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.

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.

2′-O-[2-[(N,N-dimethylamino)oxy]ethyl]-modified oligonucleotides inhibit expression of mRNA in vitro and in vivo

PubMed Central

Prakash, Thazha P.; Johnston, Joseph F.; Graham, Mark J.; Condon, Thomas P.; Manoharan, Muthiah

2004-01-01

Synthesis and antisense activity of oligonucleotides modified with 2′-O-[2-[(N,N-dimethylamino)oxy] ethyl] (2′-O-DMAOE) are described. The 2′-O-DMAOE-modified oligonucleotides showed superior metabolic stability in mice. The phosphorothioate oligonucleotide ‘gapmers’, with 2′-O-DMAOE- modified nucleoside residues at the ends and 2′-deoxy nucleosides residues in the central region, showed dose-dependent inhibition of mRNA expression in cell culture for two targets. ‘Gapmer’ oligonucleotides have one or two 2′-O-modified regions and a 2′-deoxyoligonucleotide phosphorothioate region that allows RNase H digestion of target mRNA. To determine the in vivo potency and efficacy, BalbC mice were treated with 2′-O-DMAOE gapmers and a dose-dependent reduction in the targeted C-raf mRNA expression was observed. Oligonucleotides with 2′-O-DMAOE modifications throughout the sequences reduced the intercellular adhesion molecule-1 (ICAM-1) protein expression very efficiently in HUVEC cells with an IC50 of 1.8 nM. The inhibition of ICAM-1 protein expression by these uniformly modified 2′-O-DMAOE oligonucleotides may be due to selective interference with the formation of the translational initiation complex. These results demonstrate that 2′-O-DMAOE- modified oligonucleotides are useful for antisense-based therapeutics when either RNase H-dependent or RNase H-independent target reduction mechanisms are employed. PMID:14762210

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

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

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.

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.

Interannual Variability in Soil Trace Gas (CO2, N2O, NO) Fluxes and Analysis of Controllers

NASA Technical Reports Server (NTRS)

Potter, C.; Klooster, S.; Peterson, David L. (Technical Monitor)

1997-01-01

-1988) were estimated at 57.1 Pg C-CO2yr-1, 9.8Tg (1012 g) N-NO yr-1, and 9.7 Tg N-N2O yr-1. Chemical fertilizer contributions to global soil N gas fluxes were estimated at between 1.3 to 7.3 Tg N-NO yr-1, and 1.2 to 4.0 Tg N-N2O yr-1.

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

Structure of human IFIT1 with capped RNA reveals adaptable mRNA binding and mechanisms for sensing N1 and N2 ribose 2′-O methylations

PubMed Central

Laudenbach, Beatrice Theres; Martínez-Montero, Saúl; Cencic, Regina; Habjan, Matthias; Pichlmair, Andreas; Damha, Masad J.; Pelletier, Jerry; Nagar, Bhushan

2017-01-01

IFIT1 (IFN-induced protein with tetratricopeptide repeats-1) is an effector of the host innate immune antiviral response that prevents propagation of virus infection by selectively inhibiting translation of viral mRNA. It relies on its ability to compete with the translation initiation factor eIF4F to specifically recognize foreign capped mRNAs, while remaining inactive against host mRNAs marked by ribose 2′-O methylation at the first cap-proximal nucleotide (N1). We report here several crystal structures of RNA-bound human IFIT1, including a 1.6-Å complex with capped RNA. IFIT1 forms a water-filled, positively charged RNA-binding tunnel with a separate hydrophobic extension that unexpectedly engages the cap in multiple conformations (syn and anti) giving rise to a relatively plastic and nonspecific mode of binding, in stark contrast to eIF4E. Cap-proximal nucleotides encircled by the tunnel provide affinity to compete with eIF4F while allowing IFIT1 to select against N1 methylated mRNA. Gel-shift binding assays confirm that N1 methylation interferes with IFIT1 binding, but in an RNA-dependent manner, whereas translation assays reveal that N1 methylation alone is not sufficient to prevent mRNA recognition at high IFIT1 concentrations. Structural and functional analysis show that 2′-O methylation at N2, another abundant mRNA modification, is also detrimental for RNA binding, thus revealing a potentially synergistic role for it in self- versus nonself-mRNA discernment. Finally, structure-guided mutational analysis confirms the importance of RNA binding for IFIT1 restriction of a human coronavirus mutant lacking viral N1 methylation. Our structural and biochemical analysis sheds new light on the molecular basis for IFIT1 translational inhibition of capped viral RNA. PMID:28251928

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.

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

PubMed

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

2010-10-14

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

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

NASA Astrophysics Data System (ADS)

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

2010-10-01

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

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.

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.

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.

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.

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.

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.

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

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2015-07-14

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

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

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

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

High Level ab initio Predictions of the Energetics of mCO2•(H2O)n (n = 1-3, m = 1-12) Clusters

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

Thanthiriwatte, Sahan; Duke, Jessica R.; Jackson, Virgil E.

Electronic structure calculations at the correlated molecular orbital theory and density functional theory levels have been used to generate a reliable set of clustering energies for up to three water molecules in carbon dioxide clusters up to n = 12. The structures and energetics are dominated by Lewis acid-base interactions with hydrogen bonding interactions playing a lesser energetic role. The actual binding energies are somewhat larger than might be expected. The correlated molecular orbital MP2 method and density functional theory with the ωB97X exchange-correlation functional provide good results for the energetics of the clusters but the B3LYP and ωB97X-D functionalsmore » do not. Seven CO2 molecules form the first solvent shell about a single H2O with four CO2 molecules interacting with the H2O via Lewis acid-base interactions, two CO2 interacting with the H2O by hydrogen bonds, and the seventh CO2 completing the shell. The Lewis acid-base and weak hydrogen bond interactions between the water molecules and the CO2 molecules are strong enough to disrupt the trimer ring configuration for as few as seven CO2 molecules. Calculated 13C NMR chemical shifts for mCO2•(H2O)n show little change with respect to the number of H2O or CO2 molecules in the cluster. The O-H stretching frequencies do exhibit shifts that can provide information about the interactions between water and CO2 molecules.« less

Chemical stabilization and high pressure synthesis of Ba-free Hg-based superconductors, (Hg,M)Sr2Ca(n-1)Cu(n)O(y)(n=1 to approximately 3)

NASA Technical Reports Server (NTRS)

Kishio, K.; Shimoyama, J.; Hahakura, S.; Kitazawa, K.; Yamaura, K.; Hiroi, Z.; Takano, M.

1995-01-01

A homologous series of new Hg-based HTSC compounds, (Hg,M)Sr2Ca(n - 1)Cu(n)P(y) with n = 1 to 3, have been synthesized. The stabilization of the pure phases have been accomplished by chemical doping of third elements such as M = Cr, Mo and Re. While the Hgl2O1(n = 1) phase was readily obtained in this way, it was necessary to simultaneously dope Y into the Ca site to stabilize the Hg1212(n = 2) phase. On the other hand, single-phase Y-free Hg1212(n = 2) and Hg1223 (n = 3) samples were synthesized only under a high pressure of 6 GPa. In sharp contrast to the Ba containing compounds, all the samples prepared in the present study have been quite stable during the synthesis and no deterioration in air has been observed after the preparation.

Beyond the Methanogenic Black-Box: Greenhouse Gas Fluxes (CO2, CH4, N2O) as Evidence for Wetlands as Dynamic Redox Systems

NASA Astrophysics Data System (ADS)

Mcnicol, G.; Knox, S. H.; Sturtevant, C. S.; Baldocchi, D. D.; Silver, W. L.

2015-12-01

Seminal wetland research in the 1990s demonstrated that annual methane (CH4) fluxes scaled positively with ecosystem production across distinctive wetlands globally. This relationship implies a model of flooded wetland ecosystems as 'methanogenic black-boxes'; poised at a low redox state, and tending to release a fixed fraction of incoming annual productivity as CH4. In contrast, recent studies have reported high ratios of carbon dioxide (CO2) to CH4 emissions, and are adding to a body of evidence suggesting wetlands can vary more widely in their redox state. To explore this apparent incongruence we used principles of redox thermodynamics and laboratory experiments to develop predictions of wetland greenhouse gas (GHG) fluxes under different redox regimes. We then used a field study to test the hypothesis that ecosystem seasonality in gross primary productivity (GPP) and temperature would drive changes in GHG emissions, mediated by a dynamic - as opposed to static - redox regime. We estimated wetland GHG emissions from an emergent marsh in the Sacramento Delta, CA from March 2014-2015. We measured CO2, CH4 and N2O emissions via diffusion and ebullition with manual sampling, and whole-ecosystem fluxes of CO2 and CH4 using eddy-covariance. Ebullition and diffusive CH4 fluxes were strongly seasonal, with minimum rates (0.86 and 0.35 mg C-CH­­4 m-2 yr-1, respectively) during winter, and maximum rates (1.3 and 1.8 g C-CH­­4 m-2 yr-1, respectively) during the summer growing season. In contrast, winter diffusive CO2 fluxes (494 g C-CO2 m-2 yr-1) and fall bubble CO2 concentrations (1.49%) were highest, despite being seasons of lower GPP, temperature, and CH4 flux. Further, diffusive and ebullition fluxes of N2O showed zero net flux only during spring and summer months, whereas the wetland was a significant source of N2O during winter (81.2 ± 24.4 mg N-N2O m-2 yr-1). These seasonal flux dynamics contradict a 'methanogenic black box' model of wetland redox, which

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

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

A theoretical study of the positive and dipositive ions of M(NH3)n and M(H2O)n for M = Mg, Ca, or Sr

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Sodupe, Mariona; Partridge, Harry

1992-01-01

The structure and binding energies are determined for many of the M(H2O)n(+) and M(H2O)n(2+) species, for n = 1-3 and M = Mg, Ca, or Sr. The trends are explained in terms of metal sp or sd-sigma hybridization and core polarization. The M(NH3)n(+) systems, with M = Mg or Sr, are also studied. For the positive ions, the low-lying excited states are also studied and compared with experiment. The calculations suggest an alternative interpretation of the SrNH3(+) spectrum.

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

short period of one month. Landscape position strongly affected cumulative N2O emissions which were more than three times higher in footslope position (annual budget of 4 kg N-N2O ha-1 yr-1) than in shoulder (1.1 kg N-N2O ha-1 yr-1) or slope positions (1.1 and 1.2 kg N-N2O ha-1 yr-1), where soil water contents were higher (mean 68.4% WFPS in footslope position whereas mean WFPS were 50.4 and 60.5% in slope positions and 58% in shoulder position). N2O emissions were relatively low (0.5 kg N-N2O ha-1 yr-1) and did not show much annual variation in unfertilized riparian buffer. Garnier, J., Billen, G., Vilain, G., Martinez, A., Silvestre, M., Mounier, E., & Toche, F., 2009. Nitrous oxide (N2O) in the Seine river and basin: Observations and budgets. Agriculture, Ecosystems & Environment 133, 223-233. IPCC, 2007. Climate change 2007: the physical science basis. Summary for Policy Makers, Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change. Izaurralde, R. C., Lemke, R. L., Goddard, T. W., McConkey, B., & Zhang, Z., 2004. Nitrous Oxide Emissions from Agricultural Toposequences in Alberta and Saskatchewan. Soil Sci Soc Am J 68, 1285-1294.

Phase coexistence and exchange-bias effect in LiM n2O4 nanorods

NASA Astrophysics Data System (ADS)

Zhang, X. K.; Yuan, J. J.; Xie, Y. M.; Yu, Y.; Kuang, F. G.; Yu, H. J.; Zhu, X. R.; Shen, H.

2018-03-01

In this paper, the magnetic properties of LiM n2O4 nanorods with an average diameter of ˜100 nm and length of ˜1 μ m are investigated. The temperature dependences of dc and ac susceptibility measurements show that LiM n2O4 nanorods experience multiple magnetic phase transitions upon cooling, i.e., paramagnetic (PM), antiferromagnetic (AFM), canted antiferromagnetic (CAFM), and cluster spin glass (SG). The coexistence between a long-range ordered AFM phase due to a M n4 +-M n4 + interaction and a cluster SG phase originating from frozen AFM clusters at low temperature in LiM n2O4 nanorods is elucidated. Field-cooled hysteresis loops (FC loops) and magnetic training effect (TE) measurements confirm the presence of an exchange-bias (EB) effect in LiM n2O4 nanorods below the Néel temperature (TN˜60 K ) . Furthermore, by analyzing the TE, we conclude that the observed EB effect originates completely from an exchange coupling interaction at the interface between the AFM and cluster SG states. A phenomenological model based on phase coexistence is proposed to interpret the origin of the EB effect below 60 K in the present compound. In turn, the appearance of the EB effect further supports the coexistence of AFM order along with a cluster SG state in LiM n2O4 nanorods.

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.

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.

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.

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.

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.

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.

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

Broadband Dielectric Spectroscopy of Ruddlesden-Popper Srn+1TinO3n+1 (n = 1,2,3) Thin Films

DTIC Science & Technology

2009-01-29

permittivity, strontium compounds N. D. Orloff, W. Tian, C. J. Fennie , C. H. Lee, D. Gu, J. Mateu, X. X. Xi, K. M. Rabe, D. G. Schlom, I. Takeuchi, J...of Ruddlesden–Popper Srn+1TinO3n+1 (n = 1,2,3) thin films N. D. Orloff, W. Tian, C. J. Fennie , C. H. Lee, D. Gu et al. Citation: Appl. Phys. Lett... Fennie ,4 C. H. Lee,3,5 D. Gu,2 J. Mateu,6 X. X. Xi,5 K. M. Rabe,7 D. G. Schlom,3 I. Takeuchi,1 and J. C. Booth2 1Department of Materials Science and

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.

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.

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

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.

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.

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.

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.

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.

The Regulation of CH4 and N2O fluxes by Wetlands at Landscape Level

NASA Astrophysics Data System (ADS)

Soosaar, K.; Maddison, M.; Salm, J. O.; Järveoja, J.; Hansen, R.; Mander, Ü.

2012-04-01

: median values 4.2, 1.4, 1.1, and 0.9 kg N2O-N ha-1 y-1, respectively. In peatlands, median values of CH4-C were 85.2, 23.7, 0.07 and 0.12 kg ha-1 yr-1, and N2O-N -0.05, -0.01, 0.18 and 0.19 kg ha-1 yr-1, respectively. There were significantly higher emissions of N2O from abandoned and active peat mining areas, whereas CH4 emissions were significantly higher in natural and drained areas. We also found that the buffering capacity of long-term loaded riparian alder forests in agricultural landscapes will decrease over time, which calls for the careful management of these riparian forests. Mitsch, W.J, Zhang, L., Stefanik, K.C., Nahlik, A.M., Anderson, C.J., Bernal, B., Hernandez, M., Song, K. 2012. Creating wetlands: Primary succession, water quality changes, and self-design over 15 years. BioScience in press Zedler, JB. 2003. Wetlands at your service: reducing impacts of agriculture at the watershed scale. Front. Ecol. Environ., 1, pp. 65-72 Teiter, S., Mander, U. 2005. Emission of N2O, N2, CH4, and CO2 from constructed wetlands for wastewater treatment and from riparian buffer zones. Ecol. Eng., 25, pp. 528-541 Thiere, G., Stadmark, J., Weisner, SEB. 2011. Nitrogen retention versus methane emission: Environmental benefits and risks of large-scale wetland creation. Ecol. Eng., 37, pp. 6-15

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.

Soil-atmospheric exchange of CO2, CH4, and N2O in three subtropical forest ecosystems in southern China

USGS Publications Warehouse

Tang, X.; Liu, S.; Zhou, G.; Zhang, Dongxiao; Zhou, C.

2006-01-01

The magnitude, temporal, and spatial patterns of soil-atmospheric greenhouse gas (hereafter referred to as GHG) exchanges in forests near the Tropic of Cancer are still highly uncertain. To contribute towards an improvement of actual estimates, soil-atmospheric CO2, CH4, and N2O fluxes were measured in three successional subtropical forests at the Dinghushan Nature Reserve (hereafter referred to as DNR) in southern China. Soils in DNR forests behaved as N2O sources and CH4 sinks. Annual mean CO2, N2O, and CH4 fluxes (mean ?? SD) were 7.7 ?? 4.6MgCO2-Cha-1 yr-1, 3.2 ?? 1.2 kg N2ONha-1 yr-1, and 3.4 ?? 0.9 kgCH4-Cha-1 yr-1, respectively. The climate was warm and wet from April through September 2003 (the hot-humid season) and became cool and dry from October 2003 through March 2004 (the cool-dry season). The seasonality of soil CO2 emission coincided with the seasonal climate pattern, with high CO2 emission rates in the hot-humid season and low rates in the cool-dry season. In contrast, seasonal patterns of CH4 and N2O fluxes were not clear, although higher CH4 uptake rates were often observed in the cool-dry season and higher N2O emission rates were often observed in the hot-humid season. GHG fluxes measured at these three sites showed a clear increasing trend with the progressive succession. If this trend is representative at the regional scale, CO2 and N2O emissions and CH4 uptake in southern China may increase in the future in light of the projected change in forest age structure. Removal of surface litter reduced soil CO2 effluxes by 17-44% in the three forests but had no significant effect on CH4 absorption and N2O emission rates. This suggests that microbial CH4 uptake and N2O production was mainly related to the mineral soil rather than in the surface litter layer. ?? 2006 Blackwell Publishing Ltd.

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

PubMed

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

2015-08-10

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Structural and electronic properties of U{sub n}O{sub m} (n=1-3,m=1-3n) clusters: A theoretical study using screened hybrid density functional theory

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

Yang, Yu; Liu, Haitao; Zhang, Ping, E-mail: zhang-ping@iapcm.ac.cn

The structural and electronic properties of small uranium oxide clusters U{sub n}O{sub m} (n=1-3, m=1-3n) are systematically studied within the screened hybrid density functional theory. It is found that the formation of U–O–U bondings and isolated U–O bonds are energetically more stable than U–U bondings. As a result, no uranium cores are observed. Through fragmentation studies, we find that the U{sub n}O{sub m} clusters with the m/n ratio between 2 and 2.5 are very stable, hinting that UO{sub 2+x} hyperoxides are energetically stable. Electronically, we find that the O-2p states always distribute in the deep energy range, and the U-5fmore » states always distribute at the two sides of the Fermi level. The U-6d states mainly hybridize with the U-5f states in U-rich clusters, while hybridizing with O-2p states in O-rich clusters. Our work is the first one on the screened hybrid density functional theory level studying the atomic and electronic properties of the actinide oxide clusters.« less

Soil CO2 CH4 and N2O fluxes from an afforested lowland raised peatbog in Scotland: implications for drainage and restoration

NASA Astrophysics Data System (ADS)

Yamulki, S.; Anderson, R.; Peace, A.; Morison, J. I. L.

2013-02-01

The effect of tree (lodgepole pine) planting with and without intensive drainage on soil greenhouse gas (GHG) fluxes was assessed after 45 yr at a raised peatbog in West Flanders Moss, central Scotland. Fluxes of CO2 CH4 and N2O from the soil were monitored over a 2-yr period every 2 to 4 weeks using the static opaque chamber method in a randomised experimental block trial with the following treatments: drained and planted (DP), undrained and planted (uDP), undrained and unplanted (uDuP) and for reference also from an adjoining near-pristine area of bog at East Flanders Moss (n-pris). There was a strong seasonal pattern in both CO2 and CH4 effluxes which were significantly higher in late spring and summer months because of warmer temperatures. Effluxes of N2O were low and no significant differences were observed between the treatments. Annual CH4 emissions increased with the proximity of the water table to the soil surface across treatments in the order: DP < uDP < uDuP < n-pris with mean annual effluxes over the 2-yr monitoring period of 0.15, 0.64, 7.70 and 22.63 g CH4 m-2 yr-1, respectively. For CO2, effluxes increased in the order uDP < DP< n-pris < uDuP, with mean annual effluxes of 1.23, 1.66, 1.82 and 2.55 kg CO2 m-2 yr-1, respectively. CO2 effluxes dominated the total net GHG emission, calculated using the global warming potential (GWP) of the three GHGs for each treatment (76-98%), and only in the n-pris site was CH4 a substantial contribution (23%). Based on soil effluxes only, the near pristine (n-pris) peatbog had 43% higher total net GHG emission compared with the DP treatment because of high CH4 effluxes and the DP treatment had 33% higher total net emission compared with the uDP because drainage increased CO2 effluxes. Restoration is likely to increase CH4 emissions, but reduce CO2 effluxes. Our study suggests that if estimates of CO2 uptake by vegetation from similar peatbog sites were included, the total net GHG emission of restored peatbog would

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

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.

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.

Nitrogen availability and soil N2O emissions following conversion of forests to coffee in southern Sumatra

NASA Astrophysics Data System (ADS)

Verchot, Louis V.; Hutabarat, Lusida; Hairiah, Kurniatun; van Noordwijk, Meine

2006-12-01

Changes in land use impact on the N cycle with both local and global consequences. We examined how conversion of forest to agriculture in one catchment in southern Sumatra altered N availability and soil N2O emission. Measurements were made along a chronosequence of forest land converted to coffee gardens. A number of different management practices were also examined. Inorganic N stocks and N cycling rates were highest in the forest and lower in the coffee gardens. The forest and young conversion sites appeared to be N limited, whereas the older agricultural sites and the more intensively managed sites were not as strongly N limited. N2O emissions were low in the forest (<2 kgN ha-1yr-1) and increased sharply following deforestation. Emissions on recently cleared land were 4.6 kgN ha-1yr-1 and 8.4 kgN ha-1yr-1 in a 1-year-old coffee garden. Emissions in the older coffee gardens were lower with the lowest flux observed in a 10 year old site (1.8 kgN ha-1yr-1). We explored the effects of different types of management approaches that farmers are using in this landscape. Emissions in an 18-year-old multistrata coffee garden with a significant overstory of N fixing trees were 5 times greater (15.5 kg ha-1yr-1) than emissions from forests. We also found that intensive organic matter management produced high emissions. To understand the spatial and temporal variability of the N2O emissions we used the hole-in-the-pipe conceptual model. N2O fluxes were lowest on N limited sites. Soil water content also played an important role and emissions were highest when water filled pore space (WFPS) was between 85 and 95%. A number of formulations of this model have been applied in different ways over the years to explain spatial and temporal variation in the soil N-oxide flux, and in this study we found the mechanistic explanation useful. Our study suggests that land use change and intensification of agriculture in N limited highland landscapes may significantly increase the

Continuous multi-plot measurements of CO2, CH4, N2O and H2O in a managed boreal forest - The importance of accounting for all greenhouse gases

NASA Astrophysics Data System (ADS)

Vestin, P.; Mölder, M.; Sundqvist, E.; Båth, A.; Lehner, I.; Weslien, P.; Klemedtsson, L.; Lindroth, A.

2015-12-01

In order to assess the effects of different management practices on the exchange of greenhouse gases (GHG), it is desirable to perform repeated and parallel measurements on both experimental and control plots. Here we demonstrate how a system system combining eddy covariance and gradient techniques can be used to perform this assessment in a managed forest ecosystem.The net effects of clear-cutting and stump harvesting on GHG fluxes were studied at the ICOS site Norunda, Sweden. Micrometeorological measurements (i.e., flux-gradient measurements in 3 m tall towers) allowed for quantification of CO2, CH4 and H2O fluxes (from May 2010) as well as N2O and H2O fluxes (from June 2011) at two stump harvested plots and two control plots. There was one wetter and one drier plot of each treatment. Air was continuously sampled at two heights in the towers and gas concentrations were analyzed for CH4, CO2, H2O (LGR DLT-100, Los Gatos Research) and N2O, H2O (QCL Mini Monitor, Aerodyne Research). Friction velocities and sensible heat fluxes were measured by sonic anemometers (Gill Windmaster, Gill Instruments Ltd). Automatic chamber measurements (CO2, CH4, H2O) were carried out in the adjacent forest stand and at the clear-cut during 2010.Average CO2 emissions for the first year ranged between 14.4-20.2 ton CO2 ha-1 yr-1. The clear-cut became waterlogged after harvest and a comparison of flux-gradient data and chamber data (from the adjacent forest stand) indicated a switch from a weak CH4 sink to a significant source at all plots. The CH4 emissions ranged between 0.8-4.5 ton CO2-eq. ha-1 yr-1. N2O emissions ranged between 0.4-2.6 ton CO2-eq. ha-1 yr-1. Enhanced N2O emission on the drier stump harvested plot was the only clear treatment effect on GHG fluxes that was observed. Mean CH4 and N2O emissions for the first year of measurements amounted up to 29% and 20% of the mean annual CO2 emissions, respectively. This highlights the importance of including all GHGs

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.

Ground and canopy soil N2O fluxes from smallholder oil palm plantations following deforestation in Sumatra, Indonesia

NASA Astrophysics Data System (ADS)

Hassler, Evelyn; Corre, Marife D.; Kurniawan, Syahrul; Allen, Kara; Veldkamp, Edzo

2017-04-01

Due to an increasing global demand in cheap oils and biofuels, forest conversion to oil palm plantations is rapidly increasing in Indonesia. Although forest conversion is known to influence soil N2O fluxes, measurements from oil palm are scarce. Our study aimed to (1) quantify changes in soil N2O fluxes with forest conversion to oil palm plantations, (2) quantify the contribution of oil-palm canopy soil (lodged between the stems and leaf axils) to N2O fluxes, and (3) determine their controlling factors. In Jambi, Sumatra, we selected two landscapes that mainly differed in soil texture but both on heavily weathered soils: loam and clay Acrisol soils. Within each landscape, we investigated lowland forest, jungle rubber (rubber trees interspersed in secondary forest), both as the reference (previous) land uses, and the converted oil palm plantations by smallholders. Each land use had four replicate plots within each landscape. Each replicate plot had four permanently placed chambers, and soil N2O fluxes were measured monthly from December 2012 to December 2013 by placing vented static covers on chamber bases for 30 minutes for gas flux measurement. For oil-palm canopy soil, each replicate plot was represented by five oil palms, and each oil palm stem was delineated into three 1-m sections (low, middle, and top) in order to represent possible gradients of canopy soil conditions that influence N2O fluxes. Measurements were conducted from February 2013 to May 2014 by collecting canopy soil from each stem section and incubating it in-situ in an air-tight glass jar. Land-use conversion to smallholder plantations had no effect on soil N-oxide fluxes (P = 0.58 to 0.76) due to the inherently low soil N availability and the low N fertilization rates (commonly 48 to 88 kg N ha-1 yr-1) of smallholder oil palm plantations. Soil N2O fluxes (kg N ha-1 yr-1) were: 0.6 ± 0.1 to 1.2 ± 0.6 from the reference land uses and 1.0 ± 0.2 to 1.1 ± 0.5 from the smallholder oil palm

Production of NO and N2O by soil nitrifying bacteria

NASA Technical Reports Server (NTRS)

Lipschultz, F.; Wofsy, S. C.; Mcelroy, M. B.; Zafiriou, O. C.; Valois, F. W.; Watson, S. W.

1981-01-01

The composition of the atmosphere is influenced both directly and indirectly by biological activity. Evidence is presented here to suggest that nitrification in soil is a potentially significant source of both NO and N2O. Between 0.3 and 10% of the ammonium oxidized by cultures of the soil bacterium Nitrosomonas europaea is converted to these gases. The global source for NO associated with nitrification could be as large as 15,000,000 tonnes N/yr, with a source for N2O of 5,000,000-10,000,000 tonnes N/yr. Nitric oxide has a key role in tropospheric chemistry, participating in a complex set of reactions regulating OH and O3. Nitrous oxide is a dominant source of stratospheric NO and has a significant influence on climate.

Stratospheric CFCl3, CF2Cl2, and N2O height profile measurements at several latitudes

NASA Astrophysics Data System (ADS)

Goldan, P. D.; Kuster, W. C.; Albritton, D. L.; Schmeltekopf, A. L.

1980-01-01

The mixing ratios of CFCl3, CF2Cl2, and N2O have been measured as a function of altitude from 6 to 37 km above sea level by using a balloon-borne grab-sampling system. The 24 flights were made during the period July 1976 to March 1979 from Wyoming, Panama, Brazil, and Antarctica. These data are reported here both numerically and graphically, the latter being examined for latitudinal and temporal trends. A mean tropopause height for each location and date was used as the reference for the height profiles. The resulting set of CF2Cl2 and N2O profiles show a discernible dependence on latitude; the lapse rate of these mixing ratios is greater for the mid-latitudes when compared to the equatorial latitudes. The upper tropospheric portion of the CFCl3 and CF2Cl2 data show annual increases of 10.4±3.9 and 10.7±1.9%/yr, respectively, in the northern hemisphere for the middle of the measurement period (end of 1977). Furthermore, the limited number of southern hemispheric data for these constituents are about 8% lower than the northern hemispheric values but have a comparable annual increase. The corresponding N2O data show no interhemispheric differences and the possibility of only a slight increase (less than 2%/yr).

Effects of soil moisture and temperature on NO, NO2, and N2O emissions from European forest soils

NASA Astrophysics Data System (ADS)

Schindlbacher, Andreas; Zechmeister-Boltenstern, Sophie; Butterbach-Bahl, Klaus

2004-09-01

Emissions of NO, NO2, and N2O to the atmosphere were measured with a fully automated laboratory system from undisturbed soil columns obtained from five different temperate and one boreal forest sites. The soils were chosen to cover a transect through Europe, sandy and loamy textures, and different atmospheric nitrogen deposition rates. In a two-factorial experimental design, soil cores were kept under varying conditions with respect to temperature (range 5-20°C) and soil moisture (range 0-300 kPa). The combination of soil temperature and soil moisture could explain a better part of variations in NO (up to 74%) and N2O (up to 86%) emissions for individual soils, but average emissions differed significantly between various forest soils. Generally, NO and N2O were emitted from all soils except from the boreal pine forest soil, where NO was consumed. NO emissions from the German spruce forest receiving highest yearly nitrogen inputs of >35 kg ha-1 yr-1 ranged from 1.3 to 608.9 μg NO-N m-2 h-1 and largely exceeded emissions from other soils. Average N2O emissions from this soil tended also to be highest (171.7 ± 42.2 μg N2O-N m-2 h-1), but did not differ significantly from other soils. NO2 deposition occurred in all soils and strongly correlated to NO emissions. NO and N2O emissions showed a positive exponential relationship to soil temperature. With activation energies between 57 and 133 kJ mol-1, N2O emissions from the various soils responded more uniformely to temperature than NO emissions with 41 and 199 kJ mol-1. The two Austrian beech forest soils showed exceptionally high activation energies for NO emissions, which might be attributed to chemodenitrification. N2O emissions increased with increasing water filled pore space (WFPS) or decreasing water tension, respectively. Maximal N2O emissions were measured between 80 and 95% WFPS or 0 kPa water tension. Optimal moisture for NO emission differed significantly between the soils, and ranged between 15% WFPS in

Chemical stabilization and high pressure synthesis of Ba-free Hg-based superconductors, (Hg,M)Sr{sub 2}Ca{sub n-1}Cu{sub n}O{sub y}(N=1{approximately}3)

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

Kishio, K.; Shimoyama, J.; Hahakura, S.

1994-12-31

A homologous series of new Hg-based HTSC compounds, (Hg,M)Sr{sub 2}Ca{sub n-1}Cu{sub n}O{sub y} with n=1 to 3, have been synthesized. The stabilization of the pure phases have been accomplished by chemical doping of third elements such as M=Cr, Mo and Re. While the Hg1201(n=1) phase was readily obtained in this way, it was necessary to simultaneously dope Y into the Ca site to stabilize the Hg1212(n=2) phase. On the other hand, single-phase Y-free Hg1212(n=2) and Hg1223(n=3) samples were synthesized only under a high pressure of 6 GPa. In sharp contrast to the Ba-containing compounds, all the samples prepared in themore » present study have been quite stable during the synthesis and no deterioration in air has been observed after the preparation.« less

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.

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.

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

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.

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

(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.

(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 ↓.

N2O emissions in tropical rainforest and rubber plantation, the indicator from landuse changing in Xishuangbanna, Southwest China

NASA Astrophysics Data System (ADS)

Zhou, W. J.; Zhu, J.; Ji, H. L.; Zhang, Y.; Zhang, J.; Zheng, X.

2016-12-01

To understand the effects of landuse on N2O emissions and local climate change in the tropics, we measured N2O fluxes from a primary tropical rainforest (TRF, with treatments of litter removal and control) and a fertilized rubber plantation (RP, with treatments of fertilization (75 kg N ha-1 yr-1) and unfertilization) at Xishuangbanna, southwest China since 2012. The results have shown: 1) Fertilized RP N2O emission is bimodel, one peak after dry season fertilizer, another after rainy season fertilizer. Otherwise, the unfertilized RP and TRF have the similar seasonal dynamic with one peak in the middle of rainy season. 2) due to the fertilizer influence, the poaitive correlation between soil temperature/soil moisture and N2O was more significantly in unfertilized RP than fertilized RP respectively litter input changed the dominated controller of N2O emission in TRF: litter carbon input and soil DOC content for control treatment and, soil temperature and soil NO3- -N for litter removal treatment. 3) lab incubation indicated denitrification and nitrification as the main source for N2O emission in TRF and RP, respectively. 4) The N2O emissions from the fertilized and unfertilized plots in RP were 4.0 and 2.5 kg N ha-1 yr-1, respectively, from control and litter removal plots in TRF were 0.48 and 0.32 kg N ha-1 yr-1,respectively. 5) 100-year carbon dioxide equivalence of N2O from fertilized RP offsets 5.8% and 31.5% of carbon sink of the rubber plantation and local TRF, respectively. Upscaling it to the whole Xishuangbanna, N2O emissions from fertilized RP offset 17.1% of the tropical rainforest's carbon sink. When tropical rainforests are converted to fertilized rubber plantations, the N2O emission seasonal dynamic and mechanisms changed, the global warming effect is enhanced.

N2O emissions in tropical rainforest and rubber plantation, the indicator from landuse changing in Xishuangbanna, Southwest China

NASA Astrophysics Data System (ADS)

Zhou, Wenjun; Zhu, Jing; Ji, Hong-li; Zhang, Yi-Ping; Sha, Li-Qing; Gao, Jin-Bo; Zhang, Jun-Hui; Zheng, Xunhua

2017-04-01

To understand the effects of landuse on N2O emissions and local climate change in the tropics, we measured N2O fluxes from a primary tropical rainforest (TRF, with treatments of litter removal and control) and a fertilized rubber plantation (RP, with treatments of fertilization (75 kg N ha-1 yr-1) and unfertilization) at Xishuangbanna, southwest China since 2012. The results have shown: 1) Fertilized RP N2O emission is bimodel, one peak after dry season fertilizer, another after rainy season fertilizer. Otherwise, the unfertilized RP and TRF have the similar seasonal dynamic with one peak in the middle of rainy season. 2) due to the fertilizer influence, the poaitive correlation between soil temperature/soil moisture and N2O was more significantly in unfertilized RP than fertilized RP respectively litter input changed the dominated controller of N2O emission in TRF: litter carbon input and soil DOC content for control treatment and, soil temperature and soil NO3- -N for litter removal treatment. 3) lab incubation indicated denitrification and nitrification as the main source for N2O emission in TRF and RP, respectively. 4) The N2O emissions from the fertilized and unfertilized plots in RP were 4.0 and 2.5 kg N ha-1 yr-1, respectively, from control and litter removal plots in TRF were 0.48 and 0.32 kg N ha-1 yr-1,respectively. 5) 100-year carbon dioxide equivalence of N2O from fertilized RP offsets 5.8% and 31.5% of carbon sink of the rubber plantation and local TRF, respectively. Upscaling it to the whole Xishuangbanna, N2O emissions from fertilized RP offset 17.1% of the tropical rainforest's carbon sink. When tropical rainforests are converted to fertilized rubber plantations, the N2O emission seasonal dynamic and mechanisms changed, the global warming effect is enhanced.

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.

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

Riverine N2O concentrations, exports to estuary and emissions to atmosphere from the Changjiang River in response to increasing nitrogen loads

NASA Astrophysics Data System (ADS)

Yan, Weijin; Yang, Libiao; Wang, Fang; Wang, Jianing; Ma, Pei

2012-12-01

This study investigated the variations of dissolved N2O and emissions over diurnal and seasonal temporal scales in 2009, as well as the time series of riverine N2O export to estuary and emission to atmosphere in response to increasing anthropogenic nitrogen loads in the Changjiang River. For the diurnal study, N2O concentrations ranged from 0.26 to 0.34 and from 0.44 to 0.52 μg N-N2O L-1 in August and October 2009, respectively. The dissolved N2O was supersaturated with a mean value of 197%. Studies on N2O emissions, also taken in August and October, ranged from 2.67 to 11.6 and from 6.72 to 15.2 μg N-N2O m-2 h-1, respectively. For the seasonal study (June through December 2009), N2O concentrations ranged from 0.34 to 0.72 μg N-N2O L-1 and were supersaturated in all the samples (average 212%). N2O emissions ranged from 1.87 to 40.8 μg N-N2O m-2 h-1. Our study found no significant differences in diurnal patterns of N2O saturation but detected significant difference in seasonal patterns of N2O saturation: higher during summer while lower during autumn and winter. We found a significant relationship between dissolved N2O and river nitrate, which can predict the variation of N2O concentrations in the River. The net production of N2 ranged from 0.01 to 0.47 mg N-N2 L-1. These excess N2 values were significantly correlated to the N2O production and are suggestive of denitrification in the river. Applying the Global News model to the river system using measures taken during the 1970 to 2002 period, we estimated N2O emissions to atmosphere increased from 330 to 3650 ton N-N2O yr-1. During that same 1970-2002 period, N2O exports to estuary increased from 91 to 470 ton N-N2O yr-1. Taken together, the findings reported here suggest that both the river N2O concentrations and emissions would increase in response to rising anthropogenic nitrogen loads. Our study showed that the mean emission factor based on the ratio of the total N2O flux to NO3- flux is four times greater

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

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.

1,2-Dibenzyl and -Diaryltetradimethylamido-dimolybdenum and -Ditungsten Compounds: M2R2(NMe2)4 (M=M). Structural Effects of Me2N-to-M Alpha-Bonding.

DTIC Science & Technology

1982-07-07

CHETCUTI, M H CHISHOLM. K FOLTING N00OON 79-C 00144 UNCL’ASS IF IED INDU/DC/TR-82/2-MC NL mh~hEhEEo. OFFICE OF NAVAL RESEARCH Contract No. N00014-79...ldo i, n,.aowy a"d Identf ’ mko.) ’ / a, From the reactions between RMgCI (R = CH C H and CH-p-tolyl) or LiR.(R C6H, ~~,-- ;n 6o5 C"-tolyl) (2euv . 6...ligands u-donate to metal atomic Availability Codes V Avail and/or D special 4 orbitals which would otherwise be available for mischevious M--- H -C

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.

Hydrostatic pressure study on high temperature superconductors: HgBa(2)Casb(m-1)Cu(m)O(2m+2+delta) (m = 1 to 6) and (Cu,C)Ba(2)Ca(m-1)Cu(m)O(2m+3) (m = 3 and 4)

NASA Astrophysics Data System (ADS)

Cao, Yong

1998-12-01

Over the last decade, numerous extensive as well as intensive experimental and theoretical investigations have been carried out since the great discovery of high temperature superconductivity (HTSy) in cuprate superconductors Lasb{2-x}Basb{x}CuOsb4,\\ YBasb2Cusb2Osb{7-delta} and other compounds. Although there is still no widely accepted microscopic theory on the mechanism responsible for such high superconducting transition temperatures (Tsb{c}), systematic trends of the evolution of HTSy with various parameters have been studied and analyzed. One of them is the universal inverse parabolic correlation between the Tsb{c} and the number of carriers per CuOsb2 plane (n) in various cuprate superconductors. The high pressure technique provides a clean way to change the distance between atoms without causing the side effects typical of chemical doping, and thus has long been used to test and provide guidance for theoretical models, as well as give hints about the synthesis of compounds with higher Tsb{c}. Therefore, we have done a systematic study on the pressure effect on Tsb{c} of two homologous superconducting compound series: HgBasb2Casb{m-1}Cusb{m}Osb{2m+2+delta} (Hg-12(m-1)m) (m = 1 to 6) and (Cu,C)Basb2Casb{m-1}Cusb{m}Osb{2m+3+delta} ((Cu,C)-12(m-1)m) (m = 3 and 4). Several factors which influence the hydrostatic pressure effect on Tsb{c} have been systematically analyzed. They include the n, the type of charge reservoir layer, and the number of CuOsb2 layers per unit cell (m). We came to several conclusion: (1) The inverse parabolic Tsb{c}(n) correlation and its universal parameters are valid only under conditions more restrictive than originally expected, and the rigid band model may not hold for some cuprate superconductors under pressure. (2) The pressure coefficient (dTsb{c}/dP) may have a different dependence on n. The compounds with Cu-O chains in their charge reservoir usually show a large linear variation of dTsb{c}/dP with n, while no significant

Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

PubMed

Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

2001-02-01

The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

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.

[(S)-1-Carbamoylethyl]bis(dimethylglyoximato-kappa2N,N')[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato-kappa2N,N')[(R)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III) monohydrate.

PubMed

Orisaku, Keiko Komori; Hagiwara, Mieko; Ohgo, Yoshiki; Arai, Yoshifusa; Ohgo, Yoshiaki

2005-04-01

The title complexes, [Co(C3H6NO)(C4H7N2O2)2(C8H11N)] and [Co(C4H8NO)(C4H7N2O2)2(C8H11N)].H2O, were resolved from [(RS)-1-carbamoylethyl]bis(dimethylglyoximato)[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato)[(RS)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III), respectively, and their crystal structures were determined in order to reveal the absolute configuration of the major enantiomer produced in the photoisomerization of each series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloxime complexes.

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.

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.

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.

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.

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

Predicting Coupled Emissions of N2O, CO2 and CH4 from Arable Fields in Ireland Using the ECOSSE Model

NASA Astrophysics Data System (ADS)

Khalil, M. I.; Smith, J.; Abdalla, M.; O'Brien, P.; Smith, P.; Müller, C.

2011-12-01

Agriculture and associated land-use changes contribute a significant portion to global greenhouse gas (GHG) emissions; mainly as N2O, CO2 and CH4. Improved modelling of soil processes will greatly enhance the value of national inventories, both in terms of more accurate reporting and better mitigation policy options. In Ireland, Agriculture and Land Use, Land Use Change and Forestry, is currently a priority research focus, aimed at reducing uncertainty in estimates of GHG emissions and sinks. The ECOSSE model has several advantages, including limited meteorological and soil data requirements, compared to other models. It can simulate the impacts of land-use, management and climate change on C and N emissions and stocks for both mineral and organic soils at field and national scales. In this study, ECOSSE has been used to predict GHG emissions and SOC changes in arable lands cropped with spring barley receiving different rates of N application. The simulated outputs are evaluated against measured data available from a two-year field study. The modelled responses of N2O fluxes are found to be consistent with the measured values. The bias in the total difference between measured values and the corresponding modelled N2O fluxes was large due to the impact of a few unexpected measurements. In the fertilized fields, significant correlation between modelled and measured N2O fluxes was observed, with correlation coefficients of 0.54-0.60 and root mean square errors of 18.6-20.8 g N ha-1 d-1. The measured seasonal (crop growth period) N2O losses (integrated) were 0.41 and 0.50% of the N applied at rates of 70-79 and 140-159 kg ha-1, respectively. As a further comparison, the simulated values for the dates when measurements were taken were similarly integrated. The corresponding simulated seasonal N2O losses were 0.69 and 1.11% of the added N, suggesting an overestimation by 70-123% of the measured values. However, this could be due to missed emissions associated with the

Iron-Catalyzed Intramolecular C(sp(2))-N Cyclization of 1-(N-Arylpyrrol-2-yl)ethanone O-Acetyl Oximes toward Pyrrolo[1,2-a]quinoxaline Derivatives.

PubMed

Zhang, Zhiguo; Li, Junlong; Zhang, Guisheng; Ma, Nana; Liu, Qingfeng; Liu, Tongxin

2015-07-02

An efficient and convenient iron-catalyzed protocol has been developed for the synthesis of substituted pyrrolo[1,2-a]quinoxalines from 1-(N-arylpyrrol-2-yl)ethanone O-acetyl oximes through N-O bond cleavage and intramolecular directed C-H arylation reactions in acetic acid.

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

. Investigations were carried out over a study period of one year following grassland renewal and grassland conversion to maize cropping on two different soil sites (Plaggic Anthrosol and Histic Gleysol) near Oldenburg, Lower Saxony Germany. Our observations indicate heterotrophic bacterial denitrification and/or nitrifier denitrification as the main source of N2O production, with a significant contribution of N2O reduction to N2 rather than nitrification (i.e. hydroxylamine oxidation) and fungal denitrification throughout the entire study period. A tendency to a higher contribution of N2O reduction to N2 was observed for the often water-saturated Histic Gleysol, while lower N2O reduction was found for the Plaggic Anthrosol. For two samples, we attempt to validate our results from the isotopocule mapping approach with a parallel 15N labelling study at the field scale (Buchen et al., 2016), as conditions of soil moisture, nitrate availability and N2O flux were similar. References: Buchen, C., Lewicka-Szczebak, D., Fuß, R., Helfrich, M., Flessa, H., Well, R., 2016. Fluxes of N2 and N2O and contributing processes in summer after grassland renewal and grassland conversion to maize cropping on a Plaggic Anthrosol and a Histic Gleysol. Soil Biology and Biochemistry 101, 6-19.

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.

Urbanisation-related land use change from forest and pasture into turf grass modifies soil nitrogen cycling and increases N2O emissions

NASA Astrophysics Data System (ADS)

van Delden, Lona; Rowlings, David W.; Scheer, Clemens; Grace, Peter R.

2016-11-01

Urbanisation is becoming increasingly important in terms of climate change and ecosystem functionality worldwide. We are only beginning to understand how the processes of urbanisation influence ecosystem dynamics, making peri-urban environments more vulnerable to nutrient losses. Brisbane in South East Queensland has the most extensive urban sprawl of all Australian cities. This research estimated the environmental impact of land use change associated with urbanisation by examining soil nitrogen (N) turnover and subsequent nitrous oxide (N2O) emissions using a fully automated system that measured emissions on a sub-daily basis. There was no significant difference in soil N2O emissions between the native dry sclerophyll eucalypt forest and an extensively grazed pasture, wherefrom only low annual emissions were observed amounting to 0.1 and 0.2 kg N2O ha-1 yr-1, respectively. The establishment of a fertilised turf grass lawn increased soil N2O emissions 18-fold (1.8 kg N2O ha-1 yr-1), with highest emissions occurring in the first 2 months after establishment. Once established, the turf grass lawn presented relatively low N2O emissions for the rest of the year, even after fertilisation and rain events. Soil moisture was significantly higher, and mineralised N accumulated in the fallow plots, resulting in the highest N2O emissions (2.8 kg N2O ha-1 yr-1) and significant nitrate (NO3-) losses, with up to 63 kg N ha-1 lost from a single rain event due to reduced plant cover removal. The study concludes that urbanisation processes creating peri-urban ecosystems can greatly modify N cycling and increase the potential for losses in the form of N2O and NO3-.

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

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.

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.

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

Mitigating effects of ex situ application of rice straw on CH4 and N2O emissions from paddy-upland coexisting system

NASA Astrophysics Data System (ADS)

Wang, Wei; Wu, Xiaohong; Chen, Anlei; Xie, Xiaoli; Wang, Yunqiu; Yin, Chunmei

2016-11-01

The in situ application of rice straw enhances CH4 emissions by a large margin. The ex situ application of rice straw in uplands, however, may mitigate total global warming potential (GWP) of CH4 and N2O emissions from paddy-upland coexisting systems. To evaluate the efficiency of this practice, two field trials were conducted in rice-rice-fallow and maize-rape cropping systems, respectively. Year-round measurements of CH4 and N2O emissions were conducted to evaluate the system-scaled GWP. The results showed that CH4 accounted for more than 98% of GWP in paddy. Straw removal from paddy decreased 44.7% (302.1 kg ha-1 yr-1) of CH4 emissions and 51.2% (0.31 kg ha-1 yr-1) of N2O emissions, thus decreased 44.8% (7693 kg CO2-eqv ha-1 yr-1) of annual GWP. N2O accounted for almost 100% of GWP in upland. Straw application in upland had insignificant effects on CH4 and N2O emissions, which increased GWP only by 91 kg CO2-eqv ha-1 yr-1. So, the transfer of straw from paddy to upland could decrease GWP by 7602 kg CO2-eqv ha-1 yr-1. Moreover, straw retention during late rice season contributed to 88.2% of annual GWP increment. It is recommended to transfer early rice straw to upland considering GWP mitigation, nutrient recycling and labor cost.

Continuous measurements of N2O emissions from arable fields

NASA Astrophysics Data System (ADS)

Wallman, Magdalena; Lammirato, Carlo; Rütting, Tobias; Delin, Sofia; Weslien, Per; Klemedtsson, Leif

2017-04-01

Agriculture represents 59 % of the anthropogenic nitrous oxide (N2O) emissions, according to the IPCC (Ciais et al. 2013). N2O emissions are typically irregular and vary widely in time and space, which makes it difficult to get a good representation of the emissions (Henault et al. 2012), particularly if measurements have low frequency and/or cover only a short time period. Manual measurements are, for practical reasons, often short-term and low-frequent, or restricted to periods where emissions are expected to be high, e.g. after fertilizing. However, the nature of N2O emissions, being largely unpredictable, calls for continuous or near-continuous measurements over long time periods. So far, rather few long-term, high resolution measurements of N2O emissions from arable fields are reported; among them are Flessa et al. (2002) and Senapati et al. (2016). In this study, we have a two-year data set (2015-2017) with hourly measurements from ten automatic chambers, covering unfertilized controls as well as different nitrogen fertilizer treatments. Grain was produced on the field, and effects of tillage, harvest and other cropping measures were covered. What we can see from the experiment is that (a) the unfertilized control plots seem to follow the same emission pattern as the fertilized plots, at a level similar to the standard mineral fertilized plots (120 kg N ha-1 yr-1) and (b) freeze/thaw emissions are comparable in size to emissions after fertilizing. These two findings imply that the importance of fertilizing to the overall N2O emissions from arable soils may be smaller than previously expected. References: Ciais, P., C. Sabine, G. Bala, L. Bopp, V. Brovkin, J. Canadell et al. 2013: Carbon and Other Biogeochemical Cycles. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung et

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.

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

PubMed

Mizuse, Kenta; Fujii, Asuka

2011-04-21

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

Poly[[sesqui[mu2-1,4-bis(imidazol-1-ylmethyl)benzene-kappa(2)N:N'](carbonato-kappa(2)O,O')copper(II)] 1,4-bis(imidazol-1-ylmethyl)benzene hemisolvate pentahydrate].

PubMed

Dai, Yu-Mei; Tang, En; Huang, Jin-Feng; Yang, Qiu-Yan

2008-10-01

The asymmetric unit of the title compound, {[Cu(CO(3))(C(14)H(14)N(4))(1.5)] x 0.5 C(14)H(14)N(4) x 5 H(2)O}(n), contains one Cu(II) cation in a slightly distorted square-pyramidal coordination environment, one CO(3)(2-) anion, one full and two half 1,4-bis(imidazol-1-ylmethyl)benzene (bix) ligands, one half-molecule of which is uncoordinated, and five uncoordinated water molecules. One of the coordinated bix ligands and the uncoordinated bix molecule are situated about centers of symmetry, located at the centers of the benzene rings. The coordinated bix ligands link the copper(II) ions into a [Cu(bix)(1.5)](n) molecular ladder. These molecular ladders do not form interpenetrated ladders but are arranged in an ABAB parallel terrace, i.e. with the ladders arranged one above another, with sequence A translated with respect to B by 8 A. To best of our knowledge, this arrangement has not been observed in any of the molecular ladder frameworks synthesized to date. The coordination environment of the Cu(II) atom is completed by two O atoms of the CO(3)(2-) anion. The framework is further strengthened by extensive O-H...O and O-H...N hydrogen bonds involving the water molecules, the O atoms of the CO(3)(2-) anion and the N atoms of the bix ligands. This study describes the first example of a molecular ladder coordination polymer based on bix and therefore demonstrates further the usefulness of bix as a versatile multidentate ligand for constructing coordination polymers with interesting architectures.

Integral Representation of the Pictorial Proof of Sum of [superscript n][subscript k=1]k[superscript 2] = 1/6n(n+1)(2n+1)

ERIC Educational Resources Information Center

Kobayashi, Yukio

2011-01-01

The pictorial proof of the sum of [superscript n][subscript k=1] k[superscript 2] = 1/6n(n+1)(2n+1) is represented in the form of an integral. The integral representations are also applicable to the sum of [superscript n][subscript k-1] k[superscript m] (m greater than or equal to 3). These representations reveal that the sum of [superscript…

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

Hydrogen bonding in microsolvation: photoelectron imaging and theoretical studies on Au(x)(-)-(H2O)(n) and Au(x)(-)-(CH3OH)(n) (x = 1, 2; n = 1, 2) complexes.

PubMed

Wu, Xia; Tan, Kai; Tang, Zichao; Lu, Xin

2014-03-14

We have combined photoelectron velocity-map imaging (VMI) spectroscopy and theoretical calculations to elucidate the geometry and energy properties of Aux(-)(Solv)n clusters with x = 1, 2; n = 1, 2; and Solv = H2O and CH3OH. Besides the blue-shifted vertical electron detachment energies (VDEs) of the complexes Au1,2(-)(Solv)n with the increase of the solvation number (n), we independently probed two distinct Au(-)(CH3OH)2 isomers, which combined with MP2/aug-cc-pVTZ(pp) calculations represent a competition between O···H-O hydrogen bonds (HBs) and Au···H-O nonconventional hydrogen bonds (NHBs). Complementary calculations provide the total binding energies of the low-energy isomers. Moreover, the relationship between the total binding energies and total VDEshift is discussed. We found that the Au1,2(-) anions exhibit halide-analogous behavior in microsolvation. These findings also demonstrate that photoelectron velocity map imaging spectroscopy with the aid of the ab initio calculations is an effective tool for investigating weak-interaction complexes.

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.

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.

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.

Vibrational spectroscopy of (SO4(2-)).(H2O)n clusters, n=1-5: harmonic and anharmonic calculations and experiment.

PubMed

Miller, Yifat; Chaban, Galina M; Zhou, Jia; Asmis, Knut R; Neumark, Daniel M; Gerber, R Benny

2007-09-07

The vibrational spectroscopy of (SO4(2-)).(H2O)n is studied by theoretical calculations for n=1-5, and the results are compared with experiments for n=3-5. The calculations use both ab initio MP2 and DFT/B3LYP potential energy surfaces. Both harmonic and anharmonic calculations are reported, the latter with the CC-VSCF method. The main findings are the following: (1) With one exception (H2O bending mode), the anharmonicity of the observed transitions, all in the experimental window of 540-1850 cm(-1), is negligible. The computed anharmonic coupling suggests that intramolecular vibrational redistribution does not play any role for the observed linewidths. (2) Comparison with experiment at the harmonic level of computed fundamental frequencies indicates that MP2 is significantly more accurate than DFT/B3LYP for these systems. (3) Strong anharmonic effects are, however, calculated for numerous transitions of these systems, which are outside the present observation window. These include fundamentals as well as combination modes. (4) Combination modes for the n=1 and n=2 clusters are computed. Several relatively strong combination transitions are predicted. These show strong anharmonic effects. (5) An interesting effect of the zero point energy (ZPE) on structure is found for (SO4(2-)).(H2O)(5): The global minimum of the potential energy corresponds to a C(s) structure, but with incorporation of ZPE the lowest energy structure is C2v, in accordance with experiment. (6) No stable structures were found for (OH-).(HSO4-).(H2O)n, for n

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.

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.

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.

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.

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

Complementing the topsoil information of the Land Use/Land Cover Area Frame Survey (LUCAS) with modelled N2O emissions.

PubMed

Lugato, Emanuele; Paniagua, Lily; Jones, Arwyn; de Vries, Wim; Leip, Adrian

2017-01-01

Two objectives of the Common Agricultural Policy post-2013 (CAP, 2014-2020) in the European Union (EU) are the sustainable management of natural resources and climate smart agriculture. To understand the CAP impact on these priorities, the Land Use/Cover statistical Area frame Survey (LUCAS) employs direct field observations and soil sub-sampling across the EU. While a huge amount of information can be retrieved from LUCAS points for monitoring the environmental status of agroecosystems and assessing soil carbon sequestration, a fundamental aspect relating to climate change action is missing, namely nitrous oxide (N2O) soil emissions. To fill this gap, we ran the DayCent biogeochemistry model for more than 11'000 LUCAS sampling points under agricultural use, assessing also the model uncertainty. The results showed that current annual N2O emissions followed a skewed distribution with a mean and median values of 2.27 and 1.71 kg N ha-1 yr-1, respectively. Using a Random Forest regression for upscaling the modelled results to the EU level, we estimated direct soil emissions of N2O in the range of 171-195 Tg yr-1 of CO2eq. Moreover, the direct regional upscaling using modelled N2O emissions in LUCAS points was on average 0.95 Mg yr-1 of CO2eq. per hectare, which was within the range of the meta-model upscaling (0.92-1.05 Mg ha-1 yr-1 of CO2eq). We concluded that, if information on management practices would be made available and model bias further reduced by N2O flux measurement at representative LUCAS points, the combination of the land use/soil survey with a well calibrated biogeochemistry model may become a reference tool to support agricultural, environmental and climate policies.

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).

New cyclic sulfides, garlicnins I2, M, N, and O, from Allium sativum.

PubMed

Nohara, Toshihiro; Ono, Masateru; Nishioka, Naho; Masuda, Fuka; Fujiwara, Yukio; Ikeda, Tsuyoshi; Nakano, Daisuke; Kinjo, Junei

2018-01-01

One atypical thiolane-type sulfide, garlicnin I 2 (1), two 3,4-dimethylthiolane-type sulfides, garlicnins M (2) and N (3), and one thiabicyclic-type sulfide, garlicnin O (4), were isolated from the acetone extracts of Chinese garlic bulbs, Allium sativum and their structures were characterized. Hypothetical pathways for the production of the respective sulfides were discussed.

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.

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.

UV and fluorescence spectral changes induced by neodymium binding of N,N'-ethylenebis[2-(o-hydroxyphenolic)glycine] and N,N'-di(2-hydroxybenzyl)ethylenediamine-N,N' diacetic acid.

PubMed

Wang, Zhijun; Yang, Binsheng

2006-11-01

In 0.01 M 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (Hepes), pH 7.4 and room temperature, the binding of neodymium to N,N'-ethylenebis[2-(o-hydroxyphenolic)glycine] (EHPG), or N,N'-di(2-hydroxybenzyl)ethylenediamine-N,N' diacetic acid (HBED) had been studied from 210 to 330 nm by means of difference UV spectra. Two peaks at 240 and 292 nm appear in difference UV spectra after neodymium binding to EHPG or HBED. The 1:1 stable complex can be confirmed from spectral titration curves. The molar extinction coefficient of Nd-EHPG and Nd-HBED complexes are Deltaepsilon(Nd-EHPG)=(12.93+/-0.21) x 10(3)cm(-1)M(-1), Deltaepsilon(Nd-HBED)=(14.45+/-0.51) x 10(5)cm(-1)M(-1) at 240 nm, respectively. Using EDTA as a competitor, the conditional equilibrium constants of the complexes are logK(Nd-EHPG)=11.89+/-0.09 and logK(Nd-HBED)=12.19+/-0.15, respectively. At the same conditions, fluorescence measurements show that neodymium binding to EHPG leads to a quenching of the fluorescence of EHPG at near 310 nm. However, there is no obvious fluorescence change of HBED at 318 nm with the binding of neodymium to HBED.

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

CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

PubMed

Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

2015-07-16

The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

Probing the electronic properties of ternary A n M3n-1B2n (n = 1: A = Ca, Sr; M = Rh, Ir and n = 3: A = Ca, Sr; M = Rh) phases: observation of superconductivity.

PubMed

Takeya, Hiroyuki; ElMassalami, Mohammed; Terrazos, Luis A; Rapp, Raul E; Capaz, Rodrigo B; Fujii, Hiroki; Takano, Yoshihiko; Doerr, Mathias; Granovsky, Sergey A

2013-06-01

We follow the evolution of the electronic properties of the titled homologous series when n as well as the atomic type of A and M are varied where for n = 1, A = Ca, Sr and M = Rh, Ir while for n = 3, A = Ca, Sr and M = Rh. The crystal structure of n = 1 members is known to be CaRh 2 B 2 -type ( Fddd ), while that of n = 3 is Ca 3 Rh 8 B 6 -type ( Fmmm ); the latter can be visualized as a stacking of structural fragments from AM 3 B 2 ( P 6/ mmm ) and AM 2 B 2 . The metallic properties of the n = 1 and 3 members are distinctly different: on the one hand, the n = 1 members are characterized by a linear coefficient of the electronic specific heat γ ≈ 3 mJ mol -1 K -2 , a Debye temperature θ D ≈ 300 K, a normal conductivity down to 2 K and a relatively strong linear magnetoresistivity for fields up to 150 kOe. The n = 3 family, on the other hand, exhibits γ ≈ 18 mJ mol -1 K -2 , θ D ≈ 330 K, a weak linear magnetoresistivity and an onset of superconductivity (for Ca 3 Rh 8 B 6 , T c = 4.0 K and H c2 = 14.5 kOe, while for Sr 3 Rh 8 B 6 , T c = 3.4 K and H c2 ≈ 4.0 kOe). These remarkable differences are consistent with the findings of the electronic band structures and density of state (DOS) calculations. In particular, satisfactory agreement between the measured and calculated γ was obtained. Furthermore, the Fermi level, E F , of Ca 3 Rh 8 B 6 lies at almost the top of a pronounced local DOS peak, while that of CaRh 2 B 2 lies at a local valley: this is the main reason behind the differences between the, e.g., superconducting properties. Finally, although all atoms contribute to the DOS at E F , the contribution of the Rh atoms is the strongest.

Solubility and diffusivity of N{sub 2}O and CO{sub 2} in (diethanolamine + N-methyldiethanolamine + water) and in (diethanolamine + 2-amino-2-methyl-1-propanol + water)

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

Li, M.H.; Lee, W.C.

1996-05-01

Acid gases such as CO{sub 2} and H{sub 2}S are frequently removed from natural gas, synthetic natural gas, and other process gas streams by means of absorption into aqueous alkanol-amine solutions. The solubility and diffusivity of N{sub 2}O in (diethanolamine + N-methyldiethanolamine + water) and in (diethanolamine + 2-amino-2-methyl-1-propanol + water) were measured at (30, 35, and 40)C and at atmospheric pressure. Five (diethanolamine + N-methyldiethanolamine + water) and four (diethanolamine + 2-amino-2-methyl-1-propanol + water) systems were studied. The total amine mass percent in all cases was 30. A solubility apparatus was used to measure the solubility of N{sub 2}Omore » in amine solutions. The diffusivity was measured by a wetted wall column absorber. The N{sub 2}O analogy was used to estimate the solubility and diffusivity of CO{sub 2} in (diethanolamine + N-methyldiethanolamine + water) and in (diethanolamine + 2-amino-2-methyl-1-propanol + water).« less

Modeling the effects of different N fertilizer rates on N2O emissions and nitrate leaching from arable soils in Korea

NASA Astrophysics Data System (ADS)

Kim, Y.; Berger, S.; Tenhunen, J. D.; Gebauer, G.; Kiese, R.

2012-12-01

interrow resulting in total direct emissions of about 1.5 to 2.3 kg N ha-1 yr-1 (area weighted average of row and interrow). Compared with the IPCC approach (EF = 0.01) these values are rather low which can be explained by high rates of simulated and measured nitrate leaching across all N treatments (row: 214 - 240 kg N ha-1 yr-1; interrow: 259 - 263 kg N ha-1 yr-1). Seasonal dynamic and magnitude of measured and simulated NO3 concentrations in soil water in different soil depths agreed well which give further evidence for the simulated nitrate leaching. Using the IPCC EF of 0.0075, nitrate leaching results in indirect N2O emissions of additionally 1.8 kg N ha-1 yr-1. Only slight increase of measured and simulated yields (4 to 5.2 t DW ha-1) with higher rates of N fertilization indicate that actual farmer practices can be improved and optimizing agricultural management considering the specific climatic and soil conditions has a high potential to reduce environmental impacts of crop cultivations in the study area of the Haean catchment.

Spectroscopic and electrochemical properties of group 12 acetates of di-2-pyridylketone thiophene-2-carboxylic acid hydrazone (dpktch-H) complexes. The structure of [Cd(η³-N,N,O-dpktch-H)₂].

PubMed

Bakir, Mohammed; Lawrence, Mark A W; McBean, Shameal

2015-07-05

The reaction between [dpktch] and [M(OAc)2] (M=group 12 metal atom) in refluxing CH3CN gave [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O (n=0 or 1). The infrared and (1)H NMR spectra are consistent with the coordination of [η(2)-O,O-OAc] and [η(3)-N,N,O-dpktch-H](-) and the proposed formulations. The electronic absorption spectra of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O measured in non-aqueous solvents revealed a highly intense intra-ligand-charge transfer (ILCT) transition due to π-π∗ of dpk followed by dpk→thiophene charge transfer. The electronic transitions of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O are solvent and concentration dependent. Spectrophotometric titrations of dmso solutions of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O with benzoic acid revealed irreversible inter-conversion between [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O and it conjugate acid [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch)]·nH2O pointing to ligand exchange between the acetate and benzoate anions. When CH2Cl2 solutions of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O were titrated with dmso, changes appeared pointing to solvolysis or ligand exchange reactions. Electrochemical measurements on dmso solutions of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O divulged irreversible redox transformations consistent with electrochemical decomposition of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O. The solid state structure of a single crystal of [Cd(η(3)-N,N,O-dpktch-H)2] obtained from a dmso solution of [Cd(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O confirmed the ligand scrambling of [M(η(2)-O,O-OAc)(η(3)-N,N,O-dpktch-H)]·nH2O. The extended structure of [Cd(η(3)-N,N,O-dpktch-H)2] revealed stacks of [Cd(η(3)-N,N,O-dpktch-H)2] locked via a network of hydrogen bonds. A significant amount of empty space (35.5%) was observed in the solid state structure of [Cd(η(3)-N,N,O-dpktch-H)2]. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Broad N2H+ Emission toward the Protostellar Shock L1157-B1

NASA Astrophysics Data System (ADS)

Codella, C.; Viti, S.; Ceccarelli, C.; Lefloch, B.; Benedettini, M.; Busquet, G.; Caselli, P.; Fontani, F.; Gómez-Ruiz, A.; Podio, L.; Vasta, M.

2013-10-01

We present the first detection of N2H+ toward a low-mass protostellar outflow, namely, the L1157-B1 shock, at ~0.1 pc from the protostellar cocoon. The detection was obtained with the IRAM 30 m antenna. We observed emission at 93 GHz due to the J = 1-0 hyperfine lines. Analysis of this emission coupled with HIFI CHESS multiline CO observations leads to the conclusion that the observed N2H+(1-0) line originated from the dense (>=105 cm-3) gas associated with the large (20''-25'') cavities opened by the protostellar wind. We find an N2H+ column density of a few 1012 cm-2 corresponding to an abundance of (2-8) × 10-9. The N2H+ abundance can be matched by a model of quiescent gas evolved for more than 104 yr, i.e., for more than the shock kinematical age (sime2000 yr). Modeling of C-shocks confirms that the abundance of N2H+ is not increased by the passage of the shock. In summary, N2H+ is a fossil record of the pre-shock gas, formed when the density of the gas was around 104 cm-3, and then further compressed and accelerated by the shock.

Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

NASA Astrophysics Data System (ADS)

Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

2017-09-01

Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

Di-μ-cyanido-1:2κC:N,2:3κN:C-hexa-cyanido-1κC,3κC-tetra-kis(1,10-phenanthroline)-1κN,N';2κN,N';3κN,N'-1,3-dicobalt(III)-2-iron(II) tetra-hydrate.

PubMed

Zhang, Ying; Yuan, Ai-Hua; Zhou, Hu; Guo, Ji-Xi; Liu, Lang

2009-08-08

The hydro-thermal reaction of CoCl(2)·6H(2)O, 1,10-phenanthroline (phen) and K(3)[Fe(CN)(6)] in deionized water yielded the title cyanide-bridged trinuclear cluster, [Co(2)Fe(CN)(8)(C(12)H(8)N(2))(4)]·4H(2)O or [{Co(III)(phen)(CN)(4)}(2){Fe(II)(phen)(2)}]·4H(2)O, which contains two Co(III) centers and one Fe(II) center linked by cyanide bridges. The combination of coordinative bonds, O-H⋯N and O-H⋯O hydrogen bonds and π-π stacking inter-actions [centroid-centroid distance = 3.630 (2) Å] results in the stabilization of a supra-molecular structure. All uncoordinated water molecules are disordered. Thermogravimetric analysis reveals that the title complex loses the four crystal water mol-ecules at about 333 K, then the anhydrous phase loses no further mass up to about 573 K, above which decomposition occurs.

N2 Fluxes From Amazon Cropland Are a Significant Component of Watershed N Budgets.

NASA Astrophysics Data System (ADS)

Fox, R. J.; Neill, C.; Macedo, M.; Davidson, E. A.; Lefebvre, P.; Jankowski, K.; Maracahipes-Santos, L.

2017-12-01

Amazon tropical rainforests have experienced significant deforestation and conversion to cropland. Recently, cropping has intensified to include higher application rates of N fertilizer, typically in a soybean-corn rotation. Our previous work in Mato Grosso, Brazil, suggests that the addition of N fertilizer (80 Kg N ha-1 yr-1) has not increased N2O fluxes from soils or elevated dissolved N concentrations in streams or groundwater. Here, we investigate whether N fertilizer is converted to N2 in groundwater. We collected samples during January and October 2016 from streams and well transects across riparian forest buffers bordering cropland or within intact riparian forests. Samples were collected using a positive pressure pump and analyzed using Membrane Inlet Mass Spectrometry (MIMS) for N2, Ar, and O2 and gas chromatography for N2O and CH4. N2 concentrations in excess of solubility (based on Ar) were measured at nearly all locations in January and ranged from -15 to 220 in cropland and -2 to 93 µmol N2-N L-1 in intact forest. N2 concentrations were generally lower in October and ranged from -0.9 to 95 in cropland and -0.6 to 52 µmol N2-N L-1 in intact forest. Higher N2 concentrations accumulated at lower dissolved oxygen concentrations and at the borders between cropland and riparian forest. N2O concentrations were significantly lower than N2 concentrations on both dates and ranged between 0.01 and 0.33 µmol N2O-N L-1. Preliminary estimates suggest that N2 losses from cropland ranged from 10 to 20 kg N ha-1 y-1 and losses from forests ranged from 2 to 12 kg N ha-1 y-1. High concentrations of N2 in groundwater have been found in and around agricultural fields in temperate regions, but direct N2 measurements in tropical agricultural regions have not been previously documented. These results suggest that N2 fluxes from tropical cropland receiving modest amounts of N fertilizer could be substantial.

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.

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

Comparison of the physical, chemical and electrical properties of ALD Al 2 O 3 on c- and m- plane GaN: Comparison of the physical, chemical and electrical properties of ALD Al 2 O 3 on c- and m- plane GaN

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

Wei, D.; Hossain, T.; Nepal, N.

2014-02-01

Our study compares the physical, chemical and electrical properties of Al 2O 3 thin films deposited on gallium polar c- and nonpolar m -plane GaN substrates by atomic layer deposition (ALD). Correlations were sought between the film's structure, composition, and electrical properties. The thickness of the Al 2O 3 films was 19.2 nm as determined from a Si witness sample by spectroscopic ellipsometry. We measured the gate dielectric was slightly aluminum-rich (Al:O=1:1.3) from X-ray photoelectron spectroscopy (XPS) depth profile, and the oxide-semiconductor interface carbon concentration was lower on c -plane GaN. The oxide's surface morphology was similar on both substrates,more » but was smoothest on c -plane GaN as determined by atomic force microscopy (AFM). Circular capacitors (50-300 μm diameter) with Ni/Au (20/100 nm) metal contacts on top of the oxide were created by standard photolithography and e-beam evaporation methods to form metal-oxide-semiconductor capacitors (MOSCAPs). Moreover, the alumina deposited on c -plane GaN showed less hysteresis (0.15 V) than on m -plane GaN (0.24 V) in capacitance-voltage (CV) characteristics, consistent with its better quality of this dielectric as evidenced by negligible carbon contamination and smooth oxide surface. These results demonstrate the promising potential of ALD Al 2O 3 on c -plane GaN, but further optimization of ALD is required to realize the best properties of Al 2O 3 on m -plane GaN.« less

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.