Sample records for factors affecting n2o

  1. Soil invertebrate fauna affect N2 O emissions from soil.

    PubMed

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

    2013-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

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

  3. 2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

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

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

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

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

    PubMed

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

    2018-04-01

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

  5. N2O emission characteristics and its affecting factors in rain-fed potato fields in Wuchuan County, China

    NASA Astrophysics Data System (ADS)

    Wang, Liwei; Wang, Cheng; Pan, Zhihua; Xu, Hui; Gao, Lin; Zhao, Peiyi; Dong, Zhiqiang; Zhang, Jingting; Cui, Guohui; Wang, Sen; Han, Guolin; Zhao, hui

    2017-05-01

    Representing an important greenhouse gas, nitrous oxide (N2O) emission from cultivated land is a hot topic in current climate change research. This study examined the influences of nitrogen fertilisation, temperature and soil moisture on the ammonia monooxygenase subunit A ( amoA) gene copy numbers and N2O emission characteristics. The experimental observation of N2O fluxes was based on the static chamber-gas chromatographic method. The ammonia-oxidising bacteria (AOB) and ammonia-oxidising archaea (AOA) gene copy numbers in different periods were measured by real-time polymerase chain reaction (PCR). The results indicated that rain-fed potato field was a N2O source, and the average annual N2O emission was approximately 0.46 ± 0.06 kgN2O-N/ha/year. N2O emissions increased significantly with increase in fertilisation, temperatures below 19.6 °C and soil volumetric water content under 15%. Crop rotation appreciably decreases N2O emissions by 34.4 to 52.4% compared to continuous cropping in rain-fed potato fields. The significant correlation between N2O fluxes and AOB copy numbers implied that N2O emissions were primarily controlled by AOB in rain-fed potato fields. The research has important theoretical and practical value for understanding N2O emissions from rain-fed dry farmland fields.

  6. N2O emission characteristics and its affecting factors in rain-fed potato fields in Wuchuan County, China.

    PubMed

    Wang, Liwei; Wang, Cheng; Pan, Zhihua; Xu, Hui; Gao, Lin; Zhao, Peiyi; Dong, Zhiqiang; Zhang, Jingting; Cui, Guohui; Wang, Sen; Han, Guolin; Zhao, Hui

    2017-05-01

    Representing an important greenhouse gas, nitrous oxide (N 2 O) emission from cultivated land is a hot topic in current climate change research. This study examined the influences of nitrogen fertilisation, temperature and soil moisture on the ammonia monooxygenase subunit A (amoA) gene copy numbers and N 2 O emission characteristics. The experimental observation of N 2 O fluxes was based on the static chamber-gas chromatographic method. The ammonia-oxidising bacteria (AOB) and ammonia-oxidising archaea (AOA) gene copy numbers in different periods were measured by real-time polymerase chain reaction (PCR). The results indicated that rain-fed potato field was a N 2 O source, and the average annual N 2 O emission was approximately 0.46 ± 0.06 kgN 2 O-N/ha/year. N 2 O emissions increased significantly with increase in fertilisation, temperatures below 19.6 °C and soil volumetric water content under 15%. Crop rotation appreciably decreases N 2 O emissions by 34.4 to 52.4% compared to continuous cropping in rain-fed potato fields. The significant correlation between N 2 O fluxes and AOB copy numbers implied that N 2 O emissions were primarily controlled by AOB in rain-fed potato fields. The research has important theoretical and practical value for understanding N 2 O emissions from rain-fed dry farmland fields.

  7. Soil Nitrification and N2O Production: the connection with N concentration and Soil Water Content

    NASA Astrophysics Data System (ADS)

    Zhu-Barker, X.; Horwath, W. R.

    2016-12-01

    The development of mitigation strategies to reduce nitrous oxide (N2O) emission from soils is dependent on explicating the biophysical factors affecting different N2O production pathways. Ammonia oxidation and heterotrophic denitrification are the main pathways of N2O production, depending on soil conditions such as soil moisture content, oxygen (O2) content and N substrate. Many researchers have reported that N2O production increased as substrate concentration and soil moisture content increased. However, less understood is how N fertilizer concentration and moisture content interact to affect N2O production pathways. To investigate interaction and its effect on O2 consumption, we incubated three agricultural soils (clay, sandy loam, and peat) with different concentrations of (NH4)2SO4 (0-1000 µg N g-1) under 50 %, 75%, and 100% of water holding capacity. All treatments received 15N -KNO3 to bring the concentrations of NO3-_N in soils to 50 mg kg-1 soil and the NO3- pool to an enrichment of 10 atom% 15N. In all soils, the total amount of O2 consumption and N2O production increased as soil ammonical N concentration increased. The increased soil moisture significantly promoted N2O production in sandy loam and clay loam soils, compared to the peat soil. These results indicate that N2O production increased as substrate concentration increased likely due to the onset of O2 limitation caused by ammonia oxidation.

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

    PubMed

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

    2012-06-19

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

  9. Seasonal effect on N2O formation in nitrification in constructed wetlands.

    PubMed

    Inamori, Ryuhei; Wang, Yanhua; Yamamoto, Tomoko; Zhang, Jixiang; Kong, Hainan; Xu, Kaiqin; Inamori, Yuhei

    2008-10-01

    Constructed wetlands are considered to be important sources of nitrous oxide (N(2)O). In order to investigate the contribution of nitrification in N(2)O formation, some environmental factors, plant species and ammonia-oxidizing bacteria (AOB) in active layers have been compared. Vegetation cells indicated remarkable effect of seasons and different plant species on N(2)O emission and AOB amount. Nitrous oxide data showed large temporal and spatial fluctuations ranging 0-52.8 mg N(2)O m(-2)d(-1). Higher AOB amount and N(2)O flux rate were observed in the Zizania latifolia cell, reflecting high potential of global warming. Roles of plants as ecosystem engineers are summarized with rhizosphere oxygen release and organic matter transportation to affect nitrogen transformation. The Phragmites australis cell contributed to keeping high T-N removal performance and lower N(2)O emission. The distribution of AOB also supported this result. Statistical analysis showed several environmental parameters affecting the strength of observed greenhouse gases emission, such as water temperature, water level, TOC, plant species and plant cover.

  10. Controlling factors of nitrous oxide (N2O) emissions at the field-scale in an agricultural slope

    NASA Astrophysics Data System (ADS)

    Vilain, Guillaume; Garnier, Josette; Tallec, Gaëlle; Tournebize, Julien; Cellier, Pierre; Flipo, Nicolas

    2010-05-01

    Agricultural practices widely contribute to the atmospheric nitrous oxide (N2O) concentration increase and are the major source of N2O which account for 24% of the global annual emission (IPCC, 2007). Soil nitrification and denitrification are the microbial processes responsible for the production of N2O, which also depends on soil characteristics and management. Besides their control by various factors, such as climate, soil conditions and management (content of NO3- and NH4+, soil water content, presence of degradable organic material…), the role of topography is less known although it can play an important role on N2O emissions (Izaurralde et al., 2004). Due to the scarcity of data on N2O direct vs. indirect emission rate from agriculture in the Seine Basin (Garnier et al., 2009), one of the objectives of the study conducted here was to determine the N2O emission rates of the various land use representative for the Seine Basin, in order to better assess the direct N2O emissions, and to explore controlling factor such as meteorology, topography, soil properties and crop successions. The main objective of this study was at the same time to characterize N2O fluxes variability along a transect from an agricultural plateau to a river and to analyze the influence of landscape position on these emissions. We conducted this study in the Orgeval catchment (Seine basin, France; between 48°47' and 48°55' N, and 03°00' and 03°55' E) from May 2008 to August 2009 on two agricultural fields cropped with wheat, barley, oats, corn. N2O fluxes were monitored from weekly to bimonthly using static manual chambers placed along the chosen transect in five different landscape positions from the plateau to the River. This study has shown that soil moisture (expressed as Water Filled Pore Space) and NO3- soil concentrations explained most of the N2O flux variability during the sampling period. Most of N2O was emitted directly after N fertilization application during a relatively

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

    PubMed

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

    2014-05-05

    This study aims at estimating the performance of the Bacillus atrophaeus spores inactivation by the UV treatment with addition of H2O2. The effect of factors affecting the inactivation was investigated, including initial H2O2 dose, UV irradiance, initial cell density, initial solution pH and various inorganic anions. Under the experimental conditions, the B. atrophaeus spores inactivation followed both the modified Hom Model and the Chick's Model. The results revealed that the H2O2 played dual roles in the reactions, while the optimum reduction of 5.88lg was received at 0.5mM H2O2 for 10min. The inactivation effect was affected by the UV irradiance, while better inactivation effect was achieved at higher irradiance. An increase in the initial cell density slowed down the inactivation process. A slight acid condition at pH 5 was considered as the optimal pH value. The inactivation effect within 10min followed the order of pH 5>pH 7>pH 9>pH 3>pH 11. The effects of three added inorganic anions were investigated and compared, including sulfate (SO4(2)(-)), nitrate (NO3(-)) and carbonate (CO3(2)(-)). The sequence of inactivation effect within 10min followed the order of control group>SO4(2)(-)>NO3(-)>CO3(2)(-). Copyright © 2014 Elsevier B.V. All rights reserved.

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

    NASA Technical Reports Server (NTRS)

    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

  13. Evaluation of factors affecting nitrous oxide emission and N transformation in a sandy loam soil

    USDA-ARS?s Scientific Manuscript database

    A better understanding of the complex factors affecting nitrous oxide (N2O) emission and potential mitigation practices will assist in developing strategies to improve the sustainability of agricultural production systems. Using surface soil collected from a pomegranate orchard, a series of laborato...

  14. Effects of crop management, soil type, and climate on N2O emissions from Austrian Soils

    NASA Astrophysics Data System (ADS)

    Zechmeister-Boltenstern, Sophie; Sigmund, Elisabeth; Kasper, Martina; Kitzler, Barbara; Haas, Edwin; Wandl, Michael; Strauss, Peter; Poetzelsberger, Elisabeth; Dersch, Georg; Winiwarter, Wilfried; Amon, Barbara

    2015-04-01

    Within the project FarmClim ("Farming for a better climate") we assessed recent N2O emissions from two selected regions in Austria. Our aim was to deepen the understanding of Austrian N2O fluxes regarding region specific properties. Currently, N2O emissions are estimated with the IPCC default emission factor which only considers the amount of N-input as an influencing factor for N2O emissions. We evaluated the IPCC default emission factor for its validity under spatially distinct environmental conditions. For this two regions for modeling with LandscapeDNDC have been identified in this project. The benefit of using LandscapeDNDC is the detailed illustration of microbial processes in the soil. Required input data to run the model included daily climate data, vegetation properties, soil characteristics and land management. The analysis of present agricultural practices was basis for assessing the hot spots and hot moments of nitrogen emissions on a regional scale. During our work with LandscapeDNDC we were able to adapt specific model algorithms to Austrian agricultural conditions. The model revealed a strong dependency of N2O emissions on soil type. We could estimate how strongly soil texture affects N2O emissions. Based on detailed soil maps with high spatial resolution we calculated region specific contribution to N2O emissions. Accordingly we differentiated regions with deviating gas fluxes compared to the predictions by the IPCC inventory methodology. Taking region specific management practices into account (tillage, irrigation, residuals) calculation of crop rotation (fallow, catch crop, winter wheat, barley, winter barley, sugar beet, corn, potato, onion and rapeseed) resulted in N2O emissions differing by a factor of 30 depending on preceding crop and climate. A maximum of 2% of N fertilizer input was emitted as N2O. Residual N in the soil was a major factor stimulating N2O emissions. Interannual variability was affected by varying N-deposition even in case

  15. Abiotic controls on N2O emissions from soils and wetlands

    NASA Astrophysics Data System (ADS)

    Horwath, W. R.

    2016-12-01

    The increase in atmospheric nitrous oxide (N2O) is a critical climate change issue contributing to global warming. Most studies on N2O production attribute microbial processes and their associated enzymatic reactions to be the main driver affecting emissions. The role of redox capable iron, manganese and organic compounds that can react with intermediates in the nitrogen cycle has also been shown to produce N2O abiotically. The importance of the abiotic pathways, however, is highly debated. The abiotic production of N2O is related to biophysiochemical controls and unique isotopic signatures of nitrogen cycle intermediates (hydroxylamine, nitric oxide, and nitrite), redox-active metals (iron and manganese) and organic matter (humic and fulvic acids). In a range of soils, we find that the iron directly associated with organic compounds is the strongest variable relating to N2O emissions. In addition to these factors, management is also assumed to affect abiotic N2O production through its impact on nitrogen cycle intermediates, but the environmental and physiochemical conditions that are changed by management are rarely considered in the abiotic production of N2O. We find that the amount and quality of organic compounds in soils directly determines the fate of soil N2O production (i.e. be emitted or consumed). Water depth in rice paddies and wetlands also plays a significant role in partitioning production and consumption of N2O. What is evident from studies on N2O emission is that abiotic reactions are coupled to biotic processes and they cannot be easily separated. The biotic/abiotic interactions have important ecological outcomes that influence abiotic production mechanisms and should be recognized as important controllers of N2O production and consumption processes in soils and sediments.

  16. Partitioning Residue-derived and Residue-induced Emissions of N2O Using 15N-labelled Crop Residues

    NASA Astrophysics Data System (ADS)

    Farrell, R. E.; Carverhill, J.; Lemke, R.; Knight, J. D.

    2014-12-01

    Estimates of N2O emissions in Canada indicate that 17% of all agriculture-based emissions are associated with the decomposition of crop residues. However, research specific to the western Canadian prairies (including Saskatchewan) has shown that the N2O emission factor for N sources in this region typically ranges between 0.2 and 0.6%, which is well below the current IPCC default emission factor of 1.0%. Thus, it stands to reason that emissions from crop residues should also be lower than those calculated using the current IPCC emission factor. Current data indicates that residue decomposition, N mineralization and N2O production are affected by a number of factors such as C:N ratio and chemical composition of the residue, soil type, and soil water content; thus, a bench-scale incubation study was conducted to examine the effects of soil type and water content on N2O emissions associated with the decomposition of different crop residues. The study was carried out using soils from the Black, Dark Brown, Brown, and Gray soil zones and was conducted at both 50% and 70% water-filled pore space (WFPS); the soils were amended with 15N-labeled residues of wheat, pea, canola, and flax, or with an equivalent amount of 15N-labeled urea; 15N2O production was monitored using a Picarro G5101-i isotopic N2O analyzer. Crop residue additions to the soils resulted in both direct and indirect emissions of N2O, with residue derived emissions (RDE; measured as 15N2O) generally exceeding residue-induced emissions (RIE) at 50% WFPS—with RDEs ranging from 42% to 88% (mean = 58%) of the total N2O. Conversely, at 70% WFPS, RDEs were generally lower than RIEs—ranging from 21% to 83% (mean = 48%). Whereas both water content and soil type had an impact on N2O production, there was a clear and consistent trend in the emission factors for the residues; i.e., emissions were always greatest for the canola residue and lowest for the wheat residue and urea fertilizer; and intermediate for pea

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

    PubMed

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

    2015-09-01

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

  18. Multivariate regulation of soil CO2 and N2 O pulse emissions from agricultural soils.

    PubMed

    Liang, Liyin L; Grantz, David A; Jenerette, G Darrel

    2016-03-01

    Climate and land-use models project increasing occurrence of high temperature and water deficit in both agricultural production systems and terrestrial ecosystems. Episodic soil wetting and subsequent drying may increase the occurrence and magnitude of pulsed biogeochemical activity, affecting carbon (C) and nitrogen (N) cycles and influencing greenhouse gas (GHG) emissions. In this study, we provide the first data to explore the responses of carbon dioxide (CO2 ) and nitrous oxide (N2 O) fluxes to (i) temperature, (ii) soil water content as percent water holding capacity (%WHC), (iii) substrate availability throughout, and (iv) multiple soil drying and rewetting (DW) events. Each of these factors and their interactions exerted effects on GHG emissions over a range of four (CO2 ) and six (N2 O) orders of magnitude. Maximal CO2 and N2 O fluxes were observed in environments combining intermediate %WHC, elevated temperature, and sufficient substrate availability. Amendments of C and N and their interactions significantly affected CO2 and N2 O fluxes and altered their temperature sensitivities (Q10 ) over successive DW cycles. C amendments significantly enhanced CO2 flux, reduced N2 O flux, and decreased the Q10 of both. N amendments had no effect on CO2 flux and increased N2 O flux, while significantly depressing the Q10 for CO2 , and having no effect on the Q10 for N2 O. The dynamics across DW cycles could be attributed to changes in soil microbial communities as the different responses to wetting events in specific group of microorganisms, to the altered substrate availabilities, or to both. The complex interactions among parameters influencing trace gas fluxes should be incorporated into next generation earth system models to improve estimation of GHG emissions. © 2015 John Wiley & Sons Ltd.

  19. Pig slurry acidification and separation techniques affect soil N and C turnover and N2O emissions from solid, liquid and biochar fractions.

    PubMed

    Gómez-Muñoz, B; Case, S D C; Jensen, L S

    2016-03-01

    The combined effects of pig slurry acidification, subsequent separation techniques and biochar production from the solid fraction on N mineralisation and N2O and CO2 emissions in soil were investigated in an incubation experiment. Acidification of pig slurry increased N availability from the separated solid fractions in soil, but did not affect N2O and CO2 emissions. However acidification reduced soil N and C turnover from the liquid fraction. The use of more advanced separation techniques (flocculation and drainage > decanting centrifuge > screw press) increased N mineralisation from acidified solid fractions, but also increased N2O and CO2 emissions in soil amended with the liquid fraction. Finally, the biochar production from the solid fraction of pig slurry resulted in a very recalcitrant material, which reduced N and C mineralisation in soil compared to the raw solid fractions. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

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

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

    2004-11-01

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

  1. Factors Controlling Fluxes of Nitrous Oxide (N-N2O) in AN Upland Tropical Forest (atlantic Forest) - Brazil, Rio de Janeiro

    NASA Astrophysics Data System (ADS)

    Perry, I.; de Mello, W. Z.; McDowell, W. H.

    2010-12-01

    Atlantic Forest is located along the Brazilian coast and inland to Paraguay and Argentina. It has been largely devastated years ago by anthropogenic activities, such as agriculture and urbanization. Only ten percent of its original area remains (100.000 km2), which is concentrated on high lands. Atlantic Forest is a biodiversity hotspot that receives high nitrogen (N) input through atmospheric deposition in forests of Rio de Janeiro; however, not much is known about the consequences of this N addition. This study has been conducted in the Serra dos Orgaos National Park (SONP - 22.782 km2) located a few kilometers Northeast of Rio de Janeiro Metropolitan Region, Sea Mountain. The forest, characterized as Tropical Moist Forest, is rigorously protected. Vegetation varies along the altitudinal gradient, where the highest peak is at 2,200m asl. Previous studies reported that N atmospheric deposition in SONP varies from 14 to 24 kg ha-1 year-1. The high N deposition on tropical forests increases emission to the atmosphere of N-N2O, a greenhouse gas. There is a lack of N-N2O measurements in tropical forests, mainly in upland tropical forests. We present fluxes of N-N2O from a Brazilian upland tropical forest, and assess the factors controlling N-N2O fluxes. Samples were collected from eight grids (48m2), between 330-451m asl (Subtropical vegetation) and eight grids between 1137-1251m (Montane vegetation), during the dry (July 2008) and wet (Jan-Feb 2009) seasons. Daily, N-N2O (N=372) and soil (N=185) were collected. Nitrous oxide emission was 0,7 (lower altitude) and 0,3 kgN ha-1 year-1 (higher altitude), which is lower than in other upland tropical forests, such as Luquillo Experimental Forest, Puerto Rico, where atmospheric N input (4 kg ha-1 year-1) is not as high as in SONP. Water filled pore space, soil temperature, phosphorus and C:N are the main factors controlling N-N2O fluxes. Manganese was not a good indicator for presence or absence of N-N2O. Higher N-N2O

  2. N2O emissions from an intermittently aerated semi-aerobic aged refuse bioreactor: Combined effect of COD and NH4+-N in influent leachate.

    PubMed

    Li, Weihua; Sun, Yingjie; Bian, Rongxing; Wang, Huawei; Zhang, Dalei

    2017-11-01

    The carbon-nitrogen ratio (COD/NH 4 + -N) is an important factor affecting nitrification and denitrification in wastewater treatment; this factor also influences nitrous oxide (N 2 O) emissions. This study investigated two simulated intermittently aerated semi-aerobic aged refuse bioreactors (SAARB) filled with 8-year old aged refuse (AR). The research analyzed how differences in and the combination of influent COD and NH 4 + -N impact N 2 O emissions in leachate treatment. Experimental results showed that N 2 O emissions increased as the influent COD/NH 4 + -N decreased. The influent COD had a greater effect on N 2 O emissions than NH 4 + -N at the same influent ratios of COD/NH 4 + -N (2.7 and 8.0, respectively). The maximum N 2 O emission accounted for 8.82±2.65% of the total nitrogen removed from the influent leachate; the maximum level occurred when the COD was 2000mg/L. An analysis of differences in influent carbon sources at the same COD/NH 4 + -N ratios concluded that the availability of biodegradable carbon substrates (i.e. glucose) is an important factor affecting N 2 O emissions. At a low influent COD/NH 4 + -N ratio (2.7), the N 2 O conversion rate was greater when there were more biodegradable carbon substrates. Although the SAARB included the N 2 O generation and reduction processes, N 2 O reduction mainly occurred later in the process, after leachate recirculation. The maximum N 2 O emission rate occurred in the first hour of single-period (24h) experiments, as leachate contacted the surface AR. In practical SAARB applications, N 2 O emissions may be reduced by measures such as reducing the initial recirculation loading of NH 4 + -N substrates, adding a later supplement of biodegradable carbon substrates, and/or prolonging hydraulic retention time (HRT) of influent leachate. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. DMPP-added nitrogen fertilizer affects soil N2O emission and microbial activity in Southern Italy

    NASA Astrophysics Data System (ADS)

    Vitale, Luca; De Marco, Anna; Maglione, Giuseppe; Polimeno, Franca; Di Tommasi, Paul; Magliulo, Vincenzo

    2014-05-01

    plots, whereas an opposite trend for basal respiration was observed, thus evidencing a stressful condition for nitrifying microbial population. After 57 and 71 DAS, when fertilizer was applied as 30 kg N ha-1, the microbial biomass was similar between C and DMPP plots, whereas basal respiration resulted statistically lower in DMPP plots than C plots. During these periods, average DMPP N2O fluxes were also comparable or lower. In conclusion, our data evidence a stressful condition for soil microbes and in particular for nitrifiers when a higher DMPP quantity is supplied. On the contrary, when lower quantities of DMPP-added fertilizers are supplied (e.s. 30 kg N ha-1) effectiveness of DMPP in reducing soil N2O emission is guaranteed by reducing the nitrifiers activity without negatively affecting their growth.

  4. [Emission of CH4, N2O and NH3 from vegetable field applied with animal manure composts].

    PubMed

    Wan, He-Feng; Zhao, Chen-Yang; Zhong, Jia; Ge, Zhen; Wei, Yuan-Song; Zheng, Jia-Xi; Wu, Yu-Long; Han, Sheng-Hui; Zheng, Bo-Fu; Li, Hong-Mei

    2014-03-01

    Greenhouse gas (GHG) emission from vegetable land is of great concern recently because agriculture land is one of the major sources contributing to global GHG emission. In this study, an experiment of Lactuca sativa L. land applied with different animal manure composts was carried out in a greenhouse vegetable land located in the surburb of Beijing to monitor the emission of GHG (CH4 and N2O) and ammonia in situ, and to analyze the affecting factors of GHG and ammonia emission. Results showed that the emission factors (EFs) of CH4 from Treatment NRM, RM and CF were 0.2%, 0.027% and 0.004%, respectively,the EFs of N2O from these three treatments were 0.18%, 0.63% and 0.74%, respectively, and the EFs of ammonia were 2.00%, 3.98% and 2.53%, respectively. CH4 emission flux was significantly affected by soil temperature and humidity, while N2O emission flux was related to soil temperature, surface temperature and humidity. The emission fluxes of CH4, N2O and NH3 were significantly affected by soil moisture, but there was little relation between CH4, N2O and NH3 emissions and the ambient temperature in the greenhouse.

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

    NASA Technical Reports Server (NTRS)

    Ajello, J. M.; Rayermann, P.

    1975-01-01

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

  6. Observational Insights into N2O5 Heterogeneous Chemistry: Influencing Factors and Contribution to Wintertime Air Pollution

    NASA Astrophysics Data System (ADS)

    McDuffie, E. E.; Fibiger, D. L.; Womack, C.; Dube, W. P.; Lopez-Hilfiker, F.; Goldberger, L.; Thornton, J. A.; Shah, V.; Jaegle, L.; Guo, H.; Weber, R. J.; Schroder, J. C.; Campuzano Jost, P.; Jimenez, J. L.; Franchin, A.; Middlebrook, A. M.; Baasandorj, M.; Brown, S. S.

    2017-12-01

    Chemical mechanisms that underlie wintertime air pollution, including tropospheric ozone and aerosol nitrate, are poorly characterized. Due to colder temperatures and fewer hours of solar radiation, nocturnal heterogeneous uptake of N2O5 plays a relatively larger role during wintertime in controlling the oxidation of NOx (=NO+NO2) and its influence on ozone and soluble nitrate. After uptake to aerosol, N2O5 can act as both a nocturnal NOx reservoir and sink depending on the partitioning between its nitric acid and photo labile, ClNO2 reaction products. In addition, N2O5 itself can act as a NOx reservoir if the aerosol uptake coefficient is small. As a result, the nocturnal fate of N2O5 dictates the amount of NOx in an air parcel and the subsequent formation of aerosol nitrate and following-day ozone. Models of winter air pollution therefore require accurate parameterization of the N2O5 uptake coefficient, as well as factors that control its magnitude and N2O5 product partitioning. There are currently only a small number of ambient N2O5 and ClNO2 observations during the winter season concurrent with measurements of relevant variables such as aerosol size distributions and composition. The Wintertime INvestigation of Transport, Emissions, and Reactivity (WINTER) campaign conducted 10 nighttime research flights with the NCAR C-130 over the eastern U.S. during February and March, 2015. The more recent Utah Wintertime Fine Particulate Study (UWFPS) conducted over 20 research flights with the NOAA twin otter aircraft during January-February 2017 in three mountain basins near and including Salt Lake City, Utah. The two campaigns were similarly instrumented and have provided the first aircraft observations of N2O5, ClNO2, and aerosol composition in the wintertime boundary layer in these urban-influenced regions. Analysis of heterogeneous chemistry under a wide range of real environmental conditions provides insight into the factors controlling the N2O5 uptake coefficient

  7. Middle-high latitude N2O distributions related to the arctic vortex breakup

    NASA Astrophysics Data System (ADS)

    Zhou, L. B.; Zou, H.; Gao, Y. Q.

    2006-03-01

    The relationship of N2O distributions with the Arctic vortex breakup is first analyzed with a probability distribution function (PDF) analysis. The N2O concentration shows different distributions between the early and late vortex breakup years. In the early breakup years, the N2O concentration shows low values and large dispersions after the vortex breakup, which is related to the inhomogeneity in the vertical advection in the middle and high latitude lower stratosphere. The horizontal diffusion coefficient (K,,) shows a larger value accordingly. In the late breakup years, the N2O concentration shows high values and more uniform distributions than in the early years after the vortex breakup, with a smaller vertical advection and K,, after the vortex breakup. It is found that the N2O distributions are largely affected by the Arctic vortex breakup time but the dynamically defined vortex breakup time is not the only factor.

  8. 40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

  9. 40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2017-03-21

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

  12. [Research advances in control of N2O emission from municipal solid waste landfill sites].

    PubMed

    Cai, Chuan-Yu; Li, Bo; Lü, Hao-Hao; Wu, Wei-Xiang

    2012-05-01

    Landfill is one of the main approaches for municipal solid waste treatment, and landfill site is a main emission source of greenhouse gases nitrous oxide (N2O) and methane (CH4). As a high-efficient trace greenhouse gas, N2O has a very high warming potential, with a warming capacity 296 times of CO2, and has a long-term stability in atmosphere, giving greater damage to the ozone layer. Aiming at the researches in the control of N2O emission from municipal solid waste landfill sites, this paper summarized the characteristics and related affecting factors of the N2O emission from the landfill sites, and put forward a series of the measures adaptable to the N2O emission control of present municipal solid waste landfill sites in China. Some further research focuses on the control of N2O emission from the landfill sites were also presented.

  13. Modeling global annual N2O and NO emissions from fertilized fields

    NASA Astrophysics Data System (ADS)

    Bouwman, A. F.; Boumans, L. J. M.; Batjes, N. H.

    2002-12-01

    Information from 846 N2O emission measurements in agricultural fields and 99 measurements for NO emissions was used to describe the influence of various factors regulating emissions from mineral soils in models for calculating global N2O and NO emissions. Only those factors having a significant influence on N2O and NO emissions were included in the models. For N2O these were (1) environmental factors (climate, soil organic C content, soil texture, drainage and soil pH); (2) management-related factors (N application rate per fertilizer type, type of crop, with major differences between grass, legumes and other annual crops); and (3) factors related to the measurements (length of measurement period and frequency of measurements). The most important controls on NO emission include the N application rate per fertilizer type, soil organic-C content and soil drainage. Calculated global annual N2O-N and NO-N emissions from fertilized agricultural fields amount to 2.8 and 1.6 Mtonne, respectively. The global mean fertilizer-induced emissions for N2O and NO amount to 0.9% and 0.7%, respectively, of the N applied. These overall results account for the spatial variability of the main N2O and NO emission controls on the landscape scale.

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

    NASA Technical Reports Server (NTRS)

    Slanger, Tom G.; Copeland, Richard A.

    1997-01-01

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

  15. Influence of N2 annealing on TiO2 tubes structure and its photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoxiang; Pan, Zhanchang; Yu, Ke; Xiao, Jun; Wu, Shoukun; Li, Jinghong; Chen, Chun; Lin, Yingsheng; Hu, Guanghui; Xu, Yanbin

    2018-02-01

    In this work, the TiO2 tubes (TBs) were prepared by solvothermal method. The morphology and phase structure of TiO2 TBs is significantly affected by N2 annealing temperature. XRD was used to characterize the phase structure of the as-prepared samples. The morphology and surface areas were characterized by SEM and N2 adsorption-desorption, which show that the tubes were assembled with about 100-nm nanosheets and small ball particles under 400 and 600 °C N2 annealing; when temperature reached 800 °C, the surface of tubes appeared a lot of collapse and many large holes. In addition, the surface areas of 400 °C TiO2, 600 °C TiO2, and 800 °C TiO2 TBs were significantly affected by N2 annealing. Most importantly, the UV-vis and electrochemical tests demonstrate 600 °C TiO2 TBs exhibit higher absorption intensity and photocurrent; thus, it possess on better photocatalytic activity. Therefore, the photocatalytic performance for TiO2 TBs is significantly co-affected by surface area and mix-phase. [Figure not available: see fulltext.

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  17. When the Sun's Away, N2O5 Comes Out to Play: An Updated Analysis of Ambient N2O5 Heterogeneous Chemistry

    NASA Astrophysics Data System (ADS)

    McDuffie, E. E.; Brown, S. S.

    2017-12-01

    The heterogeneous chemistry of N2O5 impacts the budget of tropospheric oxidants, which directly controls air quality at Earth's surface. The reaction between gas-phase N2O5 and aerosol particles occurs largely at night, and is therefore more important during the less-intensively-studied winter season. Though N2O5-aerosol interactions are vital for the accurate understanding and simulation of tropospheric chemistry and air quality, many uncertainties persist in our understanding of how various environmental factors influence the reaction rate and probability. Quantitative and accurate evaluation of these factors directly improves the predictive capabilities of atmospheric models, used to inform mitigation strategies for wintertime air pollution. In an update to last year's presentation, The Wintertime Fate of N2O5: Observations and Box Model Analysis for the 2015 WINTER Aircraft Campaign, this presentation will focus on recent field results regarding new information about N2O5 heterogeneous chemistry and future research directions.

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

    PubMed

    Lorenz, Britney D; Anderson, David T

    2007-05-14

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

  19. Functional diversity of soil invertebrates: a potential tool to explain N2O emission?

    NASA Astrophysics Data System (ADS)

    Lubbers, Ingrid; De Deyn, Gerlinde; Drake, Harold; Hunger, Sindy; Oppermann, Timo; van Groenigen, Jan Willem

    2017-04-01

    Soil biota play a crucial role in the mineralization of nutrients from organic material. However, they can thereby increase emissions of the potent greenhouse gas nitrous oxide (N2O). Our current lack of understanding of the factors controlling N2O production and emission is impeding the development of effective mitigation strategies. It is the challenge to control N2O emissions from production systems without reducing crop yield, and diversity of soil fauna may play a key role. A high functional diversity of soil invertebrates is known to stimulate nitrogen mineralization and thereby plant growth, however, it is unknown whether a high functional diversity of soil invertebrates can concurrently diminish N2O emissions. We hypothesized that increased functional diversity of soil invertebrates reduces faunal-induced N2O emissions by facilitating more complete denitrification through (i) stimulating the activity of denitrifying microbes, and (ii) affecting the distribution of micro and macro pores, creating more anaerobic reaction sites. Using state-of-the-art X-ray tomography and next-generation sequencing, we studied effects of functional diversity on soil structural properties and the diversity of the microbial community (16S rRNA genes and 16S rRNA), and linked these to soil N2O emissions. In a 120-day study we found that the functional composition of the soil invertebrate community determined N2O emissions: earthworm activity was key to faunal-induced N2O emissions (a 32-fold increase after 120 days, P<0.001). No proof was found to explain faunal-induced N2O emissions through differences in stimulated microbial activity. On the other hand, soil structural properties (mean pore size, pore size distribution) were found to be radically altered by earthworm activity. We conclude that the presence of a few functional groups (ecosystem engineers) is more important than overall increased functional diversity in explaining faunal-affected N2O emissions.

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

    NASA Astrophysics Data System (ADS)

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

    1994-05-01

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

  1. Isotopomer fractionation during N2O consumption within soil mesocosms as a function of water filled pore space

    NASA Astrophysics Data System (ADS)

    Jinuntuya, M.; Ostrom, N. E.; Ostrom, P.; Sutka, R.

    2005-12-01

    Our prior research has demonstrated that the intramolecular distribution of 15N within the N2O molecule can be used to distinguish N2O derived from nitrification and denitrification. For this approach to be successful, however, the affect of fractionation during consumption of N2O by denitrification must be understood. Stable isotope and isotopomer analysis of soil mesocosm experiments were used to investigate fractionation of N2O during consumption at four different levels of water filled pores space (WFPS) 60, 80, 100 and 110% Uncultivated soil from the Long Term Ecological Research Site at Kellogg Biological Station was used to establish that the fractionation factors for δ15N, δ18O-N2O, δ15Nα and δ15Nβ ranged from -4.2 to -7.8 ‰, -12.5 to -19.1 ‰,-5.3 to -9.7‰ and -2.0 to -6.0 ‰, respectively. Lower fractionation factors were observed at higher WFPS demonstrating the importance of diffusion in limiting the expression of fractionation. The small degree of fractionation for δ15Nα and δ15Nβ indicates that consumption must be marked (e.g. >50%) before a significant isotope effect is observed. Our characterization of fractionation factors as a function of WFPS provides a basis to apportion the origins of N2O even when consumption is evident.

  2. Biochar type and factors affecting N transformation, ammonia volatilization, and nitrous oxide emissions

    USDA-ARS?s Scientific Manuscript database

    Soil amendment with biochar has shown the potential to improve nitrogen (N) availability for plant uptake and reduce environmental losses via ammonia (NH3) and nitrous oxide (N2O) emissions. There are still many unknowns on how biochar type and soil conditions affect N dynamics and processes associa...

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

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

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

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

    PubMed

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-14

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

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

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

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

  9. Slowdown of N2O emissions from China's croplands

    NASA Astrophysics Data System (ADS)

    Zhou, F.; Shang, Z.; Ciais, P.; Piao, S.; Tian, H.; Saikawa, E.; Zaehle, S.; Del Grosso, S. J.; Galloway, J. N.

    2016-12-01

    To feed the increasing population, China has experienced a rapid agricultural development over past decades, accompanied by increased fertilizer consumptions in croplands, but the magnitude, trend, and causes of the associated nitrous oxide (N2O) emissions has remain unclear. The primary sources of this uncertainty are conflicting estimates of fertilizer consumption and emission factors, the latter being uncertain because of very few regional representativeness of the Nrate-flux relationships in China. Here we re-estimate China's N2O emissions from croplands using three different methods: flux upscaling technique, process-based models and atmospheric inversion, and also analyze the corresponding drivers using an attribution approach. The three methods produce similar estimates of N2O emissions in the range of 0.67 ± 0.08 to 0.62± 0.11 Tg nitrogen per year, which is 29% larger than the estimates by the Emission Database for Global Atmospheric Research (EDGAR) that is adopted by Intergovernmental Panel on Climate Change (IPCC) as the emission baseline and twofold larger than the latest Chinese national report submitted to the United Nations Framework Convention on Climate Change, but the revised trend slows down after 2005. Fertilizer N application per area is the dominant factor driving the increase in N2O emissions across most cropping regions from 1990 to 2004, but climate-induced change of emission factors has also controlled N2O flux from 2005 onwards. Our findings suggest that, as precipitation would increase in North China but decline in the South in future, EF will increasingly control China's agri. soil emissions of N2O, unless offset by larger reductions of fertilizer consumptions.

  10. 40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

  11. 40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

  12. 40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

  13. Modelling site-specific N2O emission factors from Austrian agricultural soils for targeted mitigation measures (NitroAustria)

    NASA Astrophysics Data System (ADS)

    Amon, Barbara; Zechmeister-Boltenstern, Sophie; Kasper, Martina; Foldal, Cecilie; Schiefer, Jasmin; Kitzler, Barbara; Schwarzl, Bettina; Zethner, Gerhard; Anderl, Michael; Sedy, Katrin; Gaugitsch, Helmut; Dersch, Georg; Baumgarten, Andreas; Haas, Edwin; Kiese, Ralf

    2016-04-01

    Results from a previous project "FarmClim" highlight that the IPCC default emission factor is not able to reflect region specific N2O emissions from Austrian arable soils. The methodology is limited in identifying hot spots and hot moments of N2O emissions. When estimations are based on default emission factors no recommendations can be given on optimisation measures that would lead to a reduction of soil N2O emissions. The better the knowledge is about Nitrogen and Carbon budgets in Austrian agricultural managed soils the better the situation can be reflected in the Austrian GHG emission inventory calculations. Therefore national and regionally modelled emission factors should improve the evidence for national deviation from the IPCC default emission factors and reduce the uncertainties. The overall aim of NitroAustria is to identify the drivers for N2O emissions on a regional basis taking different soil types, climate, and agricultural management into account. We use the LandscapeDNDC model to update the N2O emission factors for N fertilizer and animal manure applied to soils. Key regions in Austria were selected and region specific N2O emissions calculated. The model runs at sub-daily time steps and uses data such as maximum and minimum air temperature, precipitation, radiation, and wind speed as meteorological drivers. Further input data are used to reflect agricultural management practices, e.g., planting/harvesting, tillage, fertilizer application, irrigation and information on soil and vegetation properties for site characterization and model initialization. While at site scale, arable management data (crop cultivation, rotations, timings etc.) is obtained by experimental data from field trials or observations, at regional scale such data need to be generated using region specific proxy data such as land use and management statistics, crop cultivations and yields, crop rotations, fertilizer sales, manure resulting from livestock units etc. The farming

  14. Environmental conditions affecting concentrations of He, CO2, O2 and N2 in soil gases

    USGS Publications Warehouse

    Hinkle, Margaret E.

    1994-01-01

    The measurement of concentrations of volatile species in soil gases has potential for use in geochemical exploration for concealed ore deposits and for monitoring of subsurface contaminants. However, the interpretation of anomalies in surficial gases can be difficult because soil-gas concentrations are dependent on both meteorological and environmental conditions.For this study, concentrations of He, CO2, O2 and N2 and meteorological conditions were monitored for 10–14 months at eight nonmineralized sites in both humid and dry environments. Gases were collected at 0.6–0.7-m depth at seven sites. At one site, gases were collected from 0.3-, 0.6-, 1.2-, and 2.0-m depths; diurnal monitoring studies were conducted at this site also. Rain and snowfall, soil and air temperatures, barometric pressure, and relative humidity were monitored at all the sites. The sand, silt and clay content, and the organic carbon content of surficial soil were measured at each site.Meteorological conditions generally affected He and CO2 concentrations in the same way at all the sites; however, these effects were modified by local environmental conditions. Both seasonal and diurnal concentration changes occurred. The most important seasonal concentration changes were related to rain and snowfall and soil and air temperatures. Seasonal changes tended to be larger then the diurnal changes, but both could be related to the same processes. Local conditions of soil type and organic content affected the amount of pore space and moisture present in the soil and therefore the soil-gas concentrations.

  15. 40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6...

  16. 40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10− 02 1.6...

  17. N loss to drain flow and N2O emissions from a corn-soybean rotation with winter rye.

    PubMed

    Gillette, K; Malone, R W; Kaspar, T C; Ma, L; Parkin, T B; Jaynes, D B; Fang, Q X; Hatfield, J L; Feyereisen, G W; Kersebaum, K C

    2018-03-15

    Anthropogenic perturbation of the global nitrogen cycle and its effects on the environment such as hypoxia in coastal regions and increased N 2 O emissions is of increasing, multi-disciplinary, worldwide concern, and agricultural production is a major contributor. Only limited studies, however, have simultaneously investigated NO 3 - losses to subsurface drain flow and N 2 O emissions under corn-soybean production. We used the Root Zone Water Quality Model (RZWQM) to evaluate NO 3 - losses to drain flow and N 2 O emissions in a corn-soybean system with a winter rye cover crop (CC) in central Iowa over a nine year period. The observed and simulated average drain flow N concentration reductions from CC were 60% and 54% compared to the no cover crop system (NCC). Average annual April through October cumulative observed and simulated N 2 O emissions (2004-2010) were 6.7 and 6.0kgN 2 O-Nha -1 yr -1 for NCC, and 6.2 and 7.2kgNha -1 for CC. In contrast to previous research, monthly N 2 O emissions were generally greatest when N loss to leaching were greatest, mostly because relatively high rainfall occurred during the months fertilizer was applied. N 2 O emission factors of 0.032 and 0.041 were estimated for NCC and CC using the tested model, which are similar to field results in the region. A local sensitivity analysis suggests that lower soil field capacity affects RZWQM simulations, which includes increased drain flow nitrate concentrations, increased N mineralization, and reduced soil water content. The results suggest that 1) RZWQM is a promising tool to estimate N 2 O emissions from subsurface drained corn-soybean rotations and to estimate the relative effects of a winter rye cover crop over a nine year period on nitrate loss to drain flow and 2) soil field capacity is an important parameter to model N mineralization and N loss to drain flow. Published by Elsevier B.V.

  18. The pH dependency of N-converting enzymatic processes, pathways and microbes: effect on net N2 O production.

    PubMed

    Blum, Jan-Michael; Su, Qingxian; Ma, Yunjie; Valverde-Pérez, Borja; Domingo-Félez, Carlos; Jensen, Marlene Mark; Smets, Barth F

    2018-05-01

    Nitrous oxide (N 2 O) is emitted during microbiological nitrogen (N) conversion processes, when N 2 O production exceeds N 2 O consumption. The magnitude of N 2 O production vs. consumption varies with pH and controlling net N 2 O production might be feasible by choice of system pH. This article reviews how pH affects enzymes, pathways and microorganisms that are involved in N-conversions in water engineering applications. At a molecular level, pH affects activity of cofactors and structural elements of relevant enzymes by protonation or deprotonation of amino acid residues or solvent ligands, thus causing steric changes in catalytic sites or proton/electron transfer routes that alter the enzymes' overall activity. Augmenting molecular information with, e.g., nitritation or denitrification rates yields explanations of changes in net N 2 O production with pH. Ammonia oxidizing bacteria are of highest relevance for N 2 O production, while heterotrophic denitrifiers are relevant for N 2 O consumption at pH > 7.5. Net N 2 O production in N-cycling water engineering systems is predicted to display a 'bell-shaped' curve in the range of pH 6.0-9.0 with a maximum at pH 7.0-7.5. Net N 2 O production at acidic pH is dominated by N 2 O production, whereas N 2 O consumption can outweigh production at alkaline pH. Thus, pH 8.0 may be a favourable pH set-point for water treatment applications regarding net N 2 O production. © 2018 Society for Applied Microbiology and John Wiley & Sons Ltd.

  19. N2O and CO2 emissions following repeated application of organic and mineral N fertiliser from a vegetable crop rotation.

    PubMed

    De Rosa, Daniele; Rowlings, David W; Biala, Johannes; Scheer, Clemens; Basso, Bruno; Grace, Peter R

    2018-05-11

    Accounting for nitrogen (N) release from organic amendments (OA) can reduce the use of synthetic N-fertiliser, sustain crop production, and potentially reduce soil borne greenhouse gases (GHG) emissions. However, it is difficult to assess the GHG mitigation potential for OA as a substitute of N-fertiliser over the long term due to only part of the organic N added to soil is being released in the first year after application. High-resolution nitrous oxide (N 2 O) and carbon dioxide (CO 2 ) emissions monitored from a horticultural crop rotation over 2.5 years from conventional urea application rates were compared to treatments receiving an annual application of raw and composted chicken manure combined with conventional and reduced N-fertiliser rates. The repeated application of composted manure did not increase annual N 2 O emissions while the application of raw manure resulted in N 2 O emissions up to 35.2 times higher than the zero N fertiliser treatment and up to 4.7 times higher than conventional N-fertiliser rate due to an increase in C and N availability following the repeated application of raw OA. The main factor driving N 2 O emissions was the incorporation of organic material accompanied by high soil moisture while the application of synthetic N-fertiliser induced only short-term N 2 O emission pulse. The average annual N 2 O emission factor calculated accounting for the total N applied including OA was equal to 0.27 ± 0.17%, 3.7 times lower than the IPCC default value. Accounting for the estimated N release from OA only enabled a more realistic N 2 O emission factor to be defined for organically amended field that was equal to 0.48 ± 0.3%. This study demonstrated that accounting for the N released from repeated application of composted rather than raw manure can be a viable pathway to reduce N 2 O emissions and maintain soil fertility. Copyright © 2017. Published by Elsevier B.V.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  2. Controlled carrier screening in p-n NiO/GaN piezoelectric generators by an Al2O3 insertion layer

    NASA Astrophysics Data System (ADS)

    Johar, Muhammad Ali; Jeong, Dae Kyung; Afifi Hassan, Mostafa; Kang, Jin-Ho; Ha, Jun-Seok; Key Lee, June; Ryu, Sang-Wan

    2017-12-01

    The performance of a piezoelectric generator (PG) depends significantly on the internal screening process inside the device. As piezoelectric charges appear on both ends of the piezoelectric crystal, internal screening starts to decrease the piezoelectric bias. Therefore, the piezoelectric energy generated by external stress is not fully utilized by external circuit, which is the most challenging aspect of high-efficiency PGs. In this work, the internal screening effect of a NiO/GaN p-n PG was analyzed and controlled with an Al2O3 insertion layer. Internal screening in the p-n diode PG was categorized into free-carrier screening in neutral regions and junction screening due to charge drift across the junction. It was observed that junction screening could be significantly suppressed by inserting an Al2O3 layer and that effect was dominant in a leaky diode PG. With this implementation, the piezoelectric bias of the NiO/GaN PG was improved by a factor of ~100 for high-leakage diodes and a factor of ~1.6 for low-leakage diodes. Consequently, NiO/Al2O3/GaN PGs under a stress of 5 MPa provided a piezoelectric bias of 12.1 V and a current density of 2.25 µA cm-2. The incorporation of a highly resistive Al2O3 layer between p-NiO and n-GaN layers in NiO/GaN heterojunctions provides an efficient means of improving the piezoelectric performance by controlling the internal screening of the piezoelectric field.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  4. Isotopologue fractionation during N(2)O production by fungal denitrification.

    PubMed

    Sutka, Robin L; Adams, Gerard C; Ostrom, Nathaniel E; Ostrom, Peggy H

    2008-12-01

    Identifying the importance of fungi to nitrous oxide (N2O) production requires a non-intrusive method for differentiating between fungal and bacterial N2O production such as natural abundance stable isotopes. We compare the isotopologue composition of N2O produced during nitrite reduction by the fungal denitrifiers Fusarium oxysporum and Cylindrocarpon tonkinense with published data for N2O production during bacterial nitrification and denitrification. The fractionation factors for bulk nitrogen isotope values for fungal denitrification were in the range -74.7 to -6.6 per thousand. There was an inverse relationship between the absolute value of the fractionation factors and the reaction rate constant. We interpret this in terms of variation in the relative importance of the rate constants for diffusion and enzymatic reduction in controlling the net isotope effect for N2O production during fungal denitrification. Over the course of nitrite reduction, the delta(18)O values for N2O remained constant and did not exhibit a relationship with the concentration characteristic of an isotope effect. This probably reflects isotopic exchange with water. Similar to the delta(18)O data, the site preference (SP; the difference in delta(15)N between the central and outer N atoms in N2O) was unrelated to concentration during nitrite reduction and, therefore, has the potential to act as a conservative tracer of production from fungal denitrification. The SP values of N2O produced by F. oxysporum and C. tonkinense were 37.1 +/- 2.5 per thousand and 36.9 +/- 2.8 per thousand, respectively. These SP values are similar to those obtained in pure culture studies of bacterial nitrification but quite distinct from SP values for bacterial denitrification. The large magnitude of the bulk nitrogen isotope fractionation and the delta(18)O values associated with fungal denitrification are distinct from bacterial production pathways; thus multiple isotopologue data holds much promise for

  5. Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-10-01

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

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

    PubMed

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

    2007-10-11

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

  8. Ranking factors affecting emissions of GHG from incubated agricultural soils.

    PubMed

    García-Marco, S; Ravella, S R; Chadwick, D; Vallejo, A; Gregory, A S; Cárdenas, L M

    2014-07-01

    Agriculture significantly contributes to global greenhouse gas (GHG) emissions and there is a need to develop effective mitigation strategies. The efficacy of methods to reduce GHG fluxes from agricultural soils can be affected by a range of interacting management and environmental factors. Uniquely, we used the Taguchi experimental design methodology to rank the relative importance of six factors known to affect the emission of GHG from soil: nitrate (NO 3 - ) addition, carbon quality (labile and non-labile C), soil temperature, water-filled pore space (WFPS) and extent of soil compaction. Grassland soil was incubated in jars where selected factors, considered at two or three amounts within the experimental range, were combined in an orthogonal array to determine the importance and interactions between factors with a L 16 design, comprising 16 experimental units. Within this L 16 design, 216 combinations of the full factorial experimental design were represented. Headspace nitrous oxide (N 2 O), methane (CH 4 ) and carbon dioxide (CO 2 ) concentrations were measured and used to calculate fluxes. Results found for the relative influence of factors (WFPS and NO 3 - addition were the main factors affecting N 2 O fluxes, whilst glucose, NO 3 - and soil temperature were the main factors affecting CO 2 and CH 4 fluxes) were consistent with those already well documented. Interactions between factors were also studied and results showed that factors with little individual influence became more influential in combination. The proposed methodology offers new possibilities for GHG researchers to study interactions between influential factors and address the optimized sets of conditions to reduce GHG emissions in agro-ecosystems, while reducing the number of experimental units required compared with conventional experimental procedures that adjust one variable at a time.

  9. Ranking factors affecting emissions of GHG from incubated agricultural soils

    PubMed Central

    García-Marco, S; Ravella, S R; Chadwick, D; Vallejo, A; Gregory, A S; Cárdenas, L M

    2014-01-01

    Agriculture significantly contributes to global greenhouse gas (GHG) emissions and there is a need to develop effective mitigation strategies. The efficacy of methods to reduce GHG fluxes from agricultural soils can be affected by a range of interacting management and environmental factors. Uniquely, we used the Taguchi experimental design methodology to rank the relative importance of six factors known to affect the emission of GHG from soil: nitrate (NO3−) addition, carbon quality (labile and non-labile C), soil temperature, water-filled pore space (WFPS) and extent of soil compaction. Grassland soil was incubated in jars where selected factors, considered at two or three amounts within the experimental range, were combined in an orthogonal array to determine the importance and interactions between factors with a L16 design, comprising 16 experimental units. Within this L16 design, 216 combinations of the full factorial experimental design were represented. Headspace nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations were measured and used to calculate fluxes. Results found for the relative influence of factors (WFPS and NO3− addition were the main factors affecting N2O fluxes, whilst glucose, NO3− and soil temperature were the main factors affecting CO2 and CH4 fluxes) were consistent with those already well documented. Interactions between factors were also studied and results showed that factors with little individual influence became more influential in combination. The proposed methodology offers new possibilities for GHG researchers to study interactions between influential factors and address the optimized sets of conditions to reduce GHG emissions in agro-ecosystems, while reducing the number of experimental units required compared with conventional experimental procedures that adjust one variable at a time. PMID:25177207

  10. Quantifying Uncertainties in N2O Emission Due to N Fertilizer Application in Cultivated Areas

    PubMed Central

    Philibert, Aurore; Loyce, Chantal; Makowski, David

    2012-01-01

    Nitrous oxide (N2O) is a greenhouse gas with a global warming potential approximately 298 times greater than that of CO2. In 2006, the Intergovernmental Panel on Climate Change (IPCC) estimated N2O emission due to synthetic and organic nitrogen (N) fertilization at 1% of applied N. We investigated the uncertainty on this estimated value, by fitting 13 different models to a published dataset including 985 N2O measurements. These models were characterized by (i) the presence or absence of the explanatory variable “applied N”, (ii) the function relating N2O emission to applied N (exponential or linear function), (iii) fixed or random background (i.e. in the absence of N application) N2O emission and (iv) fixed or random applied N effect. We calculated ranges of uncertainty on N2O emissions from a subset of these models, and compared them with the uncertainty ranges currently used in the IPCC-Tier 1 method. The exponential models outperformed the linear models, and models including one or two random effects outperformed those including fixed effects only. The use of an exponential function rather than a linear function has an important practical consequence: the emission factor is not constant and increases as a function of applied N. Emission factors estimated using the exponential function were lower than 1% when the amount of N applied was below 160 kg N ha−1. Our uncertainty analysis shows that the uncertainty range currently used by the IPCC-Tier 1 method could be reduced. PMID:23226430

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

    PubMed

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

    2012-08-01

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

  12. Glacial-Interglacial and Holocene N2O Stable Isotope Changes Constrain Terrestrial N Cycling

    NASA Astrophysics Data System (ADS)

    Schmitt, J.; Spahni, R.; Bock, M.; Seth, B.; Stocker, B. D.; Ri, X.; Schilt, A.; Brook, E.; Otto-Bliesner, B. L.; Liu, Z.; Prentice, I. C.; Fischer, H.; Joos, F.

    2015-12-01

    The land biosphere contributes most to the natural source of the long-lived greenhouse gas nitrous oxide (N2O), with N2O emissions being dependent on the turnover rate of both the terrestrial nitrogen (N) and carbon (C) cycle. The C:N stoichiometry of vegetation and soil organic matter links the cycles intimately. Sustained plant productivity increase must be supported by biological N fixation. Intensified N cycling in turn enhances N loss and thereby N2O emissions. The temporal and spatial dynamics of terrestrial N and C cycles and related terrestrial N2O emissions are poorly constrained over the glacial-interglacial transition and the Holocene. Here we reconstruct increased terrestrial N2O emissions since the Last Glacial Maximum based on N2O concentration and isotope measurements on several ice cores and show that this N2O increase can be explained by N cycle modelling - provided N fixation is allowed to respond dynamically to increasing N demand and turnover. The Ice core reconstructions suggest a deglacial increase of 1.1 ± 0.4 Tg N/yr in terrestrial and 0.6 ± 0.4 Tg/yr in oceanic N2O emissions, but relatively constant terrestrial emissions over the Holocene. Transient simulations with a Dynamic Global Vegetation Model are shown to represent the climate and CO2 induced changes in terrestrial N2O emission, and suggest a deglacial increase in biological N fixation by 20%, independently of its absolute magnitude. Deciphering the response of biological N fixation during climatic changes is an important factor for our understanding of plant growth and the land carbon sink, alongside anthropogenic greenhouse gas emissions.

  13. Evaluating four N2O emission algorithms in RZWQM2 in response to N rate on an irrigated corn field

    USDA-ARS?s Scientific Manuscript database

    Nitrous oxide (N2O) emissions from agricultural soils are major contributors to greenhouse gases. Correctly assessing the effects of the interactions between agricultural practices and environmental factors on N2O emissions is required for better crop and nitrogen (N) management. We used an enhanced...

  14. Effect of sulfation on the surface activity of CaO for N2O decomposition

    NASA Astrophysics Data System (ADS)

    Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Dong, Changqing; Yang, Yongping

    2015-12-01

    Limestone addition to circulating fluidized bed boilers for sulfur removal affects nitrous oxide (N2O) emission at the same time, but mechanism of how sulfation process influences the surface activity of CaO for N2O decomposition remains unclear. In this paper, we investigated the effect of sulfation on the surface properties and catalytic activity of CaO for N2O decomposition using density functional theory calculations. Sulfation of CaO (1 0 0) surface by the adsorption of a single gaseous SO2 or SO3 molecule forms stable local CaSO3 or CaSO4 on the CaO (1 0 0) surface with strong hybridization between the S atom of SOx and the surface O anion. The formed local CaSO3 increases the barrier energy of N2O decomposition from 0.989 eV (on the CaO (1 0 0) surface) to 1.340 eV, and further sulfation into local CaSO4 remarkably increases the barrier energy to 2.967 eV. Sulfation from CaSO3 into CaSO4 is therefore the crucial step for deactivating the surface activity for N2O decomposition. Completely sulfated CaSO4 (0 0 1) and (0 1 0) surfaces further validate the negligible catalytic ability of CaSO4 for N2O decomposition.

  15. Microhabitat Effects on N2O Emissions from Floodplain Soils under Controlled Conditions

    NASA Astrophysics Data System (ADS)

    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

  16. Affect of dairy cow manure, urine, and slurry on N<2>O, CO<2>, and CH<4> emissions from Pasture

    NASA Astrophysics Data System (ADS)

    Dorich, C.; Varner, R. K.; Contosta, A.; Li, C.

    2012-12-01

    Agriculture is responsible for roughly 25% of total anthropogenic emission of greenhouse gases (GHG) globally. These agricultural emissions are primarily in the form of methane (CH<4>) and nitrous oxide (N<2>O) where they account for roughly 40 and 80 percent of anthropogenic emissions of their gas, respectively. Measuring and modeling of these gases has remained difficult however as management varies between farms and N<2>O fluxes have been difficult to link to climate and site conditions. Most of these N<2>O fluxes occur during soil freeze-thaw and wetting-drying cycles as well as fertilizer addition moments, all of which are difficult to measure and harder yet to model. Thus the N<2>O flux remains poorly understood and may be underestimated in literature. This provides a problem in agriculture emissions as N use efficiency has been suggested as a proxy for farm scale emissions. On a farm scale these large fluxes of N<2>O from soil "hot moments" can account for up to 60% of the total GHG emissions and thus it is essential to capture the full flux. At the University of New Hampshire Agriculture Experiment Station's (NHAES) organic dairy farm a manure fertilizer experiment was conducted. Manure, urine, and slurry from the UNH dairy farms were collected, analyzed, and applied to pasture plots in May 2012 in order to examine N<2>O flux hot moments. Sites were measured at least bi-weekly with manual static flux chambers taken with soil temperature and moisture along with measurements for soil inorganic N, soil C:N, plant biomass and C:N, and soil pH. Gas samples were analyzed for CO<2>, CH<4>, and N<2>O. Emissions were compared with other fluxes from the farm ecosystem including; corn silage, free stall bedding, composting and solid manure, and a manure slurry tank.

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

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

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

  18. Influence of Lumbricus terrestris and Folsomia candida on N2 O formation pathways in two different soils - with particular focus on N2 emissions.

    PubMed

    Schorpp, Quentin; Riggers, Catharina; Lewicka-Szczebak, Dominika; Giesemann, Anette; Well, Reinhard; Schrader, Stefan

    2016-11-15

    The gaseous N losses mediated by soil denitrifiers are generally inferred by measuring N 2 O fluxes, but should include associated N 2 emissions, which may be affected by abiotic soil characteristics and biotic interactions. Soil fauna, particularly anecic earthworms and euedaphic collembola, alter the activity of denitrifiers, creating hotspots for denitrification. These soil fauna are abundant in perennial agroecosystems intended to contribute to more sustainable production of bioenergy. Two microcosm experiments were designed to evaluate gaseous N emissions from a silty loam and a sandy soil, both provided with litter from the bioenergy crop Silphium perfoliatum (cup-plant) and inoculated with an anecic earthworm (Lumbricus terrestris), which was added alone or together with an euedaphic collembola (Folsomia candida). In experiment 1, litter-derived N flux was determined by adding 15 N-labelled litter, followed by mass spectrometric analysis of N 2 and N 2 O isotopologues. In experiment 2, the δ 18 O values and 15 N site preference of N 2 O were determined by isotope ratio mass spectrometry to reveal underlying N 2 O formation pathways. Lumbricus terrestris significantly increased litter-derived N 2 emissions in the loamy soil, from 174.5 to 1019.3 μg N 2 -N kg -1 soil, but not in the sandy soil (non-significant change from 944.7 to 1054.7 μg N 2 -N kg -1 soil). Earthworm feeding on plant litter resulted in elevated N 2 O emissions in both soils, derived mainly from turnover of the soil mineral N pool during denitrification. Folsomia candida did not affect N losses but showed a tendency to redirect N 2 O formation pathways from fungal to bacterial denitrification. The N 2 O/(N 2  + N 2 O) product ratio was predominantly affected by abiotic soil characteristics (loamy soil: 0.14, sandy soil: 0.26). When feeding on S. perfoliatum litter, the anecic L. terrestris, but not the euedaphic F. candida, has the potential to cause substantial N losses. Biotic

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

    NASA Astrophysics Data System (ADS)

    Barnes, Jonathan; Upstill-Goddard, Robert C.

    2018-01-01

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

  20. Oceanic nitrogen cycling and N2O flux perturbations in the Anthropocene

    NASA Astrophysics Data System (ADS)

    Landolfi, A.; Somes, C. J.; Koeve, W.; Zamora, L. M.; Oschlies, A.

    2017-08-01

    There is currently no consensus on how humans are affecting the marine nitrogen (N) cycle, which limits marine biological production and CO2 uptake. Anthropogenic changes in ocean warming, deoxygenation, and atmospheric N deposition can all individually affect the marine N cycle and the oceanic production of the greenhouse gas nitrous oxide (N2O). However, the combined effect of these perturbations on marine N cycling, ocean productivity, and marine N2O production is poorly understood. Here we use an Earth system model of intermediate complexity to investigate the combined effects of estimated 21st century CO2 atmospheric forcing and atmospheric N deposition. Our simulations suggest that anthropogenic perturbations cause only a small imbalance to the N cycle relative to preindustrial conditions (˜+5 Tg N y-1 in 2100). More N loss from water column denitrification in expanded oxygen minimum zones (OMZs) is counteracted by less benthic denitrification, due to the stratification-induced reduction in organic matter export. The larger atmospheric N load is offset by reduced N inputs by marine N2 fixation. Our model predicts a decline in oceanic N2O emissions by 2100. This is induced by the decrease in organic matter export and associated N2O production and by the anthropogenically driven changes in ocean circulation and atmospheric N2O concentrations. After comprehensively accounting for a series of complex physical-biogeochemical interactions, this study suggests that N flux imbalances are limited by biogeochemical feedbacks that help stabilize the marine N inventory against anthropogenic changes. These findings support the hypothesis that strong negative feedbacks regulate the marine N inventory on centennial time scales.

  1. Microhabitat Effects on N2O Emissions from Floodplain Soils under Controlled Conditions

    NASA Astrophysics Data System (ADS)

    Ley, Martin; Lehmann, Moritz; Niklaus, Pascal; Frey, Beat; Kuhn, Thomas; Luster, Jörg

    2015-04-01

    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 hot spots under field conditions, and of the microbial pathways that underlie net N2O production (ammonium oxidation, nitrifier-denitrification, and denitrification) is challenging in the environment because of the 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 microbial pathways that produce or consume N2O. The availability of oxygen, reactive organic carbon, and dissolved nitrogen substrates likely play key roles with regards to the net production of N2O. Previous field studies demonstrated, for example, that flooding can trigger "hot moments" of enhanced N2O emission through a close coupling of niches with high and low oxygen availabilities. Such microhabitat effects likely depend on soil aggregate formation, plant soil interactions in the rhizosphere 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 model soils comprising various mixtures of N-rich floodplain soil aggregates (4000 - 250 µm representing large aggregates, or <250 µm representing small aggregates) and inert matrix material (glass beads of 150 - 250 µm size, or quartz sand of 2000 - 3200 µm size, respectively). Soils containing the different aggregate size groups were either planted with willow (Salix viminalis L.), mixed with leaf litter or left untreated. At several time points before, during and after a simulated flood event, we measure the net efflux rate of N2O. In addition, soil water content, redox potential as well as carbon and nitrogen substrate availability are monitored. In order to

  2. N2O molecular tagging velocimetry

    NASA Astrophysics Data System (ADS)

    ElBaz, A. M.; Pitz, R. W.

    2012-03-01

    A new seeded velocity measurement technique, N2O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide "laughing gas" is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N2O to O(1D) that subsequently reacts with N2O to form NO. O2 fluorescence induced by the ArF laser "writes" the original position of the NO line. After a time delay, the shifted NO line is "read" by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N2O in air, ˜1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800-1200 ppm of NO for 190-750 K at 1 atm and 850-1000 ppm of NO for 0.25-1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N2O MTV method amenable to low- and high-speed air flow measurements. The N2O MTV technique is demonstrated in air jet to measure its velocity profile. The N2O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N2O with O(1D) from N2O photodissociation and thus does not depend on the bulk gas composition.

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

    PubMed

    Wang, Jian-Fei; Lin, Jian-Li

    2010-09-30

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

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

    NASA Astrophysics Data System (ADS)

    Dors, Mirosław; Mizeraczyk, Jerzy

    1996-10-01

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

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

    PubMed

    Tang, Jian; McKellar, A R W

    2005-09-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

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

    PubMed

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

    2008-10-18

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

  8. Post-harvest N2O emissions were not affected by various types of oilseed straw incorporated into soil

    NASA Astrophysics Data System (ADS)

    Köbke, Sarah; Senbayram, Mehmet; Hegewald, Hannes; Christen, Olaf; Dittert, Klaus

    2015-04-01

    Oilseed rape post-harvest N2O emissions are seen highly critical as so far they are considered as one of the most crucial drawbacks in climate-saving bioenergy production systems. N2O emissions may substantially counterbalance the intended savings in CO2 emissions. Carbon-rich crop residues in conjunction with residual soil nitrate are seen as a key driver since they may serve as energy source for denitrification and, they may alter soil-borne N2O emissions. As oilseed rape straw is known to have high N/C ratio compared to other crop residues, its soil incorporation may specifically trigger post-harvest N2O emissions. Therefore, the aim of the present study was to determine post-harvest N2O emissions in soils amended with various types of oilseed rape straw (with different N/C ratio) and barley straw in field and incubation experiments. In the incubation experiment, oilseed rape or 15N labelled barley straw were mixed with soil at a rate of 1.3 t DM ha-1 and studied for 43 days. Treatments consisted of non-treated control soil (CK), 15N labelled barley straw (BST), oilseed rape straw (RST), 15N labelled barley straw + N (BST+N), or oilseed rape straw + N (RST+N). N fertilizer was applied to the soil surface as ammonium-nitrate at a rate of 100 kg N ha-1 and soil moisture was adjusted to 80% water-holding capacity. In the field experiment, during the vegetation period 15N labelled fertilizer (15NH415NO3) was used to generate 15N labelled oilseed rape straw (up to 5 at%). Here, the three fertilizer treatments consisted of 5 kg N ha-1 (RST-5), 150 kg N ha-1 (RST-150) and 180 kg N ha-1 (RST-180). Post-harvest N2O emissions were determined during the period of August 2013 to February 2014 by using static flux chambers. In the incubation trial, cumulative N2O emissions were 5, 29, 40 g N2O-N ha-1 148 days-1 in non-fertilized control, BST and RST treatments, respectively. Here, emissions were slightly higher in RST than BST (p

  9. Biologically produced volatile compounds: N2O emissions from soils

    NASA Technical Reports Server (NTRS)

    Banin, A.

    1985-01-01

    Tropospheric nitrous concentration has increased by 0.2 0.4% per year over the period 1975 to 1982, amounting to net addition to the atmosphere of 2.8 - 5.6 Tg N2O-N per year. This perturbation, if continued into the future, will affect stratospheric chemical cycles, and the thermal balance of the Earth. In turn it will have direct and indirect global effects on the biosphere. Though the budget and cycles of N2O on Earth are not yet fully resolved, accumulating information and recent modelling efforts permit a more complete evaluation and better definition of gaps in our knowledge.

  10. Two years monitoring of soil N_{2}O emissions on durum wheat in a Mediterranean area: the effect of tillage intensity and N-fertilizer rate.

    NASA Astrophysics Data System (ADS)

    Volpi, Iride; Bosco, Simona; Triana, Federico; Di Nasso, Nicoletta Nassi o.; Laville, Patricia; Virgili, Giorgio; Bonari, Enrico

    2016-04-01

    Evaluating the magnitude and the key factors affecting N2O emissions from agriculture has a scientific and practical relevance, in fact emissions from agricultural and natural soils account for 56-70% of all global N2O sources (Syakila and Kroeze, 2011). Moreover, the necessity to increase the food production rate minimizing greenhouse gas emissions require a deeper understanding of the effect of the agricultural practices on direct soil emissions. Therefore, the aim of this work is to assess the effect of tillage intensity and nitrogen rate on soil N2O emissions on durum wheat. A two years monitoring campaign was carried out using a high-sensibility transportable instrument developed within the LIFE+ "Improved flux Prototypes for N2O emission from Agriculture" IPNOA project (Bosco et al., 2015; Laville et al., 2015). The project aims at improving the measurement technique of N2O flux directly in field using the flow-through non-steady state chamber technique. The monitoring campaign on durum wheat lasted for two growing seasons and two fallow periods (2013-14 and 2014-15). Treatment on the main plot was tillage intensity with two levels, ploughing and minimum tillage, and three different nitrogen rates were distributed to the subplots (N0: 0 kg ha-1, N1: 110 kg ha-1, N2: 170 kg ha-1). Ancillary measurements concerned meteorological data, soil temperature and moisture, NO3-, NH4+ soil concentration. Main results of the two years highlighted N rate as the main driver for both N2O daily flux and cumulative emissions during the growing season, while in the fallow period treatments did not affect the emission magnitude. Tillage intensity was not a key factor for N2O emissions. N2O emissions were significantly different in the two years. In particular, cumulative emissions of 2013-14 were about five times higher than in 2014-15, respectively on average 2885±260 g N-N2O ha-1 and 534±53 g N-N2O ha-1 for a similar monitoring period of about 300 days. Differences could be

  11. Effects of temperature on nitrous oxide (N2O) emission from intensive aquaculture system.

    PubMed

    Paudel, Shukra Raj; Choi, Ohkyung; Khanal, Samir Kumar; Chandran, Kartik; Kim, Sungpyo; Lee, Jae Woo

    2015-06-15

    This study examines the effects of temperature on nitrous oxide (N2O) emissions in a bench-scale intensive aquaculture system rearing Koi fish. The water temperature varied from 15 to 24 °C at interval of 3 °C. Both volumetric and specific rate for nitrification and denitrification declined as the temperature decreased. The concentrations of ammonia and nitrite, however, were lower than the inhibitory level for Koi fish regardless of temperature. The effects of temperature on N2O emissions were significant, with the emission rate and emission factor increasing from 1.11 to 1.82 mg N2O-N/d and 0.49 to 0.94 mg N2O-N/kg fish as the temperature decreased from 24 to 15 °C. A global map of N2O emission from aquaculture was established by using the N2O emission factor depending on temperature. This study demonstrates that N2O emission from aquaculture is strongly dependent on regional water temperatures as well as on fish production. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    PubMed

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

    2011-05-01

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

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

    PubMed

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

    2010-10-14

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1992-05-01

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

  16. Emissions of N2O and NO from fertilized fields: Summary of available measurement data

    NASA Astrophysics Data System (ADS)

    Bouwman, A. F.; Boumans, L. J. M.; Batjes, N. H.

    2002-12-01

    Information from 846 N2O emission measurements in agricultural fields and 99 measurements for NO emissions was summarized to assess the influence of various factors regulating emissions from mineral soils. The data indicate that there is a strong increase of both N2O and NO emissions accompanying N application rates, and soils with high organic-C content show higher emissions than less fertile soils. A fine soil texture, restricted drainage, and neutral to slightly acidic conditions favor N2O emission, while (though not significant) a good soil drainage, coarse texture, and neutral soil reaction favor NO emission. Fertilizer type and crop type are important factors for N2O but not for NO, while the fertilizer application mode has a significant influence on NO only. Regarding the measurements, longer measurement periods yield more of the fertilization effect on N2O and NO emissions, and intensive measurements (≥1 per day) yield lower emissions than less intensive measurements (2-3 per week). The available data can be used to develop simple models based on the major regulating factors which describe the spatial variability of emissions of N2O and NO with less uncertainty than emission factor approaches based on country N inputs, as currently used in national emission inventories.

  17. Diet effects on urine composition of cattle and N2O emissions.

    PubMed

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

    2013-06-01

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

  18. Global terrestrial N2O budget for present and future

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  19. [Effects of warming and precipitation exclusion on soil N2O fluxes in subtropical forests.

    PubMed

    Tang, Cai di; Zhang, Zheng; Cai, Xiao Zhen; Guo, Jian Fen; Yang, Yu Sheng

    2017-10-01

    In order to explore how soil warming and precipitation exclusion influence soil N2O fluxes, we used related functional genes as markers, and four treatments were set up, i.e. , control (CT), soil warming (W, 5 ℃ above the ambient temperature of the control), 50% precipitation reduction (P), soil warming plus 50% precipitation reduction (WP). The results showed that precipitation exclusion reduced soil ammonium nitrogen concentration significantly. Soil warming decreased soil N2O flux and soil denitrification potential significantly. Soil microbial biomass nitrogen (MBN) in warming treatment (W) and precipitation exclusion treatment (P) was significantly lower than that in the control. The amoA gene abundance of AOA was negatively correlated with MBN and ammonium nitrogen contents, but neither soil nitrification potential nor soil N2O flux was correlated with the amoA gene abundance of AOA. Path analysis showed that the denitrification potential affected soil N2O flux directly, while microbial biomass phosphorus (MBP) and warming affected soil N2O flux indirectly through their direct effects on denitrification potential. Temperature might be the main driver of N2O flux in subtropical forest soils. Global warming would reduce N2O emissions from subtropical forest soils.

  20. Effect of N fertilization and tillage on nitrous oxide (N2O) loss from soil under wheat production

    USGS Publications Warehouse

    Bansal, Sheel; Aberle, Ezra; Teboh, Jasper; Yuja, Szilvia; Liebig, Mark; Meier, Jacob; Boyd, Alec

    2017-01-01

    Nitrous oxide (N2O-N) is one of the most important gases in the atmosphere because it is 300 times more powerful than carbon dioxide in its ability to trap heat, and is a key chemical agent of ozone depletion. The amount of N2O-N emitted from agricultural fields can be quite high, depending on the complex interplay between N fertility and residue management, plant N uptake, microbial processes, environmental conditions, and wet-up and dry-down events. High N fertilizer rates generally increase yields, but may disproportionately increase N2O-N losses due to prolonged residence time in soil when not used by the crop, and incomplete decomposition of excess N-compounds by microbes. Tillage could also affect N2O-N losses through changes in soil moisture content. Though nitrogen monoxide (NO) is one form of N lost from the soil, especially under conventional tillage, this study objective was to quantify N2O loss in wheat fields from applied urea on soil under no-till (NT) versus incorporated urea under conventional till (CT).

  1. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures.

    PubMed

    Liu, Shurong; Berns, Anne E; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH 2 OH) to nitrous oxide (N 2 O) is a possible mechanism of N 2 O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO 2 ) and organic matter (OM) content of soil as well as soil pH are important control variables of N 2 O formation in the soil. But until now, their combined effect on abiotic N 2 O formation from NH 2 OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO 2 and OM, respectively, and quantified the interactive effects of the three variables on the NH 2 OH-to-N 2 O conversion ratio (R NH2OH-to-N2O ). Furthermore, the effect of OM quality on R NH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO 2 and OM on R NH2OH-to-N2O . In general, increasing MnO 2 and decreasing pH increased R NH2OH-to-N2O , while increasing OM content was associated with a decrease in R NH2OH-to-N2O . Organic matter quality also affected R NH2OH-to-N2O . However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

  2. Interactive effects of MnO2, organic matter and pH on abiotic formation of N2O from hydroxylamine in artificial soil mixtures

    NASA Astrophysics Data System (ADS)

    Liu, Shurong; Berns, Anne E.; Vereecken, Harry; Wu, Di; Brüggemann, Nicolas

    2017-02-01

    Abiotic conversion of the reactive nitrification intermediate hydroxylamine (NH2OH) to nitrous oxide (N2O) is a possible mechanism of N2O formation during nitrification. Previous research has demonstrated that manganese dioxide (MnO2) and organic matter (OM) content of soil as well as soil pH are important control variables of N2O formation in the soil. But until now, their combined effect on abiotic N2O formation from NH2OH has not been quantified. Here, we present results from a full-factorial experiment with artificial soil mixtures at five different levels of pH, MnO2 and OM, respectively, and quantified the interactive effects of the three variables on the NH2OH-to-N2O conversion ratio (RNH2OH-to-N2O). Furthermore, the effect of OM quality on RNH2OH-to-N2O was determined by the addition of four different organic materials with different C/N ratios to the artificial soil mixtures. The experiments revealed a strong interactive effect of soil pH, MnO2 and OM on RNH2OH-to-N2O. In general, increasing MnO2 and decreasing pH increased RNH2OH-to-N2O, while increasing OM content was associated with a decrease in RNH2OH-to-N2O. Organic matter quality also affected RNH2OH-to-N2O. However, this effect was not a function of C/N ratio, but was rather related to differences in the dominating functional groups between the different organic materials.

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

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

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

  4. Effects of Different Vegetation Zones on CH4 and N2O Emissions in Coastal Wetlands: A Model Case Study

    PubMed Central

    Liu, Yuhong; Wang, Lixin; Bao, Shumei; Liu, Huamin; Yu, Junbao; Wang, Yu; Shao, Hongbo; Ouyang, Yan; An, Shuqing

    2014-01-01

    The coastal wetland ecosystems are important in the global carbon and nitrogen cycle and global climate change. For higher fragility of coastal wetlands induced by human activities, the roles of coastal wetland ecosystems in CH4 and N2O emissions are becoming more important. This study used a DNDC model to simulate current and future CH4 and N2O emissions of coastal wetlands in four sites along the latitude in China. The simulation results showed that different vegetation zones, including bare beach, Spartina beach, and Phragmites beach, produced different emissions of CH4 and N2O in the same latitude region. Correlation analysis indicated that vegetation types, water level, temperature, and soil organic carbon content are the main factors affecting emissions of CH4 and N2O in coastal wetlands. PMID:24892044

  5. Low-Temperature Sintering of AlN Ceramics by Sm2O3-Y2O3-CaO Sintering Additives Formed via Decomposition of Nitrate Solutions

    NASA Astrophysics Data System (ADS)

    Zhan, Jun; Cao, Ye; Zhang, Hao; Guo, Jun; Zhang, Jianhua; Geng, Chunlei; Shi, Changdong; Cui, Song; Tang, Wenming

    2017-01-01

    The Sm, Y and Ca anhydrous nitrates were mixed with the AlN powder in ethanol and then decomposed into the Sm2O3-Y2O3-CaO sintering additives via calcining. Low-temperature sintering of the AlN ceramics was carried out at temperature range from 1675 to 1750 °C. Effects of the composition and adding amount of the sintering additives on the phases, microstructures and properties of the AlN ceramics were investigated. During sintering the AlN ceramics, main secondary phases of CaYAl3O7 and CaSmAl3O7 form. The relative density, bending strength and thermal conductivity of the AlN ceramics increase with the increase in the rare-earth oxides in them. The thermal conductivity of the sintered AlN ceramics is also greatly affected by the distribution of the secondary phases. As sintered at 1750 °C, the AlN ceramics by adding the sintering additives of 2 wt.% Sm2O3, 2 wt.% Y2O3 and 1 wt.% CaO formed via decomposition of their nitrates is fully dense and have the optimal bending strength and thermal conductivity of 402.1 MPa and 153.7 W/(m K), respectively.

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

    PubMed

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

    2012-04-19

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

  7. Managed grassland alters soil N dynamics and N2O emissions in temperate steppe.

    PubMed

    Xu, Lijun; Xu, Xingliang; Tang, Xuejuan; Xin, Xiaoping; Ye, Liming; Yang, Guixia; Tang, Huajun; Lv, Shijie; Xu, Dawei; Zhang, Zhao

    2018-04-01

    Reclamation of degraded grasslands as managed grasslands has been increasingly accelerated in recent years in China. Land use change affects soil nitrogen (N) dynamics and nitrous oxide (N 2 O) emissions. However, it remains unclear how large-scale grassland reclamation will impact the grassland ecosystem as a whole. Here, we investigated the effects of the conversion from native to managed grasslands on soil N dynamics and N2O emissions by field experiments in Hulunber in northern China. Soil (0-10cm), nitrate (NO 3 - ), ammonium (NH 4 + ), and microbial N were measured in plots in a temperate steppe (Leymus chinensis grassland) and two managed grasslands (Medicago sativa and Bromus inermis grasslands) in 2011 and 2012. The results showed conversion of L. chinensis grassland to M. sativa or B. inermis grasslands decreased concentrations of NO 3 - -N, but did not change NH 4 + -N. Soil microbial N was slightly decreased by the conversion of L. chinensis grassland to M. sativa, but increased by the conversion to B. inermis. The conversion of L. chinensis grassland to M. sativa (i.e., a legume grass) increased N 2 O emissions by 26.2%, while the conversion to the B. inermis (i.e., a non-legume grass) reduced N 2 O emissions by 33.1%. The conversion from native to managed grasslands caused large created variations in soil NO 3 - -N and NH 4 + -N concentrations. Net N mineralization rates did not change significantly in growing season or vegetation type, but to net nitrification rate. These results provide evidence on how reclamation may impact the grassland ecosystem in terms of N dynamics and N 2 O emissions. Copyright © 2017. Published by Elsevier B.V.

  8. Site-specific 15N isotopic signatures of abiotically produced N2O

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

  9. Quantification of N2O and NO emissions from a small-scale pond-ditch circulation system for rural polluted water treatment.

    PubMed

    Ma, Lin; Tong, Weijun; Chen, Hongguang; Sun, Jian; Wu, Zhenbin; He, Feng

    2018-04-01

    The pond-ditch circulation system (PDCS) is an efficient and economical solution for the restoration of degraded rural water environments. However, little is known about nitrous oxide (N 2 O) and nitric oxide (NO) emissions in the microbial removal process of nitrogen in PDCSs, and their contribution to nitrogen removal. The aim of this study was to quantify N 2 O and NO emissions from the PDCS, evaluate their capacities, and elucidate the key environmental factors controlling them. The results showed that N 2 O and NO fluxes were in the ranges 1.1-2055.1μgNm -2 h -1 and 0.1-6.8μgNm -2 h -1 for the PDCS, respectively. Meanwhile, the N 2 O and NO fluxes from the two ponds in the PDCS were significantly higher than those in the static system. Moreover, the amount of N 2 O and NO emissions in the PDCS accounted for 0.17-4.32% of the total nitrogen (TN) removal. According to the partial least squares (PLS) approach and Pearson's correlation coefficients, nitrate nitrogen in water (W-NO 3 - -N), dissolved oxygen in water (W-DO), dissolved oxygen in sediment (DO), pH in water (W-pH), pH in sediment (pH), total kjeldahl nitrogen (TKN), and soil organic carbon (SOC) significantly affected the N 2 O flux (p<0.05), whereas W-NO 3 - -N, DO, and nitrite nitrogen in sediment (NO 2 - -N) significantly affected the NO emission (p<0.05). Copyright © 2017 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. Effect of watershed urbanization on N2O emissions from the Chongqing metropolitan river network, China

    NASA Astrophysics Data System (ADS)

    He, Yixin; Wang, Xiaofeng; Chen, Huai; Yuan, Xingzhong; Wu, Ning; Zhang, Yuewei; Yue, Junsheng; Zhang, Qiaoyong; Diao, Yuanbin; Zhou, Lilei

    2017-12-01

    Watershed urbanization, an integrated anthropogenic perturbation, is another considerable global concern in addition to that of global warming and may significantly enrich the N loadings of watersheds, which then greatly influences the nitrous oxide (N2O) production and fluxes of these aquatic systems. However, little is known about the N2O dynamics in human-dominated metropolitan river networks. In this study, we present the temporal and spatial variations in N2O saturation and emission in the Chongqing metropolitan river network, which is undergoing intensified urbanization. The N2O saturation and fluxes at 84 sampling sites ranged from 126% to 10536% and from 4.5 to 1566.8 μmol N2O m-2 d-1, with means of 1780% and 261 μmol N2O m-2 d-1. The riverine N2O saturation and fluxes increased along with the urbanization gradient and urbanization rate, with disproportionately higher values in urban rivers due to the N2O-rich sewage inputs and enriched in situ N substrates. We found a clear seasonal pattern of N2O saturation, which was co-regulated by both water temperature and precipitation. Regression analysis indicated that the N substrates and dissolved oxygen (DO) that controlled nitrogen metabolism acted as good predictors of the N2O emissions of urban river networks. Particularly, phosphorus (P) and hydromorphological factors (water velocity, river size and bottom substrate) had stronger relationships with the N2O saturation and could also be used to predict the N2O emission hotspots in regions with rapid urbanization. In addition, the default emission factors (EF5-r) used in the Intergovernmental Panel on Climate Change (IPCC) methodology may need revision given the differences among the physical and chemical factors in different rivers, especially urban rivers.

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

    NASA Astrophysics Data System (ADS)

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

    1994-12-01

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

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

    PubMed

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

    2015-07-06

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

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed

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

    2007-12-06

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

  16. Historical Pattern and Future Trajectories of Terrestrial N2O Emission driven by Multi-factor Global Changes

    NASA Astrophysics Data System (ADS)

    Lu, C.; Tian, H.; Yang, J.; Zhang, B.; Xu, R.

    2015-12-01

    Nitrous oxide (N2O) is among the most important greenhouse gases only next to carbon dioxide (CO2) and methane (CH4) due to its long life time and high radiative forcing (with a global warming potential 265 times as much as CO2 at 100-year time horizon). The Atmospheric concentration of N2O has increased by 20% since pre-industrial era, and this increase plays a significant role in shaping anthropogenic climate change. However, compared to CO2- and CH4-related research, fewer studies have been performed in assessing and predicting the spatiotemporal patterns of N2O emission from natural and agricultural soils. Here we used a coupled biogeochemical model, DLEM, to quantify the historical and future changes in global terrestrial N2O emissions resulting from natural and anthropogenic perturbations including climate variability, atmospheric CO2 concentration, nitrogen deposition, land use and land cover changes, and agricultural land management practices (i.e., synthetic nitrogen fertilizer use, manure application, and irrigation etc.) over the period 1900-2099. We focused on inter-annual variation and long-term trend of terrestrial N2O emission driven by individual and combined environmental changes during historical and future periods. The sensitivity of N2O emission to climate, atmospheric composition, and human activities has been examined at biome-, latitudinal, continental and global scales. Future projections were conducted to identify the hot spots and hot time periods of global N2O emission under two emission scenarios (RCP2.6 and RCP8.5). It provides a modeling perspective for understanding human-induced N2O emission growth and developing potential management strategies to mitigate further atmospheric N2O increase and climate warming.

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

    PubMed

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

    2012-02-20

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2015-08-14

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

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

    PubMed

    Olabe, José A; Estiú, Guillermina L

    2003-08-11

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

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

    NASA Astrophysics Data System (ADS)

    Hinshaw, S.; Dahlgren, R. A.

    2010-12-01

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

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

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

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

    1984-03-01

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

  3. Sunflower N2O emissions under two different water regimes in Mediterranean climate

    NASA Astrophysics Data System (ADS)

    Monaco, Eugenia; Vitale, Luca; Di Tommasi, Paul; Tedeschi, Anna; Tosca, Maurizio; Magliulo, Vincenzo

    2017-04-01

    Human activities are altering the atmospheric greenhouse gases (GHGs) concentration with negative effects on global climate and environment. Cropland represents about 12 % of earth's surface and largely contribute to GHGs production, in particular N2O, due to a massive use of nitrogen fertilization. In particular, agriculture and intensive livestock farming may significantly affect biogeochemical cycles included nitrogen cycle. However, it is often difficult to predict the total amount of fluxes caused by agricultural management, which impact on both the whole agro-ecosystem. The objective of the experiment was to evaluate soil N2O fluxes under two different irrigation managements. The experimental trial was conducted in a farm in surrounding of Naples, southern Italy. The crop monitored was sunflower for biomass uses. Two irrigation levels were performed: returning 100% (optimal irrigation) and 50% (deficit irrigation) of soil field capacity for the layer 0.0-0.50 m. 314 Kg ha-1 of urea fertilizer was supplied in two times: at sowing and 40 days later. Before sowing, six autochambers were inserted 3 cm into the soil and connected to a gas chromatograph and a scanning apparatus. A program for chambers' management was implemented to monitor soil N2O fluxes measured different times of the day. Biometric parameters such as LAI, root depth, above- and below-ground biomass were monitored during the experiment. Results shows that soil N2O fluxes were affected by irrigation regime; in particular, the deficit irrigation determined lower N2O fluxes compared to optimal irrigation but the total biomass production and yield were comparable between the two water regimes. So low input farm management could be take in account to reduce the total N2O emission and maintain at the same time high productivity level in terms of biomass and yield. Keywords: N2O fluxes, Irrigation schedule, sunflower

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

    PubMed

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

    2005-08-31

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

  5. Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China

    PubMed Central

    Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

    2016-01-01

    Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m2 open-top chambers (OTCs) during three growing seasons to examine how warming (+0.8–1.2 °C) affects the fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from alpine tundra soils. Results showed that OTC warming increased soil CO2 efflux by 141% in the first growing season and by 45% in the second and third growing season. The mean CH4 flux of the three growing seasons was −27.6 and −16.7 μg CH4-C m−2h−1 in the warmed and control treatment, respectively. Fluxes of N2O switched between net uptake and emission. Warming didn’t significantly affect N2O emission during the first and the second growing season, but stimulated N2O uptake in the third growing season. The global warming potential of GHG was clearly dominated by soil CO2 effluxes (>99%) and was increased by the OTC warming. In conclusion, soil temperature is the main controlling factor for soil respiration in this tundra. Climate warming will lead to higher soil CO2 emissions but also to an enhanced CH4 uptake with an overall increase of the global warming potential for tundra. PMID:26880107

  6. Changing the thickness of two layers: i-ZnO nanorods, p-Cu2O and its influence on the carriers transport mechanism of the p-Cu2O/i-ZnO nanorods/n-IGZO heterojunction.

    PubMed

    Ke, Nguyen Huu; Trinh, Le Thi Tuyet; Phung, Pham Kim; Loan, Phan Thi Kieu; Tuan, Dao Anh; Truong, Nguyen Huu; Tran, Cao Vinh; Hung, Le Vu Tuan

    2016-01-01

    In this study, two layers: i-ZnO nanorods and p-Cu2O were fabricated by electrochemical deposition. The fabricating process was the initial formation of ZnO nanorods layer on the n-IGZO thin film which was prepared by sputtering method, then a p-Cu2O layer was deposited on top of rods to form the p-Cu2O/i-ZnO nanorods/n-ZnO heterojunction. The XRD, SEM, UV-VIS, I-V characteristics methods were used to define structure, optical and electrical properties of these heterojunction layers. The fabricating conditions and thickness of the Cu2O layers significantly affected to the formation, microstructure, electrical and optical properties of the junction. The length of i-ZnO nanorods layer in the structure of the heterojunction has strongly affected to the carriers transport mechanism and performance of this heterojunction.

  7. Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

    NASA Technical Reports Server (NTRS)

    Brown, L. R.; Toth, R. A.

    1985-01-01

    The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

  8. 40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment ENVIRONMENTAL... Manufacturing Pt. 98, Subpt. AA, Table AA -2 Table AA-2 to Subpart AA of Part 98—Kraft Lime Kiln and Calciner...

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

    PubMed

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

    2015-01-01

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

  10. Stimulation of N2 O emission by manure application to agricultural soils may largely offset carbon benefits: a global meta-analysis.

    PubMed

    Zhou, Minghua; Zhu, Bo; Wang, Shijie; Zhu, Xinyu; Vereecken, Harry; Brüggemann, Nicolas

    2017-10-01

    Animal manure application as organic fertilizer does not only sustain agricultural productivity and increase soil organic carbon (SOC) stocks, but also affects soil nitrogen cycling and nitrous oxide (N 2 O) emissions. However, given that the sign and magnitude of manure effects on soil N 2 O emissions is uncertain, the net climatic impact of manure application in arable land is unknown. Here, we performed a global meta-analysis using field experimental data published in peer-reviewed journals prior to December 2015. In this meta-analysis, we quantified the responses of N 2 O emissions to manure application relative to synthetic N fertilizer application from individual studies and analyzed manure characteristics, experimental duration, climate, and soil properties as explanatory factors. Manure application significantly increased N 2 O emissions by an average 32.7% (95% confidence interval: 5.1-58.2%) compared to application of synthetic N fertilizer alone. The significant stimulation of N 2 O emissions occurred following cattle and poultry manure applications, subsurface manure application, and raw manure application. Furthermore, the significant stimulatory effects on N 2 O emissions were also observed for warm temperate climate, acid soils (pH < 6.5), and soil texture classes of sandy loam and clay loam. Average direct N 2 O emission factors (EFs) of 1.87% and 0.24% were estimated for upland soils and rice paddy soils receiving manure application, respectively. Although manure application increased SOC stocks, our study suggested that the benefit of increasing SOC stocks as GHG sinks could be largely offset by stimulation of soil N 2 O emissions and aggravated by CH 4 emissions if, particularly for rice paddy soils, the stimulation of CH 4 emissions by manure application was taken into account. © 2017 John Wiley & Sons Ltd.

  11. Measuring and modeling of soil N2O emissions - How well are we doing?

    NASA Astrophysics Data System (ADS)

    Butterbach-Bahl, K.; Ralf, K.; Werner, C.; Wolf, B.

    2017-12-01

    Microbial processes in soils are the primarily source of atmospheric N2O. Fertilizer use to boost food and feed production of agricultural systems as well as nitrogen deposition to natural and semi-natural ecosystems due to emissions of NOx and NH3 from agriculture and energy production and re-deposition to terrestrial ecosystems has likely nearly doubled the pre-industrial source strength of soils for atmospheric N2O. Quantifying soil emissions and identifying mitigation options is becoming a major focus in the climate debate as N2O emissions from agricultural soils are a major contributor to the greenhouse gas footprint of agricultural systems, with agriculture incl. land use change contributing up to 30% to total anthropogenic GHG emissions. The increasing number of annual datasets show that soil emissions a) are largely depended on soil N availability and thus e.g. fertilizer application, b) vary with management (e.g. timing of fertilization, residue management, tillage), c) depend on soil properties such as organic matter content and pH, e) are affected by plant N uptake, and e) are controlled by environmental factors such as moisture and temperature regimes. It is remarkable that the magnitude of annual emissions is largely controlled by short-term N2O pulses occurring due to fertilization, wetting and drying or freezing and thawing of soils. All of this contributes to a notorious variability of soil N2O emissions in space and time. Overcoming this variability for quantification of source strengths and identifying tangible mitigation options requires targeted measuring approaches as well as the translation of our knowledge on mechanisms underlying emissions into process oriented models, which finally might be used for upscaling and scenario studies. This paper aims at reviewing current knowledge on measurements, modelling and upscaling of soil N2O emissions, thereby identifying short comes and uncertainties of the various approaches and fields for future

  12. New observations of stratospheric N2O5

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Toon, G. C.; Farmer, C. B.; Norton, R. H.; Namkung, J. S.

    1989-01-01

    The unequivocal detection of N2O5 in the stratosphere was reported by Toon et al. based on measurements of the absorption by the N2O5 bands at 1246 and 1720/cm in solar occulation spectra recorded at sunrise near 47 S latitude by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment during the Spacelab 3 (SL3) shuttle mission. Additional measurements and analysis of stratospheric N2O5 derived from the ATMOS/SL3 spectra are reported. The primary results are the detection and measurement of N2O5 absorption at sunset in the lower stratosphere, the inversion of a precise (approximately 10 percent) N2O5 sunrise vertical distribution between 25.5 and 37.5 km altitude, and the identification and measurement of absorption by the N2O5 743/cm band at sunrise. Assuming 4.32 x 10(sup -17) and 4.36 x 10(sup -17)/cm/molecule/sq cm respectively for the integrated intensities of the 1246 and 743/cm bands at stratospheric temperatures, retrieved volume mixing ratios in parts per billion by volume (ppbv) at sunrise (47 S latitude) are 1.32 + or - 0.34 at 37.5 km, 1.53 + or - 0.35 at 35.5 km, 1.63 + or - 0.36 at 33.5 km, 1.60 + or - 0.34 at 31.5 km, 1.43 + or - 0.30 at 29.5 km, 1.15 + or - 0.24 at 27.5 km, and 0.73 + or - 0.15 at 25.5 km. Retrieved VMRs in ppbv at sunset (30 N latitude) are 0.13 + or - 0.05 at 29.5 km, 0.14 + or - 0.05 at 27.5 km, and 0.10 + or - 0.04 at 25.5 km. Quoted error limits (1 sigma) include the error in the assumed band intensities (approximately 20 percent). Within the error limits of the measurements, the inferred mixing ratios at sunrise agree with diurnal photochemical model predictions obtained by two groups using current photochemical data. The measured mixing ratios at sunset are lower than the model predictions with differences of about a factor of 2 at 25 km altitude.

  13. Leachate treatment in landfills is a significant N2O source.

    PubMed

    Wang, Xiaojun; Jia, Mingsheng; Zhang, Chengliang; Chen, Shaohua; Cai, Zucong

    2017-10-15

    The importance of methane (CH 4 ) emissions from landfills has been extensively documented, while the nitrous oxide (N 2 O) emissions from landfills are considered negligible. In this study, three landfills were selected to measure CH 4 and N 2 O emissions using the static chamber method. Dongbu (DB) and Dongfu (DF) landfills, both located in Xiamen city, Fujian Province, were classified as sanitary. The former started to receive solid waste from Xiamen city in 2009, and the latter was closed in 2009. Nanjing (NJ) landfill, located in Nanjing county, Fujian Province, was classified as managed. Results showed that for the landfill reservoirs, CH 4 emissions were significant, while N 2 O emissions occurred mainly in operating areas (on average, 16.3 and 19.0mgN 2 Om -2 h -1 for DB and NJ landfills, respectively) and made a negligible contribution to the total greenhouse gas emissions in term of CO 2 equivalent. However, significant N 2 O emissions were observed in the leachate treatment systems of sanitary landfills and contributed 72.8% and 45.6% of total emissions in term of CO 2 equivalent in DB and DF landfills, respectively. The N 2 O emission factor (EF) of the leachate treatment systems was in the range of 8.9-11.9% of the removed nitrogen. The total N 2 O emissions from the leachate treatment systems of landfills in Xiamen city were estimated to be as high as 8.55gN 2 O-Ncapita -1 yr -1 . These results indicated that N 2 O emissions from leachate treatment systems of sanitary landfills were not negligible and should be included in national and/or local inventories of greenhouse gas emissions. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Ocean N2O Emissions : Recent Global Estimates and Anthropogenically Influenced Changes

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

    Oceanic N2O is produced by microbial activity during organic matter cycling in the subsurface ocean; its production mechanisms display sensitivity to ambient oxygen level. In the oxic ocean, N2O is produced as a byproduct during the oxidation of ammonia to nitrate, mediated by ammonia oxidizing bacteria and archea. N2O is also produced and consumed in sub-oxic and anoxic waters through the action of marine denitrifiers during the multi-step reduction of nitrate to gaseous nitrogen. The oceanic N2O distribution therefore displays significant heterogeneity with background levels of 10-20 nmol/l in the well-oxygenated ocean basins, high concentrations (> 40 nmol/l) in hypoxic waters, and N2O depletion in the core of ocean oxygen minimum zones (OMZs). Oceanic N2O emissions are estimated to account for up to a third of the pre-industrial N2O fluxes to the atmosphere, however the natural cycle of ocean N2O has been perturbed in recent decades by inputs of anthropogenically derived nutrient, and by the impacts of climate change. Anthropogenic nitrogen inputs (e.g., NOx and NHy from fossil fuel combustion and agricultural fertilizer) enter the ocean via atmospheric deposition and riverine fluxes, influencing oceanic N2O production via their impact on the marine organic matter cycle. In addition, climate variations associated with surface ocean warming affect oceanic circulation and nutrient transport pathways, influencing marine productivity and the ventilation of oxygen minimum zones. Recent studies have suggested that possible expansion of oceanic OMZs in a warming climate could lead to significant changes in N2O production and fluxes from these regions. We will summarise the current state of knowledge on the ocean N2O budget and net flux to the atmosphere. Recently reported estimates have been based on (i) empirical relationships derived from ocean tracer data (e.g., involving excess N2O and Apparent Oxygen Utilization (AOU) correlations), (ii) ocean biogeochemical

  15. Tracing changes in soil N transformations to explain the doubling of N2O emissions under elevated CO2 in the Giessen FACE

    NASA Astrophysics Data System (ADS)

    Moser, Gerald; Brenzinger, Kristof; Gorenflo, Andre; Clough, Tim; Braker, Gesche; Müller, Christoph

    2017-04-01

    To reduce the emissions of greenhouse gases (CO2, CH4 & N2O) it is important to quantify main sources and identify the respective ecosystem processes. While the main sources of N2O emissions in agro-ecosystems under current conditions are well known, the influence of a projected higher level of CO2 on the main ecosystem processes responsible for N2O emissions has not been investigated in detail. A major result of the Giessen FACE in a managed temperate grassland was that a +20% CO2 level caused a positive feedback due to increased emissions of N2O to 221% related to control condition. To be able to trace the sources of additional N2O emissions a 15N tracing study was conducted. We measured the N2O emission and its 15N signature, together with the 15N signature of soil and plant samples. The results were analyzed using a 15N tracing model which quantified the main changes in N transformation rates under elevated CO2. Directly after 15N fertilizer application a much higher dynamic of N transformations was observed than in the long run. Absolute mineralisation and DNRA rates were lower under elevated CO2 in the short term but higher in the long term. During the one year study period beginning with the 15N labelling a 1.8-fold increase of N2O emissions occurred under elevated CO2. The source of increased N2O was associated with NO3- in the first weeks after 15N application. Elevated CO2 affected denitrification rates, which resulted in increased N2O emissions due to a change of gene transcription rates (nosZ/(nirK+nirS)) and resulting enzyme activity (see: Brenzinger et al.). Here we show that the reported enhanced N2O emissions for the first 8 FACE years do prevail even in the long-term (> 15 years). The effect of elevated CO2 on N2O production/emission can be explained by altered activity ratios within a stable microbial community.

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

    PubMed

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

    2012-04-01

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

  17. Distinct N2O yields of AOB and AOA driven ammonia oxidation across a range of Oregon forest soils

    NASA Astrophysics Data System (ADS)

    Tzanakakis, Vasileios; Dörsch, Peter; Taylor, Anne E.; Giguere, Andrew T.; Bakken, Lars R.; Bottomley, Peter J.; Myrold, David D.

    2017-04-01

    Ammonia oxidation, as the first and limiting step of nitrification, is a critical process in global N cycling and an important source of nitrous oxide (N2O). Previous studies reported strong contrasts in potential nitrification rates and niche separation of ammonia oxidizing bacteria (AOB) and archaea (AOA) in three acid Oregon forest soils depending on tree stands. In the present study we were interested in the potential contribution of AOB and AOA to nitrification-derived N2O in these soils. We performed soil slurry incubations amended with NH4+ and determined the specific N2O yields of AOB and AOA using inhibitor techniques. Despite large differences in edaphic factors, potential nitrification rates, and niche partitioning, AOB- and AOA-mediated nitrification displayed fairly stable and distinct N2O yields. The N2O yields ranged from 0.11 to 0.17% for AOB and from 0.03 to 0.08% for AOA, which is in agreement with findings of previous pure culture and soil studies. Nitrite accumulation was observed in only one soil, upon NH4+ stimulation of AOB growth, without showing any effect on the apparent N2O yield. The partitioning between AOB and AOA activity was strongly affected by soil pH and nitrogen status, but there was no effect of these variables on the group-specific N2O yield. Together, this suggests that N2O yields of different ammonia oxidizing microorganisms are under tight biochemical control and that the potential contribution of nitrification to N2O emission in acid forest soils can be predicted from AOB - AOA partitioning.

  18. Simultaneous retrieval of the solar EUV flux and neutral thermospheric O, O2, N2, and temperature from twilight airglow

    NASA Technical Reports Server (NTRS)

    Fennelly, J. A.; Torr, D. G.; Richards, P. G.; Torr, M. R.

    1994-01-01

    We present a method to retrieve neutral thermospheric composition and the solar EUV flux from ground-based twilight optical measurements of the O(+) ((exp 2)P) 7320 A and O((exp 1)D) 6300 A airglow emissions. The parameters retrieved are the neutral temperature, the O, O2, N2 density profiles, and a scaling factor for the solar EUV flux spectrum. The temperature, solar EUV flux scaling factor, and atomic oxygen density are first retrieved from the 7320-A emission, which are then used with the 6300-A emission to retrieve the O2 and N2 densities. The retrieval techniques have been verified by computer simulations. We have shown that the retrieval technique is able to statistically retrieve values, between 200 and 400 km, within an average error of 3.1 + or - 0.6% for thermospheric temperature, 3.3 + or - 2.0% for atomic oxygen, 2.3 + or - 1.3% for molecular oxygen, and 2.4 + or - 1.3% for molecular nitrogen. The solar EUV flux scaling factor was found to have a retrieval error of 5.1 + or - 2.3%. All the above errors have a confidence level of 95%. The purpose of this paper is to prove the viability and usefulness of the retrieval technique by demonstrating the ability to retrieve known quantities under a realistic simulation of the measurement process, excluding systematic effects.

  19. Effect of fertilizer application on NO and N2O fluxes from agricultural fields

    NASA Astrophysics Data System (ADS)

    Harrison, Roy M.; Yamulki, Sirwan; Goulding, K. W. T.; Webster, C. P.

    1995-12-01

    Losses of fertilizer as NO and N2O were studied at Broadbalk field, Rothamsted Experimental Station in England, on which subplots have been subject to differing constant levels of fertilizer application for many years. Fluxes of NO and N2O were measured using open- and closed-chamber techniques, respectively. Fluxes from unfertilized soil ranged from 0.3 to 4.8 ng N m-2 s-1 for NO and 0.23 to 3.0 ng N m-2 s-1 for N2O. The corresponding fluxes from the plot with the highest fertilizer application (92 kg N ha-1 yr-1 as NH4NO3) ranged from 0.5 to 64 ng N m-2 s-1 for NO and 0.4 to 240 ng N m-2 s-1 for N2O. Application of increasing amounts of fertilizer substantially enhanced emission rates of both NO and N2O. However, the amount of increase was controlled by competition between the crop and the microorganisms for the available soil nutrients, and loss of N2O to the atmosphere increased sharply at superoptimal levels of fertilizer application. The fertilizer-derived NO and N2O emissions represented approximately 90% of the total emission of these gases during the 25-day sampling period after fertilizer application. The results suggest that while increasing the amount of fertilizer increases both NO and N2O fluxes simultaneously, the NO/N2O emission ratio decreases. Results from laboratory experiments showed that the magnitude of the fertilizer loss as N2O was strongly affected by the form of the applied fertilizer.

  20. Reducing N2O and NO emissions while sustaining crop productivity in a Chinese vegetable-cereal double cropping system.

    PubMed

    Yao, Zhisheng; Yan, Guangxuan; Zheng, Xunhua; Wang, Rui; Liu, Chunyan; Butterbach-Bahl, Klaus

    2017-12-01

    High nitrogen (N) inputs in Chinese vegetable and cereal productions played key roles in increasing crop yields. However, emissions of the potent greenhouse gas nitrous oxide (N 2 O) and atmospheric pollutant nitric oxide (NO) increased too. For lowering the environmental costs of crop production, it is essential to optimize N strategies to maintain high crop productivity, while reducing the associated N losses. We performed a 2 year-round field study regarding the effect of different combinations of poultry manure and chemical N fertilizers on crop yields, N use efficiency (NUE) and N 2 O and NO fluxes from a Welsh onion-winter wheat system in the North China Plain. Annual N 2 O and NO emissions averaged 1.14-3.82 kg N ha -1 yr -1 (or 5.54-13.06 g N kg -1 N uptake) and 0.57-1.87 kg N ha -1 yr -1 (or 2.78-6.38 g N kg -1 N uptake) over all treatments, respectively. Both N 2 O and NO emissions increased linearly with increasing total N inputs, and the mean annual direct emission factors (EF d ) were 0.39% for N 2 O and 0.19% for NO. Interestingly, the EF d for chemical N fertilizers (N 2 O: 0.42-0.48%; NO: 0.07-0.11%) was significantly lower than for manure N (N 2 O: 1.35%; NO: 0.76%). Besides, a negative power relationship between yield-scaled N 2 O, NO or N 2 O + NO emissions and NUE was observed, suggesting that improving NUE in crop production is crucial for increasing crop yields while decreasing nitrogenous gas release. Compared to the current farmers' fertilization rate, alternative practices with reduced chemical N fertilizers increased NUE and decreased annual N 2 O + NO emissions substantially, while crop yields remained unaffected. As a result, annual yield-scaled N 2 O + NO emissions were reduced by > 20%. Our study shows that a reduction of current application rates of chemical N fertilizers by 30-50% does not affect crop productivity, while at the same time N 2 O and NO emissions would be reduced significantly. Copyright © 2017 Elsevier Ltd. All rights

  1. N2O emissions from a nitrogen-enriched river

    USGS Publications Warehouse

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

    1999-01-01

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

  2. Under-recognized pathways of N2O production in coastal sediments: Increased fungal and chemo-denitrification in response to elevated N loading

    NASA Astrophysics Data System (ADS)

    Wankel, S. D.; Ziebis, W.; Buchwald, C.; Charoenpong, C.; de Beer, D.

    2016-02-01

    Increasing atmospheric levels of nitrous oxide (N2O), a greenhouse gas with a 100-year global warming potential more than 300 times that of carbon dioxide, have been strongly linked to human activities - especially the dramatic increase in nitrogen loading to aquatic and marine ecosystems worldwide. While many studies have demonstrated that N2O is formed through a number of microbially mediated pathways, the factors regulating the emission of N2O to the atmosphere remain difficult to predict and the global N2O budget remains poorly constrained. In particular, coastal ecosystems, which bear much of the brunt of anthropogenically-derived nitrogen from watershed inputs and rapidly growing coastal human populations, represent large gaps in our understanding of sources and sinks of atmospheric N2O. In large part, these challenges stem from the fact that a diverse number of N2O production pathways are operative under the dynamic redox conditions encountered in coastal and estuarine sediments, complicating our ability to understand their relative roles in N2O fluxes. Here, we use whole-core sediment incubations together with a suite of conventional and novel stable isotopic tools to identify both factors influencing N2O flux as well as those underlying biogeochemical processes responding to those factors. We find that under elevated N loading to coastal sediments, an observed increase in N2O flux to the overlying water is not mediated by direct bacterial activity, but instead is catalyzed by fungal denitrification and/or abiotic interactions with reduced iron (e.g., chemodenitrification). These findings shed new light on the complexity of nitrogen cycling in coastal sedimentary environments and highlight the need for an improved understanding of eukaryotic and abiotic processes in regulating fluxes of climatically important gases such as N2O.

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

    NASA Astrophysics Data System (ADS)

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

    2012-08-01

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

  4. Turbulence in Supercritical O2/H2 and C7H16/N2 Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, Josette; Harstad, Kenneth; Okong'o, Nora

    2003-01-01

    This report presents a study of numerical simulations of mixing layers developing between opposing flows of paired fluids under supercritical conditions, the purpose of the study being to elucidate chemical-species-specific aspects of turbulence. The simulations were performed for two different fluid pairs O2/H2 and C7H16/N2 at similar reduced initial pressures (reduced pressure is defined as pressure divided by critical pressure). Thermodynamically, O2/H2 behaves more nearly like an ideal mixture and has greater solubility, relative to C7H16/N2, which departs strongly from ideality. Because of a specified smaller initial density stratification, the C7H16/N2 layers exhibited greater levels of growth, global molecular mixing, and turbulence. However, smaller density gradients at the transitional state for the O2/H2 system were interpreted as indicating that locally, this system exhibits enhanced mixing as a consequence of its greater solubility and closer approach to ideality. These thermodynamic features were shown to affect entropy dissipation, which was found to be larger for O2/H2 and concentrated in high-density-gradient-magnitude regions that are distortions of the initial density-stratification boundary. In C7H16/N2, the regions of largest dissipation were found to lie in high-density-gradient-magnitude regions that result from mixing of the two fluids.

  5. Influences of Root Hydraulic Redistribution on N2O Emissions at AmeriFlux Sites

    NASA Astrophysics Data System (ADS)

    Fu, Congsheng; Lee, Xuhui; Griffis, Timothy J.; Wang, Guiling; Wei, Zhongwang

    2018-05-01

    It has long been suspected that root hydraulic redistribution (HR) affects the carbon and nitrogen cycles. Nitrous oxide (N2O) is an important greenhouse gas and is the primary stratospheric ozone-depleting substance. To our knowledge, the influences of HR on N2O emissions have not been investigated. Here we use the HR schemes of Ryel et al. and Amenu and Kumar incorporated into CLM4.5 to examine N2O emissions at five AmeriFlux sites. The results show that HR reduced N2O emissions by 28-92% in the four natural ecosystems experiencing a dry season, whereas it had a very limited effect on the Corn Belt site that has strong emissions but with no distinct dry season. We hypothesize that N2O emissions in ecosystems with a distinct dry season are likely overestimated by CENTURY-based Earth system models.

  6. Microbial CH4 and N2O Consumption in Acidic Wetlands

    PubMed Central

    Kolb, Steffen; Horn, Marcus A.

    2012-01-01

    Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

  7. Reaction of N2O5 with H2O on carbonaceous surfaces

    NASA Technical Reports Server (NTRS)

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

    1986-01-01

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

  8. Phylogenetic and functional potential links pH and N2O emissions in pasture soils.

    PubMed

    Samad, Md Sainur; Biswas, Ambarish; Bakken, Lars R; Clough, Timothy J; de Klein, Cecile A M; Richards, Karl G; Lanigan, Gary J; Morales, Sergio E

    2016-10-26

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N 2 O and N 2 emissions. Soil pH regulates the reduction of N 2 O to N 2 , however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N 2 O emission ratio (N 2 O/(NO + N 2 O + N 2 )) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N 2 O emission ratio and community changes. Soil pH was negatively associated with N 2 O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir &nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N 2 O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N 2 O emission ratio through more efficient conversion of N 2 O to N 2 .

  9. Phylogenetic and functional potential links pH and N2O emissions in pasture soils

    NASA Astrophysics Data System (ADS)

    Samad, M. D. Sainur; Biswas, Ambarish; Bakken, Lars R.; Clough, Timothy J.; de Klein, Cecile A. M.; Richards, Karl G.; Lanigan, Gary J.; Morales, Sergio E.

    2016-10-01

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N2O and N2 emissions. Soil pH regulates the reduction of N2O to N2, however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N2O emission ratio (N2O/(NO + N2O + N2)) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N2O emission ratio and community changes. Soil pH was negatively associated with N2O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir & nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N2O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N2O emission ratio through more efficient conversion of N2O to N2.

  10. Phylogenetic and functional potential links pH and N2O emissions in pasture soils

    PubMed Central

    Samad, M. d. Sainur; Biswas, Ambarish; Bakken, Lars R.; Clough, Timothy J.; de Klein, Cecile A. M.; Richards, Karl G.; Lanigan, Gary J.; Morales, Sergio E.

    2016-01-01

    Denitrification is mediated by microbial, and physicochemical, processes leading to nitrogen loss via N2O and N2 emissions. Soil pH regulates the reduction of N2O to N2, however, it can also affect microbial community composition and functional potential. Here we simultaneously test the link between pH, community composition, and the N2O emission ratio (N2O/(NO + N2O + N2)) in 13 temperate pasture soils. Physicochemical analysis, gas kinetics, 16S rRNA amplicon sequencing, metagenomic and quantitative PCR (of denitrifier genes: nirS, nirK, nosZI and nosZII) analysis were carried out to characterize each soil. We found strong evidence linking pH to both N2O emission ratio and community changes. Soil pH was negatively associated with N2O emission ratio, while being positively associated with both community diversity and total denitrification gene (nir & nos) abundance. Abundance of nosZII was positively linked to pH, and negatively linked to N2O emissions. Our results confirm that pH imposes a general selective pressure on the entire community and that this results in changes in emission potential. Our data also support the general model that with increased microbial diversity efficiency increases, demonstrated in this study with lowered N2O emission ratio through more efficient conversion of N2O to N2. PMID:27782174

  11. The effects of nitrogen fertilization on N2O emissions from a rubber plantation

    NASA Astrophysics Data System (ADS)

    Zhou, Wen-Jun; Ji, Hong-Li; Zhu, Jing; Zhang, Yi-Ping; Sha, Li-Qing; Liu, Yun-Tong; Zhang, Xiang; Zhao, Wei; Dong, Yu-Xin; Bai, Xiao-Long; Lin, You-Xin; Zhang, Jun-Hui; Zheng, Xun-Hua

    2016-06-01

    To gain the effects of N fertilizer applications on N2O emissions and local climate change in fertilized rubber (Hevea brasiliensis) plantations in the tropics, we measured N2O fluxes from fertilized (75 kg N ha-1 yr-1) and unfertilized rubber plantations at Xishuangbanna in southwest China over a 2-year period. The N2O emissions from the fertilized and unfertilized plots were 4.0 and 2.5 kg N ha-1 yr-1, respectively, and the N2O emission factor was 1.96%. Soil moisture, soil temperature, and the area weighted mean ammoniacal nitrogen (NH4+-N) content controlled the variations in N2O flux from the fertilized and unfertilized rubber plantations. NH4+-N did not influence temporal changes in N2O emissions from the trench, slope, or terrace plots, but controlled spatial variations in N2O emissions among the treatments. On a unit area basis, the 100-year carbon dioxide equivalence of the fertilized rubber plantation N2O offsets 5.8% and 31.5% of carbon sink of the rubber plantation and local tropical rainforest, respectively. When entire land area in Xishuangbanna is considered, N2O emissions from fertilized rubber plantations offset 17.1% of the tropical rainforest’s carbon sink. The results show that if tropical rainforests are converted to fertilized rubber plantations, regional N2O emissions may enhance local climate warming.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Technical Reports Server (NTRS)

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

    1974-01-01

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

  14. Disaggregated N2O emission factors in China based on cropping parameters create a robust approach to the IPCC Tier 2 methodology

    PubMed Central

    Shepherd, Anita; Yan, Xiaoyuan; Nayak, Dali; Newbold, Jamie; Moran, Dominic; Dhanoa, Mewa Singh; Goulding, Keith; Smith, Pete; Cardenas, Laura M.

    2015-01-01

    China accounts for a third of global nitrogen fertilizer consumption. Under an International Panel on Climate Change (IPCC) Tier 2 assessment, emission factors (EFs) are developed for the major crop types using country-specific data. IPCC advises a separate calculation for the direct nitrous oxide (N2O) emissions of rice cultivation from that of cropland and the consideration of the water regime used for irrigation. In this paper we combine these requirements in two independent analyses, using different data quality acceptance thresholds, to determine the influential parameters on emissions with which to disaggregate and create N2O EFs. Across China, the N2O EF for lowland horticulture was slightly higher (between 0.74% and 1.26% of fertilizer applied) than that for upland crops (values ranging between 0.40% and 1.54%), and significantly higher than for rice (values ranging between 0.29% and 0.66% on temporarily drained soils, and between 0.15% and 0.37% on un-drained soils). Higher EFs for rice were associated with longer periods of drained soil and the use of compound fertilizer; lower emissions were associated with the use of urea or acid soils. Higher EFs for upland crops were associated with clay soil, compound fertilizer or maize crops; lower EFs were associated with sandy soil and the use of urea. Variation in emissions for lowland vegetable crops was closely associated with crop type. The two independent analyses in this study produced consistent disaggregated N2O EFs for rice and mixed crops, showing that the use of influential cropping parameters can produce robust EFs for China. PMID:26865831

  15. Disaggregated N2O emission factors in China based on cropping parameters create a robust approach to the IPCC Tier 2 methodology

    NASA Astrophysics Data System (ADS)

    Shepherd, Anita; Yan, Xiaoyuan; Nayak, Dali; Newbold, Jamie; Moran, Dominic; Dhanoa, Mewa Singh; Goulding, Keith; Smith, Pete; Cardenas, Laura M.

    2015-12-01

    China accounts for a third of global nitrogen fertilizer consumption. Under an International Panel on Climate Change (IPCC) Tier 2 assessment, emission factors (EFs) are developed for the major crop types using country-specific data. IPCC advises a separate calculation for the direct nitrous oxide (N2O) emissions of rice cultivation from that of cropland and the consideration of the water regime used for irrigation. In this paper we combine these requirements in two independent analyses, using different data quality acceptance thresholds, to determine the influential parameters on emissions with which to disaggregate and create N2O EFs. Across China, the N2O EF for lowland horticulture was slightly higher (between 0.74% and 1.26% of fertilizer applied) than that for upland crops (values ranging between 0.40% and 1.54%), and significantly higher than for rice (values ranging between 0.29% and 0.66% on temporarily drained soils, and between 0.15% and 0.37% on un-drained soils). Higher EFs for rice were associated with longer periods of drained soil and the use of compound fertilizer; lower emissions were associated with the use of urea or acid soils. Higher EFs for upland crops were associated with clay soil, compound fertilizer or maize crops; lower EFs were associated with sandy soil and the use of urea. Variation in emissions for lowland vegetable crops was closely associated with crop type. The two independent analyses in this study produced consistent disaggregated N2O EFs for rice and mixed crops, showing that the use of influential cropping parameters can produce robust EFs for China.

  16. Fungi regulate response of N2O production to warming and grazing in a Tibetan grassland

    NASA Astrophysics Data System (ADS)

    Zhong, Lei; Wang, Shiping; Xu, Xingliang; Wang, Yanfen; Rui, Yichao; Zhou, Xiaoqi; Shen, Qinhua; Wang, Jinzhi; Jiang, Lili; Luo, Caiyun; Gu, Tianbao; Ma, Wenchao; Chen, Guanyi

    2018-03-01

    Lack of understanding of the effects of warming and winter grazing on soil fungal contribution to nitrous oxide (N2O) production has limited our ability to predict N2O fluxes under changes in climate and land use management, because soil fungi play an important role in driving terrestrial N cycling. Here, we examined the effects of 10 years' warming and winter grazing on soil N2O emissions potential in an alpine meadow. Our results showed that soil bacteria and fungi contributed 46 % and 54 % to nitrification, and 37 % and 63 % to denitrification, respectively. Neither warming nor winter grazing affected the activity of enzymes responsible for overall nitrification and denitrification. However, warming significantly increased the enzyme activity of bacterial nitrification and denitrification to 53 % and 55 %, respectively. Warming significantly decreased enzyme activity of fungal nitrification and denitrification to 47 % and 45 %, respectively, while winter grazing had no such effect. We conclude that soil fungi could be the main source for N2O production potential in the Tibetan alpine grasslands. Warming and winter grazing may not affect the potential for soil N2O production potential, but climate warming can alter biotic pathways responsible for N2O production. These findings indicate that characterizing how fungal nitrification/denitrification contributes to N2O production, as well as how it responds to environmental and land use changes, can advance our understanding of N cycling. Therefore, our results provide some new insights about ecological controls on N2O production and lead to refine greenhouse gas flux models.

  17. Maize endosperm-specific transcription factors O2 and PBF network the regulation of protein and starch synthesis

    PubMed Central

    Zhang, Zhiyong; Zheng, Xixi; Yang, Jun; Messing, Joachim; Wu, Yongrui

    2016-01-01

    The maize endosperm-specific transcription factors opaque2 (O2) and prolamine-box binding factor (PBF) regulate storage protein zein genes. We show that they also control starch synthesis. The starch content in the PbfRNAi and o2 mutants was reduced by ∼5% and 11%, respectively, compared with normal genotypes. In the double-mutant PbfRNAi;o2, starch was decreased by 25%. Transcriptome analysis reveals that >1,000 genes were affected in each of the two mutants and in the double mutant; these genes were mainly enriched in sugar and protein metabolism. Pyruvate orthophosphate dikinase 1 and 2 (PPDKs) and starch synthase III (SSIII) are critical components in the starch biosynthetic enzyme complex. The expression of PPDK1, PPDK2, and SSIII and their protein levels are further reduced in the double mutants as compared with the single mutants. When the promoters of these genes were analyzed, we found a prolamine box and an O2 box that can be additively transactivated by PBF and O2. Starch synthase IIa (SSIIa, encoding another starch synthase for amylopectin) and starch branching enzyme 1 (SBEI, encoding one of the two main starch branching enzymes) are not directly regulated by PBF and O2, but their protein levels are significantly decreased in the o2 mutant and are further decreased in the double mutant, indicating that o2 and PbfRNAi may affect the levels of some other transcription factor(s) or mRNA regulatory factor(s) that in turn would affect the transcript and protein levels of SSIIa and SBEI. These findings show that three important traits—nutritional quality, calories, and yield—are linked through the same transcription factors. PMID:27621432

  18. Simulating N2O emissions under different tillage systems of irrigated corn using RZ-Shaw model

    USDA-ARS?s Scientific Manuscript database

    Nitrous oxide (N2O) is potent greenhouse gas (GHG) and agriculture is a global source of N2O emissions from soil fertility management. Yet emissions vary by agronomic practices and environmental factors that govern soil moisture and temperature. Ecosystem models are important tools to estimate N2O e...

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

    NASA Technical Reports Server (NTRS)

    Banin, Amos

    1987-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

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

    PubMed

    Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

    2016-02-01

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

  2. Introducing ionic and/or hydrogen bonds into the SAM//Ga2O3 top-interface of Ag(TS)/S(CH2)nT//Ga2O3/EGaIn junctions.

    PubMed

    Bowers, Carleen M; Liao, Kung-Ching; Yoon, Hyo Jae; Rappoport, Dmitrij; Baghbanzadeh, Mostafa; Simeone, Felice C; Whitesides, George M

    2014-06-11

    Junctions with the structure Ag(TS)/S(CH2)nT//Ga2O3/EGaIn (where S(CH2)nT is a self-assembled monolayer, SAM, of n-alkanethiolate bearing a terminal functional group T) make it possible to examine the response of rates of charge transport by tunneling to changes in the strength of the interaction between T and Ga2O3. Introducing a series of Lewis acidic/basic functional groups (T = -OH, -SH, -CO2H, -CONH2, and -PO3H) at the terminus of the SAM gave values for the tunneling current density, J(V) in A/cm(2), that were indistinguishable (i.e., differed by less than a factor of 3) from the values observed with n-alkanethiolates of equivalent length. The insensitivity of the rate of tunneling to changes in the terminal functional group implies that replacing weak van der Waals contact interactions with stronger hydrogen- or ionic bonds at the T//Ga2O3 interface does not change the shape (i.e., the height or width) of the tunneling barrier enough to affect rates of charge transport. A comparison of the injection current, J0, for T = -CO2H, and T = -CH2CH3--two groups having similar extended lengths (in Å, or in numbers of non-hydrogen atoms)--suggests that both groups make indistinguishable contributions to the height of the tunneling barrier.

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

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

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

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

  4. Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  5. Does environmental exposure to the greenhouse gas, N2O, contribute to etiological factors in neurodevelopmental disorders? A mini-review of the evidence.

    PubMed

    Fluegge, Keith

    2016-10-01

    Neurodevelopmental disorders are increasing in prevalence worldwide. Previous work suggests that exposure to the environmental air pollutant and greenhouse gas - nitrous oxide (N 2 O) - may be an etiological factor in neurodevelopmental disorders through the targeting of several neural correlates. While a number of recent systematic reviews have addressed the role of general anesthesia in the surgical setting and neurodevelopmental outcomes, a narrative mini-review was conducted to first define and characterize the relevant variables (i.e., N 2 O, attention-deficit hyperactivity disorder [ADHD] and autism spectrum disorders [ASD]) and their potential interactions into a coherent, hypothesis-generating work. The narrative mini-review merges basic principles in environmental science, anesthesiology, and psychiatry to more fully develop the novel hypotheses that neurodevelopmental impairment found in conditions like ADHD and ASD may be due to exposure to the increasing air pollutant, N 2 O. The results of the present mini-review indicate that exposure to N 2 O, even at non-toxic doses, may modulate central neurotransmission and target many neural substrates directly implicated in neurodevelopmental disorders, including the glutamatergic, opioidergic, cholinergic, and dopaminergic systems. Epidemiological studies also indicate that early and repeated exposure to general anesthesia, including N 2 O, may contribute to later adverse neurodevelopmental outcomes in children. The current evidence and subsequent hypotheses suggest that a renewed interest be taken in the toxicological assessment of environmental N 2 O exposure using validated biomarkers and psychiatric endpoints. Given the relevance of N 2 O as a greenhouse gas, societies may also wish to engage in a more robust monitoring and reporting of N 2 O levels in the environment for climactic benefit as well. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Determination of the astrophysical 12N(p,γ)13O reaction rate from the 2H(12N,13O)n reaction and its astrophysical implications

    NASA Astrophysics Data System (ADS)

    Guo, B.; Su, J.; Li, Z. H.; Wang, Y. B.; Yan, S. Q.; Li, Y. J.; Shu, N. C.; Han, Y. L.; Bai, X. X.; Chen, Y. S.; Liu, W. P.; Yamaguchi, H.; Binh, D. N.; Hashimoto, T.; Hayakawa, S.; Kahl, D.; Kubono, S.; He, J. J.; Hu, J.; Xu, S. W.; Iwasa, N.; Kume, N.; Li, Z. H.

    2013-01-01

    The evolution of massive stars with very low-metallicities depends critically on the amount of CNO nuclides which they produce. The 12N(p,γ)13O reaction is an important branching point in the rap processes, which are believed to be alternative paths to the slow 3α process for producing CNO seed nuclei and thus could change the fate of massive stars. In the present work, the angular distribution of the 2H(12N, 13O)n proton transfer reaction at Ec.m.=8.4 MeV has been measured for the first time. Based on the Johnson-Soper approach, the square of the asymptotic normalization coefficient (ANC) for the virtual decay of 13Og.s. → 12N+p was extracted to be 3.92±1.47 fm-1 from the measured angular distribution and utilized to compute the direct component in the 12N(p,γ)13O reaction. The direct astrophysical S factor at zero energy was then found to be 0.39±0.15 keV b. By considering the direct capture into the ground state of 13O, the resonant capture via the first excited state of 13O and their interference, we determined the total astrophysical S factors and rates of the 12N(p,γ)13O reaction. The new rate is two orders of magnitude slower than that from the REACLIB compilation. Our reaction network calculations with the present rate imply that 12N(p,γ)13O will only compete successfully with the β+ decay of 12N at higher (˜2 orders of magnitude) densities than initially predicted.

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

    NASA Astrophysics Data System (ADS)

    Khatami Firoozabadi, Seyed Reza

    of fragmentation (prior or after ignition) and the number of fragments depended on the type of the lignite and on the particle shape. Temperatures and burnout times of particles were also affected by the combustion mode. In nearly all bituminous and biomass particles combustion, sooty envelope flames were formed around the particles. Replacement of background N 2 by CO2 gas decreased the average soot volume fraction, fv, whereas increasing O2 from 20% to 30--40% increased the fv and then further increasing O2 to 100% decreased the soot volume fraction drastically. bituminous coal particle flames generated lower soot volume fractions in the range 2x10 -5--9x10-5, depending on O2 mole fraction. Moreover, biomass particle flames were optically thin and of equal-sized at all O2 mole fractions. (Abstract shortened by UMI.).

  8. Heterogeneous interaction of SiO2 with N2O5: aerosol flow tube and single particle optical levitation-Raman spectroscopy studies.

    PubMed

    Tang, M J; Camp, J C J; Rkiouak, L; McGregor, J; Watson, I M; Cox, R A; Kalberer, M; Ward, A D; Pope, F D

    2014-09-25

    Silica (SiO2) is an important mineral present in atmospheric mineral dust particles, and the heterogeneous reaction of N2O5 on atmospheric aerosol is one of the major pathways to remove nitrogen oxides from the atmosphere. The heterogeneous reaction of N2O5 with SiO2 has only been investigated by two studies previously, and the reported uptake coefficients differ by a factor of >10. In this work two complementary laboratory techniques were used to study the heterogeneous reaction of SiO2 particles with N2O5 at room temperature and at different relative humidities (RHs). The uptake coefficients of N2O5, γ(N2O5), were determined to be (7.2 ± 0.6) × 10(-3) (1σ) at 7% RH and (5.3 ± 0.8) × 10(-3) (1σ) at 40% RH for SiO2 particles, using the aerosol flow tube technique. We show that γ(N2O5) determined in this work can be reconciled with the two previous studies by accounting for the difference in geometric and BET derived aerosol surface areas. To probe the particle phase chemistry, individual micrometer sized SiO2 particles were optically levitated and exposed to a continuous flow of N2O5 at different RHs, and the composition of levitated particles was monitored online using Raman spectroscopy. This study represents the first investigation into the heterogeneous reactions of levitated individual SiO2 particles as a surrogate for mineral dust. Relative humidity was found to play a critical role: while no significant change of particle composition was observed by Raman spectroscopy during exposure to N2O5 at RH of <2%, increasing the RH led to the formation of nitrate species on the particle surface which could be completely removed after decreasing the RH back to <2%. This can be explained by the partitioning of HNO3 between the gas and adsorbed phases. The atmospheric implications of this work are discussed.

  9. N2O, NO, N2 and CO2 emissions from tropical savanna and grassland of northern Australia: an incubation experiment with intact soil cores

    NASA Astrophysics Data System (ADS)

    Werner, C.; Reiser, K.; Dannenmann, M.; Hutley, L. B.; Jacobeit, J.; Butterbach-Bahl, K.

    2014-11-01

    Strong seasonal variability of hygric and thermal soil conditions are a defining environmental feature in northern Australia. However, how such changes affect the soil-atmosphere exchange of nitrous oxide (N2O), nitric oxide (NO) and dinitrogen (N2) is still not well explored. By incubating intact soil cores from four sites (three savanna, one pasture) under controlled soil temperatures (ST) and soil moisture (SM) we investigated the release of the trace gas fluxes of N2O, NO and carbon dioxide (CO2). Furthermore, the release of N2 due to denitrification was measured using the helium gas flow soil core technique. Under dry pre-incubation conditions NO and N2O emissions were very low (<7.0 ± 5.0 μg NO-N m-2 h-1; <0.0 ± 1.4 μg N2O-N m-2 h-1) or in the case of N2O, even a net soil uptake was observed. Substantial NO (max: 306.5 μg N m-2 h-1) and relatively small N2O pulse emissions (max: 5.8 ± 5.0 μg N m-2 h-1) were recorded following soil wetting, but these pulses were short lived, lasting only up to 3 days. The total atmospheric loss of nitrogen was generally dominated by N2 emissions (82.4-99.3% of total N lost), although NO emissions contributed almost 43.2% to the total atmospheric nitrogen loss at 50% SM and 30 °C ST incubation settings (the contribution of N2 at these soil conditions was only 53.2%). N2O emissions were systematically higher for 3 of 12 sample locations, which indicates substantial spatial variability at site level, but on average soils acted as weak N2O sources or even sinks. By using a conservative upscale approach we estimate total annual emissions from savanna soils to average 0.12 kg N ha-1 yr-1 (N2O), 0.68 kg N ha-1 yr-1 (NO) and 6.65 kg N ha-1 yr-1 (N2). The analysis of long-term SM and ST records makes it clear that extreme soil saturation that can lead to high N2O and N2 emissions only occurs a few days per year and thus has little impact on the annual total. The potential contribution of nitrogen released due to pulse events

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

    PubMed

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

    2002-09-11

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

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  12. CO2 and N2O emissions from Lou soils of greenhouse tomato fields under aerated irrigation

    NASA Astrophysics Data System (ADS)

    Hou, Huijing; Chen, Hui; Cai, Huanjie; Yang, Fan; Li, Dan; Wang, Fangtong

    2016-05-01

    The change of O2 content in soil caused by aerated irrigation (AI) must inevitably affect the production and emissions of CO2 and N2O from soils. This paper described in-situ observation of CO2 and N2O emissions from AI soils with static chamber-GC technique, in order to reveal the effects of AI on CO2 and N2O emissions from soils of greenhouse tomato fields in autumn-winter season. CO2 and N2O emissions from AI soils mainly concentrated in the blooming and fruit setting period compared to other periods. AI increased cumulative emissions of CO2 and N2O by 11.8% (p = 0.394) and 10.0% (p = 0.480), respectively, compared to the control. The integrative global warming potential of CO2 and N2O on a 100-year horizon for the AI treatment was 6430.60 kg ha-1, increased by 11.7% compared with that for the control (p = 0.356). Both the emissions of CO2 and N2O from AI soils had the exponential positive correlation with soil water-filled pore space (WFPS). The highest peak of CO2 and N2O fluxes from AI soils was observed at 46.7% and 47.5% WFPS, with WFPS ranging from 43.3% to 51.5% and from 45.6% to 52.3% during the whole growth stage, respectively. In addition, the average yield for the AI treatment (34.52 t ha-1) was significantly greater (17.4%) compared with that of the control (p = 0.018). These results suggest that AI do not significantly increase the integrative greenhouse effect caused by CO2 and N2O from soils of greenhouse tomato fields, but significantly increase the tomato yield. The research results provide certain theoretical foundation and scientific basis for accurately evaluating the farmland ecological effect of AI technique.

  13. Microcosm N2O emissions wth calibration

    EPA Pesticide Factsheets

    The dataset consists of measurements of soil nitrous oxide emissions from soils under three different amendments: glucose, cellulose, and manure. Data includes the four isotopomers of nitrous oxide (14N15N16O, 15N14N16O, 14N14N18O, 14N14N16O), and the site preference.This dataset is associated with the following publication:Chen , H., D. Williams , P. Deshmukh , F. Birgand, B. Maxwell, and J. Walker. Probing the Biological Sources of Soil N2O Emissions by Quantum Cascade Laser-Based 15N Isotopocule Analysis. SOIL SCIENCE SOCIETY OF AMERICA JOURNAL. Soil Science Society of America, Madison, WI, USA, 100(0): 175-181, (2016).

  14. Aircraft Observations of Nitrous Oxide (N2O) in the San Joaquin Valley of California

    NASA Astrophysics Data System (ADS)

    Muto, S.; Herrera, S.; Pusede, S.

    2017-12-01

    Agriculture is the largest source of anthropogenic nitrous oxide (N2O) in the U.S. While it is generally known which processes produce N2O, there is considerable uncertainty in controls over N2O emissions. Factors that determine N2O fluxes, such as soil properties and manure management, are highly variable in space and time, and, as a result, it has proven difficult to upscale chamber-derived soil flux measurements to regional spatial scales. Aircraft observations provide a regional picture of the N2O spatial distribution, but, because N2O is very long-lived, it is challenging to attribute measured concentrations of N2O to distinct local sources, especially over areas with complex and integrated land use. This study takes advantage of a novel aircraft N2O dataset collected onboard the low-flying, slow-moving NASA C-23 Sherpa in the San Joaquin Valley (SJV) of California, a region with a variety of N2O sources, including dairies, feedlots, fertilized cropland, and industrial facilities. With these measurements, we link observed N2O enhancements to specific sources at sub-inventory spatial scales. We compare our results with area-weighted emission profiles obtained by integrating detailed emission inventory data, agricultural statistics, and GIS source mapping.

  15. Photoeletrocatalytic activity of an n-ZnO/p-Cu2O/n-TNA ternary heterojunction electrode for tetracycline degradation.

    PubMed

    Li, Jinhua; Lv, Shubin; Liu, Yanbiao; Bai, Jing; Zhou, Baoxue; Hu, Xiaofang

    2013-11-15

    In this study, a novel ternary heterojunction n-ZnO/p-Cu2O/n-TiO2 nanotube arrays (n-ZnO/p-Cu2O/n-TNA) nanophotocatalyst with a sandwich-like nanostructure was constructed and applied for the photoelectrocatalytic (PEC) degradation of typical PPCPs, tetracycline (TC). The ternary heterojunction n-ZnO/p-Cu2O/n-TNA was obtained by depositing Cu2O on the surface of TNA via sonoelectrochemical deposition (SED) and subsequently building a layer of ZnO onto the p-Cu2O/n-TNA surface through hydrothermal synthesis. After being deposited by the Cu2O, the absorption-band edge of the p-Cu2O/n-TNA was obviously red-shifted to the visible region (to 505 nm), and the band gap was reduced from its original 3.20 eV to 2.46 eV. The band gap absorption edge of the ternary n-ZnO/p-Cu2O/n-TNA is similar to that of p-Cu2O/n-TN and extends the visible spectrum absorption to 510 nm, corresponding to an Eg value of about 2.43 eV. Under illumination of visible light, the photocurrent density of the ternary heterojunction n-ZnO/p-Cu2O/n-TNA electrode at 0.5 V (vs. Ag/AgCl) was more than 106 times as high as that of the pure TNAs electrode, 3.6 times as high as that of the binary heterojunction p-Cu2O/n-TNA electrode. The degradation of TC indicated that the ternary heterojunction n-ZnO/p-Cu2O/n-TNA electrode maintained a very high photoelectrocatalytic activity and excellent stability and reliability. Such kind of ternary heterojunction electrode material has a broad application prospect not only in pollution control but also in many other fields. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Carbon dioxide(CO2) and nitrous oxide (N2O) fluxes in an agro-ecosystems under changing physical and biological conditions

    NASA Astrophysics Data System (ADS)

    Liang, L.; Eberwein, J.; Oikawa, P.; Jenerette, D.; Grantz, D. A.

    2013-12-01

    Liyin Liang1, Jennifer Eberwein1, Patty Oikawa1, Darrel Jenerette1, David Grantz1 1Department of Botany and Plant Sciences, University of California, Riverside, CA 92521, USA Carbon dioxide (CO2) and nitrous oxide (N2O) are the major greenhouse gases and together produce a strong positive radiative forcing in the atmosphere. The fluxes of CO2 and N2O from soil to atmosphere vary with physical and biological factors, e.g., temperature, soil moisture, pH value, soil organic carbon contents, microorganism communities and so on. Understanding the interactions among these factors is critical to estimation of CO2 and N2O emissions. We investigate these fluxes in an extreme production environment with very high maximum temperatures, at the agricultural experiment station of University of California-Desert Research Center in the Imperial Valley of southern California. In this research, we measured the CO2 and N2O fluxes from soil incubation under controlled laboratory conditions, in surface chambers under field conditions and by eddy covariance. We explore the variation of CO2 and N2O fluxes and relationship between them in this extreme biofuel production environment. The discrete chamber measurements showed that the N2O flux in our field sites is 2.39×0.70 μg N m-2 hr-1, with a 95% confidence interval (CI) from 0.86 to 3.92 μg N m-2 hr-1. Compared to the previous reported value (0.45~26.26 μg N m-2 hr-1) of N2O flux in California, the N2O flux from biofuel crop land is in the lower level, although more observations should be took to confirm it. The N2O flux also shows very high variability within a field of biomass Sorghum, ranging from 0.40 to 8.19 μg N m-2 hr-1 across 11 sites owning to the high variability of physical and biological factors. Soil incubation measurements will be conducted to identify the sources of this variability. The eddy covariance measurements will allow calculation of the CO2 and N2O emissions at the ecosystem level as a step in quantifying

  17. Surveying N2O-producing pathways in bacteria.

    PubMed

    Stein, Lisa Y

    2011-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  19. Organically fertilized tea plantation stimulates N2O emissions and lowers NO fluxes in subtropical China

    NASA Astrophysics Data System (ADS)

    Yao, Z.; Wei, Y.; Liu, C.; Zheng, X.; Xie, B.

    2015-07-01

    Tea plantations are rapidly expanding in China and other countries in the tropical and subtropical zones, but so far there are very few studies including direct measurements on nitrogenous gases fluxes from tea plantations. On the basis of 2 year field measurements from 2012 to 2014, we provided an insight into the assessment of annual nitrous oxide (N2O) and nitric oxide (NO) fluxes from Chinese subtropical tea plantations under three practices of conventional urea application, alternative oilcake incorporation and no nitrogen fertilization. Clearly, the N2O and NO fluxes exhibited large intra- and inter-annual variations, and furthermore their temporal variability could be well described by a combination of soil environmental factors including soil mineral N, water-filled pore space and temperature, based on a revised "hole-in-the-pipe" model. Averaged over 2 years, annual background N2O and NO emissions were approximately 4.0 and 1.6 kg N ha-1 yr-1, respectively. Compared to no nitrogen fertilization, both urea and oilcake application significantly stimulated annual N2O and NO emissions, amounting to 14.4-32.7 kg N2O-N ha-1 yr-1 and at least 12.3-19.4 kg NO-N ha-1 yr-1. In comparison with conventional urea treatment, on average, the application of organic fertilizer significantly increased N2O emission by 71 % but decreased NO emission by 22 %. Although the magnitude of N2O and NO fluxes was substantially influenced by N source, the annual direct emission factors of fertilizer N were estimated to be 2.8-5.9, 2.7-4.0 and 6.8-9.1 % for N2O, NO and N2O + NO, respectively, which are significantly higher than those defaults for global upland croplands. This indicated that the rarely determined N2O and NO formation appeared to be a significant pathway in the nitrogen cycle of tea plantations, which are a potential source of national nitrogenous gases inventory.

  20. Organically fertilized tea plantation stimulates N2O emissions and lowers NO fluxes in subtropical China

    NASA Astrophysics Data System (ADS)

    Yao, Z.; Wei, Y.; Liu, C.; Zheng, X.; Xie, B.

    2015-10-01

    Tea plantations are rapidly expanding in China and other countries in the tropical and subtropical zones, but so far there are very few studies including direct measurements of nitrogenous gas fluxes from tea plantations. On the basis of 2-year field measurements from 2012 to 2014, we provided an insight into the assessment of annual nitrous oxide (N2O) and nitric oxide (NO) fluxes from Chinese subtropical tea plantations under three practices of conventional urea application, alternative oilcake incorporation and no nitrogen fertilization. Clearly, the N2O and NO fluxes exhibited large intra- and inter-annual variations, and furthermore, their temporal variability could be well described by a combination of soil environmental factors including soil mineral N, water-filled pore space and temperature, based on a revised "hole-in-the-pipe" model. Averaged over a 2-year study, annual background N2O and NO emissions were approximately 4.0 and 1.6 kg N ha-1 yr-1, respectively. Compared to no nitrogen fertilization, both urea and oilcake application significantly stimulated annual N2O and NO emissions, amounting to 14.4-32.7 kg N2O-N ha-1 yr-1 and at least 12.3-19.4 kg NO-N ha-1 yr-1, respectively. In comparison with conventional urea treatment, on average, the application of organic fertilizer significantly increased N2O emission by 71 % but decreased NO emission by 22 %. Although the magnitude of N2O and NO fluxes was substantially influenced by the source of N, the annual direct emission factors of N fertilizer were estimated to be 2.8-5.9, 2.7-4.0 and 6.8-9.1 % for N2O, NO and N2O+NO, respectively, which are significantly higher than those defaults for global upland croplands. This indicated that the rarely determined N2O and NO formation appeared to be a significant pathway in the nitrogen cycle of tea plantations, which are a potential source of national nitrogenous gases inventory.

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

    PubMed Central

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

    2017-01-01

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

  2. [Enhanced remediation of 4-chloronitrobenzene contaminated groundwater with nanoscale zero-valence iron (nZVI) catalyzed hydrogen peroxide (H2O2)].

    PubMed

    Fu, Rong-Bing

    2014-04-01

    Chemical oxidation-reduction technology is an important way to quickly remedy contaminated groundwater. Nanoscale zero-valent iron (nZVI) was produced by liquid-phase reduction using FeSO4 and NaBH4, and characterized by SEM and XRD. The remediation of 4-chloronitrobezene (4-CINB) contaminated groundwater at ambient temperature and pressure was conducted with the nZVI catalytic H2O2 process, and the affecting factors and degradation mechanisms were investigated. The results indicated that under initial pH 3.0 at the temperature of 30 degrees C, after 30 mins of reaction, 4-ClNB in groundwater was completely degraded when the concentrations of nZVI and H2O2 were 268.8 mg x L(-1) and 4.90 mmol x L(-1), respectively. 4-chloronitrosobenzene, 4-chlorophenylhydroxylamine, 4-chloroazoxybenzene, 4-chloroaniline, 4-chloroazobenzene, 4-benzoquinone, acetic acid, formic acid, oxalic acid and chlorine ion were identified as the major intermediates of 4-ClNB degradation after the process. A tentative pathway for the degradation of 4-ClNB was proposed.

  3. [Zn(phen)(O,N,O)(H2O)] and [Zn(phen)(O,N)(H2O)] with O,N,O is 2,6-dipicolinate and N,O is L-threoninate: synthesis, characterization, and biomedical properties.

    PubMed

    Chin, Lee-Fang; Kong, Siew-Ming; Seng, Hoi-Ling; Tiong, Yee-Lian; Neo, Kian-Eang; Maah, Mohd Jamil; Khoo, Alan Soo-Beng; Ahmad, Munirah; Hor, Tzi-Sum Andy; Lee, Hong-Boon; San, Swee-Lan; Chye, Soi-Moi; Ng, Chew-Hee

    2012-10-01

    Two ternary Zn(II) complexes, with 1,10-phenanthroline (phen) as the main ligand and a carboxylate-containing ligand [dipicolinate (dipico) or L-threoninate (L-Thr)] as the subsidiary ligand, were prepared and characterized by elemental analysis, Fourier transform IR, UV, and fluorescence spectroscopy, X-ray diffraction, molar conductivity, and electrospray ionization mass spectrometry. X-ray structure analysis shows that both [Zn(phen)(dipico)(H(2)O)]·H(2)O (1) and [Zn(phen)(L-Thr)(H(2)O)Cl]·2H(2)O (2) have octahedral geometry about the Zn(II) atom. Both complexes can inhibit topoisomerase I, and have better anticancer activity than cisplatin against nasopharyngeal cancer cell lines, HK1 and HONE-1, with concentrations causing 50 % inhibition of cell proliferation (IC(50)) in the low micromolar range. Complex 2 has the highest therapeutic index for HK1. Both Zn(II) complexes can induce cell death by apoptosis. Changing the subsidiary ligand in the Zn(II) complexes affects the UV-fluorescence spectral properties of the coordinated phen ligand, the binding affinity for some DNA sequences, nucleobase sequence-selective binding, the phase at which cell cycle progression was arrested for treated cancer cells, and their therapeutic index.

  4. N2O production, a widespread trait in fungi

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  5. N2O production, a widespread trait in fungi.

    PubMed

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

    2015-04-20

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

  6. Biochar reduces efficiency of nitrification inhibitor 3,4-dymethylpyrazole phospate (DMPP) mitigating N2O emissions.

    NASA Astrophysics Data System (ADS)

    Fuertes-Mendizábal, Teresa; Huérfano, Ximena; Menéndez, Sergio; González-Murua, Carmen; Begoña González-Moro, Mª; Ippolito, James; Kamann, Claudia; Wrage-Mönnig, Nicole; Borchard, Nils; Cayuela, Maria Luz; Spokas, Kurt; Sigua, Gilbert; Novak, Jeff; Estavillo, José Mª

    2017-04-01

    Nitrous oxide (N2O) is the strongest greenhouse gas associated with agricultural soils. Current agricultural practices, based on the use of N fertilizers, can lead to environmental N losses, with some losses occurring as N2O emissions. Among the strategies suggested by the Intergovernmental Panel on Climate Change to decrease N losses through agriculture is the utilization of nitrification inhibitors, such as DMPP (3,4-dimethylpyrazole phosphate). This compound inhibits nitrification, thus reducing N2O emissions. However, the efficiency of DMPP might be affected by soil amendments. One soil amendment is biochar, which typically increases soil C, can reduce N2O emissions, affect the retention of water, and alter the C and N cycle. Nevertheless, these effects are not uniformly observed across varying soil types, N fertilization schemes and biochar properties. Assuming that both DMPP and biochars with C/N > 30 ratios are presumably able to reduce soil N2O emissions, the aim of this study was to evaluate the synergic effect of a woody biochar applied in combination with DMPP on N2O emissions. For this purpose, a laboratory incubation study was conducted with a silt loam grassland soil and a biochar obtained from Pinus taeda at 500°C. The experimental design consisted of an arrangement including two biochar levels (0 and 2% (w/w)), three fertilization levels (unfertilized, fertilized and fertilized+DMPP) and two soil water content levels (40% and 80% of water filled pore space, WFPS), giving rise to 12 different individual treatments with four replications of each treatment. Soil N2O emissions were monitored over the incubation period (163 days). Results showed that DMPP reduced N2O emissions to levels comparable to the unfertilized controls. Biochar showed ability to mitigate N2O emissions only at the low soil water content (40% WFPS). However, when DMPP was applied to the biochar amended soil, a counteracting effect was observed, since the reduction in N2O emissions

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  8. Linking N2O emissions from biochar-amended soil to the structure and function of the N-cycling microbial community

    PubMed Central

    Harter, Johannes; Krause, Hans-Martin; Schuettler, Stefanie; Ruser, Reiner; Fromme, Markus; Scholten, Thomas; Kappler, Andreas; Behrens, Sebastian

    2014-01-01

    Nitrous oxide (N2O) contributes 8% to global greenhouse gas emissions. Agricultural sources represent about 60% of anthropogenic N2O emissions. Most agricultural N2O emissions are due to increased fertilizer application. A considerable fraction of nitrogen fertilizers are converted to N2O by microbiological processes (that is, nitrification and denitrification). Soil amended with biochar (charcoal created by pyrolysis of biomass) has been demonstrated to increase crop yield, improve soil quality and affect greenhouse gas emissions, for example, reduce N2O emissions. Despite several studies on variations in the general microbial community structure due to soil biochar amendment, hitherto the specific role of the nitrogen cycling microbial community in mitigating soil N2O emissions has not been subject of systematic investigation. We performed a microcosm study with a water-saturated soil amended with different amounts (0%, 2% and 10% (w/w)) of high-temperature biochar. By quantifying the abundance and activity of functional marker genes of microbial nitrogen fixation (nifH), nitrification (amoA) and denitrification (nirK, nirS and nosZ) using quantitative PCR we found that biochar addition enhanced microbial nitrous oxide reduction and increased the abundance of microorganisms capable of N2-fixation. Soil biochar amendment increased the relative gene and transcript copy numbers of the nosZ-encoded bacterial N2O reductase, suggesting a mechanistic link to the observed reduction in N2O emissions. Our findings contribute to a better understanding of the impact of biochar on the nitrogen cycling microbial community and the consequences of soil biochar amendment for microbial nitrogen transformation processes and N2O emissions from soil. PMID:24067258

  9. Temporal integration of soil N2O fluxes: validation of IPNOA station automatic chamber prototype.

    PubMed

    Laville, P; Bosco, S; Volpi, I; Virgili, G; Neri, S; Continanza, D; Bonari, E

    2017-09-04

    The assessment of nitrous oxide (N 2 O) fluxes from agricultural soil surfaces still poses a major challenge to the scientific community. The evaluations of integrated soil fluxes of N 2 O are difficult owing to their lower emissions when compared with CO 2 . These emissions are also sporadic as environmental conditions act as a limiting factor. A station prototype was developed to integrate annual N 2 O and CO 2 emissions using an automatic chamber technique and infrared spectrometers within the LIFE project (IPNOA: LIFE11 ENV/IT/00032). It was installed from June 2014 to October 2015 in an experimental maize field in Tuscany. The detection limits for the fluxes were evaluated up to 1.6 ng N-N 2 O m 2  s -1 and 0.3 μg C-CO 2  m 2  s -1 . A cross-comparison carried out in September 2015 with the "mobile IPNOA prototype"; a high-sensibility transportable instrument already validated provided evidence of very similar values and highlighted flux assessment limitations according to the gas analyzers used. The permanent monitoring device showed that temporal distribution of N 2 O fluxes can be very large and discontinuous over short periods of less than 10 days and that N 2 O fluxes were below the detection limit of the instrumentation during approximately 70% of the measurement time. The N 2 O emission factors were estimated to 1.9% in 2014 and 1.7% in 2015, within the range of IPCC assessments.

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

    NASA Technical Reports Server (NTRS)

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

    1996-01-01

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

  11. Soil biochar amendment shapes the composition of N2O-reducing microbial communities.

    PubMed

    Harter, Johannes; Weigold, Pascal; El-Hadidi, Mohamed; Huson, Daniel H; Kappler, Andreas; Behrens, Sebastian

    2016-08-15

    Soil biochar amendment has been described as a promising tool to improve soil quality, sequester carbon, and mitigate nitrous oxide (N2O) emissions. N2O is a potent greenhouse gas. The main sources of N2O in soils are microbially-mediated nitrogen transformation processes such as nitrification and denitrification. While previous studies have focused on the link between N2O emission mitigation and the abundance and activity of N2O-reducing microorganisms in biochar-amended soils, the impact of biochar on the taxonomic composition of the nosZ gene carrying soil microbial community has not been subject of systematic study to date. We used 454 pyrosequencing in order to study the microbial diversity in biochar-amended and biochar-free soil microcosms. We sequenced bacterial 16S rRNA gene amplicons as well as fragments of common (typical) nosZ genes and the recently described 'atypical' nosZ genes. The aim was to describe biochar-induced shifts in general bacterial community diversity and taxonomic variations among the nosZ gene containing N2O-reducing microbial communities. While soil biochar amendment significantly altered the 16S rRNA gene-based community composition and structure, it also led to the development of distinct functional traits capable of N2O reduction containing typical and atypical nosZ genes related to nosZ genes found in Pseudomonas stutzeri and Pedobacter saltans, respectively. Our results showed that biochar amendment can affect the relative abundance and taxonomic composition of N2O-reducing functional microbial traits in soil. Thus these findings broaden our knowledge on the impact of biochar on soil microbial community composition and nitrogen cycling. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Temperature dependent electrical characterisation of Pt/HfO{sub 2}/n-GaN metal-insulator-semiconductor (MIS) Schottky diodes

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

    Shetty, Arjun, E-mail: arjun@ece.iisc.ernet.in; Vinoy, K. J.; Roul, Basanta

    2015-09-15

    This paper reports an improvement in Pt/n-GaN metal-semiconductor (MS) Schottky diode characteristics by the introduction of a layer of HfO{sub 2} (5 nm) between the metal and semiconductor interface. The resulting Pt/HfO{sub 2}/n-GaN metal-insulator-semiconductor (MIS) Schottky diode showed an increase in rectification ratio from 35.9 to 98.9(@ 2V), increase in barrier height (0.52 eV to 0.63eV) and a reduction in ideality factor (2.1 to 1.3) as compared to the MS Schottky. Epitaxial n-type GaN films of thickness 300nm were grown using plasma assisted molecular beam epitaxy (PAMBE). The crystalline and optical qualities of the films were confirmed using high resolutionmore » X-ray diffraction and photoluminescence measurements. Metal-semiconductor (Pt/n-GaN) and metal-insulator-semiconductor (Pt/HfO{sub 2}/n-GaN) Schottky diodes were fabricated. To gain further understanding of the Pt/HfO{sub 2}/GaN interface, I-V characterisation was carried out on the MIS Schottky diode over a temperature range of 150 K to 370 K. The barrier height was found to increase (0.3 eV to 0.79 eV) and the ideality factor decreased (3.6 to 1.2) with increase in temperature from 150 K to 370 K. This temperature dependence was attributed to the inhomogeneous nature of the contact and the explanation was validated by fitting the experimental data into a Gaussian distribution of barrier heights.« less

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

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

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

  14. N2O and NO2 Emissions from Heavy-Duty Diesel Trucks with Advanced Emission Controls

    NASA Astrophysics Data System (ADS)

    Preble, C.; Harley, R.; Kirchstetter, T.

    2014-12-01

    Diesel engines are the largest source of nitrogen oxides (NOx) emissions nationally, and also a major contributor to the black carbon (BC) fraction of fine particulate matter (PM). Recently, diesel particle filter (DPF) and selective catalytic reduction (SCR) emission control systems that target exhaust PM and NOx have become standard equipment on new heavy-duty diesel trucks. However, the deliberate catalytic oxidation of engine-out nitric oxide (NO) to nitrogen dioxide (NO2) in continuously regenerating DPFs leads to increased tailpipe emission of NO2. This is of potential concern due to the toxicity of NO2 and the resulting increases in atmospheric formation of other air pollutants such as ozone, nitric acid, and fine PM. While use of SCR reduces emissions of both NO and NO2, it may lead to increased emissions of nitrous oxide (N2O), a potent greenhouse gas. Here we report results from on-road measurements of heavy-duty diesel truck emissions conducted at the Port of Oakland and the Caldecott Tunnel in the San Francisco Bay Area. Emission factors (g pollutant per kg of diesel) were linked via recorded license plates to individual truck attributes, including engine model year and installed emission control equipment. Between 2009 and 2013, the fraction of DPF-equipped trucks at the Port of Oakland increased from 2 to 99%, and median engine age decreased from 11 to 6 years. Over the same period, fleet-average emission factors for black carbon and NOx decreased by 76 ± 22% and 53 ± 8%, respectively. However, direct emissions of NO2 increased, and consequently the NO2/NOx emission ratio increased from 0.03 ± 0.02 to 0.18 ± 0.03. Older trucks retrofitted with DPFs emitted approximately 3.5 times more NO2 than newer trucks equipped with both DPF and SCR. Preliminary data from summer 2014 measurements at the Caldecott Tunnel suggest that some older trucks have negative emission factors for N2O, and that for newer trucks, N2O emission factors have changed sign and

  15. Investigation of Heterogeneous N2O5 Uptake and ClNO2 Yield at a Rural and a Mountain-top Site in Northern China

    NASA Astrophysics Data System (ADS)

    Wang, Z.; Tham, Y. J.; Wang, W.; LI, Q.; Yun, H.; Wang, X.; Xue, L.; Wang, T.

    2017-12-01

    Dinitrogen pentoxide (N2O5) is a reactive intermediate in the atmospheric oxidation of nitrogen oxides (NOx), and its heterogeneous reaction plays key roles in the chemical transformation and removal of NOx, as well as the production of nitrate and nitryl chloride (ClNO2) that affects the radical budget and photochemical ozone formation. Ambient measurements at a rural site and a mountain top site in northern China in the summer of 2014 revealed significant ClNO2 mixing ratios (up to 2.1 ppbv) produced by fast heterogeneous N2O5 uptake on atmospheric aerosols. Frequently intercepted ClNO2-laden plumes at the mountain site indicate significant ClNO2 production occurred in the nocturnal residual layer, and could help explain the sustained ClNO2 peaks after sunrise observed in the ground site in the region. The meteorological and chemical analysis suggested that elevated ClNO2 plumes were mostly associated with nocturnal buoyant emission from point combustion sources, such as power and industry plants. The uptake coefficients (γ) of N2O5 and yields (ϕ) of ClNO2 were then derived for different plumes observed at the ground and mountain sites, and the factors affecting the variability of γ and ϕ under different conditions were also investigated. The uptake coefficients and yields obtained in this study in northern China will be compared with other observations in the world, and also compared to the existing parameterizations based on aerosol compositions. The contribution of fast N2O5 heterogeneous reaction to the nocturnal NOx processing and nitrate aerosol formation will be further examined, to better understand the impacts of heterogeneous reactive nitrogen chemistry on air quality in northern China.

  16. Ti n O2n-1-Coated Li4Ti5O12 Composite Anode Material for Lithium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoyan; Xu, Wen; Liu, Wanying; Li, Xing; Zhong, Xiaoxi; Lin, Yuanhua

    2018-01-01

    In an effort to enhance the rate capability of Li4Ti5O12, the Ti n O2n-1-coated Li4Ti5O12 (Li4Ti5O12-Ti n O2n-1, 3 < n < 10) composite has been synthesized through a sol-gel process followed by heat treatment in H2 atmosphere. Compared with pure Li4Ti5O12, Li4Ti5O12-Ti n O2n-1 composite shows higher specific capacity, better rate capability and cycle stability. The initial discharge capacity of the Li4Ti5O12-Ti n O2n-1 composite electrode is 171.2 mAh g-1 at 0.2°C, and 103.8 mAh g-1 at 20°C. Moreover, the discharge capacity remains 79.5 mAh g-1 after 100 cycles at 20°C with a capacity loss of 23.4%. The improved rate capacity and cycling stability clarify the positive effects of Ti n O2n-1 coating layer in Li4Ti5O12-Ti n O2n-1 composite as an anode material for lithium ion batteries.

  17. Climate change reduces the net sink of CH4 and N2O in a semiarid grassland.

    PubMed

    Dijkstra, Feike A; Morgan, Jack A; Follett, Ronald F; Lecain, Daniel R

    2013-06-01

    Atmospheric concentrations of methane (CH4 ) and nitrous oxide (N2 O) have increased over the last 150 years because of human activity. Soils are important sources and sinks of both potent greenhouse gases where their production and consumption are largely regulated by biological processes. Climate change could alter these processes thereby affecting both rate and direction of their exchange with the atmosphere. We examined how a rise in atmospheric CO2 and temperature affected CH4 and N2 O fluxes in a well-drained upland soil (volumetric water content ranging between 6% and 23%) in a semiarid grassland during five growing seasons. We hypothesized that responses of CH4 and N2 O fluxes to elevated CO2 and warming would be driven primarily by treatment effects on soil moisture. Previously we showed that elevated CO2 increased and warming decreased soil moisture in this grassland. We therefore expected that elevated CO2 and warming would have opposing effects on CH4 and N2 O fluxes. Methane was taken up throughout the growing season in all 5 years. A bell-shaped relationship was observed with soil moisture with highest CH4 uptake at intermediate soil moisture. Both N2 O emission and uptake occurred at our site with some years showing cumulative N2 O emission and other years showing cumulative N2 O uptake. Nitrous oxide exchange switched from net uptake to net emission with increasing soil moisture. In contrast to our hypothesis, both elevated CO2 and warming reduced the sink of CH4 and N2 O expressed in CO2 equivalents (across 5 years by 7% and 11% for elevated CO2 and warming respectively) suggesting that soil moisture changes were not solely responsible for this reduction. We conclude that in a future climate this semiarid grassland may become a smaller sink for atmospheric CH4 and N2 O expressed in CO2 -equivalents. © 2013 Blackwell Publishing Ltd.

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

    PubMed

    Daković, Marijana; Popović, Zora

    2007-11-01

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

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

    PubMed

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

    2008-02-01

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

  20. Amplified spontaneous emission from ZnO in n-ZnO/ZnO nanodots-SiO(2) composite/p-AlGaN heterojunction light-emitting diodes.

    PubMed

    Shih, Ying Tsang; Wu, Mong Kai; Li, Wei Chih; Kuan, Hon; Yang, Jer Ren; Shiojiri, Makoto; Chen, Miin Jang

    2009-04-22

    This study demonstrates amplified spontaneous emission (ASE) of the ultraviolet (UV) electroluminescence (EL) from ZnO at lambda~380 nm in the n-ZnO/ZnO nanodots-SiO(2) composite/p- Al(0.12)Ga(0.88)N heterojunction light-emitting diode. A SiO(2) layer embedded with ZnO nanodots was prepared on the p-type Al(0.12)Ga(0.88)N using spin-on coating of SiO(2) nanoparticles followed by atomic layer deposition (ALD) of ZnO. An n-type Al-doped ZnO layer was deposited upon the ZnO nanodots-SiO(2) composite layer also by the ALD technique. High-resolution transmission electron microscopy (HRTEM) reveals that the ZnO nanodots embedded in the SiO(2) matrix have diameters of 3-8 nm and the wurtzite crystal structure, which allows the transport of carriers through the thick ZnO nanodots-SiO(2) composite layer. The high quality of the n-ZnO layer was manifested by the well crystallized lattice image in the HRTEM picture and the low-threshold optically pumped stimulated emission. The low refractive index of the ZnO nanodots-SiO(2) composite layer results in the increase in the light extraction efficiency from n-ZnO and the internal optical feedback of UV EL into n-ZnO layer. Consequently, significant enhancement of the UV EL intensity and super-linear increase in the EL intensity, as well as the spectral narrowing, with injection current were observed owing to ASE in the n-ZnO layer.

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

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

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

  2. 40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

  3. 40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

  4. 40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

  5. 40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

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

    PubMed

    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.

  7. Flooding-related increases in CO2 and N2O emissions from a temperate coastal grassland ecosystem

    NASA Astrophysics Data System (ADS)

    Gebremichael, Amanuel W.; Osborne, Bruce; Orr, Patrick

    2017-05-01

    Given their increasing trend in Europe, an understanding of the role that flooding events play in carbon (C) and nitrogen (N) cycling and greenhouse gas (GHG) emissions will be important for improved assessments of local and regional GHG budgets. This study presents the results of an analysis of the CO2 and N2O fluxes from a coastal grassland ecosystem affected by episodic flooding that was of either a relatively short (SFS) or long (LFS) duration. Compared to the SFS, the annual CO2 and N2O emissions were 1.4 and 1.3 times higher at the LFS, respectively. Mean CO2 emissions during the period of standing water were 144 ± 18.18 and 111 ± 9.51 mg CO2-C m-2 h-1, respectively, for the LFS and SFS sites. During the growing season, when there was no standing water, the CO2 emissions were significantly larger from the LFS (244 ± 24.88 mg CO2-C m-2 h-1) than the SFS (183 ± 14.90 mg CO2-C m-2 h-1). Fluxes of N2O ranged from -0.37 to 0.65 mg N2O-N m-2 h-1 at the LFS and from -0.50 to 0.55 mg N2O-N m-2 h-1 at the SFS, with the larger emissions associated with the presence of standing water at the LFS but during the growing season at the SFS. Overall, soil temperature and moisture were identified as the main drivers of the seasonal changes in CO2 fluxes, but neither adequately explained the variations in N2O fluxes. Analysis of total C, N, microbial biomass and Q10 values indicated that the higher CO2 emissions from the LFS were linked to the flooding-associated influx of nutrients and alterations in soil microbial populations. These results demonstrate that annual CO2 and N2O emissions can be higher in longer-term flooded sites that receive significant amounts of nutrients, although this may depend on the restriction of diffusional limitations due to the presence of standing water to periods of the year when the potential for gaseous emissions are low.

  8. Effect of Soil pH Increase by Biochar on NO, N2O and N2 Production during Denitrification in Acid Soils

    PubMed Central

    Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

    2015-01-01

    Biochar (BC) application to soil suppresses emission of nitrous- (N2O) and nitric oxide (NO), but the mechanisms are unclear. One of the most prominent features of BC is its alkalizing effect in soils, which may affect denitrification and its product stoichiometry directly or indirectly. We conducted laboratory experiments with anoxic slurries of acid Acrisols from Indonesia and Zambia and two contrasting BCs produced locally from rice husk and cacao shell. Dose-dependent responses of denitrification and gaseous products (NO, N2O and N2) were assessed by high-resolution gas kinetics and related to the alkalizing effect of the BCs. To delineate the pH effect from other BC effects, we removed part of the alkalinity by leaching the BCs with water and acid prior to incubation. Uncharred cacao shell and sodium hydroxide (NaOH) were also included in the study. The untreated BCs suppressed N2O and NO and increased N2 production during denitrification, irrespective of the effect on denitrification rate. The extent of N2O and NO suppression was dose-dependent and increased with the alkalizing effect of the two BC types, which was strongest for cacao shell BC. Acid leaching of BC, which decreased its alkalizing effect, reduced or eliminated the ability of BC to suppress N2O and NO net production. Just like untreated BCs, NaOH reduced net production of N2O and NO while increasing that of N2. This confirms the importance of altered soil pH for denitrification product stoichiometry. Addition of uncharred cacao shell stimulated denitrification strongly due to availability of labile carbon but only minor effects on the product stoichiometry of denitrification were found, in accordance with its modest effect on soil pH. Our study indicates that stimulation of denitrification was mainly due to increases in labile carbon whereas change in product stoichiometry was mainly due to a change in soil pH. PMID:26397367

  9. Effect of Soil pH Increase by Biochar on NO, N2O and N2 Production during Denitrification in Acid Soils.

    PubMed

    Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

    2015-01-01

    Biochar (BC) application to soil suppresses emission of nitrous- (N2O) and nitric oxide (NO), but the mechanisms are unclear. One of the most prominent features of BC is its alkalizing effect in soils, which may affect denitrification and its product stoichiometry directly or indirectly. We conducted laboratory experiments with anoxic slurries of acid Acrisols from Indonesia and Zambia and two contrasting BCs produced locally from rice husk and cacao shell. Dose-dependent responses of denitrification and gaseous products (NO, N2O and N2) were assessed by high-resolution gas kinetics and related to the alkalizing effect of the BCs. To delineate the pH effect from other BC effects, we removed part of the alkalinity by leaching the BCs with water and acid prior to incubation. Uncharred cacao shell and sodium hydroxide (NaOH) were also included in the study. The untreated BCs suppressed N2O and NO and increased N2 production during denitrification, irrespective of the effect on denitrification rate. The extent of N2O and NO suppression was dose-dependent and increased with the alkalizing effect of the two BC types, which was strongest for cacao shell BC. Acid leaching of BC, which decreased its alkalizing effect, reduced or eliminated the ability of BC to suppress N2O and NO net production. Just like untreated BCs, NaOH reduced net production of N2O and NO while increasing that of N2. This confirms the importance of altered soil pH for denitrification product stoichiometry. Addition of uncharred cacao shell stimulated denitrification strongly due to availability of labile carbon but only minor effects on the product stoichiometry of denitrification were found, in accordance with its modest effect on soil pH. Our study indicates that stimulation of denitrification was mainly due to increases in labile carbon whereas change in product stoichiometry was mainly due to a change in soil pH.

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

    PubMed

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

    2016-07-01

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

  11. Molecular approaches to understand the regulation of N2O emission from denitrifying bacteria - model strains and soil communities (Invited)

    NASA Astrophysics Data System (ADS)

    Frostegard, A.; Bakken, L. R.

    2010-12-01

    in intact soil samples from long-term liming experiments. Expression of nirS (encoding nitrite reductase) and nosZ (encoding N2OR) was generally lower at pH6 compared to pH8, but the nosZ/nirS transcript ratios were similar or even higher at pH6. These results were largely corroborated in refined experiments using extracted bacterial communities from the same soils, which allowed us to better control the pH levels experienced by the cells. The findings indicated that the higher N2O/N2 product ratios at pH6 were due to a post-transcriptional effect. Pure culture experiments using Paracoccus denitrificans demonstrated very low N2O/N2 ratios at pH7 while N2O reduction was severely inhibited by suboptimal pH, and that this inhibition occurred during protein synthesis/assembly rather than at the transcription level. The results are important for the understanding of main factors affecting N2O emissions from terrestrial ecosystems.

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

    PubMed

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

    2004-10-04

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

  13. A New High-Resolution N2O Emission Inventory for China in 2008

    NASA Astrophysics Data System (ADS)

    Shang, Z.; Zhou, F.; Ciais, P.; Tao, S.; Piao, S.; Raymond, P. A.; He, C.; Li, B.; Wang, R.; Wang, X.; Peng, S.; Zeng, Z.; Chen, H.; Ying, N.; Hou, X.; Xu, P.

    2014-12-01

    The amount and geographic distribution of N2O emissions over China remain largely uncertain. Most of existing emission inventories use uniform emission factors (EFs) and the associated parameters and apply spatial proxies to downscale national or provincial data, resulting in the introduction of spatial bias. In this study, county-level and 0.1° × 0.1° gridded anthropogenic N2O emission inventories for China (PKU-N2O) in 2008 are developed based on high-resolution activity data and regional EFs and parameters. These new estimates are compared with estimates from EDGAR v4.2, GAINS-China, National Development and Reform Commission of China (NDRC), and with two sensitivity tests: one that uses high-resolution activity data but the default IPCC methodology (S1) and the other that uses regional EFs and parameters but starts from coarser-resolution activity data. The total N2O emissions are 2150 GgN2O/yr (interquartile range from 1174 to 2787 GgN2O/yr). Agriculture contributes 64% of the total, followed by energy (17%), indirect emissions (12%), wastes (5%), industry (2.8%), and wildfires (0.2%). Our national emission total is 17% greater than that of the EDGAR v4.2 global product sampled over China and is also greater than the GAINS-China, NDRC, and S1 estimates by 10%, 50%, and 17%, respectively. We also found that using uniform EFs and parameters or starting from national/provincial data causes systematic spatial biases compared to PKU-N2O. In addition, the considerable differences between the relative contributions of the six sectors across the six Agro-Climate Zones primarily reflect the different distributions of industrial activities and land use. Eastern China (8.7% area of China) is the largest contributor of N2O emissions and accounts for nearly 25% of the total. Spatial analysis also shows nonlinear relationships between N2O emission intensities and urbanization. Per-capita and per-GDP N2O emissions increase gradually with an increase in the urban

  14. Selective inhibition of ammonium oxidation and nitrification-linked N2O formation by methyl fluoride and dimethyl ether

    USGS Publications Warehouse

    Miller, L.G.; Coutlakis, M.D.; Oremland, R.S.; Ward, B.B.

    1993-01-01

    Methyl fluoride (CH3F) and dimethyl ether (DME) inhibited nitrification in washed-cell suspensions of Nitrosomonas europaea and in a variety of oxygenated soils and sediments. Headspace additions of CH3F (10% [vol/vol]) and DME (25% [vol/vol]) fully inhibited NO2- and N2O production from NH4+ in incubations of N. europaea, while lower concentrations of these gases resulted in partial inhibition. Oxidation of hydroxylamine (NH2OH) by N. europaea and oxidation of NO2- by a Nitrobacter sp. were unaffected by CH3F or DME. In nitrifying soils, CH3F and DME inhibited N2O production. In field experiments with surface flux chambers and intact cores, CH3F reduced the release of N2O from soils to the atmosphere by 20- to 30-fold. Inhibition by CH3F also resulted in decreased NO3- + NO2- levels and increased NH4+ levels in soils. CH3F did not affect patterns of dissimilatory nitrate reduction to ammonia in cell suspensions of a nitrate- respiring bacterium, nor did it affect N2O metabolism in denitrifying soils. CH3F and DME will be useful in discriminating N2O production via nitrification and denitrification when both processes occur and in decoupling these processes by blocking NO2- and NO3- production.

  15. Emission of N 2O on pulse-rice crop rotation in upland

    NASA Astrophysics Data System (ADS)

    Ramulu, T. S.; Sahoo, S. K.; Mohapatra, R. K.; Chaudhury, G. Roy; Das, S. N.

    The Seasonally Integrated Flux (SIF) of N 2O emission during pulse cultivation in Rabi season (Season-I: December to April) in rain-fed uplands of Orissa, was found to be 17.7 ± 0.07, 18.7 ± 0.16 and 43.3 ± 0.14 gha -1 for horse gram (HG), black gram (BG) and green gram (GG) respectively. During the subsequent Rabi season (Season-II), the SIF of N 2O for BG and GG cultivated in the same fields were 20.9 ± 0.24 and 38.0 ± 0.42 gha -1 respectively. Similarly SIF values during rice cultivation with different cultivars have also been calculated to be in the range -20.05 ± 0.33 to 21.98 ± 0.29. Statistical analysis showed good correlation of N 2O emission with climatic and soil parameters like temperature, nutrient N and organic matter in soil during pulse cultivation. Multivariate analysis was carried out to factorize the results obtained. Using student ' t' test, the N 2O emission was observed to be similar for two consecutive Rabi seasons for pulses like BG and GG.

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

    NASA Astrophysics Data System (ADS)

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

    2018-02-01

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

  17. Synthesis and characterization of sodium vanadium oxide gels: the effects of water (n) and sodium (x) content on the electrochemistry of Na(x)V2OnH2O.

    PubMed

    Lee, Chia-Ying; Marschilok, Amy C; Subramanian, Aditya; Takeuchi, Kenneth J; Takeuchi, Esther S

    2011-10-28

    Sodium vanadium oxide gels, Na(x)V(2)O(5)·nH(2)O, of varying sodium content (0.12 < x < 0.32) were prepared by careful control of an ion exchange process. The water content (0.23 > n > 0.01) and interlayer spacing were found to be inversely proportional to the sodium level (x), thus control of sodium (x) content provided a direct, chimie douce approach for control of hydration level (n) and interlayer spacing, without the need for high temperature treatment to affect dehydration. Notably, the use of high temperatures to modify hydration levels can result in crystallization and collapse of the interlayer structure, highlighting the distinct advantage of our novel chimie douce synthesis strategy. Subsequent to synthesis and characterization, results from an electrochemical study of a series of Na(x)V(2)O(5)·nH(2)O samples highlight the significant impact of interlayer water on delivered capacity of the layered materials. Specifically, the sodium vanadium oxide gels with higher sodium content and lower water content provided higher capacities in lithium based cells, where capacity delivered to 2.0 V under C/20 discharge ranged from 170 mAh/g for Na(0.12)V(2)O(5)·0.23H(2)O to 300 mAh/g for Na(0.32)V(2)O(5)·0.01H(2)O. The capacity differences were maintained as the cells were cycled. This journal is © the Owner Societies 2011

  18. 2,4-Dinitrophenylhydrazine, redetermined at 120 K: a three-dimensional framework built from N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

    PubMed

    Wardell, James L; Low, John N; Glidewell, Christopher

    2006-06-01

    In the title compound, C6H6N4O4, the bond distances indicate significant bond fixation, consistent with charge-separated polar forms. The molecules are almost planar and there is an intramolecular N-H...O hydrogen bond. The molecules are linked into a complex three-dimensional framework structure by a combination of N-H...O, N-H...(O)2, N-H...pi(arene) and C-H...O hydrogen bonds.

  19. The earthworm gut: an ideal habitat for ingested N2O-producing microorganisms.

    PubMed

    Horn, Marcus A; Schramm, Andreas; Drake, Harold L

    2003-03-01

    The in vivo production of nitrous oxide (N(2)O) by earthworms is due to their gut microbiota, and it is hypothesized that the microenvironment of the gut activates ingested N(2)O-producing soil bacteria. In situ measurement of N(2)O and O(2) with microsensors demonstrated that the earthworm gut is anoxic and the site of N(2)O production. The gut had a pH of 6.9 and an average water content of approximately 50%. The water content within the gut decreased from the anterior end to the posterior end. In contrast, the concentration of N(2)O increased from the anterior end to the mid-gut region and then decreased along the posterior part of the gut. Compared to the soil in which worms lived and fed, the gut of the earthworm was highly enriched in total carbon, organic carbon, and total nitrogen and had a C/N ratio of 7 (compared to a C/N ratio of 12 in soil). The aqueous phase of gut contents contained up to 80 mM glucose and numerous compounds that were indicative of anaerobic metabolism, including up to 9 mM formate, 8 mM acetate, 3 mM lactate, and 2 mM succinate. Compared to the soil contents, nitrite and ammonium were enriched in the gut up to 10- and 100-fold, respectively. The production of N(2)O by soil was induced when the gut environment was simulated in anoxic microcosms for 24 h (the approximate time for passage of soil through the earthworm). Anoxia, high osmolarity, nitrite, and nitrate were the dominant factors that stimulated the production of N(2)O. Supplemental organic carbon had a very minimal stimulatory effect on the production of N(2)O, and addition of buffer or ammonium had essentially no effect on the initial N(2)O production rates. However, a combination of supplements yielded rates greater than that obtained mathematically for single supplements, suggesting that the maximum rates observed were due to synergistic effects of supplements. Collectively, these results indicate that the special microenvironment of the earthworm gut is ideally suited

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    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 [δ15Nbulk, δ18O, and SP (intramolecular 15N 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. δ15Nbulk and δ18O 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.

  1. Laboratory incubation experiments assessing the factor interactions affecting urine-derived nitrous oxide emissions from spatially and temporally variable upland pastures

    NASA Astrophysics Data System (ADS)

    Charteris, Alice; Loick, Nadine; Marsden, Karina; Chadwick, Dave; Whelan, Mick; Rao Ravella, Sreenivas; Mead, Andrew; Cardenas, Laura

    2017-04-01

    Urine patches deposited to soils by grazing animals represent hot-spots of nitrous oxide (N2O) emissions (Hargreaves et al., 2015), a powerful greenhouse gas (GHG) and precursor of ozone depletion in the stratosphere. Urine N2O emissions are produced via nitrification of ureolysis-derived ammonium (NH4+) and/or subsequent nitrite (NO2-) and nitrate (NO3-) denitrification (Kool et al., 2006). The dominant process and the N2O fluxes generated depend on interactions between urine characteristics (e.g. nitrogen [N] concentration and volume), soil characteristics (e.g. carbon [C] availability and pH) and preceding and prevailing environmental conditions (e.g. soil moisture and temperature; Bergstermann et al., 2011; Butterbach-Bahl et al., 2013; Dijkstra et al., 2013). The spatial and temporal variability of these interactions in grazing systems is potentially large and greatly increases the uncertainty associated with N2O emission estimates from such systems. In particular, the contribution of extensively managed upland agroecosystems, which occupy ca. 5.5 million hectares in the UK and provide the bulk of land for sheep farming (Pollott & Stone, 2004), to UK GHG emissions is poorly defined. Improving understanding of the interactions between the wide range of factors affecting urine-derived N2O production and emission from pasture soils and considering this in the context of the spatial and temporal variability of the grazing environment could therefore be extremely valuable in improving the accuracy of N2O emission estimates from such systems. The factorial laboratory incubation experiments presented have been designed to assess the interactive effects of factors such as urine N concentration, volume and soil moisture affecting soil N2O (and nitric oxide [NO], nitrogen gas [N2] and carbon dioxide [CO2]) production and emissions (García-Marco et al., 2014) using the state-of-the-art Denitrification Incubation System (DENIS). This work forms part of a wider project

  2. The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N3 )3 ], [MoO(N3 )3 ⋅2 CH3 CN], [(bipy)MoO(N3 )3 ], [MoO(N3 )5 ](2-) , [WO(N3 )4 ], and [WO(N3 )4 ⋅CH3 CN].

    PubMed

    Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

    2015-12-14

    A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF4 ] (M=Mo, W) and Me3 SiN3 . While [WO(N3 )4 ] was formed through fluoride-azide exchange in the reaction of Me3 SiN3 with WOF4 in SO2 solution, the reaction with MoOF4 resulted in a reduction of Mo(VI) to Mo(V) and formation of [MoO(N3 )3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N3 )3 ⋅2 CH3 CN] and [WO(N3 )4 ⋅CH3 CN]. Subsequent reactions of [MoO(N3 )3 ] with 2,2'-bipyridine and [PPh4 ][N3 ] resulted in the formation and isolation of [(bipy)MoO(N3 )3 ] and [PPh4 ]2 [MoO(N3 )5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N3 )4 ⋅CH3 CN], [(bipy)MoO(N3 )3 ], and [PPh4 ]2 [MoO(N3 )5 ], by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Effect of plastic mulching and nitrapyrin on N2O concentration and emissions in China under climate change

    NASA Astrophysics Data System (ADS)

    Zhao, C.; Zhu, C.

    2017-12-01

    Fertilized agricultural soils are the main source of atmospheric nitrous oxide (N2O). In this study, both soil N2O concentration in the profile and N2O emission were measured to quantify the effect of plastic mulching and nitrapyrin on N2O dynamic in an oasis cotton field. During the observation period, both N2O concentration and N2O emissions rapidly increased following fertigation, and soil temperature, moisture and mineral N content were the main factors influencing N2O. Temporal variation in N2O emission coincided with changes in N2O content in all soil layers, indicating that the accumulation of N2O likely drives the release of N2O into the atmosphere. The crop yields, N2O content (the sum of aqueous and gaseous phases) in the soil and N2O emissions increased linearly as the application of N fertilizer increased from 80 to 400 kg N ha-1. Plastic mulching increased the crop yields by 16-21%, increased the N2O contents by 88-99%, and reduced the cumulative N2O emissions by 19-28%, indicating that the application of plastic film reduced N2O emission probably through restricted the N2O diffusion process, and limited the N2O production through enhanced the N uptake of cotton. The addition of nitrapyrin to the N fertilizer significantly reduced the levels of N2O without influencing crop yield, with N2O content in the soil profile and cumulative N2O emissions decreasing by 25-32% and 23-42%, respectively. Overall, our result suggested the combined use of plastic film and nitrapyrin could be an efficient practice to reduce N2O emission in the oasis cotton field. Keywords: N2O emissions; plastic film mulching; nitrapyrin; climate change

  4. N2O release from agro-biofuel production negates global warming reduction by replacing fossil fuels

    NASA Astrophysics Data System (ADS)

    Crutzen, P. J.; Mosier, A. R.; Smith, K. A.; Winiwarter, W.

    2008-01-01

    The relationship, on a global basis, between the amount of N fixed by chemical, biological or atmospheric processes entering the terrestrial biosphere, and the total emission of nitrous oxide (N2O), has been re-examined, using known global atmospheric removal rates and concentration growth of N2O as a proxy for overall emissions. For both the pre-industrial period and in recent times, after taking into account the large-scale changes in synthetic N fertiliser production, we find an overall conversion factor of 3-5% from newly fixed N to N2O-N. We assume the same factor to be valid for biofuel production systems. It is covered only in part by the default conversion factor for "direct" emissions from agricultural crop lands (1%) estimated by IPCC (2006), and the default factors for the "indirect" emissions (following volatilization/deposition and leaching/runoff of N: 0.35-0.45%) cited therein. However, as we show in the paper, when additional emissions included in the IPCC methodology, e.g. those from livestock production, are included, the total may not be inconsistent with that given by our "top-down" method. When the extra N2O emission from biofuel production is calculated in "CO2-equivalent" global warming terms, and compared with the quasi-cooling effect of "saving" emissions of fossil fuel derived CO2, the outcome is that the production of commonly used biofuels, such as biodiesel from rapeseed and bioethanol from corn (maize), depending on N fertilizer uptake efficiency by the plants, can contribute as much or more to global warming by N2O emissions than cooling by fossil fuel savings. Crops with less N demand, such as grasses and woody coppice species, have more favourable climate impacts. This analysis only considers the conversion of biomass to biofuel. It does not take into account the use of fossil fuel on the farms and for fertilizer and pesticide production, but it also neglects the production of useful co-products. Both factors partially compensate

  5. Influence of humic acid concentration on nTiO2 attachment to quartz sand and Fe-coated quartz sand

    NASA Astrophysics Data System (ADS)

    Cheng, T.; Wu, Y.

    2016-12-01

    The transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by nTiO2 attachment to sediment grains. The objective of this study is to investigate the role of humic acid (HA) in the attachment of nTiO2 to sand at low HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in groundwater can be elucidated. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the transport of negatively-charged colloids, may influence nTiO2 in different manners. Attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at fixed pH. Experimental results show that at pH 5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in relatively high nTiO2 attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in low nTiO2 attachment. At pH 9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the attachment of nTiO2. This study demonstrates that the changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption could be a key factor that controls the attachment of nTiO2 to sediment grains.

  6. Construction of g-C3N4/CeO2/ZnO ternary photocatalysts with enhanced photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Yuan, Yuan; Huang, Gui-Fang; Hu, Wang-Yu; Xiong, Dan-Ni; Zhou, Bing-Xin; Chang, Shengli; Huang, Wei-Qing

    2017-07-01

    Promoting the spatial separation of photoexcited charge carriers is of paramount significance for photocatalysis. In this work, binary g-C3N4/CeO2 nanosheets are first prepared by pyrolysis and subsequent exfoliation method, then decorated with ZnO nanoparticles to construct g-C3N4/CeO2/ZnO ternary nanocomposites with multi-heterointerfaces. Notably, the type-II staggered band alignments existing between any two of the constituents, as well as the efficient three-level transfer of electron-holes in unique g-C3N4/CeO2/ZnO ternary composites, leads to the robust separation of photoexcited charge carriers, as verified by its photocurrent increased by 8 times under visible light irradiation. The resulting g-C3N4/CeO2/ZnO ternary nanocomposites unveil appreciably increased photocatalytic activity, faster than that of pure g-C3N4, ZnO and g-C3N4/CeO2 by a factor of 11, 4.6 and 3.7, respectively, and good stability toward methylene blue (MB) degradation. The remarkably enhanced photocatalytic activity of g-C3N4/CeO2/ZnO ternary heterostructures can be interpreted in terms of lots of active sites of nanosheet shapes and the efficient charge separation owing to the resulting type-II band alignment with more than one heterointerface and the efficient three-level electron-hole transfer. A plausible mechanism is also elucidated via active species trapping experiments with various scavengers, which indicating that the photogenerated holes and •OH radicals play a crucial role in photodegradation reaction under visible light irradiation. This work suggest that the rational design and construction of type II multi-heterostructures is powerful for developing highly efficient and reusable visible-light photocatalysts for environmental purification and energy conversion.

  7. Reducing fertilizer-derived N2O emission: Point injection vs. surface application of ammonium-N fertilizer at a loamy sand site

    NASA Astrophysics Data System (ADS)

    Deppe, Marianna; Well, Reinhard; Giesemann, Anette; Kücke, Martin; Flessa, Heinz

    2013-04-01

    N2O emitted from soil originates either from denitrification of nitrate and/or nitrification of ammonium. N fertilization can have an important impact on N2O emission rates. Injection of nitrate-free ammonium-N fertilizer, in Germany also known as CULTAN (Controlled Uptake Long-Term Ammonium Nutrition), results in fertilizer depots with ammonium concentrations of up to 10 mg N g-1 soil-1. High concentrations of ammonium are known to inhibit nitrification. However, it has not yet been clarified how N2O fluxes are affected by CULTAN. In a field experiment, two application methods of nitrogen fertilizer were used at a loamy sand site: Ammonium sulphate was applied either by point injection or by surface application. 15N-ammonium sulphate was used to distinguish between N2O originating from either fertilizer-N or soil-N. Unfertilized plots and plots fertilized with unlabeled ammonium sulphate served as control. N2O emissions were measured using static chambers, nitrate and ammonium concentrations were determined in soil extracts. Stable isotope analysis of 15N in N2O, nitrate and ammonium was used to calculate the contribution of fertilizer N to N2O emissions and the fertilizer turnover in soil. 15N analysis clearly indicated that fertilizer derived N2O fluxes were higher from surface application plots. For the period of the growing season, about 24% of the flux measured in surface application treatment and less than 10% from injection treatment plots originated from the fertilizer. In addition, a lab experiment was conducted to gain insight into processes leading to N2O emission from fertilizer depots. One aim was to examine whether the ratio of N2O to nitrate formation differs depending on the ammonium concentration. Loamy sand soil was incubated in microcosms continuously flushed with air under conditions favouring nitrification. 15N-labeled nitrate was used to differentiate between nitrification and denitrification. Stable isotope analyses of 15N were performed on

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

    NASA Technical Reports Server (NTRS)

    Sekercioglu, I.; Wills, R. R.

    1979-01-01

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

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

    PubMed

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

    2013-12-07

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

  10. Collision cross sections and transport coefficients of O-, O2 -, O3 - and O4 - negative ions in O2, N2 and dry air for non-thermal plasmas modelling

    NASA Astrophysics Data System (ADS)

    Hennad, Ali; Yousfi, Mohammed

    2018-02-01

    The ions interaction data such as interaction potential parameters, elastic and inelastic collision cross sections and the transport coefficients (reduced mobility and diffusion coefficients) have been determined and analyzed in the case of the main negative oxygen ions (O-, O2 -, O3 - and O4 -) present in low temperature plasma at atmospheric pressure when colliding O2, N2 and dry air. The ion transport has been determined from an optimized Monte Carlo simulation using calculated elastic and experimentally fitted inelastic collision cross sections. The elastic momentum transfer collision cross sections have been calculated from a semi-classical JWKB approximation based on a ( n-4) rigid core interaction potential model. The cross sections sets involving elastic and inelastic processes were then validated using measured reduced mobility data and also diffusion coefficient whenever available in the literature. From the sets of elastic and inelastic collision cross sections thus obtained for the first time for O3-/O2, O2 -/N2, O3 -/N2, and O4 -/N2 systems, the ion transport coefficients were calculated in pure gases and dry air over a wide range of the density reduced electric field E/N.

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

    PubMed

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

    2017-10-05

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

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

    NASA Technical Reports Server (NTRS)

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

    2003-01-01

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

  13. Unintended consequences of carbon enhancement in agricultural soils: The N2O problem

    NASA Astrophysics Data System (ADS)

    Venterea, R. T.; Breuillin-Sessoms, F.; Baker, J. M.; Griffis, T. J.; Spokas, K.; Turner, P. A.

    2016-12-01

    The potential of agricultural soils to accumulate C as a means of removing greenhouse gases (GHGs) from the atmosphere is complicated by the inherent coupling of the C and N cycles in soil. Practices that increase soil C content can have the unintended consequence of stimulating N mineralization, nitrification and/or denitrification; which can in turn promote production of N2O as well as other forms of reactive N that can be later transformed to N2O. These effects, combined with the large global warming potential of N2O, may partially or completely offset any gains in soil C from a GHG accounting perspective. Thus, ideally, management of soil C and N must be considered together in attempts to reduce net GHG budgets. However, the knowledge base for defining practices that optimize management of soil C and N together is still quite limited. In this presentation, we will illustrate these challenges with results from several recent studies examining effects of tillage, cover crops, biochar and other practices which aim to enhance soil C. Interactions of these practices with N management, climate, and other factors and their effects on N2O will be discussed with implications for improved management and future research.

  14. (Carbonato-κO,O')bis-(di-2-pyridyl-amine-κN,N')cobalt(III) bromide.

    PubMed

    Czapik, Agnieszka; Papadopoulos, Christos; Lalia-Kantouri, Maria; Gdaniec, Maria

    2011-04-01

    In the title compound, [Co(CO(3))(C(10)H(9)N(3))(2)]Br, a distorted octa-hedral coordination of the Co(III) atom is completed by four N atoms of the two chelating di-2-pyridyl-amine ligands and two O atoms of the chelating carbonate anion. The di-2-pyridyl-amine ligands are nonplanar and the dihedral angles between the 2-pyridyl groups are 29.11 (9) and 37.15 (12)°. The coordination cation, which has approximate C(2) symmetry, is connected to the bromide ion via an N-H⋯Br(-) hydrogen bond. The ionic pair thus formed is further assembled into a dimer via N-H⋯O inter-actions about an inversion centre. A set of weaker C-H⋯O and C-H⋯Br(-) inter-actions connect the dimers into a three-dimensional network.

  15. Effects and mechanism of freeze-thawing cycles on the soil N2O fluxes in the temperate semi-arid steppe.

    PubMed

    Wang, Liqin; Qi, Yuchun; Dong, Yunshe; Peng, Qin; Guo, Shufang; He, Yunlong; Li, Zhaolin

    2017-06-01

    High nitrous oxide (N 2 O) emissions during freeze-thawing period (FTP) have been observed in many different ecosystems. However, the knowledge about the dynamic of soil N 2 O emissions and its main driving mechanism during the freeze-thawing processes in grassland ecosystem is still limited. An in-situ experiment was conducted during the FTP on the sites with 0 and 15% surplus of the average rainfall and two levels of N addition (0,10gN/(m 2 ·year)) during growing season (marked as W0N0, W15N0, W0N10, W15N10, respectively) to explore the effects of water and N background on soil N 2 O emissions during FTPs and the relationship between soil N 2 O emissions and environmental factors. The results indicated that water and N treatments conducted during growing season did not show significant effect on the N 2 O effluxes of FTP, but the soil mineral N contents of W0N10 treatment were significantly higher than those of W0N0, W15N0, W15N10 treatments (p<0.05). The soil PLFA concentrations of microbial groups monitored during 2015 spring freeze-thawing period (2015S-FTP) were lower than those during winter freeze-thawing period of 2014 (2014W-FTP), while cumulative soil N 2 O emissions of 2015S-FTP were higher than those of 2014W-FTP. The correlations between soil N 2 O effluxes and most of the measured environmental factors were insignificant, multiple stepwise regression analysis indicated that the soil temperature, soil NH 4 + -N content and air temperature were the major environmental factors which significantly influenced the N 2 O effluxes during 2014W-FTP, and air temperature and soil water content were the significant influencing factors during 2015S-FTP. Copyright © 2016. Published by Elsevier B.V.

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

    PubMed

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

    2018-02-15

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

  17. Distribution of N2O in the atmosphere under global warming - a simulation study with the MPI Earth System Model

    NASA Astrophysics Data System (ADS)

    Kracher, Daniela; Manzini, Elisa; Reick, Christian H.; Schultz, Martin; Stein, Olaf

    2014-05-01

    Climate change is driven by an increasing release of anthropogenic greenhouse gases (GHGs) such as carbon dioxide and nitrous oxide (N2O). Besides fossil fuel burning, also land use change and land management are anthropogenic sources of GHGs. Especially inputs of reactive nitrogen via fertilizer and deposition lead to enhanced emissions of N2O. One effect of a drastic future increase in surface temperature is a modification of atmospheric circulation, e.g. an accelerated Brewer Dobson circulation affecting the exchange between troposphere and stratosphere. N2O is inert in the troposphere and decayed only in the stratosphere. Thus, changes in atmospheric circulation, especially changes in the exchange between troposphere and stratosphere, will affect the atmospheric transport, decay, and distribution of N2O. In our study we assess the impact of global warming on atmospheric circulation and implied effects on the distribution and lifetime of atmospheric N2O. As terrestrial N2O emissions are highly determined by inputs of reactive nitrogen - the location of which being determined by human choice - we examine in particular the importance of latitudinal source regions of N2O for its global distribution. For this purpose we apply the Max Planck Institute Earth System Model, MPI-ESM. MPI-ESM consists of the atmospheric general circulation model ECHAM, the land surface model JSBACH, and MPIOM/HAMOCC representing ocean circulation and ocean biogeochemistry. Prognostic atmospheric N2O concentrations in MPI-ESM are determined by land N2O emissions, ocean N2O exchange and atmospheric tracer transport. As stratospheric chemistry is not explicitly represented in MPI-ESM, stratospheric decay rates of N2O are prescribed from a MACC MOZART simulation.

  18. Astrophysical S factor for the radiative capture {sup 12}N(p,{gamma}){sup 13}O determined from the {sup 14}N({sup 12}N,{sup 13}O){sup 13}C proton transfer reaction

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

    Banu, A.; Al-Abdullah, T.; Fu, C.

    2009-02-15

    The cross section of the radiative proton capture reaction on the drip line nucleus {sup 12}N was investigated using the asymptotic normalization coefficient (ANC) method. We have used the {sup 14}N({sup 12}N,{sup 13}O){sup 13}C proton transfer reaction at 12 MeV/nucleon to extract the ANC for {sup 13}O{yields}{sup 12}N+p and calculate from it the direct component of the astrophysical S factor of the {sup 12}N(p,{gamma}){sup 13}O reaction. The optical potentials used and the distorted-wave Born approximation analysis of the proton transfer reaction are discussed. For the entrance channel, the optical potential was inferred from an elastic scattering measurement carried out atmore » the same time as the transfer measurement. From the transfer, we determined the square of the ANC, C{sub p{sub 1/2}}{sup 2}({sup 13}O{sub g.s.})=2.53{+-}0.30 fm{sup -1}, and hence a value of 0.33(4) keV b was obtained for the direct astrophysical S factor at zero energy. Constructive interference at low energies between the direct and resonant captures leads to an enhancement of S{sub total}(0)=0.42(6) keV b. The {sup 12}N(p,{gamma}){sup 13}O reaction was investigated in relation to the evolution of hydrogen-rich massive Population III stars, for the role that it may play in the hot pp-chain nuclear burning processes, possibly occurring in such objects.« less

  19. Sorption of pure N2O to biochars and other organic and inorganic materials under anhydrous conditions

    USGS Publications Warehouse

    Cornelissen, Gerard; Rutherford, David W.; Arp, Hans Peter H.; Dorsch, Peter; Kelly, Charlene N.; Rostad, Colleen E.

    2013-01-01

    Suppression of nitrous oxide (N2O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N2O sorption to biochar. The sorption of N2O and carbon dioxide (CO2) to four biochars was measured in an anhydrous system with pure N2O. The biochar data were compared to those for two activated carbons and other components potentially present in soils—uncharred pine wood and peat—and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities (Qmax) for N2O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17–73 cm3 g–1 at 20 °C (median 51 cm3 g–1), with Langmuir affinities (b) of 2–5 atm–1 (median 3.4 atm–1). Both Qmaxand b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [Qmax 1–34 cm3 g–1 (median 7 cm3 g–1); b 0.4–1.7 atm–1 (median 0.7 atm–1)]. This indicates that biochar can bind N2O more strongly than both mineral and organic soil materials. Qmax and b for CO2 were comparable to those for N2O. Modeled sorption coefficients obtained with an independent polyparameter—linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5–24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N2O were mostly between −20 and −30 kJ mol–1, slightly more exothermic than enthalpies of condensation (−16.1 kJ mol–1). Qmax of N2O on biochar (50000–130000 μg g–1 biochar at 20 °C) exceeded the N2O emission suppressions observed in the literature (range 0.5–960 μg g–1 biochar; median 16 μg g–1) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N2O to biochar is a mechanism of N2O emission suppression.

  20. Gaseous Nitrogen Losses from Tropical Savanna Soils of Northern Australia: Dynamics, Controls and Magnitude of N2O, NO, and N2 emissions

    NASA Astrophysics Data System (ADS)

    Werner, C.; Hickler, T.; Hutley, L. B.; Butterbach-Bahl, K.

    2014-12-01

    Tropical savanna covers a large fraction of the global land area and thus may have a substantial effect on the global soil-atmosphere exchange of nitrogen. The pronounced seasonality of hygric conditions in this ecosystem affects strongly microbial process rates in the soil. As these microbial processes control the uptake, production, and release of nitrogen compounds, it is thought that this seasonality finally leads to strong temporal dynamics and varying magnitudes of gaseous losses to the atmosphere. However, given their areal extent and in contrast to other ecosystems, still few in-situ or laboratory studies exist that assess the soil-atmosphere exchange of nitrogen. We present laboratory incubation results from intact soil cores obtained from a natural savanna site in Northern Australia, where N2O, NO, and N2 emissions under controlled environmental conditions were investigated. Furthermore, in-situ measurements of high temporal resolution at this site recorded with automated static and dynamic chamber systems are discussed (N2O, NO). This data is then used to assess the performance of a process-based biogeochemical model (LandscapeDNDC), and the potential magnitude and dynamics of components of the site-scale nitrogen cycle where no measurements exist (biological nitrogen fixation and nitrate leaching). Our incubation results show that severe nutrient limitation of the soil only allows for very low N2O emissions (0.12 kg N ha-1 yr-1) and even a periodic N2O uptake. Annual NO emissions were estimated at 0.68 kg N ha-1 yr-1, while the release of inert nitrogen (N2) was estimated at 6.75 kg N ha-1 yr-1 (data excl. contribution by pulse emissions). We observed only minor N2O pulse emissions after watering the soil cores and initial rain events of the dry to wet season transition in-situ, but short-lived NO pulse emissions were substantial. Interestingly, some cores exhibited a very different N2O emission potential, indicating a substantial spatial variability of

  1. N2O release from agro-biofuel production negates global warming reduction by replacing fossil fuels

    NASA Astrophysics Data System (ADS)

    Crutzen, P. J.; Mosier, A. R.; Smith, K. A.; Winiwarter, W.

    2007-08-01

    The relationship, on a global basis, between the amount of N fixed by chemical, biological or atmospheric processes entering the terrestrial biosphere, and the total emission of nitrous oxide (N2O), has been re-examined, using known global atmospheric removal rates and concentration growth of N2O as a proxy for overall emissions. The relationship, in both the pre-industrial period and in recent times, after taking into account the large-scale changes in synthetic N fertiliser production and deforestation, is consistent, showing an overall conversion factor of 3-5%. This factor is covered only in part by the ~1% of "direct" emissions from agricultural crop lands estimated by IPCC (2006), or the "indirect" emissions cited therein. This means that the extra N2O entering the atmosphere as a result of using N to produce crops for biofuels will also be correspondingly greater than that estimated just on the basis of IPCC (2006). When the extra N2O emission from biofuel production is calculated in "CO2-equivalent" global warming terms, and compared with the quasi-cooling effect of "saving" emissions of fossil fuel derived CO2, the outcome is that the production of commonly used biofuels, such as biodiesel from rapeseed and bioethanol from corn (maize), can contribute as much or more to global warming by N2O emissions than cooling by fossil fuel savings. Crops with less N demand, such as grasses and woody coppice species have more favourable climate impacts. This analysis only considers the conversion of biomass to biofuel. It does not take into account the use of fossil fuel on the farms and for fertilizer and pesticide production, but it also neglects the production of useful co-products. Both factors partially compensate each other. This needs to be analyzed in a full life cycle assessment.

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

    NASA Astrophysics Data System (ADS)

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

    1991-06-01

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

  3. Surface Nitrification: A Major Uncertainty in Marine N2O Emissions

    NASA Technical Reports Server (NTRS)

    Zamora, Lauren M.; Oschlies, Andreas

    2014-01-01

    The ocean is responsible for up to a third of total global nitrous oxide (N2O) emissions, but uncertainties in emission rates of this potent greenhouse gas are high (approaching 100%). Here we use a marine biogeochemical model to assess six major uncertainties in estimates of N2O production, thereby providing guidance in how future studies may most effectively reduce uncertainties in current and future marine N2O emissions. Potential surface N2O production from nitrification causes the largest uncertainty in N2O emissions (estimated up to approximately 1.6 Tg N/yr (sup -1) or 48% of modeled values), followed by the unknown oxygen concentration at which N2O production switches to N2O consumption (0.8 Tg N/yr (sup -1)or 24% of modeled values). Other uncertainties are minor, cumulatively changing regional emissions by less than 15%. If production of N2O by surface nitrification could be ruled out in future studies, uncertainties in marine N2O emissions would be halved.

  4. A kinetic study of the reactions FeO+ + O, Fe+.N2 + O, Fe+.O2 + O and FeO+ + CO: implications for sporadic E layers in the upper atmosphere.

    PubMed

    Woodcock, K R S; Vondrak, T; Meech, S R; Plane, J M C

    2006-04-21

    These gas-phase reactions were studied by pulsed laser ablation of an iron target to produce Fe(+) in a fast flow tube, with detection of the ions by quadrupole mass spectrometry. Fe(+).N(2) and Fe(+).O(2) were produced by injecting N(2) and O(2), respectively, into the flow tube. FeO(+) was produced from Fe(+) by addition of N(2)O, or by ligand-switching from Fe(+).N(2) following the addition of atomic O. The following rate coefficients were measured: k(FeO(+) + O --> Fe(+) + O(2), 186-294 K) = (3.2 +/- 1.5) x 10(-11); k(Fe(+).N(2) + O --> FeO(+)+ N(2), 294 K) = (4.6 +/- 2.5) x 10(-10); k(Fe(+).O(2) + O --> FeO(+) + O(2), 294 K) = (6.3 +/- 2.7) x 10(-11); and k(FeO(+) + CO --> Fe(+) + CO(2), 294 K) = (1.59 +/- 0.34) x 10(-10) cm(3) molecule(-1) s(-1), where the quoted uncertainties are a combination of the 1sigma standard errors in the kinetic data and the systematic experimental errors. The surprisingly slow reaction between FeO(+) and O is examined using ab initio quantum calculations of the relevant potential energy surfaces. The importance of this reaction for controlling the lifetime of sporadic E layers is then demonstrated using a model of the upper mesosphere and lower thermosphere.

  5. Effects of Eriophorum vaginatum on N_{2}O emissions at a restored peatland

    NASA Astrophysics Data System (ADS)

    Brummell, Martin; Lazcano, Cristina; Strack, Maria

    2016-04-01

    Restoration of peatlands extracted for horticultural peat production includes both deliberate and accidental introduction of a wide range of plant species, including vascular plants and bryophytes. The roots of vascular plants provide a channel for the movement of greenhouse gases (GHG) including N2O in many soil ecosystems, and may stimulate production of N2O or have other effects via the release of root exudates that are then taken up by soil microorganisms such as heterotrophic denitrifiers. Here we carried out a field study in order to evaluate the effects of Eriophorum vaginatum, an abundant sedge at the harvested peatland at Seba Beach, Alberta, Canada, (53° 27'17.2"N 114° 52'52.0"W) where restoration efforts began in late 2012, and is the dominant ground cover in some areas. We hypothesized that E. vaginatum would increase net N2O production from peat compared to areas of bare peat or moss. We measured net GHG exchange for CO2, CH4, and N2O over one growing season (May-September 2015) using static chambers within this peatland to compare between plots containing E. vaginatum and plots lacking vascular plants. Plots were located along a transect of increasing water table, in order to discriminate between the effects of E. vaginatum and the prevailing hydrological conditions on N2O fluxes. Net fluxes of N2O from the peat to the atmosphere were observed throughout the experimental area, as well as fluxes in the opposite direction, in which the peat removed N2O from the atmosphere inside the chamber. Non-zero fluxes were highly variable in both occurrence and magnitude, though a small number of plots accounted for the majority of measured fluxes. Neither aboveground biomass of E. vaginatum nor its presence in a plot was correlated with either frequency or direction of N2O flux measurements. Other factors, such as water table fluctuations and temperature may be stronger drivers of these microbially-mediated processes than vegetation at this stage of the

  6. Influence of immersion cycles during n-β-Bi2O3 sensitization on the photoelectrochemical behaviour of N-F-codoped TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Hoyos, Lina J.; Rivera, Diego F.; Gualdrón-Reyes, Andrés F.; Ospina, Rogelio; Rodríguez-Pereira, Jhonatan; Ropero-Vega, Jose L.; Niño-Gómez, Martha E.

    2017-11-01

    Sensitization of TiO2 nanotube (TNT)-based photoanodes with narrow-band gap semiconductors is an important alternative to improving the photoelectrochemical properties of the material. However, the interaction between the sensitizer and TNT is not understood deeply enough to relate charge carrier transport into the composite photoanode with its photoactivity. In this contribution, we studied the photoelectrochemical behaviour of N-F-self codoped TiO2 nanotubes (N-F-TNTs) that were grown by anodization of titanium plates and sensitized with β-Bi2O3 by immersing the TNTs into a Bi2O3 sol solution by dip-coating. The number of immersion cycles was varied. The as-fabricated photoanodes were characterized by FESEM, GIXRD, DRS and XPS, while their photoelectrochemical and semiconducting properties were investigated by photovoltammetry, electrochemical impedance spectroscopy and Mott-Schottky analysis in 0.1 M HClO4. The photoelectrocatalytic activity of the composite photoanodes was evaluated for glycerol oxidation under acidic and alkaline conditions. The N-F-TNTs exhibit a well-oriented structure after β-Bi2O3 deposition. The presence of substitutions of both N and F, identified by XPS, indicates the self-doping of the TNTs during anodization. The visible-light harvesting of the N-F-TNT photoanode was enhanced after three -immersion cycles during β-Bi2O3 sensitization, establishing an adequate n-n heterojunction at the N-F-TNT/Bi2O3 interface. In addition, bismuth migration from the sensitizer to the TNT lattice was promoted during thermal treatment, forming Bi-N-F-tridoping of TNT (Bi-N-F-TNT). The suitable band alignment between TNT and β-Bi2O3 and incorporation of the Bi3+ energy levels into TiO2 facilitate charge carrier separation and electron transport throughout the cell. Nevertheless, increasing the number of immersion cycles over three creates an excess of Bi3+ species at the N-F-TNT/β-Bi2O3 interface, producing an energetic barrier that hinders electron

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

    PubMed Central

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

    2012-01-01

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

  8. Photooxidative desulfurization for diesel using Fe / N - TiO2 photocatalyst

    NASA Astrophysics Data System (ADS)

    Khan, Muhammad Saqib; Kait, Chong Fai; Mutalib, Mohd Ibrahim Abdul

    2014-10-01

    A series of N - TiO2 with different mol% N was synthesized via sol-gel method and characterized using thermal gravimetric analyzer and raman spectroscopy. 0.2 wt% Fe was incorporated onto the calcined (200°C) N - TiO2 followed by calcination at 200°C, 250°C and 300°C. Photooxidative desulfurization was conducted in the presence of 0.2wt% Fe / N - TiO2 with different mol% N with and without oxidant (H2O2). Oxidative desulfurization was only achieved when H2O2 was used while without H2O2 no major effect on the sulfur removal. 0.2Fe -30N - H2O2 photocatalysts showed best performance at all calcination temperatures as compared to other mol% N - H2O2 photocatalysts. 16.45% sulfur removal was achieved using photocatalysts calcined at 300 °C.

  9. Comparison of APSIM and DNDC simulations of nitrogen transformations and N2O emissions.

    PubMed

    Vogeler, I; Giltrap, D; Cichota, R

    2013-11-01

    Various models have been developed to better understand nitrogen (N) cycling in soils, which is governed by a complex interaction of physical, chemical and biological factors. Two process-based models, the Agricultural Production Systems sIMulator (APSIM) and DeNitrification DeComposition (DNDC), were used to simulate nitrification, denitrification and nitrous oxide (N2O) emissions from soils following N input from either fertiliser or excreta deposition. The effect of environmental conditions on N transformations as simulated by the two different models was compared. Temperature had a larger effect in APSIM on nitrification, whereas in DNDC, water content produced a larger response. In contrast, simulated denitrification showed a larger response to temperature and also organic carbon content in DNDC. And while denitrification in DNDC is triggered by rainfall ≥5mm/h, in APSIM, the driving factor is soil water content, with a trigger point at water content at field capacity. The two models also showed different responses to N load, with nearly linearly increasing N2O emission rates with N load simulated by DNDC, and a lower rate by APSIM. Increasing rainfall intensity decreased APSIM-simulated N2O emissions but increased those simulated by DNDC. Copyright © 2012 Elsevier B.V. All rights reserved.

  10. The source of stratospheric NO and N2O

    NASA Technical Reports Server (NTRS)

    Slanger, T. G.

    1984-01-01

    The photodissociation of O3 was investigated as a possible sources of N2O production in the stratosphere. Photolysis was conducted at 1576 A to generate the excited O2 states that react with N2 to form N2O. At this wavelength, there is a quantum yield of two for prompt production of oygen atoms, which is a consequence of the existence of two photodissociative channels giving comparable yields. One of these channels gives O(D1) and O2(b1sigma(+)subg), with a quantum yield of 0.6, whereas the other results in fragmentation of the O3, with production of three ground state oxygen atoms. The O2(b) is generated with vibrational excitation, and there are comparable populations in levels O to 3. These observations are the first to show O2(b) production from any photodissociative process, and were made under conditions in which the kinetics of vibrationally excited O2(b) can be studied. It appears that O3 photodissociation at 1576 A is not a good system for generating the higher electronic states of O2; it is likely that better results will be obtained at 1930 A.

  11. (CaO)nIrO2 (n = 1, 2, 4) family: Chemical scissors effects of CaO on structural characteristics correlated to physical properties. Ab initio study

    NASA Astrophysics Data System (ADS)

    Matar, Samir F.; Etourneau, Jean

    2017-11-01

    Based on crystal chemistry analysis within Ca-Ir-O ternary, the generic (CaO)nIrO2 formula leading to CaIrO3 for n = 1, Ca2IrO4 for n = 2 and Ca4IrO6 for n = 4 actual chemical compounds show significant structural changes regarding the spatial arrangement of IrO6 octahedra whereby increasing amounts of CaO act as 'chemical scissor' decreasing the dimensionality of stacking octahedra from 3D (IrO2) to 0D (Ca4IrO6). This is accompanied by changes in the electronic structure investigated within density functional theory. Such changes are particularly exhibited by linear increase of Ir density of states at the Fermi level revealing increasing localization of d states with crystal field effects. Eventually only for Ca4IrO6 a magnetic instability occurs in non magnetic configuration. Spin polarized calculations lead to development of small magnitude but finite magnetization on Ir with M 0.50 μB totally polarized along minority spin channel ↓.

  12. Effect of granulated wood ash fertilization on N2O emissions in boreal peat forests

    NASA Astrophysics Data System (ADS)

    Liimatainen, Maarit; Martikainen, Pertti J.; Hytönen, Jyrki; Maljanen, Marja

    2016-04-01

    Peatlands cover one third of the land surface area in Finland and over half of that are drained for forestry. Natural peatlands are either small sources of nitrous oxide (N2O) or they can also act as a sinks of N2O. When peatlands are drained, oxygen concentration in the peat increases, organic matter decomposition accelerates and N2O emissions may increase significantly, especially in nutrient rich peat soils. Hence drainage and land-use changes can have a big impact on N2O fluxes in peatlands. The annual consumption of wood chips is to be increased to 13.5 M m3 from the present 8.7 M m3 in Finland. This will also increase the amount of wood ash in the power plants. Wood ash contains considerable amounts of mineral nutrients but lacks nitrogen. Therefore, it has been used as a fertilizer in nitrogen rich peatland forests lacking other nutrients. Recycling of ash would also return the nutrients lost during biomass harvesting back to the forests. We studied the effects of granulated wood ash as a fertilizer in peat soils drained for forestry. Ash is nowadays granulated mainly to facilitate its handling and spreading. Granulation also stabilizes the ash decreasing the solubility of most of the nutrients and minimizing harmful effects of ash spread over the vegetation. Granulated wood ash increases soil pH less than loose ash. Drainage of peatland forests increases microbial activity in the soil which is furthermore intensified with the addition of ash promoting organic matter decomposition and possibly affecting N2O emissions. We studied the effect of granulated wood ash on N2O fluxes in three different peat forests in Finland in both field and laboratory experiments. In the field, N2O emissions were not affected by granulated wood ash fertilization but the soil respiration rate increased. However, in the laboratory studies we observed a clear decrease in N2O production due to wood ash addition, although changes in pH values were only minor. We studied what could

  13. Comparison of N2O Emissions from Soils at Three Temperate Agricultural Sites

    NASA Technical Reports Server (NTRS)

    Frolking, S. E.; Moiser, A. R.; Ojima, D. S.; Li, C.; Parton, W. J.; Potter, C. S.; Priesack, E.; Stenger, R.; Haberbosch, C.; Dorsch, P.; hide

    1997-01-01

    Nitrous oxide (N2O) flux simulations by four models were compared with year-round field measurements from five temperate agricultural sites in three countries. The field sites included an unfertilized, semi-arid rangeland with low N2O fluxes in eastern Colorado, USA; two fertilizer treatments (urea and nitrate) on a fertilized grass ley cut for silage in Scotland; and two fertilized, cultivated crop fields in Germany where N2O loss during the winter was quite high. The models used were daily trace gas versions of the CENTURY model, DNDC, ExpertN, and the NASA-Ames version of the CASA model. These models included similar components (soil physics, decomposition, plant growth, and nitrogen transformations), but in some cases used very different algorithms for these processes. All models generated similar results for the general cycling of nitrogen through the agro-ecosystems, but simulated nitrogen trace gas fluxes were quite different. In most cases the simulated N20 fluxes were within a factor of about 2 of the observed annual fluxes, but even when models produced similar N2O fluxes they often produced very different estimates of gaseous N loss as nitric oxide (NO), dinitrogen (N2), and ammonia (NH3). Accurate simulation of soil moisture appears to be a key requirement for reliable simulation of N2O emissions. All models simulated the general pattern of low background fluxes with high fluxes following fertilization at the Scottish sites, but they could not (or were not designed to) accurately capture the observed effects of different fertilizer types on N2O flux. None of the models were able to reliably generate large pulses of N2O during brief winter thaws that were observed at the two German sites. All models except DNDC simulated very low N2O fluxes for the dry site in Colorado. The US Trace Gas Network (TRAGNET) has provided a mechanism for this model and site intercomparison. Additional intercomparisons are needed with these and other models and additional data

  14. Generating Breathable Air Through Dissociation of N2O

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Frankie, Brian

    2006-01-01

    A nitrous oxide-based oxygen-supply system (NOBOSS) is an apparatus in which a breathable mixture comprising 2/3 volume parts of N2 and 1/3 volume part of O2 is generated through dissociation of N2O. The NOBOSS concept can be adapted to a variety of applications in which there are requirements for relatively compact, lightweight systems to supply breathable air. These could include air-supply systems for firefighters, divers, astronauts, and workers who must be protected against biological and chemical hazards. A NOBOSS stands in contrast to compressed-gas and cryogenic air-supply systems. Compressed-gas systems necessarily include massive tanks that can hold only relatively small amounts of gases. Alternatively, gases can be stored compactly in greater quantities and at low pressures when they are liquefied, but then cryogenic equipment is needed to maintain them in liquid form. Overcoming the disadvantages of both compressed-gas and cryogenic systems, the NOBOSS exploits the fact that N2O can be stored in liquid form at room temperature and moderate pressure. The mass of N2O that can be stored in a tank of a given mass is about 20 times the mass of compressed air that can be stored in a tank of equal mass. In a NOBOSS, N2O is exothermically dissociated to N2 and O2 in a main catalytic reactor. In order to ensure the dissociation of N2O to the maximum possible extent, the temperature of the reactor must be kept above 400 C. At the same time, to minimize concentrations of nitrogen oxides (which are toxic), it is necessary to keep the reactor temperature at or below 540 C. To keep the temperature within the required range throughout the reactor and, in particular, to prevent the formation of hot spots that would be generated by local concentrations of the exothermic dissociation reaction, the N2O is introduced into the reactor through an injector tube that features carefully spaced holes to distribute the input flow of N2O widely throughout the reactor. A NOBOSS

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

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

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

  16. Method for synthesizing N.sub.2 O.sub.5

    DOEpatents

    McGuire, Raymond R.; Coon, Clifford L.; Harrar, Jackson E.; Pearson, Richard K.

    1985-01-01

    A method and apparatus for electrochemically synthesizing N.sub.2 O.sub.5 includes oxidizing a solution of N.sub.2 O.sub.4 /HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /HNO.sub.3 solution and the anode. A potential of about 1.35 to 2.0 V vs. SCE is preferred, while a potential of about 1.80 V vs. SCE is most preferred. Thereafter, the N.sub.2 O.sub.5 is reacted with either 1.5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) or 1,3,5,7-tetraacetyl-1,3,5,7-tetraazacyclooctane (TAT) to form cyclotetramethylenetetraamine (HMX).

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

    PubMed

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

    2002-03-01

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

  18. Oceanic N2O emissions in the 21st century

    NASA Astrophysics Data System (ADS)

    Martinez-Rey, J.; Bopp, L.; Gehlen, M.; Tagliabue, A.; Gruber, N.

    2014-12-01

    The ocean is a substantial source of nitrous oxide (N2O) to the atmosphere, but little is known on how this flux might change in the future. Here, we investigate the potential evolution of marine N2O emissions in the 21st century in response to anthropogenic climate change using the global ocean biogeochemical model NEMO-PISCES. We implemented two different parameterizations of N2O production, which differ primarily at low oxygen (O2) conditions. When forced with output from a climate model simulation run under the business-as-usual high CO2 concentration scenario (RCP8.5), our simulations suggest a decrease of 4 to 12% in N2O emissions from 2005 to 2100, i.e., a reduction from 4.03/3.71 to 3.54/3.56 Tg N yr-1 depending on the parameterization. The emissions decrease strongly in the western basins of the Pacific and Atlantic oceans, while they tend to increase above the Oxygen Minimum Zones (OMZs), i.e., in the Eastern Tropical Pacific and in the northern Indian Ocean. The reduction in N2O emissions is caused on the one hand by weakened nitrification as a consequence of reduced primary and export production, and on the other hand by stronger vertical stratification, which reduces the transport of N2O from the ocean interior to the ocean surface. The higher emissions over the OMZ are linked to an expansion of these zones under global warming, which leads to increased N2O production associated primarily with denitrification. From the perspective of a global climate system, the averaged feedback strength associated with the projected decrease in oceanic N2O emissions amounts to around -0.009 W m-2 K-1, which is comparable to the potential increase from terrestrial N2O sources. However, the assesment for a compensation between the terrestrial and marine feedbacks calls for an improved representation of N2O production terms in fully coupled next generation of Earth System Models.

  19. Effects of N2-O2 and CO2-O2 tensions on growth of fungi isolated from damaged flue-cured tobacco.

    PubMed

    Yang, H; Lucas, G B

    1970-02-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N(2)-O(2) or CO(2)-O(2). A 1 to 5% concentration of O(2) in an N(2) atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O(2) for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O(2). High O(2) concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O(2) in the N(2) atmosphere, furrows formed in mycelial mats between 5 and 40% O(2) in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O(2) decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO(2)-O(2) mixtures radial growth of all species increased with each quantitative decrease of CO(2). All species except A. niger grew faster in air than in 10% CO(2). In contrast to N(2)-O(2) mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O(2) concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

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

  1. Toxic effect of Cr(VI) in presence of n-TiO2 and n-Al2O3 particles towards freshwater microalgae.

    PubMed

    Dalai, Swayamprava; Pakrashi, Sunandan; Bhuvaneshwari, M; Iswarya, V; Chandrasekaran, N; Mukherjee, Amitava

    2014-01-01

    The reactivity and toxicity of the soluble toxicants in the presence of the engineered nanomaterials is not well explored. In this study, the probable effects of TiO2 and Al2O3 nanoparticles (n-TiO2, n-Al2O3) on the toxicity of Cr(VI) were assessed with the dominant freshwater algae, Scenedesmus obliquus, in a low range of exposure concentrations (0.05, 0.5 and 1μg/mL). In the presence of 0.05μg/mL n-TiO2, the toxicity of Cr(VI) decreased considerably, which was presumably due to the Cr(VI) adsorption on the nanoparticle surface leading to its aggregation and precipitation. The elevated n-TiO2 concentrations (0.5 and 1μg/mL) did not significantly influence Cr(VI) bio-availability, and a dose dependent toxicity of Cr(VI) was observed. On the other hand, n-Al2O3 did not have any significant effect on the Cr(VI) toxicity. The microscopic observations presented additional information on the morphological changes of the algal cells in the presence of the binary toxicants. The generation of reactive oxygen species (ROS) suggested contribution of oxidative stress on toxicity and LDH release confirmed membrane permeability of algal cells upon stress. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. [Effects of different fertilization measures on N2O emission in oil sunflower field in irrigation area of upper Yellow River].

    PubMed

    Chen, Zhe; Chen, Yuan-yuan; Gao, Ji; Liu, Ru-liang; Yang, Zheng-li; Zhang, Ai-ping

    2015-01-01

    Agricultural soil has become the largest anthropogenic source of atmospheric nitrous oxide (N20). To estimate the impacts of long-term combined application of organic and inorganic fertilizers on N20 emission in a typical winter wheat-oil sunflower cropping system in the Ningxia irrigation area, we measured N20 fluxes using the static opaque chamber-gas chromatograph method and monitored the seasonal dynamics of related factors. Our results showed that nitrogen addition in the previous crop field significantly stimulated N2O emissions during the following oil-sunflower cultivation, and the mean fluxes of N300-OM, N240-OM1/2, N300 and N240 were (34.16 ± 9.72), (39.69 ±10.70), (27.75 ±9.57) and (26.30 ± 8.52) µg . m-2 . h-1, respectively, which were 4.09, 4.75, 3.32 and 3.15 times of the control groups. The total cumulative N2O emissions of fertilizer treatments in growing season was as high as 796.7 to 1242.5 g . hm-2, which was 2.99 to 4.67 times of the control groups. During the growing season, the rates of N2O emission in each month organic and inorganic fertlizers combined treatments were similar at high levels. N2O emission in chemical fertilizer treatments gradually decreased, and the main period of N2O emission occurred at the beginning of growing season. Taking July for example, N2O emission accounted for 41.3% to 41. 8% of total cumulative amount. The amounts of N20 emission under organic and inorganic fertilizers combined treatments were significantly higher than under chemical fertilizer treatments. The N2O emissions were not significantly different between conventional and optimized applications of nitrogen fertilizer under the same fertilizing method, either between N300-OM and N240-OM1/2, or between N300 and N240. On account of the drought, N2O emission in each treatment was mainly affected by soil moisture. N2O emission had a significant positive correlation with soil ammonium nitrogen content under combined applications of organic and inorganic

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

    PubMed

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

    2007-02-15

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

  4. Diagnosing ozone recovery using the O3-N2O relationship

    NASA Astrophysics Data System (ADS)

    Butler, A. H.; Gao, R. S.; Maycock, A.; Portmann, R. W.; Thornberry, T. D.; Rosenlof, K. H.; Fahey, D. W.

    2016-12-01

    The ubiquitous compact correlation between collocated values of stratospheric ozone (O3) and the tracer nitrous oxide (N2O) results from the stratospheric photochemical processes that produce ozone and destroy N2O combined with common transport and mixing processes. Changes in the correlation slope under certain circumstances reflect changes in the production and loss balance of ozone. This approach has been used extensively to diagnose and quantify ozone loss in polar spring. Using a coupled atmosphere-ocean model with interactive chemistry (CESM/WACCM), we show that this relationship can be used to diagnose ozone recovery in the lower extratropical stratosphere. We then consider in situ measurements of O3 and N2O from ATTREX, GloPac, and HIPPO as well as satellite measurements from ACE and Aura MLS to consider whether ozone recovery can be detected in observations during the period 2004-2016.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  6. Measurements of the O+ plus N2 and O+ plus O2 reaction rates from 300 to 900 K

    NASA Technical Reports Server (NTRS)

    Chen, A.; Johnsen, R.; Biondi, M. A.

    1977-01-01

    Rate coefficients for the O(+) + N2 atom transfer and O(+) + O2 charge transfer reactions are determined at thermal energies between 300 K and 900 K difference in a heated drift tube mass spectrometer apparatus. At 300 K the values K(O(+) + N2) = (1.2 plus or minus 0.1) x 10 to the negative 12 power cubic cm/sec and k(O(+) + O2) = (2.1 plus or minus 0.2) x 10 to the negative 11 power cubic cm/sec were obtained, with a 50% difference decrease in the reaction rates upon heating to 700 K. These results are in good agreement with heated flowing afterglow results, but the O(+) + O2 thermal rate coefficients are systematically lower than equivalent Maxwellian rates inferred by conversion of nonthermal drift tube and flow drift data.

  7. Synthesis and Characterization of LaTiO2N

    NASA Astrophysics Data System (ADS)

    Rugen, Evan E.

    Photocatalysts offer an excellent opportunity to shift the global energy landscape from a fossil fuel-dependent paradigm to sustainable and carbon-neutral solar fuels. Oxynitride materials such as LaTiO2N are potential photocatalysts for the water splitting reaction due to their high oxidative stability and their narrow band gaps, which are suitable for visible light absorption. However, facile synthetic routes to metal oxynitrides with controlled morphologies are rare, and the local structures of these materials are under-characterized. Ultrasonic spray synthesis (USS) offers a facile method toward complex metal oxides which can potentially be converted to oxynitrides with preservation of the microsphere structures that typify the products from such aerosol routes. Here, La-Ti-O microspheres were facilely produced by USS and converted by ammonolysis to LaTiO2N microspheres with porous shells and hollow interiors. This particle architecture is accounted for by coupling suitable combustion chemistry with the aerosol technique, producing precursor particles where the La3+ and Ti4+ are well-mixed at small length scales; this feature enables preservation of the microsphere morphology during nitridation despite the crystallographic changes that occur. The LaTiO2N microspheres are comparable oxygen evolving photocatalysts to samples produced by conventional solid state methods. Pair distribution function (PDF) analysis is a local probe designed to examine the structure of disordered crystalline materials, and is an ideal technique for characterizing the ordering of anions in oxynitrides. Preliminary studies using PDF analysis to determine the presence of anion ordering and local structure in LaTiO2N produced by solid state methods are presented here. Future experiments are proposed that will grant detailed insight into the factors driving the degree of anion ordering in these types of materials. These results demonstrate the utility of USS as a facile, potentially

  8. N3 and O2 protonated tautomeric conformations of 2'-deoxycytidine and cytidine coexist in the gas phase.

    PubMed

    Wu, R R; Yang, Bo; Frieler, C E; Berden, G; Oomens, J; Rodgers, M T

    2015-05-07

    Infrared multiple photon dissociation action spectra of the protonated forms of the cytidyl nucleosides, 2'-deoxycytidine, [dCyd+H](+), and cytidine, [Cyd+H](+), are acquired over the IR fingerprint and hydrogen-stretching regions. Electronic structure calculations are performed at the B3LYP/6-311+G(d,p) level to determine the stable low-energy tautomeric conformations of these species generated upon electrospray ionization (ESI) and to generate the linear IR absorption spectra of these protonated nucleosides. Comparison between the experimental and theoretical spectra allows the tautomeric conformations of [dCyd+H](+) and [Cyd+H](+) populated by ESI to be determined. B3LYP predicts N3 as the preferred protonation site for both [dCyd+H](+) and [Cyd+H](+), whereas MP2 suggests that protonation at O2 is more favorable. The 2'-hydroxyl substituent does not significantly alter the structures of the B3LYP N3 and MP2 O2 protonated ground tautomeric conformations of [dCyd+H](+) vs [Cyd+H](+). [dCyd+H](+) and [Cyd+H](+) exhibit very similar spectral signatures in both regions. Nonetheless, the 2'-hydroxyl does affect the relative intensities of the IRMPD bands of [dCyd+H](+) vs [Cyd+H](+). The spectral features observed in the hydrogen-stretching region complement those of the fingerprint region and allow the N3 and O2 protonated tautomeric conformations to be readily distinguished. Comparison between the measured and computed spectra indicates that both N3 and O2 protonated tautomeric conformations coexist in the experiments, and the populations are dominated by the most stable N3 and O2 protonated tautomeric conformations. Least-squares fitting of the IRMPD spectra to the IR spectra for these most stable conformers suggests relative populations of ∼55% N3 vs 45% O2 protonated conformers of [dCyd+H](+), whereas ∼47% N3 vs 53% O2 protonated conformers of [Cyd+H](+). This change in the preferred site of protonation indicates that the 2'-hydroxyl substituent plays an

  9. Diode laser-based cavity ring-down instrument for NO3, N2O5, NO, NO2 and O3 from aircraft

    NASA Astrophysics Data System (ADS)

    Wagner, N. L.; Dubé, W. P.; Washenfelder, R. A.; Young, C. J.; Pollack, I. B.; Ryerson, T. B.; Brown, S. S.

    2011-06-01

    This article presents a diode laser-based, cavity ring-down spectrometer for simultaneous in situ measurements of four nitrogen oxide species, NO3, N2O5, NO, NO2, as well as O3, designed for deployment on aircraft. The instrument measures NO3 and NO2 by optical extinction at 662 nm and 405 nm, respectively; N2O5 is measured by thermal conversion to NO3, while NO and O3 are measured by chemical conversion to NO2. The instrument has several advantages over previous instruments developed by our group for measurement of NO2, NO3 and N2O5 alone, based on a pulsed Nd:YAG and dye laser. First, the use of continuous wave diode lasers reduces the requirements for power and weight and eliminates hazardous materials. Second, detection of NO2 at 405 nm is more sensitive than our previously reported 532 nm instrument, and does not have a measurable interference from O3. Third, the instrument includes chemical conversion of NO and O3 to NO2 to provide measurements of total NOx (= NO + NO2) and Ox (= NO2 + O3) on two separate channels; mixing ratios of NO and O3 are determined by subtraction of NO2. Finally, all five species are calibrated against a single standard based on 254 nm O3 absorption to provide high accuracy. Disadvantages include an increased sensitivity to water vapor on the 662 nm NO3 and N2O5 channels and a modest reduction in sensitivity for these species compared to the pulsed laser instrument. The in-flight detection limit for both NO3 and N2O5 is 3 pptv (2 σ, 1 s) and for NO, NO2 and O3 is 140, 90, and 120 pptv (2 σ, 1 s) respectively. Demonstrated performance of the instrument in a laboratory/ground based environment is better by approximately a factor of 2-3. The NO and NO2 measurements are less precise than research-grade chemiluminescence instruments. However, the combination of these five species in a single instrument, calibrated to a single analytical standard, provides a complete and accurate picture of nighttime nitrogen oxide chemistry. The

  10. Stability of nTiO2 particles and their attachment to sand: Effects of humic acid at different pH.

    PubMed

    Wu, Yang; Cheng, Tao

    2016-01-15

    The fate and transport of nano-scale or micro-scale titanium dioxide particles (nTiO2) in subsurface environments are strongly influenced by the stability of nTiO2 and their attachment to sediment grains. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively-charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand at HA concentrations that are relevant to typical groundwater conditions, so that mechanisms that control nTiO2 immobilization and transport in natural systems can be elucidated. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand are experimentally measured under a range of HA concentrations at pH5 and 9. Results show that at pH5, negatively-charged HA strongly adsorbs to positively-charged nTiO2 and Fe oxyhydroxide, which, at low HA concentrations, partially neutralizes the positive charges on nTiO2 and Fe oxyhydroxide, and therefore decreases the repulsive electrostatic forces between the surfaces, resulting in nTiO2 aggregation and attachment. At high HA concentrations, adsorbed HA reverses the surface charges of nTiO2 and Fe oxyhydroxide, and makes nTiO2 and Fe oxyhydroxide strongly negatively charged, resulting in stable nTiO2 suspension and low nTiO2 attachment. At pH9, HA, nTiO2, and Fe oxyhydroxide are all negatively charged, and HA adsorption is low and does not have a strong impact on the stability and attachment of nTiO2. Overall, this study shows that changes in surface charges of nTiO2 and Fe oxyhydroxide coating caused by HA adsorption is a key factor that influences the stability and attachment of nTiO2. Copyright © 2015 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

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

    PubMed

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

    2012-06-01

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

  13. Quantification of nitrous oxide (N2O) emissions and soluble microbial product (SMP) production by a modified AOB-NOB-N2O-SMP model.

    PubMed

    Kim, MinJeong; Wu, Guangxue; Yoo, ChangKyoo

    2017-03-01

    A modified AOB-NOB-N 2 O-SMP model able to quantify nitrous oxide (N 2 O) emissions and soluble microbial product (SMP) production during wastewater treatment is proposed. The modified AOB-NOB-N 2 O-SMP model takes into account: (1) two-step nitrification by ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), (2) N 2 O production by AOB denitrification under oxygen-limited conditions and (3) SMP production by microbial growth and endogenous respiration. Validity of the modified model is demonstrated by comparing the simulation results with experimental data from lab-scale sequencing batch reactors (SBRs). To reliably implement the modified model, a model calibration that adjusts model parameters to fit the model outputs to the experimental data is conducted. The results of this study showed that the modeling accuracy of the modified AOB-NOB-N 2 O-SMP model increases by 19.7% (NH 4 ), 51.0% (NO 2 ), 57.8% (N 2 O) and 16.7% (SMP) compared to the conventional model which does not consider the two-step nitrification and SMP production by microbial endogenous respiration. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

    PubMed

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

    2017-12-01

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

  15. N2O production by nitrifier denitrification in the Benguela Upwelling System

    NASA Astrophysics Data System (ADS)

    Frame, C. H.; Hou, L.; Lehmann, M. F.

    2014-12-01

    The Benguela upwelling system off the coast of southwestern Africa is an important zone of marine N2O production whose upwelling rates vary seasonally. Here we present N2O stable isotopic and isotopomeric data collected during a period of high upwelling (September 2013) and low upwelling (January 2014). During both periods, 15N-nitrite and 15N-ammonium tracer inucbation experiments were used to investigate N2O production by ammonia oxidizing microorganisms in the top 150m of the water column. N2O production from 15N-ammonium was not measurable during these incubations. However, we detected N2O production from 15N-nitrite, suggesting that nitrifier denitrification is a source of shallow N2O in this region. Furthermore, decreasing the pH of the incubation water enhanced the amount of N2O produced, suggesting that upwelling of CO2-rich/low-pH deep water may enhance N2O production in this region. Finally, we present our incubation data in the larger context of the N2O and nitrite isotopic and concentration profiles, with an eye toward comparing incubation-based N2O production rates with profile-based estimates.

  16. Yield-scaled N2O emissions were effectively reduced by biochar amendment of sandy loam soil under maize - wheat rotation in the North China Plain

    NASA Astrophysics Data System (ADS)

    Niu, Yuhui; Chen, Zengming; Müller, Christoph; Zaman, Monhammad M.; Kim, Donggill; Yu, Hongyan; Ding, Weixin

    2017-12-01

    It is increasingly recognized that the addition of biochar to soil has potential to mitigate climate change and increase soil fertility by enhancing carbon (C) storage. However, the effect of biochar on yield and nitrous oxide (N2O) emissions from upland fields remains unclear. In this study, a one-year field experiment was conducted in an area of calcareous fluvo-aquic soil to assess and quantify the effect of maize straw biochar in reducing N2O loss during 2014-2015 in the North China Plain. Eight treatments were designed as follows: no nitrogen (N) fertilizer (control, CK); biochar application at rates of 3 (B3), 6 (B6) and 12 (B12) t ha-1; chemical fertilizer (NPK) application at 200 kg N ha-1 (F); and fertilizer plus biochar application at rates of 3 (FB3), 6 (FB6) and 12 (FB12) t ha-1. Crop yield, N2O fluxes, soil mineral N concentrations, and soil auxiliary parameters were measured following the application of treatments during each season. During the maize growing season, N2O emission was 0.57 kg N2O-N ha-1 under CK treatment, and increased to 0.88, 0.93 and 1.10 kg N2O-N ha-1 under B3, B6 and B12, respectively. In contrast, N2O emissions were significantly reduced by 31.4-39.9% (P < 0.05) under FB treatments compared with F, and the N2O emission factor of the applied N was reduced from 1.36% under F to 0.71-0.85% under FB. There was also a significant interaction effect of fertilizer and biochar on N2O emissions (P < 0.01). During the wheat growing season, biochar had no effect on N2O emissions regardless of the fertilizer regime. Biochar application did not affect maize yield; however, a significant increase in wheat yield of 16.6-25.9% (P < 0.05) was observed without N fertilization. Nevertheless, a reduction in wheat yield was measured at a biochar rate of 12 t ha-1 with fertilization. Overall, under maize cropping, N2O emissions per unit yield of grain, biomass, grain N and biomass N (yield-scaled N2O emissions) were significantly reduced by 32

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

    PubMed

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

    2013-03-01

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

  18. Airborne testing and demonstration of a new flight system based on an Aerodyne N2O-CO2-CO-H2O mini-spectrometer

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

    Nitrous oxide (N2O) is a powerful greenhouse gas and ozone depleting substance. With high atmospheric backgrounds and small relative signals, N2O emissions have been challenging to observe and understand on regional scales with traditional instrumentation. Fast-response airborne measurements with high precision and accuracy can potentially bridge this observational gap. Here we present flight assessments of a new flight system based on an Aerodyne mini-spectrometer as well as a Los Gatos N2O/CO analyzer during the Fertilizer Emissions Airborne Study (FEAST). With the Scientific Aviation Mooney aircraft, we conducted test flights for both analyzers where a known calibration gas was sampled throughout the flight (`null' tests). Clear altitude/cabin-pressure dependencies were observed for both analyzers if operated in an "off-the-shelf' manner. For the remainder of test flights and the FEAST campaign we used a new flight system based on an Aerodyne mini-spectrometer with the addition of a custom pressure control/calibration system. Instead of using traditional approaches with spectral-zeros and infrequent in-flight calibrations, we employ a high-flow system with stable flow control to enable high frequency (2 minutes), short duration (15 seconds) sampling of a known calibration gas. This approach, supported by the null test, enables correction for spectral drift caused by a variety of factors while maintaining a 90% duty cycle for 1Hz sampling from an aircraft. Preliminary in-flight precisions are estimated at 0.05 ppb, 0.1 ppm, 1 ppb, and 10 ppm for N2O, CO2, CO, and H2O respectively. We also present a further 40 hours of inter-comparison in flight with a Picarro 2301-f ring-down spectrometer demonstrating consistency between CO2 and H2O measurements and no altitude dependent error.

  19. Electrical and carrier transport properties of the Au/Y2O3/n-GaN metal-insulator-semiconductor (MIS) diode with rare-earth oxide interlayer

    NASA Astrophysics Data System (ADS)

    Venkata Prasad, C.; Rajagopal Reddy, V.; Choi, Chel-Jong

    2017-04-01

    The electrical and transport properties of rare-earth Y2O3 on n-type GaN with Au electrode have been investigated by current-voltage and capacitance-voltage techniques at room temperature. The Au/Y2O3/n-GaN metal-insulator-semiconductor (MIS) diode shows a good rectification behavior compared to the Au/n-GaN metal-semiconductor (MS) diode. Statistical analysis showed that a mean barrier height (BH) and ideality factor are 0.78 eV and 1.93, and 0.96 eV and 2.09 for the Au/n-GaN MS and Au/Y2O3/n-GaN MIS diodes, respectively. Results indicate that the high BH is obtained for the MIS diode compared to the MS diode. The BH, ideality factor and series resistance are also estimated by Cheung's function and Norde method. From the forward current-voltage data, the interface state density ( N SS) is estimated for both the MS and MIS Schottky diodes, and found that the estimated N SS is lower for the MIS diode compared to the MS diode. The results reveal that the introduction of Y2O3 interlayer facilitated the reduction of N SS of the Au/n-GaN interface. Experimental results suggest that the Poole-Frenkel emission is a dominant conduction mechanism in the reverse bias region of both Au/n-GaN MS and Au/Y2O3/n-GaN MIS diodes.

  20. Emission and control of N2O and composition of ash derived from cattle manure combustion using a pilot-scale fluidized bed incinerator.

    PubMed

    Oshita, Kazuyuki; Kawaguchi, Koji; Takaoka, Masaki; Matsukawa, Kazutsugu; Fujimori, Takashi; Fujiwara, Taku

    2015-10-06

    This study investigates the emission of nitrous oxide (N 2 O) and discusses the reduction of N 2 O emissions during the 24-h combustion of cattle manure using a pilot-scale fluidized bed incinerator under various experimental conditions. The results of these experiments were then validated against previously reported data. In addition, the characteristics of cattle manure incineration ash and their changes under different combustion conditions were estimated. In incineration experiments with composted cattle manure, N 2 O concentrations using multi-stage combustion were 75% lower than the concentrations resulting from normal combustion without additional auxiliary fuel, since N 2 O could be decomposed in the high-temperature zone formed by the inlet of the secondary combustion air. The N 2 O emission factor under normal combustion conditions (800°C) was 6.0% g-N 2 O-N/g-N. This result is similar to the values found in previous studies at the same temperature. The N 2 O emission factor was decreased to 1.6% g-N 2 O-N/g-N using a multi-stage combustion procedure. The current Japanese N 2 O emission factor of 0.1% g-N 2 O-N/g-N is an underestimate for some conditions and should be uniquely specified for each condition. Finally, cattle manure ash contains ample fertilizer elements, little Fe, Al and Zn, but abundant Cl. Therefore if Cl could be removed by some kind of pretreatment, cattle manure ash could be used as a favourable fertilizer.

  1. Hydrogen sensors based on Sc2O3/AlGaN/GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Kang, B. S.; Mehandru, R.; Kim, S.; Ren, F.; Fitch, R. C.; Gillespie, J. K.; Moser, N.; Jessen, G.; Jenkins, T.; Dettmer, R.; Via, D.; Crespo, A.; Baik, K. H.; Gila, B. P.; Abernathy, C. R.; Pearton, S. J.

    2005-05-01

    Pt contacted AlGaN/GaN high electron mobility transistors with Sc2O3 gate dielectrics show reversible changes in drain-source current upon exposure to H2-containing ambients, even at room temperature. The changes in current (as high as 3 mA for relatively low gate voltage and drain-source voltage at 25 °C for the HEMTs and a change in forward current of 40 μA at a bias of 2.5 V was obtained for the MOS-diodes in response to a change in ambient from pure N2 to 10% H2/90% N2. The current changes in the latter case are almost linearly proportional to the testing temperature and reach around 400 μA at 400 °C. These signals are approximately an order of magnitude larger than for Pt /GaN Schottky diodes and a factor of 5 larger than Sc2O3/AlGaN/GaN metal-oxide semiconductor (MOS) diodes exposed under the same conditions. This shows the advantage of using a transistor structure in which the gain produces larger current changes upon exposure to hydrogen-containing ambients. The increase in current is the result of a decrease in effective barrier height of the MOS gate of 30-50 mV at 25 °C for 10%H2/90%N2 ambients relative to pure N2 and is due to catalytic dissociation of the H2 on the Pt contact, followed by diffusion to the Sc2O3/AlGaN interface.

  2. Effects of N2-O2 and CO2-O2 Tensions on Growth of Fungi Isolated from Damaged Flue-Cured Tobacco 1

    PubMed Central

    Yang, H.; Lucas, G. B.

    1970-01-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N2-O2 or CO2-O2. A 1 to 5% concentration of O2 in an N2 atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O2 for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O2. High O2 concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O2 in the N2 atmosphere, furrows formed in mycelial mats between 5 and 40% O2 in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O2 decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO2-O2 mixtures radial growth of all species increased with each quantitative decrease of CO2. All species except A. niger grew faster in air than in 10% CO2. In contrast to N2-O2 mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O2 concentrations. PMID:5461786

  3. A pure inorganic 1D chain based on {Mo8O28} clusters and Mn(II) ions: [Mn(H2O)2Mo8O28 ] n 6 n -

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaofen; Yan, Yonghong; Wu, Lizhou; Yu, Chengxin; Dong, Xinbo; Hu, Huaiming; Xue, Ganglin

    2016-01-01

    A new pure inorganic polymer, (NH4)6n[Mn(H2O)2Mo8O28)]n(H2O)2n(1), has been synthesized and characterized by elemental analyses, IR spectrum, UV-vis absorption spectra, TG-DSC and electrochemical studies. In 1, [Mo8O28]8- anions act as tetradentate ligands and are alternately linked by Mn(H2O)2 2 + ions into a one-dimensional chain structure. It is interesting that 1 represents the first example of pure inorganic-inorganic hybrid based on octamolybdate and transition metal ions. Moreover, it was indicated that 1 had definite catalytic activities on the probe reaction of benzyl alcohol oxidation to benzaldehyde with H2O2.

  4. N2O eddy covariance fluxes: From field measurements to flux calculation

    NASA Astrophysics Data System (ADS)

    Lognoul, Margaux; Debacq, Alain; Heinesch, Bernard; Aubinet, Marc

    2017-04-01

    -lag optimization suggested by EddyPro was not used as it gave inconsistent values for our dataset. 3) The effect of high frequency spectral correction was also investigated by comparing different in-situ methods to evaluate how using spectra or co-spectra - averaged or not - can affect results. Finally, a preliminary analysis of N2O fluxes dynamics will be presented.

  5. NO versus N2O emissions from an NH4 +-amended Bermuda grass pasture

    NASA Astrophysics Data System (ADS)

    Hutchinson, G. L.; Brams, E. A.

    1992-06-01

    We used an enclosure technique to monitor soil NO and N2O emissions during early summer regrowth of Bermuda grass (Cynodon dactylon) on sandy loam in a humid, subtropical region of southern Texas. The evolution of both gases was substantially higher from plots harvested at the beginning of the experiment and fertilized 5 days later with 52 kg N ha-1 as (NH4)2SO4 than from plots not harvested or fertilized. Emission of NO, but not N2O, was stimulated by clipping and removing the grass, probably because eliminating the shading provided by the dense grass canopy changed these plots from cooler to warmer than unharvested plots, thereby stimulating the activity of soil microorganisms responsible for NO production. Neither gas flux was significantly affected by application of N until the next rainfall dissolved and moved the surface-applied fertilizer into the soil. Immediately thereafter, emissions of NO and N2O increased dramatically to peaks of 160 and 12 g N ha-1 d-1, respectively, and then declined at rates that closely paralleled the nitrification rate of added NH4+, indicating that the gases resulted from the activity of nitrifying microorganisms, rather than denitrifiers. Nitric oxide emissions during the 9-week measurement period averaged 7.2 times greater than N2O emissions and accounted for 3.2% of the added N. The data indicate that humid, subtropical grasslands, which not only have large geographical extent but also have been subject to intense anthropogenic disturbance, contribute significantly to the global atmospheric NOx budget.

  6. NO versus N2O emissions from an NH4(+)-amended Bermuda grass pasture

    NASA Technical Reports Server (NTRS)

    Hutchinson, G. L.; Brams, E. A.

    1992-01-01

    An enclosure technique is used to monitor soil NO and N2O emissions during early summer regrowth of Bermuda grass (Cynodon dactylon) on sandy loam in a humid, subtropical region of southern Texas. The evolution of both gases was substantially higher from plots harvested at the beginning of the experiment and fertilized five days later with 52 kg N/ha as (NH4)2SO4 than from plots not harvested or fertilized. Emission of NO, but not N2O, was stimulated by clipping and removing the grass, probably because eliminating the shading provided by the dense grass canopy changed these plots from cooler to warmer than unharvested plots, thereby stimulating the activity of soil microorganisms responsible for NO production. Neither gas flux was significantly affected by application of N until the next rainfall dissolved and moved the surface-applied fertilizer into the soil. Immediately thereafter, emissions of NO and N2O increased dramatically to peaks of 160 and 12 g N/ha/d, respectively, and then declined at rates that closely parallel the nitrification rate of added NH4(+), indicating that the gases resulted from the activity of nitrifying microorganisms, rather than denitrifiers. Nitric oxide emissions during the nine-week measurement period averaged 7.2 times greater than N2O emissions and accounted for 3.2 percent of the added N. The data indicate that humid, subtropical grasslands, which not only have large geographical extent but also have been subject to intense anthropogenic disturbance, contribute significantly to the global atmospheric NO(x) budget.

  7. Effects of warming on N2O fluxes in a boreal peatland of Permafrost region, Northeast China.

    PubMed

    Cui, Qian; Song, Changchun; Wang, Xianwei; Shi, Fuxi; Yu, Xueyang; Tan, Wenwen

    2018-03-01

    Climate warming is expected to increasingly influence boreal peatlands and alter their greenhouse gases emissions. However, the effects of warming on N 2 O fluxes and the N 2 O budgets were ignored in boreal peatlands. Therefore, in a boreal peatland of permafrost zone in Northeast China, a simulated warming experiment was conducted to investigate the effects of warming on N 2 O fluxes in Betula. Fruticosa community (B. Fruticosa) and Ledum. palustre community (L. palustre) during the growing seasons from 2013 to 2015. Results showed that warming treatment increased air temperature at 1.5m aboveground and soil temperature at 5cm depth by 0.6°C and 2°C, respectively. The average seasonal N 2 O fluxes ranged from 6.62 to 9.34μgm -2 h -1 in the warming plot and ranged from 0.41 to 4.55μgm -2 h -1 in the control plots. Warming treatment increased N 2 O fluxes by 147% and transformed the boreal peatlands from a N 2 O sink to a source. The primary driving factors for N 2 O fluxes were soil temperature and active layer depth, whereas soil moisture showed a weak correlation with N 2 O fluxes. The results indicated that warming promoted N 2 O fluxes by increasing soil temperature and active layer depth in a boreal peatland of permafrost zone in Northeast China. Moreover, elevated N 2 O fluxes persisted in this region will potentially drive a noncarbon feedback to ongoing climate change. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Alberti, Michael; Weber, Roman; Mancini, Marco

    2018-01-01

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

  9. Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on ammonia oxidizers and N2O emissions in a grazed pasture soil.

    PubMed

    Dai, Yu; Di, Hong J; Cameron, Keith C; He, Ji-Zheng

    2013-11-01

    Ammonia oxidizers, including ammonia oxidizing bacteria (AOB) and ammonia oxidizing archaea (AOA) are important drivers of a key step of the nitrogen cycle - nitrification, which affects the production of the potent greenhouse gas, nitrous oxide (N2O). A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of AOB and AOA and on N2O emissions in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha(-1) and animal urine at 300 and 600 kg N ha(-1). DCD was applied to some of the N treatments at 10 kg ha(-1). The results showed that the AOB amoA gene copy numbers were greater than those of AOA. The highest ratio of the AOB to AOA amoA gene copy numbers was 106.6 which occurred in the urine-N 600 treatment. The AOB amoA gene copy numbers increased with increasing nitrogen application rates. DCD had a significant impact in reducing the AOB amoA gene copy numbers especially in the high nitrogen application rates. N2O emissions increased with the N application rates. DCD had the most significant effect in reducing the daily and total N2O emissions in the highest nitrogen application rate. The greatest reduction of total N2O emissions by DCD was 69% in the urine-N 600 treatment. The reduction in the N2O emission factor by DCD ranged from 58% to 83%. The N2O flux and NO3(-)-N concentrations were significantly correlated to the growth of AOB, rather than AOA. This study confirms the importance of AOB in nitrification and the effect of DCD in inhibiting AOB growth and in decreasing N2O emissions in grazed pasture soils under field conditions. Copyright © 2012 Elsevier B.V. All rights reserved.

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

    NASA Technical Reports Server (NTRS)

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

    1989-01-01

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

  11. Increasing the availability of l-arginine and nitric oxide increases sensitivity of nitrous oxide (N2O)-insensitive inbred mice to N2O-induced antinociception.

    PubMed

    Chung, Eunhee; Ohgami, Yusuke; Quock, Raymond M

    2016-07-01

    Nitrous oxide (N2O)-induced antinociception in mice is dependent on the neuromodulator nitric oxide (NO). In contrast to C57BL/6J (B6) mice, DBA/2J (D2) mice fail to respond to N2O with a robust antinociceptive response or with an increase in brain nitric oxide synthase (NOS) enzyme activity, suggesting that failure of D2 mice to respond to N2O might result from a deficit of NO function. Therefore, it was of interest to determine whether increasing the availability of NO might increase sensitivity of D2 mice to N2O. Male D2 mice were pretreated with sub-antinociceptive intracerebroventricular doses of the NO donor 3-morpholinosydnoimine or the NO precursor l-arginine then assessed for responsiveness to N2O-induced antinociception using the acetic acid abdominal constriction test. Both pretreatments increased the antinociceptive responsiveness of D2 mice to N2O. These results indicate that the NOS enzyme in D2 mice is functional and that the deficit in NO function that obstructs sensitivity to N2O-induced antinociception may lie in availability or utilization of l-arginine. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Ternary composite of TiO2 nanotubes/Ti plates modified by g-C3N4 and SnO2 with enhanced photocatalytic activity for enhancing antibacterial and photocatalytic activity.

    PubMed

    Faraji, Masoud; Mohaghegh, Neda; Abedini, Amir

    2018-01-01

    A series of g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plates were fabricated via simple dipping of TiO 2 nanotubes/Ti in a solution containing SnCl 2 and g-C 3 N 4 nanosheets and finally annealing of the plates. Synthesized plates were characterized by various techniques. The SEM analysis revealed that the g-C 3 N 4 -SnO 2 nanosheets with high physical stability have been successfully deposited onto the surface of TiO 2 nanotubes/Ti plate. Photocatalytic activity was investigated using two probe chemical reactions: oxidative decomposition of acetic acid and oxidation of 2-propanol under irradiation. Antibacterial activities for Escherichia coli (E. coli) bacteria were also investigated in dark and under UV/Vis illuminations. Detailed characterization and results of photocatalytic and antibacterial activity tests revealed that semiconductor coupling significantly affected the photocatalyst properties synthesized and hence their photocatalytic and antibacterial activities. Modification of TiO 2 nanotubes/Ti plates with g-C 3 N 4 -SnO 2 deposits resulted in enhanced photocatalytic activities in both chemical and microbial systems. The g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plate exhibited the highest photocatalytic and antibacterial activity, probably due to the heterojunction between g-C 3 N 4 -SnO 2 and TiO 2 nanotubes/Ti in the ternary composite plate and thus lower electron/hole recombination rate. Based on the obtained results, a photocatalytic and an antibacterial mechanism for the degradation of E. coli bacteria and chemical pollutants over g-C 3 N 4 -SnO 2 /TiO 2 nanotubes/Ti plate were proposed and discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. [County-scale N2O emission inventory of China's manure management system].

    PubMed

    Wang, Chuan; Gao, Wei; Zhou, Feng; Chen, Qing; Ying, Na; Xu, Peng; Hou, Xi-Kang

    2013-10-01

    Manure is one of the two largest contributors to China's N2O emission. By using the county-scale activity data and the regional emission factors and related parameters with spatial differentiation in China in 2008, this paper assessed the N2O emission loading, sources profile, spatial pattern, and uncertainty, aimed to establish a high-resolution N2O emission inventory of China's manure management system in 2008. As compared with the research results based on the IPCC, EDGAR, and other works, the proposed emission inventory was more reliable and comprehensive. The total China' s N2O emission from manure in 2008 was estimated as 572 Gg, among which, the emission from the manure except pasture/range/paddock was 322 Gg (56.3%), from the manure in pasture/range/paddock was 180 Gg (31.5%), and the indirect emission from atmospheric volatilized N deposition and leaching/runoff was 45.8 Gg (8.0%) and 1.23 Gg (0.2%), respectively. The spatial pattern of China's N2O emission from manure was more centralized, and mainly concentrated in Jilin, Shandong, Sichuan, Hunan, Henan, Heilongjiang, and Liaoning provinces, contributing 52.4% of the total emission, and more than 25% being from 84 counties (only < 3% of the whole counties). The proposed emission inventory had a higher spatial resolution and accuracy. Different with this inventory, the IPCC underestimated the direct emission while overestimated the indirect emission, with the regions of higher emission rate being underestimated by -1.5%-6.0% and those of lower emission rate being overestimated by 1.6%-13%. As for the EDGAR, the regions of higher emission rate were underestimated by -18. 8--50.0%, and those of lower emission rate were mostly overestimated by 25%-54.1%.

  14. N2O production and consumption from stable isotopic and concentration data in the Peruvian coastal upwelling system

    NASA Astrophysics Data System (ADS)

    Bourbonnais, Annie; Letscher, Robert T.; Bange, Hermann W.; Échevin, Vincent; Larkum, Jennifer; Mohn, Joachim; Yoshida, Naohiro; Altabet, Mark A.

    2017-04-01

    The ocean is an important source of nitrous oxide (N2O) to the atmosphere, yet the factors controlling N2O production and consumption in oceanic environments are still not understood nor constrained. We measured N2O concentrations and isotopomer ratios, as well as O2, nutrient and biogenic N2 concentrations, and the isotopic compositions of nitrate and nitrite at several coastal stations during two cruises off the Peru coast ( 5-16°S, 75-81°W) in December 2012 and January 2013. N2O concentrations varied from below equilibrium values in the oxygen deficient zone (ODZ) to up to 190 nmol L-1 in surface waters. We used a 3-D-reaction-advection-diffusion model to evaluate the rates and modes of N2O production in oxic waters and rates of N2O consumption versus production by denitrification in the ODZ. Intramolecular site preference in N2O isotopomer was relatively low in surface waters (generally -3 to 14‰) and together with modeling results, confirmed the dominance of nitrifier-denitrification or incomplete denitrifier-denitrification, corresponding to an efflux of up to 0.6 Tg N yr-1 off the Peru coast. Other evidence, e.g., the absence of a relationship between ΔN2O and apparent O2 utilization and significant relationships between nitrate, a substrate during denitrification, and N2O isotopes, suggest that N2O production by incomplete denitrification or nitrifier-denitrification decoupled from aerobic organic matter remineralization are likely pathways for extreme N2O accumulation in newly upwelled surface waters. We observed imbalances between N2O production and consumption in the ODZ, with the modeled proportion of N2O consumption relative to production generally increasing with biogenic N2. However, N2O production appeared to occur even where there was high N loss at the shallowest stations.

  15. A field robot for autonomous laser-based N2O flux measurements

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  16. Structural and spectroscopic properties of the polar antiferromagnet N i2MnTe O6

    NASA Astrophysics Data System (ADS)

    Retuerto, Maria; Skiadopoulou, Stella; Borodavka, Fedir; Kadlec, Christelle; Kadlec, Filip; Prokleška, Jan; Deng, Zheng; Alonso, Jose A.; Fernandez-Diaz, Maria T.; Saouma, Felix O.; Jang, Joon I.; Legut, Dominik; Kamba, Stanislav; Greenblatt, Martha

    2018-04-01

    We present a structural and spectroscopic study of the compound N i2MnTe O6 , closely related to the polar antiferromagnet N i3Te O6 known to show a colossal magnetoelectric effect and pronounced elementary magnetoelectric excitations. We prepared single crystals and polycrystalline samples of N i2MnTe O6 showing the same polar structure as N i3Te O6 from room temperature down to 4 K with the R 3 space-group symmetry. Magnetic and dielectric measurements have indicated an antiferromagnetic phase transition at TN≈70 K , almost 20 K higher than that of N i3Te O6 . Extensive infrared, Raman, and terahertz spectroscopy experiments were employed for investigating lattice and spin excitations, revealing all phonons predicted by the factor group analysis. Terahertz spectra below TN reveal one new excitation, which is strongly influenced by external magnetic field, thus assigned to a magnon.

  17. Influence of Humic Acid on Stability and Attachment of nTiO2 Particles to Sand at Different pH

    NASA Astrophysics Data System (ADS)

    Cheng, T.

    2015-12-01

    Stability of nano-scale or micro-scale titanium dioxide particles (nTiO2) and their attachment to sediment grains have important implications to the fate and transport of nTiO2 in subsurface environments. nTiO2 may carry either positive or negative charges in natural water, therefore, environmental factors such as pH, humic substances, and Fe oxyhydroxide coatings on sediment grains, which are known to control the stability and transport of negatively charged colloids, may influence nTiO2 in different manners. The objective of this study is to investigate the effects of pH and humic acid (HA) on the stability and attachment of nTiO2 to sand, with special attention to low HA concentration ranges that are relevant to groundwater conditions. Stability and attachment of nTiO2 to quartz sand and Fe oxyhydroxide coated quartz sand were experimentally measured under a range of low HA concentrations at pH 5 and 9. Results showed that HA can either promote or hinder nTiO2 stability, depending on pH and HA concentration. We also found that HA can either enhance or reduce nTiO2 attachment to Fe oxyhydroxide coating at pH 5, depending on HA concentration. Results further showed that at pH 5, Fe oxyhydroxide coating reduced nTiO2 attachment to sand in the absence of HA but increased nTiO2 attachment in the presence of low concentration of HA. Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was invoked to analyze particle-to-particle and particle-to-sand interactions in order to elucidate the roles of pH, HA, quartz, and Fe coating in nTiO2 stability and attachment. Overall, this study showed that changes in zeta potential of nTiO2 and Fe coating due to pH changes and/or HA adsorption are the key factors that influence stability and attachment of nTiO2.

  18. Chirality in distorted square planar Pd(O,N)2 compounds.

    PubMed

    Brunner, Henri; Bodensteiner, Michael; Tsuno, Takashi

    2013-10-01

    Salicylidenimine palladium(II) complexes trans-Pd(O,N)2 adopt step and bowl arrangements. A stereochemical analysis subdivides 52 compounds into 41 step and 11 bowl types. Step complexes with chiral N-substituents and all the bowl complexes induce chiral distortions in the square planar system, resulting in Δ/Λ configuration of the Pd(O,N)2 unit. In complexes with enantiomerically pure N-substituents ligand chirality entails a specific square chirality and only one diastereomer assembles in the lattice. Dimeric Pd(O,N)2 complexes with bridging N-substituents in trans-arrangement are inherently chiral. For dimers different chirality patterns for the Pd(O,N)2 square are observed. The crystals contain racemates of enantiomers. In complex two independent molecules form a tight pair. The (RC) configuration of the ligand induces the same Δ chirality in the Pd(O,N)2 units of both molecules with varying square chirality due to the different crystallographic location of the independent molecules. In complexes and atrop isomerism induces specific configurations in the Pd(O,N)2 bowl systems. The square chirality is largest for complex [(Diop)Rh(PPh3 )Cl)], a catalyst for enantioselective hydrogenation. In the lattice of two diastereomers with the same (RC ,RC) configuration in the ligand Diop but opposite Δ and Λ square configurations co-crystallize, a rare phenomenon in stereochemistry. © 2013 Wiley Periodicals, Inc.

  19. Comparison and mechanism of photocatalytic activities of N-ZnO and N-ZrO2 for the degradation of rhodamine 6G.

    PubMed

    Sudrajat, Hanggara; Babel, Sandhya

    2016-05-01

    N-doped ZnO (N-ZnO) and N-doped ZrO2 (N-ZrO2) are synthesized by novel, simple thermal decomposition methods. The catalysts are evaluated for the degradation of rhodamine 6G (R6G) under visible and UV light. N-ZnO exhibits higher dye degradation under both visible and UV light compared to N-ZrO2 due to possessing higher specific surface area, lower crystalline size, and lower band gap. However, it is less reusable than N-ZrO2 and its photocatalytic activity is also deteriorated at low pH. At the same intensity of 3.5 W/m(2), UVC light is shown to be a better UV source for N-ZnO, while UVA light is more suitable for N-ZrO2. At pH 7 with initial dye concentration of 10 mg/L, catalyst concentration of 1 g/L, and UVC light, 94.3 % of R6G is degraded by N-ZnO within 2 h. Using UVA light under identical experimental conditions, 93.5 % degradation of R6G is obtained by N-ZrO2. Moreover, the type of light source is found to determine the reactive species produced in the R6G degradation by N-ZnO and N-ZrO2. Less oxidative reactive species such as superoxide radical and singlet oxygen play a major role in the degradation of R6G under visible light. On the contrary, highly oxidative hydroxyl radicals are predominant under UVC light. Based on the kinetic study, the adsorption of R6G on the catalyst surface is found to be the controlling step.

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

    PubMed

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

    2012-06-01

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

  1. Facile fabrication and electrical investigations of nanostructured p-Si/n-TiO2 hetero-junction diode

    NASA Astrophysics Data System (ADS)

    Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

    2018-05-01

    In this work, we have fabricated the nanostructured p-Si/n-TiO2 hetero-junction diode by using a facile spin-coating method. The XRD analysis suggests the presence of well crystalline anatase TiO2 film on Si with small grain size (˜16 nm). We have drawn the band alignment using Anderson model to understand the electrical transport across the junction. The current-voltage (J-V) characteristics analysis reveals the good rectification ratio (103 at ± 3 V) and slightly higher ideality factor (4.7) of our device. The interface states are responsible for the large ideality factor as Si/TiO2 form a dissimilar interface and possess a large number of dangling bonds. The study reveals the promises to be used Si/TiO2 diode as an alternative to the traditional p-n homo-junction diode, which typically require high budget.

  2. A meta-analysis of fertilizer-induced soil NO and combined NO+N2 O emissions.

    PubMed

    Liu, Shuwei; Lin, Feng; Wu, Shuang; Ji, Cheng; Sun, Yi; Jin, Yaguo; Li, Shuqing; Li, Zhaofu; Zou, Jianwen

    2017-06-01

    Soils are among the important sources of atmospheric nitric oxide (NO) and nitrous oxide (N 2 O), acting as a critical role in atmospheric chemistry. Updated data derived from 114 peer-reviewed publications with 520 field measurements were synthesized using meta-analysis procedure to examine the N fertilizer-induced soil NO and the combined NO+N 2 O emissions across global soils. Besides factors identified in earlier reviews, additional factors responsible for NO fluxes were fertilizer type, soil C/N ratio, crop residue incorporation, tillage, atmospheric carbon dioxide concentration, drought and biomass burning. When averaged across all measurements, soil NO-N fluxes were estimated to be 4.06 kg ha -1  yr -1 , with the greatest (9.75 kg ha -1  yr -1 ) in vegetable croplands and the lowest (0.11 kg ha -1  yr -1 ) in rice paddies. Soil NO emissions were more enhanced by synthetic N fertilizer (+38%), relative to organic (+20%) or mixed N (+18%) sources. Compared with synthetic N fertilizer alone, synthetic N fertilizer combined with nitrification inhibitors substantially reduced soil NO emissions by 81%. The global mean direct emission factors of N fertilizer for NO (EF NO ) and combined NO+N 2 O (EF c ) were estimated to be 1.16% and 2.58%, with 95% confidence intervals of 0.71-1.61% and 1.81-3.35%, respectively. Forests had the greatest EF NO (2.39%). Within the croplands, the EF NO (1.71%) and EF c (4.13%) were the greatest in vegetable cropping fields. Among different chemical N fertilizer varieties, ammonium nitrate had the greatest EF NO (2.93%) and EF c (5.97%). Some options such as organic instead of synthetic N fertilizer, decreasing N fertilizer input rate, nitrification inhibitor and low irrigation frequency could be adopted to mitigate soil NO emissions. More field measurements over multiyears are highly needed to minimize the estimate uncertainties and mitigate soil NO emissions, particularly in forests and vegetable croplands. © 2016 John Wiley

  3. Regional N2O fluxes in Amazonia derived from aircraft vertical profiles

    NASA Astrophysics Data System (ADS)

    D'Amelio, M. T. S.; Gatti, L. V.; Miller, J. B.; Tans, P.

    2009-11-01

    Nitrous oxide (N2O) is the third most important anthropogenic greenhouse gas. Globally, the main sources of N2O are nitrification and denitrification in soils. About two thirds of the soil emissions occur in the tropics and approximately 20% originate in wet rainforest ecosystems, like the Amazon forest. The work presented here involves aircraft vertical profiles of N2O from the surface to 4 km over two sites in the Eastern and Central Amazon: Tapajós National Forest (SAN) and Cuieiras Biologic Reserve (MAN), and the estimation of N2O fluxes for regions upwind of these sites. To our knowledge, these regional scale N2O measurements in Amazonia are unique and represent a new approach to looking regional scale emissions. The fluxes upwind of MAN exhibited little seasonality, and the annual mean was 2.1±1.0 mg N2O m-2 day-1, higher than that for fluxes upwind of SAN, which averaged 1.5±1.6 mg N2O m-2 day-1. The higher rainfall around the MAN site could explain the higher N2O emissions, as a result of increased soil moisture accelerating microbial nitrification and denitrification processes. For fluxes from the coast to SAN seasonality is present for all years, with high fluxes in the months of March through May, and in November through December. The first peak of N2O flux is strongly associated with the wet season. The second peak of high N2O flux recorded at SAN occurs during the dry season and can not be easily explained. However, about half of the dry season profiles exhibit significant correlations with CO, indicating a larger than expected source of N2O from biomass burning. The average CO:N2O ratio for all profiles sampled during the dry season is 94±77 mol CO:mol N2O and suggests a larger biomass burning contribution to the global N2O budget than previously reported.

  4. Regional N2O fluxes in Amazonia derived from aircraft vertical profiles

    NASA Astrophysics Data System (ADS)

    D'Amelio, M. T. S.; Gatti, L. V.; Miller, J. B.; Tans, P.

    2009-08-01

    Nitrous oxide (N2O) is the third most important anthropogenic greenhouse gas. Globally, the main sources of N2O are nitrification and denitrification in soils. About two thirds of the soil emissions occur in the tropics and approximately 20% originate in wet rainforest ecosystems, like the Amazon forest. The work presented here involves aircraft vertical profiles of N2O from the surface to 4 km over two sites in the Eastern and Central Amazon: Tapajós National Forest (SAN) and Cuieiras Biologic Reserve (MAN), and the estimation of N2O fluxes for regions upwind of these sites. To our knowledge, these regional scale N2O measurements in Amazonia are unique and represent a new approach to looking regional scale emissions. The fluxes upwind of MAN exhibited little seasonality, and the annual mean was 2.1±1.0 mg N2O m-2 day-1, higher than that for fluxes upwind of SAN, which averaged 1.5±1.6 mg N2O m-2 day-1. The higher rainfall around the MAN site could explain the higher N2O emissions. For fluxes from the coast to SAN seasonality is present for all years, with high fluxes in the months of March through May, and in November through December. The first peak of N2O flux is strongly associated with the wet season. The second peak of high N2O flux recorded at SAN occurs during the dry season and can not be easily explained. However, about half of the dry season profiles exhibit significant correlations with CO, indicating a larger than expected source of N2O from biomass burning. The average CO:N2O ratio for all profiles sampled during the dry season is 94±77 mol CO:mol N2O and suggests a larger biomass burning contribution to the global N2O budget than previously reported.

  5. Wavelength-dependent UV photodesorption of pure N2 and O2 ices

    NASA Astrophysics Data System (ADS)

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

    2013-08-01

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

  6. A study of nitrogen behavior in the formation of Ta/TaN and Ti/TaN alloyed metal electrodes on SiO2 and HfO2 dielectrics

    NASA Astrophysics Data System (ADS)

    Gassilloud, R.; Maunoury, C.; Leroux, C.; Piallat, F.; Saidi, B.; Martin, F.; Maitrejean, S.

    2014-04-01

    We studied Ta, TaN, and sub-stoichiometric TaNx electrodes (obtained by nitrogen redistribution in Ta/TaN or Ti/TaN bilayers) deposited on thermal SiO2 and HfO2/IL (0.8 nm SiO2 IL, i.e., interlayer) stacks. Effective work-functions (WF) were extracted on MOS capacitor structures on SiO2 bevelled insulator of 4.2 eV for pure Ta, 4.6 eV for TaN, and 4.3 eV for sub-stoichiometric TaNx. This intermediate WF value is explained by TaN nitrogen redistribution with reactive Ta or Ti elements shifting the gate work-function toward the Si conduction band. The same electrodes deposited on an HfO2/IL dielectric showed different behavior: First, the Ta/HfO2/IL stack shows a +200 meV WF increase (towards the Si valence band) compared to the SiO2 dielectric stack. This increase is explained by the well-known HfO2/IL dipole formation. Second, in contrast to electrodes deposited on SiO2, sub-stoichiometric TaNx/HfO2 is found to have a lower WF (4.3 eV), than pure Ta on HfO2 (4.4 eV). This inversion in work-function behavior measured on SiO2 vs. HfO2 is explained by the nitrogen redistribution in Ta/TaN bilayer together with diffusion of nitrogen through the HfO2 layer, leading to Si-N formation which prevents dipole formation at the HfO2/IL interface.

  7. Molecular and Dissociative Adsorption of Water on (TiO 2 ) n Clusters, n = 1–4

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

    Chen, Mingyang; Straatsma, Tjerk P.; Dixon, David A.

    In the low energy structures of the (TiO 2) n(H 2O) m (n ≤ 4, m ≤ 2n) and (TiO 2) 8(H 2O) m (m = 3, 7, 8) clusters were predicted using a global geometry optimization approach, with a number of new lowest energy isomers being found. Water can molecularly or dissociatively adsorb on pure and hydrated TiO 2 clusters. Dissociative adsorption is the dominant reaction for the first two H 2O adsorption reactions for n = 1, 2, and 4, for the first three H 2O adsorption reactions for n = 3, and for the first four Hmore » 2O adsorption reactions for n = 8. As more H 2O’s are added to the hydrated (TiO 2)n cluster, dissociative adsorption becomes less exothermic as all the Ti centers become 4-coordinate. Furthermore two types of bonds can be formed between the molecularly adsorbed water and TiO 2 clusters: a Lewis acid–base Ti–O(H 2) bond or an O···H hydrogen bond. The coupled cluster CCSD(T) results show that at 0 K the H 2O adsorption energy at a 4-coordinate Ti center is ~15 kcal/mol for the Lewis acid–base molecular adsorption and ~7 kcal/mol for the H-bond molecular adsorption, in comparison to that of 8–10 kcal/mol for the dissociative adsorption. The cluster size and geometry independent dehydration reaction energy, ED, for the general reaction 2(-TiOH) → -TiOTi– + H 2O at 4-coordinate Ti centers was estimated from the aggregation reaction of nTi(OH) 4 to form the monocyclic ring cluster (TiO 3H 2) n + nH 2O. E D is estimated to be -8 kcal/mol, showing that intramolecular and intermolecular dehydration reactions are intrinsically thermodynamically allowed for the hydrated (TiO 2) n clusters with all of the Ti centers 4-coordinate, which can be hindered by cluster geometry changes caused by such processes. Finally by bending force constants for the TiOTi and OTiO bonds are determined to be 7.4 and 56.0 kcal/(mol·rad 2). Infrared vibrational spectra were calculated using density functional theory, and the new bands appearing upon water adsorption

  8. Molecular and Dissociative Adsorption of Water on (TiO 2 ) n Clusters, n = 1–4

    DOE PAGES

    Chen, Mingyang; Straatsma, Tjerk P.; Dixon, David A.

    2015-10-20

    In the low energy structures of the (TiO 2) n(H 2O) m (n ≤ 4, m ≤ 2n) and (TiO 2) 8(H 2O) m (m = 3, 7, 8) clusters were predicted using a global geometry optimization approach, with a number of new lowest energy isomers being found. Water can molecularly or dissociatively adsorb on pure and hydrated TiO 2 clusters. Dissociative adsorption is the dominant reaction for the first two H 2O adsorption reactions for n = 1, 2, and 4, for the first three H 2O adsorption reactions for n = 3, and for the first four Hmore » 2O adsorption reactions for n = 8. As more H 2O’s are added to the hydrated (TiO 2)n cluster, dissociative adsorption becomes less exothermic as all the Ti centers become 4-coordinate. Furthermore two types of bonds can be formed between the molecularly adsorbed water and TiO 2 clusters: a Lewis acid–base Ti–O(H 2) bond or an O···H hydrogen bond. The coupled cluster CCSD(T) results show that at 0 K the H 2O adsorption energy at a 4-coordinate Ti center is ~15 kcal/mol for the Lewis acid–base molecular adsorption and ~7 kcal/mol for the H-bond molecular adsorption, in comparison to that of 8–10 kcal/mol for the dissociative adsorption. The cluster size and geometry independent dehydration reaction energy, ED, for the general reaction 2(-TiOH) → -TiOTi– + H 2O at 4-coordinate Ti centers was estimated from the aggregation reaction of nTi(OH) 4 to form the monocyclic ring cluster (TiO 3H 2) n + nH 2O. E D is estimated to be -8 kcal/mol, showing that intramolecular and intermolecular dehydration reactions are intrinsically thermodynamically allowed for the hydrated (TiO 2) n clusters with all of the Ti centers 4-coordinate, which can be hindered by cluster geometry changes caused by such processes. Finally by bending force constants for the TiOTi and OTiO bonds are determined to be 7.4 and 56.0 kcal/(mol·rad 2). Infrared vibrational spectra were calculated using density functional theory, and the new bands appearing upon water adsorption

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

    PubMed Central

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

    2009-01-01

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

  10. Estimates of N2O, NO and NH3 Emissions From Croplands in East, Southeast and South Asia

    NASA Astrophysics Data System (ADS)

    Yan, X.; Ohara, T.; Akimoto, H.

    2002-12-01

    Agricultural activities have greatly altered the global nitrogen cycle and produced nitrogenous gases of environmentally significance. More than half of the global chemical nitrogen fertilizer is used for crop production in East, Southeast and South Asia where rice the center of nutrition. Emissions of nitrous oxide (N2O), nitric oxide (NO) and ammonia (NH3) from croplands in this region were estimated by considering both background emission and emissions resulted from nitrogen added to croplands, including chemical nitrogen, animal manure used as fertilizer, biological fixed nitrogen and nitrogen in crop residue returned to field. Background emission fluxes of N2O and NO from croplands were estimated at 1.16 and 0.52 kg N ha-1yr-1, respectively. A fertilizer-induced N2O emission factor of 1.25% for upland was adopted from IPCC guidelines, and a factor of 0.25% was derived for paddy field from measurements. Total N2O emission from croplands in the region was estimated at 1.16 Tg N yr-1, with 41% contributed by background emission which was not considered in previous global estimates. However, the average fertilizer-induced N2O emission is only 0.93%, lower than the default IPCC value of 1.25% due to the low emission factor from paddy field. A fertilizer-induced NO emission factor of 0.66% for upland was derived from field measurements, and a factor of 0.13% was assumed for paddy field. Total NO emission was 572 Gg N yr-1 in the region, with 38% due to background emission. Average fertilizer-induce NO emission factor was 0.48%. Extrapolating this estimate to global scale will result in a global NO emission from cropland of 1.6 Tg N yr-1, smaller than other global estimates. Total NH3 emission was estimated at 11.8 Tg N yr-1. The use of urea and ammonium bicarbonate and the cultivation of rice lead to a high average NH3 loss rate of chemical fertilizer in the region. Emissions were distributed at 0.5° grid by using a global landuse database.

  11. N2O FIELD STUDY

    EPA Science Inventory

    The report gives results of measurements of nitrous oxide (N2O) emissions from coal-fired utility boilers at three electric power generating stations. Six units were tested, two at each site, including sizes ranging from 165 to 700 MW. Several manufacturers and boiler firing type...

  12. Insight into effects of mature compost recycling on N2O emission and denitrification genes in sludge composting.

    PubMed

    Wang, Ke; Wu, Yiqi; Li, Weiguang; Wu, Chuandong; Chen, Zhiqiang

    2018-03-01

    Mature compost recycling is widely used to reduce the dosage of organic bulking agent in actual composting process. In this study, the effects of mature compost amendment on N 2 O emission and denitrification genes were investigated in 47 days composting of sewage sludge and rice husks. The results showed that mature compost amendment dramatically augmented N 2 O emission rate in mesophilic phase and CO 2 emission rate in thermophilic phase of composting, respectively. The cumulative amount of N 2 O emission increased by more than 23 times compared to the control. Mature compost amendment not only reduced moisture and pH, but also significantly increased NO 3 - -N and NO 2 - -N concentrations. The correlation matrices indicated that NO 3 - -N, narG and norB were the main factors influencing N 2 O emission rate in sludge composting with mature compost recycling, but the N 2 O emission rate was significantly correlated to NO 2 - -N, nirK and norB in the control. Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Constraints on global oceanic emissions of N2O from observations and models

    NASA Astrophysics Data System (ADS)

    Buitenhuis, Erik T.; Suntharalingam, Parvadha; Le Quéré, Corinne

    2018-04-01

    We estimate the global ocean N2O flux to the atmosphere and its confidence interval using a statistical method based on model perturbation simulations and their fit to a database of ΔpN2O (n = 6136). We evaluate two submodels of N2O production. The first submodel splits N2O production into oxic and hypoxic pathways following previous publications. The second submodel explicitly represents the redox transformations of N that lead to N2O production (nitrification and hypoxic denitrification) and N2O consumption (suboxic denitrification), and is presented here for the first time. We perturb both submodels by modifying the key parameters of the N2O cycling pathways (nitrification rates; NH4+ uptake; N2O yields under oxic, hypoxic and suboxic conditions) and determine a set of optimal model parameters by minimisation of a cost function against four databases of N cycle observations. Our estimate of the global oceanic N2O flux resulting from this cost function minimisation derived from observed and model ΔpN2O concentrations is 2.4 ± 0.8 and 2.5 ± 0.8 Tg N yr-1 for the two N2O submodels. These estimates suggest that the currently available observational data of surface ΔpN2O constrain the global N2O flux to a narrower range relative to the large range of results presented in the latest IPCC report.

  14. Suppression of N2O and NO from denitrification by biochar: the role of pH

    NASA Astrophysics Data System (ADS)

    Obia, Alfred; Cornelissen, Gerard; Mulder, Jan; Dörsch, Peter

    2015-04-01

    Denitrification reduces NO3- to N2 and returns excess nitrogen to the atmosphere. NO and N2O are gaseous intermediates of denitrification which, once escaped to the atmosphere, have adverse effects on chemistry and radiative forcing in the atmosphere. We studied the effect of biochar on denitrification and its gaseous intermediates in two acidic soils and tried to distinguish between the alkalizing effect of biochars on soil pH, and other, unknown effects of biochar on denitrification. Anoxic soil slurries were incubated with untreated biochars or biochars from which part of the alkalinity had been removed by water- and acid leaching. Soils amended with NaOH and uncharred cacao shell were used as controls. Biochar addition stimulated overall denitrification depending on biochar and soil type. This stimulation was not strictly coupled to pH increase, suggesting that biochar fueled respiration processes by contributing microbially available C. High resolution gas kinetics of NO, N2O and N2 showed that biochar amended soils induced denitrification enzymes earlier and with higher activity, resulting in less NO and N2O accumulation relative to N2 production. The extent to which biochar suppressed NO and N2O was dose-dependent and clearly related to the effective pH increase during incubation. Acid leaching of BC reduced or eliminated its ability to suppress N2O and NO net production. Comparison of BC with NaOH-amended soils showed that the reduction of N2O and NO net production was mainly an effect of increase in soil pH. Even though other factors supporting N2O reductase activity could not be excluded, our results indicate that soil pH increase might be an important driver behind the often-reported suppression of N2O emissions after biochar addition.

  15. High temperature exposure did not affect induced 2n pollen viability in Populus.

    PubMed

    Tian, Mengdi; Zhang, Yuan; Liu, Yan; Kang, Xiangyang; Zhang, Pingdong

    2018-02-11

    High temperature exposure is widely used as a physical mutagenic agent to induce 2n gametes in Populus. However, whether high temperature exposure affects induced 2n pollen viability remains unknown. To clarify whether high temperature exposure affected the induced 2n pollen viability, 2n pollen induced by 38 and 41 °C temperatures, pollen morphology, 2n pollen germination in vitro, and crossing induced 2n pollen with normal gametes to produce a triploid was, based on observations of meiosis, conducted in Populus canescens. We found that the dominant meiotic stages (F = 56.6, p < .001) and the treatment duration (F = 21.4, p < .001) significantly affected the occurrence rate of induced 2n pollen. A significant decrease in pollen production and an increase in aborted pollen were observed (p < .001). High temperature sometimes affected in ectexine deposition and some narrow furrows were also analysed via details of ectexine structure. However, no significant difference in 2n pollen germination rate was observed between natural 2n pollen (26.7%) and high-temperature-induced 2n pollen (26.2%), and 42 triploids were created by crossing high-temperature-induced 2n pollen, suggesting that 38 and 41 °C temperatures exposure will not result in dysfunctional induced 2n pollen. © 2018 John Wiley & Sons Ltd.

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

    PubMed Central

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

    2016-01-01

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

  17. EMISSIONS AND COST ESTIMATES FOR GLOBALLY SIGNIFICANT ANTHROPOGENIC COMBUSTION SOURCES OF NOX, N2O, CH4, CO AND CO2

    EPA Science Inventory

    The report discusses the development of emission factors for CO2, CO, CH4, NOx, and N2O for about 80 globally significant combustion sources in seven source categories: utility, industrial, fuel production, transportation, residential, commercial, and kilns/ovens/dryers. ecause o...

  18. Soil water content drives spatiotemporal patterns of CO2 and N2O emissions from a Mediterranean riparian forest soil

    NASA Astrophysics Data System (ADS)

    Poblador, Sílvia; Lupon, Anna; Sabaté, Santiago; Sabater, Francesc

    2017-09-01

    Riparian zones play a fundamental role in regulating the amount of carbon (C) and nitrogen (N) that is exported from catchments. However, C and N removal via soil gaseous pathways can influence local budgets of greenhouse gas (GHG) emissions and contribute to climate change. Over a year, we quantified soil effluxes of carbon dioxide (CO2) and nitrous oxide (N2O) from a Mediterranean riparian forest in order to understand the role of these ecosystems on catchment GHG emissions. In addition, we evaluated the main soil microbial processes that produce GHG (mineralization, nitrification, and denitrification) and how changes in soil properties can modify the GHG production over time and space. Riparian soils emitted larger amounts of CO2 (1.2-10 g C m-2 d-1) than N2O (0.001-0.2 mg N m-2 d-1) to the atmosphere attributed to high respiration and low denitrification rates. Both CO2 and N2O emissions showed a marked (but antagonistic) spatial gradient as a result of variations in soil water content across the riparian zone. Deep groundwater tables fueled large soil CO2 effluxes near the hillslope, while N2O emissions were higher in the wet zones adjacent to the stream channel. However, both CO2 and N2O emissions peaked after spring rewetting events, when optimal conditions of soil water content, temperature, and N availability favor microbial respiration, nitrification, and denitrification. Overall, our results highlight the role of water availability on riparian soil biogeochemistry and GHG emissions and suggest that climate change alterations in hydrologic regimes can affect the microbial processes that produce GHG as well as the contribution of these systems to regional and global biogeochemical cycles.

  19. Arbuscular mycorrhizal fungi reduce nitrous oxide emissions from N2 O hotspots.

    PubMed

    Storer, Kate; Coggan, Aisha; Ineson, Phil; Hodge, Angela

    2017-12-05

    Nitrous oxide (N 2 O) is a potent, globally important, greenhouse gas, predominantly released from agricultural soils during nitrogen (N) cycling. Arbuscular mycorrhizal fungi (AMF) form a mutualistic symbiosis with two-thirds of land plants, providing phosphorus and/or N in exchange for carbon. As AMF acquire N, it was hypothesized that AMF hyphae may reduce N 2 O production. AMF hyphae were either allowed (AMF) or prevented (nonAMF) access to a compartment containing an organic matter and soil patch in two independent microcosm experiments. Compartment and patch N 2 O production was measured both before and after addition of ammonium and nitrate. In both experiments, N 2 O production decreased when AMF hyphae were present before inorganic N addition. In the presence of AMF hyphae, N 2 O production remained low following ammonium application, but increased in the nonAMF controls. By contrast, negligible N 2 O was produced following nitrate application to either AMF treatment. Thus, the main N 2 O source in this system appeared to be via nitrification, and the production of N 2 O was reduced in the presence of AMF hyphae. It is hypothesized that AMF hyphae may be outcompeting slow-growing nitrifiers for ammonium. This has significant global implications for our understanding of soil N cycling pathways and N 2 O production. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

  20. Fundamental Insulation Characteristics of Air, N2, CO2, N2/O2 and SF6/N2 Mixed Gases

    NASA Astrophysics Data System (ADS)

    Rokunohe, Toshiaki; Yagihashi, Yoshitaka; Endo, Fumihiro; Oomori, Takashi

    SF6 gas has excellent dielectric strength and interruption performance. For these reasons, it has been widely used for gas insulated switchgear (GIS). However, use of SF6 gas has become regulated under agreements set at the 1997 COP3. Presently, development of a gas circuit breaker (GCB) using CO2 gas and development of a high voltage vacuum circuit breaker (VCB) are being pursued. GIS consists of disconnectors (DS), earthing switches (ES) and buses in addition to GCB. Since the interruption performance is not an important requirement for DS, ES and BUS, use of a gas with high dielectric strength is better than use of a gas with good interruption performance. Air and N2 are not greenhouse gases, and their dielectric strengths are higher than those of other SF6 alternative gases, but only about one-third of the dielectric strength of SF6 gas. This paper deals with a suitable insulation gas which has no greenhouse effect as an SF6 alternative gas. The N2/O2 mixed gas was investigated by changing the ratio of O2. Moreover, the effect of an insulation coating was investigated and compared with the dielectric strength of SF6/N2 mixed gas. The dielectric strength of air under the coating condition was equal to that of 10%SF6/N2 mixed gas.

  1. Heterogeneous reaction of N2O5 with airborne TiO2 particles and its implication for stratospheric particle injection

    NASA Astrophysics Data System (ADS)

    Tang, M. J.; Telford, P. J.; Pope, F. D.; Rkiouak, L.; Abraham, N. L.; Archibald, A. T.; Braesicke, P.; Pyle, J. A.; McGregor, J.; Watson, I. M.; Cox, R. A.; Kalberer, M.

    2014-06-01

    Injection of aerosol particles (or their precursors) into the stratosphere to scatter solar radiation back into space has been suggested as a solar-radiation management scheme for the mitigation of global warming. TiO2 has recently been highlighted as a possible candidate particle because of its high refractive index, but its impact on stratospheric chemistry via heterogeneous reactions is as yet unknown. In this work the heterogeneous reaction of airborne sub-micrometre TiO2 particles with N2O5 has been investigated for the first time, at room temperature and different relative humidities (RH), using an atmospheric pressure aerosol flow tube. The uptake coefficient of N2O5 onto TiO2, γ(N2O5), was determined to be ~1.0 × 10-3 at low RH, increasing to ~3 × 10-3 at 60% RH. The uptake of N2O5 onto TiO2 is then included in the UKCA chemistry-climate model to assess the impact of this reaction on stratospheric chemistry. While the impact of TiO2 on the scattering of solar radiation is chosen to be similar to the aerosol from the Mt Pinatubo eruption, the impact of TiO2 injection on stratospheric N2O5 is much smaller.

  2. Verifying the UK N_{2}O emission inventory with tall tower measurements

    NASA Astrophysics Data System (ADS)

    Carnell, Ed; Meneguz, Elena; Skiba, Ute; Misselbrook, Tom; Cardenas, Laura; Arnold, Tim; Manning, Alistair; Dragosits, Ulli

    2016-04-01

    Nitrous oxide (N2O) is a key greenhouse gas (GHG), with a global warming potential ˜300 times greater than that of CO2. N2O is emitted from a variety of sources, predominantly from agriculture. Annual UK emission estimates are reported, to comply with government commitments under the United Nations Framework Convention on Climate Change (UNFCCC). The UK N2O inventory follows internationally agreed protocols and emission estimates are derived by applying emission factors to estimates of (anthropogenic) emission sources. This approach is useful for comparing anthropogenic emissions from different countries, but does not capture regional differences and inter-annual variability associated with environmental factors (such as climate and soils) and agricultural management. In recent years, the UK inventory approach has been refined to include regional information into its emissions estimates (e.g. agricultural management data), in an attempt to reduce uncertainty. This study attempts to assess the difference between current published inventory methodology (default IPCC methodology) and a revised approach, which incorporates the latest thinking, using data from recent work. For 2013, emission estimates made using the revised approach were 30 % lower than those made using default IPCC methodology, due to the use of lower emission factors suggested by recent projects (www.ghgplatform.org.uk, Defra projects: AC0116, AC0213 and MinNO). The 2013 emissions estimates were disaggregated on a monthly basis using agricultural management (e.g. sowing dates), climate data and soil properties. The temporally disaggregated emission maps were used as input to the Met Office atmospheric dispersion model NAME, for comparison with measured N2O concentrations, at three observation stations (Tacolneston, E England; Ridge Hill, W England; Mace Head, W Ireland) in the UK DECC network (Deriving Emissions linked to Climate Change). The Mace Head site, situated on the west coast of Ireland, was

  3. A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

    NASA Astrophysics Data System (ADS)

    Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

    2014-12-01

    Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar

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

    PubMed

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

    2014-03-28

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

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

    PubMed Central

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

    2016-01-01

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

  6. Effects of tillage practice on soil structure, N2O emissions and economics in cereal production under current socio-economic conditions in central Bosnia and Herzegovina

    PubMed Central

    Sitaula, Bishal Kumar; Čustović, Hamid; Žurovec, Jasminka; Dörsch, Peter

    2017-01-01

    Conservation tillage is expected to have a positive effect on soil physical properties, soil Carbon (C) storage, while reducing fuel, labour and machinery costs. However, reduced tillage could increase soil nitrous oxide (N2O) emissions and offset the expected gains from increased C sequestration. To date, conservation tillage is barely practiced or studied in Bosnia and Herzegovina (BH). Here, we report a field study on the short-term effects of reduced (RT) and no tillage (NT) on N2O emission dynamics, yield-scaled N2O emissions, soil structure and the economics of cereal production, as compared with conventional tillage (CT). The field experiment was conducted in the Sarajevo region on a clayey loam under typical climatic conditions for humid, continental BH. N2O emissions were monitored in a Maize-Barley rotation over two cropping seasons. Soil structure was studied at the end of the second season. In the much wetter 2014, N2O emission were in the order of CT > RT > NT, while in the drier 2015, the order was RT > CT > NT. The emission factors were within or slightly above the uncertainty range of the IPCC Tier 1 factor, if taking account for the N input from the cover crop (alfalfa) preceding the first experimental year. Saturated soils in spring, formation of soil crusts and occasional droughts adversely affected yields, particularly in the second year (barley). In 2014, yield-scaled N2O emissions ranged from 83.2 to 161.7 g N Mg-1 grain (corn) but were much greater in the second year due to crop failure (barley). RT had the smallest yield-scaled N2O emission in both years. NT resulted in economically inacceptable returns, due to the increased costs of weed control and low yields in both years. The reduced number of operations in RT reduced production costs and generated positive net returns. Therefore, RT could potentially provide agronomic and environmental benefits in crop production in BH. PMID:29117229

  7. Effects of tillage practice on soil structure, N2O emissions and economics in cereal production under current socio-economic conditions in central Bosnia and Herzegovina.

    PubMed

    Žurovec, Ognjen; Sitaula, Bishal Kumar; Čustović, Hamid; Žurovec, Jasminka; Dörsch, Peter

    2017-01-01

    Conservation tillage is expected to have a positive effect on soil physical properties, soil Carbon (C) storage, while reducing fuel, labour and machinery costs. However, reduced tillage could increase soil nitrous oxide (N2O) emissions and offset the expected gains from increased C sequestration. To date, conservation tillage is barely practiced or studied in Bosnia and Herzegovina (BH). Here, we report a field study on the short-term effects of reduced (RT) and no tillage (NT) on N2O emission dynamics, yield-scaled N2O emissions, soil structure and the economics of cereal production, as compared with conventional tillage (CT). The field experiment was conducted in the Sarajevo region on a clayey loam under typical climatic conditions for humid, continental BH. N2O emissions were monitored in a Maize-Barley rotation over two cropping seasons. Soil structure was studied at the end of the second season. In the much wetter 2014, N2O emission were in the order of CT > RT > NT, while in the drier 2015, the order was RT > CT > NT. The emission factors were within or slightly above the uncertainty range of the IPCC Tier 1 factor, if taking account for the N input from the cover crop (alfalfa) preceding the first experimental year. Saturated soils in spring, formation of soil crusts and occasional droughts adversely affected yields, particularly in the second year (barley). In 2014, yield-scaled N2O emissions ranged from 83.2 to 161.7 g N Mg-1 grain (corn) but were much greater in the second year due to crop failure (barley). RT had the smallest yield-scaled N2O emission in both years. NT resulted in economically inacceptable returns, due to the increased costs of weed control and low yields in both years. The reduced number of operations in RT reduced production costs and generated positive net returns. Therefore, RT could potentially provide agronomic and environmental benefits in crop production in BH.

  8. Inhibition effect of zinc in wastewater on the N2O emission from coastal loam soils.

    PubMed

    Huang, Yan; Ou, Danyun; Chen, Shunyang; Chen, Bin; Liu, Wenhua; Bai, Renao; Chen, Guangcheng

    2017-03-15

    The effects of zinc (Zn) on nitrous oxide (N 2 O) fluxes from coastal loam soil and the abundances of soil nitrifier and denitrifier were studied in a tidal microcosm receiving livestock wastewater with different Zn levels. Soil N 2 O emission significantly increased due to discharge of wastewater rich in ammonia (NH 4 + -N) while the continuous measurements of gas flux showed a durative reduction in N 2 O flux by high Zn input (40mgL -1 ) during the low tide period. Soil inorganic nitrogen concentrations increased at the end of the experiment and even more soil NH 4 + -N was measured in the high-Zn-level treatment, indicating an inhibition of ammonia oxidation by Zn input. Quantitative PCR of soil amoA, narG and nirK genes encoding ammonia monooxygenase, nitrate reductase and nitrite reductase, respectively, showed that the microbial abundances involved in these metabolisms were neither affected by wastewater discharge nor Zn contamination. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Effects of interfacial layer on characteristics of TiN/ZrO2 structures.

    PubMed

    Kim, Younsoo; Kang, Sang Yeol; Choi, Jae Hyoung; Lim, Jae Soon; Park, Min Young; Chung, Suk-Jin; Chung, Jaegwan; Lee, Hyung Ik; Kim, Ki Hong; Kyoung, Yong Koo; Heo, Sung; Yoo, Cha Young; Kang, Ho-Kyu

    2011-09-01

    To minimize the formation of unwanted interfacial layers, thin interfacial layer (ZrCN layer) was deposited between TiN bottom electrode and ZrO2 dielectric in TiN/ZrO2/TiN capacitor. Carbon and nitrogen were also involved in the layer because ZrCN layer was thermally deposited using TEMAZ without any reactant. Electrical characteristics of TiN/ZrO2/TiN capacitor were improved by insertion of ZrCN layer. The oxidation of TiN bottom electrode was largely inhibited at TiN/ZrCN/ZrO2 structure compared to TiN/ZrO2 structure. While the sheet resistance of TiN/ZrCN/ZrO2 structure was constantly sustained with increasing ZrO2 thickness, the large increase of sheet resistance was observed in TiN/ZrO2 structure after 6 nm ZrO2 deposition. When ZrO2 films were deposited on ZrCN layer, the deposition rate of ZrO2 also increased. It is believed that ZrCN layer acted both as a protection layer of TiN oxidation and a seed layer of ZrO2 growth.

  10. Hydrogen-induced reversible changes in drain current in Sc2O3/AlGaN/GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Kang, B. S.; Mehandru, R.; Kim, S.; Ren, F.; Fitch, R. C.; Gillespie, J. K.; Moser, N.; Jessen, G.; Jenkins, T.; Dettmer, R.; Via, D.; Crespo, A.; Gila, B. P.; Abernathy, C. R.; Pearton, S. J.

    2004-06-01

    Pt contacted AlGaN/GaN high electron mobility transistors with Sc2O3 gate dielectrics show reversible changes in drain-source current upon exposure to H2-containing ambients, even at room temperature. The changes in current (as high as 3 mA for relatively low gate voltage and drain-source voltage) are approximately an order of magnitude larger than for Pt/GaN Schottky diodes and a factor of 5 larger than Sc2O3/AlGaN/GaN metal-oxide-semiconductor (MOS) diodes exposed under the same conditions. This shows the advantage of using a transistor structure in which the gain produces larger current changes upon exposure to hydrogen-containing ambients. The increase in current is the result of a decrease in effective barrier height of the MOS gate of 30-50 mV at 25 °C for 10% H2/90% N2 ambients relative to pure N2 and is due to catalytic dissociation of the H2 on the Pt contact, followed by diffusion to the Sc2O3/AlGaN interface.

  11. (Cu 0.5Tl 0.5)Ba 2Ca n-1 Cu n- yGe yO 2 n+4- δ ( n = 3, 4 and y = 0.5, 0.75, 1.0); superconductors with GeO 2 planes

    NASA Astrophysics Data System (ADS)

    Khan, Nawazish A.; Irfan, M.

    2008-12-01

    We have successfully synthesized germanium doped (Cu 0.5Tl 0.5)Ba 2Ca n-1 Cu n- yGe yO 2 n+4- δ ( n = 3, 4 and y = 0, 0.5, 0.75, 1.0) superconductors and investigated the effect of Ge doping on the superconducting properties of these compounds. The solubility of Ge till y = 1 in the CuO 2 planes of (Cu 0.5Tl 0.5)Ba 2Ca 2Cu 3- yGe yO 10- δ, have been found to give superconductivity above 77 K. To our surprise an enhanced superconductivity is observed with the doping of semiconductor germanium in some samples. The enhanced superconductivity associated with mixed CuO 2/GeO 2 planes can be extremely useful for the understanding of mechanism of superconductivity; since we very well know the properties of germanium based semiconductors.

  12. Efficient photocatalytic degradation of tetrabromodiphenyl ethers and simultaneous hydrogen production by TiO2-Cu2O composite films in N2 atmosphere: Influencing factors, kinetics and mechanism.

    PubMed

    Hu, Zhe; Wang, Xi; Dong, Haitai; Li, Shangyi; Li, Xukai; Li, Laisheng

    2017-10-15

    TiO 2 -Cu 2 O photocatalyst composite film with a heterostructure was synthesized on a copper substrate for 2,2',4,4'-tetrabromodiphenyl ether (BDE47) reduction. First, Cu 2 O film was synthesized by the electrochemical deposition method, and then TiO 2 was coated on the surface of the Cu 2 O film. The morphology, surface chemical composition and optical characteristics of TiO 2 -Cu 2 O film were characterized. The degradation efficiency of BDE47 and hydrogen production by TiO 2 -Cu 2 O films was higher than those by pure TiO 2 or Cu 2 O films. The highest BDE47 degradation efficiency of 90% and hydrogen production of 12.7mmolL liq -1 after 150min were achieved by 67%TiO 2 -Cu 2 O films. The influencing factors were investigated in terms of film component, solvent condition, and initial pH. A kinetics study demonstrated that BDE47 degradation followed a pseudo-first-order model. Photocatalytic apparent reaction rate constant of BDE47 by TiO 2 -Cu 2 O films was 0.0070min -1 , which was 3.3 times of that by directly photolysis process. During photocatalytic debrmination process, the photogenerated holes were reserved in the valance band of Cu 2 O to oxidize methanol. Meanwhile, the partial photogenerated electrons transferred to the conduction band of TiO 2 and directly eliminated the ortho-Br of BDE47 and yielded BDE28 and BDE15. The other partial photogenerated electrons reduced protons (H + ) to form atomic hydrogen (H°), which could substitute the para-Br of BDE47 and generated BDE17 and produce hydrogen. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Single photon ionization of van der Waals clusters with a soft x-ray laser: (CO2)n and (CO2)n(H2O)m.

    PubMed

    Heinbuch, S; Dong, F; Rocca, J J; Bernstein, E R

    2006-10-21

    Pure neutral (CO2)n clusters and mixed (CO2)n(H2O)m clusters are investigated employing time of flight mass spectroscopy and single photon ionization at 26.5 eV. The distribution of pure (CO2)n clusters decreases roughly exponentially with increasing cluster size. During the ionization process, neutral clusters suffer little fragmentation because almost all excess cluster energy above the vertical ionization energy is taken away by the photoelectron and only a small part of the photon energy is deposited into the (CO2)n cluster. Metastable dissociation rate constants of (CO2)n+ are measured in the range of (0.2-1.5) x 10(4) s(-1) for cluster sizes of 5< or =n< or =16. Mixed CO2-H2O clusters are studied under different generation conditions (5% and 20% CO2 partial pressures and high and low expansion pressures). At high CO2 concentration, predominant signals in the mass spectrum are the (CO2)n+ cluster ions. The unprotonated cluster ion series (CO2)nH2O+ and (CO2)n(H2O)2+ are also observed under these conditions. At low CO2 concentration, protonated cluster ions (H2O)nH+ are the dominant signals, and the protonated CO2(H2O)nH+ and unprotonated (H2O)n+ and (CO2)(H2O)n+ cluster ion series are also observed. The mechanisms and dynamics of the formation of these neutral and ionic clusters are discussed.

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

    PubMed

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

    2017-02-08

    We demonstrate that the complex adsorption behavior of H 2 O on InGaN/GaN nanowire arrays is directly revealed by their ambient-dependent photoluminescence properties. Under low-humidity, ambient-temperature, and low-excitation-light conditions, H 2 O adsorbates cause a quenching of the photoluminescence. In contrast, for high humidity levels, elevated temperature, and high excitation intensity, H 2 O adsorbates act as efficient photoluminescence enhancers. We show that this behavior, which can only be detected due to the low operation temperature of the InGaN/GaN nanowires, can be explained on the basis of single H 2 O adsorbates forming surface recombination centers and multiple H 2 O adsorbates forming surface passivation layers. Reversible creation of such passivation layers is induced by the photoelectrochemical splitting of adsorbed water molecules and by the interaction of reactive H 3 O + and OH - ions with photoactivated InGaN surfaces. Due to electronic coupling of adsorbing molecules with photoactivated surfaces, InGaN/GaN nanowires act as sensitive nanooptical probes for the analysis of photoelectrochemical surface processes.

  15. Equation of state for Eu-doped SrSi2O2N2

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  16. Short-term nitrogen additions can shift a coastal wetland from a sink to a source of N2O

    USGS Publications Warehouse

    Moseman-Valtierra, Serena; Gonzalez, Rosalinda; Kroeger, Kevin D.; Tang, Jianwu; Chao, Wei Chun; Crusius, John; Bratton, John F.; Green, Adrian; Shelton, James

    2011-01-01

    Coastal salt marshes sequester carbon at high rates relative to other ecosystems and emit relatively little methane particularly compared to freshwater wetlands. However, fluxes of all major greenhouse gases (N2O, CH4, and CO2) need to be quantified for accurate assessment of the climatic roles of these ecosystems. Anthropogenic nitrogen inputs (via run-off, atmospheric deposition, and wastewater) impact coastal marshes. To test the hypothesis that a pulse of nitrogen loading may increase greenhouse gas emissions from salt marsh sediments, we compared N2O, CH4 and respiratory CO2fluxes from nitrate-enriched plots in a Spartina patens marsh (receiving single additions of NaNO3 equivalent to 1.4 g N m−2) to those from control plots (receiving only artificial seawater solutions) in three short-term experiments (July 2009, April 2010, and June 2010). In July 2009, we also compared N2O and CH4 fluxes in both opaque and transparent chambers to test the influence of light on gas flux measurements. Background fluxes of N2O in July 2009 averaged −33 μmol N2O m−2 day−1. However, within 1 h of nutrient additions, N2O fluxes were significantly greater in plots receiving nitrate additions relative to controls in July 2009. Respiratory rates and CH4 fluxes were not significantly affected. N2O fluxes were significantly higher in dark than in transparent chambers, averaging 108 and 42 μmol N2O m−2 day−1 respectively. After 2 days, when nutrient concentrations returned to background levels, none of the greenhouse gas fluxes differed from controls. In April 2010, N2O and CH4 fluxes were not significantly affected by nitrate, possibly due to higher nitrogen demands by growing S. patens plants, but in June 2010 trends of higher N2O fluxes were again found among nitrate-enriched plots, indicating that responses to nutrient pulses may be strongest during the summer. In terms of carbon equivalents, the highest average N2O and CH4 fluxes observed, exceeded half

  17. Low-Temperature Desorption of N2O from NO on Rutile TiO2(110)-1x1

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

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

    2014-05-08

    We find that NO dosed on rutile TiO2(110)-1×1 at substrate temperatures as low as 50 K readily reacts to produce N2O which desorbs promptly from the surface leaving an oxygen adatom behind. The desorption rate of N2O reaches a maximum value after 1 – 2 sec at an NO flux of 1.2 ×1014 NO/cm2∙sec and then decreases rapidly as the initially clean, reduced TiO2(110) surface with ~5% oxygen vacancies (VO’s) becomes covered with oxygen adatoms and unreacted NO. The maximum desorption rate is also found to increase as the substrate temperature is raised up to about 100 K. Interestingly, themore » N2O desorption during the low-temperature (LT) NO dose is strongly suppressed when molecular oxygen is predosed, whereas it persists on the surface with VO’s passivated by surface hydroxyls. Our results show that the surface charge, not the VO sites, plays a dominant role in the LT N2O desorption induced by a facile NO reduction at such low temperatures.« less

  18. Effect of CaO on the selectivity of N2O decomposition products: A combined experimental and DFT study

    NASA Astrophysics Data System (ADS)

    Wu, Lingnan; Hu, Xiaoying; Qin, Wu; Gao, Pan; Dong, Changqing; Yang, Yongping

    2016-09-01

    The effect of CaO on N2O decomposition and the selectivity of its decomposition products (NO and N2) was investigated using a fixed-bed flow reactor with varying temperatures from 317 °C to 947 °C. The selectivity of NO from CaO-catalyzed N2O decomposition is much lower than the N2 selectivity with the N2/NO products ratio greater than 12.1. Compared to N2O homogeneous decomposition with the minimum N2/NO products ratio of 6.2 at 718 °C, CaO also decreases the NO selectivity from 718 °C to 947 °C. Density functional theory calculations provide possible N2O decomposition routes on the CaO (1 0 0) surface considering both N2 and NO as N2O decomposition products. The N2 formation route is more favorable than the NO formation route in terms of energy barrier and reaction energy, and NO formation on the CaO (1 0 0) surface is likely to proceed via N2O + Osurf2- → N2 + O2 , surf2- and N2O + O2 , surf2- → 2NO + Osurf2-.

  19. SnO2-gated AlGaN/GaN high electron mobility transistors based oxygen sensors

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

    Hung, S.T.; Chung, Chi-Jung; Chen, Chin Ching

    2012-01-01

    Hydrothermally grown SnO2 was integrated with AlGaN/GaN high electron mobility transistor (HEMT) sensor as the gate electrode for oxygen detection. The crystalline of the SnO2 was improved after annealing at 400 C. The grain growth kinetics of the SnO2 nanomaterials, together with the O2 gas sensing properties and sensing mechanism of the SnO2 gated HEMT sensors were investigated. Detection of 1% oxygen in nitrogen at 100 C was possible. A low operation temperature and low power consumption oxygen sensor can be achieved by combining the SnO2 films with the AlGaN/GaN HEMT structure

  20. Nitrous oxide emission factors from N-fertilizer in sugarcane production in Brazil

    NASA Astrophysics Data System (ADS)

    Galdos, M. V.; Siqueira Neto, M.; Feigl, B. J.; Carvalho, J. L.; Cerri, C. E.; Cerri, C. C.

    2013-12-01

    The Brazilian sugarcane production is rapidly expanding due to the increase of global demand for ethanol. Concurrently the necessary inputs to culture, especially N-fertilizer, are growing, since N is one of the key element to maintain sugarcane productivity. However, it is known that N-fertilizer is responsible for the largest share of N2O emissions from agricultural soils. The Intergovernmental Panel on Climate Changes (IPCC) estimated that under favorable climatic conditions approximately 1% of the N-fertilizer applied can be emitted as N2O. Our goal was to estimate N2O emission factors from N-fertilizer used in the sugarcane ratoon for ethanol production. A field study was conducted at the Capuava Mill, located in southeastern Brazil. The experimental design was completely randomized, with four replications in a factorial scheme (2 x 2): two N sources (urea and ammonium nitrate), two application rates (80 and 120 kg ha-1), and a control treatment. N2O concentrations were determined by gas chromatography using a Shimadzu© GC-mini. N2O fluxes were calculated from linear regressions of concentration versus incubation time in the soil static chambers. The N2O emission factor of N-fertilizer was calculated according to the methodology described in the Guidelines for National Greenhouse Gas Inventories (IPCC). Comparatively, ammonium nitrate emitted 45 to 75% less N2O than urea application. There was no significant difference in N2O emission between the two applied rates of urea. Also the N2O emission factor of ammonium nitrate (0.3×0.2%) was lower than that of urea (1.1×0.4%). Our results indicated that on average the N fertilization of sugarcane plantation has an emission factor of 0.7×0.5% suggesting that N-fertilizer management can be used to reduce greenhouse gas emissions in order to improve the sustainability of bioethanol from sugarcane.

  1. The combined effect of dissolved oxygen and nitrite on N2O production by ammonia oxidizing bacteria in an enriched nitrifying sludge.

    PubMed

    Peng, Lai; Ni, Bing-Jie; Ye, Liu; Yuan, Zhiguo

    2015-04-15

    Both nitrite [Formula: see text] and dissolved oxygen (DO) play important roles in nitrous oxide (N2O) production by ammonia oxidizing bacteria (AOB). However, few studies focused on the combined effect of them on N2O production by AOB as well as the corresponding mechanisms. In this study, N2O production by an enriched nitrifying sludge, consisting of both AOB and nitrite-oxidizing bacteria (NOB), was investigated under various [Formula: see text] and DO concentrations. At each investigated DO level, both the biomass specific N2O production rate and the N2O emission factor (the ratio between N2O nitrogen emitted and the ammonium nitrogen converted) increased as [Formula: see text] concentration increased from 3 mg N/L to 50 mg N/L. However, at each investigated [Formula: see text] level, the maximum biomass specific N2O production rate occurred at DO of 0.85 mg O2/L, while the N2O emission factor decreased as DO increased from 0.35 to 3.5 mg O2/L. The analysis of the process data using a mathematical N2O model incorporating both the AOB denitrification and hydroxylamine (NH2OH) oxidation pathways indicated that the contribution of AOB denitrification pathway increased as [Formula: see text] concentration increased, but decreased as DO concentration increased, accompanied by a corresponding change in the contribution of NH2OH oxidation pathway to N2O production. The AOB denitrification pathway was predominant in most cases, with the NH2OH oxidation pathway making a comparable contribution only at high DO level (e.g. 3.5 mg O2/L). Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Hierarchical Honeycomb Br-, N-Codoped TiO2 with Enhanced Visible-Light Photocatalytic H2 Production.

    PubMed

    Zhang, Chao; Zhou, Yuming; Bao, Jiehua; Sheng, Xiaoli; Fang, Jiasheng; Zhao, Shuo; Zhang, Yiwei; Chen, Wenxia

    2018-06-06

    The halogen elements modification strategy of TiO 2 encounters a bottleneck in visible-light H 2 production. Herein, we have for the first time reported a hierarchical honeycomb Br-, N-codoped anatase TiO 2 catalyst (HM-Br,N/TiO 2 ) with enhanced visible-light photocatalytic H 2 production. During the synthesizing process, large amounts of meso-macroporous channels and TiO 2 nanosheets were fabricated in massive TiO 2 automatically, constructing the hierarchical honeycomb structure with large specific surface area (464 m 2 g -1 ). cetyl trimethylammonium bromide and melamine played a key role in constructing the meso-macroporous channels. Additionally, HM-Br,N/TiO 2 showed a high visible-light H 2 production rate of 2247 μmol h -1 g -1 , which is far more higher than single Br- or N-doped TiO 2 (0 or 63 μmol h -1 g -1 , respectively), thereby demonstrating the excellent synergistic effects of Br and N elements in H 2 evolution. In HM-Br,N/TiO 2 catalytic system, the codoped Br-N atoms could reduce the band gap of TiO 2 to 2.88 eV and the holes on acceptor levels (N acceptor) can passivate the electrons on donor levels (Br donor), thereby preventing charge carriers recombination significantly. Furthermore, the proposed HM-Br,N/TiO 2 fabrication strategy had a wide range of choices for N source (e.g., melamine, urea, and dicyandiamide) and it can be applied to other TiO 2 materials (e.g., P25) as well, thereby implying its great potential application in visible-light H 2 production. Finally, on the basis of experimental results, a possible photocatalytic H 2 production mechanism for HM-Br,N/TiO 2 was proposed.

  3. Coupling of N2O and CO2 fluxes from agriculture in Michigan

    NASA Astrophysics Data System (ADS)

    Cui, M.; Tang, J.; Hastings, M. G.; Gelfand, I.; Tao, L.; Sun, K.

    2012-12-01

    CO2 has been known to cause global warming, and N2O is the largest contributor to the greenhouse gas burden of cropping systems in the United States due to application of fertilizer. In our study, fluxes of N2O and CO2 were measured at two maize fields and one reference grassland from Kellogg Biological Station in Southwest Michigan. Here we compared two measuring systems, traditional GC method and LGR/Li-Cor system. Our initial results show that the two measuring systems are consistent (N2O slope=0.96, R2=0.96; and CO2 slope= 1.03, R2=0.86 measuring from the same chamber). Measurements done in pairs of chambers suggest great spatial variations, despite that the chambers were only 0.5 meter apart. The two systems are still comparable by averaging 8 pairs of chambers distributed within one site. Increase of CO2 fluxes were observed the second day after fertilization, but no significant change of N2O fluxes was shown. After artificial rainfall, boosting N2O fluxes and further increase in CO2 fluxes were demonstrated. Our result indicates that precipitation is necessary before a prominent N2O peak. In our LGR/Li-Cor system, CO was also measured from chambers. Interesting CO fluxes were shown in our experiment. Soil, which is usually considered as a CO sink, emits CO in some chambers during our measurement, which is probably related to the nationwide forest fires and lack of precipitation during the period.

  4. Conditions Inducing Excessive O-GlcNAcylation Inhibit BMP2-Induced Osteogenic Differentiation of C2C12 Cells.

    PubMed

    Gu, Hanna; Song, Mina; Boonanantanasarn, Kanitsak; Baek, Kyunghwa; Woo, Kyung Mi; Ryoo, Hyun-Mo; Baek, Jeong-Hwa

    2018-01-09

    Hyperglycemic conditions in diabetic patients can affect various cellular functions, including the modulation of osteogenic differentiation. However, the molecular mechanisms by which hyperglycemia affects osteogenic differentiation are yet to be clarified. This study aimed to investigate whether the aberrant increase in protein O -linked-β- N -acetylglucosamine glycosylation ( O -GlcNAcylation) contributes to the suppression of osteogenic differentiation due to hyperglycemia. To induce osteogenic differentiation, C2C12 cells were cultured in the presence of recombinant human bone morphogenetic protein 2 (BMP2). Excessive protein O -GlcNAcylation was induced by treating C2C12 cells with high glucose, glucosamine, or N -acetylglucosamine concentrations or by O -GlcNAc transferase (OGT) overexpression. The effect of O -GlcNAcylation on osteoblast differentiation was then confirmed by examining the expression levels of osteogenic marker gene mRNAs, activity of alkaline phosphatase, and transcriptional activity of Runx2, a critical transcription factor for osteoblast differentiation and bone formation. Cell treatment with high glucose, glucosamine or N -acetylglucosamine increased O -GlcNAcylation of Runx2 and the total levels of O -GlcNAcylated proteins, which led to a decrease in the transcriptional activity of Runx2, expression levels of osteogenic marker genes (Runx2, osterix, alkaline phosphatase, and type I collagen), and activity of alkaline phosphatase. These inhibitory effects were rescued by lowering protein O -GlcNAcylation levels by adding STO45849, an OGT inhibitor, or by overexpressing β- N -acetylglucosaminidase. Our findings suggest that excessive protein O -GlcNAcylation contributes to high glucose-suppressed osteogenic differentiation.

  5. Annual mean mixing ratios of N2, Ar, O2, and CO in the martian atmosphere

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2017-09-01

    The precise mixing ratios of N2, Ar, O2, and CO measured by the MSL Curiosity quadrupole mass spectrometer must be corrected for the seasonal variations of the atmospheric pressure to reproduce annual mean mixing ratios on Mars. The corrections are made using measurements for the first year of the Viking Landers 1 and 2 and the Mars Climate Database data. The mean correction factor is 0.899 ± 0.006 resulting in annual mean mixing ratios of (1.83 ± 0.03)% for N2, (1.86 ± 0.02)% for Ar, (1.56 ± 0.06) × 10-3 for O2, and 673 ± 2.6 ppm for CO. The O2 mixing ratio agrees with the Herschel value within its uncertainty, the ground-based observations corrected for the dust extinction, and photochemical models by Nair et al. (1994) and Krasnopolsky (2010). The CO mixing ratio is in excellent agreement with the MRO/CRISM value of 700 ppm and with 667, 693, and 684 ppm recently observed at LS = 60, 89, and 110° and corrected to the annual mean conditions. Lifetimes of N2 and Ar are very long in the martian atmosphere, and differences between the MSL and Viking data on these species cannot be attributed to their variations.

  6. The δ15N and δ18O values of N2O produced during the co-oxidation of ammonia by methanotrophic bacteria

    USGS Publications Warehouse

    Mandernack, Kevin W.; Mills, Christopher T.; Johnson, Craig A.; Rahn, Thomas; Kinney, Chad

    2009-01-01

    In order to determine if the δ15N and δ18O values of N2O produced during co-oxidation of NH4+ by methanotrophic (methane oxidizing) bacteria can be isotopically distinguished from N2O produced either by autotrophic nitrifying or denitrifying bacteria, we conducted laboratory incubation experiments with pure cultures of methanotrophic bacteria that were provided NH4Cl as an oxidation substrate. The N2O produced during NH4+ oxidation by methanotrophic bacteria showed nitrogen isotope fractionation between NH4+ and N2ON2O–NH4+) of − 48 and − 55‰ for Methylomonas methanica and Methylosinus trichosporium, OB3b respectively. These large fractionations are similar to those previously measured for autotrophic nitrifying bacteria and consistent with N2O formation by multiple rate limiting steps that include NH4+oxidation by the methane monooxygenase enzyme and reduction of NO2− to N2O. Consequently, N2O formed by NH4+ oxidation via methanotrophic or autotrophic nitrifying bacteria might generally be characterized by lower δ15NN2O values than that formed by denitrificaiton, although this also depends on the variability of δ15N of available nitrogen sources (e.g., NH4+, NO3−, NO2−). Additional incubations with M. trichosporium OB3b at high and low CH4 conditions in waters of different δ18O values revealed that 19–27% of the oxygen in N2O was derived from O2 with the remainder from water. The biochemical mechanisms that could explain this amount of O2 incorporation are discussed. The δ18O of N2O formed under high CH4 conditions was ~ + 15‰ more positive than that formed under lower CH4 conditions. This enrichment resulted in part from the incorporation of O2 into N2O that was enriched in 18O due to an isotope fractionation effect of − 16.1 ± 2.0‰ and − 17.5 ± 5.4‰ associated with O2 consumption during the high and low methane concentration incubations, respectively. Therefore, N2O formed by NH4+

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

    PubMed

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

    2017-06-09

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

  8. Using stable isotopes to follow excreta N dynamics and N2O emissions in animal production systems.

    PubMed

    Clough, T J; Müller, C; Laughlin, R J

    2013-06-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the dominant anthropogenic stratospheric ozone-depleting emission. The tropospheric concentration of N2O continues to increase, with animal production systems constituting the largest anthropogenic source. Stable isotopes of nitrogen (N) provide tools for constraining emission sources and, following the temporal dynamics of N2O, providing additional insight and unequivocal proof of N2O source, production pathways and consumption. The potential for using stable isotopes of N is underutilised. The intent of this article is to provide an overview of what these tools are and demonstrate where and how these tools could be applied to advance the mitigation of N2O emissions from animal production systems. Nitrogen inputs and outputs are dominated by fertiliser and excreta, respectively, both of which are substrates for N2O production. These substrates can be labelled with 15N to enable the substrate-N to be traced and linked to N2O emissions. Thus, the effects of changes to animal production systems to reduce feed-N wastage by animals and fertiliser wastage, aimed at N2O mitigation and/or improved animal or economic performance, can be traced. Further 15N-tracer studies are required to fully understand the dynamics and N2O fluxes associated with excreta, and the biological contribution to these fluxes. These data are also essential for the new generation of 15N models. Recent technique developments in isotopomer science along with stable isotope probing using multiple isotopes also offer exciting capability for addressing the N2O mitigation quest.

  9. Wetlands and Agriculture in Africa: Major Sources of N2O?

    NASA Astrophysics Data System (ADS)

    Gettel, G. M.

    2015-12-01

    Papyrus wetlands in East Africa are rapidly being converted to agricultural production in an effort to increase food security. This conversion is often seasonal, with wetlands being used for grazing and crop production of maize, sugarcane, and rice during dry seasons, and flooding occurring during wet seasons. An important question with respect to greenhouse gas production is whether wetland conversion to agriculture increases N2O fluxes. This trend has been shown in temperate regions where increased N2O fluxes are positively related to low soil C:N ratios, especially when soil moisture content remains high. In order to examine whether denitrification contributes to N2O flux, we measured potential denitrification rates (PDR by acetylene block method) in intact papyrus wetlands and agricultural converted wetlands in Kenya, Tanzania, Uganda, and Rwanda, and also performed multivariate analysis to relate soil characteristics to PDR. Agricultural land-cover types included maize, sugarcane, rice, and grazing. Results showed that intact wetlands are potentially important sources of N2O, as PDR in papyrus vegetation were consistently the highest (p<0.05; 128 - 601 μg N2O g DW-1 hour-1) while grazing sites showed the lowest (0.1 - 0.5 μg N2O g DW-1 hour-1). Rates were second highest in rice fields (2.3 - 303 μg N2O g DW-1 hour-1), and intermediate in maize and sugarcane (6.5 - 75 μmg N2O g DW-1 hour-1 and 5 - 30 μg N2O g DW-1 hour-1 respectively). PDR across all sites was inversely related to soil C:N ratio, with nitrate consistently limiting PDR in the wetland sites while soil carbon limited PDR in agricultural sites. This is seemingly in contrast with other findings that show that lower C:N ratios result in high N2O fluxes from drained wetland sites. However, flux measurements along with more realistic process-based measurements of denitrification are urgently needed to more fully understand the effect of agricultural conversion of wetlands in East Africa.

  10. Factors Affecting the Inclusion Potency for Acicular Ferrite Nucleation in High-Strength Steel Welds

    NASA Astrophysics Data System (ADS)

    Kang, Yongjoon; Jeong, Seonghoon; Kang, Joo-Hee; Lee, Changhee

    2016-06-01

    Factors affecting the inclusion potency for acicular ferrite nucleation in high-strength weld metals were investigated and the contribution of each factor was qualitatively evaluated. Two kinds of weld metals with different hardenabilities were prepared, in both, MnTi2O4-rich spinel formed as the predominant inclusion phase. To evaluate the factors determining the inclusion potency, the inclusion characteristics of size, phase distribution in the multiphase inclusion, orientation relationship with ferrite, and Mn distribution near the inclusion were analyzed. Three factors affecting the ferrite nucleation potency of inclusions were evaluated: the Baker-Nutting (B-N) orientation relationship between ferrite and the inclusion; the formation of an Mn-depleted zone (MDZ) near the inclusion; and the strain energy around the inclusion. Among these, the first two factors were found to be the most important. In addition, it was concluded that the increased chemical driving force brought about by the formation of an MDZ contributed more to the formation of acicular ferrite in higher-strength weld metals, because the B-N orientation relationship between ferrite and the inclusion was less likely to form as the transformation temperature decreased.

  11. TES/Aura L2 Ozone (O3) Nadir V6 (TL2O3N)

    Atmospheric Science Data Center

    2018-01-18

    TES/Aura L2 Ozone (O3) Nadir (TL2O3N) News:  TES News Join ... Project Title:  TES Discipline:  Tropospheric Composition Version:  V6 Level:  L2 Platform:  TES/Aura L2 Ozone Spatial Coverage:  5.3 x 8.5 km nadir ...

  12. Effect of annealing temperature on the electrical properties of Au/Ta2O5/n-GaN metal-insulator-semiconductor (MIS) structure

    NASA Astrophysics Data System (ADS)

    Prasanna Lakshmi, B.; Rajagopal Reddy, V.; Janardhanam, V.; Siva Pratap Reddy, M.; Lee, Jung-Hee

    2013-11-01

    We report on the effect of an annealing temperature on the electrical properties of Au/Ta2O5/n-GaN metal-insulator-semiconductor (MIS) structure by current-voltage ( I- V) and capacitance-voltage ( C- V) measurements. The measured Schottky barrier height ( Φ bo) and ideality factor n values of the as-deposited Au/Ta2O5/n-GaN MIS structure are 0.93 eV ( I- V) and 1.19. The barrier height (BH) increases to 1.03 eV and ideality factor decreases to 1.13 upon annealing at 500 ∘C for 1 min under nitrogen ambient. When the contact is annealed at 600 ∘C, the barrier height decreases and the ideality factor increases to 0.99 eV and 1.15. The barrier heights obtained from the C- V measurements are higher than those obtained from I- V measurements, and this indicates the existence of spatial inhomogeneity at the interface. Cheung’s functions are also used to calculate the barrier height ( Φ bo), ideality factor ( n), and series resistance ( R s ) of the Au/Ta2O5/n-GaN MIS structure. Investigations reveal that the Schottky emission is the dominant mechanism and the Poole-Frenkel emission occurs only in the high voltage region. The energy distribution of interface states is determined from the forward bias I- V characteristics by taking into account the bias dependence of the effective barrier height. It is observed that the density value of interface states for the annealed samples with interfacial layer is lower than that of the density value of interface states of the as-deposited sample.

  13. Annual mean mixing ratios of N2, Ar, O2, and CO in the martian atmosphere

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, V.

    2017-09-01

    The precise mixing ratios of N2, Ar, O2, and CO measured by the MSL Curiosity quadrupole mass spectrometer must be corrected for the seasonal variations of the atmospheric pressure to reproduce annual mean mixing ratios on Mars. The corrections are made using measurements the Viking Landers and the Mars Climate Database data. The mean correction factor is 0.899 ± 0.006 resulting in annual mean mixing ratios of (1.83 ± 0.03)% for N2, (1.86 ± 0.02)% for Ar, (1.56 ± 0.06)×10-3 for O2, and 673 ± 2.6 ppm for CO. The O2 mixing ratio agrees with the Herschel value within its uncertainty, the ground-based observations corrected for the dust extinction, and photochemical models by Nair et al. (1994) and Krasnopolsky (2010). The CO mixing ratio is in excellent agreement with the MRO/CRISM value of 700 ppm and with 667, 693, and 684 ppm recently observed at LS = 60, 89, and 110° and corrected to the annual mean conditions. Lifetimes of N2 and Ar are very long in the martian atmosphere, and differences between the MSL and Viking data on these species cannot be attributed to their variations.

  14. Sensitivity of terrestrial N2O emission to atmospheric nitrogen deposition

    NASA Astrophysics Data System (ADS)

    Ito, A.; Sudo, K.; Nishina, K.; Ishijima, K.; Inatomi, M. I.

    2015-12-01

    Terrestrial N2O emission is generated from several nitrogen sources including biological fixation, agricultural fertilizer, and atmospheric deposition. There remain large uncertainties how much N2O is produced from atmospheric deposition. This is a crosscutting issue between global warming and atmospheric pollution. In this study, we assessed the sensitivity of global terrestrial N2O emission to atmospheric deposition, using a process-based model VISIT. In the model, N2O emission is estimated separately for nitrification and denitrfication with the NGAS parameterization. The global simulations were conducted from 1901 to 2014 at spatial resolution of 0.5 degree. Atmospheric deposition of ammonium, NOy, and organic nitrogen simulated by the atmospheric chemistry model CHASER from the pre-industrial time to the present was used. Annual total nitrogen deposition was estimated to increase from 27 Tg N in 1901 to 77 Tg N in 2014. The total N2O emission was also estimated to increase in the period, but it was largely attributable to the increased emission from croplands. We need further investigations for the N2O emission from natural soils, which may be nitrogen-limited.

  15. A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

    NASA Astrophysics Data System (ADS)

    Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

    2017-08-01

    The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

  16. The effect of pH on N2O production under aerobic conditions in a partial nitritation system.

    PubMed

    Law, Yingyu; Lant, Paul; Yuan, Zhiguo

    2011-11-15

    Ammonia-oxidising bacteria (AOB) are a major contributor to nitrous oxide (N(2)O) emissions during nitrogen transformation. N(2)O production was observed under both anoxic and aerobic conditions in a lab-scale partial nitritation system operated as a sequencing batch reactor (SBR). The system achieved 55 ± 5% conversion of the 1g NH(4)(+)-N/L contained in a synthetic anaerobic digester liquor to nitrite. The N(2)O emission factor was 1.0 ± 0.1% of the ammonium converted. pH was shown to have a major impact on the N(2)O production rate of the AOB enriched culture. In the investigated pH range of 6.0-8.5, the specific N(2)O production was the lowest between pH 6.0 and 7.0 at a rate of 0.15 ± 0.01 mg N(2)O-N/h/g VSS, but increased with pH to a maximum of 0.53 ± 0.04 mg N(2)O-N/h/g VSS at pH 8.0. The same trend was also observed for the specific ammonium oxidation rate (AOR) with the maximum AOR reached at pH 8.0. A linear relationship between the N(2)O production rate and AOR was observed suggesting that increased ammonium oxidation activity may have promoted N(2)O production. The N(2)O production rate was constant across free ammonia (FA) and free nitrous acid (FNA) concentrations of 5-78 mg NH(3)-N/L and 0.15-4.6 mg HNO(2)-N/L, respectively, indicating that the observed pH effect was not due to changes in FA or FNA concentrations. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. Assessing uncertainties in crop and pasture ensemble model simulations of productivity and N2 O emissions.

    PubMed

    Ehrhardt, Fiona; Soussana, Jean-François; Bellocchi, Gianni; Grace, Peter; McAuliffe, Russel; Recous, Sylvie; Sándor, Renáta; Smith, Pete; Snow, Val; de Antoni Migliorati, Massimiliano; Basso, Bruno; Bhatia, Arti; Brilli, Lorenzo; Doltra, Jordi; Dorich, Christopher D; Doro, Luca; Fitton, Nuala; Giacomini, Sandro J; Grant, Brian; Harrison, Matthew T; Jones, Stephanie K; Kirschbaum, Miko U F; Klumpp, Katja; Laville, Patricia; Léonard, Joël; Liebig, Mark; Lieffering, Mark; Martin, Raphaël; Massad, Raia S; Meier, Elizabeth; Merbold, Lutz; Moore, Andrew D; Myrgiotis, Vasileios; Newton, Paul; Pattey, Elizabeth; Rolinski, Susanne; Sharp, Joanna; Smith, Ward N; Wu, Lianhai; Zhang, Qing

    2018-02-01

    Simulation models are extensively used to predict agricultural productivity and greenhouse gas emissions. However, the uncertainties of (reduced) model ensemble simulations have not been assessed systematically for variables affecting food security and climate change mitigation, within multi-species agricultural contexts. We report an international model comparison and benchmarking exercise, showing the potential of multi-model ensembles to predict productivity and nitrous oxide (N 2 O) emissions for wheat, maize, rice and temperate grasslands. Using a multi-stage modelling protocol, from blind simulations (stage 1) to partial (stages 2-4) and full calibration (stage 5), 24 process-based biogeochemical models were assessed individually or as an ensemble against long-term experimental data from four temperate grassland and five arable crop rotation sites spanning four continents. Comparisons were performed by reference to the experimental uncertainties of observed yields and N 2 O emissions. Results showed that across sites and crop/grassland types, 23%-40% of the uncalibrated individual models were within two standard deviations (SD) of observed yields, while 42 (rice) to 96% (grasslands) of the models were within 1 SD of observed N 2 O emissions. At stage 1, ensembles formed by the three lowest prediction model errors predicted both yields and N 2 O emissions within experimental uncertainties for 44% and 33% of the crop and grassland growth cycles, respectively. Partial model calibration (stages 2-4) markedly reduced prediction errors of the full model ensemble E-median for crop grain yields (from 36% at stage 1 down to 4% on average) and grassland productivity (from 44% to 27%) and to a lesser and more variable extent for N 2 O emissions. Yield-scaled N 2 O emissions (N 2 O emissions divided by crop yields) were ranked accurately by three-model ensembles across crop species and field sites. The potential of using process-based model ensembles to predict jointly

  18. Effects of soil temperature, flooding, and organic matter addition on N2O emissions from a soil of Hongze Lake wetland, China.

    PubMed

    Lu, Yan; Xu, Hongwen

    2014-01-01

    The objectives of this study were to test the effects of soil temperature, flooding, and raw organic matter input on N2O emissions in a soil sampled at Hongze Lake wetland, Jiangsu Province, China. The treatments studied were-peat soil (I), peat soil under flooding (II), peat soil plus raw organic matter (III), and peat soil under flooding plus organic matter. These four treatments were incubated at 20°C and 35°C. The result showed that temperature increase could enhance N2O emissions rate and cumulative emissions significantly; moreover, the flooded soil with external organic matter inputs showed the lowest cumulative rise in N2O emissions due to temperature increment. Flooding might inhibit soil N2O emissions, and the inhibition was more pronounced after organic matter addition to the original soil. Conversely, organic matter input explained lower cumulative N2O emissions under flooding. Our results suggest that complex interactions between flooding and other environmental factors might appear in soil N2O emissions. Further studies are needed to understand potential synergies or antagonisms between environmental factors that control N2O emissions in wetland soils.

  19. MOCVD of HfO2 and ZrO2 high-k gate dielectrics for InAlN/AlN/GaN MOS-HEMTs

    NASA Astrophysics Data System (ADS)

    Abermann, S.; Pozzovivo, G.; Kuzmik, J.; Strasser, G.; Pogany, D.; Carlin, J.-F.; Grandjean, N.; Bertagnolli, E.

    2007-12-01

    We apply metal organic chemical vapour deposition (MOCVD) of HfO2 and of ZrO2 from β-diketonate precursors to grow high-k gate dielectrics for InAlN/AlN/GaN metal oxide semiconductor (MOS)-high electron mobility transistors (HEMTs). High-k oxides of about 12 nm-14 nm are deposited for the MOS-HEMTs incorporating Ni/Au gates, whereas as a reference, Ni-contact-based 'conventional' Schottky-barrier (SB)-HEMTs are processed. The processed dielectrics decrease the gate current leakage of the HEMTs by about four orders of magnitude if compared with the SB-gated HEMTs and show superior device characteristics in terms of IDS and breakdown.

  20. Band-Bending of Ga-Polar GaN Interfaced with Al2O3 through Ultraviolet/Ozone Treatment.

    PubMed

    Kim, Kwangeun; Ryu, Jae Ha; Kim, Jisoo; Cho, Sang June; Liu, Dong; Park, Jeongpil; Lee, In-Kyu; Moody, Baxter; Zhou, Weidong; Albrecht, John; Ma, Zhenqiang

    2017-05-24

    Understanding the band bending at the interface of GaN/dielectric under different surface treatment conditions is critically important for device design, device performance, and device reliability. The effects of ultraviolet/ozone (UV/O 3 ) treatment of the GaN surface on the energy band bending of atomic-layer-deposition (ALD) Al 2 O 3 coated Ga-polar GaN were studied. The UV/O 3 treatment and post-ALD anneal can be used to effectively vary the band bending, the valence band offset, conduction band offset, and the interface dipole at the Al 2 O 3 /GaN interfaces. The UV/O 3 treatment increases the surface energy of the Ga-polar GaN, improves the uniformity of Al 2 O 3 deposition, and changes the amount of trapped charges in the ALD layer. The positively charged surface states formed by the UV/O 3 treatment-induced surface factors externally screen the effect of polarization charges in the GaN, in effect, determining the eventual energy band bending at the Al 2 O 3 /GaN interfaces. An optimal UV/O 3 treatment condition also exists for realizing the "best" interface conditions. The study of UV/O 3 treatment effect on the band alignments at the dielectric/III-nitride interfaces will be valuable for applications of transistors, light-emitting diodes, and photovoltaics.

  1. Acidification Enhances Hybrid N2O Production Associated with Aquatic Ammonia-Oxidizing Microorganisms

    PubMed Central

    Frame, Caitlin H.; Lau, Evan; Nolan, E. Joseph; Goepfert, Tyler J.; Lehmann, Moritz F.

    2017-01-01

    Ammonia-oxidizing microorganisms are an important source of the greenhouse gas nitrous oxide (N2O) in aquatic environments. Identifying the impact of pH on N2O production by ammonia oxidizers is key to understanding how aquatic greenhouse gas fluxes will respond to naturally occurring pH changes, as well as acidification driven by anthropogenic CO2. We assessed N2O production rates and formation mechanisms by communities of ammonia-oxidizing bacteria (AOB) and archaea (AOA) in a lake and a marine environment, using incubation-based nitrogen (N) stable isotope tracer methods with 15N-labeled ammonium (15NH4+) and nitrite (15NO2−), and also measurements of the natural abundance N and O isotopic composition of dissolved N2O. N2O production during incubations of water from the shallow hypolimnion of Lake Lugano (Switzerland) was significantly higher when the pH was reduced from 7.54 (untreated pH) to 7.20 (reduced pH), while ammonia oxidation rates were similar between treatments. In all incubations, added NH4+ was the source of most of the N incorporated into N2O, suggesting that the main N2O production pathway involved hydroxylamine (NH2OH) and/or NO2− produced by ammonia oxidation during the incubation period. A small but significant amount of N derived from exogenous/added 15NO2− was also incorporated into N2O, but only during the reduced-pH incubations. Mass spectra of this N2O revealed that NH4+ and 15NO2− each contributed N equally to N2O by a “hybrid-N2O” mechanism consistent with a reaction between NH2OH and NO2−, or compounds derived from these two molecules. Nitrifier denitrification was not an important source of N2O. Isotopomeric N2O analyses in Lake Lugano were consistent with incubation results, as 15N enrichment of the internal N vs. external N atoms produced site preferences (25.0–34.4‰) consistent with NH2OH-dependent hybrid-N2O production. Hybrid-N2O formation was also observed during incubations of seawater from coastal Namibia

  2. Kinetics of nitrous oxide (N2O) formation and reduction by Paracoccus pantotrophus.

    PubMed

    Read-Daily, B L; Sabba, F; Pavissich, J P; Nerenberg, R

    2016-12-01

    Nitrous oxide (N 2 O) is a powerful greenhouse gas emitted from wastewater treatment, as well as natural systems, as a result of biological nitrification and denitrification. While denitrifying bacteria can be a significant source of N 2 O, they can also reduce N 2 O to N 2 . More information on the kinetics of N 2 O formation and reduction by denitrifying bacteria is needed to predict and quantify their impact on N 2 O emissions. In this study, kinetic parameters were determined for Paracoccus pantotrophus, a common denitrifying bacterium. Parameters included the maximum specific reduction rates, [Formula: see text], growth rates, [Formula: see text], and yields, Y, for reduction of NO 3 - (nitrate) to nitrite (NO 2 - ), NO 2 - to N 2 O, and N 2 O to N 2 , with acetate as the electron donor. The [Formula: see text] values were 2.9 gN gCOD -1 d -1 for NO 3 - to NO 2 - , 1.4 gN gCOD -1  d -1 for NO 2 - to N 2 O, and 5.3 gN gCOD -1  d -1 for N 2 O to N 2 . The [Formula: see text] values were 2.7, 0.93, and 1.5 d -1 , respectively. When N 2 O and NO 3 - were added concurrently, the apparent (extant) kinetics, [Formula: see text], assuming reduction to N 2 , were 6.3 gCOD gCOD -1  d -1 , compared to 5.4 gCOD gCOD -1  d -1 for NO 3 - as the sole added acceptor. The [Formula: see text] was 1.6 d -1 , compared to 2.5 d -1 for NO 3 - alone. These results suggest that NO 3 - and N 2 O were reduced concurrently. Based on this research, denitrifying bacteria like P. pantotrophus may serve as a significant sink for N 2 O. With careful design and operation, treatment plants can use denitrifying bacteria to minimize N 2 O emissions.

  3. Wetting-induced pulses produced unexpectedly high emissions of N2O and NOx in a desert ecosystem

    NASA Astrophysics Data System (ADS)

    Eberwein, J. R.; Carey, C.; Aronson, E. L.; Jenerette, D.

    2015-12-01

    Approximately one third of Earth's land surface is subjected to arid conditions, and aridland soils have the potential for significant feedbacks to global climate change drivers, such as anthropogenic nitrogen deposition. This study examined wetting-induced pulses of N2O and NOx along a nitrogen deposition gradient in the Colorado Desert of southern California. Measurements were made before and following water (to simulate a 2 cm rain event) and nitrogen plus water additions (30 kg NH4NO3 ha-1) at 15 minutes, 12 hours and 24 hours post-wetting. We found nitrogenous fluxes that were substantially higher than expected. N2O fluxes, in particular were remarkably high reaching up to 200 ng N2O-N m-2 s-1, similar to agriculture levels and in the range of peat bog emissions. There was a clear transition between N2O emissions, which peaked 15 minutes after wetting, and NOx emissions, which peaked at the 12 hour timepoint. NOx emissions were also considerable, reaching as high as 350 ng NOx-N m-2 s-1. Both N2O and NOx fluxes responded strongly to water additions, demonstrating a clear wetting-induced pulse response. While N2O was not affected by nitrogen additions, NOx fluxes demonstrated a significant increase with nitrogen plus water over water alone (p=0.016). These results suggest that gaseous nitrogen export, particularly N2O emissions, is a greater form of nitrogen loss in arid systems than is currently assumed. This potential for high nitrogen emissions and the capacity for anthropogenic nitrogen deposition to increase these emissions present serious implications for local air quality and significant soil feedbacks to climate change.

  4. Effects of S and N doping on the structural, magnetic and electronic properties of rutile CrO2

    NASA Astrophysics Data System (ADS)

    Xie, You; Zhou, An-Ning; Sun, Kai-Gang; Zhang, Ya-Ting; Huo, Yi-Ping; Wang, Su-Fang; Zhang, Jian-Min

    2016-05-01

    Magnetic and electronic properties of S- and N-doped CrO2 are studied by using the first-principle projector augmented wave potential within the generalized gradient approximation. The optimized lattice constants for CrO2 agree well with the previous work. With increasing S doping (N doping), the lattice constants of CrO2-xSx (CrO2-xNx) (x=0.5, 1 and 1.5) all increase (decrease), While these compounds remain the tetragonal structure. CrO1.5S0.5, CrO1.5N0.5 and CrON compounds remain the half-metallicity, while the band gap is determined by different factors. It is also found that the change of the total magnetic moment with equivalent atom S doping in CrO2 compound is small except for x=1.

  5. Endothelial Heparan Sulfate 6-O-Sulfation Levels Regulate Angiogenic Responses of Endothelial Cells to Fibroblast Growth Factor 2 and Vascular Endothelial Growth Factor*

    PubMed Central

    Ferreras, Cristina; Rushton, Graham; Cole, Claire L.; Babur, Muhammad; Telfer, Brian A.; van Kuppevelt, Toin H.; Gardiner, John M.; Williams, Kaye J.; Jayson, Gordon C.; Avizienyte, Egle

    2012-01-01

    Fibroblast growth factor 2 (FGF2) and vascular endothelial growth factor 165 (VEGF165) are potent pro-angiogenic growth factors that play a pivotal role in tumor angiogenesis. The activity of these growth factors is regulated by heparan sulfate (HS), which is essential for the formation of FGF2/FGF receptor (FGFR) and VEGF165/VEGF receptor signaling complexes. However, the structural characteristics of HS that determine activation or inhibition of such complexes are only partially defined. Here we show that ovarian tumor endothelium displays high levels of HS sequences that harbor glucosamine 6-O-sulfates when compared with normal ovarian vasculature where these sequences are also detected in perivascular area. Reduced HS 6-O-sulfotransferase 1 (HS6ST-1) or 6-O-sulfotransferase 2 (HS6ST-2) expression in endothelial cells impacts upon the prevalence of HS 6-O-sulfate moieties in HS sequences, which consist of repeating short, highly sulfated S domains interspersed by transitional N-acetylated/N-sulfated domains. 1–40% reduction in 6-O-sulfates significantly compromises FGF2- and VEGF165-induced endothelial cell sprouting and tube formation in vitro and FGF2-dependent angiogenesis in vivo. Moreover, HS on wild-type neighboring endothelial or smooth muscle cells fails to restore endothelial cell sprouting and tube formation. The affinity of FGF2 for HS with reduced 6-O-sulfation is preserved, although FGFR1 activation is inhibited correlating with reduced receptor internalization. These data show that 6-O-sulfate moieties in endothelial HS are of major importance in regulating FGF2- and VEGF165-dependent endothelial cell functions in vitro and in vivo and highlight HS6ST-1 and HS6ST-2 as potential targets of novel antiangiogenic agents. PMID:22927437

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  7. Harmonisation and diagnostics of MIPAS ESA CH4 and N2O profiles using data assimilation

    NASA Astrophysics Data System (ADS)

    Errera, Quentin; Ceccherini, Simone; Christophe, Yves; Chabrillat, Simon; Hegglin, Michaela I.; Lambert, Alyn; Ménard, Richard; Raspollini, Piera; Skachko, Sergey; van Weele, Michiel; Walker, Kaley A.

    2016-12-01

    This paper discusses assimilation experiments of methane (CH4) and nitrous oxide (N2O) profiles retrieved from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Here we focus on data versions 6 and 7 provided by the ESA processor. These data sets have been assimilated by the Belgian Assimilation System for Chemical ObsErvations (BASCOE). The CH4 and N2O retrieved profiles can oscillate, especially in the tropical lower stratosphere. Using the averaging kernels of the observations and a background error covariance matrix, which has previously been calibrated, allows the system to partly remedy this issue and provide assimilated fields that are more regular vertically. In general, there is a good agreement between the BASCOE analyses and independent observations from ACE-FTS (CH4 and N2O) and MLS (N2O), demonstrating the general good quality of CH4 and N2O retrievals provided by MIPAS ESA. Nevertheless, this study also identifies two issues in these data sets. First, time series of the observations show unexpected discontinuities due to an abrupt change in the gain of MIPAS band B, generally occurring after the instrument decontamination. Since the calibration is performed weekly, the abrupt change in the gain affects the measurements until the subsequent calibration is performed. Second, the correlations between BASCOE analyses and independent observations are poor in the lower stratosphere, especially in the tropics, probably due to the presence of outliers in the assimilated data. In this region, we recommend using MIPAS CH4 and N2O retrievals with caution.

  8. Simple radiosensitizing of hypoxic tumor tissues by N2O/Br(-) mixture.

    PubMed

    Billik, P

    2015-07-01

    The radiosensitization model of hypoxic tumor tissues based on the N2O/Br(-) mixture is described. The well-documented radiolysis of water in the presence of N2O and Br(-) ions at a low concentration supports this model. An aqueous solution saturated with N2O gas during the radiolysis generates OH radicals in a large extent. In N2O/Br- media at pH<9, Br2 is formed. Br2 hydrolyzes in an aqueous solution to form a very reactive hypobromous (HOBr) acid. Such process is described by the following chemical reaction: H2O + Br(-) + N2O + ionizing radiation (IR) --> HOBr + OH(-). In vivo formed HOBr as a long-lived product with a high biological activity induces the hypoxic tumor cell damage via many unique mechanisms. A local application or inhalation of an N2O-O2 mixture before or during the radiotherapy to enhance the saturation of tissues with N2O is a key prerequisite. Since the extracellular concentration of Br(-) ions is very low (0.02-0.05 mM), an oral or local application of NaBr should be used to shift the extracellular concentration of Br(-) ions to the mM region. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Understanding N2O sources and sinks with laser based isotopic analysis

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Harris, Eliza; Tuzson, Béla; Emmenegger, Lukas

    2015-04-01

    Nitrous oxide (N2O) is a potent greenhouse gas and the strongest ozone-destroying substance. The main emissions of N2O are linked to different microbial processes, therefore the sources are disperse and highly variable, complicating the development of effective mitigation strategies. Isotopic measurements have great potential to unravel spatial and temporal variations in sources, sinks and chemistry of N2O. Recent developments in quantum cascade laser spectroscopy (QCLAS) [1] allow both the intermolecular distribution of 15N substitutions ('site preference'; 15N14N16O versus 14N15N16O) and the oxygen isotopic composition (d18O) of N2O to be measured in real-time and at high precision of <0.2 ‰ [2]. Additionally, N2O isotopic analysis by QCLAS has demonstrated excellent compatibility to the standard technique isotope-ratio mass-spectrometry [3]. In a number of laboratory and pilot plant studies we investigated the isotopic signature of distinct microbial and abiotic N2O production and consumption pathways in soil and aqueous solution [e.g. 4]. Specific pathways were favoured by selection of the nitrogen substrates and process conditions and their isotopic signatures identified by real-time laser spectroscopic analysis. Results from our laboratory studies are in accordance with pure culture experiments and can therefore be applied to other ecosystems. Recently, high precision isotopic analysis at ambient N2O is also feasible by combining laser spectroscopy with automated preconcentration [5]. The field deployment was demonstrated by real-time monitoring isotopic composition of N2O emissions from an intensively managed grassland in central Switzerland for three months. The responses of the N2O isotopic signatures were analysed with respect to management events and weather influences [2]. In a follow-up project we intend to combine real-time N2O isotopic analysis at a tall tower in central Switzerland with atmospheric transport simulations and a biogeochemical model

  10. Isotopomeric characterization of N2O produced, consumed, and emitted by automobiles.

    PubMed

    Toyoda, Sakae; Yamamoto, Sei-ichiro; Arai, Shinji; Nara, Hideki; Yoshida, Naohiro; Kashiwakura, Kiriko; Akiyama, Ken-ichi

    2008-01-01

    Fossil fuel combustion is the second largest anthropogenic source of nitrous oxide (N2O) after agriculture. The estimated global N2O flux from combustion sources, as well as from other sources, still has a large uncertainty. Herein, we characterize automobile sources using N2O isotopomer ratios (nitrogen and oxygen isotope ratios and intramolecular site preference of 15N, SP) to assess their contributions to total global sources and to deconvolute complex production/consumption processes during combustion and subsequent catalytic treatments of exhaust. Car exhaust gases were sampled under running and idling state, and N2O isotopomer ratios were measured by mass spectrometry. The N2O directly emitted from an engine of a vehicle running at constant velocity had almost constant isotopomer ratios (delta15Nbulk = -28.7 +/- 1.2 per thousand, delta18O = 28.6 +/- 3.3 per thousand, and SP = 4.2 +/- 0.8 per thousand) irrespective of the velocity. After passing through catalytic converters, the isotopomer ratios showed an increase which varied with the temperature and the aging of the catalysts. The increase suggests that both production and consumption of N2O occur on the catalyst and that their rates can be comparable. It was noticed that in the idling state, the N2O emitted from a brand new car has higher isotopomer ratios than that from used cars, which indicate that technical improvements in catalytic converters can reduce the N2O from mobile combustion sources. On average, the isotopomeric signatures of N2O finally emitted from automobiles are not sensitive to running/idling states or to aging of the catalysts. Characteristic average isotopomer ratios of N2O from automobile sources are estimated at -4.9 +/- 8.2 per thousand, 43.5 +/- 13.9 per thousand, and 12.2 +/- 9.1 per thousand for delta15Nbulk, delta18O, and SP, respectively.

  11. The N2O activation by Rh5 clusters. A quantum chemistry study.

    PubMed

    Olvera-Neria, Oscar; Avilés, Roberto; Francisco-Rodríguez, Héctor; Bertin, Virineya; García-Cruz, Raúl; González-Torres, Julio César; Poulain, Enrique

    2015-04-01

    Nitrous oxide (N2O) is a by-product of exhaust pipe gases treatment produced by motor vehicles. Therefore, the N2O reduction to N2 is necessary to meet the actual environmental legislation. The N2O adsorption and dissociation assisted by the square-based pyramidal Rh5 cluster was investigated using the density functional theory and the zero-order regular approximation (ZORA). The Rh5 sextet ground state is the most active in N2O dissociation, though the quartet and octet states are also active because they are degenerate. The Rh5 cluster spontaneously activates the N2O cleavage, and the reaction is highly exothermic ca. -75 kcal mol(-1). The N2O breaking is obtained for the geometrical arrangement that maximizes the overlap and electron transfers between the N2O and Rh5 frontier orbitals. The Rh5 high activity is due to the Rh 3d orbitals are located between the N2O HOMO and LUMO orbitals, which makes possible the interactions between them. In particular, the O 2p states strongly interact with Rh 3d orbitals, which finally weaken the N2O bond. The electron transfer is from the Rh5 HOMO orbital to the N2O antibonding orbital.

  12. Theoretical prediction of a self-forming gallium oxide layer at an n-type GaN/SiO2 interface

    NASA Astrophysics Data System (ADS)

    Chokawa, Kenta; Narita, Tetsuo; Kikuta, Daigo; Kachi, Tetsu; Shiozaki, Koji; Shiraishi, Kenji

    2018-03-01

    We examine the energy band diagram at the n-type GaN (n-GaN)/SiO2 interface and show that electron transfer from n-GaN to SiO2 leads to the formation of negatively charged oxygen vacancies in the SiO2, resulting in the self-formation of an n-GaN/Ga2O3/SiO2 structure. On the other hand, it is difficult to automatically form Ga2O3 at a p-type GaN (p-GaN)/SiO2 interface. This electron-transfer-induced self-formation of Ga2O3 causes an interface dipole, which leads to band bending, resulting in an increase in the conduction band offset between GaN and SiO2. Accordingly, by using this self-forming phenomenon, GaN MOSFETs with lower leakage current can be realized.

  13. Identification and isolation of active N2O reducers in rice paddy soil

    PubMed Central

    Ishii, Satoshi; Ohno, Hiroki; Tsuboi, Masahiro; Otsuka, Shigeto; Senoo, Keishi

    2011-01-01

    Dissolved N2O is occasionally detected in surface and ground water in rice paddy fields, whereas little or no N2O is emitted to the atmosphere above these fields. This indicates the occurrence of N2O reduction in rice paddy fields; however, identity of the N2O reducers is largely unknown. In this study, we employed both culture-dependent and culture-independent approaches to identify N2O reducers in rice paddy soil. In a soil microcosm, N2O and succinate were added as the electron acceptor and donor, respectively, for N2O reduction. For the stable isotope probing (SIP) experiment, 13C-labeled succinate was used to identify succinate-assimilating microbes under N2O-reducing conditions. DNA was extracted 24 h after incubation, and heavy and light DNA fractions were separated by density gradient ultracentrifugation. Denaturing gradient gel electrophoresis and clone library analysis targeting the 16S rRNA and the N2O reductase gene were performed. For culture-dependent analysis, the microbes that elongated under N2O-reducing conditions in the presence of cell-division inhibitors were individually captured by a micromanipulator and transferred to a low-nutrient medium. The N2O-reducing ability of these strains was examined by gas chromatography/mass spectrometry. Results of the SIP analysis suggested that Burkholderiales and Rhodospirillales bacteria dominated the population under N2O-reducing conditions, in contrast to the control sample (soil incubated with only 13C-succinate). Results of the single-cell isolation technique also indicated that the majority of the N2O-reducing strains belonged to the genera Herbaspirillum (Burkholderiales) and Azospirillum (Rhodospirillales). In addition, Herbaspirillum strains reduced N2O faster than Azospirillum strains. These results suggest that Herbaspirillum spp. may have an important role in N2O reduction in rice paddy soils. PMID:21677691

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

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

  15. Marine N2O Emissions From Nitrification and Denitrification Constrained by Modern Observations and Projected in Multimillennial Global Warming Simulations

    NASA Astrophysics Data System (ADS)

    Battaglia, G.; Joos, F.

    2018-01-01

    Nitrous oxide (N2O) is a potent greenhouse gas (GHG) and ozone destructing agent; yet global estimates of N2O emissions are uncertain. Marine N2O stems from nitrification and denitrification processes which depend on organic matter cycling and dissolved oxygen (O2). We introduce N2O as an obligate intermediate product of denitrification and as an O2-dependent by-product from nitrification in the Bern3D ocean model. A large model ensemble is used to probabilistically constrain modern and to project marine N2O production for a low (Representative Concentration Pathway (RCP)2.6) and high GHG (RCP8.5) scenario extended to A.D. 10,000. Water column N2O and surface ocean partial pressure N2O data serve as constraints in this Bayesian framework. The constrained median for modern N2O production is 4.5 (±1σ range: 3.0 to 6.1) Tg N yr-1, where 4.5% stems from denitrification. Modeled denitrification is 65.1 (40.9 to 91.6) Tg N yr-1, well within current estimates. For high GHG forcing, N2O production decreases by 7.7% over this century due to decreasing organic matter export and remineralization. Thereafter, production increases slowly by 21% due to widespread deoxygenation and high remineralization. Deoxygenation peaks in two millennia, and the global O2 inventory is reduced by a factor of 2 compared to today. Net denitrification is responsible for 7.8% of the long-term increase in N2O production. On millennial timescales, marine N2O emissions constitute a small, positive feedback to climate change. Our simulations reveal tight coupling between the marine carbon cycle, O2, N2O, and climate.

  16. Validation of a station-prototype designed to integrate temporally soil N2O fluxes: IPNOA Station prototype.

    NASA Astrophysics Data System (ADS)

    Laville, Patricia; Volpi, Iride; Bosco, Simona; Virgili, Giorgio; Neri, Simone; Continanza, Davide; Bonari, Enrico

    2016-04-01

    Nitrous oxide (N2O) flux measurements from agricultural soil surface still accounts for the scientific community as major challenge. The evaluations of integrated soil N2O fluxes are difficult because these emissions are lower than for the other greenhouse gases sources (CO2, CH4). They are also sporadic, because highly dependent on few environmental conditions acting as limiting factors. Within a LIFE project (IPNOA: LIFE11 ENV/IT/00032) a station prototype was developed to integrate annually N2O and CO2 emissions using automatically chamber technique. Main challenge was to develop a device enough durable to be able of measuring in continuous way CO2 and N2O fluxes with sufficient sensitivity to allow make reliable assessments of soil GHG measurements with minimal technical field interventions. The IPNOA station prototype was developed by West System SRL and was set up during 2 years (2014 -2015) in an experimental maize field in Tuscan. The prototype involved six automatic chambers; the complete measurement cycle was of 2 hours. Each chamber was closing during 20 min and biogas accumulations were monitoring in line with IR spectrometers. Auxiliary's measurements including soil temperatures and water contents as weather data were also monitoring. All data were managed remotely with the same acquisition software installed in the prototype control unit. The operation of the prototype during the two cropping years allowed testing its major features: its ability to evaluate the temporal variation of N2O soil fluxes during a long period with weather conditions and agricultural managements and to prove the interest to have continuous measurements of fluxes. The temporal distribution of N2O fluxes indicated that emissions can be very large and discontinuous over short periods less ten days and that during about 70% of the time N2O fluxes were around detection limit of the instrumentation, evaluated to 2 ng N ha-1 day-1. N2O emission factor assessments were 1.9% in 2014

  17. Nitrous Oxide (N2O) Emissions by Termites: Does the Feeding Guild Matter?

    PubMed

    Brauman, Alain; Majeed, Muhammad Zeeshan; Buatois, Bruno; Robert, Alain; Pablo, Anne-Laure; Miambi, Edouard

    2015-01-01

    In the tropics, termites are major players in the mineralization of organic matter leading to the production of greenhouse gases including nitrous oxide (N2O). Termites have a wide trophic diversity and their N-metabolism depends on the feeding guild. This study assessed the extent to which N2O emission levels were determined by termite feeding guild and tested the hypothesis that termite species feeding on a diet rich in N emit higher levels of N2O than those feeding on a diet low in N. An in-vitro incubation approach was used to determine the levels of N2O production in 14 termite species belonging to different feeding guilds, collected from a wide range of biomes. Fungus-growing and soil-feeding termites emit N2O. The N2O production levels varied considerably, ranging from 13.14 to 117.62 ng N2O-N d(-1) (g dry wt.)(-1) for soil-feeding species, with Cubitermes spp. having the highest production levels, and from 39.61 to 65.61 ng N2O-N d(-1) (g dry wt.)(-1) for fungus-growing species. Wood-feeding termites were net N2O consumers rather than N2O producers with a consumption ranging from 16.09 to 45.22 ng N2O-N d(-1) (g dry wt.)(-1). Incubating live termites together with their mound increased the levels of N2O production by between 6 and 13 fold for soil-feeders, with the highest increase in Capritermes capricornis, and between 14 and 34 fold for fungus-growers, with the highest increase in Macrotermes muelleri. Ammonia-oxidizing (amoA-AOB and amoA-AOA) and denitrifying (nirK, nirS, nosZ) gene markers were detected in the guts of all termite species studied. No correlation was found between the abundance of these marker genes and the levels of N2O production from different feeding guilds. Overall, these results support the hypothesis that N2O production rates were higher in termites feeding on substrates with higher N content, such as soil and fungi, compared to those feeding on N-poor wood.

  18. Adsorption of H2O, H2, O2, CO, NO, and CO2 on graphene/g-C3N4 nanocomposite investigated by density functional theory

    NASA Astrophysics Data System (ADS)

    Wu, Hong-Zhang; Bandaru, Sateesh; Liu, Jin; Li, Li-Li; Wang, Zhenling

    2018-02-01

    Motivated by the photocatalytic reactions of small molecules on g-C3N4 by these insights, we sought to explore the adsorption of H2O and CO2 molecules on the graphene side and H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side of hybrid g-C3N4/graphene nanocomposite using first-principles calculations. The atomic structure and electronic properties of hybrid g-C3N4/graphene nanocomposite is explored. The adsorption of small molecules on graphene/g-C3N4 nanocomposite is thoroughly investigated. The computational studies revels that all small molecules on graphene/g-C3N4 nanocomposite are the physisorption. The adsorption characteristics of H2O and CO2 molecules on the graphene side are similar to that on graphene. The adsorption of H2O, H2, O2, CO, NO, and CO2 molecules on the g-C3N4 side always leads to a buckle structure of graphene/g-C3N4 nanocomposite. Graphene as a substrate can significantly relax the buckle degree of g-C3N4 in g-C3N4/graphene nanocomposite.

  19. Detection mechanism and characteristics of ZnO-based N2O sensors operating with photons

    NASA Astrophysics Data System (ADS)

    Jeong, T. S.; Yu, J. H.; Mo, H. S.; Kim, T. S.; Youn, C. J.; Hong, K. J.

    2013-11-01

    N2O sensors made with ZnO-based ZnCdO films were grown on Pyrex substrates by using the RF co-sputtering method. The structure of the N2O sensor was electrode/sensor/glass/illuminant. The mechanism of the photo-assisted oxidation and reduction process on the surface of the N2O sensors was investigated using light from a UV lamp and violet light emitting diode (LED). For photon exposure wavelengths of 365 and 405 nm, the sensitivity of the ZnO-based ZnCdO sensors was measured. From these measurements, the values of the sensitivity of the sensors with x = 0, 0.01, and 0.05 were found to be S = 1.44, 1.39, and 1.33 under LED light with a wavelength of 405 nm, respectively. These sensitivities were compared to those of SnO2 and WO3 materials measured at operating temperatures of 300-600 °C. Also, under exposure with UV light, the response times were observed to be 130 to 270 sec. These response times were slightly slower than that for the traditional method of thermal heating. However, they indicate that the described photon exposure method for N2O detection can replace the conventional heating mode. Consequently, we demonstrated that portable N2O sensors for room-temperature operation could be fabricated without thermal heating.

  20. Coupled effects of straw and nitrogen management on N2O and CH4 emissions of rainfed agriculture in Northwest China

    NASA Astrophysics Data System (ADS)

    Htun, Yin Min; Tong, Yanan; Gao, Pengcheng; Xiaotang, Ju

    2017-05-01

    Straw incorporation is a common agricultural practice, but the additional carbon source may increase greenhouse gas emissions by stimulating microbial activity in soil, particularly when straw is applied at the same time as nitrogen (N) fertilizer. We investigated the coupled effects of straw and N fertilizer on greenhouse gas emissions in a rainfed winter wheat-summer fallow system in Northwest China. Simultaneous applications of straw and N fertilizer increased N2O emissions by up to 88%, net greenhouse gas (NGHG) emission and net greenhouse gas intensity (NGHGI) by over 90%, and the N2O emission factor by over 2-fold. When straw was applied before N fertilizer, the emission factor (0.22%) decreased by approximately one-half compared with that for simultaneous applications (0.45%). In addition, early straw incorporation decreased N2O emissions, NGHG, and NGHGI by 35% (0.62 kg N2O-N ha-1 yr-1), 40% (242 kg CO2-eq ha-1 yr-1), and 38% (42 kg CO2-eq t-1 grain), respectively. We identified the period 30-35 days after N fertilization as a crucial period for evaluating the effectiveness of management practices on N2O emissions. The time between straw and fertilizer applications was negatively related to N2O emission (R2 = 0.8031; p < 0.01) but positively related to soil CH4 uptake (R2 = 0.7662; p < 0.01). Therefore, early straw incorporation can effectively mitigate greenhouse gas emissions by reducing N2O flux and increasing soil CH4 uptake without significantly decreasing grain yield.

  1. Pseudomonas stutzeri N2O reductase contains CuA-type sites.

    PubMed Central

    Scott, R A; Zumft, W G; Coyle, C L; Dooley, D M

    1989-01-01

    N2O reductase (N2O----N2) is the terminal enzyme in the energy-conserving denitrification pathway of soil and marine denitrifying bacteria. The protein is composed of two identical subunits and contains eight copper ions per enzyme molecule. The magnetic circular dichroism spectrum of resting (oxidized) N2O reductase is strikingly similar to the magnetic circular dichroism spectrum of the CuA site in mammalian cytochrome c oxidase [Greenwood, C., Hull, B. C., Barber, D., Eglinton, D. G. & Thomson, A. J. (1983) Biochem. J. 215, 303-316] and is unlike the magnetic circular dichroism spectra of all other biological copper chromophores obtained to date. Sulfur (or chlorine) scatterers are required to fit the copper extended x-ray absorption fine structure data of both the oxidized and reduced forms of N2O reductase. Satisfactory fits require a Cu-N or Cu-O [denoted Cu-(N, O)] interaction at 2.0 A, a Cu-(S, Cl) interaction at 2.3 A and an additional Cu(S, Cl) interaction at approximately 2.6 A (oxidized) or approximately 2.7 A (reduced). Approximately eight sulfur ions (per eight copper ions) at approximately 2.3 A are required to fit the extended x-ray absorption fine structure data for both the oxidized and reduced N2O reductase. The 2.3-A Cu-(S, Cl) distance is nearly identical to that previously determined for the CuA site in cytochrome c oxidase. A 2.6-2.7 A Cu-(S, Cl) interaction is also present in resting and fully reduced cytochrome c oxidase. Comparison of the N2O reductase sequence, determined by translating the structural NosZ gene, with cytochrome c oxidase subunit II sequences from several sources indicates that a Gly-Xaa-Xaa-Xaa-Xaa-Xaa-Cys-Ser-Xaa-Xaa-Cys-Xaa-Xaa-Xaa-His stretch is highly conserved. This sequence contains three of the probable ligands (two cysteines and one histidine) in a CuA-type site. Collectively these data establish that Pseudomonas stutzeri N2O reductase contains CuA-type sites. PMID:2542963

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

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

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

  3. Factors Affecting Career Decision-Making: Further Validation of the O'Neil Career-Sex Role Model and the Career Factor Checklist.

    ERIC Educational Resources Information Center

    Meinecke, Christine; O'Neil, James M.

    Many correlates of vocational choice have been suggested by career development theorists. A career decision-making model developed by O'Neil, Meeker, and Borgers suggests six factors (individual, societal, familial, socioeconomic, situational, psychosocial-emotional) that affect both sex role socialization and career decision-making. The validity…

  4. Geographic Inventory Framework (GiF) for estimating N2O and CH4 emissions from agriculture in the province of Alberta, Canada

    NASA Astrophysics Data System (ADS)

    Dimitrov, D. D.; Wang, J.

    2016-12-01

    A Geographic Information Framework (GiF) has been created to estimate and map agricultural N2O and CH4 emissions of the province of Alberta, Canada. The GiF consists of a modelling component, a GIS component, and application software to communicate between the model, database and census data. For compatibility, GiF follows the IPCC Tier 1 method and contains census data for animal populations, crop areas, and farms for the main IPCC animal and plant types (dairy cows, cattle cows, pigs, sheep, poultry, other animals, grasses, legumes, other crops), and estimated N2O and CH4 emissions from manure management, enteric fermentation, direct soil emissions (with applied manure, synthetic fertilizer, crop residue degradation, biological fixation) and indirect soil emissions (with atmospheric deposition and leaching). Methane emissions from enteric fermentation (609.24 Gg) prevailed over those from manure (44.99 Gg), and nitrous oxide emission from manure (22.01 Gg) prevailed over those from soil (17.73 Gg), with cattle cows emitting most N2O and CH4, followed by plant N2O emissions, and pigs and dairy cows CH4 emissions. The GIS maps showed discernible pattern of N2O and CH4 emissions increasing from North and West to the central Alberta and then slightly declining to South and East, which could be useful to address various mitigation strategies. The framework allows easy replacement of Tier 1 emission factors by Tire 2 or 3 ones from process-based models. Future applying of the latter will allow accounting for CO2 source/sink strength of agricultural ecosystems, hence their complete GHG balance affected by soil, water, and climate.

  5. N2O and N2 emissions from contrasting soil environments - interactive effects of soil nitrogen, hydrology and microbial communities

    NASA Astrophysics Data System (ADS)

    Christiansen, Jesper; Elberling, Bo; Ribbons, Relena; Hedo, Javier; José Fernández Alonso, Maria; Krych, Lukasz; Sandris Nielsen, Dennis; Kitzler, Barbara

    2016-04-01

    Reactive nitrogen (N) in the environment has doubled relative to the natural global N cycle with consequences for biogeochemical cycling of soil N. Also, climate change is expected to alter precipitation patterns and increase soil temperatures which in Arctic environments may accelerate permafrost thawing. The combination of changes in the soil N cycle and hydrological regimes may alter microbial transformations of soil N with unknown impacts on N2O and N2 emissions from temperate and Arctic soils. We present the first results of soil N2O and N2 emissions, chemistry and microbial communities over soil hydrological gradients (upslope, intermediate and wet) across a global N deposition gradient. The global gradient covered an N-limited high Arctic tundra (Zackenberg-ZA), a pacific temperate rain forest (Vancouver Island-VI) and an N saturated forest in Austria (Klausenleopoldsdorf-KL). The N2O and N2 emissions were measured from intact cores at field moisture in a He-atmosphere system. Extractable NH4+ and NO3-, organic and microbial C and N and potential enzyme-activities were determined on soil samples. Soil genomic DNA was subjected to MiSeq-based tag-encoded 16S rRNA and ITS gene amplicon sequencing for the bacterial and fungal community structure. Similar soil moisture levels were observed for the upslope, intermediate and wet locations at ZA, VI and KL, respectively. Extractable NO3- was highest at the N rich KL and lowest at ZA and showed no trend with soil moisture similar to NH4+. At ZA and VI soil NH4+ was higher than NO3- indicating a tighter N cycling. N2O emissions increased with soil moisture at all sites. The N2O emissions for the wet locations ranked similarly to NO3- with the largest response to soil moisture at KL. N2 emissions were remarkably similar across the sites and increased with soil wetness. Microbial C and N also increased with soil moisture and were overall lowest at the N rich KL site. The potential activity of protease enzyme was site

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

    NASA Astrophysics Data System (ADS)

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

    1983-12-01

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

  7. Modulation of Protein Metabolism to Mitigate Nitrous Oxide (N2O) Emission from Excreta of Livestock.

    PubMed

    Zhao, Guangyong

    2017-01-01

    Dietary protein is the main source of the body needed protein for animals. A great number of domestic animals including cattle, sheep, goats, pigs and chicken and other species are raised in the world to supply meat, milk and eggs that contain high quality of protein for human consumption. Domestic animals consume a great amount of feeds and water and excrete a large amount of faeces and urine. The conversion rate of dietary nitrogen (N, mainly dietary protein) to product N in livestock is low and the amount of N excretion is high and the nitrogenous compounds in excreta can be used as materials for nitrous oxide (N2O) formation in the processes of nitrification and denitrification in storage of excreta. Hence livestock farms and grazing pastures are important sources of N2O. N2O is a potent greenhouse gas and the key factor that damages the ozonosphere of the earth. Therefore, it is urgent to reveal the dietary protein metabolism processes and the regulation mechanism, which will help to reduce N2O emission. The nutritional options to reduce N excretion from livestock and consequently N2O emission include feeding low N rations and supplementing essential amino acid (AA) such as lysine and methionine to balance the AA profile of rations for pigs and ruminants. Other options include regulating partition of N excretion from urine to faeces and urinary nitrogenous constituents by decreasing urea N and increasing hippuric acid in ruminants. Supplementing tannic acid in the ration of ruminants has the potential to decrease the ratio of urinary N/faecal N and regulate the urinary nitrogenous components of ruminants and possibly reduce N2O emission in storage of excreta. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  8. Analysis of SAW properties in ZnO/AlxGa1-xN/c-Al2O3 structures.

    PubMed

    Chen, Ying; Emanetoglu, Nuri William; Saraf, Gaurav; Wu, Pan; Lu, Yicheng; Parekh, Aniruddh; Merai, Vinod; Udovich, Eric; Lu, Dong; Lee, Dong S; Armour, Eric A; Pophristic, Milan

    2005-07-01

    Piezoelectric thin films on high acoustic velocity nonpiezoelectric substrates, such as ZnO, AlN, or GaN deposited on diamond or sapphire substrates, are attractive for high frequency and low-loss surface acoustic wave devices. In this work, ZnO films are deposited on AlxGa1-xN/c-Al2O3 (0 < or = chi < or = 1) substrates using the radio frequency (RF) sputtering technique. In comparison with a single AlxGa1-xN layer deposited on c-Al2O3 with the same total film thickness, a ZnO/AlxGa1-xN/c-Al2O3 multilayer structure provides several advantages, including higher order wave modes with higher velocity and larger electromechanical coupling coefficient (K2). The surface acoustic wave (SAW) velocities and coupling coefficients of the ZnO/AlxGa1-xN/c-Al2O3 structure are tailored as a function of the Al mole percentage in AlxGa1-xN films, and as a function of the ZnO (h1) to AlxGa1-xN (h2) thickness ratio. It is found that a wide thickness-frequency product (hf) region in which coupling is close to its maximum value, K(2)max, can be obtained. The K(2)max of the second order wave mode (h1 = h2) is estimated to be 4.3% for ZnO/GaN/c-Al2O3, and 3.8% for ZnO/AlN/c-Al2O3. The bandwidth of second and third order wave modes, in which the coupling coefficient is within +/- 0.3% of K(2)max, is calculated to be 820 hf for ZnO/GaN/c-Al2O3, and 3620 hf for ZnO/AlN/c-Al2O3. Thus, the hf region in which the coupling coefficient is close to the maximum value broadens with increasing Al content, while K(2)max decreases slightly. When the thickness ratio of AlN to ZnO increases, the K(2)max and hf bandwidth of the second and third higher wave modes increases. The SAW test devices are fabricated and tested. The theoretical and experimental results of velocity dispersion in the ZnO/AlxGa1-xN/c-Al2O3 structures are found to be well matched.

  9. Nitrous oxide in fresh water systems: An estimate for the yield of atmospheric N2O associated with disposal of human waste

    NASA Technical Reports Server (NTRS)

    Kaplan, W. A.; Elkins, J. W.; Kolb, C. E.; Mcelroy, M. B.; Wofsy, S. C.; Duran, A. P.

    1977-01-01

    The N2O content of waters in the Potomac and Merrimack Rivers was measured on a number of occasions over the period April to July 1977. The concentrations of dissolved N2O exceeded those which would apply in equilibrium with air by factors ranging from about 46 in the Potomac to 1.2 in the Merrimack. Highest concentrations of dissolved N2O were associated with sewage discharges from the vicinity of Washington, D. C., and analysis indicates a relatively high yield, 1.3 to 11%, for prompt conversion of waste nitrogen to N2O. Measurements of dissolved N2O in fresh water ponds near Boston demonstrated that aquatic systems provide both strong sources and sinks for atmospheric N2O.

  10. Determining oxide trapped charges in Al2O3 insulating films on recessed AlGaN/GaN heterostructures by gate capacitance transients measurements

    NASA Astrophysics Data System (ADS)

    Fiorenza, Patrick; Greco, Giuseppe; Schilirò, Emanuela; Iucolano, Ferdinando; Lo Nigro, Raffaella; Roccaforte, Fabrizio

    2018-05-01

    This letter presents time-dependent gate-capacitance transient measurements (C–t) to determine the oxide trapped charges (N ot) in Al2O3 films deposited on recessed AlGaN/GaN heterostructures. The C–t transients acquired at different temperatures under strong accumulation allowed to accurately monitor the gradual electron trapping, while hindering the re-emission by fast traps that may affect conventional C–V hysteresis measurements. Using this method, an increase of N ot from 2 to 6 × 1012 cm‑2 was estimated between 25 and 150 °C. The electron trapping is ruled by an Arrhenius dependence with an activation energy of 0.12 eV which was associated to points defects present in the Al2O3 films.

  11. P-type ZnO:N Films Prepared by Thermal Oxidation of Zn3N2

    NASA Astrophysics Data System (ADS)

    Zhang, Bin; Li, Min; Wang, Jian-Zhong; Shi, Li-Qun

    2013-02-01

    We prepare p-type ZnO:N films by annealing Zn3N2 films in oxygen over a range of temperatures. The prepared films are characterized by various techniques, such as Rutherford backscattering spectroscopy, x-ray diffraction, x-ray photoemission spectroscopy, the Hall effect and photoluminescence spectra. The results show that the Zn3N2 films start to transform to ZnO at 300°C and the N content decreases with an increase in annealing temperature. N has two local chemical states: zinc oxynitride (ZnO1-xNx) and substitutional NO in O-rich local environments (α -NO). The conduction type changes from n-type to p-type upon oxidation at 400-600°C, indicating that N is an effective acceptor in the ZnO film. The photoluminescence spectra show the UV emission and defect-related emissions of ZnO:N films. The mechanism and efficiency of p-type doping are briefly discussed.

  12. Effects of cover crops incorporation and nitrogen fertilization on N2O and CO2 emissions

    NASA Astrophysics Data System (ADS)

    Kandel, T. P.; Gowda, P. H.; Northup, B. K.; DuPont, J.; Somenahally, A. C.; Rocateli, A.

    2017-12-01

    In this study, we measured N2O and CO2 fluxes from plots planted to hairy vetch (winter cover crop) and broadleaf vetch (spring cover crop) as N sources for the following crabgrass (summer forage crop) in El Reno, Oklahoma, USA. Comparisons also included 0 and 60 kg ha-1 mineral N fertilizer supplied as dry urea. No significant N2O fluxes were observed during rapid growing periods of cover crops (March-April, 2017), however, large fluxes were observed after hairy vetch incorporation. Immediately after the hairy vetch biomass incorporation, large rainfall events were recorded. The fluxes subsided gradually with drying soil condition but were enhanced after every consecutive rainfall events. A rainfall induced flux measuring up to 8.2 kg N2O ha-1 day-1 was observed after 26 days of biomass incorporation. In total, 29 kg N2O ha-1 (18 kg N ha-1) was emitted within a month after biomass incorporation from hairy vetch plots. Growth of broadleaf vetch was poor and N2O fluxes were also lower. Similarly, plots fertilized with 60 kg N ha-1 had significant fluxes of N2O but the magnitude was much lower than the hairy vetch plots. Dynamics of N2O and CO fluxes correlated strongly. The results thus indicated that although cover crops may provide many environmental/agronomic benefits such as N fixation, soil carbon built-up, weed suppression and erosion control, high N2O emissions may dwarf these benefits.

  13. Time-dependent one-dimensional simulation of atmospheric dielectric barrier discharge in N2/O2/H2O using COMSOL Multiphysics

    NASA Astrophysics Data System (ADS)

    Sohbatzadeh, F.; Soltani, H.

    2018-04-01

    The results of time-dependent one-dimensional modelling of a dielectric barrier discharge (DBD) in a nitrogen-oxygen-water vapor mixture at atmospheric pressure are presented. The voltage-current characteristics curves and the production of active species are studied. The discharge is driven by a sinusoidal alternating high voltage-power supply at 30 kV with frequency of 27 kHz. The electrodes and the dielectric are assumed to be copper and quartz, respectively. The current discharge consists of an electrical breakdown that occurs in each half-period. A detailed description of the electron attachment and detachment processes, surface charge accumulation, charged species recombination, conversion of negative and positive ions, ion production and losses, excitations and dissociations of molecules are taken into account. Time-dependent one-dimensional electron density, electric field, electric potential, electron temperature, densities of reactive oxygen species (ROS) and reactive nitrogen species (RNS) such as: O, O-, O+, {O}2^{ - } , {O}2^{ + } , O3, {N}, {N}2^{ + } , N2s and {N}2^{ - } are simulated versus time across the gas gap. The results of this work could be used in plasma-based pollutant degradation devices.

  14. Potential short-term losses of N2O and N2 from high concentrations of biogas digestate in arable soils

    NASA Astrophysics Data System (ADS)

    Fiedler, Sebastian Rainer; Augustin, Jürgen; Wrage-Mönnig, Nicole; Jurasinski, Gerald; Gusovius, Bertram; Glatzel, Stephan

    2017-09-01

    Biogas digestate (BD) is increasingly used as organic fertilizer, but has a high potential for NH3 losses. Its proposed injection into soils as a countermeasure has been suggested to promote the generation of N2O, leading to a potential trade-off. Furthermore, the effect of high nutrient concentrations on N2 losses as they may appear after injection of BD into soil has not yet been evaluated. Hence, we performed an incubation experiment with soil cores in a helium-oxygen atmosphere to examine the influence of soil substrate (loamy sand, clayey silt), water-filled pore space (WFPS; 35, 55, 75 %) and application rate (0, 17.6 and 35.2 mL BD per soil core, 250 cm3) on the emission of N2O, N2 and CO2 after the usage of high loads of BD. To determine the potential capacity for gaseous losses, we applied anaerobic conditions by purging with helium for the last 24 h of incubation. Immediate N2O and N2 emissions as well as the N2 / (N2O+N2) product ratio depended on soil type and increased with WFPS, indicating a crucial role of soil gas diffusivity for the formation and emission of nitrogenous gases in agricultural soils. However, emissions did not increase with the application rate of BD. This is probably due to an inhibitory effect of the high NH4+ content of BD on nitrification. Our results suggest a larger potential for N2O formation immediately following BD injection in the fine-textured clayey silt compared to the coarse loamy sand. By contrast, the loamy sand showed a higher potential for N2 production under anaerobic conditions. Our results suggest that short-term N losses of N2O and N2 after injection may be higher than probable losses of NH3 following surface application of BD.

  15. Experimental Study on the Behavior of TiN and Ti2O3 Inclusions in Contact with CaO‐Al2O3‐SiO2‐MgO Slags

    PubMed Central

    Bernhard, C.

    2017-01-01

    TiN and Ti2O3 are the predominant inclusion types in Ti-alloyed ferritic chromium stainless steels. In order to ensure the required steel cleanness level, an effective removal of such inclusions in the slag during secondary metallurgy is essential. This inclusion removal predominantly takes place via dissolution of the inclusion in the slag. The dissolution behavior of TiN and Ti2O3 in CaO-SiO2-Al2O3-MgO slags as well as their agglomeration behavior in the liquid steel is investigated using High Temperature Laser Scanning Confocal Microscopy and Tammann Furnace experiments. Thermodynamic calculations are performed using FactSage 7.0. The behavior of TiN is observed to be completely different to that of oxides. Ti2O3 dissolves quickly in slags, and its dissolution behavior is comparable to that of other already well examined oxides. In contrast, TiN shows a very intense gas reaction which is attributed to the release of nitrogen during contact with slag. Slags with higher SiO2 content show a significantly higher ability for the dissolution of TiN as compared to Al2O3-rich slags. The gas reaction is found to also significantly influence the final steel cleanness. Despite the easy absorption of TiN in the slag, the formed nitrogen supports the formation of pinholes in the steel. PMID:29109805

  16. Upland Trees Contribute to Exchange of Nitrous Oxide (N2O) in Forest Ecosystems

    NASA Astrophysics Data System (ADS)

    Tian, H.; Thompson, R.; Canadell, J.; Winiwarter, W.; Machacova, K.; Maier, M.; Halmeenmäki, E.; Svobodova, K.; Lang, F.; Pihlatie, M.; Urban, O.

    2017-12-01

    The increase in atmospheric nitrous oxide (N2O) concentration contributes to the acceleration of the greenhouse effect. However, the role of trees in the N2O exchange of forest ecosystems is still an open question. While the soils of temperate and boreal forests were shown to be a natural source of N2O, trees have been so far overlooked in the forest N2O inventories. We determined N2O fluxes in common tree species of boreal and temperate forests: Scots pine (Pinus sylvestris), Norway spruce (Picea abies), downy and silver birch (Betula pubescens, B. pendula), and European beech (Fagus sylvatica). We investigated (1) whether these tree species exchange N2O with the atmosphere under natural field conditions, (2) how the tree N2O fluxes contribute to the forest N2O balance, and (3) whether these fluxes show seasonal dynamics. The studies were performed in a boreal forest (SMEAR II station, Finland; June 2014 - May 2015) and two temperate mountain forests (White Carpathians, Czech Republic; Black Forest, Germany; June and July 2015). Fluxes of N2O in mature tree stems and forest floor were measured using static chamber systems followed by chromatographic and photo-acoustic analyses of N2O concentration changes. Pine, spruce and birch trees were identified as net annual N2O sources. Spruce was found the strongest emitter (0.27 mg ha-1 h-1) amounting thus up to 2.5% of forest floor N2O emissions. All tree species showed a substantial seasonality in stem N2O flux that was related to their physiological activity and climatic variables. In contrast, stems of beech trees growing at soils consuming N2O may act as a substantial sink of N2O from the atmosphere. Consistent N2O consumption by tree stems ranging between -12.1 and -35.2 mg ha-1 h-1 and contributing by up to 3.4% to the forest floor N2O uptake is a novel finding in contrast to current studies presenting trees as N2O emitters. To understand these fluxes, N2O exchange of photoautotrophic organisms associated with

  17. Raman study of HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) superconductors

    NASA Astrophysics Data System (ADS)

    Zhou, Xingjiang; Cardona, M.; Chu, C. W.; Lin, Q. M.; Loureiro, S. M.; Marezio, M.

    1996-02-01

    Polarized micro-Raman scattering measurements have been performed on the five members of the HgBa 2Ca n-1 Cu nO 2 n+2+ δ ( n=1,2,3,4 and 5) high- Tc superconductor family using different laser frequencies. Local laser annealing measurements were carried out to investigate the variation of the Raman spectra with the excess oxygen content, δ. A systematic evolution of the spectra, which display mainly peaks near 590, 570, 540 and 470 cm -1, with increasing number of CuO 2 layers has been observed; its origin has been shown to lie in the variation of the interstitial oxygen content. In addition to confirming that the 590 cm -1 mode represents vibration of apical oxygens in the absence of neighboring excess oxygen, the 570 cm -1 mode, which may be composed of some finer structures, has been assigned to the vibration of the apical oxygen modified by the presence of the neighboring excess oxygens. The 540 and 470 cm -1 modes may represent the direct vibration of excess oxygens. The implication of possible different distribution sites of excess oxygens is discussed. All other observed lower-frequency modes are also assigned.

  18. Tris(5,6-dimethyl-1H-benzimidazole-κN(3))(pyridine-2,6-dicarboxyl-ato-κ(3)O(2),N,O(6))nickel(II).

    PubMed

    Li, Yue-Hua; Li, Feng-Feng; Liu, Xin-Hua; Zhao, Ling-Yan

    2012-06-01

    The title mononuclear complex, [Ni(C(7)H(3)NO(4))(C(9)H(10)N(2))(3)], shows a central Ni(II) atom which is coordinated by two carboxyl-ate O atoms and the N atom from a pyridine-2,6-dicarboxyl-ate ligand and by three N atoms from different 5,6-dimethyl-1H--benzimidazole ligands in a distorted octa-hedral geometry. The crystal structure shows intermolecular N-H⋯O hydrogen bonds.

  19. Human land uses enhance sediment denitrification and N2O production in Yangtze lakes primarily by influencing lake water quality

    NASA Astrophysics Data System (ADS)

    Liu, W.; Yao, L.; Wang, Z.; Xiong, Z.; Liu, G.

    2015-10-01

    Sediment denitrification in lakes alleviates the effects of eutrophication through the removal of nitrogen to the atmosphere as N2O and N2. However, N2O contributes notably to the greenhouse effect and global warming. Human land uses (e.g. agricultural and urban areas) strongly affect lake water quality and sediment characteristics, which, in turn, may regulate lake sediment denitrification and N2O production. In this study, we investigated sediment denitrification and N2O production and their relationships to within-lake variables and watershed land uses in 20 lakes from the Yangtze River basin in China. The results indicated that both lake water quality and sediment characteristics were significantly influenced by watershed land uses. N2O production rates increased with increasing background denitrification rates. Background denitrification and N2O production rates were positively related to water nitrogen concentrations but were not significantly correlated with sediment characteristics and plant community structure. A significant positive relationship was observed between background denitrification rate and percentage of human-dominated land uses (HDL) in watersheds. Structural equation modelling revealed that the indirect effects of HDL on sediment denitrification and N2O production in Yangtze lakes were mediated primarily through lake water quality. Our findings also suggest that although sediments in Yangtze lakes can remove large quantities of nitrogen through denitrification, they may also be an important source of N2O, especially in lakes with high nitrogen content.

  20. Direct stimulation of human fibroblasts by nCeO2 in vitro is attenuated with an amorphous silica coating.

    PubMed

    Davidson, Donna C; Derk, Raymond; He, Xiaoqing; Stueckle, Todd A; Cohen, Joel; Pirela, Sandra V; Demokritou, Philip; Rojanasakul, Yon; Wang, Liying

    2016-05-04

    Nano-scaled cerium oxide (nCeO2) is used in a variety of applications, including use as a fuel additive, catalyst, and polishing agent, yet potential adverse health effects associated with nCeO2 exposure remain incompletely understood. Given the increasing utility and demand for engineered nanomaterials (ENMs) such as nCeO2, "safety-by-design" approaches are currently being sought, meaning that the physicochemical properties (e.g., size and surface chemistry) of the ENMs are altered in an effort to maximize functionality while minimizing potential toxicity. In vivo studies have shown in a rat model that inhaled nCeO2 deposited deep in the lung and induced fibrosis. However, little is known about how the physicochemical properties of nCeO2, or the coating of the particles with a material such as amorphous silica (aSiO2), may affect the bio-activity of these particles. Thus, we hypothesized that the physicochemical properties of nCeO2 may explain its potential to induce fibrogenesis, and that a nano-thin aSiO2 coating on nCeO2 may counteract that effect. Primary normal human lung fibroblasts were treated at occupationally relevant doses with nCeO2 that was either left uncoated or was coated with aSiO2 (amsCeO2). Subsequently, fibroblasts were analyzed for known hallmarks of fibrogenesis, including cell proliferation and collagen production, as well as the formation of fibroblastic nodules. The results of this study are consistent with this hypothesis, as we found that nCeO2 directly induced significant production of collagen I and increased cell proliferation in vitro, while amsCeO2 did not. Furthermore, treatment of fibroblasts with nCeO2, but not amsCeO2, significantly induced the formation of fibroblastic nodules, a clear indicator of fibrogenicity. Such in vitro data is consistent with recent in vivo observations using the same nCeO2 nanoparticles and relevant doses. This effect appeared to be mediated through TGFβ signaling since chemical inhibition of the TGF

  1. Soil Greenhouse Gas Fluxes, Environmental Controls, and the Partitioning of N2O Sources in UK Natural and Seminatural Land Use Types

    NASA Astrophysics Data System (ADS)

    Sgouridis, Fotis; Ullah, Sami

    2017-10-01

    Natural and seminatural terrestrial ecosystems (unmanaged peatlands and forests and extensive and intensive grasslands) have been under-represented in the UK greenhouse gas (GHG) inventory. Mechanistic studies of GHG fluxes and their controls can improve the prediction of the currently uncertain GHG annual emission estimates. The source apportionment of N2O emissions can further inform management plans for GHG mitigation. We have measured in situ GHG fluxes monthly in two replicated UK catchments and evaluated their environmental controlling factors. An adapted 15N-gas flux method with low addition of 15N tracer (0.03-0.5 kg 15N ha-1) was used to quantify the relative contribution of denitrification to net N2O production. Total N2O fluxes were 40 times higher in the intensive grasslands than in the peatlands (range: -1.32 to 312.3 μg N m-2 h-1). The contribution of denitrification to net N2O emission varied across the land use types and ranged from 9 to 60%. Soil moisture was the key parameter regulating the partitioning of N2O sources (r2 = 0.46). Total N2O fluxes were explained by a simple model (r2 = 0.83) including parameters such as total dissolved nitrogen, organic carbon, and water content. A parsimonious model with the soil moisture content as a single scalar parameter explained 84% of methane flux variability across land uses. The assumption that 1% of the atmospherically deposited N on natural ecosystems is emitted as N2O could be overestimated or underestimated (0.3-1.6%). The use of land use-specific N2O emission factors and further information on N2O source partitioning should help constrain this uncertainty.

  2. Spin dynamics and magnetoelectric coupling mechanism of C o4N b2O9

    NASA Astrophysics Data System (ADS)

    Deng, Guochu; Cao, Yiming; Ren, Wei; Cao, Shixun; Studer, Andrew J.; Gauthier, Nicolas; Kenzelmann, Michel; Davidson, Gene; Rule, Kirrily C.; Gardner, Jason S.; Imperia, Paolo; Ulrich, Clemens; McIntyre, Garry J.

    2018-02-01

    Neutron powder diffraction experiments reveal that C o4N b2O9 forms a noncollinear in-plane magnetic structure with C o2 + moments lying in the a b plane. The spin-wave excitations of this magnet were measured by using inelastic neutron scattering and soundly simulated by a dynamic model involving nearest- and next-nearest-neighbor exchange interactions, in-plane anisotropy, and the Dzyaloshinskii-Moriya interaction. The in-plane magnetic structure of C o4N b2O9 is attributed to the large in-plane anisotropy, while the noncollinearity of the spin configuration is attributed to the Dzyaloshinskii-Moriya interaction. The high magnetoelectric coupling effect of C o4N b2O9 in fields can be explained by its special in-plane magnetic structure.

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

    NASA Technical Reports Server (NTRS)

    Nguyen, Quang-Viet

    2008-01-01

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

  4. Verifying the UK agricultural N2O emission inventory with tall tower measurements

    NASA Astrophysics Data System (ADS)

    Carnell, E. J.; Meneguz, E.; Skiba, U. M.; Misselbrook, T. H.; Cardenas, L. M.; Arnold, T.; Manning, A.; Dragosits, U.

    2016-12-01

    Nitrous oxide (N2O) is a key greenhouse gas (GHG), with a global warming potential 300 times greater than that of CO2. N2O is emitted from a variety of sources, predominantly from agriculture. Annual UK emission estimates are reported, to comply with government commitments under the United Nations Framework Convention on Climate Change (UNFCCC). The UK N2O inventory follows internationally agreed protocols and emission estimates are derived by applying emission factors to estimates of (anthropogenic) emission sources. This approach is useful for comparing anthropogenic emissions from different countries, but does not capture regional differences and inter-annual variability associated with environmental factors (such as climate and soils) and agricultural management. In recent years, the UK inventory approach has been refined to include regional information into its emissions estimates, in an attempt to reduce uncertainty. This study attempts to assess the difference between current published inventory methodology (default IPCC methodology) and an alternative approach, which incorporates the latest thinking, using data from recent work. For 2013, emission estimates made using the alternative approach were 30 % lower than those made using default IPCC methodology, due to the use of lower emission factors suggested by recent projects (Defra projects: AC0116, AC0213 and MinNO). The 2013 emissions estimates were disaggregated on a monthly basis using agricultural management (e.g. sowing dates), climate data and soil properties. The temporally disaggregated emission maps were used as input to the Met Office atmospheric dispersion model NAME, for comparison with measured N2O concentrations, at three observation stations (Tacolneston, E. England; Ridge Hill, W. England; Mace Head, W. Ireland) in the UK DECC network (Deriving Emissions linked to Climate Change). The Mace Head site, situated on the west coast of Ireland, was used to establish baseline concentrations. The

  5. Comparing N2O emissions at varying N rates from irrigated and rainfed corn in the US Midwest

    NASA Astrophysics Data System (ADS)

    Millar, N.; Kahmark, K.; Basso, B.; Robertson, G. P.

    2011-12-01

    Global N2O emissions from agriculture are estimated to be ~2.8 Pg CO2e yr-1 accounting for 60% of total anthropogenic emissions. N2O is the largest contributor to the GHG burden of cropping systems in the US, with annual estimated emissions of ~0.5 Tg primarily due to N fertilizer inputs and other soil management activities. Currently 23 million acres of corn, soybean and wheat are irrigated annually in the US with increased N2O emissions due to the practice likely under-reported in GHG inventories. Here we compare N2O emissions and yield from irrigated and rainfed corn at varying N rates between 0 and 246 kg N ha-1 from the Kellogg Biological Station in SW Michigan. Initial results show that N2O emissions increase with increasing N rate and are significantly higher from irrigated corn compared to rainfed corn at the same N rate. At increasing N rates daily emissions following an irrigation event were between 2.4 - 77.5 g N2O-N ha-1 from irrigated corn and 1.6 - 13.0 g N2O-N ha-1 from rainfed corn. Emissions data from automated and static chambers will be presented and trade-offs between N2O emissions, N fertilizer rate, crop yield and irrigation practice will be evaluated from an environmental and economic standpoint.

  6. Synthesis and characterization study of n-Bi2O3/p-Si heterojunction dependence on thickness

    NASA Astrophysics Data System (ADS)

    Al-Maiyaly, Bushra K. H.; Hussein, Bushra H.; Salih, Ayad A.; Shaban, Auday H.; Mahdi, Shatha H.; Khudayer, Iman H.

    2018-05-01

    In this work, Bi2O3 was deposited as a thin film of different thickness (400, 500, and 600 ±20 nm) by using thermal oxidation at 573 K with ambient oxygen of evaporated bismuth (Bi) thin films in a vacuum on glass substrate and on Si wafer to produce n-Bi2O3/p-Si heterojunction. The effect of thickness on the structural, electrical, surface and optical properties of Bi2O3 thin films was studied. XRD analysis reveals that all the as deposited Bi2O3 films show polycrystalline tetragonal structure, with preferential orientation in the (201) direction, without any change in structure due to increase of film thickness. AFM and SEM images are used to investigate the influences of film thickness on surface properties. The optical measurement were taken for the wave length range (400-1100) nm showed that the nature of the optical transition has been direct allowed with average band gap energies varies in the range of (2.9-2.25) eV with change thickness parameter. The extent and nature of transmittance, absorbance, reflectance and optimized band gap of the material assure to utilize it for photovoltaic applications. Hall measurements showed that all the films are n-type. The electrical properties of n-Bi2O3/p-Si heterojunction (HJ) were obtained by I-V (dark and illuminated) and C-V measurement at frequency (10 MHz) at different thickness. The ideality factor saturation current density, depletion width, built-in potential and carrier concentration are characterized under different thickness. The results show these HJ were of abrupt type. The photovoltaic measurements short-circuit current density, open-circuit voltage, fill factor and efficiencies are determined for all samples. Finally thermal oxidation allowed fabrication n-Bi2O3/p-Si heterojunction with different thickness for solar cell application.

  7. Mechanisms of nitrous oxide (N2 O) formation and reduction in denitrifying biofilms.

    PubMed

    Sabba, Fabrizio; Picioreanu, Cristian; Nerenberg, Robert

    2017-12-01

    Nitrous oxide (N 2 O) is a potent greenhouse gas that can be formed in wastewater treatment processes by ammonium oxidizing and denitrifying microorganisms. While N 2 O emissions from suspended growth systems have been extensively studied, and some recent studies have addressed emissions from nitrifying biofilms, much less is known about N 2 O emissions from denitrifying biofilm processes. This research used modeling to evaluate the mechanisms of N 2 O formation and reduction in denitrifying biofilms. The kinetic model included formation and consumption of key denitrification species, including nitrate (NO3-), nitrite (NO2-), nitric oxide (NO), and N 2 O. The model showed that, in presence of excess of electron donor, denitrifying biofilms have two distinct layers of activity: an outer layer where there is net production of N 2 O and an inner layer where there is net consumption. The presence of oxygen (O 2 ) had an important effect on N 2 O emission from suspended growth systems, but a smaller effect on biofilm systems. The effects of NO3- and O 2 differed significantly based on the biofilm thickness. Overall, the effects of biofilm thickness and bulk substrate concentrations on N 2 O emissions are complex and not always intuitive. A key mechanism for denitrifying biofilms is the diffusion of N 2 O and other intermediates from one zone of the biofilm to another. This leads to zones of N 2 O formation or consumption transformations that would not exist in suspended growth systems. © 2017 Wiley Periodicals, Inc.

  8. Ab initio electron correlated studies on the intracluster reaction of NO+ (H2O)(n) → H3O+ (H2O)(n-2) (HONO) (n = 4 and 5).

    PubMed

    Asada, Toshio; Nagaoka, Masataka; Koseki, Shiro

    2011-01-28

    Hydrated nitrosonium ion clusters NO(+)(H(2)O)(n) (n = 4 and 5) were investigated by using MP2/aug-cc-pVTZ level of theory to clarify isomeric reaction pathways for formation of HONO and fully hydrated hydride ions. We found some new isomers and transition state structures in each hydration number, whose lowest activation energies of the intracluster reactions were found to be 4.1 and 3.4 kcal mol(-1) for n = 4 and n = 5, respectively. These thermodynamic properties and full quantum mechanical molecular dynamics simulation suggest that product isomers with HONO and fully hydrated hydride ions can be obtained at n = 4 and n = 5 in terms of excess hydration binding energies which can overcome these activation barriers.

  9. The kinetic friction of ZnO nanowires on amorphous SiO2 and SiN substrates

    NASA Astrophysics Data System (ADS)

    Roy, Aditi; Xie, Hongtao; Wang, Shiliang; Huang, Han

    2016-12-01

    ZnO nanowires were bent on amorphous SiO2 and SiN substrates in an ambient atmosphere using optical nanomanipulation. The kinetic friction between the nanowires and substrate was determined from the bent shape of the nanowires. The kinetic friction force per unit area, i.e. frictional shear stress, for the ZnO/SiO2 and ZnO/SiN nanowire/substrate systems being measured were 1.05 ± 0.28 and 2.08 ± 0.33 MPa, respectively. The surface roughness and the Hamaker constant of SiO2 and SiN substrates had significant effect on the frictional stresses.

  10. Short-term drought response of N 2O and CO 2 emissions from mesic agricultural soils in the US Midwest

    DOE PAGES

    Gelfand, Ilya; Cui, Mengdi; Tang, Jianwu; ...

    2015-07-17

    Climate change is causing the intensification of both rainfall and droughts in temperate climatic zones, which will affect soil drying and rewetting cycles and associated processes such as soil greenhouse gas (GHG) fluxes. Here, we investigated the effect of soil rewetting following a prolonged natural drought on soil emissions of nitrous oxide (N 2O) and carbon dioxide (CO 2) in an agricultural field recently converted from 22 years in the USDA Conservation Reserve Program (CRP). We compared responses to those in a similarly managed field with no CRP history and to a CRP reference field. We additionally compared soil GHGmore » emissions measured by static flux chambers with off-site laboratory analysis versus in situ analysis using a portable quantum cascade laser and infrared gas analyzer. Under growing season drought conditions, average soil N 2O fluxes ranged between 0.2 and 0.8 μg N m -2 min -1 and were higher in former CRP soils and unaffected by nitrogen (N) fertilization. After 18 days of drought, a 50 mm rewetting event increased N 2O fluxes by 34 and 24 fold respectively in the former CRP and non-CRP soils. Average soil CO 2 emissions during drought ranged from 1.1 to 3.1 mg C m -2 min -1 for the three systems. CO 2 emissions increased ~2 fold after the rewetting and were higher from soils with higher C contents. Observations are consistent with the hypothesis that during drought soil N 2O emissions are controlled by available C and following rewetting additionally influenced by N availability, whereas soil CO 2 emissions are independent of short-term N availability. Finally, soil GHG emissions estimated by off-site and in situ methods were statistically identical.« less

  11. Integrated measurements and modeling of CO2, CH4, and N2O fluxes using soil microsite frequency distributions

    NASA Astrophysics Data System (ADS)

    Davidson, Eric; Sihi, Debjani; Savage, Kathleen

    2017-04-01

    Soil fluxes of greenhouse gases (GHGs) play a significant role as biotic feedbacks to climate change. Production and consumption of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are affected by complex interactions of temperature, moisture, and substrate supply, which are further complicated by spatial heterogeneity of the soil matrix. Models of belowground processes of these GHGs should be internally consistent with respect to the biophysical processes of gaseous production, consumption, and transport within the soil, including the contrasting effects of oxygen (O2) as either substrate or inhibitor. We installed automated chambers to simultaneously measure soil fluxes of CO2 (using LiCor-IRGA), CH4, and N2O (using Aerodyne quantum cascade laser) along soil moisture gradients at the Howland Forest in Maine, USA. Measured fluxes of these GHGs were used to develop and validate a merged model. While originally intended for aerobic respiration, the core structure of the Dual Arrhenius and Michaelis-Menten (DAMM) model was modified by adding M-M and Arrhenius functions for each GHG production and consumption process, and then using the same diffusion functions for each GHG and for O2. The area under a soil chamber was partitioned according to a log-normal probability distribution function, where only a small fraction of microsites had high available-C. The probability distribution of soil C leads to a simulated distribution of heterotrophic respiration, which translates to a distribution of O2 consumption among microsites. Linking microsite consumption of O2 with a diffusion model generates microsite concentrations of O2, which then determine the distribution of microsite production and consumption of CH4 and N2O, and subsequently their microsite concentrations using the same diffusion function. At many moisture values, there are some microsites of production and some of consumption for each gas, and the resulting simulated microsite concentrations of CH4

  12. Uptake of copper and cerium by alfalfa, lettuce and cucumber exposed to nCeO2 and nCuO through the foliage or the roots: Impacts on food quality, physiological and agronomical parameters

    NASA Astrophysics Data System (ADS)

    Hong, Jie

    , with 50, 100, 200 mg/L of nCeO2, nCuO and the respective bulk material suspensions. Photosynthetic rate (Pn), stomatal conductance (gs), and transpiration (E) of cucumber leaves were measured with a portable gas exchange system. Nutritional elements and Ce/Cu uptake were determined by ICP-OES. Quality of cucumber fruits was evaluated after harvest. Results showed that cucumber absorbed Ce and Cu through foliar applied nCeO2 and nCuO and translocate them to new leaves and fruits. Photosynthetic and transpiration rates were only affected in new leaves. None of the treatment significantly affected cucumber, yield, length, and diameter of fruits. However, both nCeO2 and nCuO significantly reduced the firmness of the fruit. Mineral element determination in fruit showed that Zn decreased by 25% with 200 mg/L of both nCeO2 and bulk CeO 2 and in fruit Mo decreased by 51% and 44% with both nCuO and bulk CuO at 200 mg/L, respectively. For the aim III, 15 day-old hydroponically grown lettuce and alfalfa were exposed to 0, 5, 10, and 20 mg/L nCu, bulk Cu, nCuO, bulk CuO, Cu(OH)2 (CuPRO 2005, Kocide 3000), and CuCl2. The concentration of Cu, macro and microelements in plants were measured by using ICP-OES. The size of the plants and the activity of catalase and ascorbate peroxidase were also determined. Results showed that all Cu NPs/compounds reduced the root length by 49% in both plant species. Under all treatments, Cu, P, and S were increased (>100%, >50%, and >20%, respectively) in alfalfa shoots; while P and Fe were decreased (>50% and >50%, respectively) in lettuce shoot. In addition, catalase activity was reduced in alfalfa (root and shoot) and ascorbate peroxidase activity was increased in roots of both plant species. Our findings show that increasing concentration of atmospheric nCeO2 can affect the nutritional value of crop plants with unknown consequences for the food chain. In addition Cu NPs/compounds could impact the growth of plants and altered the quality of crops

  13. Validating soil denitrification models based on laboratory N_{2} and N_{2}O fluxes and underlying processes derived by stable isotope approaches

    NASA Astrophysics Data System (ADS)

    Well, Reinhard; Böttcher, Jürgen; Butterbach-Bahl, Klaus; Dannenmann, Michael; Deppe, Marianna; Dittert, Klaus; Dörsch, Peter; Horn, Marcus; Ippisch, Olaf; Mikutta, Robert; Müller, Carsten; Müller, Christoph; Senbayram, Mehmet; Vogel, Hans-Jörg; Wrage-Mönnig, Nicole

    2016-04-01

    Robust denitrification data suitable to validate soil N2 fluxes in denitrification models are scarce due to methodical limitations and the extreme spatio-temporal heterogeneity of denitrification in soils. Numerical models have become essential tools to predict denitrification at different scales. Model performance could either be tested for total gaseous flux (NO + N2O + N2), individual denitrification products (e.g. N2O and/or NO) or for the effect of denitrification factors (e.g. C-availability, respiration, diffusivity, anaerobic volume, etc.). While there are numerous examples for validating N2O fluxes, there are neither robust field data of N2 fluxes nor sufficiently resolved measurements of control factors used as state variables in the models. To the best of our knowledge there has been only one published validation of modelled soil N2 flux by now, using a laboratory data set to validate an ecosystem model. Hence there is a need for validation data at both, the mesocosm and the field scale including validation of individual denitrification controls. Here we present the concept for collecting model validation data which is be part of the DFG-research unit "Denitrification in Agricultural Soils: Integrated Control and Modelling at Various Scales (DASIM)" starting this year. We will use novel approaches including analysis of stable isotopes, microbial communities, pores structure and organic matter fractions to provide denitrification data sets comprising as much detail on activity and regulation as possible as a basis to validate existing and calibrate new denitrification models that are applied and/or developed by DASIM subprojects. The basic idea is to simulate "field-like" conditions as far as possible in an automated mesocosm system without plants in order to mimic processes in the soil parts not significantly influenced by the rhizosphere (rhizosphere soils are studied by other DASIM projects). Hence, to allow model testing in a wide range of conditions

  14. Visible spectrum photofragmentation of O{sub 3}{sup −}(H{sub 2}O){sub n}, n ≤ 16

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

    Lehman, Julia H.; Lineberger, W. Carl, E-mail: wcl@jila.colorado.edu

    2014-10-21

    Photofragmentation of ozonide solvated in water clusters, O{sub 3}{sup −}(H{sub 2}O){sub n}, n ≤ 16, has been studied as a function of photon energy as well as the degree of solvation. Using mass selection, the effect of the presence of the solvent molecule on the O{sub 3}{sup −} photodissociation process is assessed one solvent molecule at a time. The O{sub 3}{sup −} acts as a visible light chromophore within the water cluster, namely the O{sub 3}{sup −}(H{sub 2}O) total photodissociation cross-section exhibits generally the same photon energy dependence as isolated O{sub 3}{sup −} throughout the visible wavelength range studied (430–620more » nm). With the addition of a single solvent molecule, new photodissociation pathways are opened, including the production of recombined O{sub 3}{sup −}. As the degree of solvation of the parent anion increases, recombination to O{sub 3}{sup −}-based products accounts for close to 40% of photoproducts by n = 16. The remainder of the photoproducts exist as O{sup −}-based; no O{sub 2}{sup −}-based products are observed. Upper bounds on the O{sub 3}{sup −} solvation energy (530 meV) and the O{sup −}-OO bond dissociation energy in the cluster (1.06 eV) are derived.« less

  15. Matrix isolation infrared spectra of O2 and N2 insertion reactions with atomic uranium

    NASA Astrophysics Data System (ADS)

    Hunt, Rodney D.; Toth, L. Mac; Yustein, Jason T.; Andrews, Lester

    1993-10-01

    Laser ablation of refractory metals can be an effective source of vapor for matrix isolation IR studies. This combination of techniques was used for the first time to study the mechanisms of U vapor reactions with atmospheric components. U atoms and O2 were codeposited with excess Ar at 12 K. The dominant codeposition products were UO2 and UO3. In contrast, the UO yield was always small because UO2 is formed by an insertion mechanism. This mechanism was verified in the 16O2/18O2 experiments which failed to produce 16OU18O. The effects of UV photolysis and matrix annealings were also examined. The U atoms and O2 reaction requires little or no activation energy since UO2 was formed from cold reagents. New charge-transfer species, (UO2+2)(O2-2) and (UO+2)(O-2), and a weak complex, UO3-O2, were primarily produced under conditions which favored further O2 reactions. Similar U atom and N2 experiments produced only linear NUN which is also produced by an insertion mechanism. This U reaction represents the first time that atom was observed breaking and inserting into the triple bond of N2. Photolysis dramatically increased the NUN yield by 3-fold. Matrix annealings produced weak UN2-N2 and UN2-2N2 complexes.

  16. Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment in an aerobic bioreactor packed with carbon fibers.

    PubMed

    Yamashita, Takahiro; Yamamoto-Ikemoto, Ryoko; Yokoyama, Hiroshi; Kawahara, Hirofumi; Ogino, Akifumi; Osada, Takashi

    2015-03-01

    Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment was demonstrated in an aerobic bioreactor packed with carbon fibers (CF reactor). The CF reactor had a demonstrated advantage in mitigating N2 O emission and avoiding NOx (NO3  + NO2 ) accumulation. The N2 O emission factor was 0.0003 g N2 O-N/gTN-load in the CF bioreactor compared to 0.03 gN2 O-N/gTN-load in an activated sludge reactor (AS reactor). N2 O and CH4 emissions from the CF reactor were 42 g-CO2 eq/m(3) /day, while those from the AS reactor were 725 g-CO2 eq/m(3) /day. The dissolved inorganic nitrogen (DIN) in the CF reactor removed an average of 156 mg/L of the NH4 -N, and accumulated an average of 14 mg/L of the NO3 -N. In contrast, the DIN in the AS reactor removed an average 144 mg/L of the NH4 -N and accumulated an average 183 mg/L of the NO3 -N. NO2 -N was almost undetectable in both reactors. © 2014 Japanese Society of Animal Science.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  18. Fe-N co-doped SiO2@TiO2 yolk-shell hollow nanospheres with enhanced visible light photocatalytic degradation

    NASA Astrophysics Data System (ADS)

    Wan, Hengcheng; Yao, Weitang; Zhu, Wenkun; Tang, Yi; Ge, Huilin; Shi, Xiaozhong; Duan, Tao

    2018-06-01

    SiO2@TiO2 yolk@shell hollow nanospheres (STNSs) is considered as an outstanding photocatalyst due to its tunable structure and composition. Based on this point, we present an unprecedentedly excellent photocatalytic property of STNSs toward tannic acid via a Fe-N co-doped strategy. Their morphologies, compositions, structure and properties are characterized. The Fe-N co-doped STNSs formed good hollow yolk@shell structure. The results show that the energy gap of the composites can be downgraded to 2.82 eV (pure TiO2 = 3.2 eV). Photocatalytic degradation of tannic acid (TA, 30 mg L-1) under visible light (380 nm < λ < 780 nm) irradiation is used to evaluate the photocatalytic activity of the composites. Compared with pure TiO2 nanospheres, non-doped STNSs and N-doped STNSs, the Fe-N co-doped STNSs exhibits the highest activity, which can degrade 99.5% TA into CO2 and H2O in 80 min. The probable degradation mechanism of the composites is simultaneously proposed, the band gap of STNSs becomes narrow by co-doping Fe-N, so that the TiO2 shell can stimulate electrons under visible light exposure, generate the ions of radOH and radO2- with a strong oxidizing property. Therefore this approach works is much desired for radioactive organic wastewater photocatalytic degradation.

  19. Monitoring N2O Production Using a cNOR Modeled Active Site

    NASA Astrophysics Data System (ADS)

    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.

  20. Global and regional emissions estimates for N2O

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

  1. Crystal structure, chemical composition, and extended defects of the high-Tc (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta compounds.

    PubMed

    Eibl, O

    1995-02-15

    This paper summarizes results obtained by high-resolution transmission electron microscopy on the crystal structure and microstructure of the (Bi,Pb)2Sr2Ca(n)-1CunO4 + 2n + delta high-Tc superconducting oxides. The experimental basis for the work presented here are high-resolution structure images obtained at ultra-thin (3 nm) areas of carefully prepared transmission electron microscope (TEM) samples. The analysis was carried out on a 400 kV TEM equipped with a pole piece yielding 0.17 nm point-to-point resolution. From the images obtained the projected crystal potential of the cations can be extracted directly, as confirmed by detailed image simulation. Structural analysis of the oxygen sublattice remains an unsolved problem by high-resolution TEM (HRTEM), mainly because of the small scattering factors, and thus the contribution of the oxygen sublattice to the image contrast is small. The (BiPb)2Sr2Ca(n)-1CunO4 + 2n + delta phases are modulated structures that can be understood as an average structure plus a superimposed displacement field. The crystal structure consists of BiO double layers and perovskite-type cuboids (containing Sr, Ca, Cu, and O), which are sandwiched between the BiO double layers. The displacement field can be directly analyzed by HRTEM, and the largest displacement amplitudes of 70 pm were determined for the Bi atoms in the n = 1 compound. The chemical composition of the n = 2 and n = 3 compounds was determined by EDX in the TEM for the cation sublattice. A significant (Ca + Sr) deficiency (approximately 10%) with respect to Cu was found. The (Sr + Ca)/Cu mole fraction ratio was 1.31 for the Bi-2212 phase and 1.14 for the Bi(Pb)-2223 phase. The oxygen content cannot be determined by EDX in the TEM with the accuracy necessary for a correlation with electrical and superconducting properties. The defect structure present in these materials, that is, intergrown lamellae with different crystal structures and equal or different chemical

  2. Frozen Cropland Soil in Northeast China as Source of N2O and CO2 Emissions

    PubMed Central

    Qiao, Yunfa; Han, Xiaozeng; Brancher Franco, Roberta

    2014-01-01

    Agricultural soils are important sources of atmospheric N2O and CO2. However, in boreal agro-ecosystems the contribution of the winter season to annual emissions of these gases has rarely been determined. In this study, soil N2O and CO2 fluxes were measured for 6 years in a corn-soybean-wheat rotation in northeast China to quantify the contribution of wintertime N2O and CO2 fluxes to annual emissions. The treatments were chemical fertilizer (NPK), chemical fertilizer plus composted pig manure (NPKOM), and control (Cont.). Mean soil N2O fluxes among all three treatments in the winter (November–March), when soil temperatures are below −7°C for extended periods, were 0.89–3.01 µg N m−2 h−1, and in between the growing season and winter (October and April), when freeze-thaw events occur, 1.73–5.48 µg N m−2 h−1. The cumulative N2O emissions were on average 0.27–1.39, 0.03–0.08 and 0.03–0.11 kg N2O–N ha−1 during the growing season, October and April, and winter, respectively. The average contributions of winter N2O efflux to annual emissions were 6.3–12.1%. In all three seasons, the highest N2O emissions occurred in NPKOM, while NPK and Cont. emissions were similar. Cumulative CO2 emissions were 2.73–4.94, 0.13–0.20 and 0.07–0.11 Mg CO2-C ha−1 during growing season, October and April, and winter, respectively. The contribution of winter CO2 to total annual emissions was 2.0–2.4%. Our results indicate that in boreal agricultural systems in northeast China, CO2 and N2O emissions continue throughout the winter. PMID:25536036

  3. Nano-sized TiO2 (nTiO2) induces metabolic perturbations in Physarum polycephalum macroplasmodium to counter oxidative stress under dark conditions.

    PubMed

    Zhang, Zhi; Liang, Zhi Cheng; Zhang, Jian Hua; Tian, Sheng Li; Le Qu, Jun; Tang, Jiao Ning; De Liu, Shi

    2018-06-15

    Nano-sized TiO 2 (nTiO 2 ) exerts an oxidative effect on cells upon exposure to solar or UV irradiation and ecotoxicity of the nTiO 2 is an urgent concern. Little information is available regarding the effect of TiO 2 on cells under dark conditions. Metabolomics is a unique approach to the discovery of biomarkers of nTiO 2 cytotoxicity, and leads to the identification of perturbed metabolic pathways and the mechanism underlying nTiO 2 toxicity. In the present study, gas chromatography mass spectrometry (GC/MS)-based metabolomics was performed to investigate the effect of nTiO 2 on sensitive cells (P. polycephalum macroplasmodium) under dark conditions. According to the multivariate pattern recognition analysis, at least 60 potential metabolic biomarkers related to sugar metabolism, amino acid metabolism, nucleotide metabolism, polyamine biosynthesis, and secondary metabolites pathways were significantly perturbed by nTiO 2 . Notably, many metabolic biomarkers and pathways were related to anti-oxidant mechanisms in the living organism, suggesting that nTiO 2 may induce oxidative stress, even under dark conditions. This speculation was further validated by the biochemical levels of reactive oxygen species (ROS), 8-hydroxy-2-deoxyguanosine (8-OHdG), and total soluble phenols (TSP). We inferred that the oxidative stress might be related to nTiO 2 -induced imbalance of cellular ROS. To the best of our knowledge, the present study is the first to investigate the nTiO 2 -induced metabolic perturbations in slime mold, provide a new perspective of the mechanism underlying nTiO 2 toxicity under dark conditions, and show that metabolomics can be employed as a rapid, reliable and powerful tool to investigate the interaction among organisms, the environment, and nanomaterials. Copyright © 2018 Elsevier Inc. All rights reserved.

  4. Optimizing biochars to mitigate N2O emissions in Mediterranean areas

    NASA Astrophysics Data System (ADS)

    Cayuela, Maria Luz; Sanchez-Garcia, Maria; Roig, Asuncion; Sanchez-Monedero, Miguel Angel

    2017-04-01

    Some of the most productive agricultural soils stand in Mediterranean-type climate areas of the world (e.g. California's Central Valley, Andalucia region in South Spain, and Lombardy region in Italy). Many of these soils are under intensive agricultural production, bearing the addition of substantial amounts of N fertilizers, which are known to promote soil N2O emissions. Laboratory studies have shown the potential of biochar to decrease N2O emissions in soils from Mediterranean areas. These soils generally have alkaline pH and low concentrations of organic C and several laboratory experiments found that applying biochar at a rate of 2% in weight could decrease N2O emissions up to 90%. However, field studies carried out in areas of California, Italy and Spain (all under Mediterranean climate) showed none or very limited N2O mitigation with biochar. We postulate that this discrepancy may be because biochar-soil combinations were not optimal in field studies and that developing biochars adjusted to specific soil properties is crucial for their successful application to mitigate N2O emissions. Thus, in this study we aimed at (i) collecting and characterizing a variety of the most representative Mediterranean agricultural residues (olive tree, almond and orange tree pruning, olive mill waste, rice straw, horticultural residues, etc.), (ii) exploring their suitability as feedstocks for biochar production and (iii) analyzing their impact on N2O emissions in a Mediterranean agricultural soil. Biochars were produced by slow pyrolysis with a heating rate of 5˚C min-1 at two pyrolysis temperatures (400 and 600˚C) and a retention time of two hours. Soil incubations were set up simulating conditions of highly intensive crop production (high N fertilization, high moisture) to test how the biochars produced from different feedstocks and under two pyrolysis temperatures influence N2O emissions. Our starting hypothesis was that it is possible to optimize biochar characteristics

  5. The effect of nitrification inhibitors on NH3 and N2O emissions in highly N fertilized irrigated Mediterranean cropping systems.

    PubMed

    Recio, Jaime; Vallejo, Antonio; Le-Noë, Julia; Garnier, Josette; García-Marco, Sonia; Álvarez, José Manuel; Sanz-Cobena, Alberto

    2018-09-15

    There is an increasing concern about the negative impacts associated to the release of reactive nitrogen (N) from highly fertilized agro-ecosystems. Ammonia (NH 3 ) and nitrous oxide (N 2 O) are harmful N pollutants that may contribute both directly and indirectly to global warming. Surface applied manure, urea and ammonium (NH 4 + ) based fertilizers are important anthropogenic sources of these emissions. Nitrification inhibitors (NIs) have been proposed as a useful technological approach to reduce N 2 O emission although they can lead to large NH 3 losses due to increasing NH 4 + pool in soils. In this context, a field experiment was carried out in a maize field with aiming to simultaneously quantify NH 3 volatilization and N 2 O emission, assessing the effect of two NIs 3,4‑dimethilpyrazol phosphate (DMPP) and 3,4‑dimethylpyrazole succinic acid (DMPSA). The first treatment was pig slurry (PS) before seeding (50 kg N ha -1 ) and calcium ammonium nitrate (CAN) at top-dressing (150 kg N ha -1 ), and the second was DMPP diluted in PS (PS + DMPP) (50 kg N ha -1 ) and CAN + DMPSA (150 kg N ha -1 ) also before seeding and at top-dressing, respectively. Ammonia emissions were quantified by a micrometeorological method during 20 days after fertilization and N 2 O emissions were assessed using manual static chambers during all crop period. The treatment with NIs was effective in reducing c. 30% cumulative N 2 O losses. However, considering only direct N 2 O emissions after second fertilization event, a significant reduction was not observed using CAN+DMPSA, probably because high WFPS of soil, driven by irrigation, favored denitrification. Cumulative NH 3 losses were not significantly affected by NIs. Indeed, NH 3 volatilization accounted 14% and 10% of N applied in PS + DMPP and PS plots, respectively and c. 2% of total N applied in CAN+DMPSA and CAN plots. Since important NH 3 losses still exist even although abating strategies

  6. Dissociative attachment of electrons to N2O

    NASA Technical Reports Server (NTRS)

    Krishnakumar, E.; Srivastava, S. K.

    1990-01-01

    Cross sections for the production of O(-) from N2O by the process of dissociative electron attachment have been measured for electron-impact energies ranging from 0 to 50 eV. Three new O(-) peaks are observed. The present data above 5-eV electron-impact energy differ considerably from the previous measurements.

  7. Interface science of virtual GaN substrates on Si(111) via Sc2O3/Y2O3 buffers: Experiment and theory

    NASA Astrophysics Data System (ADS)

    Tarnawska, L.; Dabrowski, J.; Grzela, T.; Lehmann, M.; Niermann, T.; Paszkiewicz, R.; Storck, P.; Schroeder, T.

    2013-06-01

    The final film quality of GaN on foreign substrates is known to crucially depend on the initial GaN interface and nucleation characteristics. To shed light on these characteristics of recently pioneered virtual, hexagonal GaN(0001) substrates on Si(111) via step graded Sc2O3(111)/Y2O3(111) buffers, a complex GaN(0001)/Sc2O3(111) interface structure model and the initial nucleation scenario is derived from a combined experimental (reflection high energy electron diffraction and X-ray photoelectron spectroscopy) and theoretical ab initio study. It is shown that the GaN/Sc2O3 interface chemistry is determined by a N-Ga-O-Sc atomic arrangement leading to N-polar GaN films. However, the atomic GaN(0001)/Sc2O3(111) interface configuration is complex and local perturbations might be at the origin of Ga-polar inversion domains in the mainly N-polar GaN films. The initial growth of GaN on Sc2O3 is characterized by an ultrathin N-Ga-O-Sc wetting layer which carries tensile strain and relaxes with increasing thickness. Further GaN deposition results in the formation of 3D islands which fully relax before island coalescence occurs. The implications of the GaN/Sc2O3 interface configuration, the 3D nucleation growth mode, and the coalescence process of misaligned islands are discussed with respect to the defect characteristics (inversion domains, cubic inclusions, threading dislocations) of the final GaN layer.

  8. [Effects of diurnal warming on soil N2O emission in soybean field].

    PubMed

    Hu, Zheng-Hua; Zhou, Ying-Ping; Cui, Hai-Ling; Chen, Shu-Tao; Xiao, Qi-Tao; Liu, Yan

    2013-08-01

    To investigate the impact of experimental warming on N2O emission from soil of soybean field, outdoor experiments with simulating diurnal warming were conducted, and static dark chamber-gas chromatograph method was used to measure N2O emission fluxes. Results indicated that: the diurnal warming did not change the seasonal pattern of N2O emissions from soil. In the whole growing season, comparing to the control treatment (CK), the warming treatment (T) significantly enhanced the N2O flux and the cumulative amount of N2O by 17.31% (P = 0.019), and 20.27% (P = 0.005), respectively. The significant correlations were found between soil N2O emission and soil temperature, moisture. The temperature sensitivity values of soil N2O emission under CK and T treatments were 3.75 and 4.10, respectively. In whole growing stage, T treatment significantly increased the crop aboveground and total biomass, the nitrate reductase activity, and total nitrogen in leaves, while significantly decreased NO3(-) -N content in leaves. T treatment significantly increased soil NO3(-) -N content, but had no significant effect on soil organic carbon and total nitrogen contents. The results of this study suggested that diurnal warming enhanced N2O emission from soil in soybean field.

  9. A novel fuzzy-logic control strategy minimizing N2O emissions.

    PubMed

    Boiocchi, Riccardo; Gernaey, Krist V; Sin, Gürkan

    2017-10-15

    A novel control strategy for achieving low N 2 O emissions and low effluent NH 4 + concentration is here proposed. The control strategy uses the measurements of ammonium and nitrate concentrations in inlet and outlet of the aerobic zone of a wastewater treatment plant to calculate a ratio indicating the balance among the microbial groups. More specifically, the ratio will indicate if there is a complete nitrification. In case nitrification is not complete, the controller will adjust the aeration level of the plant in order to inhibit the production of N 2 O from AOB and HB denitrification. The controller was implemented using the fuzzy logic approach. It was comprehensively tested for different model structures and different sets of model parameters with regards to its ability of mitigating N 2 O emissions for future applications in real wastewater treatment plants. It is concluded that the control strategy is useful for those plants having AOB denitrification as the main N 2 O producing process. However, in treatment plants having incomplete NH 2 OH oxidation as the main N 2 O producing pathway, a cascade controller configuration adapting the oxygen supply to respect only the effluent ammonium concentration limits was found to be more effective to ensure low N 2 O emissions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Diffusivity in surficial sediments and benthic mats determined by use of a combined N 2O-O 2 microsensor

    NASA Astrophysics Data System (ADS)

    Glud, Ronnie Nøhr; Jensen, Kim; Revsbech, Niels Peter

    1995-01-01

    Diffusional characteristics of two biologically active surface sediments were determined by use of a combined N 2O-O 2 microsensor. By analyzing changes in the N2O-gradients in these sediments, it was possible to determine the product ( φDs) for this species with submillimetre depth resolution, where φ is the porosity and Ds the substrate diffusion coefficient. The ( φDs)-value for O 2 could be calculated then from ( φDs)-value for N 2O, because the diffusivity of the two molecules were modified in the same way within the sediment. Both sediments exhibited fine-scale horizontal and vertical variability in diffusion characteristics, and this must be accounted for when analyzing microprofile data. The average ( φDs)-value for N 2O at 20°C for an estuarine surface sediment was 0.93 × 10 -5 cm2 s -1 (at 0-4 mm depth), while the value for the upper 2 mm of a stream sediment covered by a microbial mat was 1.42 × 10 -5 cm 2 s -1. Biological inactivation and oxidation by exposure to an O 2 atmosphere had no effect on the measured ( φDs) for the estuarine sediment; however, the value for the sediment covered by a microbial mat, with dense populations of meiofauna, decreased by 20%. The method presented is ideal for measurements of diffusivity at a high spatial resolution in surficial sediments and densely packed microbial communities.

  11. Terahertz characterization of Y2O3-added AlN ceramics

    NASA Astrophysics Data System (ADS)

    Kang, Seung Beom; Chung, Dong Chul; Kim, Sung-Jin; Chung, Jun-Ki; Park, Sang-Yeup; Kim, Ki-Chul; Kwak, Min Hwan

    2016-12-01

    Terahertz optical and dielectric properties of AlN ceramics fabricated by hot pressed sintering are investigated by THz time-domain spectroscopy in the frequency range of 0.2-3.5 THz. The measured properties of the pure AlN ceramic are compared with those of Y2O3-added AlN ceramic. Two prominent resonance modes, which are essentially responsible for the dielectric properties of the Y2O3-added AlN in terahertz regime, are characterized at ωTO1/(2π) = 2.76 THz (92 cm-1) and ωTO2/(2π) = 18.2 THz (605 cm-1) and are well described by the pseudo-harmonic oscillator model through theoretical fitting. The resonance ωTO1 at 2.76 THz is proposed to be due to the formation of a YAG (Y3Al5O12) secondary phase in Y2O3-added AlN ceramic. From the experimental results, good correlation is observed between the prominent peak of YAG secondary phase at 2.76 THz and thermal conductivity. Additionally, there is a high correlation between densification and refractive index of AlN ceramics fabricated by hot pressed sintering.

  12. Difluorophosphoryl nitrene F2P(O)N: matrix isolation and unexpected rearrangement to F2PNO.

    PubMed

    Zeng, Xiaoqing; Beckers, Helmut; Willner, Helge; Neuhaus, Patrik; Grote, Dirk; Sander, Wolfram

    2009-12-14

    Triplet difluorophosphoryl nitrene F(2)P(O)N (X(3)A'') was generated on ArF excimer laser irradiation (lambda=193 nm) of F(2)P(O)N(3) in solid argon matrix at 16 K, and characterized by its matrix IR, UV/Vis, and EPR spectra, in combination with DFT and CBS-QB3 calculations. On visible light irradiation (lambda>420 nm) at 16 K F(2)P(O)N reacts with molecular nitrogen and some of the azide is regenerated. UV irradiation (lambda=255 nm) of F(2)P(O)N (X(3)A'') induced a Curtius-type rearrangement, but instead of a 1,3-fluorine shift, nitrogen migration to give F(2)PON is proposed to be the first step of the photoisomerization of F(2)P(O)N into F(2)PNO (difluoronitrosophosphine). Formation of novel F(2)PNO was confirmed with (15)N- and (18)O-enriched isotopomers by IR spectroscopy and DFT calculations. Theoretical calculations predict a rather long P-N bond of 1.922 A [B3LYP/6-311+G(3df)] and low bond-dissociation energy of 76.3 kJ mol(-1) (CBS-QB3) for F(2)PNO.

  13. Assessment of nitric oxide (NO) redox reactions contribution to nitrous oxide (N2 O) formation during nitrification using a multispecies metabolic network model.

    PubMed

    Perez-Garcia, Octavio; Chandran, Kartik; Villas-Boas, Silas G; Singhal, Naresh

    2016-05-01

    Over the coming decades nitrous oxide (N2O) is expected to become a dominant greenhouse gas and atmospheric ozone depleting substance. In wastewater treatment systems, N2O is majorly produced by nitrifying microbes through biochemical reduction of nitrite (NO2(-)) and nitric oxide (NO). However it is unknown if the amount of N2O formed is affected by alternative NO redox reactions catalyzed by oxidative nitrite oxidoreductase (NirK), cytochromes (i.e., P460 [CytP460] and 554 [Cyt554 ]) and flavohemoglobins (Hmp) in ammonia- and nitrite-oxidizing bacteria (AOB and NOB, respectively). In this study, a mathematical model is developed to assess how N2O formation is affected by such alternative nitrogen redox transformations. The developed multispecies metabolic network model captures the nitrogen respiratory pathways inferred from genomes of eight AOB and NOB species. The performance of model variants, obtained as different combinations of active NO redox reactions, was assessed against nine experimental datasets for nitrifying cultures producing N2O at different concentration of electron donor and acceptor. Model predicted metabolic fluxes show that only variants that included NO oxidation to NO2(-) by CytP460 and Hmp in AOB gave statistically similar estimates to observed production rates of N2O, NO, NO2(-) and nitrate (NO3(-)), together with fractions of AOB and NOB species in biomass. Simulations showed that NO oxidation to NO2(-) decreased N2O formation by 60% without changing culture's NO2(-) production rate. Model variants including NO reduction to N2O by Cyt554 and cNor in NOB did not improve the accuracy of experimental datasets estimates, suggesting null N2O production by NOB during nitrification. Finally, the analysis shows that in nitrifying cultures transitioning from dissolved oxygen levels above 3.8 ± 0.38 to <1.5 ± 0.8 mg/L, NOB cells can oxidize the NO produced by AOB through reactions catalyzed by oxidative NirK. © 2015 Wiley Periodicals, Inc.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  15. Hemoglobin-based O2 carrier O2 affinity and capillary inlet pO2 are important factors that influence O2 transport in a capillary.

    PubMed

    Dimino, Michael L; Palmer, Andre F

    2007-01-01

    Hemopure (Biopure; Cambridge, MA) and PolyHeme (Northfield Laboratories; Evanston, IL) are two acellular hemoglobin-based O2 carriers (HBOCs) currently in phase III clinical trials for use as red blood cell substitutes. The most common adverse side effect that these HBOCs exhibit is increased vasoconstriction. Autoregulatory theory has been presented as a possible explanation for this physiological effect, where it is hypothesized that low-affinity HBOCs over-deliver O2 to tissues surrounding arterioles, thereby eliciting vasoconstriction. In this paper, we wanted to investigate HBOC oxygenation of tissue surrounding a capillary, which is the smallest element of the circulatory system. An a priori model has been developed in which the performance of mixtures of acellular HBOCs (synthesized by our group and others) and human red blood cells (hRBCs) has been simulated using a Krogh tissue cylinder model (KTCM) comprising a capillary surrounded by a capillary membrane and skeletal muscle tissue in cylindrical coordinates with specified tissue O2 consumption rates and Michaelis-Menten kinetics. In this study, the total hemoglobin (hRBCs and HBOCs) concentration was kept constant. The HBOCs studied possessed O2 affinities that were higher and lower compared to hRBCs (P50's spanned 5-55 mmHg), and the equilibrium binding/release of oxygen to/from the HBOCs was modeled using the Adair equation. At normoxic inlet pO2's, there was no correlation between O2 flux out of the capillary and the O2 affinity of the HBOC. However, a correlation was found between the average pO2 tension in the capillary and the O2 affinity of the HBOC. Additionally, we studied the change in the O2 equilibrium curve of HBOCs with different O2 affinities over a wide range of inlet pO2's and found that changing the inlet pO2 greatly affected which HBOC, having a unique O2 affinity, best delivered O2 to the surrounding tissue. The analysis of oxygen transport presented could lead to a better prediction

  16. Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material

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

    Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao

    Functional multivalent intercalation cathodes represent one of the largest hurdles in the development of Mg batteries. While there are many reports of Mg cathodes, many times the evidence of intercalation chemistry is only circumstantial. In this work, direct evidence of Mg intercalation into a bilayer structure of V2OnH2O xerogel is confirmed, and the nature of the Mg intercalated species is reported. The interlayer spacing of V2OnH2O contracts upon Mg intercalation and expands for Mg deintercalation due to the strong electrostatic interaction between the divalent cation and the cathode. A combination of NMR, pair distribution function (PDF) analysis, and X-ray absorptionmore » near edge spectroscopy (XANES) confirmed reversible Mg insertion into the V2OnH2O material, and structural evolution of Mg intercalation leads to the formation of multiple new phases. Structures of V2OnH2O with Mg intercalation were further supported by the first principle simulations. A solvent cointercalated Mg in V2OnH2O is observed for the first time, and the 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to elucidate the structure obtained upon electrochemical cycling. Specifically, existence of a well-defined Mg–O environment is revealed for the Mg intercalated structures. Information reported here reveals the fundamental Mg ion intercalation mechanism in a bilayer structure of V2OnH2O material and provides insightful design metrics for future Mg cathodes.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  18. A comparative study of three-terminal Hanle signals in CoFe/SiO{sub 2}/n{sup +}-Si and Cu/SiO{sub 2}/n{sup +}-Si tunnel junctions

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

    Lee, Jeong-Hyeon; Cho, B. K., E-mail: chobk@gist.ac.kr; Grünberg Center for Magnetic Nanomaterials, Gwangju Institute of Science and Technology

    We performed three-terminal (3T) Hanle measurement for two types of sample series, CoFe/SiO{sub 2}/n{sup +}-Si and Cu/SiO{sub 2}/n{sup +}-Si, with various tunnel resistances. Clear Hanle signal and anomalous scaling between spin resistance-area product and tunnel resistance-area product were observed in CoFe/SiO{sub 2}/n{sup +}-Si devices. In order to explore the origin of the Hanle signal and the impurity-assisted tunneling effect on the Hanle signal in our devices, Hanle measurement in Cu/SiO{sub 2}/n{sup +}-Si devices was performed as well. However, no detectable Hanle signal was observed in Cu/SiO{sub 2}/n{sup +}-Si, even though a lot of samples with various tunnel resistances were studiedmore » in wide temperature and bias voltage ranges. Through a comparative study, it is found that the impurity-assisted tunneling magnetoresistance mechanism would not play a dominant role in the 3T Hanle signal in CoFe/SiO{sub 2}/n{sup +}-Si tunnel junctions, where the SiO{sub 2} was formed by plasma oxidation to minimize impurities.« less

  19. Simulation of atmospheric N2O with GEOS-Chem and its adjoint: evaluation of observational constraints

    NASA Astrophysics Data System (ADS)

    Wells, K. C.; Millet, D. B.; Bousserez, N.; Henze, D. K.; Chaliyakunnel, S.; Griffis, T. J.; Luan, Y.; Dlugokencky, E. J.; Prinn, R. G.; O'Doherty, S.; Weiss, R. F.; Dutton, G. S.; Elkins, J. W.; Krummel, P. B.; Langenfelds, R.; Steele, L. P.; Kort, E. A.; Wofsy, S. C.; Umezawa, T.

    2015-07-01

    We describe a new 4D-Var inversion framework for N2O based on the GEOS-Chem chemical transport model and its adjoint, and apply this framework in a series of observing system simulation experiments to assess how well N2O sources and sinks can be constrained by the current global observing network. The employed measurement ensemble includes approximately weekly and quasi-continuous N2O measurements (hourly averages used) from several long-term monitoring networks, N2O measurements collected from discrete air samples aboard a commercial aircraft (CARIBIC), and quasi-continuous measurements from an airborne pole-to-pole sampling campaign (HIPPO). For a two-year inversion, we find that the surface and HIPPO observations can accurately resolve a uniform bias in emissions during the first year; CARIBIC data provide a somewhat weaker constraint. Variable emission errors are much more difficult to resolve given the long lifetime of N2O, and major parts of the world lack significant constraints on the seasonal cycle of fluxes. Current observations can largely correct a global bias in the stratospheric sink of N2O if emissions are known, but do not provide information on the temporal and spatial distribution of the sink. However, for the more realistic scenario where source and sink are both uncertain, we find that simultaneously optimizing both would require unrealistically small errors in model transport. Regardless, a bias in the magnitude of the N2O sink would not affect the a posteriori N2O emissions for the two-year timescale used here, given realistic initial conditions, due to the timescale required for stratosphere-troposphere exchange (STE). The same does not apply to model errors in the rate of STE itself, which we show exerts a larger influence on the tropospheric burden of N2O than does the chemical loss rate over short (< 3 year) timescales. We use a stochastic estimate of the inverse Hessian for the inversion to evaluate the spatial resolution of emission

  20. Study of GaN nanorods converted from β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Li, Yuewen; Xiong, Zening; Zhang, Dongdong; Xiu, Xiangqian; Liu, Duo; Wang, Shuang; Hua, Xuemei; Xie, Zili; Tao, Tao; Liu, Bin; Chen, Peng; Zhang, Rong; Zheng, Youdou

    2018-05-01

    We report here high-quality β-Ga2O3 nanorods (NRs) grown on sapphire substrates by hydrothermal method. Ammoniating the β-Ga2O3 NRs results in strain-free wurtzite gallium nitride (GaN) NRs. It was shown by XRD and Raman spectroscopy that β-Ga2O3 was partially converted to GaN/β-Ga2O3 at 1000 °C and then completely converted to GaN NRs at 1050 °C, as confirmed by high-resolution transmission electron microscopy (HRTEM). There is no band-edge emission of β-Ga2O3 in the cathodoluminescence spectrum, and only a deep-level broad emission observed at 3.68-3.73 eV. The band edge emission (3.39 eV) of GaN NRs converted from β-Ga2O3 can also be observed.

  1. The Impact of Iron on Soil N2O Production Depends on Oxygen Availability

    NASA Astrophysics Data System (ADS)

    Zhu, X.; Doane, T. A.; Burger, M.; Horwath, W. R.

    2014-12-01

    The continuous increase of nitrous oxide (N2O) abundance in the atmosphere is a global concern. Soils are both an important source and sink of N2O, which is produced and consumed through biological processes including ammonia oxidation, heterotrophic denitrification, codenitrification, and through abiotic processes such as chemodenitrification. Iron is the most abundant element in the earth and is also the most prevalent redox-active metal in the biosphere. Its role in both chemical and biochemical reactions in N biogeochemistry cycling is well recognized. However, iron's significance to N2O production is poorly understood, especially under varying O2 concentration. We examined N2O production under different O2 concentrations following amorphous iron (III) oxyhydroxide and ammonical N fertilizer additions in four soil slurries and two static soils (soil moisture was 50% of water holding capacity). Under 21% O2, the addition of iron (III) significantly decreased N2O production in all the soil slurries and static soils, while the opposite phenomenon was observed once the O2 concentration became limited (≤3% in the soil slurry and ≤0.5% in the static soil). Our results show that the influence of iron on soil N2O production depends on O2 availability, which is the dominant controller of N2O production pathways. We hypothesize that under ambient O2 conditions, iron can react with nitrite produced during ammonia oxidation, thus reducing the probability of NO2- being used by nitrifiers as electron acceptor in nitrifier denitrification. In contrast, under anaerobic conditions (O2<0.5%), less nitrite was detected in the presence of the iron addition. Under these conditions, iron may have inhibited N2O reductase, or reduced iron (II) reacted with nitrite, both of which would lead to greater release of N2O.These findings imply that management practices which focus on mitigating N2O emission should avoid the application of iron-rich materials such as biosolids when

  2. Implications of the (H2O)n + CO ↔ trans-HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions for primordial atmospheres of Venus and Earth

    NASA Astrophysics Data System (ADS)

    Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.

    2018-04-01

    The forward and backward (H2O)n + CO ↔ HCOOH + (H2O)n-1 (n = 1, 2, and 3) reactions were studied in order to furnish trustworthy thermochemical and kinetic data. Stationary point structures involved in these chemical processes were achieved at the B2PLYP/cc-pVTZ level so that the corresponding vibrational frequencies, zero-point energies, and thermal corrections were scaled to consider anharmonicity effects. A complete basis set extrapolation was also employed with the CCSD(T) method in order to improve electronic energy descriptions and providing therefore more accurate results for enthalpies, Gibbs energies, and rate constants. Forward and backward rate constants were encountered at the high-pressure limit between 200 and 4000 K. In turn, modified Arrhenius' equations were fitted from these rate constants (between 700 and 4000 K). Next, considering physical and chemical conditions that have supposedly prevailed on primitive atmospheres of Venus and Earth, our main results indicate that 85-88 per cent of all water forms on these atmospheres were monomers, whereas (H2O)2 and (H2O)3 complexes would represent 12-15 and ˜0 per cent, respectively. Besides, we estimate that Earth's and Venus' primitive atmospheres could have been composed by ˜0.001-0.003 per cent of HCOOH when their temperatures were around 1000-2000 K. Finally, the water loss process on Venus may have occurred by a mechanism that includes the formic acid as intermediate species.

  3. Electrical characterization of the flowing afterglow of N{sub 2} and N{sub 2}/O{sub 2} microwave plasmas at reduced pressure

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

    Afonso Ferreira, J.; Stafford, L., E-mail: luc.stafford@umontreal.ca; Leonelli, R.

    2014-04-28

    A cylindrical Langmuir probe was used to analyze the spatial distribution of the number density of positive ions and electrons as well as the electron energy distribution function (EEDF) in the flowing afterglow of a 6 Torr N{sub 2} and N{sub 2}/O{sub 2} plasma sustained by a propagating electromagnetic surface wave in the microwave regime. In pure N{sub 2} discharges, ion densities were in the mid 10{sup 14} m{sup −3} in the pink afterglow and in the mid 10{sup 12} m{sup −3} early in the late afterglow. In both pink and late afterglows, the ion population was much higher than the electron population,more » indicating non-macroscopically neutral media. The EEDF was close to a Maxwellian with an electron temperature of 0.5 ± 0.1 eV, except in the pink afterglow where the temperature rose to 1.1 ± 0.2 eV. This latter behavior is ascribed to N{sub 2} vibration-vibration pumping in the pink afterglow that increases the concentration of high N{sub 2} vibrational states and thus rises the electron temperature by vibration-electron collisions. After addition of small amounts of O{sub 2} in the nominally pure N{sub 2} discharge, the charged particles densities and average electron energy first strongly increased and then decreased with increasing O{sub 2} concentration. Based on these data and the evolution of the N{sub 2}{sup +}(B) band emission intensities, it is concluded that a significant change in the positive ion composition of the flowing afterglow occurs, going from N{sub 2}{sup +} in nominally pure N{sub 2} discharges to NO{sup +} after addition of trace amounts of O{sub 2} in N{sub 2}.« less

  4. Hg-sensitized photolysis of diethylamine in the absence and presence of O/sub 2/ or N/sub 2/O

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

    DeStefano, G.; Heicklen, J.

    1986-09-11

    The Hg-sensitized photolysis of diethylamine (DEA) was studied in the absence and presence of O/sub 2/ or N/sub 2/O at room temperature. In the absence of foreign gases, the products were H/sub 2/, CH/sub 3/CH=NC/sub 2/H/sub 5/ and N,N'-diethylbutane-2,3-diamine (III), with respective quantum yields of 1.0, 1.0, and similarly ordered 0.02. Thus CH/sub 3/CHNHC/sub 2/H/sub 5/ radicals are produced exclusively and they are removed by self reaction: 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. DEA + CH/sub 3/CH=NC/sub 2/H/sub 5/ (4a) and 2CH/sub 3/CHNHC/sub 2/H/sub 5/ ..-->.. diamine III (4b), with k/sub 4a//k/sub 4b/ = 47.0 +/- 5.6. In the presence ofmore » O/sub 2/ the radicals are scavenged exclusively by abstraction of the H atom on the nitrogen to give the imine CH/sub 3/CH=NC/sub 2/H/sub 5/ as the exclusive product: (CH/sub 3/CHNHC/sub 2/H/sub 5/ + O/sub 2/ ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + HO/sub 2/ (5). The Hg-sensitized photolysis of N/sub 2/O gives O(/sup 3/P) atoms, which in the presence of DEA react to give the imine and (C/sub 2/H/sub 5/)/sub 2/NOH (DEHA) as products in concerted parallel steps: O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. CH/sub 3/CH=NC/sub 2/H/sub 5/ + H/sub 2/O (9a) and O(/sup 3/P) + (C/sub 2/H/sub 5/)/sub 2/NH ..-->.. (C/sub 2/H/sub 5/)/sub 2/NOH (9b), with k/sub 9a//k/sub 9b/ similarly ordered 9.5 +/- 1.7.« less

  5. N(2)O in small para-hydrogen clusters: Structures and energetics.

    PubMed

    Zhu, Hua; Xie, Daiqian

    2009-04-30

    We present the minimum-energy structures and energetics of clusters of the linear N(2)O molecule with small numbers of para-hydrogen molecules with pairwise additive potentials. Interaction energies of (p-H(2))-N(2)O and (p-H(2))-(p-H(2)) complexes were calculated by averaging the corresponding full-dimensional potentials over the H(2) angular coordinates. The averaged (p-H(2))-N(2)O potential has three minima corresponding to the T-shaped and the linear (p-H(2))-ONN and (p-H(2))-NNO structures. Optimization of the minimum-energy structures was performed using a Genetic Algorithm. It was found that p-H(2) molecules fill three solvation rings around the N(2)O axis, each of them containing up to five p-H(2) molecules, followed by accumulation of two p-H(2) molecules at the oxygen and nitrogen ends. The first solvation shell is completed at N = 17. The calculated chemical potential oscillates with cluster size up to the completed first solvation shell. These results are consistent with the available experimental measurements. (c) 2009 Wiley Periodicals, Inc.

  6. Bi2O2Se nanosheet: An excellent high-temperature n-type thermoelectric material

    NASA Astrophysics Data System (ADS)

    Yu, Jiabing; Sun, Qiang

    2018-01-01

    Motivated by the recent synthesis of an ultrathin film of layered Bi2O2Se [Wu et al., Nat. Nanotechnol. 12, 530 (2017); Wu et al., Nano Lett. 17, 3021 (2017)], we have systematically studied the thermoelectric properties of a Bi2O2Se nanosheet using first principles density functional theory combined with semiclassical Boltzmann transport theory. The calculated results indicate that the Bi2O2Se nanosheet exhibits a figure of merit (ZT) of 3.35 for optimal n-type doping at 800 K, which is much larger than the ZT value of 2.6 at 923 K in SnSe known as the most efficient thermoelectric material [Zhao et al., Nature 508, 373 (2014)]. Equally important, the high ZT in the n-type doped Bi2O2Se nanosheet highlights the efficiency of the reduced dimension on improving thermoelectric performance as compared with strain engineering by which the ZT of n-type doped bulk Bi2O2Se cannot be effectively enhanced.

  7. Investigation of the N2O emission strength in the U. S. Corn Belt

    NASA Astrophysics Data System (ADS)

    Fu, Congsheng; Lee, Xuhui; Griffis, Timothy J.; Dlugokencky, Edward J.; Andrews, Arlyn E.

    2017-09-01

    Nitrous oxide (N2O) has a high global warming potential and depletes stratospheric ozone. The U. S. Corn Belt plays an important role in the global anthropogenic N2O budget. To date, studies on local surface N2O emissions and the atmospheric N2O budget have commonly used Lagrangian models. In the present study, we used an Eulerian model - Weather Research and Forecasting Chemistry (WRF-Chem) model to investigate the relationships between N2O emissions in the Corn Belt and observed atmospheric N2O mixing ratios. We derived a simple equation to relate the emission strengths to atmospheric N2O mixing ratios, and used the derived equation and hourly atmospheric N2O measurements at the KCMP tall tower in Minnesota to constrain agricultural N2O emissions. The modeled spatial patterns of atmospheric N2O were evaluated against discrete observations at multiple tall towers in the NOAA flask network. After optimization of the surface flux, the model reproduced reasonably well the hourly N2O mixing ratios monitored at the KCMP tower. Agricultural N2O emissions in the EDGAR42 database needed to be scaled up by 19.0 to 28.1 fold to represent the true emissions in the Corn Belt for June 1-20, 2010 - a peak emission period. Optimized mean N2O emissions were 3.00-4.38, 1.52-2.08, 0.61-0.81 and 0.56-0.75 nmol m- 2 s- 1 for June 1-20, August 1-20, October 1-20 and December 1-20, 2010, respectively. The simulated spatial patterns of atmospheric N2O mixing ratios after optimization were in good agreement with the NOAA discrete observations during the strong emission peak in June. Such spatial patterns suggest that the underestimate of emissions using IPCC (Inter-governmental Panel on Climate Change) inventory methodology is not dependent on tower measurement location.

  8. CH4 and N2O emissions from China's beef feedlots with ad libitum and restricted feeding in fall and spring seasons.

    PubMed

    Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang

    2015-04-01

    Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. The impact of nitrification inhibitor DMPP on N2O, NO and N2 emissions at different soil moisture conditions in grassland soil

    NASA Astrophysics Data System (ADS)

    Wu, D.; Cardenas, L. M.; Sanz, S. C.; Brueggemann, N.; Loick, N.; Liu, S.; Bol, R.

    2016-12-01

    Emissions of gaseous forms of nitrogen from soil, such as nitrous oxide (N2O) and nitric oxide (NO), have shown great impact on global warming and atmospheric chemistry. Although in soil both nitrification and denitrification could cause N2O and NO emissions, most recent studies demonstrated that denitrification is the dominant process responsible for the increase of atmospheric N2O, while nitrification produces most of NO. The use of nitrification inhibitors (NI) has repeatedly been shown to lower both N2O and NO emissions from agricultural soils; nevertheless, the efficiency of the mitigation effect varies greatly. It is generally assumed that nitrification inhibitors have no direct effect on denitrification. However, the indirect impact, due to the reduced substrate delivery (NO3-) to microsites where denitrification occurs, may have significant effects on denitrification product stoichiometry that may significantly lower soil born N2O emissions. In the present study, soil incubation experiments were carried out in a fully automated continuous-flow incubation system under a He/O2 atmosphere. Ammonium sulfate was applied with and without NI (DMPP) to a UK grassland soil under three different soil moisture conditions (50% WFPS, 65% WFPS, 80% WFPS). With every treatment glucose was applied to supply enough carbon for denitrification. We examined the effect of DMPP on NO, N2O and N2 emissions at different soil moisture conditions which favor nitrification, a mixture of both nitrification and denitrification, or denitrification, respectively. Generally cumulative NO emissions were about 17% of cumulative N2O emissions, while N2 emissions were only detected at high soil moisture condition (80% WFPS). Higher soil moisture increased both N2O and NO emissions. DMPP application increased N2 emissions at soil moisture condition favoring denitrification. Although the application of DMPP significantly mitigated both N2O and NO emissions in all DMPP treatments, the efficiency

  10. Surface passivation of n-type doped black silicon by atomic-layer-deposited SiO2/Al2O3 stacks

    NASA Astrophysics Data System (ADS)

    van de Loo, B. W. H.; Ingenito, A.; Verheijen, M. A.; Isabella, O.; Zeman, M.; Kessels, W. M. M.

    2017-06-01

    Black silicon (b-Si) nanotextures can significantly enhance the light absorption of crystalline silicon solar cells. Nevertheless, for a successful application of b-Si textures in industrially relevant solar cell architectures, it is imperative that charge-carrier recombination at particularly highly n-type doped black Si surfaces is further suppressed. In this work, this issue is addressed through systematically studying lowly and highly doped b-Si surfaces, which are passivated by atomic-layer-deposited Al2O3 films or SiO2/Al2O3 stacks. In lowly doped b-Si textures, a very low surface recombination prefactor of 16 fA/cm2 was found after surface passivation by Al2O3. The excellent passivation was achieved after a dedicated wet-chemical treatment prior to surface passivation, which removed structural defects which resided below the b-Si surface. On highly n-type doped b-Si, the SiO2/Al2O3 stacks result in a considerable improvement in surface passivation compared to the Al2O3 single layers. The atomic-layer-deposited SiO2/Al2O3 stacks therefore provide a low-temperature, industrially viable passivation method, enabling the application of highly n- type doped b-Si nanotextures in industrial silicon solar cells.

  11. [μ-10,21-Dimethyl-3,6,14,17-tetra-za-tricyclo-[17.3.1.1]tetra-cosa-1(23),2,6,8,10,12 (24),13,17,19,21-deca-ene-23,24-diolato-κN,N,O,O:κN,N,O,O]bis-(perchlorato-κO)dimanganese(II).

    PubMed

    Liu, Jing; Pan, Zhi-Quan; Zhou, Hong; Li, Yi-Zhi

    2008-11-08

    In the centrosymmetric and dinuclear title complex, [Mn(2)(C(22)H(22)N(4)O(2))(ClO(4))(2)], the two Mn atoms are bridged by two phenolate O atoms of the N(4)O(2) macrocycle with an Mn⋯Mn distance of 2.9228 (11) Å. The distorted square-pyramidal N(2)O(3) coordination geometry is completed by an O atom derived from a perchlorate anion.

  12. Progress in the analysis and interpretation of N2O isotopes: Potential and future challenges

    NASA Astrophysics Data System (ADS)

    Mohn, Joachim; Tuzson, Béla; Zellweger, Christoph; Harris, Eliza; Ibraim, Erkan; Yu, Longfei; Emmenegger, Lukas

    2017-04-01

    In recent years, research on nitrous oxide (N2O) stable isotopes has significantly advanced, addressing an increasing number of research questions in biogeochemical and atmospheric sciences [1]. An important milestone was the development of quantum cascade laser based spectroscopic devices [2], which are inherently specific for structural isomers (15N14N16O vs. 14N15N16O) and capable to collect real-time data with high temporal resolution, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. In combination with automated preconcentration, optical isotope ratio spectroscopy (OIRS) has been applied to disentangle source processes in suburban, rural and pristine environments [e.g. 3, 4]. Within the European Metrology Research Programme (EMRP) ENV52 project "Metrology for high-impact greenhouse gases (HIGHGAS)", the quality of N2O stable isotope analysis by OIRS, the comparability between laboratories, and the traceability to the international isotope ratio scales have been addressed. An inter-laboratory comparison between eleven IRMS and OIRS laboratories, organised within HIGHGAS, indicated limited comparability for 15N site preference, i.e. the difference between 15N abundance in central (N*NO) and end (*NNO) position [5]. In addition, the accuracy of the NH4NO3 decomposition reaction, which provides the link between 15N site preference and the international 15N/14N scale, was found to be limited by non-quantitative NH4NO3 decomposition in combination with substantially different isotope enrichment factors for both nitrogen atoms [6]. Results of the HIGHGAS project indicate that the following research tasks have to be completed to foster research on N2O isotopes: 1) develop improved techniques to link the 15N and 18O abundance and the 15N site preference in N2O to the international stable isotope ratio scales; 2) provide N2O reference materials, pure and diluted in an air matrix, to improve inter-laboratory compatibility. These tasks

  13. Isotope exchange in reactions between D2O and size-selected ionic water clusters containing pyridine, H+ (pyridine)m(H2O)n.

    PubMed

    Ryding, Mauritz Johan; Zatula, Alexey S; Andersson, Patrik Urban; Uggerud, Einar

    2011-01-28

    Pyridine containing water clusters, H(+)(pyridine)(m)(H(2)O)(n), have been studied both experimentally by a quadrupole time-of-flight mass spectrometer and by quantum chemical calculations. In the experiments, H(+)(pyridine)(m)(H(2)O)(n) with m = 1-4 and n = 0-80 are observed. For the cluster distributions observed, there are no magic numbers, neither in the abundance spectra, nor in the evaporation spectra from size selected clusters. Experiments with size-selected clusters H(+)(pyridine)(m)(H(2)O)(n), with m = 0-3, reacting with D(2)O at a center-of-mass energy of 0.1 eV were also performed. The cross-sections for H/D isotope exchange depend mainly on the number of water molecules in the cluster and not on the number of pyridine molecules. Clusters having only one pyridine molecule undergo D(2)O/H(2)O ligand exchange, while H(+)(pyridine)(m)(H(2)O)(n), with m = 2, 3, exhibit significant H/D scrambling. These results are rationalized by quantum chemical calculations (B3LYP and MP2) for H(+)(pyridine)(1)(H(2)O)(n) and H(+)(pyridine)(2)(H(2)O)(n), with n = 1-6. In clusters containing one pyridine, the water molecules form an interconnected network of hydrogen bonds associated with the pyridinium ion via a single hydrogen bond. For clusters containing two pyridines, the two pyridine molecules are completely separated by the water molecules, with each pyridine being positioned diametrically opposite within the cluster. In agreement with experimental observations, these calculations suggest a "see-saw mechanism" for pendular proton transfer between the two pyridines in H(+)(pyridine)(2)(H(2)O)(n) clusters.

  14. N use efficiencies and N2O emissions in two contrasting, biochar amended soils under winter wheat—cover crop—sorghum rotation

    NASA Astrophysics Data System (ADS)

    Hüppi, Roman; Neftel, Albrecht; Lehmann, Moritz F.; Krauss, Maike; Six, Johan; Leifeld, Jens

    2016-08-01

    Biochar, a carbon-rich, porous pyrolysis product of organic residues, is evaluated as an option to tackle major problems of the global food system. Applied to soil, biochar can sequester carbon and have beneficial effects on nitrogen (N) cycling, thereby enhancing crop yields and reducing nitrous oxide (N2O) emissions. There is little understanding of the underlying mechanisms, but many experiments indicated increased yields and manifold changes in N transformation, suggesting an increase in N use efficiency. Biochar’s effects can be positive in extensively managed tropical agriculture, however less is known about its use in temperate soils with intensive fertilisation. We tested the effect of slow pyrolysis wood chip biochar on N use efficiency, crop yields and N2O emissions in a lysimeter system with two soil types (sandy loamy Cambisol and silty loamy Luvisol) in a winter wheat—cover crop—sorghum rotation. 15N-labelled ammonium nitrate fertiliser (170 kg N ha-1 in 3 doses, 10% 15N) was applied to the first crop to monitor its fate in three ecosystem components (plants, soil, leachate). Green rye was sown as cover crop to keep the first year’s fertiliser N for the second year’s sorghum crop (fertilised with 110 kg N ha-1 in two doses and natural abundance 15N). We observed no effects of biochar on N fertiliser use efficiency, yield or N uptake for any crop. Biochar reduced leaching by 43 ± 19% but only towards the end of the experiment with leaching losses being generally low. For both soils N2O emissions were reduced by 15 ± 4% with biochar compared to the control treatments. Our results indicate that application of the chosen biochar induces environmental benefits in terms of N2O emission and N leaching but does not substantially affect the overall N cycle and hence crop performance in the analyzed temperate crop rotation.

  15. Reassessment of the NH4 NO3 thermal decomposition technique for calibration of the N2 O isotopic composition.

    PubMed

    Mohn, Joachim; Gutjahr, Wilhelm; Toyoda, Sakae; Harris, Eliza; Ibraim, Erkan; Geilmann, Heike; Schleppi, Patrick; Kuhn, Thomas; Lehmann, Moritz F; Decock, Charlotte; Werner, Roland A; Yoshida, Naohiro; Brand, Willi A

    2016-09-08

    In the last few years, the study of N 2 O site-specific nitrogen isotope composition has been established as a powerful technique to disentangle N 2 O emission pathways. This trend has been accelerated by significant analytical progress in the field of isotope-ratio mass-spectrometry (IRMS) and more recently quantum cascade laser absorption spectroscopy (QCLAS). Methods The ammonium nitrate (NH 4 NO 3 ) decomposition technique provides a strategy to scale the 15 N site-specific (SP ≡ δ 15 N α - δ 15 N β ) and bulk (δ 15 N bulk  = (δ 15 N α  + δ 15 N β )/2) isotopic composition of N 2 O against the international standard for the 15 N/ 14 N isotope ratio (AIR-N 2 ). Within the current project 15 N fractionation effects during thermal decomposition of NH 4 NO 3 on the N 2 O site preference were studied using static and dynamic decomposition techniques. The validity of the NH 4 NO 3 decomposition technique to link NH 4 + and NO 3 - moiety-specific δ 15 N analysis by IRMS to the site-specific nitrogen isotopic composition of N 2 O was confirmed. However, the accuracy of this approach for the calibration of δ 15 N α and δ 15 N β values was found to be limited by non-quantitative NH 4 NO 3 decomposition in combination with substantially different isotope enrichment factors for the conversion of the NO 3 - or NH 4 + nitrogen atom into the α or β position of the N 2 O molecule. The study reveals that the completeness and reproducibility of the NH 4 NO 3 decomposition reaction currently confine the anchoring of N 2 O site-specific isotopic composition to the international isotope ratio scale AIR-N 2 . The authors suggest establishing a set of N 2 O isotope reference materials with appropriate site-specific isotopic composition, as community standards, to improve inter-laboratory compatibility. This article is protected by copyright. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

    Scheer, Clemens; Dannenmann, Michael; Meier, Rudolf

    2015-04-01

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

  17. 3D nanostructured N-doped TiO2 photocatalysts with enhanced visible absorption.

    PubMed

    Cho, Sumin; Ahn, Changui; Park, Junyong; Jeon, Seokwoo

    2018-05-24

    Considering the environmental issues, it is essential to develop highly efficient and recyclable photocatalysts in purification systems. Conventional TiO2 nanoparticles have strong intrinsic oxidizing power and high surface area, but are difficult to collect after use and rarely absorb visible light, resulting in low photocatalytic efficiency under sunlight. Here we develop a new type of highly efficient and recyclable photocatalyst made of a three-dimensional (3D) nanostructured N-doped TiO2 monolith with enhanced visible light absorption. To prepare the sample, an ultrathin TiN layer (∼10 nm) was conformally coated using atomic layer deposition (ALD) on 3D nanostructured TiO2. Subsequent thermal annealing at low temperature (550 °C) converted TiN to anatase phase N-doped TiO2. The resulting 3D N-doped TiO2 showed ∼33% enhanced photocatalytic performance compared to pure 3D TiO2 of equivalent thickness under sunlight due to the reduced bandgap, from 3.2 eV to 2.75 eV through N-doping. The 3D N-doped TiO2 monolith could be easily collected and reused at least 5 times without any degradation in photocatalytic performance.

  18. Aspects of Supercritical Turbulence: Direct Numerical Simulation of O2/H2 and C7H16/N2 Temporal Mixing Layers

    NASA Technical Reports Server (NTRS)

    Bellan, J.; Okongo, N. A.; Harstad, K. G.; Hutt, John (Technical Monitor)

    2002-01-01

    Results from Direct Numerical Simulations of temporal, supercritical mixing layers for two species systems are analyzed to elucidate species-specific turbulence aspects. The two species systems, O2/H2 and C7HG16/N2, have different thermodynamic characteristics; thus, although the simulations are performed at similar reduced pressure (ratio of the pressure to the critical pressure), the former system is dose to mixture ideality and has a relatively high solubility with respect to the latter, which exhibits strong departures from mixture ideality Due to the specified, smaller initial density stratification, the C7H16/N2 layers display higher growth and increased global molecular mixing as well as larger turbulence levels. However, smaller density gradients at the transitional state for the O2/H2 system indicate that on a local basis, the layer exhibits an enhanced mixing, this being attributed to the increased solubility and to mixture ideality. These thermodynamic features are shown to affect the irreversible entropy production (i.e. the dissipation), which is larger for the O2/H2 layer and is primarily concentrated in high density-gradient magnitude regions that are distortions of the initial density stratification boundary. In contrast, the regions of largest dissipation in the C7H16/N2 layer are located in high density-gradient magnitude regions resulting from the mixing of the two fluids.

  19. Enhanced photocatalytic H2-production activity of C-dots modified g-C3N4/TiO2 nanosheets composites.

    PubMed

    Li, Yang; Feng, Xionghan; Lu, Zhexue; Yin, Hui; Liu, Fan; Xiang, Quanjun

    2018-03-01

    As a new carbon-based material, carbon dots (C-dots) have got widely preference because of its excellent electronic transfer capability. In this work, a novel ternary layered C-dots/g-C 3 N 4 /TiO 2 nanosheets (CGT) composite photocatalysts were prepared by impregnation precipitation methods. The optimal ternary CGT composite samples revealed high photocatalytic hydrogen evolution rate in triethanolamine aqueous solutions, which exceeded the rate of the optimal g-C 3 N 4 /TiO 2 composite sample by a factor of 5 times. The improved photocatalytic activity is owed to the positive effects of C-dots and layered heterojunction structure of TiO 2 nanosheets and g-C 3 N 4 sheets. C-dots in the CGT composites can serve as electron reservoirs to capture the photo-induced electrons. The well-defined layered heterojunction structure of CGT provides the intimate contact and the strong interaction of anatase TiO 2 nanosheets and g-C 3 N 4 sheets via face-to-face orientation, which restrains the recombination of photogenerated charge carriers, and thus enhances the photocatalytic H 2 -production activity. Electron paramagnetic resonance and transient photocurrent response proved the strong interaction and improved interfacial charge transfer of TiO 2 nanosheets and g-C 3 N 4 sheets, respectively. The mechanism of improving the photocatalytic H 2 -evolution activity was further confirmed by time-resolved fluorescence, electron paramagnetic resonance, transient photocurrent response and electrochemical impedance spectroscopy. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. In situ reaction mechanism studies on the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O and Ti(O{sup i}Pr){sub 3}[MeC(N{sup i}Pr){sub 2}]-D{sub 2}O atomic layer deposition processes

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

    Tomczak, Yoann, E-mail: yoann.tomczak@helsinki.fi; Knapas, Kjell; Leskelä, Markku

    2014-01-15

    Reaction mechanisms in the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O and Ti(O{sup i}Pr){sub 3}[MeC(N{sup i}Pr){sub 2}] [also written Ti(O{sup i}Pr){sub 3}(N{sup i}Pr-Me-amd)]-D{sub 2}O atomic layer deposition processes were studied in situ with quartz crystal microbalance (QCM) and quadrupole mass spectrometry (QMS) at 275 °C. For the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O process, both QCM and QMS results indicated adsorption of the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2} molecule through an exchange of at least one of its –NMe{sub 2} ligands with surface hydroxyl groups. Regarding the Ti(O{sup i}Pr){sub 3}(N{sup i}Pr-Me-amd)-D{sub 2}O process, a mismatch between the QCM and QMS results revealedmore » more complex reactions: the decomposition of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand is suggested by the shape of the QCM data and the intensity of the QMS signals belonging to fragments of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand. A simple calculation model associating the growth rate per cycle of a crystalline film and the surface area taken by the ligands remaining after saturation was also used to support the decomposition of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand. The observed high growth rate is incompatible with the whole [MeC(N{sup i}Pr){sub 2}] (also written [N{sup i}Pr-Me-amd)] ligand remaining on the surface.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  2. Flavonoids as Putative Inducers of the Transcription Factors Nrf2, FoxO, and PPARγ

    PubMed Central

    Duckstein, Nils; Hasler, Mario; Rimbach, Gerald

    2017-01-01

    Dietary flavonoids have been shown to extend the lifespan of some model organisms and may delay the onset of chronic ageing-related diseases. Mechanistically, the effects could be explained by the compounds scavenging free radicals or modulating signalling pathways. Transcription factors Nrf2, FoxO, and PPARγ possibly affect ageing by regulating stress response, adipogenesis, and insulin sensitivity. Using Hek-293 cells transfected with luciferase reporter constructs, we tested the potency of flavonoids from different subclasses (flavonols, flavones, flavanols, and isoflavones) to activate these transcription factors. Under cell-free conditions (ABTS and FRAP assays), we tested their free radical scavenging activities and used α-tocopherol and ascorbic acid as positive controls. Most of the tested flavonoids, but not the antioxidant vitamins, stimulated Nrf2-, FoxO-, and PPARγ-dependent promoter activities. Flavonoids activating Nrf2 also tended to induce a FoxO and PPARγ response. Interestingly, activation patterns of cellular stress response by flavonoids were not mirrored by their activities in ABTS and FRAP assays, which depended mostly on hydroxylation in the flavonoid B ring and, in some cases, extended that of the vitamins. In conclusion, the free radical scavenging properties of flavonoids do not predict whether these molecules can stimulate a cellular response linked to activation of longevity-associated transcription factors. PMID:28761622

  3. K-shell photoabsorption coefficients of O2, CO2, CO, and N2O

    NASA Technical Reports Server (NTRS)

    Barrus, D. M.; Blake, R. L.; Burek, A. J.; Chambers, K. C.; Pregenzer, A. L.

    1979-01-01

    The total photoabsorption coefficient has been measured from 500 to 600 eV around the K edge of oxygen in gases O2, CO2, CO, and N2O by means of a gold continuum source and crystal spectrometer with better than 1-eV resolution. The cross sections are dominated by discrete molecular-orbital transitions below the K-edge energy. A few Rydberg transitions were barely detectable. Broad shape resonances appear at or above the K edge. Additional broad, weak features above the K edge possibly arise from shake up. Quantitative results are given that have about 10% accuracy except on the very strong peaks. All the measured features are discussed in relation to other related measurements and theory.

  4. Crystal structure of (pyridine-κN)bis(quinolin-2-olato-κ2 N,O)copper(II) monohydrate

    PubMed Central

    Hawks, Benjamin; Yan, Jingjing; Basa, Prem; Burdette, Shawn

    2015-01-01

    The title complex, [Cu(C9H6NO)2(C5H4N)]·H2O, adopts a slightly distorted square-pyramidal geometry in which the axial pyridine ligand exhibits a long Cu—N bond of 2.305 (3) Å. The pyridine ligand forms dihedral angles of 79.5 (5) and 88.0 (1)° with the planes of the two quinolin-2-olate ligands, while the dihedral angle between the quinoline groups of 9.0 (3)° indicates near planarity. The water mol­ecule connects adjacent copper complexes through O—H⋯O hydrogen bonds to phenolate O atoms, forming a network inter­connecting all the complexes in the crystal lattice. PMID:25878845

  5. Simulation of atmospheric N2O with GEOS-Chem and its adjoint: evaluation of observational constraints

    NASA Astrophysics Data System (ADS)

    Wells, K. C.; Millet, D. B.; Bousserez, N.; Henze, D. K.; Chaliyakunnel, S.; Griffis, T. J.; Luan, Y.; Dlugokencky, E. J.; Prinn, R. G.; O'Doherty, S.; Weiss, R. F.; Dutton, G. S.; Elkins, J. W.; Krummel, P. B.; Langenfelds, R.; Steele, L. P.; Kort, E. A.; Wofsy, S. C.; Umezawa, T.

    2015-10-01

    We describe a new 4D-Var inversion framework for nitrous oxide (N2O) based on the GEOS-Chem chemical transport model and its adjoint, and apply it in a series of observing system simulation experiments to assess how well N2O sources and sinks can be constrained by the current global observing network. The employed measurement ensemble includes approximately weekly and quasi-continuous N2O measurements (hourly averages used) from several long-term monitoring networks, N2O measurements collected from discrete air samples onboard a commercial aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container; CARIBIC), and quasi-continuous measurements from the airborne HIAPER Pole-to-Pole Observations (HIPPO) campaigns. For a 2-year inversion, we find that the surface and HIPPO observations can accurately resolve a uniform bias in emissions during the first year; CARIBIC data provide a somewhat weaker constraint. Variable emission errors are much more difficult to resolve given the long lifetime of N2O, and major parts of the world lack significant constraints on the seasonal cycle of fluxes. Current observations can largely correct a global bias in the stratospheric sink of N2O if emissions are known, but do not provide information on the temporal and spatial distribution of the sink. However, for the more realistic scenario where source and sink are both uncertain, we find that simultaneously optimizing both would require unrealistically small errors in model transport. Regardless, a bias in the magnitude of the N2O sink would not affect the a posteriori N2O emissions for the 2-year timescale used here, given realistic initial conditions, due to the timescale required for stratosphere-troposphere exchange (STE). The same does not apply to model errors in the rate of STE itself, which we show exerts a larger influence on the tropospheric burden of N2O than does the chemical loss rate over short (< 3 year) timescales. We use a

  6. Radiation Hardened Silicon-on-Insulator Structures with N+ Ion Modified Buried SiO2 Layer

    NASA Astrophysics Data System (ADS)

    Tyschenko, I. E.; Popov, V. P.

    2009-12-01

    Radiation-resistant silicon-on-insulator structures were produced by N+ ion implantation into thermally grown SiO2 film and subsequent hydrogen transfer of the Si layer to the nitrogen-implanted substrate under conditions of vacuum wafer bonding. Accumulation of the carriers in the buried SiO2 was investigated as a function of fluence of nitrogen ions in the range (1-6)×1015 cm2 and as a function of total radiation dose ranging from 104 to 107 rad (Si). It was found that the charge generated near the nitrided bonding interface was reduced by a factor of four compared to the thermal SiO2/Si interface.

  7. Microbial N Transformations and N2O Emission after Simulated Grassland Cultivation: Effects of the Nitrification Inhibitor 3,4-Dimethylpyrazole Phosphate (DMPP).

    PubMed

    Duan, Yun-Feng; Kong, Xian-Wang; Schramm, Andreas; Labouriau, Rodrigo; Eriksen, Jørgen; Petersen, Søren O

    2017-01-01

    (DMPP) prior to grassland cultivation and investigated its efficacy in a laboratory incubation study. DMPP inhibited the growth and activity of ammonia-oxidizing bacteria but had no adverse effects on ammonia-oxidizing archaea and denitrifiers. DMPP can effectively reduce the potential for leaching of NO 3 - derived from residue decomposition, while the effect on reducing N 2 O emissions will be significant only when soil NO 3 - availability is limiting. Our findings provide insight into how DMPP affects soil nitrifier and denitrifier populations and have direct implications for improving N use efficiency and reducing environmental impacts during grassland cultivation. Copyright © 2016 American Society for Microbiology.

  8. Nitrous oxide nitrification and denitrification 15N enrichment factors from Amazon forest soils.

    PubMed

    Pérez, Tibisay; Garcia-Montiel, Diana; Trumbore, Susan; Tyler, Stanley; de Camargo, Plínio; Moreira, Marcelo; Piccolo, Marisa; Cerri, Carlos

    2006-12-01

    The isotopic signatures of 15N and 18O in N2O emitted from tropical soils vary both spatially and temporally, leading to large uncertainty in the overall tropical source signature and thereby limiting the utility of isotopes in constraining the global N2O budget. Determining the reasons for spatial and temporal variations in isotope signatures requires that we know the isotope enrichment factors for nitrification and denitrification, the two processes that produce N2O in soils. We have devised a method for measuring these enrichment factors using soil incubation experiments and report results from this method for three rain forest soils collected in the Brazilian Amazon: soil with differing sand and clay content from the Tapajos National Forest (TNF) near Santarém, Pará, and Nova Vida Farm, Rondônia. The 15N enrichment factors for nitrification and denitrification differ with soil texture and site: -111 per thousand +/- 12 per thousand and -31 per thousand +/- 11 per thousand for a clay-rich Oxisol (TNF), -102 per thousand +/- 5 per thousand and -45 per thousand +/- 5 per thousand for a sandier Ultisol (TNF), and -10.4 per thousand +/- 3.5 per thousand (enrichment factor for denitrification) for another Ultisol (Nova Vida) soil, respectively. We also show that the isotopomer site preference (delta15Nalpha - delta15Nbeta, where alpha indicates the central nitrogen atom and beta the terminal nitrogen atom in N2O) may allow differentiation between processes of production and consumption of N2O and can potentially be used to determine the contributions of nitrification and denitrification. The site preferences for nitrification and denitrification from the TNF-Ultisol incubated soils are: 4.2 per thousand +/- 8.4 per thousand and 31.6 per thousand +/- 8.1 per thousand, respectively. Thus, nitrifying and denitrifying bacteria populations under the conditions of our study exhibit significantly different 15N site preference fingerprints. Our data set strongly suggests

  9. The behavior of N2 and O2 in pure, mixed or layered CO ices

    NASA Astrophysics Data System (ADS)

    Bisschop, Suzanne E.; Fraser, Helen J.; Fuchs, Guido; Öberg, Karin I.; Acharyya, Kinsuk; van Broekhuizen, Fleur; Schlemmer, Stephan; van Dishoeck, Ewine F.

    N2 and O2 are molecules that are predicted to be abundant in dense molecular clouds. Both molecules are difficult to detect as neither has a dipole moment. The chemical abundance of N2 is mostly inferred from its daughter species N2H+, but was recently detected in the ISM for the first time, with an abundance of 3.3 × 10-7 (Knauth et al 2004). Searches for the submillimeter lines of O2 have given upper limits for the abundance of ≤ 2.6 10-7 for star forming clouds and ≤ 3 10-6 for cold dark clouds (Goldsmith et al. 2000). Pontoppidan et al. (2003) deduced from the CO line profile that CO is present in both H2O poor and H2O rich ice layers, so it follows that N2 is likely to be present in a H2O poor ice layer. In many cold and protostellar cores N2H+ is found to anti-correlate with HCO+ and CO (Bergin et al. 2001; Jørgensen et al. 2004). Models by, for example Bergin & Langer (1997), assume this is due to the balance between freeze-out and evaporation, where ratios for the binding energy for N2 compared to CO of 0.50-0.70 are used. To model these processes, and reproduce the observed abundances of each species it is important to determine empirically the binding energies, sticking probabilities and desorption kinetics of model ice systems containing CO, N2 and O2. It seems that these quantities depend on the degree to which N2 and O2 mix with CO. Therefore, CO and N2 ices were studied extensively in a Ultra High Vacuum (UHV) experiment (P ~ 1 × 10-10 Torr) (Oberg et al. 2005; Bisschop et al submitted)). Ice samples were deposited at 14 K on a polycrystalline gold sample, mounted in the UHV chamber, covering morphologies from pure CO and N2, and 1:1 mixtures, to 1/1 layers of both CO over N2 and N2 over CO, and layers of 40 L of CO (1 L ≈ 1 monolayer) covered with 5 to 50 L of N2. The ices were studied using a combination of Reflection Absorption Infrared Spectroscopy (RAIRS) and Temperature Programmed Desorption (TPD), at a ramp-rate of 0.1 K min-1. The TPD

  10. Density functional theory investigation of the geometric and electronic structures of [UO2(H2O)m(OH)n](2 - n) (n + m = 5).

    PubMed

    Ingram, Kieran I M; Häller, L Jonas L; Kaltsoyannis, Nikolas

    2006-05-28

    Gradient corrected density functional theory has been used to calculate the geometric and electronic structures of the family of molecules [UO2(H2O)m(OH)n](2 - n) (n + m = 5). Comparisons are made with previous experimental and theoretical structural and spectroscopic data. r(U-O(yl)) is found to lengthen as water molecules are replaced by hydroxides in the equatorial plane, and the nu(sym) and nu(asym) uranyl vibrational wavenumbers decrease correspondingly. GGA functionals (BP86, PW91 and PBE) are generally found to perform better for the cationic complexes than for the anions. The inclusion of solvent effects using continuum models leads to spurious low frequency imaginary vibrational modes and overall poorer agreement with experimental data for nu(sym) and nu(asym). Analysis of the molecular orbital structure is performed in order to trace the origin of the lengthening and weakening of the U-O(yl) bond as waters are replaced by hydroxides. No evidence is found to support previous suggestions of a competition for U 6d atomic orbitals in U-O(yl) and U-O(hydroxide)pi bonding. Rather, the lengthening and weakening of U-O(yl) is attributed to reduced ionic bonding generated in part by the sigma-donating ability of the hydroxide ligands.

  11. Effects of Post-Deposition Annealing on ZrO2/n-GaN MOS Capacitors with H2O and O3 as the Oxidizers

    NASA Astrophysics Data System (ADS)

    Zheng, Meijuan; Zhang, Guozhen; Wang, Xiao; Wan, Jiaxian; Wu, Hao; Liu, Chang

    2017-04-01

    GaN-based metal-oxide-semiconductor capacitors with ZrO2 as the dielectric layer have been prepared by atomic layer deposition. The accumulation and depletion regions can be clearly distinguished when the voltage was swept from -4 to 4 V. Post-annealing results suggested that the capacitance in accumulation region went up gradually as the annealing temperature increased from 300 to 500 °C. A minimum leakage current density of 3 × 10-9 A/cm2 at 1 V was obtained when O3 was used for the growth of ZrO2. Leakage analysis revealed that Schottky emission and Fowler-Nordheim tunneling were the main leakage mechanisms.

  12. Role of surface and subsurface processes in scaling N2O emissions along riverine networks

    PubMed Central

    Marzadri, Alessandra; Dee, Martha M.; Tonina, Daniele; Bellin, Alberto; Tank, Jennifer L.

    2017-01-01

    Riverine environments, such as streams and rivers, have been reported as sources of the potent greenhouse gas nitrous oxide (N2O) to the atmosphere mainly via microbially mediated denitrification. Our limited understanding of the relative roles of the near-surface streambed sediment (hyporheic zone), benthic, and water column zones in controlling N2O production precludes predictions of N2O emissions along riverine networks. Here, we analyze N2O emissions from streams and rivers worldwide of different sizes, morphology, land cover, biomes, and climatic conditions. We show that the primary source of N2O emissions varies with stream and river size and shifts from the hyporheic–benthic zone in headwater streams to the benthic–water column zone in rivers. This analysis reveals that N2O production is bounded between two N2O emission potentials: the upper N2O emission potential results from production within the benthic–hyporheic zone, and the lower N2O emission potential reflects the production within the benthic–water column zone. By understanding the scaling nature of N2O production along riverine networks, our framework facilitates predictions of riverine N2O emissions globally using widely accessible chemical and hydromorphological datasets and thus, quantifies the effect of human activity and natural processes on N2O production. PMID:28400514

  13. Annealing dependence on flexible p-CuGaO2/n-ZnO heterojunction diode deposited by RF sputtering method

    NASA Astrophysics Data System (ADS)

    Li Lam, Mui; Hafiz Abu Bakar, Muhammad; Lam, Wai Yip; Alias, Afishah; Rahman, Abu Bakar Abd; Anuar Mohamad, Khairul; Uesugi, Katsuhiro

    2017-11-01

    In this work, p-CuGaO2/n-ZnO heterojunction diodes were deposited by RF powered sputtering method on polyethylene terephthalate (PETP, PET) substrates. Structural, morphology, optical and electrical properties of CuGaO2/ZnO heterojunction was investigated as a function of annealing duration. The structural properties show the ZnO films (002) peak were stronger at the range of 34° while CuGaO2 (015) peak is not visible at 44°. The surface morphology revealed that RMS roughness become smoother as the annealing duration increase to 30 minutes and become rougher as the annealing duration is increased to 60 minutes. The optical properties of CuGaO2/ZnO heterojunction diode at 30 minutes exhibit approximately 75% optical transmittance in the invisible region. The diodes exhibited a rectifying characteristic and the maximum forward current was observed for the diode annealed for 30 minutes. The diodes show an ideality factor range from 43.69 to 71.29 and turn on voltage between 0.75 V and 1.05 V.

  14. Visible-light-driven N-TiO2@SiO2@Fe3O4 magnetic nanophotocatalysts: Synthesis, characterization, and photocatalytic degradation of PPCPs.

    PubMed

    Kumar, Ashutosh; Khan, Musharib; Fang, Liping; Lo, Irene M C

    2017-07-24

    TiO 2 -based photocatalysis offers certain advantages like rapid degradation and mineralization of organic compounds. However, the practical applicability of photocatalysts in degradation of pharmaceuticals and personal care products (PPCPs) is still restricted by challenges including their limited photocatalytic activity under visible light and difficulty in their separation from suspension. To overcome these challenges, a visible-light-driven magnetic N-TiO 2 @SiO 2 @Fe 3 O 4 nanophotocatalyst was developed through fine-tuning the pertinent factors (calcination temperature, Fe 3 O 4 loading, and nitrogen doping) involved during synthesis process, on the basis of degradation of ibuprofen (a typical PPCP). The TEM-EDX, XRD and XPS analyses confirmed the successful synthesis of nanophotocatalyst. By comparing nanophotocatalyst's performance on ibuprofen under two visible light sources, i.e., compact fluorescent lamps (CFLs) and light emitting diodes (LEDs) of similar irradiance, CFLs of irradiance 320μWcm -2 and peak emissive wavelength 543nm served as a better source, resulting in 94% degradation. Furthermore, 93% of benzophenone-3 within 5h and 71% of carbamazepine within 9h was degraded under visible light emitted by CFLs. The superparamagnetic behavior of the nanophotocatalyst enabled its successful magnetic separation (95% efficiency) from the suspension within 20-25min under an electromagnetic field of ∼200mT. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Hotspots of soil N 2O emission enhanced through water absorption by plant residue

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

    Kravchenko, A. N.; Toosi, E. R.; Guber, A. K.

    N 2O is a highly potent greenhouse gas and arable soils represent its major anthropogenic source. Field-scale assessments and predictions of soil N 2O emission remain uncertain and imprecise due to the episodic and microscale nature of microbial N 2O production, most of which occurs within very small discrete soil volumes. Such hotspots of N 2O production are often associated with decomposing plant residue. Here we quantify physical and hydrological soil characteristics that lead to strikingly accelerated N 2O emissions in plant residue-induced hotspots. Results reveal a mechanism for microscale N 2O emissions: water absorption by plant residue that createsmore » unique micro-environmental conditions, markedly different from those of the bulk soil. Moisture levels within plant residue exceeded those of bulk soil by 4–10-fold and led to accelerated N 2O production via microbial denitrification. The presence of large (Ø >35 μm) pores was a prerequisite for maximized hotspot N 2O production and for subsequent diffusion to the atmosphere. Understanding and modelling hotspot microscale physical and hydrologic characteristics is a promising route to predict N 2O emissions and thus to develop effective mitigation strategies and estimate global fluxes in a changing environment.« less

  16. Hotspots of soil N2O emission enhanced through water absorption by plant residue

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

    Kravchenko, A. N.; Toosi, E. R.; Guber, A. K.

    N2O is a highly potent greenhouse gas and arable soils represent its major anthropogenic source. Field-scale assessments and predictions of soil N2O emission remain uncertain and imprecise due to the episodic and microscale nature of microbial N2O production, most of which occurs within very small discrete soil volumes. Such hotspots of N2O production are often associated with decomposing plant residue. Here we quantify physical and hydrological soil characteristics that lead to strikingly accelerated N2O emissions in plant residue-induced hotspots. Results reveal a mechanism for microscale N2O emissions: water absorption by plant residue that creates unique micro-environmental conditions, markedly different frommore » those of the bulk soil. Moisture levels within plant residue exceeded those of bulk soil by 4–10-fold and led to accelerated N2O production via microbial denitrification. The presence of large (Ø >35 μm) pores was a prerequisite for maximized hotspot N2O production and for subsequent diffusion to the atmosphere. Understanding and modelling hotspot microscale physical and hydrologic characteristics is a promising route to predict N2O emissions and thus to develop effective mitigation strategies and estimate global fluxes in a changing environment.« less

  17. Hotspots of soil N 2O emission enhanced through water absorption by plant residue

    DOE PAGES

    Kravchenko, A. N.; Toosi, E. R.; Guber, A. K.; ...

    2017-06-05

    N 2O is a highly potent greenhouse gas and arable soils represent its major anthropogenic source. Field-scale assessments and predictions of soil N 2O emission remain uncertain and imprecise due to the episodic and microscale nature of microbial N 2O production, most of which occurs within very small discrete soil volumes. Such hotspots of N 2O production are often associated with decomposing plant residue. Here we quantify physical and hydrological soil characteristics that lead to strikingly accelerated N 2O emissions in plant residue-induced hotspots. Results reveal a mechanism for microscale N 2O emissions: water absorption by plant residue that createsmore » unique micro-environmental conditions, markedly different from those of the bulk soil. Moisture levels within plant residue exceeded those of bulk soil by 4–10-fold and led to accelerated N 2O production via microbial denitrification. The presence of large (Ø >35 μm) pores was a prerequisite for maximized hotspot N 2O production and for subsequent diffusion to the atmosphere. Understanding and modelling hotspot microscale physical and hydrologic characteristics is a promising route to predict N 2O emissions and thus to develop effective mitigation strategies and estimate global fluxes in a changing environment.« less

  18. Synthesis of mononuclear copper(II) complexes of N3O2 and N4O2 donors containing Schiff base ligands: Theoretical and biological observations

    NASA Astrophysics Data System (ADS)

    Mancha Madha, K.; Gurumoorthy, P.; Arul Antony, S.; Ramalakshmi, N.

    2017-09-01

    A new series of six mononuclear copper(II) complexes were synthesized from N3O2 and N4O2 donors containing Schiff base ligands, and characterized by various spectral methods. The geometry of the complexes was determined using UV-Vis, EPR and DFT calculations. The complexes of N3O2 donors (1-3) adopted square pyramidal geometry and the remaining complexes of N4O2 donors (4-6) show distorted octahedral geometry around copper(II) nuclei. Redox properties of the complexes show a one-electron irreversible reduction process in the cathodic potential (Epc) region from -0.74 to -0.98 V. The complexes show potent antioxidant activity against DPPH radicals. Molecular docking studies of complexes showed σ-π interaction, hydrogen bonding, electrostatic and van der Waals interactions with VEGFR2 kinase receptor. In vitro cytotoxicity of the complexes was tested against human breast cancer (MDA-MB-231) cell lines and one normal human dermal fibroblasts (NHDF) cell line through MTT assay. The morphological assessment data obtained by Hoechst 33258 and AO/EB staining revealed that the complexes induce apoptosis pathway of cell death.

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

    PubMed Central

    Yang, Jingbin; Li, Dongxu; Fang, Yuan

    2017-01-01

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

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

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

    Bejarano, Paula A.; Levendis, Yiannis A.

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

  1. Detection of stratospheric N2O5 by infrared remote sounding

    NASA Technical Reports Server (NTRS)

    Toon, G. C.; Farmer, C. B.; Norton, R. H.

    1986-01-01

    Measurements of N2O5 absorption (1230 and 1260 per cm) in infrared spectra were carried out using the Atmospheric Trace Molecule Spectroscopy (ATMOS) instruments on board Spacelab 3. The detection of stratospheric N2O5, a temporary reservoir species whose photolysis products catalyze ozone destruction, was confirmed. Preliminary analysis of spectra recorded at sunrise on 1 May 1985 indicates a peak volume mixing ratio of 1.6 x 10 the -9th at 35 km an altitude of 35 km, or a broad concentration peak pf 4 x 10 to the 8th molecules per cu cm between 21 and 35 km. Absorption was not detected in spectra measured at sunset due to the depletion of N2O5 by photolysis during the day. The volume mixing ratio profile of N2O5 between 0 and 75 km altitude is reproduced in graphic form.

  2. Spray process for in situ synthesizing Ti(C,N)-TiB2-Al2O3 composite ceramic coatings

    NASA Astrophysics Data System (ADS)

    Zhou, Jian; Liu, Hongwei; Sun, Sihao

    2017-12-01

    Using core wires with Ti-B4C-C as core and Al as strip materials, Ti(C,N)-TiB2-Al2O3 composite ceramic coatings were prepared on 45 steel substrates by the reactive arc spray technology. The influence of spray voltage, current, gas pressure and distance on the coatings was discussed. The spray parameters were optimized with porosity of the coatings as evaluation standard. The results showed that the most important factor which influences the quality of the coatings was spray distance. Then spray gas pressure, current and voltage followed in turn. The optimum process was spray current of 120A, voltage of 36, gas pressure of 0.7MPa and distance of 160mm. The porosity of coatings prepared in this spray process was only 2.11%. The coatings were composed of TiB2, TiC0.3N0.7, TiN, Al2O3 and AlN. Good properties and uniform distribution of these ceramic phases made the coatings have excellent comprehensive performances.

  3. Solubility and diffusivity of N{sub 2}O and CO{sub 2} in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-1-propanol + water)

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

    Li, M.H.; Lai, M.D.

    1995-03-01

    Solutions of amines are frequently used in gas-treating processes to remove acid gases, such as CO{sub 2} and H{sub 2}S, from gas streams in the natural gas and synthetic ammonia industries and petroleum chemical plants. The solubility and diffusivity of N{sub 2}O in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-l-propanol + water) were measured at 30, 35, and 40 C and at atmospheric pressure. Six (monoethanolamine + N-methyldiethanolamine + water) and five (monoethanolamine + 2-amino-2-methyl-l-propanol + water) systems were studied. The total amine mass percent in all cases was 30. The solubilities were measured by a solubilitymore » apparatus similar to that of Haimour and Sandall (1984). A wetted wall column absorber was used to obtain the diffusivity of N{sub 2}O in amines. The N{sub 2}O solubilities in amine solutions have been correlated on the basis of the excess Henry constant correlation of Wang et al. (1992). The N{sub 2}O analogy was used to estimate the solubility and diffusivity of CO{sub 2} in (monoethanolamine + N-methyldiethanolamine + water) and in (monoethanolamine + 2-amino-2-methyl-l-propanol + water).« less

  4. Enhancement by O6-benzyl-N2-acetylguanosine of N'-[2-chloroethyl]-N-[2-(methylsulphonyl)ethyl]-N'-nitrosourea therapeutic index on nude mice bearing resistant human melanoma.

    PubMed Central

    Debiton, E.; Cussac-Buchdhal, C.; Mounetou, E.; Rapp, M.; Dupuy, J. M.; Maurizis, J. C.; Veyre, A.; Madelmont, J. C.

    1997-01-01

    The exposure of cells to O6-benzyl-N2-acetylguanosine (BNAG) and several guanine derivatives is known to reduce the activity of O6-alkylguanine-DNA alkyltransferase (MGMT) and to enhance the sensitivity of Mer+ (methyl enzyme repair positive) tumour cells to chloroethylnitrosoureas (CENUs) in vitro and in vivo. High water solubility and the pharmacokinetic properties of BNAG make it a candidate for simultaneous administration with CENUs by the i.v. route in human clinical use. In vivo we have shown previously that BNAG significantly increases the efficiency of N'-[2-chloroethyl]-N-[2-(methylsulphonyl)ethyl]-N'-nitrosourea (cystemustine) against M4Beu melanoma cells (Mer+) through its cytostatic activity by the i.p. route, but also increases its toxicity. To investigate the toxicity of BNAG and cystemustine when administered simultaneously in mice, we compared the maximum tolerated dose and LD50 doses of cystemustine alone or in combination with 40 mg kg(-1) BNAG by the i.p. route. The toxicity of cystemustine was enhanced by a factor of almost 1.44 when combined with BNAG. To compare the therapeutic index of cystemustine alone and the cystemustine/BNAG combination, pharmacological tests were carried out in nude mice bearing Mer+ M4Beu human melanoma cells. Isotoxic doses were calculated using the 1.44 ratio. The treatments were administered three times by the i.v. route on days 1, 5 and 9 after s.c. inoculation of tumour cells. Although the toxicities of the treatments were equal, BNAG strongly enhanced tumour growth inhibition. These results demonstrate the increase of the therapeutic index of cystemustine by BNAG and justify the use of BNAG to enhance nitrosourea efficiency in vivo by i.v. co-injection. PMID:9365163

  5. Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

    USGS Publications Warehouse

    Wang, Bronwen; Burau, Richard G.

    1995-01-01

    Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.

  6. Temperature dependence of the reaction N2(A3Σu+)+O in the terrestrial thermosphere

    NASA Astrophysics Data System (ADS)

    Hill, Steven M.; Solomon, Stanley C.; Cleary, David D.; Broadfoot, A. Lyle

    2000-05-01

    Previous models for dayglow and auroral emissions of the N2(A3Σu+->X1Σg+) Vegard-Kaplan (VK) bands and O(1S) lines, when based on laboratory rate coefficients, disagree with observations. The problem has two parts: the overall rate of N2(A)+O and the state-specific yield of O(1S). Resolving these discrepancies should yield more accurate determinations of atomic oxygen density by remote sensing of the 2972 and 5577 Å lines. To solve the problem, the sources and sinks of O(1S) are considered using dayglow observations from 105 to 315 km and a numerical model. Line and band intensities are extracted from the data using a multiple regression fit to synthetic spectra. A photoelectron and photochemical model is used to analyze the resulting vertical emission profiles. N2 Second Positive (2P) altitude profiles indicate that photoelectron excitation of the N2 triplet system is modeled with an absolute uncertainty of +/-23%. The VK/2P intensity ratio suggests that laboratory rate coefficients for the reaction N2(Aν'=0,1,2)+O should be increased by a factor of 1.74 to 2.34. However, the laboratory rates were measured at room temperature. When the effect of high thermospheric temperatures on collision frequency is accounted for the rate coefficients for ν'=0, 1, and 2 are found to be (3.4+/-0.8)×10-11(T/298)1/2, (5.6+/-1.3)×10-11(T/298)1/2, and (4.8+/-1.2)×10-11(T/298)1/2cm3s-1. At 298 K, the ν'=0 and 2 values are within 5% of the laboratory values, but for ν'=1 the value is 40% larger than the laboratory value. The effective quantum yield of O(1S) by N2(A)+O is found to be 0.47+/-0.17. The observations support a photoelectron cross section for O(1S) that is consistent with laboratory measurements, but about 2.0 times larger than theoretical calculations.

  7. N2O reduction over a fullerene-like boron nitride nanocage: A DFT study

    NASA Astrophysics Data System (ADS)

    Esrafili, Mehdi D.

    2017-07-01

    We study, for the first time, the adsorption and catalytic decomposition of N2O molecule over a fullerene-like boron nitride nanocage (B12N12) using density functional theory calculations. It is found that the electron donating property of the cage plays an important role in the adsorption and activation of N2O. By the incorporation of a carbon atom into B12N12 cluster, our results indicate that the adsorption of N2O over B11N12C or B12N11C is more stronger than over pristine B12N12. The decomposition of N2O into N2 and O species over the C-doped clusters is energetically more favorable than that on B12N12. Moreover, the C-doping plays an important role in reducing the activation barrier for the CO + O* reaction over B12N12 surface.

  8. Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

    USGS Publications Warehouse

    Böhlke, J.K.; Smith, R.L.; Hannon, J.E.

    2007-01-01

    Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible δ15N and δ18O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ15N and ±0.4−1.0‰ for δ18O) and moderately enriched 15N tracer levels (±20−50‰ for δ15N near 5000‰) for 5−20 nmol of NO2- (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO2-and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

  9. Reaction chemistry in rechargeable Li-O2 batteries.

    PubMed

    Lim, Hee-Dae; Lee, Byungju; Bae, Youngjoon; Park, Hyeokjun; Ko, Youngmin; Kim, Haegyeom; Kim, Jinsoo; Kang, Kisuk

    2017-05-22

    The seemingly simple reaction of Li-O 2 batteries involving lithium and oxygen makes this chemistry attractive for high-energy-density storage systems; however, achieving this reaction in practical rechargeable Li-O 2 batteries has proven difficult. The reaction paths leading to the final Li 2 O 2 discharge products can be greatly affected by the operating conditions or environment, which often results in major side reactions. Recent research findings have begun to reveal how the reaction paths may be affected by the surrounding conditions and to uncover the factors contributing to the difficulty in achieving the reactions of lithium and oxygen. This progress report describes the current state of understanding of the electrode reaction mechanisms in Li-O 2 batteries; the factors that affect reaction pathways; and the effect of cell components such as solvents, salts, additives, and catalysts on the discharge product and its decomposition during charging. This comprehensive review of the recent progress in understanding the reaction chemistry of the Li-O 2 system will serve as guidelines for future research and aid in the development of reliable high-energy-density rechargeable Li-O 2 batteries.

  10. Development of an atmospheric N2O isotopocule model and optimization procedure, and application to source estimation

    NASA Astrophysics Data System (ADS)

    Ishijima, K.; Takigawa, M.; Sudo, K.; Toyoda, S.; Yoshida, N.; Röckmann, T.; Kaiser, J.; Aoki, S.; Morimoto, S.; Sugawara, S.; Nakazawa, T.

    2015-07-01

    This paper presents the development of an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N2O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N2O isotopocules. Comparisons of time series of atmospheric N2O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N2O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N2O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N2O fluxes, including the isotopic information as additional constraints, could be realized.

  11. Development of an atmospheric N2O isotopocule model and optimization procedure, and application to source estimation

    NASA Astrophysics Data System (ADS)

    Ishijima, K.; Takigawa, M.; Sudo, K.; Toyoda, S.; Yoshida, N.; Röckmann, T.; Kaiser, J.; Aoki, S.; Morimoto, S.; Sugawara, S.; Nakazawa, T.

    2015-12-01

    This work presents the development of an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N2O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N2O isotopocules. Comparisons of time series of atmospheric N2O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N2O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N2O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N2O fluxes, including the isotopic information as additional constraints, could be realized.

  12. Lowering N2O emissions from soils using eucalypt biochar: the importance of redox reactions

    PubMed Central

    Quin, P; Joseph, S; Husson, O; Donne, S; Mitchell, D; Munroe, P; Phelan, D; Cowie, A; Van Zwieten, L

    2015-01-01

    Agricultural soils are the primary anthropogenic source of atmospheric nitrous oxide (N2O), contributing to global warming and depletion of stratospheric ozone. Biochar addition has shown potential to lower soil N2O emission, with the mechanisms remaining unclear. We incubated eucalypt biochar (550 °C) – 0, 1 and 5% (w/w) in Ferralsol at 3 water regimes (12, 39 and 54% WFPS) – in a soil column, following gamma irradiation. After N2O was injected at the base of the soil column, in the 0% biochar control 100% of expected injected N2O was released into headspace, declining to 67% in the 5% amendment. In a 100% biochar column at 6% WFPS, only 16% of the expected N2O was observed. X-ray photoelectron spectroscopy identified changes in surface functional groups suggesting interactions between N2O and the biochar surfaces. We have shown increases in -O-C = N /pyridine pyrrole/NH3, suggesting reactions between N2O and the carbon (C) matrix upon exposure to N2O. With increasing rates of biochar application, higher pH adjusted redox potentials were observed at the lower water contents. Evidence suggests that biochar has taken part in redox reactions reducing N2O to dinitrogen (N2), in addition to adsorption of N2O. PMID:26615820

  13. C=C bond cleavage on neutral VO3(V2O5)n clusters.

    PubMed

    Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

    2009-01-28

    The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

  14. Effects of dairy manure management in annual and perennial cropping systems on soil microbial communities associated with in situ N2O fluxes

    NASA Astrophysics Data System (ADS)

    Dunfield, Kari; Thompson, Karen; Bent, Elizabeth; Abalos, Diego; Wagner-Riddle, Claudia

    2016-04-01

    Liquid dairy manure (LDM) application and ploughing events may affect soil microbial community functioning differently between perennial and annual cropping systems due to plant-specific characteristics stimulating changes in microbial community structure. Understanding how these microbial communities change in response to varied management, and how these changes relate to in situ N2O fluxes may allow the creation of predictive models for use in the development of best management practices (BMPs) to decrease nitrogen (N) losses through choice of crop, plough, and LDM practices. Our objectives were to contrast changes in the population sizes and community structures of genes associated with nitrifier (amoA, crenamoA) and denitrifier (nirK, nirS, nosZ) communities in differently managed annual and perennial fields demonstrating variation in N2O flux, and to determine if differences in these microbial communities were linked to the observed variation in N2O fluxes. Soil was sampled in 2012 and in 2014 in a 4-ha spring-applied LDM grass-legume (perennial) plot and two 4-ha corn (annual) treatments under fall or spring LDM application. Soil DNA was extracted and used to target N-cycling genes via qPCR (n=6) and for next-generation sequencing (Illumina Miseq) (n=3). Significantly higher field-scale N2O fluxes were observed in the annual plots compared to the perennial system; however N2O fluxes increased after plough down of the perennial plot. Nonmetric multidimensional scaling (NMS) indicated differences in N-cycling communities between annual and perennial cropping systems, and some communities became similar between annual and perennial plots after ploughing. Shifts in these communities demonstrated relationships with agricultural management, which were associated with differences in N2O flux. Indicator species analysis was used to identify operational taxonomic units (OTUs) most responsible for community shifts related to management. Nitrifying and denitrifying soil

  15. Structural, electronic, and magnetic properties of Y(n)O (n=2-14) clusters: Density functional study.

    PubMed

    Yang, Zhi; Xiong, Shi-Jie

    2008-09-28

    The geometries stability, electronic properties, and magnetism of Y(n)O clusters up to n=14 are systematically studied with density functional theory. In the lowest-energy structures of Y(n)O clusters, the equilibrium site of the oxygen atom gradually moves from an outer site of the cluster, via a surface site, and finally, to an interior site as the number of the Y atoms increases from 2 to 14. Starting from n=12, the O atom falls into the center of the cluster with the Y atoms forming the outer frame. The results show that clusters with n=2, 4, 8, and 12 are more stable than their respective neighbors, and that the total magnetic moments of Y(n)O clusters are all quite small except Y(12)O cluster. The lowest-energy structure of Y(12)O cluster is a perfect icosahedron with a large magnetic moment 6mu(B). In addition, we find that the total magnetic moments are quenched for n=2, 6, and 8 due to the closed-shell electronic configuration. The calculated ionization potentials and electron affinities are in good agreement with the experimental results, which imply that the present theoretical treatments are satisfactory.

  16. Strategies to mitigate N2O emissions from biological nitrogen removal systems.

    PubMed

    Desloover, Joachim; Vlaeminck, Siegfried E; Clauwaert, Peter; Verstraete, Willy; Boon, Nico

    2012-06-01

    N2O emissions from the biological treatment of sewage, manure, landfill leachates and industrial effluents have gained considerable interest among policy makers and environmental scientists. Estimated global emission rates from these sources can contribute up to 10% of the anthropogenic N2O emissions. Particularly at the level of a treatment plant, the N2O impact can be very significant and reach up to 80% of the operational CO2 footprint. Imperfect nitritation by an imbalance in the two-step nitritation metabolism of ammonia-oxidizing bacteria is considered as the main contributor to N2O production with hydroxylamine and particularly nitrite as key precursors. Monitoring of these compounds is warranted to understand and abate N2O emissions. Mitigation strategies should also comprise optimizations of the process parameters as well as bio-augmentative approaches empowered to restore the functional capacity and to deal with unwanted accumulation of intermediates. These strategies require validation for their effectiveness and costs at full-scale. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Novel microelectrode-based online system for monitoring N2O gas emissions during wastewater treatment.

    PubMed

    Marques, Ricardo; Oehmen, Adrian; Pijuan, Maite

    2014-11-04

    Clark-type nitrous oxide (N2O) microelectrodes are commonly used for measuring dissolved N2O levels, but have not previously been tested for gas-phase applications, where the N2O emitted from wastewater systems can be directly quantified. In this study, N2O microelectrodes were tested and validated for online gas measurements, and assessed with respect to their temperature, gas flow, composition dependence, gas pressure, and humidity. An exponential correlation between temperature and sensor signal was found, whereas gas flow, composition, pressure, and humidity did not have any influence on the signal. Two of the sensors were tested at different N2O concentration ranges (0-422.3, 0-50, 0-10, and 0-2 ppmv N2O) and exhibited a linear response over each range. The N2O emission dynamics from two laboratory scale sequencing batch reactors performing ammonia or nitrite oxidation were also monitored using one of the microsensors and results were compared with two other analytical methods. Results show that N2O emissions were accurately described with these microelectrodes and support their application for assessing gaseous N2O emissions from wastewater treatment systems. Advantages of the sensors as compared to conventional measurement techniques include a wider quantification range of N2O fluxes, and a single measurement system that can assess both liquid and gas-phase N2O dynamics.

  18. Cocrystals of 6-propyl-2-thiouracil: N-H···O versus N-H···S hydrogen bonds.

    PubMed

    Tutughamiarso, Maya; Egert, Ernst

    2011-11-01

    In order to investigate the relative stability of N-H···O and N-H···S hydrogen bonds, we cocrystallized the antithyroid drug 6-propyl-2-thiouracil with two complementary heterocycles. In the cocrystal pyrimidin-2-amine-6-propyl-2-thiouracil (1/2), C(4)H(5)N(3)·2C(7)H(10)N(2)OS, (I), the `base pair' is connected by one N-H···S and one N-H···N hydrogen bond. Homodimers of 6-propyl-2-thiouracil linked by two N-H···S hydrogen bonds are observed in the cocrystal N-(6-acetamidopyridin-2-yl)acetamide-6-propyl-2-thiouracil (1/2), C(9)H(11)N(3)O(22C(7)H(10)N(2)OS, (II). The crystal structure of 6-propyl-2-thiouracil itself, C(7)H(10)N(2)OS, (III), is stabilized by pairwise N-H···O and N-H···S hydrogen bonds. In all three structures, N-H···S hydrogen bonds occur only within R(2)(2)(8) patterns, whereas N-H···O hydrogen bonds tend to connect the homo- and heterodimers into extended networks. In agreement with related structures, the hydrogen-bonding capability of C=O and C=S groups seems to be comparable.

  19. Bis[4-(4-pyridyl)pyridinium] (4-carboxy­pyridine-2,6-dicarboxyl­ato-κ3 O 2,N,O 6)(pyridine-2,4,6-tricarboxyl­ato-κ3 O 2,N,O 6)ferrate(III) trihydrate

    PubMed Central

    Zhao, Li; Dong, You-Ren; Xie, Hong-Zhen

    2009-01-01

    In the title salt, (C10H9N2)2[Fe(C8H2NO6)(C8H3NO6)]·3H2O, the FeIII atom is O,N,O′-chelated by dianionic and trianionic ligands in a slightly distorted octa­hedral coordination geometry. The cations and ferrate anions are linked into a layered structure; the layers are connected through the uncoordinated water mol­ecules into a hydrogen-bonded three-dimensional supra­molecular structure. One of the uncoordinated water molecules is disordered around an inversion centre and was refined with half-occupancy for each position. PMID:21582387

  20. Potassium (2,2′-bipyridine-κ2 N,N′)bis­(carbonato-κ2 O,O′)cobaltate(III) dihydrate

    PubMed Central

    Wang, Jian-Fei; Lin, Jian-Li

    2010-01-01

    In the title compound, K[Co(CO3)2(C10H8N2)]·2H2O, 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 octa­hedral N2O4 environment. The [Co(bipy)(CO3)2]− (bipy is 2,2′-bipyridine) ­units are stacked along [100] via π–π stacking inter­actions, with inter­planar distances between the bipyridine rings of 3.36 (4) and 3.44 (6) Å, forming chains. Classical O—H⋯O hydrogen-bonding inter­actions link the chains, forming channels along (100) in which the K+ ions reside and leading to a three-dimensional supra­molecular architecture. PMID:21587447