowermost stratosphere. The air mass was encountered twice at an altitude of 11.3 km, ~800 m above the dynamical tropopause. In-situ measurements of ozone, NO, and NO_y indicate that this layer was a mixed air mass containing both air from the troposphere and stratosphere. Backward trajectory and Lagrangian particle dispersion model analysis suggest that the Falcon sampled the top of a polluted air mass originating from the coastal regions of East Asia. The anthropogenic pollution plume experienced strong up-lift in a warm conveyor belt (WCB located over the Russian east-coast. Subsequently the Asian air mass was transported across the North Pole into the sampling area, elevating the local tropopause by up to ~3 km. Mixing with surrounding Arctic stratospheric air most likely took place during the horizontal transport when the tropospheric streamer was stretched into long and narrow filaments. The mechanism illustrated in this study possibly presents an important pathway to transport pollution into the polar tropopause region.

20 years of ClO measurements in the Antarctic lower stratosphere

Science.gov (United States)

Nedoluha, Gerald E.; Connor, Brian J.; Mooney, Thomas; Barrett, James W.; Parrish, Alan; Gomez, R. Michael; Boyd, Ian; Allen, Douglas R.; Kotkamp, Michael; Kremser, Stefanie; Deshler, Terry; Newman, Paul; Santee, Michelle L.

2016-08-01

We present 20 years (1996-2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOE1) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004-2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly = HCl + ClONO2 + HOCl + 2 × Cl2 + 2 × Cl2O2 + ClO + Cl). The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be -0.5 ± 0.2, -1.4 ± 0.9, and -0.6 ± 0.4 % year-1, for zonal MLS, Scott Base MLS (both 2004-2015), and ChlOE (1996-2015) respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

Mixed OPEs in N=2 superconformal theories

International Nuclear Information System (INIS)

Ramírez, Israel A.

2016-01-01

Using superspace techniques, we compute the mixed OPE between an N=2 stress-tensor multiplet, a chiral multiplet and a flavor current multiplet. We perform a detailed analysis of the three-point function between two of the mentioned multiplets and a third arbitrary operator. We then solve all the constraints coming from the N=2 superconformal symmetry and from the equations of motion and/or conservation equations, and obtain all the possible operators that can appear in the expansion. This calculation is the first step towards a more general superconformal block analysis of mixed correlators in N=2 theories.

Experimental study of isospin mixing in 12C + n → 13C(T = 3/2) and 16O + n → 17O(T = 3/2) resonances

International Nuclear Information System (INIS)

Cierjacks, S.; Schmalz, G.; Hinterberger, F.; Rossen, P. v.

1981-12-01

Narrow resonances of 13 C and 17 O have been studied by a measurement of the total neutron cross sections of carbon and oxygen between 3 and 30 MeV. Employing the improved time-of-flight spectrometer at the Karlsruhe Isochronous Cyclotron and precise calibration methods, resonance cross sections were measured with an energy resolution of 1:2100 at 10 MeV and energy accuracies between 10 -4 and 10 -5 . Resonance analysis of the measured data provided parameters for numerous narrow states of both isospins, T = 1/2 and T = 3/2. These data in conjunction with information from broad T = 1/2 resonances provided a good means to experimentally determine isospin mixing matrix elements. Results were obtained for the first five T = 3/2 resonances in 17 O and the first T = 3/2 resonance in 13 C. The obtained mixing matrix elements are compared with previous experimental results and shell-modell predictions of this quantity. (orig.) [de

Balloon-borne stratospheric BrO measurements: comparison with Envisat/SCIAMACHY BrO limb profiles

Directory of Open Access Journals (Sweden)

M. Dorf

2006-01-01

Full Text Available For the first time, results of four stratospheric BrO profiling instruments, are presented and compared with reference to the SLIMCAT 3-dimensional chemical transport model (3-D CTM. Model calculations are used to infer a BrO profile validation set, measured by 3 different balloon sensors, for the new Envisat/SCIAMACHY (ENVIronment SATellite/SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY satellite instrument. The balloon observations include (a balloon-borne in situ resonance fluorescence detection of BrO (Triple, (b balloon-borne solar occultation DOAS measurements (Differential Optical Absorption Spectroscopy of BrO in the UV, and (c BrO profiling from the solar occultation SAOZ (Systeme d'Analyse par Observation Zenithale balloon instrument. Since stratospheric BrO is subject to considerable diurnal variation and none of the measurements are performed close enough in time and space for a direct comparison, all balloon observations are considered with reference to outputs from the 3-D CTM. The referencing is performed by forward and backward air mass trajectory calculations to match the balloon with the satellite observations. The diurnal variation of BrO is considered by 1-D photochemical model calculation along the trajectories. The 1-D photochemical model is initialised with output data of the 3-D model with additional constraints on the vertical transport, the total amount and photochemistry of stratospheric bromine as given by the various balloon observations. Total [Bry]=(20.1±2.5 pptv obtained from DOAS BrO observations at mid-latitudes in 2003, serves as an upper limit of the comparison. Most of the balloon observations agree with the photochemical model predictions within their given error estimates. First retrieval exercises of BrO limb profiling from the SCIAMACHY satellite instrument on average agree to around 20% with the photochemically-corrected balloon observations of the remote sensing instruments (SAOZ

In-situ BrO measurements in the upper troposphere / lower stratosphere. Validation of the ENVISAT satellite measurements and photochemical model studies

Energy Technology Data Exchange (ETDEWEB)

Hrechanyy, S.

2007-04-15

Inorganic bromine species form the second most important halogen family affecting stratospheric ozone (WMO, 2003). Although the stratospheric bromine mixing ratio is about two orders of magnitude lower than the chlorine one, bromine has much higher ozone depleting potential (factor of about 45) compared to chlorine. This study reports and discusses atmospheric bromine monoxide, BrO, measurements in the altitude range 15-30 km performed by the balloon-borne instrument TRIPLE and aircraft instrument HALOX employing the chemical conversion resonance fluorescence technique, which is the only proven in-situ technique for the measurements of BrO. 57 HALOX flights have been performed in the frame of five field campaigns ranging from the Arctic to tropics. Three TRIPLE flights were carried out at high and mid latitudes in the frame of the SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY) validation. Calibration, consistency checks, data analysis, and error assessment for the in-situ measurements are described. The balloon measurements have yielded vertical profiles of BrO between 15 and 30 km altitude at northern mid- and at arctic latitudes. From the aircraft measurements a meridional BrO distribution from tropical to the arctic latitudes between 15 and 20 km altitude was obtained. In order to check the reliability of the bromine chemistry in the CLaMS model the BrO profile measured by TRIPLE on June 9, 2003 in Arctic spring/summer conditions was compared to a simulated BrO profile. For the simulation the model was initialized with appropriate satellite and balloon measurements and with a total stratospheric bromine of 18.4 pptv. Very good agreement between the TRIPLE measurements and model results was found. Measurements of BrO in the tropical tropopause layer (TTL) are well suited to investigate the contribution of very short-lived bromine species (VSLS) to the inorganic bromine, Bry. Since tropical HALOX BrO measurements from TROCCINOX

The global warming potential of methane reassessed with combined stratosphere and troposphere chemistry

Science.gov (United States)

Holmes, C. D.; Archibald, A. T.; Eastham, S. D.; Søvde, O. A.

2017-12-01

Methane is a direct and indirect greenhouse gas. The direct greenhouse effect comes from the radiation absorbed and emitted by methane itself. The indirect greenhouse effect comes from radiatively active gases that are produced during methane oxidation: principally O3, H2O, and CO2. Methane also suppresses tropospheric OH, which indirectly affects numerous greenhouses gases and aerosols. Traditionally, the methane global warming potential (GWP) has included the indirect effects on tropospheric O3 and OH and stratospheric H2O, with these effects estimated independently from unrelated tropospheric and stratospheric chemistry models and observations. Using this approach the CH4 is about 28 over 100 yr (without carbon cycle feedbacks, IPCC, 2013). Here we present a comprehensive analysis of the CH4 GWP in several 3-D global atmospheric models capable of simulating both tropospheric and stratospheric chemistry (GEOS-Chem, Oslo CTM3, UKCA). This enables us to include, for the first time, the indirect effects of CH4 on stratospheric O3 and stratosphere-troposphere coupling. We diagnose the GWP from paired simulations with and without a 5% perturbation to tropospheric CH4 concentrations. Including stratospheric chemistry nearly doubles the O3 contribution to CH4 GWP because of O3 production in the lower stratosphere and because CH4 inhibits Cl-catalyzed O3 loss in the upper stratosphere. In addition, stratosphere-troposphere coupling strengthens the chemical feedback on its own lifetime. In the stratosphere, this feedback operates by a CH4 perturbation thickening the stratospheric O3 layer, which impedes UV-driven OH production in the troposphere and prolongs the CH4 lifetime. We also quantify the impact of CH4-derived H2O on the stratospheric HOx cycles but these effects are small. Combining all of the above, these models suggest that the 100-yr GWP of CH4 is over 33.5, a 20% increase over the latest IPCC assessment.

Solar UV irradiation-induced production of N2O from plant surfaces - low emissions rates but all over the world.

Science.gov (United States)

Mikkelsen, T. N.; Bruhn, D.; Ambus, P.

2016-12-01

Nitrous oxide (N2O) is an important long-lived greenhouse gas and precursor of stratospheric ozone depleting mono-nitrogen oxides. The atmospheric concentration of N2O is persistently increasing; however, large uncertainties are associated with the distinct source strengths. Here we investigate for the first time N2O emission from terrestrial vegetation in response to natural solar ultra violet radiation. We conducted field site measurements to investigate N2O atmosphere exchange from grass vegetation exposed to solar irradiance with and without UV-screening. Further laboratory tests were conducted with a range of species to study the controls and possible loci of UV-induced N2O emission from plants. Plants released N2O in response to natural sunlight at rates of c. 20-50 nmol m-2 h-1, mostly due to the UV component. The emission rate is temperature dependent with a rather high activation energy indicative for an abiotic process. The prevailing zone for the N2O formation appears to be at the very surface of leaves. However, only c. 26% of the UV-induced N2O appears to originate from plant-N. Further, the process is dependent on atmospheric oxygen concentration. Our work demonstrates that ecosystem emission of the important greenhouse gas, N2O, may be up to c. 30% higher than hitherto assumed.

Does Extreme El Niño Have a Different Effect on the Stratosphere in Boreal Winter Than Its Moderate Counterpart?

Science.gov (United States)

Zhou, Xin; Li, Jianping; Xie, Fei; Chen, Quanliang; Ding, Ruiqiang; Zhang, Wenxia; Li, Yang

2018-03-01

A robust impact of El Niño on the Northern Hemisphere (NH) polar stratosphere has been demonstrated by previous studies, although whether this applies to extreme El Niño is uncertain. The time evolution of the response of the NH stratospheric vortex to extreme El Niño, compared with that to moderate eastern Pacific El Niño, is addressed by means of composite analysis using the National Centers for Environmental Prediction/Department of Energy reanalysis data set from 1980 to 2016. Lead-lag analysis indicates that the El Niño signal actually leads the stratospheric response by 2 months. Considering the time lag, the signal of December-January-February El Niño in the NH stratospheric vortex should mature in the February-March-April season (late winter/early spring). The patterns of circulation and temperature for late winter/early spring during extreme and moderate El Niño events are significant, exhibiting similar structure. The results are confirmed with the Whole Atmosphere Community Climate Model version 4 model, which is forced with observed SSTs of extreme and moderate El Niño in winter (December-January-February) to analyze the day-to-day propagation of their signals. Note that the magnitudes of the stratospheric responses are much larger in the case of extreme El Niño, as stronger upward propagation of planetary waves leads to a weaker northern polar vortex than during moderate El Niño events.

How stratospheric are deep stratospheric intrusions? LUAMI 2008

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T. Trickl

2016-07-01

Full Text Available A large-scale comparison of water-vapour vertical-sounding instruments took place over central Europe on 17 October 2008, during a rather homogeneous deep stratospheric intrusion event (LUAMI, Lindenberg Upper-Air Methods Intercomparison. The measurements were carried out at four observational sites: Payerne (Switzerland, Bilthoven (the Netherlands, Lindenberg (north-eastern Germany, and the Zugspitze mountain (Garmisch-Partenkichen, German Alps, and by an airborne water-vapour lidar system creating a transect of humidity profiles between all four stations. A high data quality was verified that strongly underlines the scientific findings. The intrusion layer was very dry with a minimum mixing ratios of 0 to 35 ppm on its lower west side, but did not drop below 120 ppm on the higher-lying east side (Lindenberg. The dryness hardens the findings of a preceding study (“Part 1”, Trickl et al., 2014 that, e.g., 73 % of deep intrusions reaching the German Alps and travelling 6 days or less exhibit minimum mixing ratios of 50 ppm and less. These low values reflect values found in the lowermost stratosphere and indicate very slow mixing with tropospheric air during the downward transport to the lower troposphere. The peak ozone values were around 70 ppb, confirming the idea that intrusion layers depart from the lowermost edge of the stratosphere. The data suggest an increase of ozone from the lower to the higher edge of the intrusion layer. This behaviour is also confirmed by stratospheric aerosol caught in the layer. Both observations are in agreement with the idea that sections of the vertical distributions of these constituents in the source region were transferred to central Europe without major change. LAGRANTO trajectory calculations demonstrated a rather shallow outflow from the stratosphere just above the dynamical tropopause, for the first time confirming the conclusions in “Part 1” from the Zugspitze CO observations. The

Solid-State Chemistry as a Formation Mechanism for C 4N 2 Ice and Possibly the Haystack (220 cm -1 ice emission feature) in Titan's Stratosphere as Observed by Cassini CIRS

Science.gov (United States)

Anderson, Carrie; Samuelson, Robert E.; McLain, Jason L.; Nna Mvondo, Delphine; Romani, Paul; Flasar, F. Michael

2016-10-01

A profusion of organic ices containing hydrocarbons, nitriles, and combinations of their mixtures comprise Titan's complex stratospheric cloud systems, and are typically formed via vapor condensation. These ice particles are then distributed throughout the mid-to-lower stratosphere, with an increased abundance near the winter poles (see Anderson et al., 2016). The cold temperatures and the associated strong circumpolar winds that isolate polar air act in much the same way as on Earth, giving rise to compositional anomalies and stratospheric clouds that provide heterogeneous chemistry sites.Titan's C4N2 ice emission feature at 478 cm-1 and "the Haystack," a strong unidentified stratospheric ice emission feature centered at 220 cm-1, share a common characteristic. Even though both are distinctive ice emission features evident in Cassini Composite InfraRed (CIRS) far-IR spectra, no associated vapor emission features can be found in Titan's atmosphere. Without a vapor phase, solid-state chemistry provides an alternate mechanism beside vapor condensation for producing these observed stratospheric ices.Anderson et al., (2016) postulated that C4N2 ice formed in Titan's stratosphere via the solid-state photochemical reaction HCN + HC3N → C4N2 + H2 can occur within extant HCN-HC3N composite ice particles. Such a reaction, and potentially similar reactions that may produce the Haystack ice, are specific examples of solid-state chemistry in solar system atmospheres. This is in addition to the reaction HCl + ClONO2 → HNO3 + Cl2, which is known to produce HNO3 coatings on terrestrial water ice particles, a byproduct of the catalytic chlorine chemistry that produces ozone holes in Earth's polar stratosphere (see for example, Molina et al., 1987 Soloman, 1999).A combination of radiative transfer modeling of CIRS far-IR spectra, coupled with optical constants derived from thin film transmittance spectra of organic ice mixtures obtained in our Spectroscopy for Planetary ICes

Lepton mixing from Δ(3n2 and Δ(6n2 and CP

Directory of Open Access Journals (Sweden)

Claudia Hagedorn

2015-02-01

Full Text Available We perform a detailed study of lepton mixing patterns arising from a scenario with three Majorana neutrinos in which a discrete flavor group Gf=Δ(3n2 or Gf=Δ(6n2 and a CP symmetry are broken to residual symmetries Ge=Z3 and Gν=Z2×CP in the charged lepton and neutrino sectors, respectively. While we consider all possible Z3 and Z2 generating elements, we focus on a certain set of CP transformations. The resulting lepton mixing depends on group theoretical indices and one continuous parameter. In order to study the mixing patterns comprehensively for all admitted Ge and Gν, it is sufficient to discuss only three types of combinations. One of them requires as flavor group Δ(6n2. Two types of combinations lead to mixing patterns with a trimaximal column, while the third one allows for a much richer structure. For the first type of combinations the Dirac phase as well as one of the Majorana phases are trivial, whereas the other two types of combinations predict in general all CP phases to be non-trivial and also non-maximal. Already for small values of the index n of the group, n≤11, experimental data on lepton mixing can be accommodated well for particular choices of the parameters of the theory. We also comment on the relation of the used CP transformations to the automorphisms of Δ(3n2 and Δ(6n2.

Can conservation tillage reduce N2O emissions on cropland transitioning to organic vegetable production?

Science.gov (United States)

Chen, Guihua; Kolb, Lauren; Cavigelli, Michel A; Weil, Ray R; Hooks, Cerruti R R

2018-03-15

Nitrous oxide (N 2 O) is an important greenhouse gas and a catalyst of stratospheric ozone decay. Agricultural soils are the source of 75% of anthropogenic N 2 O emissions globally. Recently, significant attention has been directed at examining effects of conservation tillage on carbon sequestration in agricultural systems. However, limited knowledge is available regarding how these practices impact N 2 O emissions, especially for organic vegetable production systems. In this context, a three-year study was conducted in a well-drained sandy loam field transitioning to organic vegetable production in the Mid-Atlantic coastal plain of USA to investigate impacts of conservation tillage [strip till (ST) and no-till (NT)] and conventional tillage (CT) [with black plastic mulch (CT-BP) and bare-ground (CT-BG)] on N 2 O emissions. Each year, a winter cover crop mixture (forage radish: Raphanus sativus var. longipinnatus, crimson clover: Trifolium incarnatum L., and rye: Secale cereale L.) was grown and flail-mowed in the spring. Nearly 80% of annual N 2 O-nitrogen (N) emissions occurred during the vegetable growing season for all treatments. Annual N 2 O-N emissions were greater in CT-BP than in ST and NT, and greater in CT-BG than in NT, but not different between CT-BG and CT-BP, ST and NT, or CT-BG and ST. Conventional tillage promoted N mineralization and plastic mulch increased soil temperature, which contributed to greater N 2 O-N fluxes. Though water filled porosity in NT was higher and correlated well with N 2 O-N fluxes, annual N 2 O-N emissions were lowest in NT suggesting a lack of substrates for nitrification and denitrification processes. Crop yield was lowest in NT in Year 1 and CT-BP in Year 3 but yield-scaled N 2 O-N emissions were consistently greatest in CT-BP and lowest in NT each year. Our results suggest that for coarse-textured soils in the coastal plain with winter cover crops, conservation tillage practices may reduce N 2 O emissions in organic

Mixed (oxigen ion and n-type) conductivity and structural characterization of stabilized tetragonal zirconia in the ZrO{sub 2}-CeO{sub 2}-TiO{sub 2} system

Energy Technology Data Exchange (ETDEWEB)

Capel, F.; Moure, C.; Duran, P. [Consejo Nacional de Investigaciones Cientificas, Madrid (Spain). Ist. de Ceramica y Vidrio

2002-07-01

By using X-ray diffraction lattice parameter measurements and Raman spectroscopy studies, the solid solubility limits of titania in ceria tetragonal zirconia solid solutions (Ce-TZP, 12 mol % CeO{sub 2}) have been established. Electrical properties of the mixed conductor TiO{sub 2}-CeTZP containing 5 and 10 mol % TiO{sub 2} were measured at the 300 C to 900 C temperature range in air and in reduced oxygen partial pressures. (orig.)

Synthesis, characterization and photocatalysis enhancement of Eu2O3-ZnO mixed oxide nanoparticles

Science.gov (United States)

Mohamed, W. S.; Abu-Dief, Ahmed M.

2018-05-01

Pure ZnO nanoparticles (NPs) and mixed Eu2O3 and ZnO NPs with different Eu2O3 ratios (5%, 10%, and 15%) were synthesized by a precipitation method under optimum conditions. The synthesized samples were characterized by means of X-ray diffraction, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy, transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and UV-vis diffuse reflectance spectroscopy. The as-synthesized ZnO NPs exhibit high phase purity and a highly crystalline wurtzite ZnO structure. The mixed Eu2O3 and ZnO NPs exhibit a Eu2O3 zinc blend phase in addition to the wurtzite phase of pure ZnO, confirming the high purity and good crystallinity of the as-synthesized samples. The high-purity formation of ZnO and Eu2O3 phases was confirmed by FTIR and Raman spectra. Microstructural analysis by SEM and TEM confirmed the sphere-like morphology with different particle sizes (29-40 nm) of the as-synthesized samples. The photocatalytic activities of pure ZnO NPs and mixed Eu2O3 and ZnO NPs for the degradation of methylene blue were evaluated under ultraviolet (UV) irradiation. The results show that Eu2O3 plays an important role in the enhancement of the photocatalytic properties of ZnO NPs. We found that mixed 5% Eu2O3 and ZnO NPs exhibit the highest photocatalytic activity (degradation efficiency of 96.5% after 180 min of UV irradiation) as compared with pure ZnO NPs (degradation efficiency of 80.3% after 180 min of UV irradiation). The increased photocatalytic activity of the optimum mixed Eu2O3 and ZnO NPs is due to the high crystallinity, high surface area with small particle size, and narrow energy gap.

Estimated SAGE II ozone mixing ratios in early 1993 and comparisons with Stratospheric Photochemistry, Aerosols and Dynamic Expedition measurements

Science.gov (United States)

Yue, G. K.; Veiga, R. E.; Poole, L. R.; Zawodny, J. M.; Proffitt, M. H.

1994-01-01

An empirical time-series model for estimating ozone mixing ratios based on Stratospheric Aerosols and Gas Experiment II (SAGE II) monthly mean ozone data for the period October 1984 through June 1991 has been developed. The modeling results for ozone mixing ratios in the 10- to 30- km region in early months of 1993 are presented. In situ ozone profiles obtained by a dual-beam UV-absorption ozone photometer during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) campaign, May 1-14, 1993, are compared with the model results. With the exception of two profiles at altitudes below 16 km, ozone mixing ratios derived by the model and measured by the ozone photometer are in relatively good agreement within their individual uncertainties. The identified discrepancies in the two profiles are discussed.

Thermoluminescence induced by UV radiation in ZrO2-La2O3 and ZrO2-CeO2 mixed systems

International Nuclear Information System (INIS)

Estrada G, R.; Salas C, P.; Mendoza A, D.; Gonzalez, P.R.

2002-01-01

Nowadays, the development of catalytic materials by means of pure or mixed oxides mainly as TiO 2 , Al 2 O 3 , ZrO 2 , La 2 O 3 and CeO 2 used as support or active phases, are widely used in oxidation-reduction reactions in the chemical industry and in petroleum refining processes. the cerium and lanthanum oxides in zircon, have been studied recently in processes for reduction of pollutant gases (SO x , NO x , etc.). They result very interesting for resolving the problems of environmental pollution. Moreover, it has been observed that some of these materials are highly sensitive to ultraviolet radiation (UV), characteristic that can be took in advantage for detecting this type of radiation. In this work the preliminary obtained results on the thermoluminescent response (Tl) induced by the UV radiation in ZrO 2 -La 2 O 3 and ZrO 2 -CeO 2 mixed systems obtained by the sol-gel method are presented. The results show that the first system has a high sensitivity to UV radiation with a Tl curve composed by three peaks, two ones of greater intensity located in 70 and 140 Centigrade degrees. Likewise it was observed that for both materials, the peak located at low temperature is fadeout in few minutes after irradiation, while that the second one peak presented very good stability, resulting promising for dosimetric applications in UV radiation fields. (Author)

Deep-level optical spectroscopy investigation of N-doped TiO2 films

International Nuclear Information System (INIS)

Nakano, Yoshitaka; Morikawa, Takeshi; Ohwaki, Takeshi; Taga, Yasunori

2005-01-01

N-doped TiO 2 films were deposited on n + -GaN/Al 2 O 3 substrates by reactive magnetron sputtering and subsequently crystallized by annealing at 550 deg. C in flowing N 2 gas. The N-doping concentration was ∼8.8%, as determined from x-ray photoelectron spectroscopy measurements. Deep-level optical spectroscopy measurements revealed two characteristic deep levels located at ∼1.18 and ∼2.48 eV below the conduction band. The 1.18 eV level is probably attributable to the O vacancy state and can be active as an efficient generation-recombination center. Additionally, the 2.48 eV band is newly introduced by the N doping and contributes to band-gap narrowing by mixing with the O 2p valence band

Stratospheric cooling and polar ozone loss due to H2 emissions of a global hydrogen economy

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Feck, T.; Grooß, J.-U.; Riese, M.; Vogel, B.

2009-04-01

"Green" hydrogen is seen as a major element of the future energy supply to reduce greenhouse gas emissions substantially. However, due to the possible interactions of hydrogen (H2) with other atmospheric constituents there is a need to analyse the implications of additional atmospheric H2 that could result from hydrogen leakage of a global hydrogen infrastructure. Emissions of molecular H2 can occur along the whole hydrogen process chain which increase the tropospheric H2 burden. Across the tropical tropopause H2 reaches the stratosphere where it is oxidised and forms water vapour (H2O). This causes increased IR-emissions into space and hence a cooling of the stratosphere. Both effects, the increase of stratospheric H2O and the cooling, enhances the potential of chlorine activation on liquid sulfate aerosol and polar stratospheric clouds (PSCs), which increase polar ozone destruction. Hence a global hydrogen economy could provoke polar ozone loss and could lead to a substantial delay of the current projected recovery of the stratospheric ozone layer. Our investigations show that even if 90% of the current global fossil primary energy input could be replaced by hydrogen and approximately 9.5% of the product gas would leak to the atmosphere, the ozone loss would be increased between 15 to 26 Dobson Units (DU) if the stratospheric CFC loading would retain unchanged. A consistency check of the used approximation methods with the Chemical Lagrangian Model of the Stratosphere (CLaMS) shows that this additional ozone loss can probably be treated as an upper limit. Towards more realistic future H2 leakage rate assumptions (< 3%) the additional ozone loss would be rather small (? 10 DU). However, in all cases the full damage would only occur if stratospheric CFC-levels would retain unchanged. Due to the CFC-prohibition as a result of the Montreal Protocol the forecasts suggest a decline of the stratospheric CFC loading about 50% until 2050. In this case our calculations

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

Science.gov (United States)

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.

Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

Science.gov (United States)

Li, F.; Newman, P. A.; Pawson, S.; Perlwitz, J.

2017-12-01

The strength of the stratospheric Brewer-Dobson circulation (BDC) in a changing climate has been extensively studied, but the relative importance of greenhouse gas (GHG) increases and stratospheric ozone depletion in driving the BDC changes remains uncertain. This study separates the impacts of GHG and stratospheric ozone forcings on stratospheric mean age of air in the 1960-2010 period using the Goddard Earth Observing System Model (GEOS) Chemistry-Climate Model (CCM). The experiment compares a set of controlled simulations using a coupled atmosphere-ocean version of the GEOS CCM, in which either GHGs, or stratospheric ozone, or both factors evolve over time. The model results show that GHGs and stratospheric ozone have about equal contributions to the simulated mean age decrease. It is also found that GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: 1) a seasonal delay in the Antarctic polar vortex breakup, that inhibits young mid-latitude air from mixing with the older air inside the vortex; and 2) enhanced Antarctic downwelling, that brings older air from middle and upper stratosphere into the lower stratosphere.

Origin of visible-light sensitivity in N-doped TiO2 films

International Nuclear Information System (INIS)

Nakano, Yoshitaka; Morikawa, Takeshi; Ohwaki, Takeshi; Taga, Yasunori

2007-01-01

We report on visible-light sensitivity in N-doped TiO 2 (TiO 2 :N) films that were deposited on n + -GaN/Al 2 O 3 substrates by reactive magnetron sputtering and subsequently crystallized by annealing at 550 deg. C in flowing N 2 gas. The N-doping concentration was ∼8.8%, as determined by X-ray photoelectron spectroscopy measurements. From transmission electron microscopic observations and optical absorption measurements, yellow-colored TiO 2 :N samples showed an enhanced granular structure and strong absorption in the visible-light region. Photoelectron spectroscopy in air measurements showed a noticeable decrease in ionization energy of TiO 2 by the N doping. Deep-level optical spectroscopy measurements revealed two characteristic deep levels located at ∼1.18 and ∼2.48 eV below the conduction band. The 1.18 eV level is probably attributable to the O vacancy state and can be active as an efficient generation-recombination center. The pronounced 2.48 eV band is newly introduced by the N doping and contributes to band-gap narrowing of TiO 2 by mixing with the O 2p valence band. Therefore, this localized intraband is probably one origin of visible-light sensitivity in TiO 2 :N

DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

Science.gov (United States)

2017-10-31

VC-nH2O for Small and Water-Dominated Molecular Clusters October 31, 2017 Approved for public release; distribution is unlimited. L. Huang S.g...Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters L. Huang,1 S.G...nH2O molecular clusters using density function theory (DFT). DFT can provide interpretation of absorption spectra with respect to molecular

Aqua{2-(pyridin-2-yl-N-[(pyridin-2-ylmethylidene]ethanamine-κ3N,N′,N′′}(sulfato-κ2O,O′copper(II tetrahydrate

Directory of Open Access Journals (Sweden)

Daniel Tinguiano

2013-01-01

Full Text Available The title complex, [Cu(SO4(C13H13N3(H2O]·4H2O, was obtained by mixing copper sulfate pentahydrate and 2-(pyridin-2-yl-N-(pyridin-2-ylmethylideneethanamine in ethanol under reflux conditions. The CuII ion shows a Jahn–Teller-distorted octahedral geometry, with equatorial positions occupied by three N atoms from the tridentate ligand (average Cu—N = 2.004 Å and one O atom from a bidentate sulfate anion [Cu—O = 1.963 (2 Å]. The axial positions are occupied by one O atom from a coordinating water molecule [Cu—O = 2.230 (3 Å] and one weakly bonded O atom [Cu—O = 2.750 (2 Å] from the bidentate sulfate ion. The complex molecules are connected through O—H...O hydrogen bonds between the coordinating water molecules and sulfate ions from neighboring complexes, forming a double chain parallel to the c axis. The chains are stabilized through additional hydrogen bonds by one of the non-coordinating water molecules bridging between neighboring strands of the double chains. The remaining three water molecules fill the interstitial space between the double chains and are involved in an intricate hydrogen-bonding network that consolidates the structure.

Concentrations and uncertainties of stratospheric trace species inferred from limb infrared monitor of the stratosphere data. I - Methodology and application to OH and HO2. II - Monthly averaged OH, HO2, H2O2, and HO2NO2

Science.gov (United States)

Kaye, J. A.; Jackman, C. H.

1986-01-01

Difficulties arise in connection with the verification of multidimensional chemical models of the stratosphere. The present study shows that LIMS data, together with a photochemical equilibrium model, may be used to infer concentrations of a variety of zonally averaged trace Ox, OHx, and NOx species over much of the stratosphere. In the lower stratosphere, where the photochemical equilibrium assumption for HOx species breaks down, inferred concentrations should still be accurate to about a factor of 2 for OH and 2.5 for HO2. The algebraic nature of the considered model makes it possible to see easily to the first order the effect of variation of any model input parameter or its uncertainty on the inferred concontration of the HOx species and their uncertainties.

Space-time patterns of trends in stratospheric constituents derived from UARS measurements

Science.gov (United States)

Randel, William J.; Wu, Fei; Russell, James M.; Waters, Joe

1999-02-01

The spatial and temporal behavior of low-frequency changes (trends) in stratospheric constituents measured by instruments on the Upper Atmosphere Research Satellite (UARS) during 1991-98 is investigated. The data include CH4, H2O, HF, HCl, O3, and NO2 from the Halogen Occultation Experiment (HALOE), and O3, ClO, and HNO3 from the Microwave Limb Sounder (MLS). Time series of global anomalies are analyzed by linear regression and empirical orthogonal function analysis. Each of the constituents show significant linear trends over at least some region of the stratosphere, and the spatial patterns exhibit coupling between the different species. Several of the constituents (namely CH4, H2O, HF, HCl, O3, and NO2) exhibit a temporal change in trend rates, with strong changes prior to 1996 and weaker (or reversed) trends thereafter. Positive trends are observed in upper stratospheric ClO, with a percentage rate during 1993-97 consistent with stratospheric HCl increases and with tropospheric chlorine emission rates. Significant negative trends in ozone in the tropical middle stratosphere are found in both HALOE and MLS data during 1993-97, together with positive trends in the tropics near 25 km. These trends are very different from the decadal-scale ozone trends observed since 1979, and this demonstrates the variability of trends calculated over short time periods. Positive trends in NO2 are found in the tropical middle stratosphere, and spatial coincidence to the observed ozone decreases suggests the ozone is responding to the NO2 increase. Significant negative trends in HNO3 are found in the lower stratosphere of both hemispheres. These coupled signatures offer a fingerprint of chemical evolution in the stratosphere for the UARS time frame.

20 years of ClO measurements in the Antarctic lower stratosphere

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G. E. Nedoluha

2016-08-01

Full Text Available We present 20 years (1996–2015 of austral springtime measurements of chlorine monoxide (ClO over Antarctica from the Chlorine Oxide Experiment (ChlOE1 ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004–2015 of ClO measurements from the Aura Microwave Limb Sounder (MLS. From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column ClO on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cly  =  HCl + ClONO2 + HOCl + 2  ×  Cl2 + 2  ×  Cl2O2 + ClO + Cl. The resultant trends in Cly, which determine the long-term trend in ClO, are estimated to be −0.5 ± 0.2, −1.4 ± 0.9, and −0.6 ± 0.4 % year−1, for zonal MLS, Scott Base MLS (both 2004–2015, and ChlOE (1996–2015 respectively. These trends are within 1σ of trends in stratospheric Cly previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

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

Science.gov (United States)

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.

Measurement of PuO2 spot in the mixed-oxide fuels

International Nuclear Information System (INIS)

Yokosuka, Yoshifumi; Kaneda, Kenichiro; Ishikawa, Eiji; Nakajima, Katsuaki; Kashima, Sadamitsu

1974-01-01

The homogeneity of mixed-oxide fuel is evaluated with the maximum diameter of PuO 2 spots. PuO 2 spot distribution is influenced by fuel production process and raw materials used. Analytical measurement of the PuO 2 spot distribution was carried out. α-autoradiograph was taken with nitrocellulose film as a detector. The film was exposed for 15 and 30 minutes to the sample pellets, and etched in 10% NaOH for 2 minutes at 60 0 C. Measurement of PuO 2 spots was performed manually with a projector. PuO 2 spot distribution was measured. There is no difference of spot distribution owing to the location in a pellet. However some discrepancy exists in spot number and maximum diameter between surface and inner part. This phenomenon is explained by considering that the diffusion on surface is more effective than in inner part in sintering process. Three pellets were taken out from a lot at random, and α-autoradiograph was taken longitudinally with a pellet and transversely with the others. PuO 2 spot number counted from three autoradiographs was about 150/cm 2 , and the standard deviation was about 1.5. No difference was observed among them. Concerning the influence of mixing method on PuO 2 spot formation, three methods were examined; ball mill mixing (with and without lining) and Kneader mixing. Kneader mixing gave the worst results in maximum spot diameter and spot distribution range. (Tai, I.)

A semi-empirical model for mesospheric and stratospheric NOy produced by energetic particle precipitation

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B. Funke

2016-07-01

Full Text Available The MIPAS Fourier transform spectrometer on board Envisat has measured global distributions of the six principal reactive nitrogen (NOy compounds (HNO3, NO2, NO, N2O5, ClONO2, and HNO4 during 2002–2012. These observations were used previously to detect regular polar winter descent of reactive nitrogen produced by energetic particle precipitation (EPP down to the lower stratosphere, often called the EPP indirect effect. It has further been shown that the observed fraction of NOy produced by EPP (EPP-NOy has a nearly linear relationship with the geomagnetic Ap index when taking into account the time lag introduced by transport. Here we exploit these results in a semi-empirical model for computation of EPP-modulated NOy densities and wintertime downward fluxes through stratospheric and mesospheric pressure levels. Since the Ap dependence of EPP-NOy is distorted during episodes of strong descent in Arctic winters associated with elevated stratopause events, a specific parameterization has been developed for these episodes. This model accurately reproduces the observations from MIPAS and is also consistent with estimates from other satellite instruments. Since stratospheric EPP-NOy depositions lead to changes in stratospheric ozone with possible implications for climate, the model presented here can be utilized in climate simulations without the need to incorporate many thermospheric and upper mesospheric processes. By employing historical geomagnetic indices, the model also allows for reconstruction of the EPP indirect effect since 1850. We found secular variations of solar cycle-averaged stratospheric EPP-NOy depositions on the order of 1 GM. In particular, we model a reduction of the EPP-NOy deposition rate during the last 3 decades, related to the coincident decline of geomagnetic activity that corresponds to 1.8 % of the NOy production rate by N2O oxidation. As the decline of the geomagnetic activity level is expected to continue in the

Study of complex formation between C18H36N2O6 and UO22+ cation in some binary mixed non-aqueous solutions

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G.H. Rounaghi

2017-02-01

Full Text Available The complexation reaction between UO22+ cation and the macrobicyclic ligand C18H36N2O6 was studied in acetonitrile–dimethylformamide (AN–DMF, acetonitrile–tetrahydrofuran (AN–THF, acetonitrile–dichloromethane (AN–DCM binary solvent solutions at different temperatures using the coductometric method. In most cases, C18H36N2O6 forms a 1:1 [M:L] complex with the UO22+ cation. But in some of the studied solvent systems, in addition to formation of a 1:1 complex, a 1:2 [M:L2] complex is formed in solution. A non-linear behavior was observed for changes of logKf of the (C18H36N2O6·UO22+ complex versus the composition of the binary mixed solvents. The sequence of the stability of the (C18H36N2O6·UO22+ complex in pure solvent systems at 25 °C decreases in the order: AN > THF > DMF. In the case of binary solvent solutions, the stability constant of the complex at 25 °C was found to be: AN–DCM > AN–THF > AN–DMF. The values of thermodynamic quantities (ΔSc°,ΔHc°, for the formation of the complex were obtained from temperature dependence of the stability constant of the complex using the van't Hoff plots. The results show that in all cases, the complex is both entropy and enthalpy stabilized and both of these parameters are affected by the nature and composition of the mixed solvent systems.

Uptake of methanol on mixed HNO3/H2O clusters: An absolute pickup cross section

Science.gov (United States)

Pysanenko, A.; Lengyel, J.; Fárník, M.

2018-04-01

The uptake of atmospheric oxidized organics on acid clusters is relevant for atmospheric new particle formation. We investigate the pickup of methanol (CH3OH) on mixed nitric acid-water clusters (HNO3)M(H2O)N by a combination of mass spectrometry and cluster velocity measurements in a molecular beam. The mass spectra of the mixed clusters exhibit (HNO3)m(H2O)nH+ series with m = 0-3 and n = 0-12. In addition, CH3OH.(HNO3)m(H2O)nH+ series with very similar patterns appear in the spectra after the methanol pickup. The velocity measurements prove that the undoped (HNO3)m(H2O)nH+ mass peaks in the pickup spectra originate from the neutral (HNO3)M(H2O)N clusters which have not picked up any CH3OH molecule, i.e., methanol has not evaporated upon the ionization. Thus the fraction of the doped clusters can be determined and the mean pickup cross section can be estimated, yielding σs ¯ ≈ 20 Å2. This is compared to the lower estimate of the mean geometrical cross section σg ¯ ≈ 60 Å2 obtained from the theoretical cluster geometries. Thus the "size" of the cluster corresponding to the methanol pickup is at least 3-times smaller than its geometrical size. We have introduced a method which can yield the absolute pickup cross sections relevant to the generation and growth of atmospheric aerosols, as illustrated in the example of methanol and nitric acid clusters.

Mixed matrix membranes prepared from high impact polystyrene with dispersed TiO2 nanoparticles for gas separation

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P. Safaei

2016-01-01

Full Text Available The current study presents synthesis and characterization of high impact polystyrene - TiO2 nanoparticles mixed matrix membranes for separation of carbon dioxide from nitrogen. The solution-casting method was used for preparation of membranes. The nano mixed matrix membranes were characterized using scanning electron microscopy to ensure the suitable dispersion of nano particles in high impact polystyrene matrix. The effect of TiO2 nanoparticles loading on membrane performance was investigated. The separation performance of synthesized membranes was investigated in separation of CO2 from CO2/N2 mixture. Effect of feed pressure and TiO2 content on separation of CO2 was studied. The results revealed that increase of feed pressure decreases flux of gases through the mixed matrix membrane. The results also confirmed that the best separation performance can be obtained at TiO2 nanoparticles loading of 7 wt.%.

N2O isotopomers and N2:N2O ratio as indicators of denitrification in ecosystems

International Nuclear Information System (INIS)

Mander, Ülo; Zaman, Mohammad

2015-01-01

The world is experiencing climate change and variability due to increased greenhouse gas (GHG) emissions. The main GHG’s of concern are nitrous oxide (N 2 O), carbon dioxide (CO 2 ) and methane (CH 4 ). Agriculture contributes approximately 14% of the world’s GHG emissions. Nitrous oxide is one of the key GHG and ozone (O 3 ) depleting gas, constituting 7% of the anthropogenic greenhouse effect. On a molecular basis, N 2 O has a 310- and 16-fold greater global warming potential than each of CO 2 and CH 4 , respectively, over a 100-year period. Nitrous oxide can be produced through both chemical and biochemical pathways. They occur during denitrification (the stepwise conversion of nitrate (NO 3 - ) to nitrogen gas (N 2 ) and during nitrification by ammonia-oxidizing archea (bacteria) during the oxidation of hydroxylamine (NH 2 OH) to nitrite (NO 2 - ) which is then reduced to N 2 O and N 2 by nitrifier denitrification or heterotrophic denitrification

Inter-comparison of stratospheric O3 and NO2 abundances retrieved from balloon borne direct sun observations and Envisat/SCIAMACHY limb measurements

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A. Butz

2006-01-01

Full Text Available Stratospheric O3 and NO2 abundances measured by different remote sensing instruments are inter-compared: (1 Line-of-sight absorptions and vertical profiles inferred from solar spectra in the ultra-violet (UV, visible and infrared (IR wavelength ranges measured by the LPMA/DOAS (Limb Profile Monitor of the Atmosphere/Differential Optical Absorption Spectroscopy balloon payload during balloon ascent/descent and solar occultation are examined with respect to internal consistency. (2 The balloon borne stratospheric profiles of O3 and NO2 are compared to collocated space-borne skylight limb observations of the Envisat/SCIAMACHY satellite instrument. The trace gas profiles are retrieved from SCIAMACHY spectra using different algorithms developed at the Universities of Bremen and Heidelberg and at the Harvard-Smithsonian Center for Astrophysics. A comparison scheme is used that accounts for the spatial and temporal mismatch as well as differing photochemical conditions between the balloon and satellite borne measurements. It is found that the balloon borne measurements internally agree to within ±10% and ±20% for O3 and NO2, respectively, whereas the agreement with the satellite is ±20% for both gases in the 20 km to 30 km altitude range and in general worse below 20 km.

Optimization of CeO2-ZrO2 mixed oxide catalysts for ethyl acetate combustion

Czech Academy of Sciences Publication Activity Database

Dimitrov, M.; Ivanova, R.; Štengl, Václav; Henych, Jiří; Kovacheva, D.; Tsoncheva, T.

2015-01-01

Roč. 47, č. 1 (2015), s. 323-329 ISSN 0324-1130 Institutional support: RVO:61388980 Keywords : nanosized CeO2-ZrO2 * mixed oxide phase * ethyl acetate combustion Subject RIV: CA - Inorganic Chemistry Impact factor: 0.229, year: 2015

Greenhouse impact of CH{sub 4}, N{sub 2}O and CFC emissions in Finland and its control potential

Energy Technology Data Exchange (ETDEWEB)

Pipatti, R.; Savolainen, I.; Sinisalo, J. [VTT Energy, Espoo (Finland)

1995-12-31

Methane (CH{sub 4}), nitrous oxide (N{sub 2}O) and chlorofluorocarbon (CFC) emissions contribute considerably to the anthropogenic enhancement of Earth`s greenhouse effect. The limitation of atmospheric concentrations of CH{sub 4} and N{sub 2}O is considered important also in the Climate Convention. Chlorine released from the CFCs in the stratosphere destroys ozone (O{sub 3}) and the emissions are therefore regulated with the Montreal Protocol. The greenhouse impact of CFCs might be, at least to some extent, compensated by the depletion of O{sub 3} which is also a greenhouse gas. The objective of the presentation is to assess the role of anthropogenic CH{sub 4}, N{sub 2}O, and CFC emissions in the total direct greenhouse impact due to human activities in Finland. The emission estimates for the gases are presented, as well as scenarios for emission history, future development and control potential. The greenhouse impact of the gases is compared with that of carbon dioxide (CO{sub 2}) emissions in Finland. (author)

Greenhouse impact of CH{sub 4}, N{sub 2}O and CFC emissions in Finland and its control potential

Energy Technology Data Exchange (ETDEWEB)

Pipatti, R; Savolainen, I; Sinisalo, J [VTT Energy, Espoo (Finland)

1996-12-31

Methane (CH{sub 4}), nitrous oxide (N{sub 2}O) and chlorofluorocarbon (CFC) emissions contribute considerably to the anthropogenic enhancement of Earth`s greenhouse effect. The limitation of atmospheric concentrations of CH{sub 4} and N{sub 2}O is considered important also in the Climate Convention. Chlorine released from the CFCs in the stratosphere destroys ozone (O{sub 3}) and the emissions are therefore regulated with the Montreal Protocol. The greenhouse impact of CFCs might be, at least to some extent, compensated by the depletion of O{sub 3} which is also a greenhouse gas. The objective of the presentation is to assess the role of anthropogenic CH{sub 4}, N{sub 2}O, and CFC emissions in the total direct greenhouse impact due to human activities in Finland. The emission estimates for the gases are presented, as well as scenarios for emission history, future development and control potential. The greenhouse impact of the gases is compared with that of carbon dioxide (CO{sub 2}) emissions in Finland. (author)

MLS measurements of stratospheric hydrogen cyanide during the 2015-2016 El Niño event

Science.gov (United States)

Pumphrey, Hugh C.; Glatthor, Norbert; Bernath, Peter F.; Boone, Christopher D.; Hannigan, James W.; Ortega, Ivan; Livesey, Nathaniel J.; Read, William G.

2018-01-01

It is known from ground-based measurements made during the 1982-1983 and 1997-1998 El Niño events that atmospheric hydrogen cyanide (HCN) tends to be higher during such years than at other times. The Microwave Limb Sounder (MLS) on the Aura satellite has been measuring HCN mixing ratios since launch in 2004; the measurements are ongoing at the time of writing. The winter of 2015-2016 saw the largest El Niño event since 1997-1998. We present MLS measurements of HCN in the lower stratosphere for the Aura mission to date, comparing the 2015-2016 El Niño period to the rest of the mission. HCN in 2015-2016 is higher than at any other time during the mission, but ground-based measurements suggest that it may have been even more elevated in 1997-1998. As the MLS HCN data are essentially unvalidated, we show them alongside data from the MIPAS and ACE-FTS instruments; the three instruments agree reasonably well in the tropical lower stratosphere. Global HCN emissions calculated from the Global Fire Emissions Database (GFED v4.1) database are much greater during large El Niño events and are greater in 1997-1998 than in 2015-2016, thereby showing good qualitative agreement with the measurements. Correlation between El Niño-Southern Oscillation (ENSO) indices, measured HCN, and GFED HCN emissions is less clear if the 2015-2016 event is excluded. In particular, the 2009-2010 winter had fairly strong El Niño conditions and fairly large GFED HCN emissions, but very little effect is observed in the MLS HCN.

Hydrazinium lanthanide oxalates: synthesis, structure and thermal reactivity of N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce, Nd

International Nuclear Information System (INIS)

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

2014-01-01

New hydrazinium lanthanide oxalates N_2H_5[Ln_2(C_2O_4)_4(N_2H_5)].4H_2O, Ln = Ce (Ce-H_yO_x) and Nd (Nd- H_yO_x), 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 P2_1/c with a = 16.315(4), b = 12.127(3), c = 11.430(2) Angstroms, β = 116.638(4) degrees, V = 2021.4(7) Angstroems"3, Z = 4, and R1 = 0.0313 for 4231 independent reflections. Two distinct neodymium polyhedra are formed, NdO_9 and NdO_8N, 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 N_2H_5"+ to the metal. These polyhedra are connected through μ"2 and μ"3 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-H_yO_x) 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 CeO_2 and Ce_0_._5Nd_0_._5O_1_._7_5 are formed at low temperature from Ce-H_yO_x and CeNd-H_yO_x, respectively, thanks to a decomposition/oxidation process. Under argon flow, dioxy-mono-cyanamides Ln_2O_2CN_2 are formed. (authors)

An automated GC-C-GC-IRMS setup to measure palaeoatmospheric δ13C-CH4, δ15N-N2O and δ18O-N2O in one ice core sample

Directory of Open Access Journals (Sweden)

P. Sperlich

2013-08-01

Full Text Available Air bubbles in ice core samples represent the only opportunity to study the mixing ratio and isotopic variability of palaeoatmospheric CH4 and N2O. The highest possible precision in isotope measurements is required to maximize the resolving power for CH4 and N2O sink and source reconstructions. We present a new setup to measure δ13C-CH4, δ15N-N2O and δ18O-N2O isotope ratios in one ice core sample and with one single IRMS instrument, with a precision of 0.09, 0.6 and 0.7‰, respectively, as determined on 0.6–1.6 nmol CH4 and 0.25–0.6 nmol N2O. The isotope ratios are referenced to the VPDB scale (δ13C-CH4, the N2-air scale (δ15N-N2O and the VSMOW scale (δ18O-N2O. Ice core samples of 200–500 g are melted while the air is constantly extracted to minimize gas dissolution. A helium carrier gas flow transports the sample through the analytical system. We introduce a new gold catalyst to oxidize CO to CO2 in the air sample. CH4 and N2O are then separated from N2, O2, Ar and CO2 before they get pre-concentrated and separated by gas chromatography. A combustion unit is required for δ13C-CH4 analysis, which is equipped with a constant oxygen supply as well as a post-combustion trap and a post-combustion GC column (GC-C-GC-IRMS. The post-combustion trap and the second GC column in the GC-C-GC-IRMS combination prevent Kr and N2O interferences during the isotopic analysis of CH4-derived CO2. These steps increase the time for δ13C-CH4 measurements, which is used to measure δ15N-N2O and δ18O-N2O first and then δ13C-CH4. The analytical time is adjusted to ensure stable conditions in the ion source before each sample gas enters the IRMS, thereby improving the precision achieved for measurements of CH4 and N2O on the same IRMS. The precision of our measurements is comparable to or better than that of recently published systems. Our setup is calibrated by analysing multiple reference gases that were injected over bubble-free ice samples. We show

Ab initio studies of O2-(H2O)n and O3-(H2O)n anionic molecular clusters, n≤12

DEFF Research Database (Denmark)

Bork, Nicolai Christian; Kurtén, T.; Enghoff, Martin Andreas Bødker

2011-01-01

that anionic O2−(H2O)n and O3−(H2O)n clusters are thermally stabilized at typical atmospheric conditions for at least n = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H2O is due to normal hydrogen bonding. Although...... clustering up to 12 H2O, we find that the O2 and O3 anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O2− and O3− speicies are thus accessible for further reactions. Finally, the thermodynamics of a few relevant cluster reactions are considered....

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

Science.gov (United States)

Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

2002-01-01

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

Production of odd nitrogen in the stratosphere and mesosphere - An intercomparison of source strengths

Science.gov (United States)

Jackman, C. H.; Frederick, J. E.; Stolarski, R. S.

1980-01-01

Galactic cosmic rays (GCRs), nuclear explosions, lightning, solar proton events (SPEs), relativistic electron precipitation, and meteors are related to the oxidation of nitrous oxide by comparing several sources of odd nitrogen (ON) in the stratosphere and mesosphere. Published O3 and N2O data show that ON produced by the reaction of O(1D) with N2O peaks between 25 and 35 km; the GCRs add approximately the same amount of ON as N2O oxidation at the solar minimum for geographic latitudes over 50 deg. Nuclear explosions in 1961-1962 added 1.1 and 2.2 x 10 to the 34th NO molecules each, and SPEs produced greater amounts of ON above 50 deg than N2O oxidation during 1958 through 1960, and in 1972.

From Ba3Ta5O14N to LaBa2Ta5O13N2: Decreasing the optical band gap of a photocatalyst

International Nuclear Information System (INIS)

Anke, B.; Bredow, T.; Pilarski, M.; Wark, M.; Lerch, M.

2017-01-01

Yellow LaBa 2 Ta 5 O 13 N 2 was successfully synthesized as phase-pure material crystallizing isostructurally to previously reported Ba 3 Ta 5 O 14 N and mixed-valence Ba 3 Ta V 4 Ta IV O 15 . The electronic structure of LaBa 2 Ta 5 O 13 N 2 was studied theoretically with the range-separated hybrid method HSE06. The most stable structure was obtained when lanthanum was placed on 2a and nitrogen on 4h sites confirming Pauling's second rule. By incorporating nitrogen, the measured band gap decreases from ∼3.8 eV for the oxide via 2.74 eV for Ba 3 Ta 5 O 14 N to 2.63 eV for the new oxide nitride, giving rise to an absorption band well in the visible-light region. Calculated fundamental band gaps confirm the experimental trend. The atom-projected density of states has large contributions from N2p orbitals close to the valence band edge. These are responsible for the observed band gap reduction. Photocatalytic hydrogen formation was investigated and compared with that of Ba 3 Ta 5 O 14 N revealing significantly higher activity for LaBa 2 Ta 5 O 13 N 2 under UV-light. - Graphical abstract: X-ray powder diffraction pattern of LaBa 2 Ta 5 O 13 N 2 with the results of the Rietveld refinements. Inset: Unit cell of LaBa 2 Ta 5 O 13 N 2 and polyhedral representation of the crystal structure. - Highlights: • Synthesis of a new oxide nitride LaBa 2 Ta 5 O 13 N 2 . • Refinement of the crystal structure. • Quantum chemical calculations provided band gap close to the measured value. • New phase shows a higher photocatalytic H 2 evolution rate compared to prior tested Ba 3 Ta 5 O 14 N.

Structure-Activity Relationship in the N2O Decomposition over Ni-(Mg)-Al and Ni-(Mg)-Mn Mixed Oxides Prepared from Hydrotalcite-like Precursors

Czech Academy of Sciences Publication Activity Database

Obalová, L.; Jirátová, Květa; Kovanda, F.; Valášková, M.; Balabánová, Jana; Pacultová, K.

2006-01-01

Roč. 248, 1-2 (2006), s. 210-219 ISSN 1381-1169 R&D Projects: GA ČR(CZ) GA106/05/0366; GA ČR(CZ) GA104/04/2116 Institutional research plan: CEZ:AV0Z40720504 Keywords : N2O decomposition * mixed oxide catalyst * layered double hydroxides Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.511, year: 2006

Issues in Stratospheric Ozone Depletion.

Science.gov (United States)

Lloyd, Steven Andrew

Following the announcement of the discovery of the Antarctic ozone hole in 1985 there have arisen a multitude of questions pertaining to the nature and consequences of polar ozone depletion. This thesis addresses several of these specific questions, using both computer models of chemical kinetics and the Earth's radiation field as well as laboratory kinetic experiments. A coupled chemical kinetic-radiative numerical model was developed to assist in the analysis of in situ field measurements of several radical and neutral species in the polar and mid-latitude lower stratosphere. Modeling was used in the analysis of enhanced polar ClO, mid-latitude diurnal variation of ClO, and simultaneous measurements of OH, HO_2, H_2 O and O_3. Most importantly, such modeling was instrumental in establishing the link between the observed ClO and BrO concentrations in the Antarctic polar vortex and the observed rate of ozone depletion. The principal medical concern of stratospheric ozone depletion is that ozone loss will lead to the enhancement of ground-level UV-B radiation. Global ozone climatology (40^circS to 50^ circN latitude) was incorporated into a radiation field model to calculate the biologically accumulated dosage (BAD) of UV-B radiation, integrated over days, months, and years. The slope of the annual BAD as a function of latitude was found to correspond to epidemiological data for non-melanoma skin cancers for 30^circ -50^circN. Various ozone loss scenarios were investigated. It was found that a small ozone loss in the tropics can provide as much additional biologically effective UV-B as a much larger ozone loss at higher latitudes. Also, for ozone depletions of > 5%, the BAD of UV-B increases exponentially with decreasing ozone levels. An important key player in determining whether polar ozone depletion can propagate into the populated mid-latitudes is chlorine nitrate, ClONO_2 . As yet this molecule is only indirectly accounted for in computer models and field

Unexpected variations in the triple oxygen isotope composition of stratospheric carbon dioxide

Science.gov (United States)

Wiegel, Aaron A.; Cole, Amanda S.; Hoag, Katherine J.; Atlas, Elliot L.; Schauffler, Sue M.; Boering, Kristie A.

2013-10-01

We report observations of stratospheric CO2 that reveal surprisingly large anomalous enrichments in 17O that vary systematically with latitude, altitude, and season. The triple isotope slopes reached 1.95 ± 0.05(1σ) in the middle stratosphere and 2.22 ± 0.07 in the Arctic vortex versus 1.71 ± 0.03 from previous observations and a remarkable factor of 4 larger than the mass-dependent value of 0.52. Kinetics modeling of laboratory measurements of photochemical ozone-CO2 isotope exchange demonstrates that non-mass-dependent isotope effects in ozone formation alone quantitatively account for the 17O anomaly in CO2 in the laboratory, resolving long-standing discrepancies between models and laboratory measurements. Model sensitivities to hypothetical mass-dependent isotope effects in reactions involving O3, O(1D), or CO2 and to an empirically derived temperature dependence of the anomalous kinetic isotope effects in ozone formation then provide a conceptual framework for understanding the differences in the isotopic composition and the triple isotope slopes between the laboratory and the stratosphere and between different regions of the stratosphere. This understanding in turn provides a firmer foundation for the diverse biogeochemical and paleoclimate applications of 17O anomalies in tropospheric CO2, O2, mineral sulfates, and fossil bones and teeth, which all derive from stratospheric CO2.

Tunable Far Infrared Studies in Support of Stratospheric Measurements

Science.gov (United States)

Chance, Kelly V.; Park, K.; Nolt, I. G.; Evenson, K. M.

2001-01-01

determined from Stark effect measurements; exceptions include some molecules with large vibration-rotation interactions (NO2) and internal motions (H2O2 above the lowest torsional state). The line parameters that are still the least well determined are pressure broadening coefficients, and their temperature coefficients, These are strongly dependent on the quantum states involved in the transitions, in a way that is much more complex than the simple projection by directional cosine matrix elements involved in determination of rotational line strengths from static dipole moments. The following molecules have now been measured or detected in the atmosphere using far infrared and millimeter-wave emission spectroscopy from balloon- and satellite-borne spectrometers: OH, HO2, H2O (including minor isotopomers and hot band lines), H2O2, O3P, O2 (including minor isotopomers), O3 (including minor isotopomers and hot band lines), HOCl, HCl, HF, HBr, CIO, CO, CO2, N2O, NO2, N2O5, HNO3, ClNO3, and HCN. Many of these species have spectral lines that are saturated in stratospheric spectra. In these cases, the measured line equivalent widths are proportional to (line strength x Lorentz width) (exp 1/2) so that the pressure broadening coefficients are as important as the line intensities in determining concentration profiles. Interpretation of field measurements for these species have required ongoing measurement programs of pressure broadening measurements. Other species (HO2, HGCl, H2O2, HBr, and NO2, as examples) have required further line position studies in order to fully analyze the field measurements.

Synthesis of mixed-valent {alpha}- and {beta}-NaFe{sub 2}O{sub 3} polymorphs under controlled partial oxygen pressure

Energy Technology Data Exchange (ETDEWEB)

Bruno, Shaun R.; Blakely, Colin K. [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States); Poltavets, Viktor V., E-mail: poltavets@chemistry.msu.edu [Department of Chemistry, Michigan State University, East Lansing, MI 48824 (United States)

2012-08-15

Synthesis of mixed valent compounds, especially when multiple polymorphs exist, requires careful control of the preparation conditions. {alpha}- and {beta}-NaFe{sub 2}O{sub 3} polymorphs were synthesized under controlled partial oxygen pressure (pO{sub 2}). pO{sub 2} regions of stability at 850 Degree-Sign C were determined for both phases for the first time. A modified oxygen buffer method was developed for the facile preparation of mixed valent oxides under controlled pO{sub 2}. {beta}-NaFe{sub 2}O{sub 3} is the only known n=2 member of the AM{sub n}O{sub n+1} (A=alkali metal, M=3d metal) rock-salt related homolog series with layered cation ordering. The possibility of new members of the homolog series with other 3d metals is considered. - Graphical abstract: Schematic section of phase composition vs. partial O{sub 2} pressure diagram at 850 Degree-Sign C for Na/Fe=1/2 and structure models of {alpha}- and {beta}-NaFe{sub 2}O{sub 3}. Highlights: Black-Right-Pointing-Pointer {alpha}- and {beta}-NaFe{sub 2}O{sub 3} polymorphs were synthesized under controlled oxygen pressure. Black-Right-Pointing-Pointer {beta}-NaFe{sub 2}O{sub 3} has rock-salt related structure with layered cation ordering. Black-Right-Pointing-Pointer Existence of the rock-salt related homolog series AM{sub n}O{sub n+1} is discussed.

Characterization of catalytic supports based in mixed oxides for control reactions of NO and N2O

International Nuclear Information System (INIS)

Garcia C, M.A.; Perez H, R.; Gomez C, A.; Diaz, G.

1999-01-01

The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were prepared by the Precipitation and Coprecipitation techniques. The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were characterized by several techniques to determine: texture (Bet), crystallinity (XRD), chemical composition (Sem)(Ftir) and it was evaluated their total acidity by reaction with 2-propanol. The investigation will be continued with the cobalt addition and this will be evaluated for its catalytic activity in control reactions of N O and N 2 O. (Author)

A sublimation technique for high-precision measurements of δ13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

Directory of Open Access Journals (Sweden)

H. Fischer

2011-07-01

Full Text Available In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2 from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS. In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used. A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

Stratospheric NO2 vertical profile retrieved from ground-based Zenith-Sky DOAS observations at Kiruna, Sweden

Science.gov (United States)

Gu, Myojeong; Enell, Carl-Fredrik; Hendrick, François; Pukite, Janis; Van Roozendael, Michel; Platt, Ulrich; Raffalski, Uwe; Wagner, Thomas

2014-05-01

Stratospheric NO2 destroys ozone and acts as a buffer against halogen-catalyzed ozone loss through the formation of reservoir species (ClONO2, BrONO2). Since the importance of both mechanisms depends on the altitude, the investigation of stratospheric NO2 vertical distribution can provide more insight into the role of nitrogen compounds in the destruction of ozone. Here we present stratospheric NO2 vertical profiles retrieved from twilight ground-based zenith-sky DOAS observations at Kiruna, Sweden (68.84°N, 20.41°E) covering 1997 - 2013 periods. This instrument observes zenith scattered sunlight. The sensitivity for stratospheric trace gases is highest during twilight due to the maximum altitude of the scattering profile and the light path through the stratosphere, which vary with the solar zenith angle. The profiling algorithm, based on the Optimal Estimation Method, has been developed by IASB-BIRA and successfully applied at other stations (Hendrick et al., 2004). The basic principle behind this profiling approach is that during twilight, the mean Rayleigh scattering altitude scans the stratosphere rapidly, providing height-resolved information on the absorption by stratospheric NO2. In this study, the long-term evolution of the stratospheric NO2 profile at polar latitude will be investigated. Hendrick, F., B. Barret, M. Van Roozendael, H. Boesch, A. Butz, M. De Mazière, F. Goutail, C. Hermans, J.-C. Lambert, K. Pfeilsticker, and J.-P. Pommereau, Retrieval of nitrogen dioxide stratospheric profiles from ground-based zenith-sky UV-visible observations: Validation of the technique through correlative comparisons, Atmospheric Chemistry and Physics, 4, 2091-2106, 2004

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

Science.gov (United States)

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.

Advances in the catalysts development in base of mixed oxides for control reactions of N2O

International Nuclear Information System (INIS)

Garcia, M.A.; Perez, R.; Gomez, A.; Diaz, G.

2000-01-01

The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were prepared by the precipitation and coprecipitation techniques. The catalytic supports Al 2 O 3 , La 2 O 3 and Al 2 O 3 -La 2 O 3 were characterized by several techniques for to determine texture (BET), crystallinity (XRD), chemical composition (SEM), FTIR and it was evaluated their total acidity by the reaction with 2-propanol. It was continued with the cobalt addition by Impregnation and coprecipitation and it was evaluated its catalytic activity in the N 2 O decomposition reaction. Also it was realized the N 2 O reduction with Co using these catalysts. (Author)

Validation of MIPAS-ENVISAT H2O operational data collected between July 2002 and March 2004

Directory of Open Access Journals (Sweden)

G. Wetzel

2013-06-01

Full Text Available Water vapour (H2O is one of the operationally retrieved key species of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS instrument aboard the Environmental Satellite (ENVISAT which was launched into its sun-synchronous orbit on 1 March 2002 and operated until April 2012. Within the MIPAS validation activities, independent observations from balloons, aircraft, satellites, and ground-based stations have been compared to European Space Agency (ESA version 4.61 operational H2O data comprising the time period from July 2002 until March 2004 where MIPAS measured with full spectral resolution. No significant bias in the MIPAS H2O data is seen in the lower stratosphere (above the hygropause between about 15 and 30 km. Differences of H2O quantities observed by MIPAS and the validation instruments are mostly well within the combined total errors in this altitude region. In the upper stratosphere (above about 30 km, a tendency towards a small positive bias (up to about 10% is present in the MIPAS data when compared to its balloon-borne counterpart MIPAS-B, to the satellite instruments HALOE (Halogen Occultation Experiment and ACE-FTS (Atmospheric Chemistry Experiment, Fourier Transform Spectrometer, and to the millimeter-wave airborne sensor AMSOS (Airborne Microwave Stratospheric Observing System. In the mesosphere the situation is unclear due to the occurrence of different biases when comparing HALOE and ACE-FTS data. Pronounced deviations between MIPAS and the correlative instruments occur in the lowermost stratosphere and upper troposphere, a region where retrievals of H2O are most challenging. Altogether it can be concluded that MIPAS H2O profiles yield valuable information on the vertical distribution of H2O in the stratosphere with an overall accuracy of about 10 to 30% and a precision of typically 5 to 15% – well within the predicted error budget, showing that these global and continuous data are very valuable for scientific

A temperature dependence kinetics study of the reactions of Cl/2-P-3/2/ with O3, CH4, and H2O2

Science.gov (United States)

Watson, R.; Machado, G.; Fischer, S.; Davis, D. D.

1976-01-01

The temperature dependence of two chlorine atom reactions of considerable fundamental importance to stratospheric chemistry was studied using the technique of flash photolysis-resonance fluorescence. The reactions of interest were: (1) Cl + O3 yields ClO + O2 studied at 220-350 K, and (2) Cl + CH4 yields CH3 + HCl studied at 218-401 K. In addition, the reaction Cl + H2O2 yields HCl + HO2 was studied at 300 K. The corresponding rate constants are provided for the three reactions. The new rate data implies the need to revise downward by a factor of 2.4-3 the magnitude of the ozone perturbation due to the presence of ClO/x/ species in the stratosphere, predicted by earlier model calculations.

Triton - Stratospheric molecules and organic sediments

Science.gov (United States)

Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

1989-01-01

Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

INVESTIGATION ON PHYSICAL AND ELECTRICAL PROPERTIES OF THE SiO2-ZnO NANOCOMPOSITE AT DIFFERENT COMPOSITION MIXINGS

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Moh. Sinol

2018-01-01

Full Text Available Physical and electrical properties of The SiO2-ZnO mixing at different compositions were investigated. The experiment used simple mixing method at the sintering temperature 600oC. It was used the composition mixing ratio of SiO2:ZnO ie. 0:10; 7:3; 5:5; 3:7; and 10:0 (%Wt. Based on X-Ray Diffraction (XRD results, it obtained that a new phase in each sample was not formed even though having different diffraction peak. The mixing ratio of SiO2: ZnO nanocomposite (7:3 %wt had the biggest grain size (77,92 nm, the highest dielectric constant (3.00E+05 and the smallest conductivity (0,726549 (Ωm-1. On the other side, the mixing ratio of SiO2: ZnO nanocomposite (5:5 %wt had the smallest grain size (35.42nm, dielectric constant (3.00E+2 and the highest conductivity (25.36729  (Ωm-1. It can be concluded that the difference of composition ratio offered the change on both physical and electrical properties of SiO2-ZnO nanocomposite.

A thermodynamic study of complexation process between N, N'-dipyridoxylidene(1,4-butanediamine) and Cd2+ in some binary mixed solvents using conductometry

Science.gov (United States)

Ebrahimpoor, Sonia; Khoshnood, Razieh Sanavi; Beyramabadi, S. Ali

2016-12-01

Complexation of the Cd2+ ion with N, N'-dipyridoxylidene(1,4-butanediamine) Schiff base was studied in pure solvents including acetonitrile (AN), ethanol (EtOH), methanol (MeOH), tetrahydrofuran (THF), dimethylformamide (DMF), water (H2O), and various binary solvent mixtures of acetonitrile-ethanol (AN-EtOH), acetonitrile-methanol (AN-MeOH), acetonitrile-tetrahydrofuran (AN-THF), acetonitrile-dimethylformamide (AN-DMF), and acetonitrile-water (AN-H2O) systems at different temperatures using the conductometric method. The conductance data show that the stoichiometry of complex is 1: 1 [ML] in all solvent systems. A non-linear behavior was observed for changes of log K f of [Cd( N, N'-dipyridoxylidene(1,4-butanediamine)] complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions. The results show that the thermodynamics of complexation reaction is affected by the nature and composition of the mixed solvents.

Extreme ozone depletion in the 2010–2011 Arctic winter stratosphere as observed by MIPAS/ENVISAT using a 2-D tomographic approach

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E. Arnone

2012-10-01

Full Text Available We present observations of the 2010–2011 Arctic winter stratosphere from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS onboard ENVISAT. Limb sounding infrared measurements were taken by MIPAS during the Northern polar winter and into the subsequent spring, giving a continuous vertically resolved view of the Arctic dynamics, chemistry and polar stratospheric clouds (PSCs. We adopted a 2-D tomographic retrieval approach to account for the strong horizontal inhomogeneity of the atmosphere present under vortex conditions, self-consistently comparing 2011 to the 2-D analysis of 2003–2010. Unlike most Arctic winters, 2011 was characterized by a strong stratospheric vortex lasting until early April. Lower stratospheric temperatures persistently remained below the threshold for PSC formation, extending the PSC season up to mid-March, resulting in significant chlorine activation leading to ozone destruction. On 3 January 2011, PSCs were detected up to 30.5 ± 0.9 km altitude, representing the highest PSCs ever reported in the Arctic. Through inspection of MIPAS spectra, 83% of PSCs were identified as supercooled ternary solution (STS or STS mixed with nitric acid trihydrate (NAT, 17% formed mostly by NAT particles, and only two cases by ice. In the lower stratosphere at potential temperature 450 K, vortex average ozone showed a daily depletion rate reaching 100 ppbv day⁻¹. In early April at 18 km altitude, 10% of vortex measurements displayed total depletion of ozone, and vortex average values dropped to 0.6 ppmv. This corresponds to a chemical loss from early winter greater than 80%. Ozone loss was accompanied by activation of ClO, associated depletion of its reservoir ClONO₂, and significant denitrification, which further delayed the recovery of ozone in spring. Once the PSC season halted, ClO was reconverted primarily into ClONO₂. Compared to MIPAS observed 2003–2010 Arctic average values

Polymorphism in 'L' shaped lipids: structure of N-, O-diacylethanolamines with mixed acyl chains.

Science.gov (United States)

Tarafdar, Pradip K; Swamy, Musti J

2009-11-01

Although solid state polymorphism in lipids has been established by spectroscopic and calorimetric studies long ago, only in a few cases crystal structures of different polymorphs of the same compound have been reported, possibly due to difficulties in obtaining high quality single crystals of individual polymorphs. Recent studies show that N-, O-diacylethanolamines (DAEs) can be derived by the O-acylation of the stress-related lipids, the N-acylethanolamines under physiological conditions. In this study, two DAEs with mixed acyl chains, namely N-palmitoyl, O-octanoylethanolamine and N-palmitoyl, O-decanoylethanolamine have been synthesized and their three-dimensional structures were determined. Both the compounds were found to adopt 'L' shaped structures and exist in two polymorphic forms, alpha and beta. In the alpha form a mixed-type chain packing has been observed whereas in the beta form the chain packing is symmetric. Similar polymorphic forms are likely to exist in other 'L' shaped lipids such as 1,3-diacylglycerols and ceramides, where polymorphism has been detected earlier, but three-dimensional structures - which can give precise information about the packing at atomic resolution - have not been reported.

Unexpected high 35S concentration revealing strong downward transport of stratospheric air during the monsoon transitional period in East Asia

Science.gov (United States)

Lin, Mang; Zhang, Zhisheng; Su, Lin; Su, Binbin; Liu, Lanzhong; Tao, Jun; Fung, Jimmy C. H.; Thiemens, Mark H.

2016-03-01

October is the monsoon transitional period in East Asia (EA) involving a series of synoptic activities that may enhance the downward transport of stratospheric air to the planetary boundary layer (PBL). Here we use cosmogenic 35S in sulfate aerosols (35SO42-) as a tracer for air masses originating from the stratosphere and transported downward to quantify these mixing processes. From 1 year 35SO42- measurements (March 2014 to February 2015) at a background station in EA we find remarkably enhanced 35SO42- concentration (3150 atoms m-3) in October, the highest value ever reported for natural sulfate aerosols. A four-box 1-D model and meteorological analysis reveal that strong downward transport from the free troposphere is a vital process entraining aged stratospheric air masses to the PBL. The aged stratospheric masses are accumulated in the PBL, accelerating the SO2 transformation to SO42-. Implications for the tropospheric O3 budget and the CO2 biogeochemical cycle are discussed.

Mixed-Alkali Effect in Li2O-Na2O-K2O-B2O3 Glasses: Infrared and Optical Absorption Studies

Science.gov (United States)

Samee, M. A.; Edukondalu, A.; Ahmmad, Shaik Kareem; Taqiullah, Sair Md.; Rahman, Syed

2013-08-01

The mixed-alkali effect (MAE) has been investigated in the glass system (40 - x)Li2O- xNa2O-10K2O-50B2O3 (0 mol% ≤ x ≤ 40 mol%) through density, modulated differential scanning calorimetry (DSC), and optical absorption studies. From the absorption studies, the values of the optical band gap ( E opt) for direct transition and Urbach energy (Δ E) have been evaluated. The values of E opt and Δ E show nonlinear behavior with the compositional parameter. The density and glass-transition temperature of the present glasses also show nonlinear variation, supporting the existence of MAE. The infrared (IR) spectra of the glasses reveal the presence of three- and four-coordinated boron atoms. The specific vibrations of Li-O, Na-O, and K-O bonds were observed in the present IR study.

The Governing Processes and Timescales of Stratosphere-to-Troposphere Transport and its Contribution to Ozone in the Arctic Troposphere

Science.gov (United States)

Liang, Q.; Douglass, A. R.; Duncan, B. N.; Stolarski, R. S.; Witte, J. C.

2009-01-01

We used the seasonality of a combination of atmospheric trace gases and idealized tracers to examine stratosphere-to-troposphere transport and its influence on tropospheric composition in the Arctic. Maximum stratosphere-to-troposphere transport of CFCs and O3 occurs in April as driven by the Brewer-Dobson circulation. Stratosphere-troposphere exchange (STE) occurs predominantly between 40 deg N to 80 deg N with stratospheric influx in the mid-latitudes (30-70 deg N) accounting for 67.81 percent of the air of stratospheric origin in the Northern Hemisphere extratropical troposphere. Transport from the lower stratosphere to the lower troposphere (LT) takes three months on average, one month to cross the tropopause, the second month to travel from the upper troposphere (UT) to the middle troposphere (MT), and the third month to reach the LT. During downward transport, the seasonality of a trace gas can be greatly impacted by wet removal and chemistry. A comparison of idealized tracers with varying lifetimes suggests that when initialized with the same concentrations and seasonal cycles at the tropopause, trace gases that have shorter lifetimes display lower concentrations, smaller amplitudes, and earlier seasonal maxima during transport to the LT. STE contributes to O3 in the Arctic troposphere directly from the transport of O3 and indirectly from the transport of NOy . Direct transport of O3 from the stratosphere accounts for 78 percent of O3 in the Arctic UT with maximum contributions occurring from March to May. The stratospheric contribution decreases significantly in the MT/LT (20.25 percent of total O3) and shows a very weak March.April maximum. Our NOx budget analysis in the Arctic UT shows that during spring and summer, the stratospheric injection of NO y-rich air increases NOx concentrations above the 20 pptv threshold level, thereby shifting the Arctic UT from a regime of net photochemical ozone loss to one of net production with rates as high as +16 ppbv/month.

The governing processes and timescales of stratosphere-to-troposphere transport and its contribution to ozone in the Arctic troposphere

Science.gov (United States)

Liang, Q.; Douglass, A. R.; Duncan, B. N.; Stolarski, R. S.; Witte, J. C.

2009-05-01

We used the seasonality of a combination of atmospheric trace gases and idealized tracers to examine stratosphere-to-troposphere transport and its influence on tropospheric composition in the Arctic. Maximum stratosphere-to-troposphere transport of CFCs and O3 occurs in April as driven by the Brewer-Dobson circulation. Stratosphere-troposphere exchange (STE) occurs predominantly between 40° N to 80° N with stratospheric influx in the mid-latitudes (30-70° N) accounting for 67-81% of the air of stratospheric origin in the Northern Hemisphere extratropical troposphere. Transport from the lower stratosphere to the lower troposphere (LT) takes three months on average, one month to cross the tropopause, the second month to travel from the upper troposphere (UT) to the middle troposphere (MT), and the third month to reach the LT. During downward transport, the seasonality of a trace gas can be greatly impacted by wet removal and chemistry. A comparison of idealized tracers with varying lifetimes suggests that when initialized with the same concentrations and seasonal cycles at the tropopause, trace gases that have shorter lifetimes display lower concentrations, smaller amplitudes, and earlier seasonal maxima during transport to the LT. STE contributes to O3 in the Arctic troposphere directly from the transport of O3 and indirectly from the transport of NOy. Direct transport of O3 from the stratosphere accounts for 78% of O3 in the Arctic UT with maximum contributions occurring from March to May. The stratospheric contribution decreases significantly in the MT/LT (20-25% of total O3) and shows a very weak March-April maximum. Our NOx budget analysis in the Arctic UT shows that during spring and summer, the stratospheric injection of NOy-rich air increases NOx concentrations above the 20 pptv threshold level, thereby shifting the Arctic UT from a regime of net photochemical ozone loss to one of net production with rates as high as +16 ppbv/month.

Enhanced Ga2O3-photocatalyzed and photochemical degradation of the Fipronil insecticide by UVC irradiation in mixed aqueous/organic media under an inert atmosphere.

Science.gov (United States)

Hidaka, Hisao; Tsukamoto, Tohru; Mitsutsuka, Yoshihiro; Oyama, Toshiyuki; Serpone, Nick

2015-05-01

Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent). After 3 h of UVC irradiation (50 vol% mixed media) defluorination with Ga2O3/N2 was ∼65% greater than in aqueous media, and ca. 80% greater than the direct photolysis of Fipronil under inert (N2) conditions; under air-equilibrated conditions both Ga2O3-photocatalyzed and photochemical defluorination were significantly lower than in aqueous media. Dechlorination of Fipronil was ∼160% (Ga2O3/N2) and 140% (photochemically, N2) greater than in aqueous media; under air-equilibrated conditions, both photocatalyzed and photochemical formation of Cl(-) ions in mixed media fell rather short relative to aqueous media. The photocatalyzed (Ga2O3/N2) and photochemical (N2) conversion of the sulfur group in Fipronil to SO4(2(-)) ions was ca. 20% and 30% greater, respectively, in mixed media, while under air-equilibrated conditions photocatalyzed desulfonation was nearly twofold less than in the aqueous phase; direct photolysis showed little variations in mixed media. Denitridation of the nitrogens in Fipronil occurred mostly through the formation of ammonia (as NH4(+)) under all conditions with negligible quantities of NO3(-); again mixed media

Concentrations of ethane (C2H6) in the lower stratosphere and upper troposphere and acetylene (C2H2) in the upper troposphere deduced from Atmospheric Trace Molecule Spectroscopy/Spacelab 3 spectra

Science.gov (United States)

Rinsland, C. P.; Russell, J. M., III; Zander, R.; Farmer, C. B.; Norton, R. H.

1987-01-01

This paper reports the results of the spectroscopic analysis of C2H6 and C2H2 absorption spectra obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument flown on the Shuttle as part of the Spacelab 3 mission. The spectra were recorded during sunset occultations occurring between 25 deg N and 31 deg N latitudes, yielding volume-mixing ratio profiles of C2H6 in the lower stratosphere and the upper troposphere, and an upper tropospheric profile of C2H2. These results compare well with previous in situ and remote sounding data obtained at similar latitudes and with model calculations. The results demonstrate the feasibility of the ATMOS instrument to sound the lower atmosphere from space.

Impact of land convection on troposphere-stratosphere exchange in the tropics

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P. Ricaud

2007-11-01

Full Text Available The mechanism of troposphere-stratosphere exchange in the tropics was investigated from space-borne observations of the horizontal distributions of tropospheric-origin long-lived species, nitrous oxide (N₂O, methane (CH₄ and carbon monoxide (CO, from 150 to 70 hPa in March-April-May by the ODIN/Sub-Millimeter Radiometer (SMR, the Upper Atmosphere Research Satellite (UARS/Halogen Occultation Experiment (HALOE and the TERRA/Measurements Of Pollution In The Troposphere (MOPITT instruments in 2002–2004, completed by recent observations of the AURA/Microwave Limb Sounder (MLS instrument during the same season in 2005. The vertical resolution of the satellite measurements ranges from 2 to 4 km. The analysis has been performed on isentropic surfaces: 400 K (lower stratosphere for all the species and 360 K (upper troposphere only for CO. At 400 K (and 360 K for CO, all gases show significant longitudinal variations with peak-to-trough values of ~5–11 ppbv for N₂O, 0.07–0.13 ppmv for CH₄, and ~10 ppbv for CO (~40 ppbv at 360 K. The maximum amounts are primarily located over Africa and, depending on the species, secondary more or less pronounced maxima are reported above northern South America and South-East Asia. The lower stratosphere over the Western Pacific deep convective region where the outgoing longwave radiation is the lowest, the tropopause the highest and the coldest, appears as a region of minimum concentration of tropospheric trace species. The possible impact on trace gas concentration at the tropopause of the inhomogeneous distribution and intensity of the sources, mostly continental, of the horizontal and vertical transports in the troposphere, and of cross-tropopause transport was explored with the MOCAGE Chemistry Transport Model. In the simulations, significant longitudinal variations were found on the medium-lived CO (2-month lifetime with peak-to-trough value of ~20 ppbv at 360 K and

Optimal estimation of regional N2O emissions using a three-dimensional global model

Science.gov (United States)

Huang, J.; Golombek, A.; Prinn, R.

2004-12-01

In this study, we use the MATCH (Model of Atmospheric Transport and Chemistry) model and Kalman filtering techniques to optimally estimate N2O emissions from seven source regions around the globe. The MATCH model was used with NCEP assimilated winds at T62 resolution (192 longitude by 94 latitude surface grid, and 28 vertical levels) from July 1st 1996 to December 31st 2000. The average concentrations of N2O in the lowest four layers of the model were then compared with the monthly mean observations from six national/global networks (AGAGE, CMDL (HATS), CMDL (CCGG), CSIRO, CSIR and NIES), at 48 surface sites. A 12-month-running-mean smoother was applied to both the model results and the observations, due to the fact that the model was not able to reproduce the very small observed seasonal variations. The Kalman filter was then used to solve for the time-averaged regional emissions of N2O for January 1st 1997 to June 30th 2000. The inversions assume that the model stratospheric destruction rates, which lead to a global N2O lifetime of 130 years, are correct. It also assumes normalized emission spatial distributions from each region based on previous studies. We conclude that the global N2O emission flux is about 16.2 TgN/yr, with {34.9±1.7%} from South America and Africa, {34.6±1.5%} from South Asia, {13.9±1.5%} from China/Japan/South East Asia, {8.0±1.9%} from all oceans, {6.4±1.1%} from North America and North and West Asia, {2.6±0.4%} from Europe, and {0.9±0.7%} from New Zealand and Australia. The errors here include the measurement standard deviation, calibration differences among the six groups, grid volume/measurement site mis-match errors estimated from the model, and a procedure to account approximately for the modeling errors.

The temperature dependences of the N2+ + N2 → N4+ and O2+ + O2 → O4+ association reactions

International Nuclear Information System (INIS)

Boehringer, H.; Arnold, F.; Smith, D.; Adams, N.G.

1983-01-01

The temperature dependencies of three body association reactions have been investigated in attempts to elucidate the mechanisms of ion-molecule association. The variation with temperature of the three-body rate coefficients is described usually as a power law k approximately Tsup(-n). Experience has shown that with measurements over limited temperature ranges as with previous methods the derived coefficients n are wrong and measurements over large temperature ranges are desirable. The selected ion flow-tube and the drift tube methods developed in Birmingham and Heidelberg provide measurements over (overlapping) wide temperature rang. In collaboration of the Birmingham and the Heidelberg group the He stabilized reactions N 2 + + N 2 + He → N 4 + + He and O 2 + + O 2 + He → O 4 + + He reactions over 30 to 600 deg K. A power law dependence is found above 100 K. The temperature dependencies of the rate constants are interpred and used as a critical test of recent theories of association reactions by D.R. Bates and E. Herbst. (G.Q.)

High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 - O2 environment

Science.gov (United States)

Farrokhzad, M. A.; Khan, T. I.

2014-06-01

Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al2O3 and TiO2) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO2, 10% O2 and 75% N2. This research investigates the effects of CO2 and O2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings.

Effect of the thin Ga2O3 layer in n+-ZnO/n-Ga2O3/p-Cu2O heterojunction solar cells

International Nuclear Information System (INIS)

Minami, Tadatsugu; Nishi, Yuki; Miyata, Toshihiro

2013-01-01

The influence of inserting a Ga 2 O 3 thin film as an n-type semiconductor layer on the obtainable photovoltaic properties in Cu 2 O-based heterojunction solar cells was investigated with a transparent conductive Al-doped ZnO (AZO) thin film/n-Ga 2 O 3 thin film/p-Cu 2 O sheet structure. It was found that this Ga 2 O 3 thin film can greatly improve the performance of Cu 2 O-based heterojunction solar cells fabricated using polycrystalline Cu 2 O sheets that had been prepared by a thermal oxidization of copper sheets. The obtained photovoltaic properties in the AZO/Ga 2 O 3 /Cu 2 O heterojunction solar cells were strongly dependent on the deposition conditions of the Ga 2 O 3 films. The external quantum efficiency obtained in AZO/Ga 2 O 3 /Cu 2 O heterojunction solar cells was found to be greater at wavelengths below approximately 500 nm than that obtained in AZO/Cu 2 O heterojunction solar cells (i.e., prepared without a Ga 2 O 3 layer) at equivalent wavelengths. This improvement of photovoltaic properties is mainly attributed to a decrease in the level of defects at the interface between the Ga 2 O 3 thin film and the Cu 2 O sheet. Conversion efficiencies over 5% were obtained in AZO/Ga 2 O 3 /Cu 2 O heterojunction solar cells fabricated using an n-Ga 2 O 3 thin-film layer prepared with a thickness of 40–80 nm at an O 2 gas pressure of approximately 1.7 Pa by a pulsed laser deposition. - Highlights: • We demonstrate high-efficiency Cu 2 O-based p-n heterojunction solar cells. • A non-doped Ga 2 O 3 thin film was used as an n-type semiconductor layer. • The Ga 2 O 3 thin film was prepared at a low temperature by a low damage deposition. • p-type Cu 2 O sheets prepared by thermal oxidization of copper sheets were used. • Conversion efficiencies over 5% were obtained in AZO/n-Ga 2 O 3 /p-Cu 2 O solar cells

Sol-gel route to synthesis of microporous ceramic membranes: Thermal stability of TiO2-ZrO2 mixed oxides

International Nuclear Information System (INIS)

Qunyin Xu; Anderson, M.A.

1993-01-01

In this paper concerning the synthesis of microporous ceramic membranes, the authors focus on the preparation and thermal stability of unsupported microporous TiO 2 -ZrO 2 mixed-oxide membranes. It has been observed that, by adding up to 20% ZrO 2 into TiO 2 or up to 10% TiO 2 into ZrO 2 , these microporous membranes display improved thermal stability. They can be fired up to 500 C for 0.5 h without closing micropores. However, membranes containing almost equal percentages of each component have lost microporous features and have low surface areas and low porosities. A phase diagram of a two-component TiO 2 -ZrO 2 mixed-oxide membrane has been prepared based on DTA and X-ray diffraction data in order to better understand the microstructure changes upon firing

Effects of Greenhouse Gas Increase and Stratospheric Ozone Depletion on Stratospheric Mean Age of Air in 1960-2010

Science.gov (United States)

Li, Feng; Newman, Paul; Pawson, Steven; Perlwitz, Judith

2018-01-01

The relative impacts of greenhouse gas (GHG) increase and stratospheric ozone depletion on stratospheric mean age of air in the 1960-2010 period are quantified using the Goddard Earth Observing System Chemistry-�Climate Model. The experiment compares controlled simulations using a coupled atmosphere-�ocean version of the Goddard Earth Observing System Chemistry-�Climate Model, in which either GHGs or ozone depleting substances, or both factors evolve over time. The model results show that GHGs and ozone-depleting substances have about equal contributions to the simulated mean age decrease, but GHG increases account for about two thirds of the enhanced strength of the lower stratospheric residual circulation. It is also found that both the acceleration of the diabatic circulation and the decrease of the mean age difference between downwelling and upwelling regions are mainly caused by GHG forcing. The results show that ozone depletion causes an increase in the mean age of air in the Antarctic summer lower stratosphere through two processes: (1) a seasonal delay in the Antarctic polar vortex breakup that inhibits young midlatitude air from mixing with the older air inside the vortex, and (2) enhanced Antarctic downwelling that brings older air from middle and upper stratosphere into the lower stratosphere.

The preparation and characterization of nanostructured TiO2-ZrO2 mixed oxide electrode for efficient dye-sensitized solar cells

International Nuclear Information System (INIS)

Kitiyanan, Athapol; Ngamsinlapasathian, Supachai; Pavasupree, Soropong; Yoshikawa, Susumu

2005-01-01

The preparation of nanostructured mixed metal oxide based on a sol-gel method with surfactant-assisted mechanism, and its application for dye-sensitized solar cell (DSSC) are reported. The mixed zirconia (ZrO 2 ) and titania (TiO 2 ) mesoporous powder possessed larger surface area than the corresponding titania. For the UV action spectra of unsensitized photochemical cell, the mixed zirconia/titania electrode can absorb UV light below 380nm, corresponding to band gap (E g ) around 3.27eV, which is higher than that of pure component of titania (E g =3.2eV). Both of these improved properties, i.e., BET surface area and band gap, contributed to the improvement on a short-circuit photocurrent up to 11%, an open-circuit voltage up to 4%, and a solar energy conversion efficiency up to 17%, for the DSSC fabricated by mesoporous zirconia/titania mixed system when compared to the cell that was fabricated only by nanostructured TiO 2 . The cell fabricated by 5μm thick mixed TiO 2 -ZrO 2 electrode gave the short-circuit photocurrent about 13mA/cm 2 , open-circuit voltage about 600 mV and the conversion efficiency 5.4%

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

Science.gov (United States)

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

First results of warm mesospheric temperature over Gadanki (13.5°N, 79.2°E) during the sudden stratospheric warming of 2009

Science.gov (United States)

Sridharan, S.; Raghunath, K.; Sathishkumar, S.; Nath, D.

2010-09-01

Rayleigh lidar observations at Gadanki (13.5°N, 79.2°E) show an enhancement of the nightly mean temperature by 10-15 K at altitudes 70-80 km and of gravity wave potential energy at 60-70 km during the 2009 major stratospheric warming event. An enhanced quasi-16-day wave activity is observed at 50-70 km in the wavelet spectrum of TIMED-SABER temperatures, possibly due to the absence of a critical level in the low-latitude stratosphere because of less westward winds caused by this warming event. The observed low-latitude mesospheric warming could be due to wave breaking, as waves are damped at 80 km.

[(Nitrato-κ2 O,O′)(nitrito-κ2 O,O′)(0.25/1.75)]bis­(1,10-phenanthroline-κ2 N,N′)cadmium(II)

Science.gov (United States)

Najafi, Ezzatollah; Amini, Mostafa M.; Ng, Seik Weng

2011-01-01

The reaction of cadmium nitrate and sodium nitrite in the presence of 1,10-phenanthroline yields the mixed nitrate–nitrite title complex, [Cd(NO2)1.75(NO3)0.25(C12H8N2)2]. The metal ion is bis-chelated by two N-heterocycles as well as by the nitrate/nitrite ions in a distorted dodeca­hedral CdN4O4 coordination environment. One nitrite group is ordered; the other is disordered with respect to a nitrate group (ratio 0.75:0.25) concerning the O atom that is not involved in bonding to the metal ion. PMID:21522904

Nitrous Oxide (N2O) Emissions from California based on 2010 CalNex Airborne Measurements

Science.gov (United States)

Xiang, B.; Miller, S.; Kort, E. A.; Santoni, G. W.; Daube, B.; Commane, R.; Angevine, W. M.; Ryerson, T. B.; Trainer, M.; Andrews, A. E.; Nehrkorn, T.; Tian, H.; Wofsy, S. C.

2012-12-01

Nitrous oxide (N2O) is an important gas for climate and for stratospheric chemistry, with an atmospheric lifetime exceeding 100 years. Global concentrations have increased steadily since the 18th century, apparently due to human-associated emissions, principally from application of nitrogen fertilizers. However, quantitative studies of agricultural emissions at large spatial scales are lacking, inhibited by the difficulty of measuring small enhancements of atmospheric concentrations. Here we derive regional emission rates for N2O in the Central Valley of California, based on analysis of in-situ airborne atmospheric observations collected using a quantum cascade laser spectrometer. The data were obtained on board the NOAA P-3 research aircraft during the CalNex (California Research at the Nexus of Air Quality and Climate Change) program in May and June, 2010. We coupled WRF (Weather Research and Forecasting) model to STILT (Stochastic Time-Inverted Lagrangian Transport) to link our in-situ observations to surface emissions, and then used a variety of statistical methods to identify source areas and to extract optimized emission rates from the inversion. Our results support the view that fertilizer application is the largest source of N2O in the Central Valley. But the spatial distribution of derived surface emissions, based on California land use and activity maps, was very different than indicated in the leading emissions inventory (EDGAR 4.0), and our estimated total emission flux of N2O for California during the study period was 3 - 4 times larger than EDGAR and other inventories.

Evidence for long-lived polar vortex air in the mid-latitude summer stratosphere from in situ laser diode CH4 and H2O measurements

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G. Durry

2005-01-01

Full Text Available A balloon borne diode laser spectrometer was launched in southern France in June 2000 to yield in situ stratospheric CH4 and H2O measurements. In the altitude region ranging from 20km to 25km, striking large spatial structures were observed in the vertical concentration profiles of both species. We suggest these patterns are due to the presence of long-lived remnants of the wintertime polar vortex in the mid-latitude summer stratosphere. To support this interpretation, a high resolution advection model for potential vorticity is used to investigate the evolution of the Arctic vortex after its breakdown phase in spring 2000.

A polar stratospheric cloud parameterization for the global modeling initiative three-dimensional model and its response to stratospheric aircraft

International Nuclear Information System (INIS)

Considine, D. B.; Douglass, A. R.; Connell, P. S.; Kinnison, D. E.; Rotman, D. A.

2000-01-01

We describe a new parameterization of polar stratospheric clouds (PSCs) which was written for and incorporated into the three-dimensional (3-D) chemistry and transport model (CTM) developed for NASA's Atmospheric Effects of Aviation Project (AEAP) by the Global Modeling Initiative (GMI). The parameterization was designed to respond to changes in NO y and H 2 O produced by high-speed civilian transport (HSCT) emissions. The parameterization predicts surface area densities (SADs) of both Type 1 and Type 2 PSCs for use in heterogeneous chemistry calculations. Type 1 PSCs are assumed to have a supercooled ternary sulfate (STS) composition, and Type 2 PSCs are treated as water ice with a coexisting nitric acid trihydrate (NAT) phase. Sedimentation is treated by assuming that the PSC particles obey lognormal size distributions, resulting in a realistic mass flux of condensed phase H 2 O and HNO 3 . We examine a simulation of the Southern Hemisphere high-latitude lower stratosphere winter and spring seasons driven by temperature and wind fields from a modified version of the National Center for Atmospheric Research (NCAR) Middle Atmosphere Community Climate Model Version 2 (MACCM2). Predicted PSC SADs and median radii for both Type 1 and Type 2 PSCs are consistent with observations. Gas phase HNO 3 and H 2 O concentrations in the high-latitude lower stratosphere qualitatively agree with Cryogenic Limb Array Etalon Spectrometer (CLAES) HNO 3 and Microwave Limb Sounder (MLS) H 2 O observations. The residual denitrification and dehydration of the model polar vortex after polar winter compares well with atmospheric trace molecule spectroscopy (ATMOS) observations taken during November 1994. When the NO x and H 2 O emissions of a standard 500-aircraft HSCT fleet with a NO x emission index of 5 are added, NO x and H 2 O concentrations in the Southern Hemisphere polar vortex before winter increase by up to 3%. This results in earlier onset of PSC formation, denitrification, and

Comparisons between ground-based FTIR and MIPAS N2O and HNO3 profiles before and after assimilation in BASCOE

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C. Vigouroux

2007-01-01

Full Text Available Within the framework of the Network for Detection of Atmospheric Composition Change (NDACC, regular ground-based Fourier transform infrared (FTIR measurements of many species are performed at several locations. Inversion schemes provide vertical profile information and characterization of the retrieved products which are therefore relevant for contributing to the validation of MIPAS profiles in the stratosphere and upper troposphere. We have focused on the species HNO3 and N2O at 5 NDACC-sites distributed in both hemispheres, i.e., Jungfraujoch (46.5° N and Kiruna (68° N for the northern hemisphere, and Wollongong (34° S, Lauder (45° S and Arrival Heights (78° S for the southern hemisphere. These ground-based data have been compared with MIPAS offline profiles (v4.61 for the year 2003, collocated within 1000 km around the stations, in the lower to middle stratosphere. To get around the spatial collocation problem, comparisons have also been made between the same ground-based FTIR data and the corresponding profiles resulting from the stratospheric 4D-VAR data assimilation system BASCOE constrained by MIPAS data. This paper discusses the results of the comparisons and the usefullness of using BASCOE profiles as proxies for MIPAS data. It shows good agreement between MIPAS and FTIR N2O partial columns: the biases are below 5% for all the stations and the standard deviations are below 7% for the three mid-latitude stations, and below 10% for the high latitude ones. The comparisons with BASCOE partial columns give standard deviations below 4% for the mid-latitude stations to less than 8% for the high latitude ones. After making some corrections to take into account the known bias due to the use of different spectroscopic parameters, the comparisons of HNO3 partial columns show biases below 3% and standard deviations below 15% for all the stations except Arrival Heights (bias of 5%, standard deviation of 21%. The results for this species, which

Regional stratospheric warmings in the Pacific-Western Canada (PWC sector during winter 2004/2005: implications for temperatures, winds, chemical constituents and the characterization of the Polar vortex

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A. H. Manson

2008-11-01

Scandinavia-Europe and Canada-US. The data-archive of Aura-MLS was also used to produce height versus latitude contours of ozone and related constituents, using mixing ratios (r for ClO, N2O and HCl, for the 16° E and 253° E sectors. The Q-diagnostic was used to display the positions of the cyclonic (polar vortex, using data from the UK Meteorological Office (MetO analyses. ClO/HCL maxima/minima occurred on 1 February in both sectors, consistent with loss of ozone by heterogeneous chemistry. Low N2O values at high latitudes indicated that both sectors were inside the polar vortex, Time-difference plots show greater reductions in O3 in the Canadian sector. For the 25 February PWC warming event, O3-rich air from lower latitudes continued to be excluded from Europe, while O3 penetrated to at least 82° N over the Canadian sector. The contours for ClO, N2O and HCl at 16° E are consistent with continued ozone loss within the vortex during the event. Finally the thermal and chemical changes at these 16° E and 253° E sectors are placed into a hemispheric context using polar-cylindrical plots, with the following results. Firstly, the mixing ratios of O3, ClO, HNO3, HCL and the temperatures from Aura-MLS were consistent with consensus views of heterogeneous chemistry. Secondly, and consistent with the polar plots of C07, the vortices and their edges were strongly distorted during the 1 January, 1 and 25 February warming events, with sinusoidal shapes consistent with stationary planetary waves of wave-numbers 1 and 2. Thirdly, the distributions of the chemicals followed the curvatures (cyclonic and anticyclonic of the vortex edges with O3 losses occurring at the cold cyclonic locations. During February these were over Scandinavia-Western Europe and Central-Eastern Canada. Trajectory analysis was applied to the two February warming events. For the 1 February event, the rotation time for air parcels within the peanut-shaped vortex was 3–4 days; while the O3-rich low latitude air

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

Science.gov (United States)

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.

Theoretical study of the interaction of N2 with water molecules. (H2O)/sub n/:N2, n = 1--8

International Nuclear Information System (INIS)

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

1984-01-01

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

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

Science.gov (United States)

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.

Insulation Strength and Decomposition Characteristics of a C6F12O and N2 Gas Mixture

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Xiaoxing Zhang

2017-08-01

Full Text Available This paper explores the decomposition characteristics of a new type of environmentally friendly insulating gas C6F12O and N2 mixed gas under AC voltage. The breakdown behavior of 3% C6F12O and N2 mixed gas in quasi-uniform field was investigated through a breakdown experiment. The self-recovery of the mixed gas was analyzed by 100 breakdown experiments. The decomposition products of C6F12O and N2 under breakdown voltage were determined by gas chromatography–mass spectrometer (GC-MS. Finally, the decomposition process of the products was calculated by density functional theory, and the ionization energy, affinity, and molecular orbital gap of the decomposition products were also calculated. The properties of the decomposition products were analyzed from the aspects of insulation and environmental protection. The experimental results show that the 3% C6F12O and N2 mixed gas did not show a downward trend over 100 breakdown tests under a 0.10 MPa breakdown voltage. The decomposition products after breakdown were CF4, C2F6, C3F6, C3F8, C4F10, and C5F12. The ionization energies of several decomposition products are more than 10 eV. The Global Warming Potential (GWP values of the main products are lower than SF6. C2F6, C3F8, and C4F10 have better insulation properties.

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

Science.gov (United States)

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.

THERMAL AND CHEMICAL STRUCTURE VARIATIONS IN TITAN'S STRATOSPHERE DURING THE CASSINI MISSION

Energy Technology Data Exchange (ETDEWEB)

Bampasidis, Georgios; Coustenis, A.; Vinatier, S. [Laboratoire d' Etudes Spatiales et d' Instrumentation en Astrophysique (LESIA), Observatoire de Paris, CNRS, UPMC Univ. Paris 06, Univ. Paris-Diderot, 5, place Jules Janssen, F-92195 Meudon Cedex (France); Achterberg, R. K. [Department of Astronomy, University of Maryland, College Park, MD 20742 (United States); Lavvas, P. [GSMA, Universite Reims Champagne-Ardenne, F-51687 Reims Cedex 2 (France); Nixon, C. A.; Jennings, D. E.; Flasar, F. M.; Carlson, R. C.; Romani, P. N.; Guandique, E. A. [Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Teanby, N. A. [School of Earth Sciences, University of Bristol, Bristol BS8 1RJ (United Kingdom); Moussas, X.; Preka-Papadema, P.; Stamogiorgos, S., E-mail: gbabasid@phys.uoa.gr [Faculty of Physics, National and Kapodistrian University of Athens, Panepistimioupolis, GR 15783 Zographos, Athens (Greece)

2012-12-01

We have developed a line-by-line Atmospheric Radiative Transfer for Titan code that includes the most recent laboratory spectroscopic data and haze descriptions relative to Titan's stratosphere. We use this code to model Cassini Composite Infrared Spectrometer data taken during the numerous Titan flybys from 2006 to 2012 at surface-intercepting geometry in the 600-1500 cm{sup -1} range for latitudes from 50 Degree-Sign S to 50 Degree-Sign N. We report variations in temperature and chemical composition in the stratosphere during the Cassini mission, before and after the Northern Spring Equinox (NSE). We find indication for a weakening of the temperature gradient with warming of the stratosphere and cooling of the lower mesosphere. In addition, we infer precise concentrations for the trace gases and their main isotopologues and find that the chemical composition in Titan's stratosphere varies significantly with latitude during the 6 years investigated here, with increased mixing ratios toward the northern latitudes. In particular, we monitor and quantify the amplitude of a maximum enhancement of several gases observed at northern latitudes up to 50 Degree-Sign N around mid-2009, at the time of the NSE. We find that this rise is followed by a rapid decrease in chemical inventory in 2010 probably due to a weakening north polar vortex with reduced lateral mixing across the vortex boundary.

Preparation and infrared spectra of the Schiff base solid complexes [UO2(sal-O-phdn)(H2O)] and [UO2(sal-O-phdn) (Et3N)] (sal-O-phdn=n, n'-o-phenylenebissalicylideniminato)

International Nuclear Information System (INIS)

Sadeek, S.A.; Teleb, S.M.; Al-Kority, A.M.

1993-01-01

In the present communication, we report the preparation of the related two new complexes, [UO 2 (sal-o-phdn)(H 2 O)] and LUO 2 (sal-o-phdn)(Et 3 N)], where sal-o-phdn=N, N'-o-phenylenebis (salicylideneiminato); here U VI is seven-coordinate. The infrared spectra of these two complexes are recorded and assigned. (author). 10 refs., 1 tab

On the ability of chemical transport models to simulate the vertical structure of the N2O, NO2 and HNO3 species in the mid-latitude stratosphere

Directory of Open Access Journals (Sweden)

G. Berthet

2006-01-01

Full Text Available In this paper we study the impact of the modelling of N2O on the simulation of NO2 and HNO3 by comparing in situ vertical profiles measured at mid-latitudes with the results of the Reprobus 3-D CTM (Three-dimensional Chemical Transport Model computed with the kinetic parameters from the JPL recommendation in 2002. The analysis of the measured in situ profile of N2O shows particular features indicating different air mass origins. The measured N2O, NO2 and HNO3 profiles are not satisfyingly reproduced by the CTM when computed using the current 6-hourly ECMWF operational analysis. Improving the simulation of N2O transport allows us to calculate quantities of NO2 and HNO3 in reasonable agreement with observations. This is achieved using 3-hourly winds obtained from ECMWF forecasts. The best agreement is obtained by constraining a one-dimensional version of the model with the observed N2O. This study shows that the modelling of the NOy partitioning with better accuracy relies at least on a correct simulation of N2O and thus of total NOy.

High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 – O2 environment

International Nuclear Information System (INIS)

Farrokhzad, M A; Khan, T I

2014-01-01

Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al 2 O3 and TiO 2 ) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO 2 , 10% O 2 and 75% N 2 . This research investigates the effects of CO 2 and O 2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO 2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO 2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO 2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings

Factors affecting ultraviolet irradiation/hydrogen peroxide (UV/H2O2) degradation of mixed N-nitrosamines in water

International Nuclear Information System (INIS)

Zhou, Chao; Gao, Naiyun; Deng, Yang; Chu, Wenhai; Rong, Wenlei; Zhou, Shengdong

2012-01-01

Highlights: ► NAms with three-induced toxicity, as emerging DBPs, has caused a great public attention. ► No paper regards UV/H 2 O 2 oxidation of mixed NAms in an aquatic environment. ► The treatment effect is typically affected by a few factors in water. ► NPIP and NDPhA are the most readily and difficult to be degraded due to unique structure. ► All the NAms degradation exhibited a pseudo-first-order kinetics pattern. - Abstract: Disinfection by-products (DBPs) are a great challenge to our drinking water security. Particularly, nitrosamines (NAms), as emerging DBPs, are potently carcinogenic, mutagenic, and teratogenic, and have increasingly attained public attention. This study was to evaluate the performance of the NAms degradation by the ultraviolet (UV) irradiation (253.7 nm) in the presence of hydrogen peroxide (H 2 O 2 ). In the UV/H 2 O 2 system, hydroxyl radicals (OH·), a type of nonselective and powerful oxidant, was produced to attack the molecules of NAms. Factors affecting the treatment efficiency, including the H 2 O 2 dosage, initial NAms concentration, UV irradiation intensity, initial solution pH, and inorganic anions present in water, were evaluated. All the NAms degradation exhibited a pseudo-first-order kinetics pattern. Within 60 min, 0.1 mg/L of any NAms could be almost decomposed except NDPhA that required 120 min for complete removal, at 25 μmol/L H 2 O 2 and at initial pH 7. Results demonstrate that the UV/H 2 O 2 treatment is a viable option to control NAms in water.

Effect of rutile TiO{sub 2} on the photocatalytic performance of g-C{sub 3}N{sub 4}/brookite-TiO{sub 2-x}N{sub y} photocatalyst for NO decomposition

Energy Technology Data Exchange (ETDEWEB)

Li, Huihui, E-mail: lihh@lzu.edu.cn [Key Laboratory for Magnetism Magnetic Materials of the Ministry of Education, Lanzhou University, 222 south Tianshui Road, Lanzhou, 730000 (China); Wu, Xiaoyong [Wuhan University of Technology, 122 Luoshi Road, Wuhan 430070 (China); Yin, Shu [Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Katsumata, Kenichi [Photocatalysis International Research Center, Research Institute for Science and Technology, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba, 278-8510 (Japan); Wang, Yuhua [Key Laboratory for Magnetism Magnetic Materials of the Ministry of Education, Lanzhou University, 222 south Tianshui Road, Lanzhou, 730000 (China)

2017-01-15

Graphical abstract: g-C{sub 3}N{sub 4}/rutile-brookite TiO{sub 2-x}Ny forms a Z-scheme photocatalytic system, which shows improvement on the photocatalytic activity than that of g-C{sub 3}N{sub 4}/single brookite TiO{sub 2-x}N{sub y}. - Highlights: • g-C{sub 3}N{sub 4}/rutile-brookite TiO{sub 2-x}N{sub y} forms a Z-scheme photocatalytic system. • Photogenerated electrons can efficiently transfer from rutile TiO{sub 2} to g-C{sub 3}N{sub 4}. • Single brookite TiO{sub 2-x}N{sub y} shows lower photo-utilization efficiency than rutile-brookite mixed one. • DeNO{sub x} activities of brookite TiO{sub 2-x}N{sub y} hybrids decrease with g-C{sub 3}N{sub 4} amount increase. - Abstract: Novel g-C{sub 3}N{sub 4}/rutile-brookite TiO{sub 2-x}N{sub y} composite photocatalysts were fabricated through a facile solvothermal approach. The effect of rutile phase TiO{sub 2} with brookite TiO{sub 2} and g-C{sub 3}N{sub 4} on the photocatalytic activity of g-C{sub 3}N{sub 4}/nitrogen-doped TiO{sub 2} composite was studied. The photocatalytic performance of the photocatalyst was evaluated by measuring the degradation of NO gas under visible and UV light irradiation. It is suggested that g-C{sub 3}N{sub 4}/rutile-brookite TiO{sub 2-x}N{sub y} forms a Z-scheme photocatalytic system, which shows improvement on the photocatalytic activity than that of g-C{sub 3}N{sub 4}/single brookite TiO{sub 2-x}N{sub y}. By importing rutile phase TiO{sub 2-x}N{sub y}, the photogenerated electrons can efficiently transfer from rutile TiO{sub 2} to g-C{sub 3}N{sub 4}, which results in the separation of electron and hole pairs, enhancing the photocatalytic ability. However, single brookite TiO{sub 2-x}N{sub y} can not remove the photogenerated electrons efficiently and the photocatalytic performances of composites decrease with g-C{sub 3}N{sub 4} amount increase.

Submillimeter-wave measurements of N2 and O2 pressure broadening for HO2 radical generated by Hg-photosensitized reaction

International Nuclear Information System (INIS)

Mizoguchi, A.; Yagi, T.; Kondo, K.; Sato, T.O.; Kanamori, H.

2012-01-01

The N 2 and O 2 pressure broadening coefficients of the pure rotational transitions at 625.66 GHz (N KaKc =10 1-9 -10 0-10 , J=10.5-10.5) and 649.70 GHz (N KaKc =10 2-9 -9 2-8 , J=9.5-8.5) in the vibronic ground state X 2 A′ of the perhydroxyl (HO 2 ) radical have been determined by precise laboratory measurements. For the production of HO 2 , the mercury-photosensitized reaction of the H 2 and O 2 precursors was used to provide an optimum condition for measurement of the pressure broadening coefficient. The Superconducting Submillimeter-wave Limb Emission Sounder (SMILES) was designed to monitor the volume mixing ratio of trace gases including HO 2 in the Earth's upper atmosphere using these transitions. The precise measurement of pressure broadening coefficient γ in terms of the half width at half maximum is required in order to retrieve the atmospheric volume mixing ratio. In this work, γ coefficients of the 625.66 GHz transition were determined for N 2 and O 2 at room temperature as γ(N 2 )=4.085±0.049 MHz/Torr and γ(O 2 )=2.578±0.047 MHz/Torr with 3σ uncertainty. Similarly, the coefficients of the 649.70 GHz transition were determined as γ(N 2 )=3.489±0.094 MHz/Torr and γ(O 2 )=2.615±0.099 MHz/Torr. The air broadening coefficients for the 625.66 GHz and 649.70 GHz lines were estimated at γ(air)=3.769±0.067 MHz and 3.298±0.099 MHz respectively, where the uncertainty includes possible systematic errors. The newly determined coefficients are compared with previous results and we discuss the advantage of the mercury-photosensitized reaction for HO 2 generation. In comparison with those of other singlet molecules, the pressure broadening coefficients of the HO 2 radical are not much affected by the existence of an unpaired electron.

DUSTER: collection of meteoric CaO and carbon smoke particles in the upper stratosphere .

Science.gov (United States)

Della Corte, V.; Rietmeijer, F. J. M.; Rotundi, A.; Ferrari, M.; Palumbo, P.

Nanometer- to micrometer-size particles present in the upper stratosphere are a mixture of terrestrial and extra-terrestrial origins. They can be extraterrestrial particles condensed after meteor ablation. Meteoric dust in bolides is occasionally deposited into the lower stratosphere around 20 km altitude. Nanometer CaO and pure carbon smoke particles were collected at 38 km altitude in the upper stratosphere in the Arctic during June 2008 using DUSTER (Dust in the Upper Stratosphere Tracking Experiment and Retrieval), a balloon-borne instrument for the non-destructive collection of solid particles between 200 nm to 40 microns. We report the collection of micron sized CaCO_3 (calcite) grains. Their morphologies show evidence of melting and condensation after vaporization suggest at temperatures of approximately 3500 K. The formation environment of the collected grains was probably a dense dust cloud formed by the disintegration of a carbonaceous meteoroid during deceleration in the Earth� atmosphere. For the first time, DUSTER collected meteor ablation products that were presumably associated with the disintegration of a bolide crossing the Earth's atmosphere. The collected mostly CaO and pure carbon nanoparticles from the debris cloud of a fireball, included: 1) intact fragments; 2) quenched melted grains; and 3) vapor phase condensation products. The DUSTER project was funded by the Italian Space Agency (ASI), PRIN2008/MIUR (Ministero dell'Istruzione dell'Universitá e della Ricerca), PNRA 2013(Piano Nazionale Ricerca Antartide). CNES graciously provided this flight opportunity. We thank E. Zona and S. Inarta at the Laboratorio di Fisica Cosmica INAF, Osservatorio Astronomico di Capodimonte-Universitá di Napoli Parthenope. F.J.M.R. was supported by grant NNX07AI39G from the NASA Cosmochemistry Program. We thank three anonymous reviewers who assisted us in introducing our new instrument.

Measurements of HCl and HNO3 with the new research aircraft HALO - Quantification of the stratospheric contribution to the O3 and HNO3 budget in the UT/LS

Science.gov (United States)

Jurkat, Tina; Kaufmann, Stefan; Voigt, Christiane; Zahn, Andreas; Schlager, Hans; Engel, Andreas; Bönisch, Harald; Dörnbrack, Andreas

2013-04-01

Dynamic and chemical processes modify the ozone (O3) budget of the upper troposphere/lower stratosphere, leading to locally variable O3 trends. In this region, O3 acts as a strong greenhouse gas with a net positive radiative forcing. It has been suggested, that the correlation of the stratospheric tracer hydrochloric acid (HCl) with O3 can be used to quantify stratospheric O3 in the UT/LS region (Marcy et al., 2004). The question is, whether the stratospheric contribution to the nitric acid (HNO3) budget in the UT/LS can be determined by a similar approach in order to differentiate between tropospheric and stratospheric sources of HNO3. To this end, we performed in situ measurements of HCl and HNO3 with a newly developed Atmospheric chemical Ionization Mass Spectrometer (AIMS) during the TACTS (Transport and Composition in the UTLS) / ESMVal (Earth System Model Validation) mission in August/September 2012. The linear quadrupole mass spectrometer deployed aboard the new German research aircraft HALO was equipped with a new discharge source generating SF5- reagent ions and an in-flight calibration allowing for accurate, spatially highly resolved trace gas measurements. In addition, sulfur dioxide (SO2), nitrous acid (HONO) and chlorine nitrate (ClONO2) have been simultaneously detected with the AIMS instrument. Here, we show trace gas distributions of HCl and HNO3 measured during a North-South transect from Northern Europe to Antarctica (68° N to 65° S) at 8 to 15 km altitude and discuss their latitude dependence. In particular, we investigate the stratospheric ozone contribution to the ozone budget in the mid-latitude UT/LS using correlations of HCl with O3. Differences in these correlations in the subtropical and Polar regions are discussed. A similar approach is used to quantify the HNO3 budget of the UT/LS. We identify unpolluted atmospheric background distributions and various tropospheric HNO3 sources in specific regions. Our observations can be compared to

Selective catalytic reduction of NOx and N{sub 2}O by NH{sub 3} over Fe-FER; Developpement d'un traitement catalytique combine des NOx et de N{sub 2}O par NH{sub 3} sur Fe-Fer

Energy Technology Data Exchange (ETDEWEB)

Kieger, St. [Grande Paroisse, 76 - Grand-Quevilly (France); Navascues, L.; Gry, Ph. [Grande Paroisse, 92 - Paris la Defense (France)

2001-07-01

The emission of nitrogen oxides from anthropogenic activities is a major environmental issue. N{sub 2}O is taking part to the global warming and depletion of the stratospheric ozone layer, and NOx to acid rains. At the Kyoto Conference in 1997, the European Union committed itself to reduce by 8% the release of greenhouse gases at the horizon 2010. The selective catalytic reduction (SCR) of NOx by NH{sub 3} is nowadays the main control technology for the emissions from nitric acid plant. Therefore, Grande Paroisse and IRMA have developed a new catalyst (Fe-FER) for the SCR of N{sub 2}O by NH{sub 3}. The catalyst was evaluated in a pilot plant and in the same operating conditions than a DeNOx catalyst. At a space velocity of 9000 to 12000 h{sup -1}, a decomposition of 50% of N{sub 2}O was achieved at 440 deg C. Moreover for the same decomposition level, the temperature could be shifted to 390 deg C by adding ammonia, and the complete reduction of NOx was also observed. This new catalyst is rather bi-functional. Also after months of using, the catalyst did not show major loss of activity nor mechanical strength. (authors)

Laboratory investigation of nitrile ices of Titan's stratospheric clouds

Science.gov (United States)

Nna Mvondo, D.; Anderson, C. M.; McLain, J. L.; Samuelson, R. E.

2017-09-01

Titan's mid to lower stratosphere contains complex cloud systems of numerous organic ice particles comprised of both hydrocarbon and nitrile compounds. Most of these stratospheric ice clouds form as a result of vapor condensation formation processes. However, there are additional ice emission features such as dicyanoacetylene (C4N2) and the 220 cm-1 ice emission feature (the "Haystack") that are difficult to explain since there are no observed vapor emission features associated with these ices. In our laboratory, using a high-vacuum chamber coupled to a FTIR spectrometer, we are engaged in a dedicated investigation of Titan's stratospheric ices to interpret and constrain Cassini Composite InfraRed Spectrometer (CIRS) far-IR data. We will present laboratory transmittance spectra obtained for propionitrile (CH3CH2CN), cyanogen (C2N2) and hydrogen cyanide (HCN) ices, as well as various combinations of their mixtures, to better understand the cloud chemistry occurring in Titan's stratosphere.

Effect of ZnO, ZrO2 and B2O3 on clinkerization process. Part I. Clinkerization reactions and clinker composition

Directory of Open Access Journals (Sweden)

Palacios, M.

2008-12-01

Full Text Available The use of clay-based product waste as an alternative prime material in Portland cement raw mixes raises the ZnO, ZrO2 and B2O3 content in the clinker. These compounds are found in the enamelled surface of the tile added to the raw mix. The present study explores the effect of adding 0.5 and 2% ZnO, ZrO2 and B2O3 to the raw mix, separately and jointly, on clinkerization and the distribution and morphology of the mineral phases in the clinker. The findings showed that while ZnO and ZrO2 are fixed in the clinker, B2O3 is partially volatized. Zinc oxide acted as a flux, while neither ZrO2 nor B2O3 increased the molten phase. The addition of the oxides to the raw mix changed the content of the main mineral phases in the clinker. Zinc oxide lowered the C3S and C3A contents, ZrO2 reduced the ferritic phase and B2O3 stabilized C2S. New mineral phases, namely 3CaO·ZnO·2Al2O3 and CaZrO3, were identified in the clinkers obtained when 2% ZnO and ZrO2 were added to the raw mix.El empleo de residuos cerámicos como materia prima alternativa en la fabricación del crudo de cemento Portland, aumenta el contenido de ZnO, ZrO2 y B2O3 en el clinker. Estos elementos se encuentran en la capa esmaltada de los residuos cerámicos incorporados al crudo. Por ello el presente trabajo de investigación aborda el estudio del efecto que tiene la adición en el crudo de contenidos del 0,5 y 2% de ZnO, ZrO2 y B2O3 de manera individual y conjunta en los procesos de clinkerización, en la distribución y morfología de las fases mineralógicas del clinker.Los resultados obtenidos han demostrado que el ZnO y ZrO2 permanecen fijados en el clinker, sin embargo el B2O3 se volatiliza parcialmente. El ZnO actúa como fundente, mientras que el ZrO2 y el B2O3 no aumentan el contenido de fase fundida. La adición de estos óxidos al crudo modifica el contenido de las principales fases mineralógicas del clinker. El ZnO disminuye los contenidos de C3S y C3A, el ZrO2 disminuye

Neutronic analysis concerning the utilization of mixed U N-Pu N nitride fuel for fast reactors

International Nuclear Information System (INIS)

Renke, C.A.C.; Batista, J.L.; Waintraub, M.; Santos Bastos, W. dos; Brito Aghina, L.O. de.

1991-08-01

Neutronic behavior of mixed UN-PuN nitride fuel in substitution of the mixed oxide U O 2 - Pu O 2 for fast reactors is discussed with focus on Super Phenix I. Characteristics parameters of both cores are calculated and compared and the results presented show a great advantage for the nitride fuel, pointing out a larger performance of fuel elements in the core and an effective reduction of reactivity loss during the cycle. (author)

Lepton mixing predictions from Δ(6n2) family symmetry

International Nuclear Information System (INIS)

King, Stephen F.; Neder, Thomas; Stuart, Alexander J.

2013-01-01

We obtain predictions of lepton mixing parameters for direct models based on Δ(6n 2 ) family symmetry groups for arbitrarily large n in which the full Klein symmetry is identified as a subgroup of the family symmetry. After reviewing and developing the group theory associated with Δ(6n 2 ), we find many new candidates for large n able to yield reactor angle predictions within 3σ of recent global fits. We show that such Δ(6n 2 ) models with Majorana neutrinos predict trimaximal mixing with reactor angle θ 13 fixed up to a discrete choice, an oscillation phase of either zero or π and the atmospheric angle sum rules θ 23 =45°∓θ 13 /√(2), respectively, which are consistent with recent global fits and will be tested in the near future

Stratospheric role in interdecadal changes of El Niño impacts over Europe

Science.gov (United States)

Ayarzagüena, B.; López-Parages, J.; Iza, M.; Calvo, N.; Rodríguez-Fonseca, B.

2018-04-01

The European precipitation response to El Niño (EN) has been found to present interdecadal changes, with alternated periods of important or negligible EN impact in late winter. These periods are associated with opposite phases of multi-decadal sea surface temperature (SST) variability, which modifies the tropospheric background and EN teleconnections. In addition, other studies have shown how SST anomalies in the equatorial Pacific, and in particular, the location of the largest anomalous SST, modulate the stratospheric response to EN. Nevertheless, the role of the stratosphere on the stationarity of EN response has not been investigated in detail so far. Using reanalysis data, we present a comprehensive study of EN teleconnections to Europe including the role of the ocean background and the stratosphere in the stationarity of the signal. The results reveal multidecadal variability in the location of EN-related SST anomalies that determines different teleconnections. In periods with relevant precipitation signal over Europe, the EN SST pattern resembles Eastern Pacific EN and the stratospheric pathway plays a key role in transmitting the signal to Europe in February, together with two tropospheric wavetrains that transmit the signal in February and April. Conversely, the stratospheric pathway is not detected in periods with a weak EN impact on European precipitation, corresponding to EN-related SST anomalies primarily located over the central Pacific. SST mean state and its associated atmospheric background control the location of EN-related SST anomalies in different periods and modulate the establishment of the aforementioned stratospheric pathway of EN teleconnection to Europe too.

Magnetoresistance peak in the mixed state of the organic superconductor κ-(BEDT-TTF)2Cu[N(CN)2]Br

International Nuclear Information System (INIS)

Zuo, F.

1997-01-01

In this letter, the authors report transport measurements with field and current parallel to the b axis (perpendicular to the conducting plane) in the organic superconductor κ-(BEDT-TTF) 2 Cu[N(CN) 2 ]Br. The isothermal magnetoresistance R(H) displays a peak effect as a function of field. The peak resistance is substantially larger than that in large fields. The results are in sharp contrast to the conventional dissipation mechanisms in the mixed state of anisotropic superconductors, as in the case of Bi 2 Sr 2 CaCu 2 O 8 . Comparison with H c2 (T) obtained from magnetic measurements shows that the peak effect in R(H) occurs in the mixed state. Analysis of the data suggests a much larger Josephson junction resistance in the mixed state than that in the normal state, indicative of a new charge transport scattering mechanism in the presence of vortices

Water Vapor in Titan's Stratosphere from Cassini CIRS Far-Infrared Spectra

Science.gov (United States)

Cottini, V.; Nixon, C. A.; Jennings, D. E.; Anderson, C. M.; Gorius, N.; Bjoraker, G. L.; Coustenis, A.; Teanby, N. A.; Achterberg, R. K.; Bezard, B.;

Effects of stratospheric perturbations on the solar radiation budget

International Nuclear Information System (INIS)

Luther, F.M.

1978-04-01

The changes in solar absorption and in local heating rates due to perturbations to O 3 and NO 2 concentrations caused by stratospheric injection of NO/sub x/ and CFM pollutants are assessed. The changes in species concentration profiles are derived from theoretical calculations using a transport-kinetics model. Because of significant changes in our understanding of stratospheric chemistry during the past year, the assessment of the effect of stratospheric perturbations on the solar radiation budget differs from previous assessments. Previously, a reduction in O 3 due to an NO/sub x/ injection caused a net decrease in the gaseous solar absorption;now the same perturbation leads to a net increase. The implication of these changes on the surface temperature is also discussed

CARIBIC observations of gaseous mercury in the upper troposphere and lower stratosphere

Directory of Open Access Journals (Sweden)

Slemr F.

2013-04-01

Full Text Available A unique set of gaseous mercury measurements in the upper troposphere and lower stratosphere (UT/LS has been obtained during the monthly CARIBIC (www.caribic-atmospheric.com flights since May 2005. The passenger Airbus 340-600 of Lufthansa covered routes to the Far East, North America, India, and the southern hemisphere. The accompanying measurements of CO, O3, NOy, H2O, aerosols, halocarbons, hydrocarbons, greenhouse gases, and several other parameters as well as backward trajectories enable a detailed analysis of these measurements. Speciation tests have shown that the CARIBIC measurements represent a good approximation of total gaseous mercury (TGM concentrations. Above the tropopause TGM always decrease with increasing potential vorticity (PV and O3 which implies its conversion to particle bound mercury. The observation of the lowest TGM concentrations at the highest particle concentrations in the stratosphere provides further evidence for such conversion. We will show how a seasonally dependent conversion rate could be derived using concomitantly measured SF6 mixing ratios as a timer. Tropospheric mercury data suggest the existence of a decreasing trend in the northern hemisphere whose size is comparable with the trend derived from long-term measurements by ship cruises, at Cape Point (South Africa and Mace Head (Ireland.

Photochemistry, mixing and transport in Jupiter's stratosphere constrained by Cassini

Science.gov (United States)

Hue, V.; Hersant, F.; Cavalié, T.; Dobrijevic, M.; Sinclair, J. A.

2018-06-01

In this work, we aim at constraining the diffusive and advective transport processes in Jupiter's stratosphere, using Cassini/CIRS observations published by Nixon et al. (2007,2010). The Cassini-Huygens flyby of Jupiter on December 2000 provided the highest spatially resolved IR observations of Jupiter so far, with the CIRS instrument. The IR spectrum contains the fingerprints of several atmospheric constituents and allows probing the tropospheric and stratospheric composition. In particular, the abundances of C2H2 and C2H6, the main compounds produced by methane photochemistry, can be retrieved as a function of latitude in the pressure range at which CIRS is sensitive to. CIRS observations suggest a very different meridional distribution for these two species. This is difficult to reconcile with their photochemical histories, which are thought to be tightly coupled to the methane photolysis. While the overall abundance of C2H2 decreases with latitude, C2H6 becomes more abundant at high latitudes. In this work, a new 2D (latitude-altitude) seasonal photochemical model of Jupiter is developed. The model is used to investigate whether the addition of stratospheric transport processes, such as meridional diffusion and advection, are able to explain the latitudinal behavior of C2H2 and C2H6. We find that the C2H2 observations are fairly well reproduced without meridional diffusion. Adding meridional diffusion to the model provides an improved agreement with the C2H6 observations by flattening its meridional distribution, at the cost of a degradation of the fit to the C2H2 distribution. However, meridional diffusion alone cannot produce the observed increase with latitude of the C2H6 abundance. When adding 2D advective transport between roughly 30 mbar and 0.01 mbar, with upwelling winds at the equator and downwelling winds at high latitudes, we can, for the first time, reproduce the C2H6 abundance increase with latitude. In parallel, the fit to the C2H2 distribution is

The isotopic composition of methane in the stratosphere: high-altitude balloon sample measurements

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T. Röckmann

2011-12-01

Full Text Available The isotopic composition of stratospheric methane has been determined on a large suite of air samples from stratospheric balloon flights covering subtropical to polar latitudes and a time period of 16 yr. 154 samples were analyzed for δ¹³C and 119 samples for δD, increasing the previously published dataset for balloon borne samples by an order of magnitude, and more than doubling the total available stratospheric data (including aircraft samples published to date. The samples also cover a large range in mixing ratio from tropospheric values near 1800 ppb down to only 250 ppb, and the strong isotope fractionation processes accordingly increase the isotopic composition up to δ¹³C = −14‰ and δD = +190‰, the largest enrichments observed for atmospheric CH₄ so far. When analyzing and comparing kinetic isotope effects (KIEs derived from single balloon profiles, it is necessary to take into account the residence time in the stratosphere in combination with the observed mixing ratio and isotope trends in the troposphere, and the range of isotope values covered by the individual profile. The isotopic composition of CH₄ in the stratosphere is affected by both chemical and dynamical processes. This severely hampers interpretation of the data in terms of the relative fractions of the three important sink mechanisms (reaction with OH, O(¹D and Cl. It is shown that a formal sink partitioning using the measured data severely underestimates the fraction removed by OH, which is likely due to the insensitivity of the measurements to the kinetic fractionation in the lower stratosphere. Full quantitative interpretation of the CH₄ isotope data in terms of the three sink reactions requires a global model.

The 2017 Fertilizer Emissions Airborne Study (FEAST): Quantifying N2O emissions from croplands and fertilizer plants in the Mississippi River Valley.

Science.gov (United States)

Kort, E. A.; Gvakharia, A.; Smith, M. L.; Conley, S.; Frauhammer, K.

2017-12-01

Nitrous Oxide (N2O) is a crucial atmospheric trace gas that drives 21st century stratospheric ozone depletion and substantively impacts climate. Anthropogenic emissions drive the global imbalance and annual growth of N2O, and the dominant anthropogenic source is fertilizer production and application, both of which have large uncertainties. In this presentation we will discuss the FEAST campaign, a study designed to demonstrate new approaches to quantify N2O emissions from fertilizer production and usage with aircraft measurements. In the FEAST campaign we deployed new instrumentation along with experienced flight sensors onboard the Scientific Aviation Mooney aircraft to make 40 hours of continuous 1Hz measurements of N2O, CO2, CO, H2O, CH4, O3, T, and winds. The Mississippi River Valley provided an optimal target as this location includes significant fertilizer production facilities as well as large cropland areas (dominated by corn, soy, rice, and cotton) with substantive fertilizer application. By leveraging our payload and unique airborne capabilities we directly observe and quantify N2O emissions from individual fertilizer production facilities (as well as CO2 and CH4 emissions from these same facilities). We are also able to quantify N2O fluxes from large cropland areas ( 100's km) employing a mass balance approach, a first for N2O, and will show results highlighting differences between crop types and amounts of applied fertilizer. The ability to quantify fluxes of croplands at 100km scale enables new understanding of processes controlling emissions at spatial scales that has eluded prior studies that either rely on extrapolation of small (flux chamber, towers), or work on 1,000+ km spatial scales (regional-global inversions from atmospheric measurements).

Impacto não Linear do Marketing Mix no Desempenho em Vendas de Marcas

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Rafael Barreiros Porto

2015-01-01

Full Text Available O padrão de impacto que as atividades de marketingexercem nas vendas não tem sido evidenciado na literatura. Muitas pesquisas adotam perspectivas lineares restritas, desconsiderando as evidências empíricas. Este trabalho investigou o impacto não linear do marketingmixno volume em vendas e no volume de consumidores e de compra por consumidor. Realizou-se um estudo longitudinal em painel de marcas e de consumidores simultâneos. Analisaram-se 121 marcas durante 13 meses, com 793 compras/mês feitas pelos consumidores por meio de três equações de estimativas generalizadas. Os resultados apontam que o marketing mix, em especial brandinge precificação, impacta fortemente todas as dependentes em formato não linear, com bons ajustes dos parâmetros. Oefeito conjunto gera economias de escala para as marcas, enquanto, para cada consumidor, o efeito conjunto estimula-o a adquirir maiores quantidades gradativamente. A pesquisa demonstra oito padrões impactantes do marketingmixsobre os indicadores investigados, com alterações de sua ordem e de seu peso para marcas e consumidores.

Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

Science.gov (United States)

Thorn, Robert Peyton, Jr.

A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic

Synthesis and physico-chemical characterization of CeO2/ZrO2-SO42- mixed oxides

International Nuclear Information System (INIS)

Hernandez E, J. M.; Silva R, R.; Garcia A, R.; Garcia S, L. A.; Handy, B. E.; Cardenas G, G.; Cueto H, A.

2012-01-01

Environmentally friendly solid-acid catalysts CeO 2 /ZrO 2 -SO 4 2- were prepared by the sol gel method varying CeO 2 content (10, 20 and 30 wt %) and using sulfation in situ, maintaining the sulfate ions amount present in the materials at 20 wt %. ZrO 2 and ZrO 2 -SO 4 2- were also prepared for comparison proposes using the same synthesis method. The materials were characterized by X-ray diffraction, nitrogen physisorption, potentiometric titration with n-butylamine, decomposition of 2-propanol and n-pentane isomerization. The specific surface area of ZrO 2 -SO 4 2- was high (160 m 2 /g) compared with the unmodified ZrO 2 (80 m 2 /g), however this area decreased with increasing the CeO 2 content (37-100 m 2 /g). There was no significant effect of CeO 2 on the tetragonal structure of ZrO 2 -SO 4 2- . The variation of acid sites amount runs parallel to the change of specific surface area. The acid sites amount decreased with increasing cerium oxide content. The decomposition of 2-propanol results fundamentally in the formation of dehydration products such as propylene and diisopropyl ether, both involving acid sites. In addition, a good performance during the n-pentane isomerization was observed for these materials. The selectivity towards isopentane reaches 84% when the Pt/CeO 2 /ZrO 2 -SO 4 2- catalyst with the highest CeO 2 content was used. (Author)

Bis(acetylacetonato-κ2O,O′(2-amino-1-methyl-1H-benzimidazole-κN3oxidovanadium(IV

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Zukhra Ch. Kadirova

2009-07-01

Full Text Available The title mixed-ligand oxidovanadium(IV compound, [VO(C5H7O22(C8H9N3], contains a VIV atom in a distorted octahedral coordination, which is typical for such complexes. The vanadyl group and the N-heterocyclic ligand are cis to each other. The coordination bond is located at the endocyclic N atom of the benzimidazole ligand. Intramolecular hydrogen bonds between the exo-NH2 group H atoms and acetylacetonate O atoms stabilize the crystal structure.

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

Science.gov (United States)

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 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

Chlorine activation and ozone destruction in the northern lowermost stratosphere

NARCIS (Netherlands)

Lelieveld, J; Bregman, A; Scheeren, HA; Strom, J; Carslaw, KS; Fischer, H; Siegmund, PC; Arnold, F

1999-01-01

We report aircraft measurements from the Stratosphere-Troposphere Experiments by Aircraft Measurements (STREAM) II campaign, performed during February 1995 from Kiruna, northern Sweden, near 67 degrees N latitude. We have measured trace species, e.g., O-3, nitrogen compounds, HCl, hydrocarbons, CO,

Degradación de recubrimientos ZrO2-CaO/NiAlMo por oxidación isoterma

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Utrilla, V.

2006-12-01

Full Text Available This paper analyses the degradation of a ceramic top coating 70%ZrO2 – 30%CaO deposited onto a stainless steel AISI 304 by thermal spray, using Ni-6%Al-5%Mo as overlay coating. These thermal barrier coatings were heat treated for 48, 120 and 288 h at 800 ºC to evaluate the degradation of these materials by isothermal oxidation. The microstructure evolution during oxidation was analysed by environmental scanning electron microscopy, transmission electron microscopy, X ray microanalysis and X ray diffraction. A thermally grown oxide layer was observed between the overlay coating and the ceramic top coating after oxidation. This layer was formed by a mixed Al and Ni oxides.En este trabajo se estudia la degradación de un recubrimiento 70%ZrO2 – 30%CaO crecido por proyección térmica de oxiacetileno sobre un acero inoxidable austenítico AISI 304 y empleando una leación de Ni-6%Al-5%Mo como capa de anclaje. Los recubrimientos se trataron térmicamente en aire a 800 ºC durante 48, 120 y 288 horas para evaluar la degradación de estos materiales por oxidación isotérmica. La evolución de la microestructura de las barreras como consecuencia del proceso de oxidación se analizó mediante microscopía electrónica de barrido ambiental, microscopía electrónica de transmisión, microanálisis de rayos X (EDX y difracción de rayos X. Durante la oxidación de los recubrimientos creció una capa intermedia de óxidos (“thermally grown oxides”, TGO entre el anclaje metálico y el recubrimiento cerámico formada por una mezcla de óxidos de Al y Ni.

Solar polarimetry in the K I D2 line : A novel possibility for a stratospheric balloon

Science.gov (United States)

Quintero Noda, C.; Villanueva, G. L.; Katsukawa, Y.; Solanki, S. K.; Orozco Suárez, D.; Ruiz Cobo, B.; Shimizu, T.; Oba, T.; Kubo, M.; Anan, T.; Ichimoto, K.; Suematsu, Y.

2018-03-01

Of the two solar lines, K I D1 and D2, almost all attention so far has been devoted to the D1 line, as D2 is severely affected by an O2 atmospheric band. This, however, makes the latter appealing for balloon and space observations from above (most of) the Earth's atmosphere. We estimate the residual effect of the O2 band on the K I D2 line at altitudes typical for stratospheric balloons. Our aim is to study the feasibility of observing the 770 nm window. Specifically, this paper serves as a preparation for the third flight of the Sunrise balloon-borne observatory. The results indicate that the absorption by O2 is still present, albeit much weaker, at the expected balloon altitude. We applied the obtained O2 transmittance to K I D2 synthetic polarimetric spectra and found that in the absence of line-of-sight motions, the residual O2 has a negligible effect on the K I D2 line. On the other hand, for Doppler-shifted K I D2 data, the residual O2 might alter the shape of the Stokes profiles. However, the residual O2 absorption is sufficiently weak at stratospheric levels that it can be divided out if appropriate measurements are made, something that is impossible at ground level. Therefore, for the first time with Sunrise III, we will be able to perform polarimetric observations of the K I D2 line and, consequently, we will have improved access to the thermodynamics and magnetic properties of the upper photosphere from observations of the K I lines.

Oxide, interface, and border traps in thermal, N2O, and N2O-nitrided oxides

International Nuclear Information System (INIS)

Fleetwood, D.M.; Saks, N.S.

1996-01-01

We have combined thermally stimulated-current (TSC) and capacitance endash voltage (C endash V) measurements to estimate oxide, interface, and effective border trap densities in 6 endash 23 nm thermal, N 2 O, and N 2 O-nitrided oxides exposed to ionizing radiation or high-field electron injection. Defect densities depend strongly on oxide processing, but radiation exposure and moderate high-field stress lead to similar trapped hole peak thermal energy distributions (between ∼1.7 and ∼2.0 eV) for all processes. This suggests that similar defects dominate the oxide charge trapping properties in these devices. Radiation-induced hole and interface trap generation efficiencies (0.1%endash 1%) in the best N 2 O and N 2 O-nitrided oxides are comparable to the best radiation hardened oxides in the literature. After ∼10 Mrad(SiO 2 ) x-ray irradiation or ∼10 mC/cm 2 constant current Fowler endash Nordheim injection, effective border trap densities as high as ∼5x10 11 cm -2 are inferred from C endash V hysteresis. These measurements suggest irradiation and high-field stress cause similar border trap energy distributions. In each case, even higher densities of compensating trapped electrons in the oxides (up to 2x10 12 cm -2 ) are inferred from combined TSC and C endash V measurements. These trapped electrons prevent conventional C endash V methods from providing accurate estimates of the total oxide trap charge density in many irradiation or high-field stress studies. Fewer compensating electrons per trapped hole (∼26%±5%) are found for irradiation of N 2 O and N 2 O-nitrided oxides than for thermal oxides (∼46%±7%). (Abstract Truncated)

Tracer measurements in the tropical tropopause layer during the AMMA/SCOUT-O3 aircraft campaign

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C. D. Homan

2010-04-01

Full Text Available We present airborne in situ measurements made during the AMMA (African Monsoon Multidisciplinary Analysis/SCOUT-O3 campaign between 31 July and 17 August 2006 on board the M55 Geophysica aircraft, based in Ouagadougou, Burkina Faso. CO₂ and N₂O were measured with the High Altitude Gas Analyzer (HAGAR, CO was measured with the Cryogenically Operated Laser Diode (COLD instrument, and O₃ with the Fast Ozone ANalyzer (FOZAN.

We analyse the data obtained during five local flights to study the dominant transport processes controlling the tropical tropopause layer (TTL, here ~350–375 K and lower stratosphere above West-Africa: deep convection up to the level of main convective outflow, overshooting of deep convection, and horizontal inmixing across the subtropical tropopause. Besides, we examine the morphology of the stratospheric subtropical barrier.

Except for the flight of 13 August, distinct minima in CO₂ mixing ratios indicate convective outflow of boundary layer air in the TTL. The CO₂ profiles show that the level of main convective outflow was mostly located at potential temperatures between 350 and 360 K, and for 11 August reached up to 370 K.

While the CO₂ minima indicate quite significant convective influence, the O₃ profiles suggest that the observed convective signatures were mostly not fresh, but of older origin (several days or more. When compared with the mean O₃ profile measured during a previous campaign over Darwin in November 2005, the O₃ minimum at the main convective outflow level was less pronounced over Ouagadougou. Furthermore O₃ mixing ratios were much higher throughout the whole TTL and, unlike over Darwin, rarely showed low values observed in the regional boundary layer.

Signatures of irreversible mixing following overshooting of convective air were scarce in the tracer data. Some

[(Nitrato-κO,O')(nitrito-κO,O')(0.25/1.75)]bis-(1,10-phenanthroline-κN,N')cadmium(II).

Science.gov (United States)

Najafi, Ezzatollah; Amini, Mostafa M; Ng, Seik Weng

2011-01-22

The reaction of cadmium nitrate and sodium nitrite in the presence of 1,10-phenanthroline yields the mixed nitrate-nitrite title complex, [Cd(NO(2))(1.75)(NO(3))(0.25)(C(12)H(8)N(2))(2)]. The metal ion is bis-chelated by two N-heterocycles as well as by the nitrate/nitrite ions in a distorted dodeca-hedral CdN(4)O(4) coordination environment. One nitrite group is ordered; the other is disordered with respect to a nitrate group (ratio 0.75:0.25) concerning the O atom that is not involved in bonding to the metal ion.

Microhabitat Effects on N2O Emissions from Floodplain Soils under Controlled Conditions

Science.gov (United States)

Ley, Martin; Lehmann, Moritz F.; Niklaus, Pascal A.; Kuhn, Thomas; Luster, Jörg

2016-04-01

Semi-terrestrial soils such as floodplain soils are considered to be potential hotspots of nitrous oxide (N2O) emissions. The quantitative assessment of N2O release from these hotspots under field conditions, and of the microbial pathways that underlie net N2O production (ammonium oxidation, nitrifier-denitrification, and denitrification) is challenging because of their high spatial and temporal variability. The production and consumption of N2O appears to be linked to the presence or absence of micro-niches, providing specific conditions that may be favorable to either of the relevant microbial pathways. Flood events have been shown to trigger moments of enhanced N2O emission through a close coupling of niches with high and low oxygen availabilities. This coupling might be modulated by microhabitat effects related to soil aggregate formation, root soil interactions and the degradation of organic matter accumulations. In order to assess how these factors can modulate N2O production and consumption under simulated flooding/drying conditions, we have set up a mesocosm experiment with N-rich floodplain soils comprising different combinations of soil aggregate size classes and inert matrix material. These model soils were either planted with basket willow (Salix viminalis L.), mixed with leaf litter, or left untreated. Throughout a simulated flood event, we repeatedly measured the net N2O production rate. In addition, soil water content, redox potential, as well as C and N substrate availability were monitored. In order to gain insight into the sources of, and biogeochemical controls on N2O production, we also measured the bulk δ15N signature of the produced N2O, as well as its intramolecular 15N site preference (SP). In this presentation we focus on a period of enhanced N2O emission during the drying phase after 48 hrs of flooding. We will discuss the observed emission patterns in the context of possible treatment effects. Soils with large aggregates showed a

Reactive Nitrogen, Ozone and Ozone Production in the Arctic Troposphere and the Impact of Stratosphere-Troposphere Exchange

Science.gov (United States)

Liang, Q.; Rodriquez, J. M.; Douglass, A. R.; Crawford, J. H.; Apel, E.; Bian, H.; Blake, D. R.; Brune, W.; Chin, M.; Colarco, P. R.;

Investigation of nitrous oxide (N2O) abatement technologies. 2; Asanka chisso (N2O) no teigen taisaku ni kansuru chosa. 2

Energy Technology Data Exchange (ETDEWEB)

NONE

1997-03-01

Emission amount of nitrous oxide (N2O) from anthropogenic sources is analyzed, and reduction effects by the abatement technologies are evaluated. The concentration of nitrous oxide in the atmosphere continues to increase and emissions from agricultural and ecosystem sources are drawing particular attention. For the emission of N2O in Japan, 8.28 Gg-N2O per year is emitted from fossil fuel combustion facilities, 6.95 from waste incineration facilities, 22.5 from transportation vehicles including automobiles, 26.7 from the chemical industry including establishments engaged in adipic acid production, 2.1 from sewage treatment facilities including septic tanks, 6.3 from farmland, and 7.1 from livestock excrement. For the N2O abatement technologies for different sources, fuel improvement, high temperature combustion, acceleration of reduction decomposition reaction, and development of catalysts are significant for the combustion technologies. In connection with N2O discharged in the process of adipic acid production, major businesses have internationally committed to up to 99% abatement of the N2O emissions by 1998. With regard to wastewater and sewage treatment facilities and septic tanks, improvement in COD/NO-N ratio, retention period, pH level, and reduction process is pointed out. 204 refs., 70 figs., 53 tabs.

Thermodynamic stability and guest distribution of CH4/N2/CO2 mixed hydrates for methane hydrate production using N2/CO2 injection

International Nuclear Information System (INIS)

Lim, Dongwook; Ro, Hyeyoon; Seo, Yongwon; Seo, Young-ju; Lee, Joo Yong; Kim, Se-Joon; Lee, Jaehyoung; Lee, Huen

2017-01-01

Highlights: • We examine the thermodynamic stability and guest distribution of CH 4 /N 2 /CO 2 mixed hydrates. • Phase equilibria of the CH 4 /N 2 /CO 2 mixed hydrates were measured to determine the thermodynamic stability. • The N 2 /CO 2 ratio of the hydrate phase is almost constant despite the enrichment of CO 2 in the hydrate phase. • 13 C NMR results indicate the preferential occupation of N 2 and CO 2 in the small and large cages of sI hydrates, respectively. - Abstract: In this study, thermodynamic stability and cage occupation behavior in the CH 4 – CO 2 replacement, which occurs in natural gas hydrate reservoirs by injecting flue gas, were investigated with a primary focus on phase equilibria and composition analysis. The phase equilibria of CH 4 /N 2 /CO 2 mixed hydrates with various compositions were measured to determine the thermodynamic stability of gas hydrate deposits replaced by N 2 /CO 2 gas mixtures. The fractional experimental pressure differences (Δp/p) with respect to the CSMGem predictions were found to range from −0.11 to −0.02. The composition analysis for various feed gas mixtures with a fixed N 2 /CO 2 ratio (4.0) shows that CO 2 is enriched in the hydrate phase, and the N 2 /CO 2 ratio in the hydrate phase is independent of the feed CH 4 fractions. Moreover, 13 C NMR measurements indicate that N 2 molecules preferentially occupy the small 5 12 cages of sI hydrates while the CO 2 molecules preferentially occupy the large 5 12 6 2 cages, resulting in an almost constant area ratio of CH 4 molecules in the large to small cages of the CH 4 /N 2 /CO 2 mixed hydrates. The overall experimental results provide a better understanding of stability conditions and guest distributions in natural gas hydrate deposits during CH 4 – flue gas replacement.