Sample records for h2s ammonia nh3

  1. Copper-induced ammonia N-H functionalization.

    PubMed

    Álvarez, María; Álvarez, Eleuterio; Fructos, Manuel R; Urbano, Juan; Pérez, Pedro J

    2016-10-07

    The activation of ammonia has been achieved with the aid of the Tp(Ms)Cu core (Tp(Ms) = hydrotris(3-mesityl-pyrazolyl)borate). Complexes of the general composition Tp(Ms)Cu(amine) (1-4) including the ammonia adduct Tp(Ms)Cu(NH3) (1) have been synthesized and fully spectroscopical- and structurally characterized. Coordinated ammonia in 1 has been reacted with Ph3CPF6 yielding Tp(Ms)Cu(NH2CPh3) (5) as a result of N-H cleavage and N-C bond formation. In a parallel manner the catalytic functionalization of ammonia with ethyl diazoacetate leading to glycinate derivatives has been developed with Tp(Ms)Cu(THF) as the catalyst, in the first example of this transformation with ammonia and a copper-based system.

  2. TES/Aura L2 Ammonia (NH3) Nadir V6 (TL2NH3N)

    Atmospheric Science Data Center

    2018-01-18

    TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3N) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 x 8.5 km nadir ... Contact User Services Parameters:  Ammonia Legacy:  Retired data product , click here for ...

  3. TES/Aura L2 Ammonia (NH3) Nadir V6 (TL2NH3NS)

    Atmospheric Science Data Center

    2018-01-22

    TES/Aura L2 Ammonia (NH3) Nadir (TL2NH3NS) News:  TES News ... Level:  L2 Platform:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 x 8.5 km nadir ... Contact ASDC User Services Parameters:  Ammonia Legacy:  Retired data product , click here for ...

  4. TES/Aura L2 Ammonia (NH3) Lite Nadir V6 (TL2NH3LN)

    Atmospheric Science Data Center

    2017-07-20

    TES/Aura L2 Ammonia (NH3) Lite Nadir (TL2NH3LN) News:  TES News ... Level:  L2 Instrument:  TES/Aura L2 Ammonia Spatial Coverage:  5.3 km nadir Spatial ... OPeNDAP Access:  OPeNDAP Parameters:  Ammonia Order Data:  Earthdata Search:   Order Data ...

  5. Thermodynamics of GaN(s)-NH3(v)+N2(v)+H2(v) system - Electronic aspects of the processes at GaN(0001) surface

    NASA Astrophysics Data System (ADS)

    Kempisty, Pawel; Strak, Pawel; Sakowski, Konrad; Krukowski, Stanislaw

    2017-08-01

    Comprehensive analysis of GaN(0001) surface in equilibrium with ammonia/hydrogen mixture was undertaken using results of ab initio calculations. Adsorption energies of the species derived from ammonia and molecular hydrogen and their stable sites were obtained. It was shown that the adsorption process type and energy depend on the position of Fermi level at the surface. Hydrogen decomposes into two separate H atoms, always adsorbed in the positions on top of the surface Ga atoms (On-top). Ammonia adsorption at GaN(0001) surface proceeds molecularly to ammonia in the On-top position or dissociatively into NH2 radicals in bridge (NH2-bridge) or On-top positions or into NH radicals in H3 (NH-H3) site. Presence of these species affects Fermi level pinning at the surface due to creation of new surface states. The Fermi level pinning in function of the surface attached species concentration was determined using extended electron counting rule (EECR). Results of ab initio calculations fully proved validity of the EECR predictions. Thermodynamic analysis of the surface in equilibrium with molecular hydrogen and ammonia vapor mixture is made giving the range of ammonia and hydrogen pressures, corresponding to Fermi level pinned at Ga-broken bond state for NH-H3&H and NH3&H and NH2-bridge&H coverage and at VBM for NH3 & H coverage. As the region of Fermi level pinned at Ga broken bond state corresponds to very low pressures, at pressures close to normal, GaN(0001) surface is almost totally covered by H, NH3 and NH2 located in On-top positions. It is also shown however that dominant portion of the hydrogen and ammonia pressures corresponds to Fermi level not pinned. Among them are these corresponding to MOVPE and HVPE growth conditions in which the surface is almost fully covered by NH3, NH2 and H species in On-top positions.

  6. NH4+-NH3 removal from simulated wastewater using UV-TiO2 photocatalysis: effect of co-pollutants and pH.

    PubMed

    Vohra, M S; Selimuzzaman, S M; Al-Suwaiyan, M S

    2010-05-01

    The main objective of the present study was to investigate the efficiency of titanium dioxide (TiO2) assisted photocatalytic degradation (PCD) process for the removal of ammonium-ammonia (NH4(+)-NH3) from the aqueous phase and in the presence of co-pollutants thiosulfate (S2O3(2-)) and p-cresol (C6H4CH3OH) under varying mixed conditions. For the NH4(+)-NH3 only PCD experiments, results showed higher NH4 -NH3 removal at pH 12 compared to pH 7 and 10. For the binary NH4(+)-NH3/S2O3(2-) studies the respective results indicated a significant lowering in NH4(+)-NH3 PCD in the presence of S2O32- at pH 7/12 whereas at pH 10 a marked increase in NH4(+)-NH3 removal transpired. A similar trend was noted for the p-cresol/NH4(+)-NH3 binary system. Comparing findings from the binary (NH4(+)-NH3/S2O3(2-) and p-cresol/NH4(+)-NH3) and tertiary (NH4(+)-NH3/S2O3(2-)/p-cresol) systems, at pH 10, showed fastest NH4(+)-NH3 removal transpiring for the tertiary system as compared to the binary systems, whereas both the binary systems indicated comparable NH4(+)-NH3 removal trends. The respective details have been discussed.

  7. Fiber-Amplifier-Enhanced QEPAS Sensor for Simultaneous Trace Gas Detection of NH3 and H2S

    PubMed Central

    Wu, Hongpeng; Dong, Lei; Liu, Xiaoli; Zheng, Huadan; Yin, Xukun; Ma, Weiguang; Zhang, Lei; Yin, Wangbao; Jia, Suotang

    2015-01-01

    A selective and sensitive quartz enhanced photoacoustic spectroscopy (QEPAS) sensor, employing an erbium-doped fiber amplifier (EDFA), and a distributed feedback (DFB) laser operating at 1582 nm was demonstrated for simultaneous detection of ammonia (NH3) and hydrogen sulfide (H2S). Two interference-free absorption lines located at 6322.45 cm−1 and 6328.88 cm−1 for NH3 and H2S detection, respectively, were identified. The sensor was optimized in terms of current modulation depth for both of the two target gases. An electrical modulation cancellation unit was equipped to suppress the background noise caused by the stray light. An Allan-Werle variance analysis was performed to investigate the long-term performance of the fiber-amplifier-enhanced QEPAS sensor. Benefitting from the high power boosted by the EDFA, a detection sensitivity (1σ) of 52 parts per billion by volume (ppbv) and 17 ppbv for NH3 and H2S, respectively, were achieved with a 132 s data acquisition time at atmospheric pressure and room temperature. PMID:26506351

  8. Rotational Spectroscopy of the NH3-H2 Molecular Complex

    NASA Astrophysics Data System (ADS)

    Surin, L. A.; Tarabukin, I. V.; Schlemmer, S.; Breier, A. A.; Giesen, T. F.; McCarthy, M. C.; van der Avoird, A.

    2017-03-01

    We report the first high resolution spectroscopic study of the NH3-H2 van der Waals molecular complex. Three different experimental techniques, a molecular beam Fourier transform microwave spectrometer, a millimeter-wave intracavity jet OROTRON spectrometer, and a submillimeter-wave jet spectrometer with multipass cell, were used to detect pure rotational transitions of NH3-H2 in the wide frequency range from 39 to 230 GHz. Two nuclear spin species, (o)-NH3-(o)-H2 and (p)-NH3-(o)-H2, have been assigned as carriers of the observed lines on the basis of accompanying rovibrational calculations performed using the ab initio intermolecular potential energy surface (PES) of Maret et al. The experimental spectra were compared with the theoretical bound state results, thus providing a critical test of the quality of the NH3-H2 PES, which is a key issue for reliable computations of the collisional excitation and de-excitation of ammonia in the dense interstellar medium.

  9. Experimental and theoretical investigation of homogeneous gaseous reaction of CO2(g) + nH2O(g) + nNH3(g) → products (n = 1, 2).

    PubMed

    Li, Zhuangjie; Zhang, Baoquan

    2012-09-13

    Decreasing CO2 emissions into the atmosphere is key for reducing global warming. To facilitate the CO2 emission reduction efforts, our laboratory conducted experimental and theoretical investigations of the homogeneous gaseous reaction of CO2(g) + nH2O(g) + nNH3(g) → (NH4)HCO3(s)/(NH4)2CO3(s) (n = 1 and 2) using Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy and ab initio molecular orbital theory. Our FTIR-ATR experimental results indicate that (NH4)2CO3(s) and (NH4)HCO3(s) are formed as aerosol particulate matter when carbon dioxide reacts with ammonia and water in the gaseous phase at room temperature. Ab initio study of this chemical system suggested that the reaction may proceed through formation of NH3·H2O(g), NH3·CO2(g), and CO2·H2O(g) complexes. Subsequent complexes, NH3·H2O·CO2 and (NH3)2·H2O·CO2, can be formed by adding gaseous reactants to the NH3·H2O(g), NH3·CO2(g), and CO2·H2O(g) complexes, respectively. The NH3·H2O·CO2 and (NH3)2·H2O·CO2 complexes can then be rearranged to produce (NH4)HCO3 and (NH4)2CO3 as final products via a transition state, and the NH3 molecule acts as a medium accepting and donating hydrogen atoms in the rearrangement process. Our computational results also reveal that the presence of an additional water molecule can reduce the activation energy of the rearrangement process. The high activation energy predicted in the present work suggests that the reaction is kinetically not favored, and our experimental observation of (NH4)HCO3(s) and (NH4)2CO3(s) may be attributed to the high concentrations of reactants increasing the reaction rate of the title reactions in the reactor.

  10. Transient-state biodegradation behavior of a horizontal biotrickling filter in co-treating gaseous H2S and NH3.

    PubMed

    Jiang, Xia; Yan, Rong; Tay, Joo Hwa

    2009-01-01

    A horizontal biotrickling filter (HBTF) was used to inoculate autotrophic sulfide-oxidizing and ammonia-oxidizing microbial consortiums over H2S-exhausted carbon for co-treating H2S and NH3 waste gas in a long-term operation. In this study, several aspects (i.e., pH change, shock loading and starvation) of the dynamic behavior of the HBTF were investigated. The metabolic products of N and S bearing species in recycling liquid and biological activities of the biofilm were analyzed to explain the observed phenomena and further explore the fundamentals behind. In the pH range of 4-8.5, although the removal efficiencies of H2S and NH3 remained 96-98% and 100%, respectively, the metabolic products demonstrated different removal mechanisms and pathways. NH4-N and NO2/NO3-N were dominated at pH < or = 6 and > or = 7, respectively, indicating the differentiated contributions from physical/chemical adsorption and bio-oxidation. Moreover, the HBTF demonstrated a good dynamic stability to withstand shock loadings by recovering immediately to the original. During shock loading, only 15.4% and 17.9% of captured H2S and NH3 was biodegraded, respectively. After 2, 11, and 48 days of starvation, the HBTF system reached a full performance within reasonable re-startup times (2-80 h), possibly due to the consumption of reduced S and N species in biomass or activated carbon thus converted into SO4-S and NO3-N during starvation period. The results helped to understand the fundamental knowledge by revealing the effects of pH and transient loadings linked with individual removal mechanism for H2S and NH3 co-treatment in different conditions.

  11. Laser-Based Monitoring of CH4, CO2, NH3, and H2S in Animal Farming—System Characterization and Initial Demonstration

    PubMed Central

    Jaworski, Piotr; Nikodem, Michał

    2018-01-01

    In this paper, we present a system for sequential detection of multiple gases using laser-based wavelength modulation spectroscopy (WMS) method combined with a Herriot-type multi-pass cell. Concentration of hydrogen sulfide (H2S), methane (CH4), carbon dioxide (CO2), and ammonia (NH3) are retrieved using three distributed feedback laser diodes operating at 1574.5 nm (H2S and CO2), 1651 nm (CH4), and 1531 nm (NH3). Careful adjustment of system parameters allows for H2S sensing at single parts-per-million by volume (ppmv) level with strongly reduced interference from adjacent CO2 transitions even at atmospheric pressure. System characterization in laboratory conditions is presented and the results from initial tests in real-world application are demonstrated. PMID:29425175

  12. Partial phase diagram for the system NH3-H2O - The water-rich region

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Schwake, A.; Nicol, M.

    1984-01-01

    Phase boundaries of the H2O-NH3 system for (NH3)/x/(H2O)/1-x/ have been determined with diamond-anvil cells for mixtures in two composition ranges: (1) for x in the range from 0 to 0.3, at pressures up to 4 GPa at 21 C, and (2) for x in the range from 0.46 to 0.50, at pressures up to 5 GPa from 150 to 400 K. Phases were identified visually with a microscope and polarized optics. The NH3.2(H2O) phase is strongly anisotropic with a much smaller refractive index than that of ice VII and cracks in two nonperpendicular networks. NH3.H2O has a refractive index closer to that of Ice VII and does not appear to form cracks. Both phases are colorless. Phase boundaries were determined on both increasing and decreasing pressures, and compositions of the ammonia ices were determined by estimating relative amounts of water and ammonia ices at known overall compositions. For low-ammonia compositions (x equal to or less than 0.15), the following assemblages succedd one another as pressure increases: liquid; liquid and Ice VI (at 1.0 + GPa); liquid and Ice VII (at 2.1 GPa); Ice VII and NH3.H2O (at 3.5 GPa). For x in the range from 0.15 to 0.30, the water ice and liquid fields are replaced by the NH3.2(H2O) and liquid field at pressures down to 1.0 GPa and lower.

  13. Chemical looping of metal nitride catalysts: low-pressure ammonia synthesis for energy storage† †Electronic supplementary information (ESI) available: Experimental and computational details, free energy plots for the NH3 evolution and N2 reduction with Co3N/Co, Fe4N/Fe, Mn5N2/Mn4N, Mo2N/Mo, CrN/Cr2N, TaN/Ta2N, NbN/Nb2N, Li3N/LiH, Ba3N2/BaH2, Sr3N2/SrH2, and Ca3N2/CaH2, surface oxidation energetics, ΔGvac[NH*x, yH*] based on gas phase H2 as hydrogen source, NH3 evolution with Fe-doped Mn4N, NH3 evolution with Mn6N2.58, Ca3N2 and Sr2N after correcting for partial nitride hydrolysis, NH3 yield from Ca3N2vs. time and H2 gas flow rate. See DOI: 10.1039/c5sc00789e

    PubMed Central

    Avram, A. M.; Peterson, B. A.; Pfromm, P. H.; Peterson, A. A.

    2015-01-01

    The activity of many heterogeneous catalysts is limited by strong correlations between activation energies and adsorption energies of reaction intermediates. Although the reaction is thermodynamically favourable at ambient temperature and pressure, the catalytic synthesis of ammonia (NH3), a fertilizer and chemical fuel, from N2 and H2 requires some of the most extreme conditions of the chemical industry. We demonstrate how ammonia can be produced at ambient pressure from air, water, and concentrated sunlight as renewable source of process heat via nitrogen reduction with a looped metal nitride, followed by separate hydrogenation of the lattice nitrogen into ammonia. Separating ammonia synthesis into two reaction steps introduces an additional degree of freedom when designing catalysts with desirable activation and adsorption energies. We discuss the hydrogenation of alkali and alkaline earth metal nitrides and the reduction of transition metal nitrides to outline a promoting role of lattice hydrogen in ammonia evolution. This is rationalized via electronic structure calculations with the activity of nitrogen vacancies controlling the redox-intercalation of hydrogen and the formation and hydrogenation of adsorbed nitrogen species. The predicted trends are confirmed experimentally with evolution of 56.3, 80.7, and 128 μmol NH3 per mol metal per min at 1 bar and above 550 °C via reduction of Mn6N2.58 to Mn4N and hydrogenation of Ca3N2 and Sr2N to Ca2NH and SrH2, respectively. PMID:29218166

  14. Fluorescence Excitation Models of Ammonia and Amidogen Radical (NH2) in Comets: Application to Comet C/2004 Q2 (Machholz)

    NASA Technical Reports Server (NTRS)

    Kawakita, Hideyo; Mumma, Michael J.

    2011-01-01

    Ammonia is a major reservoir of nitrogen atoms in cometary materials. However, detections of ammonia in comets are rare, with several achieved at radio wavelengths. A few more detections were obtained through near-infrared observations (around the 3 m wavelength region), but moderate relative velocity shifts are required to separate emission lines of cometary ammonia from telluric absorption lines in the 3 micron wavelength region. On the other hand, the amidogen radical (NH2 -- a photodissociation product of ammonia in the coma) also shows rovibrational emission lines in the 3 micron wavelength region. Thus, gas production rates for ammonia can be determined from the rovibrational emission lines of ammonia (directly) and amidogen radical (indirectly) simultaneously in the near-infrared. In this article, we present new fluorescence excitation models for cometary ammonia and amidogen radical in the near-infrared, and we apply these models to the near-infrared high-dispersion spectra of comet C/2004 Q2 (Machholz) to determine the mixing ratio of ammonia to water in the comet. Based on direct detection of NH3 lines, the mixing ratio of NH3/H2O is 0.46% +/- 0.03% in C/2004 Q2 (Machholz), in agreement with other results. The mixing ratio of ammonia determined from the NH2 observations (0.31% -- 0.79%) is consistent but has relatively larger error, owing to uncertainty in the photodissociation rates of ammonia. At the present level of accuracy, we confirm that NH3 could be the sole parent of NH2 in this comet.

  15. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  16. Human SLC4A11 Is a Novel NH3/H+ Co-transporter*

    PubMed Central

    Zhang, Wenlin; Ogando, Diego G.; Bonanno, Joseph A.; Obukhov, Alexander G.

    2015-01-01

    SLC4A11 has been proposed to be an electrogenic membrane transporter, permeable to Na+, H+ (OH−), bicarbonate, borate, and NH4+. Recent studies indicate, however, that neither bicarbonate or borate is a substrate. Here, we examined potential NH4+, Na+, and H+ contributions to electrogenic ion transport through SLC4A11 stably expressed in Na+/H+ exchanger-deficient PS120 fibroblasts. Inward currents observed during exposure to NH4Cl were determined by the [NH3]o, not [NH4+]o, and current amplitudes varied with the [H+] gradient. These currents were relatively unaffected by removal of Na+, K+, or Cl− from the bath but could be reduced by inclusion of NH4Cl in the pipette solution. Bath pH changes alone did not generate significant currents through SLC4A11, except immediately following exposure to NH4Cl. Reversal potential shifts in response to changing [NH3]o and pHo suggested an NH3/H+-coupled transport mode for SLC4A11. Proton flux through SLC4A11 in the absence of ammonia was relatively small, suggesting that ammonia transport is of more physiological relevance. Methylammonia produced currents similar to NH3 but with reduced amplitude. Estimated stoichiometry of SLC4A11 transport was 1:2 (NH3/H+). NH3-dependent currents were insensitive to 10 μm ethyl-isopropyl amiloride or 100 μm 4,4′- diisothiocyanatostilbene-2,2′-disulfonic acid. We propose that SLC4A11 is an NH3/2H+ co-transporter exhibiting unique characteristics. PMID:26018076

  17. Role of NH3 and NH4+ transporters in renal acid-base transport.

    PubMed

    Weiner, I David; Verlander, Jill W

    2011-01-01

    Renal ammonia excretion is the predominant component of renal net acid excretion. The majority of ammonia excretion is produced in the kidney and then undergoes regulated transport in a number of renal epithelial segments. Recent findings have substantially altered our understanding of renal ammonia transport. In particular, the classic model of passive, diffusive NH3 movement coupled with NH4+ "trapping" is being replaced by a model in which specific proteins mediate regulated transport of NH3 and NH4+ across plasma membranes. In the proximal tubule, the apical Na+/H+ exchanger, NHE-3, is a major mechanism of preferential NH4+ secretion. In the thick ascending limb of Henle's loop, the apical Na+-K+-2Cl- cotransporter, NKCC2, is a major contributor to ammonia reabsorption and the basolateral Na+/H+ exchanger, NHE-4, appears to be important for basolateral NH4+ exit. The collecting duct is a major site for renal ammonia secretion, involving parallel H+ secretion and NH3 secretion. The Rhesus glycoproteins, Rh B Glycoprotein (Rhbg) and Rh C Glycoprotein (Rhcg), are recently recognized ammonia transporters in the distal tubule and collecting duct. Rhcg is present in both the apical and basolateral plasma membrane, is expressed in parallel with renal ammonia excretion, and mediates a critical role in renal ammonia excretion and collecting duct ammonia transport. Rhbg is expressed specifically in the basolateral plasma membrane, and its role in renal acid-base homeostasis is controversial. In the inner medullary collecting duct (IMCD), basolateral Na+-K+-ATPase enables active basolateral NH4+ uptake. In addition to these proteins, several other proteins also contribute to renal NH3/NH4+ transport. The role and mechanisms of these proteins are discussed in depth in this review.

  18. Hydrogen Storage Properties of New Hydrogen-Rich BH3NH3-Metal Hydride (TiH2, ZrH2, MgH2, and/or CaH2) Composite Systems

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

    Choi, Young Joon; Xu, Yimin; Shaw, Wendy J.

    2012-04-19

    Ammonia borane (AB = NH3BH3) is one of the most attractive materials for chemical hydrogen storage due to its high hydrogen contents of 19.6 wt.%, however, impurity levels of borazine, ammonia and diborane in conjunction with foaming and exothermic hydrogen release calls for finding ways to mitigate the decomposition reactions. In this paper we present a solution by mixing AB with metal hydrides (TiH2, ZrH2, MgH2 and CaH2) which have endothermic hydrogen release in order to control the heat release and impurity levels from AB upon decomposition. The composite materials were prepared by mechanical ball milling, and their H2 releasemore » properties were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The formation of volatile products from decomposition side reactions, such as borazine (N3B3H6) was determined by mass spectrometry (MS). Sieverts type pressure-composition-temperature (PCT) gas-solid reaction instrument was adopted to observe the kinetics of the H2 release reactions of the combined systems and neat AB. In situ 11B MAS-NMR revealed a destabilized decomposition pathway. We found that by adding specific metal hydrides to AB we can eliminate the impurities and mitigate the heat release.« less

  19. Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2006-01-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  20. Advanced ammonia (NH3) monitoring system for industrial applications

    NASA Astrophysics Data System (ADS)

    Spector, Oded; Jacobson, Esther

    1999-12-01

    The present paper describes an Electro-Optical Monitoring System developed for the real time in-situ monitoring of Ammonia (NH3) emissions, at very low concentrations in air, well below the hazardous levels. Ammonia is the starting chemical for almost all industrially produced nitrogen compounds and is therefore one of the most important inorganic raw materials. Due to its unique chemical and physical characteristics, the Ammonia (NH3) anhydrous gas is used in various industrial applications such as: Air Conditioning, Refrigeration (including space shuttles), Agriculture and Chemical Processing. NH3 gas, being a highly irritant toxic and flammable gas with a pungent odor detectable by human perception at 53 ppm, has a TLV-TWA of 25 ppm (TLV-STEL of 35 ppm) and a lower explosive limit (LEL) of 15% in air. Being extremely corrosive and irritating to the skin, eyes, nose and respiratory tract, (irritation begins at 130 - 200 ppm), exposures to high concentrations (above 2500 ppm) are life threatening, thus early detection of Ammonia at concentrations up to 50 ppm is essential to prevent its toxic influence. Existing detection methods for NH3 rely mainly on chemical sensors and analytical methods that require the gas to be sampled and introduced into the detection system via a probe, compared to various standards (for determining the concentration) and the result is not always reflecting the actual gas concentration. The emerging optical open path remote sensing technology that analyzes the specific 'finger print' absorption characteristics of NH3 in various narrow spectral bands, specifically in the UV solar blind band, is discussed including the rationale of the detection algorithm and system design. The system offers warning and alarm signals set at the above low concentration detection sensitivity, (10 - 50 ppm(DOT)m) thus providing reliable Ammonia detection over an air path from 3 (including air-duct applications) to 400 ft (1 - 120 m). Typical installations of

  1. Acute toxicity (LC50) of ammonia to carp fish (Cyprinus carpio) at different pH Levels

    NASA Astrophysics Data System (ADS)

    Ardeniswan; Dara, F.; Sukmawati, F.

    2017-03-01

    Mass death of carp fish in reservoirs and lakes in Indonesia is due to the up-welling phenomenon of ammonia generates from the decomposition of fish feed remaining in the bottom of the lakes/reservoirs by microbes. The formation of ammonia gas is very dependent on pH. Most of the ammonia gas is formed form at the high pH value. Ammonia concentration can be determined with indophenol blue method using UV-Vis spectrophotometer. Carp fish (Cyprinus carpio of 5-6 gr was exposed to the three concentration of ammonia. Acute toxicity (LC50) of ammonia (NH3) was tested on similar sizes (5-6 g) of carp fish was maintained at three different pH levels within range of 7-9 for 96-h. Results showed that the concentration of ammonia increased at higher pH. The 96-h LC50’s for exposure to ammonia were 60% (NH3 1.85 ppm at pH 8), 100% (NH3 2.16 ppm at pH 9), and insignificant result at NH3 1.68 ppm with pH 7.

  2. Acute toxicity of ammonia (NH3-N) in sewage effluent to Chironomus riparius: II. Using a generalized linear model

    USGS Publications Warehouse

    Monda, D.P.; Galat, D.L.; Finger, S.E.; Kaiser, M.S.

    1995-01-01

    Toxicity of un-ionized ammonia (NH3-N) to the midge, Chironomus riparius was compared, using laboratory culture (well) water and sewage effluent (≈0.4 mg/L NH3-N) in two 96-h, static-renewal toxicity experiments. A generalized linear model was used for data analysis. For the first and second experiments, respectively, LC50 values were 9.4 mg/L (Test 1A) and 6.6 mg/L (Test 2A) for ammonia in well water, and 7.8 mg/L (Test 1B) and 4.1 mg/L (Test 2B) for ammonia in sewage effluent. Slopes of dose-response curves for Tests 1A and 2A were equal, but mortality occurred at lower NH3-N concentrations in Test 2A (unequal intercepts). Response ofC. riparius to NH3 in effluent was not consistent; dose-response curves for tests 1B and 2B differed in slope and intercept. Nevertheless, C. riparius was more sensitive to ammonia in effluent than in well water in both experiments, indicating a synergistic effect of ammonia in sewage effluent. These results demonstrate the advantages of analyzing the organisms entire range of response, as opposed to generating LC50 values, which represent only one point on the dose-response curve.

  3. Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex

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

    Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S.

    We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo-15NH3 complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo=15NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo=15NR generates a terminal Mo≡N nitride, and a [Mo-15NH]+ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo-15NH3 complex and the formation of Mo=15NR. Acknowledgment. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Re-search Center funded by the U.S. Department of Energy (U.S. DOE), Office of Science, Officemore » of Basic Energy Sciences. EPR and mass spectrometry experiments were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. The authors thank Dr. Eric D. Walter and Dr. Rosalie Chu for assistance in performing EPR and mass spectroscopy analysis, respectively. Computational resources provided by the National Energy Re-search Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific North-west National Laboratory is operated by Battelle for the U.S. DOE.« less

  4. Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3H2 + NH2 reaction

    NASA Astrophysics Data System (ADS)

    Song, Hongwei; Yang, Minghui; Guo, Hua

    2016-10-01

    Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-of-the-art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH3H2 + NH2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH3 stretching modes, is demonstrated. It is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.

  5. Tuned sensitivity towards H{sub 2}S and NH{sub 3} with Cu doped barium strontium titanate materials

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

    Simion, C. E., E-mail: simion@infim.ro; Teodorescu, V. S.; Stănoiu, A.

    2014-11-05

    The different amount of Cu-doped Barium Strontium Titanate (BST) thick film materials have been tested for their gas-sensing performances towards NH{sub 3} and H{sub 2}S under dry and 50% relative humidity (RH) background conditions. The optimum NH{sub 3} sensitivity was attained with 0.1mol% Cu-doped BST whereas the selective detection of H{sub 2}S was highlighted using 5mol% Cu-doped BST material. No cross-sensitivity effects to CO, NO{sub 2}, CH{sub 4} and SO{sub 2} were observed for all tested materials operated at their optimum temperature (200°C) under humid conditions (50% RH). The presence of humidity clearly enhances the gas sensitivity to NH{sub 3}more » and H{sub 2}S detection.« less

  6. H2S adsorption and dissociation on NH-decorated graphene: A first principles study

    NASA Astrophysics Data System (ADS)

    Faye, Omar; Eduok, Ubong; Szpunar, Jerzy; Samoura, Almoustapha; Beye, Aboubaker

    2018-02-01

    The removal of H2S gas poses an emerging environmental concern because of the lack of knowledge of an efficient adsorbent. A detailed theoretical study of H2S adsorption and dissociation on NH-doped graphene (GNH) has been carried out by means of density theory calculations. Our results reveal that the adsorption of H2S molecule on GNH composite is enhanced by the presence of active site such as the NH radicals. These NH radical sites formed NHsbnd H bonds and increase the charge transfer from H2S to GNH. The dissociation of the adsorbed H2S molecule leads the chemisorption of SH radical via H-transfer to GNH, while the formation of GNH2 at a weight percent of 3.76 wt% of NH radical is an endothermic process with an energy of 0.299 eV and 0.358 eV for ortho and para-position respectively. However, at 7.25 wt% NH radical, we observed a complete dissociation of H2S molecule with an energy released of 0.711 eV for the chemisorbed S atom on GN2H4. Moreover, the H-transfer of the second H atom of H2S molecule at 3.76 wt% was energetic unfavorable. The trend of predicted results within this study reveals that NH-doped graphene (GNH) successfully adsorbed and eliminated of H2S molecule; this work unveils definitive theoretical procedures which can be tested and validated experimentally.

  7. Communication: Equivalence between symmetric and antisymmetric stretching modes of NH 3 in promoting H + NH 3H 2 + NH 2 reaction

    DOE PAGES

    Song, Hongwei; Yang, Minghui; Guo, Hua

    2016-10-07

    Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-ofthe- art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH 3H 2 + NH 2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH 3 stretching modes, ismore » demonstrated. In conclusion, it is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH 3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.« less

  8. Quantum dynamics study of H+NH3-->H2+NH2 reaction.

    PubMed

    Zhang, Xu Qiang; Cui, Qian; Zhang, John Z H; Han, Ke Li

    2007-06-21

    We report in this paper a quantum dynamics study for the reaction H+NH3-->NH2+H2 on the potential energy surface of Corchado and Espinosa-Garcia [J. Chem. Phys. 106, 4013 (1997)]. The quantum dynamics calculation employs the semirigid vibrating rotor target model [J. Z. H. Zhang, J. Chem. Phys. 111, 3929 (1999)] and time-dependent wave packet method to propagate the wave function. Initial state-specific reaction probabilities are obtained, and an energy correction scheme is employed to account for zero point energy changes for the neglected degrees of freedom in the dynamics treatment. Tunneling effect is observed in the energy dependency of reaction probability, similar to those found in H+CH4 reaction. The influence of rovibrational excitation on reaction probability and stereodynamical effect are investigated. Reaction rate constants from the initial ground state are calculated and are compared to those from the transition state theory and experimental measurement.

  9. [Analysis of H2S/PH3/NH3/AsH3/Cl2 by Full-Spectral Flame Photometric Detector].

    PubMed

    Ding, Zhi-jun; Wang, Pu-hong; Li, Zhi-jun; Du, Bin; Guo, Lei; Yu, Jian-hua

    2015-07-01

    Flame photometric analysis technology has been proven to be a rapid and sensitive method for sulfur and phosphorus detection. It has been widely used in environmental inspections, pesticide detection, industrial and agricultural production. By improving the design of the traditional flame photometric detector, using grating and CCD sensor array as a photoelectric conversion device, the types of compounds that can be detected were expanded. Instead of a single point of characteristic spectral lines, full spectral information has been used for qualitative and quantitative analysis of H2S, PH3, NH3, AsH3 and Cl2. Combined with chemometric method, flame photometric analysis technology is expected to become an alternative fast, real-time on-site detection technology to simultaneously detect multiple toxic and harmful gases.

  10. Performance evaluation of poly-urethane foam packed-bed chemical scrubber for the oxidative absorption of NH3 and H2S gases.

    PubMed

    Nisola, Grace M; Valdehuesa, Kris Niño G; Anonas, Alex V; Ramos, Kristine Rose M; Lee, Won-Keun; Chung, Wook-Jin

    2018-01-02

    The feasibility of open-pore polyurethane (PU) foam as packing material for wet chemical scrubber was tested for NH 3 and H 2 S removals. The foam is inexpensive, light-weight, highly porous (low pressure drop) and provides large surface area per unit volume, which are desirable properties for enhanced gas/liquid mass transfer. Conventional HCl/HOCl (for NH 3 ) and NaOH/NaOCl (for H 2 S) scrubbing solutions were used to absorb and oxidize the gases. Assessment of the wet chemical scrubbers reveals that pH and ORP levels are important to maintain the gas removal efficiencies >95%. A higher re-circulation rate of scrubbing solutions also proved to enhance the performance of the NH 3 and H 2 S columns. Accumulation of salts was confirmed by the gradual increase in total dissolved solids and conductivity values of scrubbing solutions. The critical elimination capacities at >95% gas removals were found to be 5.24 g NH 3 -N/m 3 -h and 17.2 g H 2 S-S/m 3 -h at an empty bed gas residence time of 23.6 s. Negligible pressure drops (< 4 mm H 2 O) after continuous operation demonstrate the suitability of PU as a practical packing material in wet chemical scrubbers for NH 3 and H 2 S removals from high-volume dilute emissions.

  11. Surface study and sensing activity of nanotubular indium trioxide to NH3, H2S, NO2 and CO environmental pollutants

    NASA Astrophysics Data System (ADS)

    Zamani, Mehdi

    2016-02-01

    Molecular and electronic structures of nanotubular indium trioxide were studied using B3LYP and CAM-B3LYP density functional methods. Three nanotube models including nanotubes with closed ends (CENT), one opened end (OOENT) and two opened ends (TOENT) were considered. The highest occupied molecular orbital (HOMO) of CENT is distributed over the entire nanotube; while it is distributed on the end cap of OOENT. In both CENT and OOENT, the distribution of the lowest unoccupied molecular orbital (LUMO) is on the end caps. HOMO and LUMO of TOENT are distributed on the center of nanotube. The sensing activity of OOENT to environmental pollutants was evaluated regarding the interaction of nanotube with NH3, H2S, NO2 and CO molecules. Adsorptions over different positions of OOENT are exothermic and the NH3 adsorption is thermodynamically more favorable. The selectivity of OOENT toward gaseous pollutants is investigated as NH3 > H2S > CO > NO2. Interaction of NO2 and CO over the closed end (end cap) of nanotube is preferred; while adsorption of NH3 and H2S on the opened end is more favorable.

  12. Enhanced NH3 emission from swine liquid waste

    NASA Astrophysics Data System (ADS)

    Lee, S.; Robarge, W. P.; Walker, J. T.

    2010-12-01

    Swine animal feeding operations are sources of emissions for various gases [ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), volatile organic carbons (VOCs)], and fine particulate matter. Gaseous emissions from simple aqueous systems are typically controlled by temperature, pH, wind speed, total dissolved concentration of the chemical species of interest (e.g. NH3+NH4+ = TAN), and the Henry’s law constant. Ammonia emissions from three different sources [ammonium sulfate (AS), swine anaerobic lagoon liquid (SLL), and pit liquid (SPL) from swine housing units] were evaluated using a small flow-through teflon-lined chamber (SFTC; 0.3m × 0.2m × 0.15m) under controlled laboratory conditions. The SFTC was designed for 100% collection efficiency of NH3 gas emitted from the liquids. The internal volume of the chamber, 9 L, was exchanged 1.1 times per minute. All three liquid formulations exhibit the expected response in emissions with changes in temperature and pH. However, NH3 emissions from the SPL and SLL are ~5 times those from pure solutions of AS. Furthermore, the enhancement in NH3 emissions was a function of TAN concentration, decreasing in intensity at higher TAN and approaching rates comparable to the pure solutions of AS. The difference in emissions with solutions of equivalent TAN suggests a synergistic mechanism that is enhancing NH3 emissions in SPL and SLL. Concurrent measurements as part of the National Air Emissions Monitoring Study at the swine operations originally sampled for SPL and SLL document the emissions of CO2, H2S and VOCs (primarily acetic, propionic and butyric acids) at levels that are comparable to observed NH3 emissions. To date, only additions of NaHCO3 to the SPL and SLL have been found to enhance NH3 emissions and exhibit the same response to increasing TAN as exhibited by the original SPL and SLL solutions. Possible reactions that could enhance emissions will be discussed.

  13. Experimental ammonia-free phosphate-bonded investments using Mg(H2PO4)2.

    PubMed

    Zhang, Z; Tamaki, Y; Miyazaki, T

    2001-12-01

    In previous study, we found that Mg(H2PO4)2 instead of NH4H2PO4 was available as a binder material for phosphate-bonded investments and possibly could be used to develop the phosphate-bonded investment without ammonia gas release. The purpose of the present study was to develop the experimental ammonia-free phosphate-bonded investments by investigating suitable refractories. Mg(H2PO4)2.nH2O and MgO were prepared as a binder. Cristobalite and quartz were selected as refractories. The power ratio of MgO/Mg(H2PO4)2.nH2O was set constant at 1.2 according to our previous findings. Fundamental properties of dental investment such as strength, manipulation and expansion were evaluated. Using cristobalite as the refractory material, further investigations were performed. The refractory/binder ratio was definitely effective. The increase of this ratio led to low mold strength and large mold expansion. The present findings suggested that C5 was desirable for dental investment.

  14. Modeling impacts of NH{sub 3} on uptake of H{sub 2}SO{sub 4} by charged nucleating nanoparticles in the Earth's atmosphere

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

    Nadykto, A. B., E-mail: anadykto@gmail.com; Department of Applied Mathematics, Moscow State University of Technology “STANKIN”, Vadkovsky per. 1, Moscow 127055; Nazarenko, K. M.

    2016-06-08

    The understanding of the role of ammonia, a well-known stabilizer of binary sulfuric acid-water clusters, in the gas-to-nanoparticle conversion in the Earth atmosphere is critically important for the assessment of aerosol radiative forcing associated with the climate changes. The sulfuric acid H{sub 2}SO{sub 4} is present in the atmosphere in the form of the gas-phase hydrates (H{sub 2}SO{sub 4})(H{sub 2}O){sub n}, whose interaction with NH{sub 3} leads to the formation of more stable bisulfate clusters (NH{sub 3})(H{sub 2}SO{sub 4})(H{sub 2}O){sub n}. Although the impact of NH{sub 3} on the thermochemical stability of binary clusters nucleating homogeneously has been studied inmore » some detail in the past, the effect of ammonia on other microphysical properties relevant to nucleation remains insufficiently well understood. In the present study, the effect of ammonia on the electrical dipole moment controlling the nucleation of airborne ions via the dipole-charge interaction has been investigated using the Density Functional Theory (DFT), ab initio MP2 and model chemistry G3 methods. The presence of ammonia in (H{sub 2}SO{sub 4})(H{sub 2}O){sub n} is found to lead to very large enhancement in the dipole moment, which exceeds 2.0-2.5 Debyes (∼60-80%), 3.7-5.0 Debyes (∼90-180%), 1.4-4.5 Debyes (∼50-150%) and 2.1-5.5 Debyes (∼60-700%) for n = 0, n = 1, n = 2 and n = 3, respectively. The implications of this include the significantly increased uptake of the sulfuric acid, the key atmospheric nucleation precursor, by airborne ions and neutrals (due to dipole-dipole interaction), enhanced nucleation rates and the elevated production of ultrafine particles, which cause adverse health impacts.« less

  15. A Study on the Corrosion Behavior of Carbon Steel Exposed to a H2S-Containing NH4Cl Medium

    NASA Astrophysics Data System (ADS)

    Wang, Hai-bo; Li, Yun; Cheng, Guang-xu; Wu, Wei; Zhang, Yao-heng

    2018-05-01

    NH4Cl corrosion failure often occurs in the overhead systems of hydrotreaters, and this failure is always accompanied by the appearance of H2S. A combination of electrochemical and surface spectroscopic (SEM/EDS, AFM, XRD) techniques was used to investigate the effect of different factors, including the surface roughness, temperature, dissolved oxygen, pH and H2S concentration, on the corrosion behavior of carbon steel in an NH4Cl environment with the presence of H2S. The effect of H2S concentrations (at the ppm level) on the corrosion behavior of carbon steel was systematically revealed. The experimental results clearly indicated that the corrosion rate reached a minimum value at 10 ppm H2S. The steel surface was covered by a uniform corrosion product film in a 10 ppm H2S environment, and the corrosion product film was tight and protective. The ammonia from NH4Cl helped maintaining the protectiveness of the corrosion films in this environment. Dissolved oxygen mainly accelerated the cathodic reaction. The cathodic limiting current density increased with increasing temperature, and the anodic branch polarization curves were similar at different temperatures. The anodic current density decreased as the pH decreased, and the cathodic current density increased as the pH decreased. The absolute surface roughness ( R a) of carbon steel increased from 132.856 nm at 72 h to 153.973 nm at 144 h, and the rougher surface resulted in a higher corrosion rate. The critical innovation in this research was that multiple influential factors were revealed in the NH4Cl environment with the presence of H2S.

  16. A Study on the Corrosion Behavior of Carbon Steel Exposed to a H2S-Containing NH4Cl Medium

    NASA Astrophysics Data System (ADS)

    Wang, Hai-bo; Li, Yun; Cheng, Guang-xu; Wu, Wei; Zhang, Yao-heng

    2018-04-01

    NH4Cl corrosion failure often occurs in the overhead systems of hydrotreaters, and this failure is always accompanied by the appearance of H2S. A combination of electrochemical and surface spectroscopic (SEM/EDS, AFM, XRD) techniques was used to investigate the effect of different factors, including the surface roughness, temperature, dissolved oxygen, pH and H2S concentration, on the corrosion behavior of carbon steel in an NH4Cl environment with the presence of H2S. The effect of H2S concentrations (at the ppm level) on the corrosion behavior of carbon steel was systematically revealed. The experimental results clearly indicated that the corrosion rate reached a minimum value at 10 ppm H2S. The steel surface was covered by a uniform corrosion product film in a 10 ppm H2S environment, and the corrosion product film was tight and protective. The ammonia from NH4Cl helped maintaining the protectiveness of the corrosion films in this environment. Dissolved oxygen mainly accelerated the cathodic reaction. The cathodic limiting current density increased with increasing temperature, and the anodic branch polarization curves were similar at different temperatures. The anodic current density decreased as the pH decreased, and the cathodic current density increased as the pH decreased. The absolute surface roughness (R a) of carbon steel increased from 132.856 nm at 72 h to 153.973 nm at 144 h, and the rougher surface resulted in a higher corrosion rate. The critical innovation in this research was that multiple influential factors were revealed in the NH4Cl environment with the presence of H2S.

  17. Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

    PubMed

    Mackie, John C; Bacskay, George B

    2005-12-29

    Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

  18. Ammonia-water cation and ammonia dimer cation.

    PubMed

    Kim, Hahn; Lee, Han Myoung

    2009-06-25

    We have investigated the structure, interaction energy, electronic properties, and IR spectra of the ammonia-water cation (NH(3)H(2)O)(+) using density functional theory (DFT) and high-level ab initio theory. The ammonia-water cation has three minimum-energy structures of (a) H(2)NH(+)...OH(2), (b) H(3)N(+)...OH(2), and (c) H(3)NH(+)...OH. The lowest-energy structure is (a), followed by (c) and (b). The ammonia dimer cation has two minimum-energy structures [the lowest H(3)NH(+)...NH(2) structure and the second lowest (H(3)N...NH(3))(+) structure]. The minimum transition barrier for the interconversion between (a), (b), and (c) is approximately 6 kcal/mol. Most DFT calculations with various functionals, except a few cases, overstabilize the N...O and N...N binding, predicting different structures from Moller-Plesset second-order perturbation (MP2) theory and the most reliable complete basis set (CBS) limit of coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. Thus, the validity test of the DFT functionals for these ionized molecular systems would be of importance.

  19. Large hydrogen-bonded pre-nucleation (HSO4-)(H2SO4)m(H2O)k and (HSO4-)(NH3)(H2SO4)m(H2O)k clusters in the earth's atmosphere.

    PubMed

    Herb, Jason; Xu, Yisheng; Yu, Fangqun; Nadykto, A B

    2013-01-10

    The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

  20. MetNH3: Metrology for ammonia in ambient air

    NASA Astrophysics Data System (ADS)

    Braban, Christine; Twigg, Marsailidh; Tang, Sim; Leuenberger, Daiana; Ferracci, Valerio; Martin, Nick; Pascale, Celine; Hieta, Tuomas; Pogany, Andrea; Persijn, Stefan; van Wijk, Janneke; Gerwig, Holger; Wirtze, Klaus; Tiebe, Carlo; Balslev-Harder, David; Niederhausen, Bernhardt

    2015-04-01

    Measuring ammonia in ambient air is a sensitive and priority issue due to its harmful effects on human health and ecosystems. The European Directive 2001/81/EC on 'National Emission Ceilings for Certain Atmospheric Pollutants (NEC)' regulates ammonia emissions in the member states. However, there is a lack of regulation to ensure reliable ammonia measurements namely in applicable analytical technology, maximum allowed uncertainty, quality assurance and quality control (QC/QA) procedures as well as in the infrastructure to attain metrological traceability. Validated ammonia measurement data of high quality from air monitoring networks are vitally important for identifying changes due to implementations of environment policies, for understanding where the uncertainties in current emission inventories are derived from and for providing independent verification of atmospheric model predictions. The new EURAMET project MetNH3 aims to develop improved reference gas mixtures by static and dynamic gravimetric generation methods, develop and characterise laser based optical spectrometric standards and establish the transfer from high-accuracy standards to field applicable methods. MetNH3started in June 2014 and in this presentation the first results from the metrological characterisation of a commercially available cavity ring-down spectrometer (CRDS) will be discussed. Also first tests and results from a new design, Controlled Atmosphere Test Facility (CATFAC), which is to be characterised and used to validate the performance of diffusive samplers, denuders and on-line instruments, will be reported. CAFTEC can be used to control test parameters such as ammonia concentration, relative humidity and wind speed. Outline plans for international laboratory and field intercomparisons in 2016 will be presented.

  1. H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Fronko, R. M.; Resing, H. A.; Qian, X. W.; Solin, S. A.

    1987-01-01

    For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

  2. Herschel/HIFI observations of CO, H2O and NH3 in Monoceros R2

    NASA Astrophysics Data System (ADS)

    Pilleri, P.; Fuente, A.; Cernicharo, J.; Ossenkopf, V.; Berné, O.; Gerin, M.; Pety, J.; Goicoechea, J. R.; Rizzo, J. R.; Montillaud, J.; González-García, M.; Joblin, C.; Le Bourlot, J.; Le Petit, F.; Kramer, C.

    2012-08-01

    Context. Mon R2, at a distance of 830 pc, is the only ultracompact H ii region (UCH ii) where the associated photon-dominated region (PDR) can be resolved with Herschel. Owing to its brightness and proximity, it is one of the best-suited sources for investigating the chemistry and physics of highly UV-irradiated PDRs. Aims: Our goal is to estimate the abundance of H2O and NH3 in this region and investigate their origin. Methods: We present new observations ([C ii], 12CO, 13CO, C18O, o-H2O, p-H2O, o-H_218O and o-NH3) obtained with the HIFI instrument onboard Herschel and the IRAM-30 m telescope. We investigated the physical conditions in which these lines arise by analyzing their velocity structure and spatial variations. Using a large velocity gradient approach, we modeled the line intensities and derived an average abundance of H2O and NH3 across the region. Finally, we modeled the line profiles with a non-local radiative transfer model and compared these results with the abundance predicted by the Meudon PDR code. Results: The variations of the line profiles and intensities indicate complex geometrical and kinematical patterns. In several tracers ([C ii], CO 9 → 8 and H2O) the line profiles vary significantly with position and have broader line widths toward the H ii region. The H2O lines present strong self-absorption at the ambient velocity and emission in high-velocity wings toward the H ii region. The emission in the o-H_218O ground state line reaches its maximum value around the H ii region, has smaller linewidths and peaks at the velocity of the ambient cloud. Its spatial distribution shows that the o-H_218O emission arises in the PDR surrounding the H ii region. By modeling the o-H_218O emission and assuming the standard [16O] / [18O] = 500, we derive a mean abundance of o-H2O of ~10-8 relative to H2. The ortho-H2O abundance, however, is larger (~1 × 10-7) in the high-velocity wings detected toward the H ii region. Possible explanations for this larger

  3. Tailored Engineering of an Unusual (C4 H9 NH3 )2 (CH3 NH3 )2 Pb3 Br10 Two-Dimensional Multilayered Perovskite Ferroelectric for a High-Performance Photodetector.

    PubMed

    Li, Lina; Sun, Zhihua; Wang, Peng; Hu, Weida; Wang, Sasa; Ji, Chengmin; Hong, Maochun; Luo, Junhua

    2017-09-25

    Two-dimensional (2D) layered hybrid perovskites have shown great potential in optoelectronics, owing to their unique physical attributes. However, 2D hybrid perovskite ferroelectrics remain rare. The first hybrid ferroelectric with unusual 2D multilayered perovskite framework, (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) 2 Pb 3 Br 10 (1), has been constructed by tailored alloying of the mixed organic cations into 3D prototype of CH 3 NH 3 PbBr 3 . Ferroelectricity is created through molecular reorientation and synergic ordering of organic moieties, which are unprecedented for the known 2D multilayered hybrid perovskites. Single-crystal photodetectors of 1 exhibit fascinating performances, including extremely low dark currents (ca. 10 -12  A), large on/off current ratios (ca. 2.5×10 3 ), and very fast response rate (ca. 150 μs). These merits are superior to integrated detectors of other 2D perovskites, and compete with the most active CH 3 NH 3 PbI 3 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Cluster transformation of [Cu33-H)(μ3-BH4)((PPh2)2NH)3](BF4) to [Cu33-H)(μ2,μ1-S2CH)((PPh2)2NH)3](BF4) via reaction with CS2. X-ray structural characterisation and reactivity of cationic clusters explored by multistage mass spectrometry and computational studies.

    PubMed

    Ma, Howard Z; Li, Jiaye; Canty, Allan J; O'Hair, Richard A J

    2017-11-07

    The copper nanocluster [Cu 33 -H)(μ 3 -BH 4 )L Ph 3 ](BF 4 ), 1a·BF4 (L Ph = (PPh 2 ) 2 NH = dppa), can potentially react with substrates at either the coordinated hydride or borohydride sites. Reaction of 1a·BF4 with CS 2 has given rise to [Cu 33 -H)(μ 2 ,μ 1 -S 2 CH)L Ph 3 ](BF 4 ), (2a·BF4), which was structurally characterised using electrospray ionisation (ESI) with high-resolution mass spectrometry (HRMS), X-ray crystallography, NMR, IR and UV-Vis spectroscopy. The copper(i) atoms adopt a planar trinuclear Cu 3 geometry coordinated on the bottom face by a μ 3 -hydride, on the top face by a μ 2 ,μ 1 -dithioformate and surrounded by three bridging L Ph ligands. Reaction of 1a·BF4 with elemental sulfur gives the known cluster [Cu 4 (L Ph -H + 2S) 3 ](BF 4 ), (3·BF4), which was structurally characterised via X-ray crystallography. ESI-MS of 2a·BF4 produces [Cu 3 (H)(S 2 CH)L Ph 3 ] + and its gas-phase ion chemistry was examined under multistage mass spectrometry conditions using collision-induced dissociation (CID). The primary product, [Cu 3 (H)(S 2 CH)L Ph 2 ] + , formed via ligand loss, undergoes further fragmentation via loss of thioformaldehyde to give [Cu 3 (S)L Ph 2 ] + . DFT calculations exploring rearrangement and fragmentation of the model system [Cu 3 (H)(S 2 CH)L Me 2 ] + (L Me = (PMe 2 ) 2 NH = dmpa) provide a feasible mechanism. Thus, coupling of the coordinated hydride with the dithioformate ligands gives [Cu 3 (S 2 CH 2 )L Me 2 ] + , which then undergoes CH 2 S extrusion via C-S bond cleavage to give [Cu 3 (S)L Me 2 ] + .

  5. NH3 molecule adsorption on spinel-type ZnFe2O4 surface: A DFT and experimental comparison study

    NASA Astrophysics Data System (ADS)

    Zou, Cong-yang; Ji, Wenchao; Shen, Zhemin; Tang, Qingli; Fan, Maohong

    2018-06-01

    Ammonia (NH3) is a caustic environment pollutant which contributes to haze formation and water pollution. Zinc ferrite (ZnFe2O4) exhibits good catalytic activity in NH3 removal. The density functional theory (DFT) was applied to explore the interaction mechanism of NH3 molecule adsorption on spinel-type ZnFe2O4 (1 1 0) surface with GGA-PW91 method in atomic and electronic level. The results indicated that NH3 molecule preferred to adsorb on surface Zn atom with the formation of H3Nsbnd Zn coordinate bond over ZnFe2O4 (1 1 0) surface. The H3Nsbnd Zn state was exothermic process with adsorption energy of -203.125 kJ/mol. About 0.157e were transferred from NH3 molecule to the surface which resulted in strong interaction. Higher activation degree occurred in H3Nsbnd Zn configuration with two Nsbnd H bonds elongated and NH3 structure became more flat on the surface. The PDOS change of NH3 molecule was consistent with the result of adsorption energy. It was concluded that s orbital of NH3 (N) and s, p orbitals of Zn atom overlapped at -0.619 Ha. The p orbital of NH3 (N) has interaction with d orbital of Zn atom suggesting the hybridization between them. Based on NH3 removal experimental and XPS spectra results, NH3sbnd ZnFe2O4 interaction was mainly depended on the coordination between Zn atom and NH3 molecule. The DFT calculations have deepened our understanding on NH3sbnd ZnFe2O4 interaction system.

  6. Triggering N2 Uptake via Redox Induced Expulsion of Coordinated NH3 and N2 Silylation at Trigonal Bipyramidal Iron

    PubMed Central

    Lee, Yunho; Mankad, Neal P.

    2010-01-01

    The biological reduction of nitrogen to ammonia may occur via one of two predominant pathways in which nitrogenous NxHy intermediates including hydrazine (N2H4), diazene (N2H2), nitride (N3-) and imide (NH2-) may be involved. To test the validity of hypotheses concerning iron’s direct role in the stepwise reduction of N2, iron model systems are needed. Such systems can test the chemical compatibility of iron with various proposed NxHy intermediates, and the reactivity patterns of such species. Here we describe a TBP (SiPR3)Fe-L scaffold (SiPR3 represents [Si(o-C6H4PR2)3]−; R = Ph and iPr) where the apical site is occupied by nitrogenous ligands such as N2, N2H4, NH3 and N2R. The system accommodates terminally bound N2 in the three formal oxidation states (iron(0), +1, and +2). N2 uptake is demonstrated via displacement of its reduction partners NH3 and N2H4, and N2 functionalizaton is illustrated via electrophilic silylation. PMID:20571574

  7. Treatment for GaSb surfaces using a sulphur blended (NH4)2S/(NH4)2SO4 solution

    NASA Astrophysics Data System (ADS)

    Murape, D. M.; Eassa, N.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

    2012-07-01

    A sulphur based chemical, [(NH4)2S/(NH4)2SO4] to which S has been added, not previously reported for the treatment of (1 0 0) n-GaSb surfaces, is introduced and benchmarked against the commonly used passivants Na2S·9H2O and (NH4)2S. The surfaces of the treated material were studied by scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxides present on the GaSb surface are more effectively removed when treated with ([(NH4)2S/(NH4)2SO4] + S) than with (NH4)2S or Na2S·9H2O, as evidenced by the ratio of the O506 eV to Sb457 eV AES peaks. XPS results reveal that Sb2S3/Sb2S5 "replaces" Sb2O3/Sb2O5, suggesting that sulphur atoms substitute oxygen atoms in Sb2O3/Sb2O5 to form Sbsbnd S. It seems sulphurization only partially removes Ga2O3. Treatment with ([(NH4)2S/(NH4)2SO4] + S) also results in a noteworthy improvement in the current-voltage (I-V) characteristics of Au/n-GaSb Schottky contacts compared to those fabricated on as-received material.

  8. Dynamics and fragmentation of van der Waals and hydrogen bonded cluster cations: (NH{sub 3}){sub n} and (NH{sub 3}BH{sub 3}){sub n} ionized at 10.51 eV

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

    Yuan, Bing; Bernstein, Elliot R., E-mail: erb@Colostate.edu; Shin, Joong-Won

    A 118 nm laser is employed as a high energy, single photon (10.51 eV/photon) source for study of the dynamics and fragmentation of the ammonia borane (NH{sub 3}BH{sub 3}) cation and its cluster ions through time of flight mass spectrometry. The behavior of ammonia ion and its cluster ions is also investigated under identical conditions in order to explicate the ammonia borane results. Charge distributions, molecular orbitals, and spin densities for (NH{sub 3}BH{sub 3}){sub n} and its cations are explored at both the second-order perturbation theory (MP2) and complete active space self-consistent field (CASSCF) theory levels. Initial dissociation mechanisms andmore » potential energy surfaces for ionized NH{sub 3}BH{sub 3}, NH{sub 3}, and their clusters are calculated at the MP2/6-311++G(d,p) level. Protonated clusters (NH{sub 3}){sub x}H{sup +} dominate ammonia cluster mass spectra: our calculations show that formation of (NH{sub 3}){sub n−1}H{sup +} and NH{sub 2} from the nascent (NH{sub 3}){sub n}{sup +} has the lowest energy barrier for the system. The only common features for the (NH{sub 3}){sub n}{sup +} and (NH{sub 3}BH{sub 3}){sub n}{sup +} mass spectra under these conditions are found to be NH{sub y}{sup +} (y = 0,…,4) at m/z = 14–18. Molecular ions with both {sup 11}B and {sup 10}B isotopes are observed, and therefore, product ions observed for the (NH{sub 3}BH{sub 3}){sub n} cluster system derive from (NH{sub 3}BH{sub 3}){sub n} clusters themselves, not from the NH{sub 3} moiety of NH{sub 3}BH{sub 3} alone. NH{sub 3}BH{sub 2}{sup +} is the most abundant ionization product in the (NH{sub 3}BH{sub 3}){sub n}{sup +} cluster spectra: calculations support that for NH{sub 3}BH{sub 3}{sup +}, an H atom is lost from the BH{sub 3} moiety with an energy barrier of 0.67 eV. For (NH{sub 3}BH{sub 3}){sub 2}{sup +} and (NH{sub 3}BH{sub 3}){sub 3}{sup +} clusters, a B{sup δ+}⋯H{sup δ−}⋯{sup δ−}H⋯{sup δ+}B bond can form in the respective cluster

  9. Evaluating ammonia (NH3) predictions in the NOAA National Air Quality Forecast Capability (NAQFC) using in-situ aircraft and satellite measurements from the CalNex2010 campaign

    NASA Astrophysics Data System (ADS)

    Bray, Casey D.; Battye, William; Aneja, Viney P.; Tong, Daniel; Lee, Pius; Tang, Youhua; Nowak, John B.

    2017-08-01

    Atmospheric ammonia (NH3) is not only a major precursor gas for fine particulate matter (PM2.5), but it also negatively impacts the environment through eutrophication and acidification. As the need for agriculture, the largest contributing source of NH3, increases, NH3 emissions will also increase. Therefore, it is crucial to accurately predict ammonia concentrations. The objective of this study is to determine how well the U.S. National Oceanic and Atmospheric Administration (NOAA) National Air Quality Forecast Capability (NAQFC) system predicts ammonia concentrations using their Community Multiscale Air Quality (CMAQ) model (v4.6). Model predictions of atmospheric ammonia are compared against measurements taken during the NOAA California Nexus (CalNex) field campaign that took place between May and July of 2010. Additionally, the model predictions were also compared against ammonia measurements obtained from the Tropospheric Emission Spectrometer (TES) on the Aura satellite. The results of this study showed that the CMAQ model tended to under predict concentrations of NH3. When comparing the CMAQ model with the CalNex measurements, the model under predicted NH3 by a factor of 2.4 (NMB = -58%). However, the ratio of the median measured NH3 concentration to the median of the modeled NH3 concentration was 0.8. When compared with the TES measurements, the model under predicted concentrations of NH3 by a factor of 4.5 (NMB = -77%), with a ratio of the median retrieved NH3 concentration to the median of the modeled NH3 concentration of 3.1. Because the model was the least accurate over agricultural regions, it is likely that the major source of error lies within the agricultural emissions in the National Emissions Inventory. In addition to this, the lack of the use of bidirectional exchange of NH3 in the model could also contribute to the observed bias.

  10. Interactions of methylamine and ammonia with atmospheric nucleation precursor H{sub 2}SO{sub 4} and common organic acids: Thermodynamics and atmospheric implications

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

    Xu, Y.; Jiang, L.; Bai, Z.

    Interactions of the two common atmospheric bases, ammonia (NH{sub 3}) and methylamine MA (CH{sub 3}NH{sub 2}), which are considered to be important stabilizers of binary clusters in the Earth’s atmosphere, with H{sub 2}SO{sub 4}, the key atmospheric precursor, and 14 common atmospheric organic acids (COA) (formic (CH{sub 2}O{sub 2}), acetic (C{sub 2}H{sub 4}O{sub 2}), oxalic (C{sub 2}H{sub 2}O{sub 4}), malonic (C{sub 3}H{sub 4}O{sub 4}), succinic (C{sub 4}H{sub 6}O{sub 4}), glutaric acid (C{sub 5}H{sub 8}O{sub 4}), adipic (C{sub 6}H{sub 10}O{sub 4}), benzoic (C{sub 6}H{sub 5}COOH), phenylacetic (C{sub 6}H{sub 5}CH{sub 2}COOH), pyruvic (C{sub 3}H{sub 4}O{sub 3}), maleic acid (C{sub 4}H{sub 4}O{sub 4}),more » malic (C{sub 4}H{sub 6}O{sub 5}), tartaric (C{sub 4}H{sub 6}O{sub 6}) and pinonic acid (C{sub 10}H{sub 16}O{sub 3})) have been studied using the composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA) (H{sub 2}SO{sub 4}), (COA)(B1) and (COA)(B2) dimers and (COA) (H{sub 2}SO{sub 4}) (B1) and (COA) (H{sub 2}SO{sub 4}) (B1) trimers, where B1 and B2 represent methylamine (CH{sub 3}NH{sub 2}) and ammonia (NH{sub 3}), respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H{sub 2}SO{sub 4} have been analyzed. It has been shown that in many cases the interactions of H{sub 2}SO{sub 4} with COA, ammonia and methylamine lead to the formation of heteromolecular dimers and trimers, which are certainly more stable than (H{sub 2}SO{sub 4}){sub 2} and (H{sub 2}SO{sub 4}){sub 3}. It has also been found that free energies of (COA) (H{sub 2}SO{sub 4})+ CH{sub 3}NH{sub 2}⇔(COA) (H{sub 2}SO{sub 4})(CH{sub 3}NH{sub 2}) reactions exceed 10-15 kcal mol{sup −1}. This is a clear indication that mixed trimers composed of COA, H{sub 2}SO{sub 4} and methylamine are very stable and can thus serve as possible nucleation sites. The present study leads us to conclude that the interactions of COA coexisting

  11. Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

    NASA Astrophysics Data System (ADS)

    Nemitz, E.; Sutton, M. A.; Wyers, G. P.; Jongejan, P. A. C.

    2004-07-01

    A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd), canopy resistances (Rc) and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3) fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only) using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+]) of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

  12. Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

    NASA Astrophysics Data System (ADS)

    Nemitz, E.; Sutton, M. A.; Wyers, G. P.; Jongejan, P. A. C.

    2004-03-01

    A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd), canopy resistances (Rc) and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3) fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only) using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+]) of 1200 estimated from the measurements is large for semi- natural vegetation, but smaller than indicated by previous measurements at this site.

  13. The CU mobile Solar Occultation Flux instrument: structure functions and emission rates of NH3, NO2 and C2H6

    NASA Astrophysics Data System (ADS)

    Kille, Natalie; Baidar, Sunil; Handley, Philip; Ortega, Ivan; Sinreich, Roman; Cooper, Owen R.; Hase, Frank; Hannigan, James W.; Pfister, Gabriele; Volkamer, Rainer

    2017-02-01

    We describe the University of Colorado mobile Solar Occultation Flux instrument (CU mobile SOF). The instrument consists of a digital mobile solar tracker that is coupled to a Fourier transform spectrometer (FTS) of 0.5 cm-1 resolution and a UV-visible spectrometer (UV-vis) of 0.55 nm resolution. The instrument is used to simultaneously measure the absorption of ammonia (NH3), ethane (C2H6) and nitrogen dioxide (NO2) along the direct solar beam from a moving laboratory. These direct-sun observations provide high photon flux and enable measurements of vertical column densities (VCDs) with geometric air mass factors, high temporal resolution of 2 s and spatial resolution of 5-19 m. It is shown that the instrument line shape (ILS) of the FTS is independent of the azimuth and elevation angle pointing of the solar tracker. Further, collocated measurements next to a high-resolution FTS at the National Center for Atmospheric Research (HR-NCAR-FTS) show that the CU mobile SOF measurements of NH3 and C2H6 are precise and accurate; the VCD error at high signal to noise ratio is 2-7 %. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) from 21 July to 3 September 2014 in Colorado, the CU mobile SOF instrument measured median (minimum, maximum) VCDs of 4.3 (0.5, 45) × 1016 molecules cm-2 NH3, 0.30 (0.06, 2.23) × 1016 molecules cm-2 NO2 and 3.5 (1.5, 7.7) × 1016 molecules cm-2 C2H6. All gases were detected in larger 95 % of the spectra recorded in urban, semi-polluted rural and remote rural areas of the Colorado Front Range. We calculate structure functions based on VCDs, which describe the variability of a gas column over distance, and find the largest variability for NH3. The structure functions suggest that currently available satellites resolve about 10 % of the observed NH3 and NO2 VCD variability in the study area. We further quantify the trace gas emission fluxes of NH3 and C2H6 and production rates of NO2 from concentrated animal feeding

  14. Polytherm of the CO(NH2)2-KNO3-H2O phase diagram

    NASA Astrophysics Data System (ADS)

    Yulina, I. V.; Trunin, A. S.

    2017-05-01

    The crystallization polytherm of the ternary CO(NH2)2-KNO3-H2O system is plotted for the first time via visual polythermal analysis and calculating ternary eutonics characteristics from data on the boundary elements of two-component systems. The ternary eutonics modeling error does not exceed 3.5%. In addition to the crystallization fields of individual components, the field of the redox reaction that occurs in the system between potassium nitrate and carbamide is shown in the CO(NH2)2-KNO3-H2O diagram by a dashed outline.

  15. Ecological risks posed by ammonia nitrogen (AN) and un-ionized ammonia (NH3) in seven major river systems of China.

    PubMed

    Zhang, Li; Xu, Elvis Genbo; Li, Yabing; Liu, Hongling; Vidal-Dorsch, Doris E; Giesy, John P

    2018-07-01

    Previous studies showed that continuous exposure to ammonia nitrogen (AN) contributed to regional losses of benthic invertebrate diversity in China. Yet, the overall ecological risk of AN to aquatic organisms in major riverine systems of China has not been appropriately studied. Our research then investigated temporal (seasonally/yearly) and spatial distributions of AN and un-ionized ammonia (NH 3 ) in major Chinese river basins using historic data generated between 2007 and 2014, and developed risk assessment criteria. Our results showed that the highest average AN concentrations occurred during winter (0.82-2.76 mg/L) and the lowest during summer (0.36-0.78 mg/L). NH 3 exhibited the opposite trend with the highest average concentrations mostly observed during spring (15.13-92.84 μg/L) and the lowest concentrations mainly during winter (10.53-45.43 μg/L). Both AN and NH 3 concentrations steadily increased and reached maximum levels in 2008 (AN: 1.22 mg/L and NH 3 : 50.65 μg/L), and then decreased. Temporal trends showed that the Yellow, Hai, and Huai river basins had the highest AN and NH 3 concentrations. Subsequently, conventional (hazard quotients) and probabilistic (joint probability curves) methods were applied to assess the hazards and risks posed by AN and NH 3 . The results showed that the probability of exceeding the acute toxicity threshold for 5% of species (exposed to AN or NH 3 ) was less than 13.3% and gradually decreased over time. To protect aquatic organisms, an acute criterion of 51.4 μg NH 3 /L and a chronic criterion of 1.14 mg AN/L at pH = 7.5, 20 °C were developed and are recommended for future risk assessment studies. Copyright © 2018 Elsevier Ltd. All rights reserved.

  16. Synthetic, Infrared, 1H and 13C NMR Spectral Studies on N-(2-/3-Substituted Phenyl)-4-Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br, and X = CH3 or Cl

    NASA Astrophysics Data System (ADS)

    Gowda, B. Thimme; Shetty, Mahesha; Jayalakshmi, K. L.

    2005-02-01

    Twenty three N-(2-/3-substituted phenyl)-4-substituted benzenesulphonamides of the general formula, 4-X'C6H4SO2NH(2-/3-XC6H4), where X' = H, CH3, C2H5, F, Cl or Br and X = CH3 or Cl have been prepared and characterized, and their infrared spectra in the solid state, 1H and 13C NMR spectra in solution were studied. The N-H stretching vibrations, νN-H, absorb in the range 3285 - 3199 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1376 - 1309 cm-1 and 1177 - 1148 cm-1, respectively. The S-N and C-N stretching vibrations absorb in the ranges 945 - 893 cm-1 and 1304 - 1168 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of are assigned to protons and carbons of the two benzene rings. Incremental shifts of the ring protons and carbons due to -SO2NH(2-/3-XC6H4) groups in C6H5SO2NH(2-/3-XC6H4), and 4- X'C6H4SO2- and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H5) are computed and employed to calculate the chemical shifts of the ring protons and carbons in the substituted compounds, 4-X'C6H4SO2NH(2-/3-XC6H4). The computed values agree well with the observed chemical shifts.

  17. Mechanisms of the Formation of Adenine, Guanine, and Their Analogues in UV-Irradiated Mixed NH3:H2O Molecular Ices Containing Purine

    NASA Astrophysics Data System (ADS)

    Bera, Partha P.; Stein, Tamar; Head-Gordon, Martin; Lee, Timothy J.

    2017-08-01

    We investigated the formation mechanisms of the nucleobases adenine and guanine and the nucleobase analogues hypoxanthine, xanthine, isoguanine, and 2,6-diaminopurine in a UV-irradiated mixed 10:1 H2O:NH3 ice seeded with precursor purine by using ab initio and density functional theory computations. Our quantum chemical investigations suggest that a multistep reaction mechanism involving purine cation, hydroxyl and amino radicals, together with water and ammonia, explains the experimentally obtained products in an independent study. The relative abundances of these products appear to largely follow from relative thermodynamic stabilities. The key role of the purine cation is likely to be the reason why purine is not functionalized in pure ammonia ice, where cations are promptly neutralized by free electrons from NH3 ionization. Amine group addition to purine is slightly favored over hydroxyl group attachment based on energetics, but hydroxyl is much more abundant due to higher abundance of H2O. The amino group is preferentially attached to the 6 position, giving 6-aminopurine, that is, adenine, while the hydroxyl group is preferentially attached to the 2 position, leading to 2-hydroxypurine. A second substitution by hydroxyl or amino group occurs at either the 6 or the 2 position depending on the first substitution. Given that H2O is far more abundant than NH3 in the experimentally studied ices (as well as based on interstellar abundances), xanthine and isoguanine are expected to be the most abundant bi-substituted photoproducts.

  18. Comparative 4-E analysis of a bottoming pure NH3 and NH3-H2O mixture based power cycle for condenser waste heat recovery

    NASA Astrophysics Data System (ADS)

    Khankari, Goutam; Karmakar, Sujit

    2017-06-01

    This paper proposes a comparative performance analysis based on 4-E (Energy, Exergy, Environment, and Economic) of a bottoming pure Ammonia (NH3) based Organic Rankine Cycle (ORC) and Ammonia-water (NH3-H2O) based Kalina Cycle System 11(KCS 11) for additional power generation through condenser waste heat recovery integrated with a conventional 500MWe Subcritical coal-fired thermal power plant. A typical high-ash Indian coal is used for the analysis. The flow-sheet computer programme `Cycle Tempo' is used to simulate both the cycles for thermodynamic performance analysis at different plant operating conditions. Thermodynamic analysis is done by varying different NH3 mass fraction in KCS11 and at different turbine inlet pressure in both ORC and KCS11. Results show that the optimum operating pressure of ORC and KCS11 with NH3 mass fraction of 0.90 are about 15 bar and 11.70 bar, respectively and more than 14 bar of operating pressure, the plant performance of ORC integrated power plant is higher than the KCS11 integrated power plant and the result is observed reverse below this pressure. The energy and exergy efficiencies of ORC cycle are higher than the KCS11 by about 0.903 % point and 16.605 % points, respectively under similar saturation vapour temperature at turbine inlet for both the cycles. Similarly, plant energy and exergy efficiencies of ORC based combined cycle power plant are increased by 0.460 % point and 0.420 % point, respectively over KCS11 based combined cycle power plant. Moreover, the reduction of CO2 emission in ORC based combined cycle is about 3.23 t/hr which is about 1.5 times higher than the KCS11 based combined cycle power plant. Exergy destruction of the evaporator in ORC decreases with increase in operating pressure due to decrease in temperature difference of heat exchanging fluids. Exergy destruction rate in the evaporator of ORC is higher than KCS11 when the operating pressure of ORC reduces below 14 bar. This happens due to variable

  19. Subthreshold parallel pumping experiments on the quasi one-dimensional S = {1}/{2} ferromagnets [C 6H 11NH 3]CuBr 3 and [C 6H 11NH 3]CuCl 3

    NASA Astrophysics Data System (ADS)

    Hoogerbeets, R.; Wiegers, S. A. J.; Van Duyneveldt, A. J.

    1985-04-01

    Subthreshold parallel pumping experiments on [C 6H 11NH 3]CuBr 3 (abbreviated as CHAB) and [C 6H 11NH 3]CuCl 3 (CHAC) at 9.6 and 18.3 GHz are reported. It is shown that the experimental results can be explained using the values of the parameters as have been obtained from previously reported FMR measurements.

  20. Synthetic and Spectroscopic Studies on N-(i,j-Disubstituted Phenyl)-4- Substituted Benzenesulphonamides, 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i, j = 2, 3; 2, 4; 2, 5; 2, 6 or 3, 4; and X = CH3 or Cl

    NASA Astrophysics Data System (ADS)

    Shetty, Mahesha; Gowda, B. Thimme

    2005-02-01

    Fifty four N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides of the general formula 4-X'C6H4SO2NH(i,j-X2C6H3), where X' = H, CH3, C2H5, F, Cl or Br; i,j = 2,3; 2,4; 2,5; 2,6 or 3, 4; and X = CH3 or Cl, are prepared and characterized and their infrared, 1H and 13C NMR spectra in solution are studied. The N-H stretching vibrations νN-H absorb in the range 3305 - 3205 cm-1, while the asymmetric and symmetric SO2 vibrations vary in the ranges 1377 - 1307 cm-1 and 1184 - 1128 cm-1, respectively. The N-(i,j-disubstituted phenyl)-4-substituted benzenesulphonamides show C-S, S-N and C-N stretching vibrations in the ranges 844 - 800 cm-1, 945 - 891 cm-1 and 1309 - 1170 cm-1, respectively. The compounds do not exhibit particular trends in the variation of these frequencies on substitution either at ortho or meta positions with either a methyl group or Cl. The observed 1H and 13C chemical shifts of 2.jpg" /> are assigned to protons and carbon atoms of the two benzene rings. Incremental shifts of the ring protons and carbon atoms due to -SO2NH(i,j-X2C6H3) groups in C6H5SO2NH(i,j-X2C6H3) and 4-X'C6H4SO2NH- groups in 4-X'C6H4SO2NH(C6H*) are computed and employed to calculate the chemical shifts of the ring protons and carbon atoms in the substituted compounds 4-X'C6H4SO2NH(i,j-X2C6H3). The different methods of calculation lead to almost the same values in most cases and agree well with the observed chemical shifts, indicating the validity of the principle of additivity of the substituent effects with chemical shifts in these compounds.

  1. CO2-dominated Atmosphere in Equilibrium with NH3-H2O Ocean: Application to Early Titan and Ocean Planets

    NASA Astrophysics Data System (ADS)

    Marounina, N.; Grasset, O.; Tobie, G.; Carpy, S.

    2015-12-01

    During the accretion of Titan, impact heating may have been sufficient to allow the global melting of water ice (Monteux et al. 2014) and the release of volatile compounds, with CO2 and NH3 as main constituents (Tobie et al. 2012). Thus, on primitive Titan, it is thought that a massive atmosphere was in contact with a global water ocean. Similar configurations may occur on temperate water-rich planets called ocean planets (Léger et al. 2004, Kitzmann et al. 2015).Due to its rather low solubility in liquid water, carbon dioxide is expected to be one of the major components in the atmosphere. The atmospheric amount of CO2 is a key parameter for assessing the thermal evolution of the planetary surface because of its strong greenhouse effect. However, ammonia significantly affects the solubility of CO2 in water and hence the atmosphere-ocean thermo-chemical equilibrium. For primitive Titan, estimating the mass, temperature and composition of the primitive atmosphere is important to determine mechanisms that led to the present-day N2-CH4 dominated atmosphere. Similarly, for ocean planets, the influence of ammonia on the atmospheric abundance in CO2 has consequences for the definition of the habitable zone.To investigate the atmospheric composition of the water-rich worlds for a wide range of initial compositions, we have developed a vapor-liquid equilibrium model of the NH3-CO2-H2O system, where we account for the non-ideal comportment of both vapor and liquid phases and the ion speciation of volatiles dissolved in the aqueous phase. We show that adding NH3 to the CO2-H2O binary system induces an efficient absorption of the CO2 in the liquid phase and thus a lower CO2 partial pressure in the vapor phase. Indeed, the CO2 partial pressure remains low for the CO2/NH3 ratio of liquid concentrations lower than 0.5.Assuming various initial compositions of Titan's global water ocean, we explore the thermal and compositional evolution of a massive primitive atmosphere using

  2. Mixed adenine/guanine quartets with three trans-a2 Pt(II) (a=NH(3) or MeNH(2)) cross-links: linkage and rotational isomerism, base pairing, and loss of NH(3).

    PubMed

    Albertí, Francisca M; Rodríguez-Santiago, Luis; Sodupe, Mariona; Mirats, Andrea; Kaitsiotou, Helena; Sanz Miguel, Pablo J; Lippert, Bernhard

    2014-03-17

    Of the numerous ways in which two adenine and two guanines (N9 positions blocked in each) can be cross-linked by three linear metal moieties such as trans-a2 Pt(II) (with a=NH3 or MeNH2 ) to produce open metalated purine quartets with exclusive metal coordination through N1 and N7 sites, one linkage isomer was studied in detail. The isomer trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)}2 ][(ClO4 )6 ]⋅3H2 O (1) (with 9-EtA=9-ethyladenine and 9-MeGH=9-methylguanine) was crystallized from water and found to adopt a flat Z-shape in the solid state as far as the trinuclear cation is concerned. In the presence of excess 9-MeGH, a meander-like construct, trans,trans,trans-[{Pt(NH3 )2 (N7-9-EtA-N1)2 }{Pt(MeNH2 )2 (N7-9-MeGH)2 }][(ClO4 )6 ]⋅[(9-MeGH)2 ]⋅7 H2 O (2) is formed, in which the two extra 9-MeGH nucleobases are hydrogen bonded to the two terminal platinated guanine ligands of 1. Compound 1, and likewise the analogous complex 1 a (with NH3 ligands only), undergo loss of an ammonia ligand and formation of NH4 (+) when dissolved in [D6 ]DMSO. From the analogy between the behavior of 1 and 1 a it is concluded that a NH3 ligand from the central Pt atom is lost. Addition of 1-methylcytosine (1-MeC) to such a DMSO solution reveals coordination of 1-MeC to the central Pt. In an analogous manner, 9-MeGH can coordinate to the central Pt in [D6 ]DMSO. It is proposed that the proton responsible for formation of NH4 (+) is from one of the exocyclic amino groups of the two adenine bases, and furthermore, that this process is accompanied by a conformational change of the cation from Z-form to U-form. DFT calculations confirm the proposed mechanism and shed light on possible pathways of this process. Calculations show that rotational isomerism is not kinetically hindered and that it would preferably occur previous to the displacement of NH3 by DMSO. This displacement is the most energetically costly step, but it is compensated by the proton

  3. CHEMICAL PROCESSING OF PURE AMMONIA AND AMMONIA-WATER ICES INDUCED BY HEAVY IONS

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

    Bordalo, V.; Da Silveira, E. F.; Lv, X. Y.

    Cosmic rays are possibly the main agents to prevent the freeze-out of molecules onto grain surfaces in cold dense clouds. Ammonia (NH{sub 3}) is one of the most abundant molecules present in dust ice mantles, with a concentration of up to 15% relative to water (H{sub 2}O). FTIR spectroscopy is used to monitor pure NH{sub 3} and NH{sub 3}-H{sub 2}O ice samples as they are irradiated with Ni and Zn ion beams (500-600 MeV) at GANIL/France. New species, such as hydrazine (N{sub 2}H{sub 4}), diazene (N{sub 2}H{sub 2} isomers), molecular hydrogen (H{sub 2}), and nitrogen (N{sub 2}) were identified aftermore » irradiation of pure NH{sub 3} ices. Nitrous oxide (N{sub 2}O), nitrogen oxide (NO), nitrogen dioxide (NO{sub 2}), and hydroxylamine (NH{sub 2}OH) are some of the products of the NH{sub 3}-H{sub 2}O ice radiolysis. The spectral band at 6.85 {mu}m was observed after irradiation of both types of ice. Besides the likely contribution of ammonium (NH{sub 4}{sup +}) and amino (NH{sub 2}) radicals, data suggest a small contribution of NH{sub 2}OH to this band profile after high fluences of irradiation of NH{sub 3}-H{sub 2}O ices. The spectral shift of the NH{sub 3} ''umbrella'' mode (9.3 {mu}m) band is parameterized as a function of NH{sub 3}/H{sub 2}O ratio in amorphous ices. Ammonia and water destruction cross-sections are obtained, as well as the rate of NH{sub 3}-H{sub 2}O (1:10) ice compaction, measured by the OH dangling bond destruction cross-section. Ammonia destruction is enhanced in the presence of H{sub 2}O in the ice and a power law relationship between stopping power and NH{sub 3} destruction cross-section is verified. Such results may provide relevant information for the evolution of molecular species in dense molecular clouds.« less

  4. Na{sub 3}[B{sub 20}H{sub 17}NH{sub 3}]: Synthesis and liposomal delivery to murine tumors

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

    Feakes, D.A.; Shelly, K.; Knobler, C.B.

    1994-04-12

    The polyhedral borane ion [n-B{sub 20}H{sub 18}]{sup 2{minus}} reacts with liquid ammonia in the presence of a suitable base to produce an apical-equatorial (ae) isomer of the [B{sub 20}H{sub 17}NH{sub 3}]{sup 3{minus}} ion, [1-(2{prime}-B{sub 10}H{sub 9})-2-NH{sub 3}B{sub 10}H{sub 8}]{sup 3{minus}}. The structure of this product has been confirmed by {sup 11}B NMR spectroscopy and x-ray crystallography. This species undergoes acid-catalyzed rearrangement to an apical-apical (a{sup 2}) isomer, [1-(1{prime}-B{sub 10}H{sub 9})-2-NH{sub 3}B{sub 10}H{sub 8}]{sup 3{minus}}, whose structure has been determined by {sup 11}B NMR spectroscopy. The sodium salts of both the ae and the a{sup 2} isomers of [B{sub 20}H{sub 17}NH{submore » 3}]{sup 3{minus}} have been encapsulated within small unilamellar liposomes, composed of distearoyl phosphatidyl-choline/cholesterol (1:1), and investigated as boron-delivery agents for boron neutron capture therapy (BNCT) of cancer. The biodistribution of boron was determined after the injection of liposomal suspensions into BALB/c mice bearing EMT6 tumors. Both [B{sub 20}H{sub 17}NH{sub 3}]{sup 3{minus}} isomers exhibited excellent tumor uptake and selectivity at very low injected doses, achieving peak tumor boron concentrations of 30-40 {mu}g of B/g of tissue and tumor/blood boron ratios of {approximately}5. The enhanced retention of the [B{sub 20}H{sub 17}NH{sub 3}]{sup 3{minus}} isomers by EMT6 tumors may be attributed to their facile intracellular oxidation. In another experiment, [ae-B{sub 20}H{sub 17}NH{sub 3}]{sup 3{minus}} was encapsulated in liposomes prepared with 5% PEG-2000-distearoyl phosphatidylethanolamine in the liposome membrane. As expected, these liposomes exhibited a longer circulation lifetime in the biodistribution experiment, resulting in the continued accumulation of boron in the tumor over the entire 48-hr experiment and reaching a maximum of 47 {mu}g of B/g of tumor.« less

  5. Non-Controlled Biogenic Emission of CO, H2S, NH3 and Hg0 from Lazareto's Landfill, Tenerife, Canary Islands

    NASA Astrophysics Data System (ADS)

    Nolasco, D.; Lima, R.; Salazar, J.; Hernández, P. A.; Pérez, N. M.

    2002-12-01

    Landfills are important sources of contaminant gases to the surrounding environment and a significant amount of them could be released to the atmosphere through the surface environment in a diffuse form, also known as non-controlled emission of landfill gases. CH4 and CO2 are major components in landfill gases and other gas species are only present in minor amounts. Trace compounds include both inorganic and a large number of volatile organic components. The goal of this study is to evaluate the non-controlled biogenic emission of inorganic toxic gases from Lazareto's landfill. Which is located in the city of Santa Cruz de Tenerife, with a population of about 150,000, and is used as a Palm tree park. Lazareto's landfill has an extension of 0.22 Km2 and it is not operative since 1980. A non-controlled biogenic gas emission survey of 281 sampling sites was carried out from February tod March, 2002. Surface CO2 efflux measurements were performed by means of a portable NDIR sensor according with the accumulation chamber method. Surface CO2 efflux ranged from negligible values up to 30,600 gm-2d-1. At each sampling site, surface landfill gas samples were collected at 40 cm depth using a metallic soil probe. These gas samples were analyzed within 24 hours for major and inorganic toxic gas species by means of microGC and specific electrochemical sensors. The highest concentrations of CO, H2S, NH3 and Hg0 were 3, 20, 2,227, 0.010 ppmV, respectively. Non-controlled biogenic emission rate of CO, H2S, NH3, and Hg0 were estimated by multiplying the observed surface CO2 efflux times (Inorganic Toxic Gas)i/CO2 weight ratio at each sampling site, respectively. The highest surface inorganic toxic gas efllux rates were 699 gm-2d-1 for NH3, 81, 431 and 4 mgm-2d-1 for CO, H2S and Hg0, respectively. Taking into consideration the spatial distribution of the inorganic toxic gas efflux values as well as the extension of the landfill, the non-controlled biogenic emission of CO, H2S, NH3

  6. Efficient synthesis of ammonia from N2 and H2 alone in a ferroelectric packed-bed DBD reactor

    NASA Astrophysics Data System (ADS)

    Gómez-Ramírez, A.; Cotrino, J.; Lambert, R. M.; González-Elipe, A. R.

    2015-12-01

    A detailed study of ammonia synthesis from hydrogen and nitrogen in a planar dielectric barrier discharge (DBD) reactor was carried out. Electrical parameters were systematically varied, including applied voltage and frequency, electrode gap, and type of ferroelectric material (BaTiO3 versus PZT). For selected operating conditions, power consumption and plasma electron density were estimated from Lissajous diagrams and by application of the Bolsig  +  model, respectively. Optical emission spectroscopy was used to follow the evolution of plasma species (\\text{N}{{\\text{H}}*},{{\\text{N}}*},~{N}2+~\\text{and} ~{N}2* ) as a function of applied voltage with both types of ferroelectric material. PZT gave both greater energy efficiency and higher ammonia yield than BaTiO3: 0.9 g NH3 kWh-1 and 2.7% single pass N2 conversion, respectively. This performance is substantially superior to previously published findings on DBD synthesis of NH3 from N2 and H2 alone. The influence of electrical working parameters, the beneficial effect of PZT and the importance of controlling reactant residence time are rationalized in a reaction model that takes account of the principal process variables

  7. Orthorhombic fulleride (CH3NH2)K3C60 close to Mott-Hubbard instability: Ab initio study

    NASA Astrophysics Data System (ADS)

    Potočnik, Anton; Manini, Nicola; Komelj, Matej; Tosatti, Erio; Arčon, Denis

    2012-08-01

    We study the electronic structure and magnetic interactions in methylamine-intercalated orthorhombic alkali-doped fullerene (CH3NH2)K3C60 within the density functional theory. As in the simpler ammonia intercalated compound (NH3)K3C60, the orthorhombic crystal-field anisotropy Δ lifts the t1u triple degeneracy at the Γ point and drives the system deep into the Mott-insulating phase. However, the computed Δ and conduction electron bandwidth W cannot alone account for the abnormally low experimental Néel temperature, TN=11 K, of the methylamine compound, compared to the much higher value TN=40 K of the ammonia one. Significant interactions between CH3NH2 and C603- are responsible for the stabilization of particular fullerene-cage distortions and the ensuing low-spin S=1/2 state. These interactions also seem to affect the magnetic properties, as interfullerene exchange interactions depend on the relative orientation of deformations of neighboring C603- molecules. For the ferro-orientational order of CH3NH2-K+ groups we find an apparent reduced dimensionality in magnetic exchange interactions, which may explain the suppressed Néel temperature. The disorder in exchange interactions caused by orientational disorder of CH3NH2-K+ groups could further contribute to this suppression.

  8. Experimental investigation of aminoacetonitrile formation through the Strecker synthesis in astrophysical-like conditions: reactivity of methanimine (CH2NH), ammonia (NH3), and hydrogen cyanide (HCN)

    NASA Astrophysics Data System (ADS)

    Danger, G.; Borget, F.; Chomat, M.; Duvernay, F.; Theulé, P.; Guillemin, J.-C.; Le Sergeant D'Hendecourt, L.; Chiavassa, T.

    2011-11-01

    Context. Studing chemical reactivity in astrophysical environments is an important means for improving our understanding of the origin of the organic matter in molecular clouds, in protoplanetary disks, and possibly, as a final destination, in our solar system. Laboratory simulations of the reactivity of ice analogs provide important insight into the reactivity in these environments. Here, we use these experimental simulations to investigate the Strecker synthesis leading to the formation of aminoacetonitrile in astrophysical-like conditions. The aminoacetonitrile is an interesting compound because it was detected in SgrB2, hence could be a precursor of the smallest amino acid molecule, glycine, in astrophysical environments. Aims: We present the first experimental investigation of the formation of aminoacetonitrile NH2CH2CN from the thermal processing of ices including methanimine (CH2NH), ammonia (NH3), and hydrogen cyanide (HCN) in interstellar-like conditions without VUV photons or particules. Methods: We use Fourier Transform InfraRed (FTIR) spectroscopy to monitor the ice evolution during its warming. Infrared spectroscopy and mass spectroscopy are then used to identify the aminoacetonitrile formation. Results: We demonstrate that methanimine can react with -CN during the warming of ice analogs containing at 20 K methanimine, ammonia, and [NH4+ -CN] salt. During the ice warming, this reaction leads to the formation of poly(methylene-imine) polymers. The polymer length depend on the initial ratio of mass contained in methanimine to that in the [NH4+ -CN] salt. In a methanimine excess, long polymers are formed. As the methanimine is progressively diluted in the [NH4+ -CN] salt, the polymer length decreases until the aminoacetonitrile formation at 135 K. Therefore, these results demonstrate that aminoacetonitrile can be formed through the second step of the Strecker synthesis in astrophysical-like conditions.

  9. Synthesis, PtS-type structure, and anomalous mechanics of the Cd(CN)2 precursor Cd(NH3)2[Cd(CN)4].

    PubMed

    Coates, Chloe S; Makepeace, Joshua W; Seel, Andrew G; Baise, Mia; Slater, Ben; Goodwin, Andrew L

    2018-05-15

    We report the nonaqueous synthesis of Cd(CN)2 by oxidation of cadmium metal with Hg(CN)2 in liquid ammonia. The reaction proceeds via an intermediate of composition Cd(NH3)2[Cd(CN)4], which converts to Cd(CN)2 on prolonged heating. Powder X-ray diffraction measurements allow us to determine the crystal structure of the previously-unreported Cd(NH3)2[Cd(CN)4], which we find to adopt a twofold interpenetrating PtS topology. We discuss the effect of partial oxidation on the Cd/Hg composition of this intermediate, as well as its implications for the reconstructive nature of the deammination process. Variable-temperature X-ray diffraction measurements allow us to characterise the anisotropic negative thermal expansion (NTE) behaviour of Cd(NH3)2[Cd(CN)4] together with the effect of Cd/Hg substitution; ab initio density functional theory (DFT) calculations reveal a similarly anomalous mechanical response in the form of both negative linear compressibility (NLC) and negative Poisson's ratios.

  10. Synthesis of opioidmimetics, 3-[H-Dmt-NH(CH(2))(m)]-6-[H-Dmt-NH(CH(2))(n)]-2(1H)-pyrazinones, and studies on structure-activity relationships.

    PubMed

    Shiotani, Kimitaka; Miyazaki, Anna; Li, Tingyou; Tsuda, Yuko; Yokoi, Toshio; Ambo, Akihiro; Sasaki, Yusuke; Bryant, Sharon D; Jinsmaa, Yunden; Lazarus, Lawrence H; Okada, Yoshio

    2007-11-01

    Opioidmimetics containing 3-[H-Dmt-NH-(CH(2))(m)]-6-[H-Dmt-NH-(CH(2))(n)]-2(1H)-pyrazinone symmetric (m = n, 1-4) (1 - 4) and asymmetric (m, n = 1 - 4) aliphatic chains (5 - 16) were synthesized using dipeptidyl chloromethylketone intermediates. They had high mu-affinity (K(i)mu = 0.021 - 2.94 nM), delta-affinity (K(i)delta = 1.06 - 152.6 nM), and mu selectivity (K(i)delta/K(i)mu = 14 - 3,126). The opioidmimetics (1 - 16) exhibited mu agonism in proportion to their mu-receptor affinity. delta-Agonism was essentially lacking in the compounds except (4) and (16), and (1) and (2) indicated weak delta antagonism (pA(2) = 6.47 and 6.56, respectively). The data verify that a specific length of aliphatic linker is required between the Dmt pharmacophore and the pyrazinone ring to produce unique mu-opioid receptor ligands.

  11. Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2O in alkaline electrolytes

    DOE PAGES

    Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros; ...

    2018-03-23

    Ammonia (NH 3) is considered an important chemical for both agriculture fertilizer and renewable energy. The conventional Haber-Bosh process to produce NH 3 is energy intensive and leads to significant CO 2 emission. Alternatively, electrochemical synthesis of ammonia (ESA) through the nitrogen reduction reaction (NRR) by using renewable electricity has recently attracted significant attention. Herein, we report a metal-organic framework-derived nitrogen-doped nanoporous carbon as an electrocatalyst for the NRR. It exhibits a remarkable production rate of NH 3 up to 3.4 ×10 –6 mol cm –2 h –1 with a Faradaic efficiency (FE) of 10.2% at –0.3 V vs. RHEmore » under room temperature and ambient pressure using aqueous 0.1 M KOH electrolyte. Increasing the temperature to 60 °C further improves production rates to 7.3 × 10 –6 mol cm –2 h –1. The stability of the nitrogen-doped carbon electrocatalyst was demonstrated during an 18-h continuous test with constant production rates. First principles calculations were used to elucidate the possible active sites and reaction pathway. The moiety, which consists of three pyridinic N atoms (N 3) adjacent with one carbon vacancy embedded in a carbon layer, is able to strongly adsorb N 2 and further realize N≡N triple bond dissociation for the subsequent protonation process. The rate-determining step of the NRR is predicted to be the adsorption and bond activation of N 2 molecule. Increasing overpotentials is favorable for the protonation process during NH 3 generation. Further doping Fe into the nitrogen-doped carbon likely blocks the N 3 active sites and facilitates the hydrogen evolution reaction, a strong competitor to the NRR, thus yielding negative effect on ammonia production. Furthermore, this work provides a new insight into the rational design and synthesis of nitrogen-doped and defect-rich carbon as efficient NRR catalysts for NH 3 synthesis at ambient conditions.« less

  12. Metal-organic framework-derived nitrogen-doped highly disordered carbon for electrochemical ammonia synthesis using N 2 and H 2O in alkaline electrolytes

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

    Mukherjee, Shreya; Cullen, David A.; Karakalos, Stavros

    Ammonia (NH 3) is considered an important chemical for both agriculture fertilizer and renewable energy. The conventional Haber-Bosh process to produce NH 3 is energy intensive and leads to significant CO 2 emission. Alternatively, electrochemical synthesis of ammonia (ESA) through the nitrogen reduction reaction (NRR) by using renewable electricity has recently attracted significant attention. Herein, we report a metal-organic framework-derived nitrogen-doped nanoporous carbon as an electrocatalyst for the NRR. It exhibits a remarkable production rate of NH 3 up to 3.4 ×10 –6 mol cm –2 h –1 with a Faradaic efficiency (FE) of 10.2% at –0.3 V vs. RHEmore » under room temperature and ambient pressure using aqueous 0.1 M KOH electrolyte. Increasing the temperature to 60 °C further improves production rates to 7.3 × 10 –6 mol cm –2 h –1. The stability of the nitrogen-doped carbon electrocatalyst was demonstrated during an 18-h continuous test with constant production rates. First principles calculations were used to elucidate the possible active sites and reaction pathway. The moiety, which consists of three pyridinic N atoms (N 3) adjacent with one carbon vacancy embedded in a carbon layer, is able to strongly adsorb N 2 and further realize N≡N triple bond dissociation for the subsequent protonation process. The rate-determining step of the NRR is predicted to be the adsorption and bond activation of N 2 molecule. Increasing overpotentials is favorable for the protonation process during NH 3 generation. Further doping Fe into the nitrogen-doped carbon likely blocks the N 3 active sites and facilitates the hydrogen evolution reaction, a strong competitor to the NRR, thus yielding negative effect on ammonia production. Furthermore, this work provides a new insight into the rational design and synthesis of nitrogen-doped and defect-rich carbon as efficient NRR catalysts for NH 3 synthesis at ambient conditions.« less

  13. High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates - Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) and Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O

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

    Schmidt, Corinna; Feyand, Mark; Rothkirch, Andre

    2012-04-15

    The system Ca{sup 2+}/2-aminoethylphosphonic acid/H{sub 2}O/NaOH was systematically investigated using high-throughput methods. The experiments led to one new compound Ca(O{sub 3}PC{sub 2} H{sub 4}NH{sub 2}) (1) and the crystal structure was determined using in house X-ray powder diffraction data (monoclinic, P2{sub 1}/c, a=9.7753(3), b=6.4931(2), c=8.4473(2) A, {beta}=106.46(2) Degree-Sign , V=514.20(2) A{sup 3}, Z=4). The formation of 1 was investigated by in situ energy dispersive X-ray diffraction measurements (EDXRD) at beamline F3 at HASYLAB (light source DORIS III), DESY, Hamburg. An intermediate, Ca(OH)(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3}){center_dot}2H{sub 2}O (2), was observed and could be isolated from the reaction mixture at ambientmore » temperatures by quenching the reaction. The crystal structure of 2 was determined from XRPD data using synchrotron radiation (monoclinic, P2{sub 1}/m, a=11.2193(7), b=7.1488(3), c=5.0635(2) A, {beta}=100.13(4) Degree-Sign , V=399.78(3) A{sup 3}, Z=2). - Graphical abstarct: The detailed in situ energy dispersive X-ray diffraction (EDXRD) investigation on the formation of the new inorganic-organic hybrid compound Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) leads to the discovery of a new crystalline intermediate phase. Both crystal structures were elucidated using X-ray powder diffraction data. Highlights: Black-Right-Pointing-Pointer High-throughput investigation led to new metal aminoethylphosphonate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}). Black-Right-Pointing-Pointer The formation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 2}) was followed by in situ EDXRD measurements. Black-Right-Pointing-Pointer The crystalline intermediate Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was discovered. Black-Right-Pointing-Pointer Isolation of Ca(O{sub 3}PC{sub 2}H{sub 4}NH{sub 3})(OH){center_dot}2H{sub 2}O was accomplished by quenching experiments. Black-Right-Pointing-Pointer The structures were determined using X

  14. Parallel changes in intracellular water volume and pH induced by NH(3)/NH(4)(+) exposure in single neuroblastoma cells.

    PubMed

    Blanco, Víctor M; Márquez, Martín S; Alvarez-Leefmans, Francisco J

    2013-01-01

    Increased blood levels of ammonia (NH3) and ammonium (NH4(+)), i.e. hyperammonemia, leads to cellular brain edema in humans with acute liver failure. The pathophysiology of this edema is poorly understood. This is partly due to incomplete understanding of the osmotic effects of the pair NH3/NH4(+) at the cellular and molecular levels. Cell exposure to solutions containing NH3/NH4(+) elicits changes in intracellular pH (pHi), which can in turn affect cell water volume (CWV) by activating transport mechanisms that produce net gain or loss of solutes and water. The occurrence of CWV changes caused by NH3/NH4(+) has long been suspected, but the mechanisms, magnitude and kinetics of these changes remain unknown. Using fluorescence imaging microscopy we measured, in real time, parallel changes in pHi and CWV caused by brief exposure to NH3/NH4(+) of single cells (N1E-115 neuroblastoma or NG-108 neuroblastoma X glioma ) loaded with the fluorescent indicator BCECF. Changes in CWV were measured by exciting BCECF at its intracellular isosbestic wavelength (∼438 nm), and pHi was measured ratiometrically. Brief exposure to isosmotic solutions (i.e. having the same osmolality as that of control solutions) containing NH4Cl (0.5- 30 mM) resulted in a rapid, dose-dependent swelling, followed by isosmotic regulatory volume decrease (iRVD). NH4Cl solutions in which either extracellular [NH3] or [NH4(+)] was kept constant while the other was changed by varying the pH of the solution, demonstrated that [NH3]o rather than [NH4(+)]o is the main determinant of the NH4Cl-induced swelling. The iRVD response was sensitive to the anion channel blocker NPPB, and partly dependent on external Ca(2+). Upon removal of NH4Cl, cells shrank and displayed isosmotic regulatory volume increase (iRVI). Regulatory volume responses could not be activated by comparable CWV changes produced by anisosmotic solutions, suggesting that membrane stretch or contraction by themselves are not sufficient to

  15. Analysis of gaseous ammonia (NH3) absorption in the visible spectrum of Jupiter

    NASA Astrophysics Data System (ADS)

    Irwin, Patrick G. J.; Bowles, Neil; Braude, Ashwin S.; Garland, Ryan; Calcutt, Simon

    2018-03-01

    Observations of the visible/near-infrared reflectance spectrum of Jupiter have been made with the Very Large Telescope (VLT) Multi Unit Spectroscopic Explorer (MUSE) instrument in the spectral range 0.48-0.93 μm in support of the NASA/Juno mission. These spectra contain spectral signatures of gaseous ammonia (NH3), whose abundance above the cloud tops can be determined if we have reliable information on its absorption spectrum. While there are a number of sources of NH3 absorption data in this spectral range, they cover small sub-ranges, which do not necessarily overlap and have been determined from a variety of sources. There is thus considerable uncertainty regarding the consistency of these different sources when modelling the reflectance of the entire visible/near-IR range. In this paper we analyse the VLT/MUSE observations of Jupiter to determine which sources of ammonia absorption data are most reliable. We find that the band model coefficients of Bowles et al. (2008) provide, in general, the best combination of reliability and wavelength coverage over the MUSE range. These band data appear consistent with ExoMOL ammonia line data of Yurchenko et al. (2011), at wavelengths where they overlap, but these latter data do not cover the ammonia absorption bands at 0.79 and 0.765 μm, which are prominent in our MUSE observations. However, we find the band data of Bowles et al. (2008) are not reliable at wavelengths less than 0.758 μm. At shorter wavelengths we find the laboratory observations of Lutz and Owen (1980) provide a good indication of the position and shape of the ammonia absorptions near 0.552 μm and 0.648 μm, but their absorption strengths appear inconsistent with the band data of Bowles et al. (2008) at longer wavelengths. Finally, we find that the line data of the 0.648 μm absorption band of Giver et al. (1975) are not suitable for modelling these data as they account for only 17% of the band absorption and cannot be extended reliably to the cold

  16. Looking for high-mass young stellar objects: H2O and OH masers in ammonia cores

    NASA Astrophysics Data System (ADS)

    Codella, C.; Cesaroni, R.; López-Sepulcre, A.; Beltrán, M. T.; Furuya, R.; Testi, L.

    2010-02-01

    Context. The earliest stages of high-mass star formation have yet to be characterised well, because high-angular resolution observations are required to infer the properties of the molecular gas hosting the newly formed stars. Aims: We search for high-mass molecular cores in a large sample of 15 high-mass star-forming regions that are observed at high-angular resolution, extending a pilot survey based on a smaller number of objects. Methods: The sample was chosen from surveys of H2O and OH masers to favour the earliest phases of high-mass star formation. Each source was first observed with the 32-m single-dish Medicina antenna in the (1, 1) and (2, 2) inversion transitions at 1.3 cm of ammonia, which is an excellent tracer of dense gas. High-resolution maps in the NH3(2, 2) and (3, 3) lines and the 1.3 cm continuum were obtained successively with the VLA interferometer. Results: We detect continuum emission in almost all the observed star-forming regions, which corresponds to extended and UCHii regions created by young stellar objects with typical luminosities of ˜10^4~L⊙. However, only in three cases do we find a projected overlap between Hii regions and H2O and OH maser spots. On the other hand, the VLA images detect eight ammonia cores closely associated with the maser sources. The ammonia cores have sizes of ˜10^4 AU, and high masses (up to 104M⊙), and are very dense (from ˜10^6 to a few ×10^9 cm-3). The typical relative NH3 abundance is ≤10-7, in agreement with previous measurements in high-mass star-forming regions. Conclusions: The statistical analysis of the distribution between H2O and OH masers, NH3 cores, and Hii regions confirms that the earliest stages of high-mass star formation are characterised by high-density molecular cores with temperatures of on average ≥30 K, either without a detectable ionised region or associated with a hypercompact Hii region.

  17. The Role of Lewis and Brønsted Acid Sites in NO Reduction with NH3 on Sulfur Modified TiO2-Supported V2O5 Catalyst

    NASA Astrophysics Data System (ADS)

    Zhao, Wei; Dou, Shengping; Zhong, Qin; Wu, Licheng; Wang, Qian; Wang, Aijian

    2017-12-01

    V2O5/S-doped TiO2 was prepared by the sol-gel and impregnation methods. The adsorption of NO, NH3, and O2 over the catalyst was studied by in situ DRIFTS spectroscopy to elucidate the reaction mechanism of the low-temperature selective catalytic reduction of NO with NH3. Exposing the catalyst to O2 and NO, three types of nitrates species appeared on the surface. The introduction of S to TiO2 could generate large amounts of acid sites for ammonia adsorption on the catalyst, which was believed to be an important role in the SCR reaction and hereby improved the catalytic activity. The results indicated two possible SCR reaction pathways for catalyst. One was that NO was absorbed to form nitrite species, which could react with NH3 on Lewis acid sites, producing N2 and H2O. Another way was that NH3 was adsorbed, then reacted with gas phase NO (E-R) and nitrite intermediates on the surface (L-H).

  18. The ammonia-water phase diagram and its implications for icy satellites

    NASA Technical Reports Server (NTRS)

    Johnson, M. L.; Nicol, M.

    1986-01-01

    A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

  19. The ammonia-water phase diagram and its implications for icy satellites

    NASA Technical Reports Server (NTRS)

    Johnson, Mary L.; Nicol, Malcolm

    1987-01-01

    A Holzapfel-type diamond anvil cell is used to determine the NH3 - H2O phase diagram in the region from 0 to 33 mole percent NH3, 240 to 370 K, and 0 to 5 GPa. The following phases were identified: liquid; water ices Ih, III, V, VI, VII, and VIII; ammonia monohydrate, NH3.H2O; and ammonia dihydrate NH3.2H2O. Ammonia dihydrate becomes prominent at moderate pressures (less than 1 GPa), with planetologically significant implications, including the possibility of layering in Titan's magma ocean.

  20. Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review.

    PubMed

    Krupa, S V

    2003-01-01

    At the global scale, among all N (nitrogen) species in the atmosphere and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atmospheric NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atmosphere to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a number of studies on N deposition and lichens, mosses and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concentrations. In addition to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal associations and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concentrations are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4

  1. Synthesis and structure of cesium complexes of nitrilotris(methylenephosphonic) acid [Cs-μ6-NH(CH2PO3)3H4] and [Cs2-μ10-NH(CH2PO3H)3] · H2O

    NASA Astrophysics Data System (ADS)

    Somov, N. V.; Chausov, F. F.; Zakirov, R. M.

    2017-07-01

    3D coordination polymers cesium nitrilotris(methylenephosphonate) and dicesium nitrilotris( methylenephosphonate) are synthesized and their crystal structure is determined. In the crystal of [Cs-μ6-NH(CH2PO3)3H4] (space group P, Z = 2), cesium atoms occupy two crystallographically inequivalent positions with c.n. = 10 and c.n. = 14. The phosphonate ligand plays the bridging function; its denticity is nine. The crystal packing consists of alternating layers of Cs atoms in different environments with layers of ligand molecules between them. A ligand is bound to three Cs atoms of one layer and three Cs atoms of another layer. In the crystal of [Cs2-μ10-NH(CH2PO3H)3] · H2O (space group P, Z = 2), the complex has a dimeric structure: the bridging phosphonate ligand coordinates Cs to form a three-dimensional Cs4O6 cluster. The denticity of the ligand is equal to nine; the coordination numbers of cesium atoms are seven and nine. Two-dimensional corrugated layers of Cs4O6 clusters lie in the (002) plane, and layers of ligand molecules are located between them. Each ligand molecule coordinates eight Cs atoms of one layer and two Cs atoms of the neighboring layer.

  2. Room temperature ammonia gas sensing properties of MoS2 nanostructured thin film

    NASA Astrophysics Data System (ADS)

    Sharma, Shubham; Kumar, Arvind; Kaur, Davinder

    2018-05-01

    Here, we have fabricated the MoS2 nanostructure thin films on the Si (100) substrate using DC magnetron sputtering technique. The MoS2 thin film sensor shows the selective responses towards the ammonia gas (NH3) under low detection range 10-500 ppm. The sensor displays a significantly high sensing response (Rg/Ra ˜2.2) towards 100 ppm ammonia gas with a very fast response and recovery time of 22 sec and 30 sec respectively. Selectivity and stability investigations exhibit the excellent sensing properties of MoS2 thin film sensor. The working principle and sensing mechanism behind their remarkable performance was also investigated in detail.

  3. Exploring Renner-Teller induced quenching in the reaction H(2S)+NH(a 1Delta): a combined experimental and theoretical study.

    PubMed

    Adam, L; Hack, W; McBane, G C; Zhu, H; Qu, Z-W; Schinke, R

    2007-01-21

    Experimental rate coefficients for the removal of NH(a (1)Delta) and ND(a (1)Delta) in collisions with H and D atoms are presented; all four isotope combinations are considered: NH+H, NH+D, ND+H, and ND+D. The experiments were performed in a quasistatic laser-flash photolysis/laser-induced fluorescence system at low pressures. NH(a (1)Delta) and ND(a (1)Delta) were generated by photolysis of HN(3) and DN(3), respectively. The total removal rate coefficients at room temperature are in the range of (3-5)x10(13) cm(3) mol(-1) s(-1). For two isotope combinations, NH+H and NH+D, quenching rate coefficients for the production of NH(X (3)Sigma(-)) or ND(X (3)Sigma(-)) were also determined; they are in the range of 1 x 10(13) cm(3) mol(-1) s(-1). The quenching rate coefficients directly reflect the strength of the Renner-Teller coupling between the (2)A(") and (2)A(') electronic states near linearity and so can be used to test theoretical models for describing this nonadiabatic process. The title reaction was modeled with a simple surface-hopping approach including a single parameter, which was adjusted to reproduce the quenching rate for NH+H; the same parameter value was used for all isotope combinations. The agreement with the measured total removal rate is good for all but one isotope combination. However, the quenching rates for the NH+D combination are only in fair (factor of 2) agreement with the corresponding measured data.

  4. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

    DOE PAGES

    Lin, Yu; Welchman, Evan; Thonhauser, Timo; ...

    2017-03-15

    Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

  5. The structure and unconventional dihydrogen bonding of a pressure-stabilized hydrogen-rich (NH 3BH 3)(H 2) x(x = 1.5) compound

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

    Lin, Yu; Welchman, Evan; Thonhauser, Timo

    Combining X-ray diffraction, Raman spectroscopy, and ab initio simulations we characterize an extremely hydrogen-rich phase with the chemical formula (NH 3BH 3)(H 2) x (x = 1.5). This phase was formed by compressing ammonia borane (AB, NH 3BH 3) in an environment with an excess of molecular hydrogen (H 2). This compound can store a total of 26.8 wt% hydrogen, both as molecular hydrogen and chemically bonded hydrogen in AB, making it one of the most hydrogen-rich solids currently known. The new compound possesses a layered AB structure where additional H 2 molecules reside in channels created through the weavingmore » of AB layers. The unconventional dihydrogen bonding network of the new compound is significantly modified from its parent AB phase and contains H•••H contacts between adjacent AB molecules and between AB and H 2 molecules. H–H can be either a proton donor or a proton acceptor that forms new types of dihydrogen bonding with the host AB molecules, which are depicted as H–H•••H–B or H–H•••H–N, respectively. Furthermore, this study not only demonstrates the strategy and the promise of using pressure for new material synthesis, but also unleashes the power of combining experiments and ab initio calculations for elucidating novel structures and unusual bonding configurations in dense low-Z materials.« less

  6. Collisional excitation of NH3 by atomic and molecular hydrogen

    NASA Astrophysics Data System (ADS)

    Bouhafs, N.; Rist, C.; Daniel, F.; Dumouchel, F.; Lique, F.; Wiesenfeld, L.; Faure, A.

    2017-09-01

    We report extensive theoretical calculations on the rotation-inversion excitation of interstellar ammonia (NH3) due to collisions with atomic and molecular hydrogen (both para- and ortho-H2). Close-coupling calculations are performed for total energies in the range 1-2000 cm-1 and rotational cross-sections are obtained for all transitions amongst the lowest 17 and 34 rotation-inversion levels of ortho- and para-NH3, respectively. Rate coefficients are deduced for kinetic temperatures up to 200 K. Propensity rules for the three colliding partners are discussed and we also compare the new results to previous calculations for the spherically symmetrical He and para-H2 projectiles. Significant differences are found between the different sets of calculations. Finally, we test the impact of the new rate coefficients on the calibration of the ammonia thermometer. We find that the calibration curve is only weakly sensitive to the colliding partner and we confirm that the ammonia thermometer is robust.

  7. Synthesis of zinc sulfide nanoparticles during zinc oxidization by H2S and H2S/H2O supercritical fluids

    NASA Astrophysics Data System (ADS)

    Vostrikov, A. A.; Fedyaeva, O. N.; Sokol, M. Ya.; Shatrova, A. V.

    2014-12-01

    Formation of zinc sulfide nanoparticles was detected during interaction of bulk samples with hydrogen sulfide at supercritical parameters. Synthesis proceeds with liberation of H2 by the reaction nZn + nH2S = (ZnS) n + nH2. It has been found by the X-ray diffraction method, scanning electron microscopy, and mass spectrometry that the addition of water stimulates coupled reactions of nanoparticle synthesis nZn + nH2O = (ZnO) n + nH2 and (ZnO) n + nH2S = (ZnS) n + nH2O and brings about an increase in the synthesis rate and morphological changes of (ZnS) n nanoparticles.

  8. Raman spectra and cross sections of ammonia, chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400 1400 cm 1

    DTIC Science & Technology

    2015-11-24

    ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400... ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint...sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint

  9. Raman Spectra and Cross Sections of Ammonia, Chlorine, Hydrogen Sulfide, Phosgene, and Sulfur Dioxide Toxic Gases in the Fingerprint Region 400-1400 cm-1

    DTIC Science & Technology

    2015-12-14

    ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in the fingerprint region 400... ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (COCl2), and sulfur dioxide (SO2) toxic gases have been measured in the fingerprint...sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint region

  10. The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

    NASA Technical Reports Server (NTRS)

    Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

    1984-01-01

    The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

  11. Spatial and temporal patterns of nitrogen isotopic composition of ammonia at U.S. ammonia monitoring network sites

    NASA Astrophysics Data System (ADS)

    Felix, J. David; Elliott, Emily M.; Gay, David A.

    2017-02-01

    Ammonia (NH3) emissions and ammonium (NH4+) deposition can have harmful effects on the environment and human health but remain generally unregulated in the U.S. PM2.5 regulations require that an area not exceed an annual average PM2.5 value of 12 μg/m3 (averaged over three years), and since NH3 is a significant precursor to PM2.5 formation these are the closest indirect regulations of NH3 emissions in the U.S. If the U.S. elects to adopt NH3 emission regulations similar to those applied by the European Union, it will be imperative to first adequately quantify NH3 emission sources and transport, and also understand the factors causing varying emissions from each source. To further investigate NH3 emission sources and transport at a regional scale, NH3 was sampled monthly at a subset of nine Ammonia Monitoring Network (AMoN) sites and analyzed for nitrogen isotopic composition of NH3 (δ15N-NH3). The observed δ15N-NH3 values ranged from -42.4 to +7.1‰ with an average of -15.1 ± 9.7. The observed δ15N-NH3 values reported here provide insight into the spatial and temporal trends of the NH3 sources that contribute to ambient [NH3] in the U.S. In regions where agriculture is prevalent (i.e., U.S. Midwest), low and seasonally variable δ15N-NH3 values are observed and are associated with varying agricultural sources. In comparison, rural nonagricultural areas have higher and more seasonally consistent δ15N-NH3 values associated with a constant "natural" (e.g. soil, vegetation, bi-directional flux, ocean) NH3 source. With regards to temporal variation, the peak in U.S. spring agricultural activity (e.g. fertilizer application, livestock waste volatilization) is accompanied by a decrease in δ15N-NH3 values at a majority of the sites, whereas higher δ15N-NH3 values in other seasons could be due to shifting sources (e.g. coal-fired power plants) and/or fractionation scenarios. Fractionation processes that may mask NH3 source signatures are discussed and require

  12. Properties of planetary ices in the NH3 + CO2 ± H2O ternary system using neutron diffraction and ab initio calculations

    NASA Astrophysics Data System (ADS)

    Howard, C. M.; Wood, I. G.; Fortes, A. D.; Vocadlo, L.

    2016-12-01

    BackgroundInteractions between simple molecules are of fundamental interest across diverse areas of the physical sciences, and the ternary system NH3 + CO2 ± H2O is no exception. In the outer solar system, interaction of CO2 with aqueous ammonia is likely to occur, synthesizing `rock-forming' minerals [1], with CO2 perhaps playing a role in ammonia-water oceans and cryomagmas inside icy planetary bodies - the discovery of ammonium carbonates in a crater of Pluto's moon Charon [2] adds weight to CO2 occuring in these planetary environments. In the same context, ammonium carbonates may have some astrobiological relevance, since removal of water leads to the formation of urea. On Earth, combination of CO2 with aqueous ammonia has relevance to carbon capture schemes [3], and there is interest in using such materials for hydrogen storage in fuel cells [4]. Consequently, from earthly matters of climate change to the study of extraterrestrial ices, understanding the structures and properties of ammonium carbonates are important. Despite this, our knowledge of ammonium carbonates is limited under ambient conditions of pressure and temperature and is entirely absent at the higher pressures, severely limiting our ability to model the behaviour of NH3 + CO2 ± H2O solids and fluids in planetary environments. ResultsWe report the results of several experiments using variable pressure and temperature neutron diffraction work on ammonium carbonate monohydrate, ammonium bicarbonate and ammonium carbamate, with complementary Density Functional Theory (DFT) calculations. The excellent agreement between experiments and DFT calculations obtained so far adds weight to the accuracy of calculated material properties of ammonium sesquicarbonate monohydrate and several polymorphs of urea where little empirical data exists. These experimental and computational studies provide the structural, thermoelastic and vibrational information required for accurate planetary modelling and remote

  13. Degradation of SO 2, NO 2 and NH 3 leading to formation of secondary inorganic aerosols: An environmental chamber study

    NASA Astrophysics Data System (ADS)

    Behera, Sailesh N.; Sharma, Mukesh

    2011-08-01

    We have examined the interactions of gaseous pollutants and primary aerosols that can produce secondary inorganic aerosols. The specific objective was to estimate degradation rates of precursor gases (NH 3, NO 2 and SO 2) responsible for formation of secondary inorganic aerosols. A Teflon-based outdoor environmental chamber facility (volume 12.5 m 3) was built and checked for wall losses, leaks, solar transparency and ability to simulate photochemical reactions. The chamber was equipped with state-of-the-art instrumentation to monitor concentration-time profiles of precursor gases, ozone, and aerosol. A total of 14 experimental runs were carried out for estimating the degradation of precursor gases. The following initial conditions were maintained in the chamber: NO 2 = 246 ± 104 ppb(v), NH 3 = 548 ± 83 ppb(v), SO 2 = 238 ± 107 ppb(v), O 3 = 50 ± 11 ppb(v), PM 2.5 aerosol = 283438 ± 60524 No./litre. The concentration-time profile of gases followed first-order decay and were used for estimating degradation rates (NO 2 = 0.26 ± 0.15 h -1, SO 2 = 0.31 ± 0.17 h -1, NH 3 = 0.35 ± 0.21 h -1). We observed that degradation rates showed a statistical significant positive correlation (at 5% level of significance) with the initial PM 2.5 levels in the chamber (coefficient of correlation: 0.63 for NO 2; 0.62 for NH 3 and 0.51 for SO 2), suggesting that the existing surface of the aerosol could play a significant role in degradation of precursor gases. One or more gaseous species can be adsorbed on to the existing particles and these may undergo heterogeneous or homogeneous chemical transformation to produce secondary inorganic aerosols. Through correlation analysis, we have observed that degradation rates of precursor gases were dependent on initial molar ratio of (NH 3)/(NO 2 + SO 2), indicative of ammonia-rich and ammonia-poor situations for eventual production of ammonium salts.

  14. Order-disorder phase transition in the peroxidovanadium complex NH4[VO(O2)2(NH3)].

    PubMed

    Schwendt, Peter; Gyepes, Róbert; Chrappová, Jana; Němec, Ivan; Vaněk, Přemysl

    2018-07-05

    Complex NH 4 [VO(O 2 ) 2 (NH 3 )] (1) undergoes an order-disorder phase transition at T c ~258K. This transition is accompanied by change in the space group of the orthorhombic lattice and also by significant structural rearrangements of the constituent molecules, which are pertinent mostly to their NH 4 + ions and their ammonia ligands. The low-temperature solid state IR and Raman spectra of 1 were corroborated by solid-state computations that employed Gaussian functions as the basis set. Results of these computations yielded excellent agreement with experimental data. On the curves of temperature dependence of vibrational modes, the phase transition is expressed by an abrupt change of the slope above T c . Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

    PubMed

    Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

    2009-03-26

    The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

  16. Ammonia Vapor Removal by Cu(3)(BTC)(2) and Its Characterization by MAS NMR.

    PubMed

    Peterson, Gregory W; Wagner, George W; Balboa, Alex; Mahle, John; Sewell, Tara; Karwacki, Christopher J

    2009-07-01

    Adsorption equilibria and NMR experiments were performed to study the adsorption and interactions of ammonia with metal-organic framework (MOF) HKUST-1, or Cu(3)(BTC)(2) (BTC = 1,3,5-benzenetricarboxylate). Ammonia capacities determined from chemical breakthrough measurements show significantly higher uptake capacities than from adsorption alone, suggesting a stronger interaction involving a potential reaction with the Cu(3)(BTC)(2) framework. Indeed, (1)H MAS NMR reveals that a major disruption of the relatively simple spectrum of Cu(3)(BTC)(2) occurs to generate a composite spectrum consistent with Cu(OH)(2) and (NH(4))(3)BTC species under humid conditions-the anticipated products of a copper(II) carboxylate reacted with limited ammonia. These species are not detected under dry conditions; however, reaction stoichiometry combined with XRD results suggests the partial formation of an indeterminate diammine copper (II) complex with some residual Cu(3)(BTC)(2) structure retained. Cu(II)-induced paramagnetic shifts exhibited by various species in (1)H and (13)C MAS NMR spectra are consistent with model compounds and previous literature. Although results show extensive ammonia capacity of Cu(3)(BTC)(2), much of the capacity is due to reaction with the structure itself, causing a permanent loss in porosity and structural integrity.

  17. Ammonia Vapor Removal by Cu3(BTC)2 and Its Characterization by MAS NMR

    PubMed Central

    Peterson, Gregory W.; Wagner, George W.; Balboa, Alex; Mahle, John; Sewell, Tara; Karwacki, Christopher J.

    2009-01-01

    Adsorption equilibria and NMR experiments were performed to study the adsorption and interactions of ammonia with metal-organic framework (MOF) HKUST-1, or Cu3(BTC)2 (BTC = 1,3,5-benzenetricarboxylate). Ammonia capacities determined from chemical breakthrough measurements show significantly higher uptake capacities than from adsorption alone, suggesting a stronger interaction involving a potential reaction with the Cu3(BTC)2 framework. Indeed, 1H MAS NMR reveals that a major disruption of the relatively simple spectrum of Cu3(BTC)2 occurs to generate a composite spectrum consistent with Cu(OH)2 and (NH4)3BTC species under humid conditions—the anticipated products of a copper(II) carboxylate reacted with limited ammonia. These species are not detected under dry conditions; however, reaction stoichiometry combined with XRD results suggests the partial formation of an indeterminate diammine copper (II) complex with some residual Cu3(BTC)2 structure retained. Cu(II)-induced paramagnetic shifts exhibited by various species in 1H and 13C MAS NMR spectra are consistent with model compounds and previous literature. Although results show extensive ammonia capacity of Cu3(BTC)2, much of the capacity is due to reaction with the structure itself, causing a permanent loss in porosity and structural integrity. PMID:20161144

  18. Deuteration of ammonia in the starless core Ophiuchus/H-MM1

    NASA Astrophysics Data System (ADS)

    Harju, J.; Daniel, F.; Sipilä, O.; Caselli, P.; Pineda, J. E.; Friesen, R. K.; Punanova, A.; Güsten, R.; Wiesenfeld, L.; Myers, P. C.; Faure, A.; Hily-Blant, P.; Rist, C.; Rosolowsky, E.; Schlemmer, S.; Shirley, Y. L.

    2017-04-01

    Context. Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. The time-dependence of deuterium fractionation and the relative abundances of different nuclear spin modifications are supposed to provide a means of determining the evolutionary stages of these objects. Aims: We aim to test the current understanding of spin-state chemistry of deuterated species by determining the abundances and spin ratios of NH2D, NHD2 and ND3 in a quiescent, dense cloud. Methods: Spectral lines of NH3, NH2D, NHD2, ND3 and N2D+ were observed towards a dense, starless core in Ophiuchus with the APEX, GBT and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia and their deuterated forms. Different desorption schemes can be considered. Results: High deuterium fractionation ratios with NH2D/NH3 0.4, NHD2/ NH2D 0.2 and ND3/ NHD2 0.06 are found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but consistently predicts too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N2 on grain surfaces. Conclusions: The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of

  19. Ordered bimetallic ferromagnets of chromium(III): [Cr(NH 3) 6][Cr(CN) 6], [Cr(H 2O)(NH 3) 5][Cr(CN) 6], and trans-[Cr(en) 2(H 2O) 2]trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O

    NASA Astrophysics Data System (ADS)

    Burriel, Ramón; Casabó, Jaime; Pons, Josefina; Carnegie, David W.; Carlin, Richard L.

    1985-07-01

    The magnetic bahavior of the isomorphous compounds [Cr(NH 3) 6][Cr(CN) 6] and [Cr(H 2O)(NH 3) 5][Cr(CN) 6] has been studied by means of zero-field susceptibility measurements. The materials order ferromagnetically at 0.60 and 0.38K, respectively. The compounds behave as examples of the ferromagnetic ( S=3/2) Heisenberg body-center-cubic lattice. The susceptibilities have been analyzed and compared to the Padé approximants of the high-temperature series expansion for this model, a remarkably good fit being obtained with exchange constants 0.042 and 0.022 K, respectively. Another bimetallic substance, trans-[Cr(en) 2(H 2O) 2] trans-[Cr(en) 2(OH)F] 2(CIO 4) 5·2H 2O, with a dominant Heisenberg ferromagnetic interaction J/ kB=0.122 K in one dimension, orders antiferromagnetically at 0.14 K due to a weaker interchain interaction with exchange constant z‧ J‧/ kB=-0.019 K. The three sets of measurements have been carried out on powdered samples for which demagnetization effects are important. The exchange interactions are remarkably weak for such concentrated magnetic materials, yet they are stronger than those found in a number of other such Cr/Cr compounds.

  20. Gold(I) Complexes with N-Donor Ligands. 2.(1) Reactions of Ammonium Salts with [Au(acac-kappaC(2))(PR(3))] To Give [Au(NH(3))L](+), [(AuL)(2)(&mgr;(2)-NH(2))](+), [(AuL)(4)(&mgr;(4)-N)](+), or [(AuL)(3)(&mgr;(3)-O)](+). A New and Facile Synthesis of [Au(NH(3))(2)](+) Salts. Crystal Structure of [{AuP(C(6)H(4)OMe-4)(3)}(3)(&mgr;(3)-O)]CF(3)SO(3).

    PubMed

    Vicente, José; Chicote, María-Teresa; Guerrero, Rita; Jones, Peter G.; Ramírez De Arellano, M. Carmen

    1997-09-24

    The complexes [Au(acac-kappaC(2))(PR(3))] (acac = acetylacetonate, R = Ph, C(6)H(4)OMe-4) react with (NH(4))ClO(4) to give amminegold(I), [Au(NH(3))(PR(3))]ClO(4), amidogold(I), [(AuPR(3))(2)(&mgr;(2)-NH(2))]ClO(4), or nitridogold(I), [(AuPR(3))(4)(&mgr;(4)-N)]ClO(4), complexes, depending on the reaction conditions. Similarly, [Au(acac-kappaC(2))(PPh(3))] reacts with (NH(3)R')OTf (OTf = CF(3)SO(3)) (1:1) or with [H(3)N(CH(2))(2)NH(2)]OTf (1:1) to give (amine)gold(I) complexes [Au(NH(2)R')(PPh(3))]OTf (R' = Me, C(6)H(4)NO(2)-4) or [(AuPPh(3))(2){&mgr;(2)-H(2)N(CH(2))(2)NH(2)}](OTf)(2), respectively. The ammonium salts (NH(2)R'(2))OTf (R' = Et, Ph) react with [Au(acac-kappaC(2))(PR(3))] (R = Ph, C(6)H(4)OMe-4) (1:2) to give, after hydrolysis, the oxonium salts [(AuPR(3))(3)(&mgr;(3)-O)]OTf (R = Ph, C(6)H(4)OMe-4). When NH(3) is bubbled through a solution of [AuCl(tht)] (tht = tetrahydrothiophene), the complex [Au(NH(3))(2)]Cl precipitates. Addition of [Au(NH(3))(2)]Cl to a solution of AgClO(4) or TlOTf leads to the isolation of [Au(NH(3))(2)]ClO(4) or [Au(NH(3))(2)]OTf, respectively. The crystal structure of [(AuPR(3))(3)(&mgr;(3)-O)]OTf.Me(2)CO (R = C(6)H(4)OMe-4) has been determined: triclinic, space group P&onemacr;, a = 14.884(3) Å, b = 15.828(3) Å, c = 16.061(3) Å, alpha = 83.39(3) degrees, beta = 86.28(3) degrees, gamma = 65.54(3) degrees, R1 (wR2) = 0.0370 (0.0788). The [(AuPR(3))(3)(&mgr;(3)-O)](+) cation shows an essentially trigonal pyramidal array of three gold atoms and one oxygen atom with O-Au-P bond angles of ca. 175 degrees and Au.Au contacts in the range 2.9585(7)-3.0505(14) Å. These cations are linked into centrosymmetric dimers through two short Au.Au [2.9585(7), 3.0919(9) Å] contacts. The gold atoms of the dimer form a six-membered ring with a chair conformation.

  1. Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

    NASA Technical Reports Server (NTRS)

    T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor); Huang, Cunping (Inventor)

    2014-01-01

    Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

  2. Two-center three-electron bonding in ClNH 3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH 3 → ClNH 2 + H reaction

    DOE PAGES

    Moradi, Christopher P.; Xie, Changjian; Kaufmann, Matin; ...

    2016-04-22

    Pyrolytic dissociation of Cl 2 is employed to dope helium droplets with single Cl atoms. Sequential addition of NH 3 to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH 3 → ClNH 2 + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C 3v symmetric top. Frequency shifts from NH 3 and dipole moment measurements are consistent with a ClNH 3 complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH 3more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. As a result, computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH 3Cl and Cl–HNH 2, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH 3 → HCl + NH 2.« less

  3. A chemical model of seawater including dissolved ammonia and the stoichiometric dissociation constant of ammonia in estuarine water and seawater from -2 to 40°C

    NASA Astrophysics Data System (ADS)

    Clegg, Simon L.; Whitfield, Michael

    1995-06-01

    The calculation of the percentage of un-ionised ammonia in estuarine water and seawater requires values of the stoichiometric dissociation constant of ammonia, defined by: K*a/mol kg -1 = mNH 3mH +/ mNH +4, where m denotes molality. A thermodynamic model of seawater, including dissolved NH 3 and NH +4, is developed using an extended Pitzer formalism parameterised from available data. The model is validated using emf measurements for cells containing artificial seawater with added HCl, and NH 4Cl, and NH 3 over a range of temperatures and salinities. Calculated values of K*a are tabulated from 0 to 40 ppt salinity and -2 to 40°C, on both a free ( mH +) and total ( mH + + mHSO -4) hydrogen ion basis for use with pH measurements made on the corresponding scales. Accuracy (in K*a) is likely to be better than 5% at all temperatures and salinities.

  4. Radiative Lifetimes of NH2(\\Atilde2A1): Rotational Quantum Number Dependence and Implications for Cometary Observations

    NASA Astrophysics Data System (ADS)

    N'Doumi, M.; Halpern, J. B.

    2011-12-01

    Fluorescence (X2B1 ← \\Atilde2A1) from the first electronically excited state transition of NH2 (\\Atilde2A1), extends from 300 to 830 nm and, can be seen as a major visible emission from comets where it is a marker of ammonia NH3 concentrations via photolysis and solar excitation. Inference of ammonia concentrations from the intensity of the NH2 emission depends on knowledge of the radiative lifetime. Petrongolo et al. 2003 remeasured radiative lifetimes of various vibrational levels in the first electronically excited state NH2 (\\Atilde2A1). Their results were a factor of 2.5 or more lower than previous experimental measurements from 1985 and earlier. Collision free, radiative lifetimes from the first electronically excited state of the amidogen free radical, NH2(\\Atilde2A1) are reported here for a number of rotational states in the (0,8,0) and the (0,9,0) vibrational levels. In particular, the (0,8,0) band overlaps the strong OI emission at 630 nm and is commonly used to determine NH3 abundance and the ratio of NH3 to H2O in comets. The results from this work generally agree the older measurements and not with those of Petrolongo, et al. Further, the radiative lifetimes in a vibrational level are shown for the first time to increase with increasing rotational quantum number and also with the projection of the total electronic angular momentum along the internuclear axis. The average radiative lifetimes of the (0,9,0) Γ, τ1 = 18.4 ± 0.2 μs and (0,8,0) Φ, τ2 = 23.4 ± 0.1 μs levels were much longer than those of the (0,9,0) Σ, τ3 = 10.5 ± 0.2 μs and (0,8,0) Π, τ4 = 13.2 ± 0.3 μs states suggesting increased mixing of the first electronic excited and the ground states. This study suggests that the variation of radiative lifetime within the emission band should be taken into consideration in calculations of concentrations of NH2 in comet tails and the inferred NH3 concentration in the comets themselves. Petrongolo, C.; Fan, H.; Ionescu, I.; Kuffel

  5. Rapid ammonia gas transport accounts for futile transmembrane cycling under NH3/NH4+ toxicity in plant roots.

    PubMed

    Coskun, Devrim; Britto, Dev T; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J

    2013-12-01

    Futile transmembrane NH3/NH4(+) cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4(+) toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4(+)) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope (13)N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4(+) ion. Influx of (13)NH3/(13)NH4(+), which exceeded 200 µmol g(-1) h(-1), was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4(+)), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g(-1) h(-1)). Efflux of (13)NH3/(13)NH4(+) responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions.

  6. Adsorption of ammonia at GaN(0001) surface in the mixed ammonia/hydrogen ambient - a summary of ab initio data

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

    Kempisty, Paweł; Krukowski, Stanisław; Interdisciplinary Centre for Materials Modelling, Warsaw University, Pawińskiego 5a, 02-106 Warsaw

    Adsorption of ammonia at NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was analyzed using results of ab initio calculations. The whole configuration space of partially NH{sub 3}/NH{sub 2}/H-covered GaN(0001) surface was divided into zones of differently pinned Fermi level: at the Ga broken bond state for dominantly bare surface (region I), at the valence band maximum (VBM) for NH{sub 2} and H-covered surface (region II), and at the conduction band minimum (CBM) for NH{sub 3}-covered surface (region III). The electron counting rule (ECR) extension was formulated for the case of adsorbed molecules. The extensive ab intio calculations show the validity of themore » ECR in case of all mixed H-NH{sub 2}-NH{sub 3} coverages for the determination of the borders between the three regions. The adsorption was analyzed using the recently identified dependence of the adsorption energy on the charge transfer at the surface. For region I ammonia adsorbs dissociatively, disintegrating into a H adatom and a HN{sub 2} radical for a large fraction of vacant sites, while for region II adsorption of ammonia is molecular. The dissociative adsorption energy strongly depends on the Fermi level at the surface (pinned) and in the bulk (unpinned) while the molecular adsorption energy is determined by bonding to surface only, in accordance to the recently published theory. Adsorption of Ammonia in region III (Fermi level pinned at CBM) leads to an unstable configuration both molecular and dissociative, which is explained by the fact that broken Ga-bonds are doubly occupied by electrons. The adsorbing ammonia brings 8 electrons to the surface, necessitating the transfer of these two electrons from the Ga broken bond state to the Fermi level. This is an energetically costly process. Adsorption of ammonia at H-covered site leads to the creation of a NH{sub 2} radical at the surface and escape of H{sub 2} molecule. The process energy is close to 0.12 eV, thus not large, but the direct

  7. VizieR Online Data Catalog: MSX high-contrast IRDCs with NH3 (Chira+,

    NASA Astrophysics Data System (ADS)

    Chira, R.-A.; Beuther, H.; Linz, H.; Walmsley, C. M.; Menten, K. M.; Bonfman, L.

    2013-02-01

    Based on MSX data, a catalogue of more than 10,000 candidate IRDCs was compiled. From this catalogue we selected a complete sample of northern hemisphere high-contrast IRDCs with Galactic longitudes >=19.27° (and nine exceptions with Galactic longitudes <19°). The sample was observed in ammonia (1,1) and (2,2) inversion transitions with the Effelsberg 100-m telescope. NH3 parameters are derived for 109 sample sources. For each source galactic coordinates, brightness temperatures, line width FWHMs and optical depths of (1,1) and (2,2) inversion lines and LSR velocity of (1,1) inversion line are given. Furthermore, we derived the rotation and kinetic temperatures, ammonia column densities, kinematic distances and virial masses using the NH3 data. In addition, notes about whether the sources being associated with Spitzer sources or not are given. Using ATLASGAL data, the 870 micron flux densities gas masses, virial parameters, H2 column densities and NH3 abundances are given. In addition, we listed the sample sources where no ammonia which did not fulfil our selection criteria. (4 data files).

  8. Recovery of ammonia from swine manure using gas-permeable membranes: effect of waste strength and pH.

    PubMed

    Garcia-González, M C; Vanotti, M B

    2015-04-01

    Nitrogen recovery from swine manure was investigated using gas-permeable membranes. The process involved a continuous recirculation of an acidic solution through a gas-permeable membrane submerged in manure. Ammonia from manure was concentrated in the acidic solution increasing its pH, while pH decreased in manure. In the first set of experiments, nitrogen recovery efficiency was evaluated with no pH adjustment of manure; whereas in the second, manure with three different ammonia (NH3) concentrations (from 1070 to 2290 mg/L) was used adjusting their pH to 9 whenever pH decreased below 7.7. With no pH adjustment, NH3 recovery from manure was 55%, while NH3 recovery averaged 81% when pH of manure was adjusted. This work showed that as waste strength and available NH3 content increased in manure, more N was captured by the membrane. These results suggested that the gas-permeable membranes are a useful technology for NH3 recovery from manure, reducing environmental pollution whilst converting NH3 into a valuable ammonium (NH4(+)) salt fertilizer. Copyright © 2015 Elsevier Ltd. All rights reserved.

  9. Addition of NH{sub 3} to Al{sub 3}O{sub 3}{sup -}

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

    Wyrwas, Richard B.; Jarrold, Caroline Chick; Das, Ujjal

    2006-05-28

    Recent computational studies on the addition of ammonia (NH{sub 3}) to the Al{sub 3}O{sub 3}{sup -} cluster anion [A. Guevara-Garcia, A. Martinez, and J. V. Ortiz, J. Chem. Phys. 122, 214309 (2005)] have motivated experimental and additional computational studies, reported here. Al{sub 3}O{sub 3}{sup -} is observed to react with a single NH{sub 3} molecule to form the Al{sub 3}O{sub 3}NH{sub 3}{sup -} ion in mass spectrometric studies. This is in contrast to similarly performed studies with water, in which the Al{sub 3}O{sub 5}H{sub 4}{sup -} product was highly favored. However, the anion PE spectrum of the ammoniated species ismore » very similar to that of Al{sub 3}O{sub 4}H{sub 2}{sup -}. The adiabatic electron affinity of Al{sub 3}O{sub 3}NH{sub 3} is determined to be 2.35(5) eV. Based on comparison between the spectra and calculated electron affinities, it appears that NH{sub 3} adds dissociatively to Al{sub 3}O{sub 3}{sup -}, suggesting that the time for the Al{sub 3}O{sub 3}{sup -}{center_dot}NH{sub 3} complex to either overcome or tunnel through the barrier to proton transfer (which is higher for NH{sub 3} than for water) is short relative to the time for collisional cooling in the experiment.« less

  10. Etude des trois molecules H 2P-NH 2, ClHP-NH 2, H 2P-NHCl au moyen d'une methode de pseudopotentiels

    NASA Astrophysics Data System (ADS)

    Barthelat, M.; Mathis, R.; Mathis, F.

    The three molecules H 2P-NH 2, ClHP-NH 2 and H 2P-NHCl have been studied by a pseudo-potential method, with a minimal basis of quality mono-zeta, with 3 d functions on the phosphorus atom. The geometry of each molecule was optimized and the phosphorus-nitrogen rotation barrier calculated. The results of the calculations confirm that the polarity of the phosphorus-nitrogen bond is P +-N -. Three weak interactions appear: a partial coordinative bond between the nitrogen doublet and a 3 d orbital of the phosphorus atom, hyperconjugation between the nitrogen doublet and the P-H bonds, and participation of the 3 d orbital of phosphorus in the P-N bond.

  11. Calculations on the rate of the ion-molecule reaction between NH3(+) and H2

    NASA Technical Reports Server (NTRS)

    Herbst, Eric; Defrees, D. J.; Talbi, D.; Pauzat, F.; Koch, W.

    1991-01-01

    The rate coefficient for the ion-molecule reaction NH3(+) + H2 yields NH4(+) + H has been calculated as a function of temperature with the use of the statistical phase space approach. The potential surface and reaction complex and transition state parameters used in the calculation have been taken from ab initio quantum chemical calculations. The calculated rate coefficient has been found to mimic the unusual temperature dependence measured in the laboratory, in which the rate coefficient decreases with decreasing temperature until 50-100 K and then increases at still lower temperatures. Quantitative agreement between experimental and theoretical rate coefficients is satisfactory given the uncertainties in the ab initio results and in the dynamics calculations. The rate coefficient for the unusual three-body process NH3(+) + H2 + He yields NH4(+) + H + He has also been calculated as a function of temperature and the result found to agree well with a previous laboratory determination.

  12. The origin of mouth-exhaled ammonia.

    PubMed

    Chen, W; Metsälä, M; Vaittinen, O; Halonen, L

    2014-09-01

    It is known that the oral cavity is a production site for mouth-exhaled NH3. However, the mechanism of NH3 production in the oral cavity has been unclear. Since bacterial urease in the oral cavity has been found to produce ammonia from oral fluid urea, we hypothesize that oral fluid urea is the origin of mouth-exhaled NH3. Our results show that under certain conditions a strong correlation exists between oral fluid urea and oral fluid ammonia (NH4(+)+NH3) (rs = 0.77, p < 0.001). We also observe a strong correlation between oral fluid NH3 and mouth-exhaled NH3 (rs = 0.81, p < 0.001). We conclude that three main factors affect the mouth-exhaled NH3 concentration: urea concentration, urease activity and oral fluid pH. Bacterial urease catalyses the hydrolysis of oral fluid urea to ammonia (NH4(+)+NH3). Oral fluid ammonia (NH4(+)+NH3) and pH determine the concentration of oral fluid NH3, which evaporates from oral fluid into gas phase and turns to mouth-exhaled NH3.

  13. Reactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation.

    PubMed

    Mena, Inmaculada; García-Orduña, Pilar; Polo, Víctor; Lahoz, Fernando J; Casado, Miguel A; Oro, Luis A

    2017-08-29

    Herein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(μ-NH 2 )(tfbb)} 3 ] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH 2 )(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C-NH 2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,22 -4-κ-C 12 H 8 F 4 N)(dppp)} 2 (μ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(μ-NH 2 )(cod)} 2 ] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,33 -6-κ-C 8 H 10 )H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH 2 )(P-P)(cod)] (P-P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C-H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C-H oxidative addition to the Ir(i) center.

  14. Renal Ammonia Metabolism and Transport

    PubMed Central

    Weiner, I. David; Verlander, Jill W.

    2015-01-01

    Renal ammonia metabolism and transport mediates a central role in acid-base homeostasis. In contrast to most renal solutes, the majority of renal ammonia excretion derives from intrarenal production, not from glomerular filtration. Renal ammoniagenesis predominantly results from glutamine metabolism, which produces 2 NH4+ and 2 HCO3− for each glutamine metabolized. The proximal tubule is the primary site for ammoniagenesis, but there is evidence for ammoniagenesis by most renal epithelial cells. Ammonia produced in the kidney is either excreted into the urine or returned to the systemic circulation through the renal veins. Ammonia excreted in the urine promotes acid excretion; ammonia returned to the systemic circulation is metabolized in the liver in a HCO3−-consuming process, resulting in no net benefit to acid-base homeostasis. Highly regulated ammonia transport by renal epithelial cells determines the proportion of ammonia excreted in the urine versus returned to the systemic circulation. The traditional paradigm of ammonia transport involving passive NH3 diffusion, protonation in the lumen and NH4+ trapping due to an inability to cross plasma membranes is being replaced by the recognition of limited plasma membrane NH3 permeability in combination with the presence of specific NH3-transporting and NH4+-transporting proteins in specific renal epithelial cells. Ammonia production and transport are regulated by a variety of factors, including extracellular pH and K+, and by several hormones, such as mineralocorticoids, glucocorticoids and angiotensin II. This coordinated process of regulated ammonia production and transport is critical for the effective maintenance of acid-base homeostasis. PMID:23720285

  15. Renal ammonia metabolism and transport.

    PubMed

    Weiner, I David; Verlander, Jill W

    2013-01-01

    Renal ammonia metabolism and transport mediates a central role in acid-base homeostasis. In contrast to most renal solutes, the majority of renal ammonia excretion derives from intrarenal production, not from glomerular filtration. Renal ammoniagenesis predominantly results from glutamine metabolism, which produces 2 NH4(+) and 2 HCO3(-) for each glutamine metabolized. The proximal tubule is the primary site for ammoniagenesis, but there is evidence for ammoniagenesis by most renal epithelial cells. Ammonia produced in the kidney is either excreted into the urine or returned to the systemic circulation through the renal veins. Ammonia excreted in the urine promotes acid excretion; ammonia returned to the systemic circulation is metabolized in the liver in a HCO3(-)-consuming process, resulting in no net benefit to acid-base homeostasis. Highly regulated ammonia transport by renal epithelial cells determines the proportion of ammonia excreted in the urine versus returned to the systemic circulation. The traditional paradigm of ammonia transport involving passive NH3 diffusion, protonation in the lumen and NH4(+) trapping due to an inability to cross plasma membranes is being replaced by the recognition of limited plasma membrane NH3 permeability in combination with the presence of specific NH3-transporting and NH4(+)-transporting proteins in specific renal epithelial cells. Ammonia production and transport are regulated by a variety of factors, including extracellular pH and K(+), and by several hormones, such as mineralocorticoids, glucocorticoids and angiotensin II. This coordinated process of regulated ammonia production and transport is critical for the effective maintenance of acid-base homeostasis.

  16. Ammonia Emissions from Agriculture in China

    NASA Astrophysics Data System (ADS)

    Chen, Y.; Zhang, L.; Zhao, Y.; Huang, B.

    2016-12-01

    Ammonia (NH3) is an important alkaline pollutant in the atmosphere and it has various environmental and climatic effects. We will present an improved bottom-up estimate of ammonia emissions from agriculture in China at 0.5°×0.5° horizontal resolution and monthly variability. Ammonia emissions from fertilizer use are derived using data of crop planting area, fertilizer application time and rate for 18 main crops. Ammonia emission factors from fertilizer use are estimated as a function of soil properties such as soil pH, cation exchange capacity (CEC), and agricultural activity information such as crop type, fertilizer type, and application mode. We further consider ambient temperature and wind speed to account for the meteorological influences on ammonia emission factors of fertilizer use. We also estimate the ammonia emission from livestock over China using the mass-flow methodology. The derived ammonia emissions in China for the year 2005 are 4.55 Tg NH3 from fertilizer use and 6.96 Tg from livestock. Henan and Jiangsu provinces are the two largest emitting areas for ammonia from fertilizer use (470 Gg NH3 and 365 Gg NH3). Henan (621 Gg NH3) and Shandong (533 Gg NH3) have the largest ammonia emissions from livestock. Both ammonia emissions from fertilizer use and livestock have distinct seasonal variations; peaking in June for fertilizer use (822 Gg NH3) and in July for livestock (1244 Gg NH3), and are both lowest in January (80 Gg and 241 Gg, respectively). Combining with other ammonia source (eg. human waste and transport) estimates from the REAS v2.1 emission inventory, we show that total ammonia emissions in China for the year 2005 are 14.0 Tg NH3 a-1. Comparisons with satellite measurements of ammonia columns will also be presented.

  17. Polymeric cobalt(ii) thiolato complexes - syntheses, structures and properties of [Co(SMes)2] and [Co(SPh)2NH3].

    PubMed

    Eichhöfer, Andreas; Buth, Gernot

    2016-11-01

    Reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of MesSH (Mes = C 6 H 2 -2,4,6-(CH 3 ) 3 ) yield dark brown crystals of the one dimensional chain compound [Co(SMes) 2 ]. In contrast reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of 'Co(SPh) 2 '. Addition of aliquots of CH 3 OH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh) 2 (NH 3 ) 2 ] or [Co(SPh) 2 NH 3 ]. Single crystal XRD reveals that [Co(SPh) 2 NH 3 ] forms one-dimensional chains in the crystal via μ 2 -SPh bridges whereas [Co(SPh) 2 (NH 3 ) 2 ] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds [Co(SMes) 2 ] (J = -38.6 cm -1 ) and [Co(SPh) 2 NH 3 ] (J = -27.1 cm -1 ). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh) 2 (NH 3 ) 2 ] shows an antiferromagnetic transition at around 6 K. UV-Vis-NIR spectra display d-d bands in the NIR region between 500 and 2250 nm. Thermal gravimetric analysis of [Co(SPh) 2 (NH 3 ) 2 ] and [Co(SPh) 2 NH 3 ] reveals two well separated cleavage processes for NH 3 and SPh 2 upon heating accompanied by the stepwise formation of 'Co(SPh) 2 ' and cobalt sulfide.

  18. Low Temperature Catalyst for NH3 Removal

    NASA Technical Reports Server (NTRS)

    Monje, Oscar; Melendez, Orlando

    2013-01-01

    Air revitalization technologies maintain a safe atmosphere inside spacecraft by the removal of C02, ammonia (NH3), and trace contaminants. NH3 onboard the International Space Station (ISS) is produced by crew metabolism, payloads, or during an accidental release of thermal control refrigerant. Currently, the ISS relies on removing NH3 via humidity condensate and the crew wears hooded respirators during emergencies. A different approach to cabin NH3 removal is to use selective catalytic oxidation (SCO), which builds on thermal catalytic oxidation concepts that could be incorporated into the existing TCCS process equipment architecture on ISS. A low temperature platinum-based catalyst (LTP-Catalyst) developed at KSC was used for converting NH3 to H20 and N2 gas by SCO. The challenge of implementing SCO is to reduce formation of undesirable byproducts like NOx (N20 and NO). Gas mixture analysis was conducted using FTIR spectrometry in the Regenerable VOC Control System (RVCS) Testbed. The RVCS was modified by adding a 66 L semi-sealed chamber, and a custom NH3 generator. The effect of temperature on NH3 removal using the LTP-Catalyst was examined. A suitable temperature was found where NH3 removal did not produce toxic NO, (NO, N02) and N20 formation was reduced.

  19. Startup and long-term performance of biotrickling filters packed with polyurethane foam and poplar wood chips treating a mixture of ethylmercaptan, H2S, and NH3.

    PubMed

    Hernández, J; Lafuente, J; Prado, O J; Gabriel, D

    2013-04-01

    Treatment of a mixture of NH3, H2S, and ethylmercaptan (EM) was investigated for more than 15 months in two biotrickling filters packed with poplar wood chips and polyurethane foam. Inlet loads ranging from 5 to 10 g N-NH3 m-3 hr-1, from 5 to 16 g S-H2S m-3 hr-1, and from 0 to 5 g EM m-3 hr-1 were applied. During startup, the biotrickling filter packed with polyurethane foam was re-inoculated due to reduced biomass retention as well as a stronger effect of nitrogen compounds inhibition compared with the biotrickling filter packed with poplar wood. Accurate pH control between 7 and 7.5 favored pollutants abatement. In the long run, complete NH3 removal in the gas phase was achieved in both reactors, while H2S removal efficiencies exceeded 90%. EM abatement was significantly different in both reactors. A systematically lower elimination capacity was found in the polyurethane foam bioreactor. N fractions in the liquid phase proved that high nitrification rates were reached throughout steady-state operation in both bioreactors. CO2 production showed the extent of the organic packing material degradation, which allowed estimating its service lifetime in around 2 years. In the long run, the bioreactor packed with the organic packing material had a lower stability. However, an economic analysis indicated that poplar wood chips are a competitive alternative to inorganic packing materials in biotrickling filters. We provide new insights in the use of organic packing materials in biotrickling filters for the treatment of H2S, NH3, and mercaptans and compare them with polyurethane foam, a packing commonly used in biotrickling filters. We found interesting features related with the startup of the reactors and parameterized both the performance under steady-state conditions and the influence of the gas contact time. We provide relevant conclusions in the profitability of organic packing materials under a biotrickling filter configuration, which is infrequent but proven reliable

  20. Two-center three-electron bonding in ClNH{sub 3} revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH{sub 3} → ClNH{sub 2} + H reaction

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

    Moradi, Christopher P.; Douberly, Gary E., E-mail: douberly@uga.edu; Xie, Changjian

    2016-04-28

    Pyrolytic dissociation of Cl{sub 2} is employed to dope helium droplets with single Cl atoms. Sequential addition of NH{sub 3} to Cl-doped droplets leads to the formation of a complex residing in the entry valley to the substitution reaction Cl + NH{sub 3} → ClNH{sub 2} + H. Infrared Stark spectroscopy in the NH stretching region reveals symmetric and antisymmetric vibrations of a C{sub 3v} symmetric top. Frequency shifts from NH{sub 3} and dipole moment measurements are consistent with a ClNH{sub 3} complex containing a relatively strong two-center three-electron (2c–3e) bond. The nature of the 2c–3e bonding in ClNH{sub 3}more » is explored computationally and found to be consistent with the complexation-induced blue shifts observed experimentally. Computations of interconversion pathways reveal nearly barrierless routes to the formation of this complex, consistent with the absence in experimental spectra of two other complexes, NH{sub 3}Cl and Cl–HNH{sub 2}, which are predicted in the entry valley to the hydrogen abstraction reaction Cl + NH{sub 3} → HCl + NH{sub 2}.« less

  1. Magnetic behavior of the ferromagnetic quantum chain systems (C6H11NH3)CuCl3 (CHAC) and (C6H11NH3)CuBr3 (CHAB)

    NASA Astrophysics Data System (ADS)

    Kopinga, A.; Tinus, A. M. C.; de Jonge, W. J. M.

    1982-04-01

    Heat-capacity measurements on (C6H11NH3)CuBr3 (CHAB) in the region 0.45 < T<55 K are presented. Three-dimensional ordering is observed at Tc=1.50 K. The data are analyzed together with previously reported measurements on (C6H11NH3)CuCl3 (CHAC). Both compounds appear to be very good approximations of a ferromagnetic S=12 Heisenberg linearchain system with Jk~50 K. From the data it is inferred that the intrachain interaction of CHAC contains about 2% uniaxial anisotropy, whereas CHAB contains about 5% easy-plane anisotropy. The results are corroborated by magnetization measurements on CHAB below Tc, which also reveal a metamagnetic transition for H-->∥b (Hc=210Oe). From the value of Hc and the location of the tricitical point the interchain interactions in CHAB were found as zAFJAFk=-0.03 K, zFJFk~0.08 K.

  2. Measurements of NH 3 and CO 2 with Distributed-Feedback Diode Lasers Near 2.0 m in Bioreactor Vent Gases

    NASA Astrophysics Data System (ADS)

    Webber, Michael E.; Claps, Ricardo; Englich, Florian V.; Tittel, Frank K.; Jeffries, Jay B.; Hanson, Ronald K.

    2001-08-01

    Measurements of NH3 and CO2 were made in bioreactor vent gases with distributed-feedback diode-laser sensors operating near 2 m. Calculated spectra of NH3 and CO2 were used to determine the optimum transitions for interrogating with an absorption sensor. For ammonia, a strong and isolated absorption transition at 5016.977 cm-1 was selected for trace gas monitoring. For CO2 , an isolated transition at 5007.787 cm-1 was selected to measure widely varying concentrations [500 parts per million (ppm) to 10% ,] with sufficient signal for low mole fractions and without being optically thick for high mole fractions. Using direct absorption and a 36-m total path-length multipass flow-through cell, we achieved a minimum detectivity of 0.25 ppm for NH3 and 40 ppm for CO2 . We report on the quasi-continuous field measurements of NH3 and CO2 concentration in bioreactor vent gases that were recorded at NASA Johnson Space Center with a portable and automated sensor system over a 45-h data collection window.

  3. Defences against ammonia toxicity in tropical air-breathing fishes exposed to high concentrations of environmental ammonia: a review.

    PubMed

    Ip, Y K; Chew, S F; Wilson, J M; Randall, D J

    2004-10-01

    In the tropics, air-breathing fishes can be exposed to environmental ammonia when stranded in puddles of water during the dry season, during a stay inside a burrow, or after agricultural fertilization. At low concentrations of environmental ammonia, NH(3) excretion is impeded, as in aerial exposure, leading to the accumulation of endogenous ammonia. At high concentrations of environmental ammonia, which results in a reversed NH(3) partial pressure gradient (DeltaP(NH3)), there is retention of endogenous ammonia and uptake of exogenous ammonia. In this review, several tropical air-breathing fishes (giant mudskipper, African catfish, oriental weatherloach, swamp eel, four-eyed sleeper, abehaze and slender African lungfish), which can tolerate high environmental ammonia exposure, are used as examples to demonstrate how eight different adaptations can be involved in defence against ammonia toxicity. Four of these adaptations deal with ammonia toxicity at branchial and/or epithelial surfaces: (1) active excretion of NH(4)(+); (2) lowering of environmental pH; (3) low NH(3) permeability of epithelial surfaces; and (4) volatilization of NH(3), while another four adaptations ameliorate ammonia toxicity at the cellular and subcellular levels: (5) high tolerance of ammonia at the cellular and subcellular levels; (6) reduction in ammonia production; (7) glutamine synthesis; and (8) urea synthesis. The responses of tropical air-breathing fishes to high environmental ammonia are determined apparently by behavioural adaptations and the nature of their natural environments.

  4. The Green Bank Ammonia Survey: First Results of NH3 Mapping of the Gould Belt

    NASA Astrophysics Data System (ADS)

    Friesen, Rachel K.; Pineda, Jaime E.; co-PIs; Rosolowsky, Erik; Alves, Felipe; Chacón-Tanarro, Ana; How-Huan Chen, Hope; Chun-Yuan Chen, Michael; Di Francesco, James; Keown, Jared; Kirk, Helen; Punanova, Anna; Seo, Youngmin; Shirley, Yancy; Ginsburg, Adam; Hall, Christine; Offner, Stella S. R.; Singh, Ayushi; Arce, Héctor G.; Caselli, Paola; Goodman, Alyssa A.; Martin, Peter G.; Matzner, Christopher; Myers, Philip C.; Redaelli, Elena; The GAS Collaboration

    2017-07-01

    We present an overview of the first data release (DR1) and first-look science from the Green Bank Ammonia Survey (GAS). GAS is a Large Program at the Green Bank Telescope to map all Gould Belt star-forming regions with {A}{{V}}≳ 7 mag visible from the northern hemisphere in emission from NH3 and other key molecular tracers. This first release includes the data for four regions in the Gould Belt clouds: B18 in Taurus, NGC 1333 in Perseus, L1688 in Ophiuchus, and Orion A North in Orion. We compare the NH3 emission to dust continuum emission from Herschel and find that the two tracers correspond closely. We find that NH3 is present in over 60% of the lines of sight with {A}{{V}}≳ 7 mag in three of the four DR1 regions, in agreement with expectations from previous observations. The sole exception is B18, where NH3 is detected toward ∼40% of the lines of sight with {A}{{V}}≳ 7 mag. Moreover, we find that the NH3 emission is generally extended beyond the typical 0.1 pc length scales of dense cores. We produce maps of the gas kinematics, temperature, and NH3 column densities through forward modeling of the hyperfine structure of the NH3 (1, 1) and (2, 2) lines. We show that the NH3 velocity dispersion, {σ }v, and gas kinetic temperature, T K, vary systematically between the regions included in this release, with an increase in both the mean value and the spread of {σ }v and T K with increasing star formation activity. The data presented in this paper are publicly available (https://dataverse.harvard.edu/dataverse/GAS_DR1).

  5. Scavenging of ammonia by raindrops in Saturn's great storm clouds

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, Kevin

    2016-10-01

    Observations of the great Saturn storms of 2010-2011 by Cassini instruments showed a very large depletion in atmospheric ammonia. While dynamics will play a role, the very high solubility of ammonia in water may be another important contributor to ammonia depletion in storms. Ammonia exists in Earth's atmosphere and rainstorms dissolve ammonia to a great degree, leaving almost no NH3 in the atmosphere. Studies by Elperin et al (2011, 2013) show that scavenging of ammonia is greatest as a rainstorm starts and lessens as raindrops fall, tapering off to almost zero by the time the rain reaches the ground (Elperin et al 2009). Ammonia is reaching saturation as it dissolves in the aqueous solution. As concentration increases, NH3 is then converted to aqueous species (NH3)x.(H2O)y (Max and Chapados 2013).Ammonia has the highest solubility in water compared to all other gases in the Saturn atmosphere. The Henry's Law constant for NH3 in water is 60 M/atm at 25 C. For H2S, it is 0.001 M/atm. In Saturn storms, it is "raining UP": As water-laden storm clouds convectively rise, ammonia gas will be scavenged and go into solution to a great degree, whilst all the other gases remain mostly in the gas phase. Aqueous ammonia acts as an antifreeze: if ammonia is dissolved in water cloud droplets to the limit of its solubility, as water droplets rise, they can stay liquid (and continue to scavenge NH3) to well below their normal freezing point of 0 Celsius (273 K). The freezing point for a 30 wt % water-ammonia solution is ~189 K. The pressure level where T = 189 K is at 2.8 bars. The normal freezing point of water occurs at the 9 bar pressure level in Saturn's atmosphere. 2.8 bars occurs at the -51 km altitude (below the 1 bar level). 9 bars is at the -130 km level: a difference of 79 km. A water droplet containing 30 wt% NH3 can move upwards from 9 bars to 2.8 bars (79 km) and still remain liquid, only freezing above that altitude. Calculations by the E-AIM model show that ammonia

  6. Enhanced Synthesis of Alkyl Amino Acids in Miller's 1958 H2S Experiment

    NASA Technical Reports Server (NTRS)

    Parker, Eric T.; Cleaves, H. James; Callahan, Michael P.; Dworkin, James P.; Glavin, Daniel P.; Lazcano, Antonio; Bada, Jeffrey L.

    2011-01-01

    Stanley Miller's 1958 H2S-containing experiment, which included a simulated prebiotic atmosphere of methane (CH4), ammonia (NH3), carbon dioxide (CO2), and hydrogen sulfide (H2S) produced several alkyl amino acids, including the alpha-, beta-, and gamma-isomers of aminobutyric acid (ABA) in greater relative yields than had previously been reported from his spark discharge experiments. In the presence of H2S, aspariic and glutamic acids could yield alkyl amino acids via the formation of thioimide intermediates. Radical chemistry initiated by passing H2S through a spark discharge could have also enhanced alkyl amino acid synthesis by generating alkyl radicals that can help form the aldehyde and ketone precursors to these amino acids. We propose mechanisms that may have influenced the synthesis of certain amino acids in localized environments rich in H2S and lightning discharges, similar to conditions near volcanic systems on the early Earth, thus contributing to the prebiotic chemical inventory of the primordial Earth.

  7. Emissions of ammonia, carbon dioxide, and hydrogen sulfide from swine wastewater during and after acidification treatment: effect of pH, mixing and aeration.

    PubMed

    Dai, X R; Blanes-Vidal, V

    2013-01-30

    This study aimed at evaluating the effect of swine slurry acidification and acidification-aeration treatments on ammonia (NH(3)), carbon dioxide (CO(2)) and hydrogen sulfide (H(2)S) emissions during slurry treatment and subsequent undisturbed storage. The study was conducted in an experimental setup consisting of nine dynamic flux chambers. Three pH levels (pH = 6.0, pH = 5.8 and pH = 5.5), combined with short-term aeration and venting (with an inert gas) treatments were studied. Acidification reduced average NH(3) emissions from swine slurry stored after acidification treatment compared to emissions during storage of non-acidified slurry. The reduction were 50%, 62% and 77% when pH was reduce to 6.0, 5.8 and 5.5, respectively. However, it had no significant effect on average CO(2) and H(2)S emissions during storage of slurry after acidification. Aeration of the slurry for 30 min had no effect on average NH(3), CO(2) and H(2)S emissions both during the process and from stored slurry after venting treatments. During aeration treatment, the NH(3), CO(2) and H(2)S release pattern observed was related to the liquid turbulence caused by the gas bubbles rather than to biological oxidation processes in this study. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Acidification Enhances Hybrid N2O Production Associated with Aquatic Ammonia-Oxidizing Microorganisms

    PubMed Central

    Frame, Caitlin H.; Lau, Evan; Nolan, E. Joseph; Goepfert, Tyler J.; Lehmann, Moritz F.

    2017-01-01

    Ammonia-oxidizing microorganisms are an important source of the greenhouse gas nitrous oxide (N2O) in aquatic environments. Identifying the impact of pH on N2O production by ammonia oxidizers is key to understanding how aquatic greenhouse gas fluxes will respond to naturally occurring pH changes, as well as acidification driven by anthropogenic CO2. We assessed N2O production rates and formation mechanisms by communities of ammonia-oxidizing bacteria (AOB) and archaea (AOA) in a lake and a marine environment, using incubation-based nitrogen (N) stable isotope tracer methods with 15N-labeled ammonium (15NH4+) and nitrite (15NO2−), and also measurements of the natural abundance N and O isotopic composition of dissolved N2O. N2O production during incubations of water from the shallow hypolimnion of Lake Lugano (Switzerland) was significantly higher when the pH was reduced from 7.54 (untreated pH) to 7.20 (reduced pH), while ammonia oxidation rates were similar between treatments. In all incubations, added NH4+ was the source of most of the N incorporated into N2O, suggesting that the main N2O production pathway involved hydroxylamine (NH2OH) and/or NO2− produced by ammonia oxidation during the incubation period. A small but significant amount of N derived from exogenous/added 15NO2− was also incorporated into N2O, but only during the reduced-pH incubations. Mass spectra of this N2O revealed that NH4+ and 15NO2− each contributed N equally to N2O by a “hybrid-N2O” mechanism consistent with a reaction between NH2OH and NO2−, or compounds derived from these two molecules. Nitrifier denitrification was not an important source of N2O. Isotopomeric N2O analyses in Lake Lugano were consistent with incubation results, as 15N enrichment of the internal N vs. external N atoms produced site preferences (25.0–34.4‰) consistent with NH2OH-dependent hybrid-N2O production. Hybrid-N2O formation was also observed during incubations of seawater from coastal Namibia

  9. SiO{sub 2} nanospheres with tailorable interiors by directly controlling Zn{sup 2+} and NH{sub 3}.H{sub 2}O species in an emulsion process

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

    Liao Yuchao; Graduate University of Chinese Academy of Sciences, Beijing 100049; Wu Xiaofeng

    2011-07-15

    SiO{sub 2} nanospheres with tailorable interiors were synthesized by a facile one-spot microemulsion process using TEOS as silica source, wherein cyclohexane including triton X-100 and n-octanol as oil phase and Zn{sup 2+} or NH{sub 3}.H{sub 2}O aqueous solution as dispersive phase, respectively. The products were characterized by Scanning Electron Microscopy, Transmission Electron Microscopy and X-ray Powder Diffraction. It was suggested that the as-synthesized silica nanospheres possessed grape-stone-like porous or single hollow interior, and also found that the ammonia dosage and aging time played key roles in controlling the size and structure of silica nanospheres. Furthermore, the comparative results confirmed thatmore » in-situ zinc species [ZnO/Zn(OH){sub 2}] acted as the temporary templates to construct grape-stone-like interior, and a simultaneously competing etching process occurred owing to the soluble Zn(NH{sub 3}){sub 4}{sup 2+} complex formation while the additional excessive ammonia was introduced. With the aging time being extended, the in-situ nanocrystals tended to grow into bigger ones by Ostwald Ripening, producing single hollow interior. - Graphical Abstract: Formation process of SiO{sub 2} nanospheres with porous and single hollow interior. Highlights: > ZnO/Zn(OH){sub 2} nanocrystals as the temporary templates shape the interior structures of SiO{sub 2} nanospheres. > Fabrication of porous and single hollow interiors needs no additional processes such as roasting or dissolving. > Tailorable interiors can be easily obtained through adjusting the aging time of temporary templates.« less

  10. Modulation of sheep ruminal urea transport by ammonia and pH.

    PubMed

    Lu, Zhongyan; Stumpff, Friederike; Deiner, Carolin; Rosendahl, Julia; Braun, Hannah; Abdoun, Khalid; Aschenbach, Jörg R; Martens, Holger

    2014-09-01

    Ruminal fermentation products such as short-chain fatty acids (SCFA) and CO2 acutely stimulate urea transport across the ruminal epithelium in vivo, whereas ammonia has inhibitory effects. Uptake and signaling pathways remain obscure. The ruminal expression of SLC14a1 (UT-B) was studied using polymerase chain reaction (PCR). The functional short-term effects of ammonia on cytosolic pH (pHi) and ruminal urea transport across native epithelia were investigated using pH-sensitive microelectrodes and via flux measurements in Ussing chambers. Two variants (UT-B1 and UT-B2) could be fully sequenced from ovine ruminal cDNA. Functionally, transport was passive and modulated by luminal pH in the presence of SCFA and CO2, rising in response to luminal acidification to a peak value at pH 5.8 and dropping with further acidification, resulting in a bell-shaped curve. Presence of ammonia reduced the amplitude, but not the shape of the relationship between urea flux and pH, so that urea flux remained maximal at pH 5.8. Effects of ammonia were concentration dependent, with saturation at 5 mmol/l. Clamping the transepithelial potential altered the inhibitory potential of ammonia on urea flux. Ammonia depolarized the apical membrane and acidified pHi, suggesting that, at physiological pH (< 7), uptake of NH4 (+) into the cytosol may be a key signaling event regulating ruminal urea transport. We conclude that transport of urea across the ruminal epithelium involves proteins subject to rapid modulation by manipulations that alter pHi and the cytosolic concentration of NH4 (+). Implications for epithelial and ruminal homeostasis are discussed. Copyright © 2014 the American Physiological Society.

  11. NH3 adsorption on anatase-TiO2(101)

    NASA Astrophysics Data System (ADS)

    Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

    2018-03-01

    The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

  12. INFRARED STUDY OF UV/EUV IRRADIATION OF NAPHTHALENE IN H2O+NH3 ICE

    NASA Astrophysics Data System (ADS)

    Chen, Y.-J.; Nuevo, M.; Yeh, F.-C.; Yih, T.-S.; Sun, W.-H.; Ip, W.-H.; Fung, H.-S.; Lee, Y.-Y.; Wu, C.-Y. R.

    We have carried out photon irradiation study of naphthalene (C10H8), the smallest polycyclic aromatic hydrocarbon (PAH) in water and ammonia ice mixtures. Photons provided by a synchrotron radiation light source in two broad-band energy ranges in the ultraviolet/near extreme ultraviolet (4-20 eV) and the extreme ultraviolet (13-45 eV) ranges were used for the irradiation of H2O+NH3+C10H8 = 1:1:1 ice mixtures at 15K. We could identify several photo-products, namely CH4, C2H6, C3H8, CO, CO2, HNCO, OCN-, and probably quinoline (C9H7N) and phenanthridine (C13H9N). We found that the light hydrocarbons are preferably produced for the ice mixture subjected to 4-20 eV photons. However, the production yields of CO, CO2, and OCN- species seem to be higher for the mixture subjected to EUV photons (13-45 eV). Therefore, naphthalene and its photo-products appear to be more efficiently destroyed when high energy photons (E > 20 eV) are used. This has important consequences on the photochemical evolution of PAHs in astrophysical environments.

  13. Lattice potential energy and standard molar enthalpy in the formation of 1—dodecylamine hydrobromide (1-C12H25NH3·Br)(s)

    NASA Astrophysics Data System (ADS)

    Liu, Yu-Pu; Di, You-Ying; Dan, Wen-Yan; He, Dong-Hua; Kong, Yu-Xia; Yang, Wei-Wei

    2011-02-01

    This paper reports that 1-dodecylamine hydrobromide (1-C12H25NH3·Br)(s) has been synthesized using the liquid phase reaction method. The lattice potential energy of the compound 1-C12H25NH3·Br and the ionic volume and radius of the 1-C12H25NH3+ cation are obtained from the crystallographic data and other auxiliary thermodynamic data. The constant-volume energy of combustion of 1-C12H25NH3·Br(s) is measured to be ΔcUmo(1-C12H25NH3·Br, s) = -(7369.03±3.28) kJ·mol-1 by means of an RBC-II precision rotating-bomb combustion calorimeter at T = (298.15±0.001) K. The standard molar enthalpy of combustion of the compound is derived to be ΔcHmo(1-C12H25NH3·Br, s) = -(7384.52±3.28) kJ·mol-1 from the constant-volume energy of combustion. The standard molar enthalpy of formation of the compound is calculated to be ΔfHmo(1-C12H25NH3·Br, s)=-(1317.86±3.67) kJ·mol-1 from the standard molar enthalpy of combustion of the title compound and other auxiliary thermodynamic quantities through a thermochemical cycle.

  14. Formation of simple nitrogen hydrides NH and NH2 at cryogenic temperatures through N + NH3NH + NH2 reaction: dark cloud chemistry of nitrogen.

    PubMed

    Nourry, Sendres; Krim, Lahouari

    2016-07-21

    Although NH3 molecules interacting with ground state nitrogen atoms N((4)S) seem not to be a very reactive system without providing additional energy to initiate the chemical process, we show through this study that, in the solid phase, at very low temperature, NH3 + N((4)S) reaction leads to the formation of the amidogen radical NH2. Such a dissociation reaction previously thought to occur exclusively through UV photon or energetic particle irradiation is in this work readily occurring just by stimulating the mobility of N((4)S)-atoms in the 3-10 K temperature range in the solid sample. The N((4)S)-N((4)S) recombination may be the source of metastable molecular nitrogen N2(A), a reactive species which might trigger the NH3 dissociation or react with ground state nitrogen atoms N((4)S) to form excited nitrogen atoms N((4)P/(2)D) through energy transfer processes. Based on our obtained results, it is possible to propose reaction pathways to explain the NH2 radical formation which is the first step in the activation of stable species such as NH3, a chemical induction process that, in addition to playing an important role in the origin of molecular complexity in interstellar space, is known to require external energy supplies to occur in the gas phase.

  15. Raman Spectra and Cross Sections of Ammonia, Chlorine, Hydrogen Sulfide, Phosgene, and Sulfur Dioxide Toxic Gases in the Fingerprint Region 400-1400 cm-1

    DTIC Science & Technology

    2016-02-11

    AIP ADVANCES 6, 025310 (2016) Raman spectra and cross sections of ammonia , chlorine, hydrogen sulfide, phosgene, and sulfur dioxide toxic gases in...Received 10 December 2015; accepted 3 February 2016; published online 11 February 2016) Raman spectra of ammonia (NH3), chlorine (Cl2), hydrogen...and cross sections of ammonia (NH3), chlorine (Cl2), hydrogen sulfide (H2S), phosgene (CCl2O), and sulfur dioxide (SO2) toxic gases in the fingerprint

  16. Imaging a multidimensional multichannel potential energy surface: Photodetachment of H(-)(NH3) and NH4 (.).

    PubMed

    Hu, Qichi; Song, Hongwei; Johnson, Christopher J; Li, Jun; Guo, Hua; Continetti, Robert E

    2016-06-28

    Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH4 and the double Rydberg anion NH4 (-) represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H(-)(NH3) ion-dipole complex and the NH4 (-) DRA probes different regions on the neutral NH4 PES. Photoelectron energy and angular distributions at photon energies of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH4 Rydberg radical occurs to H + NH3 with a peak kinetic energy of 0.13 eV, showing the ground state of NH4 to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.

  17. Synthesis and characterization of two layered aluminophosphates, ( T) 2HAl 2P 3O 12 ( T=2-BuNH 3+) and ( T)H 2Al 2P 3O 12 ( T=pyH +)

    NASA Astrophysics Data System (ADS)

    Chippindale, Ann M.; Powell, Anthony V.; Bull, Lucy M.; Jones, Richard H.; Cheetham, Anthony K.; Thomas, John M.; Xu, Ruren

    1992-01-01

    Two new aluminophosphates, ( T) 2HAl 2P 3O 12 ( T=2-BuNH 3+) ( I) and ( T)H 2Al 2P 3O 12 ( T=pyH +) ( II) with the same framework stoichiometry but different layer structures have been prepared under nonaqueous conditions and the structures determined by single-crystal X-ray diffraction. Compound ( I) crystallizes in the monoclinic space group P2 1/ c ( Z=4), with lattice parameters a=9.261(1) b=8.365(6), c=27.119(4) Å, β=91.50(1)δ, and V=2100.1 Å 3 ( R=0.072 and R w=0.090). The structure consists of Al-and P-centered tetrahedra linked to form layers. Protonated 2-butylamine molecules are located in the interlayer spaces and hydrogen bonded to the layers through NH 3+ groups. Weak hydrophobic van der Waals' interactions between alkyl groups of the 2-BuNH 3+ cations hold the layers together. Compound ( II) crystallizes in the triclinic space group P-1 ( Z=2), with a=8.574(2), b=8.631(3), c=10.371(2) Å, α=81.84(3), β=87.53(2), γ=69.07(2)δ, and V=709.49Å 3 ( R=0.039 and R w=0.052). The structure contains tetrahedrally coordinated P atoms and both tetrahedral and trigonal pyramidal Al atoms linked to form layers which are held together through hydrogen bonding, creating cavities in which pyH + cations reside.

  18. Aedes aegypti Rhesus glycoproteins contribute to ammonia excretion by larval anal papillae.

    PubMed

    Durant, Andrea C; Chasiotis, Helen; Misyura, Lidiya; Donini, Andrew

    2017-02-15

    In larval Aedes aegypti , transcripts of the Rhesus-like glycoproteins AeRh50-1 and AeRh50-2 have been detected in the anal papillae, sites of ammonia (NH 3 /NH 4 + ) excretion; however, these putative ammonia transporters have not been previously localized or functionally characterized. In this study, we show that the AeRh50s co-immunolocalize with apical V-type H + -ATPase as well as with basal Na + /K + -ATPase in the epithelium of anal papillae. The double-stranded RNA-mediated knockdown of AeRh50-1 and AeRh50-2 resulted in a significant reduction in AeRh50 protein abundance in the anal papillae, and this was coupled to decreased ammonia excretion. The knockdown of AeRh50-1 resulted in decreased hemolymph [NH 4 + ] and pH whereas knockdown of AeRh50-2 had no effect on these parameters. We conclude that the AeRh50s are important contributors to ammonia excretion at the anal papillae of larval A. aegypti , which may be the basis for their ability to inhabit areas with high ammonia levels. © 2017. Published by The Company of Biologists Ltd.

  19. Effects of ammonia and hydrogen sulfide on physical and biochemical properties of the claw horn of Holstein cows

    PubMed Central

    Higuchi, Hidetoshi; Kurumado, Hisatoshi; Mori, Maya; Degawa, Aiko; Fujisawa, Hideyo; Kuwano, Atsutoshi; Nagahata, Hajime

    2009-01-01

    The effects of ammonia and hydrogen sulfide on the physical and biochemical properties of the claw horn of Holstein cows were evaluated. Significant (P < 0.05, 0.01) decreases in hardness and elasticity were found in claw horns soaked in ammonia (NH3) and hydrogen sulfide (H2S) solutions compared with those that were soaked in water for 12, 24, and 48 h. Water absorption rate, as a indicator of permeability barrier function, increased significantly (P < 0.05) over time during the soaking period and was found to be dependent on the concentrations of NH3 and H2S in the solutions. The contents of ceramide, the main lipid component for the permeability barrier system of the stratum corneum, were significantly decreased in claw horns soaked in NH3 and H2S solutions compared with the values before soaking. Quantities of eluted protein released from claw horns treated with NH3 and H2S solutions were approximately 20 times and 30 to 40 times greater than those released from claw horns treated with water alone. Interestingly, the quantities of cytokeratin 10, the main cytoskeletal protein of the stratum corneum, eluted from claw horns treated with NH3 and H2S solutions were markedly greater than the quantity released from horns soaked in water. Our results suggest that abnormal changes in the physical property of claw horn caused by NH3 and H2S treatment are due to disruption of the biochemical property of the claw horn induced by these chemical agents derived from slurry. PMID:19337390

  20. The sensitivity of particle pH to NH3: Can high NH3 cause London Fog conditions?

    NASA Astrophysics Data System (ADS)

    Weber, R. J.; Guo, H.; Nenes, A.

    2017-12-01

    High ammonia emissions from agriculture or other sources have been suggested to elevate ambient particle pH levels to near neutral acidity (pH=7), a condition that promotes rapid SO2 oxidation by NO2 to form aerosol sulfate concentration consistent with "London fog" levels. This mechanism has been used to explain pollution haze events in China. Predicted pH for locations in the US and Europe show fine particles are highly acidic with pH typically less than 2. The results are consistent with measured ammonia and nitric acid gas-particle partitioning, validating predicted pH levels. Using these data sets from representative sites around the world we conduct a thermodynamic analysis of aerosol pH and its sensitivity to ammonia levels. We find that particle pH, regardless of ammonia levels, is always acidic even for the unusually high ammonia levels found in highly polluted Asian cities, Beijing (pH=4.5) and Xi'an (pH=5), locations where sulfate production from NOx is proposed. These results indicate that sulfur dioxide oxidation through a NO2-mediated pathway is not likely in China, nor any other region of the world (e.g., US, Mediterranean) since the fine aerosol is consistently acidic. The mildly acidic conditions would, however, permit rapid oxidation of sulfur dioxide through transition metal chemistry. The limited alkalinity from the carbonate buffer in dust and seasalt can provide the only likely set of conditions where NO2-mediated oxidation of SO2 outcompetes with other well-established pathways.

  1. In-Situ and Real-time Monitoring of Mechanochemical Preparation of Li2 Mg(NH2 BH3 )4 and Na2 Mg(NH2 BH3 )4 and Their Thermal Dehydrogenation.

    PubMed

    Biliškov, Nikola; Borgschulte, Andreas; Užarević, Krunoslav; Halasz, Ivan; Lukin, Stipe; Milošević, Sanja; Milanović, Igor; Novaković, Jasmina Grbović

    2017-11-16

    For the first time, in situ monitoring of uninterrupted mechanochemical synthesis of two bimetallic amidoboranes, M 2 Mg(NH 2 BH 3 ) 4 (M=Li, Na), by means of Raman spectroscopy, has been applied. This approach allowed real-time observation of key intermediate phases, and a straightforward follow-up of the reaction course. Detailed analysis of time-dependent spectra revealed a two-step mechanism through MNH 2 BH 3NH 3 BH 3 adducts as key intermediate phases which further reacted with MgH 2 , giving M 2 Mg(NH 2 BH 3 ) 4 as final products. The intermediates partially take a competitive pathway toward the oligomeric M(BH 3 NH 2 BH 2 NH 2 BH 3 ) phases. The crystal structure of the novel bimetallic amidoborane Li 2 Mg(NH 2 BH 3 ) 4 was solved from high-resolution powder diffraction data and showed an analogous metal coordination to Na 2 Mg(NH 2 BH 3 ) 4 , but a significantly different crystal packing. Li 2 Mg(NH 2 BH 3 ) 4 thermally dehydrogenates releasing highly pure H 2 in the amount of 7 wt.%, and at a lower temperature then its sodium analogue, making it significantly more viable for practical applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Tracing the atomic nitrogen abundance in star-forming regions with ammonia deuteration

    NASA Astrophysics Data System (ADS)

    Furuya, Kenji; Persson, Magnus V.

    2018-06-01

    Partitioning of elemental nitrogen in star-forming regions is not well constrained. Most nitrogen is expected to be partitioned among atomic nitrogen (N I), molecular nitrogen (N_2), and icy N-bearing molecules, such as NH_3 and N_2. N I is not directly observable in the cold gas. In this paper, we propose an indirect way to constrain the amount of N I in the cold gas of star-forming clouds, via deuteration in ammonia ice, the [ND2H/NH2D]/[NH2D/NH3] ratio. Using gas-ice astrochemical simulations, we show that if atomic nitrogen remains as the primary reservoir of nitrogen during cold ice formation stages, the [ND2H/NH2D]/[NH2D/NH3] ratio is close to the statistical value of 1/3 and lower than unity, whereas if atomic nitrogen is largely converted into N-bearing molecules, the ratio should be larger than unity. Observability of ammonia isotopologues in the inner hot regions around low-mass protostars, where ammonia ice has sublimated, is also discussed. We conclude that the [ND2H/NH2D]/[NH2D/NH3] ratio can be quantified using a combination of Very Large Array and Atacama Large Millimeter/submillimeter Array observations with reasonable integration times, at least towards IRAS 16293-2422, where high molecular column densities are expected.

  3. Renner-Teller quantum dynamics of NH(a(1)Delta) + H reactions on the NH(2) A(2)A(1) and X(2)B(1) coupled surfaces.

    PubMed

    Defazio, P; Gamallo, P; González, M; Petrongolo, C

    2010-09-16

    Four reactions NH(a1Delta) + H′(2S) are investigated by the quantum mechanical real wavepacket method, taking into account nonadiabatic Renner-Teller (RT) and rovibronic Coriolis couplings between the involved states. We consider depletion (d) to N(2D) + H2(X1Sigmag+), exchange (e) to NH′(a1Delta) + H(2S), quenching (q) to NH(X3Sigma-) + H′(2S), and exchange-quenching (eq) to NH′(X3Sigma-) + H(2S). We extend our RT theory to a general AB + C collision using a geometry-dependent but very simple and empirical RT matrix element. Reaction probabilities, cross sections, and rate constants are presented, and RT results are compared with Born-Oppenheimer (BO), experimental, and semiclassical data. The nonadiabatic couplings open two new channels, (q) and (eq), and increase the (d) and (e) reactivity with respect to the BO one, when NH(a1Delta) is rotationally excited. In this case, the quantum cross sections are larger than the semiclassical ones at low collision energies. The calculated rate constants at 300 K are k(d) = 3.06, k(e) = 3.32, k(q) = 1.44, and k(eq) = 1.70 in 10(-11) cm3 s(-1) compared with the measured values k(d) = (3.2 =/- 1.7), k(q + eq) = (1.7 +/- 0.3), and k(total) = (4.8 +/- 1.7). The theoretical depletion rate is thus in good agreement with the experimental value, but the quenching and total rates are overestimated, because the present RT couplings are too large. This discrepancy is probably due to our simple and empirical RT matrix element.

  4. Reduction of RuVI≡N to RuIII-NH3 by Cysteine in Aqueous Solution.

    PubMed

    Wang, Qian; Man, Wai-Lun; Lam, William W Y; Yiu, Shek-Man; Tse, Man-Kit; Lau, Tai-Chu

    2018-05-21

    The reduction of metal nitride to ammonia is a key step in biological and chemical nitrogen fixation. We report herein the facile reduction of a ruthenium(VI) nitrido complex [(L)Ru VI (N)(OH 2 )] + (1, L = N, N'-bis(salicylidene)- o-cyclohexyldiamine dianion) to [(L)Ru III (NH 3 )(OH 2 )] + by l-cysteine (Cys), an ubiquitous biological reductant, in aqueous solution. At pH 1.0-5.3, the reaction has the following stoichiometry: [(L)Ru VI (N)(OH 2 )] + + 3HSCH 2 CH(NH 3 )CO 2 → [(L)Ru III (NH 3 )(OH 2 )] + + 1.5(SCH 2 CH(NH 3 )CO 2 ) 2 . Kinetic studies show that at pH 1 the reaction consists of two phases, while at pH 5 there are three distinct phases. For all phases the rate law is rate = k 2 [1][Cys]. Studies on the effects of acidity indicate that both HSCH 2 CH(NH 3 + )CO 2 - and - SCH 2 CH(NH 3 + )CO 2 - are kinetically active species. At pH 1, the reaction is proposed to go through [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a), [(L)Ru III (NH 2 SCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (3), and [(L)Ru IV (NH 2 )(OH 2 )] + (4) intermediates. On the other hand, at pH around 5, the proposed intermediates are [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 )(OH 2 )] + (2b) and [(L)Ru IV (NH 2 )(OH 2 )] + (4). The intermediate ruthenium(IV) sulfilamido species, [(L)Ru IV (NHSCH 2 CHNH 3 CO 2 H)(OH 2 )] 2+ (2a) and the final ruthenium(III) ammine species, [(L)Ru III (NH 3 )(MeOH)] + (5) (where H 2 O was replaced by MeOH) have been isolated and characterized by various spectroscopic methods.

  5. Structural study of dehydration mechanisms of NH4Th(NO3)5·9H2O

    NASA Astrophysics Data System (ADS)

    Knyazev, A. V.; Komshina, M. E.; Baranov, E. V.; Savushkin, I. A.; Nipruk, O. V.; Lukoyanov, A. Yu.

    2017-12-01

    The new pentanitrate thorium compounds NH4Th(NO3)5·nH2O were synthesized and their crystal structures were determined by X-ray diffraction analysis: space group P21/n, a = 10.5476(5), b = 14.0444(7), c = 15.5287(8) Å, β = 109.4999(7)°, Z = 4; R = 0.0246 (NH4Th(NO3)5·9H2O); space group P212121, a = 8.7039(4), b = 11.9985(6), c = 16.3531(8) Å, Z = 4; R = 0.0259 (NH4Th(NO3)5·5H2O). Features of structural changes in the dehydration were revealed. Conditions of thermal decomposition of the thorium compound were established using differential scanning calorimetry. The compound was investigated by IR spectroscopy and its bands are assigned.

  6. Chanabayaite, Cu2(N3C2H2)Cl(NH3,Cl,H2O,□)4, a new mineral containing triazolate anion

    NASA Astrophysics Data System (ADS)

    Chukanov, N. V.; Zubkova, N. V.; Möhn, G.; Pekov, I. V.; Pushcharovsky, D. Yu.; Zadov, A. E.

    2015-12-01

    A new mineral, chanabayaite, has been discovered at a guano deposit located at Mt. Pabellón de Pica near the village of Chanabaya, Iquique Province, Tarapacá region, Chile. It is associated with salammoniac, halite, joanneumite, nitratine and earlier chalcopyrite. Chanabayaite occurs as blue translucent imperfect prismatic crystals, up to 0.05 × 0.1 × 0.5 mm in size, and their radial aggregates. Chanabayaite is brittle, with a Mohs' hardness of 2. The cleavage is perfect on (001) and imperfect on (100) and (010). D meas = 1.48(2) g/cm3, D calc = 1.464 g/cm3. The mineral is optically biaxial (-), α = 1.561(2), β = 1.615(3), γ = 1.620(2), 2 V meas = 25(10)°, 2 V calc = 33°. Pleochroism is strong, Z ≈ Y (deep blue) ≫ X (pale blue with gray tint). IR spectrum is given. The chemical composition (electron microprobe data for Cu, Fe and Cl; gas chromatography data for H, N, C and O) is as follows (wt %): 32.23 Cu, 1.14 Fe, 16.13 Cl, 3.1 H, 29.9 N, 12.2 C, 3.4 O, total is 98.1. The empirical formula is ( Z = 4): Cu1.92Fe0.08Cl1.72N8.09C3.85H11.66O0.81. The structural model was based on the single-crystal X-ray diffraction data ( R = 0.1627). Chanabayaite is orthorhombic, space group Imma, a = 19.484(3), b = 7.2136(10), c = 11.999(4) Å, V = 1686.5(7) Å3, Z = 2. In chanabayaite, chains of the corner-sharing Cu(l)-centered octahedra and single Cu(2)-centered octahedra are linked via 1,2,4-triazolate anions C2N3H2 -. NH3 and Cl- are additional ligands coordinating Cu2+. Chanabayaite is a transformational mineral species formed by leaching of Na and one third of Cl and partial dehydration of the protophase Na2Cu2Cl3(N3C2H2)2(NH3)2 • 4H2O. The strongest reflections in the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are detected: 10.19 (100) (101), 6.189 (40) (011), 5.729 (23) (301), 5.216 (75) (211, 202), 4.964 (20) (400), 2.830 (20) (602, 413, 503), 2.611 (24) (123, 422, 404).

  7. A Layered Solution Crystal Growth Technique and the Crystal Structure of (C 6H 5C 2H 4NH 3) 2PbCl 4

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.

    1999-07-01

    Single crystals of the organic-inorganic perovskite (C6H5C2H4NH3)2PbCl4 have been grown at room temperature using a layered solution approach. The bottom solution layer, contained within a long straight tube, consists of PbCl2 dissolved in concentrated aqueous HCl. A less dense layer of methanol is carefully placed on top of the HCl/PbCl2 solution using a syringe. Finally, a stoichiometric quantity of C6H5C2H4NH2 (relative to the PbCl2) is added to the top of the column. As the layers slowly diffuse together, well-formed crystals of (C6H5C2H4NH3)2PbCl4 appear near the interface between the HCl/PbCl2 and C6H5C2H4NH2 solutions. The thick, plate-like crystals are well suited for X-ray crystallography studies. Room temperature intensity data were refined using a triclinic (Poverline1) cell (a=11.1463(3) Å, b=11.2181(3) Å, c=17.6966(5) Å, α= 99.173(1)°, β=104.634(1)°, γ=89.999(1)°, V=2111.8(1) Å3, Z=4, Rf/Rw=0.031/0.044). The organic-inorganic layered perovskite structure features well-ordered sheets of corner-sharing distorted PbCl6 octahedra separated by bilayers of phenethylammonium cations. Tilting and rotation of the PbCl6 octahedra within the perovskite sheets, coupled with organic cation ordering, leads to the unusual in-sheet 2ap×2ap superstructure, where ap is the lattice constant for the ideal cubic perovskite.

  8. Infrared spectrum of NH4+(H2O): Evidence for mode specific fragmentation

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

    Pankewitz, Tobias; Lagutschenkov, Anita; Niedner-schatteburg, Gereon

    2007-02-21

    The gas phase infrared spectrum (3250 to 3810 cm1) of the singly hydrated ammonium ion, NH4+(H2O), has been recorded by consequence spectroscopy of mass selected and isolated ions. The obtained four bands are assigned to N-H stretching modes and O-H stretching modes, respectively. The observed N-H stretching modes are blueshifted with respect to the corresponding modes of the free NH4+ ion, whereas a redshift is observed with respect to the modes of the free NH3 molecule. The observed O-H stretching modes are redshifted when compared to the free H2O molecule. The asymmetric stretching modes give rise to rotationally resolved perpendicularmore » transitions. The K-type equidistant rotational spacings of 11.1(2) cm1 (NH4+) and 29(3) cm1 (H2O) deviate systematically from the corresponding values of the free molecules, a fact which is rationalized in terms of a symmetric top analysis. The recorded relative band intensities compare favorably with predictions of high level ab initio calculations except for the 3(H2O) band for which the observed value is about 20 times weaker than the calculated one. This long standing puzzle motivated us to examine the a 3(H2O)/1(H2O) intensity ratios from other published action spectra in other cationic complexes. These suggest that the 3(H2O) intensities become smaller the stronger the complexes are bound. The recorded ratios vary, in particular among the data collected from action spectra that were recorded with and without rare gas tagging. The calculated anharmonic coupling constants in NH4+(H2O) further suggested that the coupling of the 3(H2O) and 1(H2O) modes to other cluster modes indeed varies by orders of magnitude. These findings altogether render the picture of a mode specific fragmentation dynamic that modulates band intensities in action spectra with respect to absorption spectra. Additional high-level electronic structure calculations at the coupled-cluster single and double with perturbative treatment of triple

  9. Behaviors of Absolute Densities of N, H, and NH3 at Remote Region of High-Density Radical Source Employing N2-H2 Mixture Plasmas

    NASA Astrophysics Data System (ADS)

    Chen, Shang; Kondo, Hiroki; Ishikawa, Kenji; Takeda, Keigo; Sekine, Makoto; Kano, Hiroyuki; Den, Shoji; Hori, Masaru

    2011-01-01

    For an innovation of molecular-beam-epitaxial (MBE) growth of gallium nitride (GaN), the measurements of absolute densities of N, H, and NH3 at the remote region of the radical source excited by plasmas have become absolutely imperative. By vacuum ultraviolet absorption spectroscopy (VUVAS) at a relatively low pressure of about 1 Pa, we obtained a N atom density of 9×1012 cm-3 for a pure nitrogen gas used, a H atom density of 7×1012 cm-3 for a gas composition of 80% hydrogen mixed with nitrogen gas were measured. The maximum density 2×1013 cm-3 of NH3 was measured by quadruple mass spectrometry (QMS) at H2/(N2+H2)=60%. Moreover, we found that N atom density was considerably affected by processing history, where the characteristic instability was observed during the pure nitrogen plasma discharge sequentially after the hydrogen-containing plasma discharge. These results indicate imply the importance of establishing radical-based processes to control precisely the absolute densities of N, H, and NH3 at the remote region of the radical source.

  10. Emission factor of ammonia (NH3) from on-road vehicles in China: tunnel tests in urban Guangzhou

    NASA Astrophysics Data System (ADS)

    Liu, Tengyu; Wang, Xinming; Wang, Boguang; Ding, Xiang; Deng, Wei; Lü, Sujun; Zhang, Yanli

    2014-05-01

    Ammonia (NH3) is the primary alkaline gas in the atmosphere that contributes to formation of secondary particles. Emission of NH3 from vehicles, particularly gasoline powered light duty vehicles equipped with three-way catalysts, is regarded as an important source apart from emissions from animal wastes and soils, yet measured emission factors for motor vehicles are still not available in China, where traffic-related emission has become an increasingly important source of air pollutants in urban areas. Here we present our tunnel tests for NH3 from motor vehicles under ‘real world conditions’ in an urban roadway tunnel in Guangzhou, a central city in the Pearl River Delta (PRD) region in south China. By attributing all NH3 emissions in the tunnel to light-duty gasoline vehicles, we obtained a fuel-based emission rate of 2.92 ± 0.18 g L-1 and a mileage-based emission factor of 229.5 ± 14.1 mg km-1. These emission factors were much higher than those measured in the United States while measured NO x emission factors (7.17 ± 0.60 g L-1 or 0.56 ± 0.05 g km-1) were contrastingly near or lower than those previously estimated by MOBILE/PART5 or COPERT IV models. Based on the NH3 emission factors from this study, on-road vehicles accounted for 8.1% of NH3 emissions in the PRD region in 2006 instead of 2.5% as estimated in a previous study using emission factors taken from the Emission Inventory Improvement Program (EIIP) in the United States.

  11. Effects on H(-) production in a multicusp ion source by mixture of H2 with H2O, NH3, CH4, N2H4, and SF6

    NASA Technical Reports Server (NTRS)

    Orient, O. J.; Chutjian, A.; Leung, K. N.

    1987-01-01

    Effects of H(-) production in a multicusp ion source are measured by separately mixing with hydrogen small amounts (0.33-10 percent) of water, ammonia, methane, and hydrazine these are molecules which produce large amounts of H(-) via dissociative attachment (DA) resonances at higher electron energies. The mixing was done in a separate reservoir, with careful measurement of individual pressures. Experimental enhancements of 1.4 and less were observed, whereas calculated enhancements, using accurate DA cross sections for ground-state H2, should have produced factors of 1.5, 3.0, 1.3, and 2.4 enhancements for water, ammonia methane, and hydrazine, respectively, at a mean electron energy of 1.0 eV in the extraction region. The difference is accounted for by including, in the enhancement calculation, vibrationally and rotationally excited H2 molecules, with v-double prime = 5-11, and J-double prime = 0-5, and the large DA cross sections for the excited H2 (v-double prime, J-double prime). The relative populations of H2 (v-double prime, J-double prime) thus obtained are found to be substantially smaller than those predicted by theoretical calculations. The effect on H(-) current was also studied by mixing small amounts of SF6 with H2. A 1.5 percent mixture was found to reduce the H(-) output by one half.

  12. Changes of ammonia, urea contents and transaminase activity in the body during aerial exposure and ammonia loading in Chinese loach Paramisgurnus dabryanus.

    PubMed

    Zhang, Yun-Long; Zhang, Hai-Long; Wang, Ling-Yu; Gu, Bei-Yi; Fan, Qi-Xue

    2017-04-01

    The Paramisgurnus dabryanus was exposed to 30 mmol L -1 NH 4 Cl solution and air to assessing the change of body ammonia and urea contents and the activities of alanine aminotransferase (ALT) and aspartate transaminase (AST). After 48 h of ammonia exposure, ammonia concentration in the plasma, brain, liver and muscle were 3.3-fold, 5.6-fold, 3.5-fold and 4.2-fold, respectively, those of the control values. Plasma, brain, liver and muscle ammonia concentrations increased to 2.2-fold, 3.3-fold, 2.5-fold and 2.9-fold, respectively, those of control values in response to 48 h of aerial exposure. Within the given treatment (ammonia or aerial exposure), there was no change in plasma, brain and liver urea concentrations between exposure durations. The plasma ALT activity was significantly affected by exposure time during aerial exposure, while the liver ALT activity was not affected by ammonia or aerial exposure. Exposure to NH 4 Cl or air had no effect on either plasma or liver AST activity. Our results suggested that P. dabryanus could accumulate quite high level of internal ammonia because of the high ammonia tolerance in its cells and tissues, and NH 3 volatilization would be a possible ammonia detoxification strategy in P. dabryanus. Urea synthesis was not an effective mechanism to deal with environmental or internal ammonia problem. The significant increase of ALT activity in plasma during aerial exposure, indicating that alanine synthesis through certain amino acid catabolism may be subsistent in P. dabryanus.

  13. The bovine TRPV3 as a pathway for the uptake of Na+, Ca2+, and NH4+

    PubMed Central

    Liebe, Franziska; Liebe, Hendrik

    2018-01-01

    Absorption of ammonia from the gastrointestinal tract results in problems that range from hepatic encephalopathy in humans to poor nitrogen efficiency of cattle with consequences for the global climate. Previous studies on epithelia and cells from the native ruminal epithelium suggest functional involvement of the bovine homologue of TRPV3 (bTRPV3) in ruminal NH4+ transport. Since the conductance of TRP channels to NH4+ has never been studied, bTRPV3 was overexpressed in HEK-293 cells and investigated using the patch-clamp technique and intracellular calcium imaging. Control cells contained the empty construct. Divalent cations blocked the conductance for monovalent cations in both cell types, with effects higher in cells expressing bTRPV3. In bTRPV3 cells, but not in controls, menthol, thymol, carvacrol, or 2-APB stimulated whole cell currents mediated by Na+, Cs+, NH4+, and K+, with a rise in intracellular Ca2+ observed in response to menthol. While only 25% of control patches showed single-channel events (with a conductance of 40.8 ± 11.9 pS for NH4+ and 25.0 ± 5.8 pS for Na+), 90% of bTRPV3 patches showed much larger conductances of 127.8 ± 4.2 pS for Na+, 240.1 ± 3.6 pS for NH4+, 34.0 ± 1.7 pS for Ca2+, and ~ 36 pS for NMDG+. Open probability, but not conductance, rose with time after patch excision. In conjunction with previous research, we suggest that bTRPV3 channels may play a role in the transport of Na+, K+, Ca2+ and NH4+ across the rumen with possible repercussions for understanding the function of TRPV3 in other epithelia. PMID:29494673

  14. The bovine TRPV3 as a pathway for the uptake of Na+, Ca2+, and NH4.

    PubMed

    Schrapers, Katharina T; Sponder, Gerhard; Liebe, Franziska; Liebe, Hendrik; Stumpff, Friederike

    2018-01-01

    Absorption of ammonia from the gastrointestinal tract results in problems that range from hepatic encephalopathy in humans to poor nitrogen efficiency of cattle with consequences for the global climate. Previous studies on epithelia and cells from the native ruminal epithelium suggest functional involvement of the bovine homologue of TRPV3 (bTRPV3) in ruminal NH4+ transport. Since the conductance of TRP channels to NH4+ has never been studied, bTRPV3 was overexpressed in HEK-293 cells and investigated using the patch-clamp technique and intracellular calcium imaging. Control cells contained the empty construct. Divalent cations blocked the conductance for monovalent cations in both cell types, with effects higher in cells expressing bTRPV3. In bTRPV3 cells, but not in controls, menthol, thymol, carvacrol, or 2-APB stimulated whole cell currents mediated by Na+, Cs+, NH4+, and K+, with a rise in intracellular Ca2+ observed in response to menthol. While only 25% of control patches showed single-channel events (with a conductance of 40.8 ± 11.9 pS for NH4+ and 25.0 ± 5.8 pS for Na+), 90% of bTRPV3 patches showed much larger conductances of 127.8 ± 4.2 pS for Na+, 240.1 ± 3.6 pS for NH4+, 34.0 ± 1.7 pS for Ca2+, and ~ 36 pS for NMDG+. Open probability, but not conductance, rose with time after patch excision. In conjunction with previous research, we suggest that bTRPV3 channels may play a role in the transport of Na+, K+, Ca2+ and NH4+ across the rumen with possible repercussions for understanding the function of TRPV3 in other epithelia.

  15. Laboratory measurements of the W band (3.2 mm) properties of phosphine (PH3) and ammonia (NH3) under simulated conditions for the outer planets

    NASA Astrophysics Data System (ADS)

    Mohammed, Priscilla N.; Steffes, Paul G.

    2004-07-01

    A model, based on the Van Vleck-Weisskopf line shape, was developed for the centimeter-wavelength opacity of PH3, which provides an order of magnitude improvement over previous models [Hoffman et al., 2001]. New laboratory measurements indicate that the model is also accurate at 94 GHz (3.2 mm) under conditions for the outer planets. Measurements of the opacity and refractivity of PH3 in a hydrogen/helium (H2/He) atmosphere were conducted at 94 GHz (3.2 mm) at pressures of 0.5 and 2 bars and at temperatures of 293 K and 213 K. Additionally, new high-precision laboratory measurements of the opacity and refractivity of NH3 in an H2/He atmosphere were conducted at the same frequency at pressures from 0.5 to 2 bars and at temperatures of 204 K, 211 K, and 290 K. Results show that existing models, which predict NH3 opacity in an H2/He environment, understate the absorption due to the pressure broadened rotational lines. A new model is proposed for use at 94 GHz (3.2 mm) which uses a Ben-Reuven line shape [Ben-Reuven, 1966] for the inversion lines and a Kinetic line shape [Gross, 1955] for the rotational lines. Results of measurements of both PH3 and NH3 can be used to better interpret maps of Saturn's emission at this wavelength and can potentially be used to deduce spatial variations in the abundances of both gases in the atmosphere of Saturn.

  16. Formation of Hydroxylamine from Ammonia and Hydroxyl Radicals

    NASA Astrophysics Data System (ADS)

    Krim, Lahouari; Zins, Emilie-Laure

    2014-06-01

    In the interstellar medium, as well as in icy comets, ammonia may be a crucial species in the first step toward the formation of amino-acids and other prebiotic molecules such as hydroxylamine (NH2OH). It is worth to notice that the NH3/H2 ratio in the ISM is 3 10-5 compared the H2O/H2 one which is only 7 10-5. Using either electron-UV irradiations of water-ammonia ices or successive hydrogenation of solid nitric oxide, laboratory experiments have already shown the feasibility of reactions that may take place on the surface of ice grains in molecular clouds, and may lead to the formation of this precursor. Herein is proposed a new reaction pathway involving ammonia and hydroxyl radicals generated in a microwave discharge. Experimental studies, at 3 and 10 K, in solid phase as well as in neon matrix have shown that this reaction proceed via a hydrogen abstraction, leading to the formation of NH2 radical, that further recombine with hydroxyl radical to form hydroxylamine, under non-energetic conditions.

  17. First-Principles Study of Novel Two-Dimensional (C4H9NH3)2PbX4 Perovskites for Solar Cell Absorbers.

    PubMed

    Wang, Da; Wen, Bo; Zhu, Ya-Nan; Tong, Chuan-Jia; Tang, Zhen-Kun; Liu, Li-Min

    2017-02-16

    Low-dimensional perovskites (A 2 BX 4 ), in which the A cations are replaced by different organic cations, may be used for photovoltaic applications. In this contribution, we systematically study the two-dimensional (2D) (C 4 H 9 NH 3 ) 2 PbX 4 (X═Cl, Br and I) hybrid perovskites by density functional theory (DFT). A clear structures-properties relationship, with the photophysical characteristics directly related to the dimensionality and material compositions, was established. The strong s-p antibonding couplings in both bulk and monolayer (C 4 H 9 NH 3 ) 2 PbI 4 lead to low effective masses for both holes (m h *) and electrons (m e *). However, m h * increases in proportion to the decreasing inorganic layer thickness, which eventually leads to a slightly shifted band edge emission found in 2D perovskites. Notably, the 2D (C 4 H 9 NH 3 ) 2 PbX 4 perovskites exhibit strong optical transitions in the visible light spectrum, and the optical absorption tunings can be achieved by varying the compositions and the layer thicknesses. Such work paves an important way to uncover the structures-properties relationship in 2D perovskites.

  18. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X=empty, H2O, NH3, H3O+: The importance of O-topology

    NASA Astrophysics Data System (ADS)

    Anick, David J.

    2010-04-01

    For (H2O)20X water clusters consisting of X enclosed by the 512 dodecahedral cage, X=empty, H2O, NH3, and H3O+, databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G∗∗. Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; |M|2, where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus |M| show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X=H3O+, one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H2O)20(NH4+) and (H2O)20(NH4+)(OH-) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H2O)20(NH4+) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low-energy water cluster geometries that may have wide applicability.

  19. Topology-energy relationships and lowest energy configurations for pentagonal dodecahedral (H2O)20X clusters, X = empty, H2O, NH3, H3O+: the importance of O-topology.

    PubMed

    Anick, David J

    2010-04-28

    For (H(2)O)(20)X water clusters consisting of X enclosed by the 5(12) dodecahedral cage, X = empty, H(2)O, NH(3), and H(3)O(+), databases are made consisting of 55-82 isomers optimized via B3LYP/6-311++G(**). Correlations are explored between ground state electronic energy (Ee) or electronic energy plus zero point energy (Ee+ZPE) and the clusters' topology, defined as the set of directed H-bonds. Linear regression is done to identify topological features that correlate with cluster energy. For each X, variables are found that account for 99% of the variance in Ee and predict it with a rms error under 0.2 kcal/mol. The method of analysis emphasizes the importance of an intermediate level of structure, the "O-topology," consisting of O-types and a list of O pairs that are bonded but omitting H-bond directions, as a device to organize the databases and reduce the number of structures one needs to consider. Relevant variables include three parameters, which count the number of H-bonds having particular donor and acceptor types; absolute value(M)(2), where M is the cluster's vector dipole moment; and the projection of M onto the symmetry axis of X. Scatter diagrams for Ee or Ee+ZPE versus absolute value(M) show that clusters fall naturally into "families" defined by the values of certain discrete parameters, the "major parameters," for each X. Combining "family" analysis and O-topologies, a small group of clusters is identified for each X that are candidates to be the global minimum, and the minimum is determined. For X = H(3)O(+), one cluster with central hydronium lies just 2.08 kcal/mol above the lowest isomer with surface hydronium. Implications of the methodology for dodecahedral (H(2)O)(20)(NH(4)(+)) and (H(2)O)(20)(NH(4)(+))(OH(-)) are discussed, and new lower energy isomers are found. For MP2/TZVP, the lowest-energy (H(2)O)(20)(NH(4)(+)) isomer features a trifurcated H-bond. The results suggest a much more efficient and comprehensive way of seeking low

  20. Densities and apparent molar volumes of atmospherically important electrolyte solutions. 2. The systems H(+)-HSO4(-)-SO4(2-)-H2O from 0 to 3 mol kg(-1) as a function of temperature and H(+)-NH4(+)-HSO4(-)-SO4)2-)-H2O from 0 to 6 mol kg(-1) at 25 °C using a Pitzer ion interaction model, and NH4HSO4-H2O and (NH4)3H(SO4)2-H2O over the entire concentration range.

    PubMed

    Clegg, S L; Wexler, A S

    2011-04-21

    A Pitzer ion interaction model has been applied to the systems H(2)SO(4)-H(2)O (0-3 mol kg(-1), 0-55 °C) and H(2)SO(4)-(NH(4))(2)SO(4)-H(2)O (0-6 mol kg(-1), 25 °C) for the calculation of apparent molar volume and density. The dissociation reaction HSO(4)(-)((aq)) ↔ H(+)((aq)) + SO(4)(2-)((aq)) is treated explicitly. Apparent molar volumes of the SO(4)(2-) ion at infinite dilution were obtained from part 1 of this work, (1) and the value for the bisulfate ion was determined in this study from 0 to 55 °C. In dilute solutions of both systems, the change in the degree of dissociation of the HSO(4)(-) ion with concentration results in much larger variations of the apparent molar volumes of the solutes than for conventional strong (fully dissociated) electrolytes. Densities and apparent molar volumes are tabulated. Apparent molar volumes calculated using the model are combined with other data for the solutes NH(4)HSO(4) and (NH(4))(3)H(SO(4))(2) at 25 °C to obtain apparent molar volumes and densities over the entire concentration range (including solutions supersaturated with respect to the salts).

  1. Chromophores from Photolyzed Ammonia Reacting with Acetylene: Application to Jupiter’s Great Red Spot

    NASA Astrophysics Data System (ADS)

    Carlson, Robert W.; Baines, K. H.; Anderson, M. S.; Filacchione, G.

    2012-10-01

    The production mechanisms of chromophores at Jupiter, and notably at the Great Red Spot (GRS), have been long-standing puzzles. A clue to the formation of the GRS coloring agent may be the great height of this storm, which can upwell ammonia to pressure levels of a few hundred mbar where solar photons capable of dissociating NH3 penetrate. Acetylene formed at higher altitudes can diffuse down and react with the NH3 photodissociation products, forming a deposit that absorbs in the ultraviolet and visible region (Ferris and Ishikawa, J. Amer. Chem. Soc. 110, 4306-4312, 1988). We have investigated the system NH3 + C2H2 + CH4 using a Zn lamp emitting at 214 nm to produce NH2 + H and subsequent reaction products. The deposits produced in these reactions were analyzed by optical and infrared spectroscopy and soft-ionization (He*) time-of-flight mass spectroscopy. The combination of NH3 + CH4 produced no visibly absorbing material, but NH3 + C2H2 and NH3 + C2H2 + CH4 mixtures both produced a yellow-orange film whose transmission spectra are similar to that of the GRS obtained by Cassini VIMS. Infrared spectra show a strong band at 2056 wavenumbers which may arise from nitrile (-CN), isonitrile (-NC), or diazide (-CNN) functional groups. The high-resolution mass spectra are consistent with compounds of the form CnH2n+1Nm, similar to the products formed in NH3 + CH4 spark discharges (Molton and Ponnamperuma, Icarus 21, 166-174, 1974). We thank NASA's Planetary Atmospheres Program for support.

  2. Determination of the Rate Constants for the NH 2 (X 2 B 1 ) + NH 2 (X 2 B 1 ) and NH 2 (X 2 B 1 ) + H Recombination Reactions in N 2 as a Function of Temperature and Pressure

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

    Altinay, Gokhan; Macdonald, R. Glen

    2015-07-16

    The recombination rate constants for the reactions NH2 + NH2 → N2H4 (reaction k1b) and NH2 + HNH3 (reaction k2b) with N2 as a third-body have been measured as a function of temperature and pressure. The temperature range was from 292 to 533 K and the pressure range from a few Torr up to 300–400 Torr, well within the pressure falloff region. The NH2 radical was produced by 193 nm pulsed-laser photolysis of NH3 in a temperature controlled flow chamber. High-resolution time-resolved laser absorption spectroscopy was used to follow the temporal concentration profiles of both NH2 and NH3, simultaneously. The NH2 radical was monitored at 14800.65 cm–1 using the 1231 (0,7,0)Ã2A1 ← 1331 (0,0,0)more » $$\\tilde{X}$$2B1 ro-vibronic transition, and NH3 monitored at 3336.39 cm–1 on the qQ3(3)s (1,0,0,0) ← (0,0,0,0) ro-vibrational transition. The necessary collisional broadening parameters for each molecule were measured in separate experiments. The pressure and temperature dependence of k1b can be represented by the Troe parameters: k0, the low-pressure three-body recombination rate constant, k0(T) = (1.14 ± 0.59) × 10–19T–(3.41±0.28) cm6 molecule–2 s–1, and Fcent, the pressure broadening parameter, Fcent = 0.15 ± 0.12, independent of temperature. The data could not be fit by three-independent parameters, and the high-pressure limiting rate constant k∞(T) = 9.33 × 10–10T–0.414 e33/T cm3 molecule–1 s–1 was taken from the high-quality theoretical calculations of Klippenstein et al. (J. Phys. Chem A 2009, 113, 10241). The pressure and temperature dependence of k2b, can be represented by the Troe parameters: k0(T) = (9.95 ± 0.58) × 10–26T(-1.76±0.092) cm6 molecule–2 s–1, Fcent = 0.5 ± 0.2, k∞ = 2.6 × 10–10 cm3 molecule–1 s–1. Again, the data could not be fit with three independent parameters, and k2b∞ was chosen to be 2.6 × 10–10 cm3 molecule–1 s–1 and fixed in the analysis.« less

  3. In situ DRIFTS investigation of NH3-SCR reaction over CeO2/zirconium phosphate catalyst

    NASA Astrophysics Data System (ADS)

    Zhang, Qiulin; Fan, Jie; Ning, Ping; Song, Zhongxian; Liu, Xin; Wang, Lanying; Wang, Jing; Wang, Huimin; Long, Kaixian

    2018-03-01

    A series of ceria modified zirconium phosphate catalysts were synthesized for selective catalytic reduction of NO with ammonia (NH3-SCR). Over 98% NOx conversion and 98% N2 selectivity were obtained by the CeO2/ZrP catalyst with 20 wt.% CeO2 loading at 250-425 °C. The interaction between CeO2 and zirconium phosphate enhanced the redox abilities and surface acidities of the catalysts, resulting in the improvement of NH3-SCR activity. The in situ DRIFTS results indicated that the NH3-SCR reaction over the catalysts followed both Eley-Rideal and Langmuir-Hinshelwood mechanisms. The amide (sbnd NH2) groups and the NH4+ bonded to Brønsted acid sites were the important intermediates of Eley-Rideal mechanism.

  4. FTMS studies of sputtered metal cluster ions (IV): size-selective effects in the chemistry of Fe{/n +} with NH3 and Pd{/n +} with D2 or C2H4

    NASA Astrophysics Data System (ADS)

    Irion, M. P.; Selinger, A.; Schnabel, P.

    1991-03-01

    Fe{/n +} and Pd{/n +} clusters up to n=19 and n=25, respectively, are produced in an external ion source by sputtering of the respective metal foils with Xe+ primary ions at 20 keV. They are transferred to the ICR cell of a home-built Fourier transform mass spectrometer, where they are thermalized to nearly room temperature and stored for several tens of seconds. During this time, their reactions with a gas leaked in at low level are studied. Thus in the presence of ammonia, most Fe{/n +} clusters react by simply adsorbing intact NH3 molecules. Only Fe{4/+} ions show dehydrogenation/adsorption to Fe4(NH){/m +} intermediates ( m=1, 2) that in a complex scheme go on adsorbing complete NH3 units. To clarify the reaction scheme, one has to isolate each species in the ion cell, which often requires the ejection of ions very close in mass. This led to the development of a special isolation technique that avoids the use of isotopically pure metal samples. Pd{n/+} cluster ions ( n=2...9) dehydrogenate C2H4 in general to yield Pd n (C2H2)+, yet Pd{6/+} appear totally unreactive. Towards D2, Pd{7/+} ions seem inert, whereas Pd{8/+} adsorb up to two molecules.

  5. On the fate of laser-produced NH 2 in a constrained pulsed expansion of trimethylamine alane and NH 3

    NASA Astrophysics Data System (ADS)

    Demchuk, Alexander; Cahill, John J.; Simpson, Steven; Koplitz, Brent

    2001-11-01

    The effects of both 193 nm radiation and NH 3 on an expansion of trimethylamine alane (TMAA) have been studied. In neat TMAA, 193 nm radiation induces small but significant clustering. When NH 3 is introduced in the absence of 193 nm photons, no visible reaction occurs. However, when NH 3 is introduced along with 193 nm photons, the H 3Al:N(CH 3) 3 parent molecule is completely replaced by H 3AlNH 2. Moreover, the clustering channels observed with neat TMAA disappear. The apparent stability or inertness of the R 3MNH 2 (R=H, CH 3 or C 2H 5; M=Ga or Al) species in a variety of metal nitride reactive environments is discussed.

  6. Lead-free Perovskite Materials (NH4 )3 Sb2 Ix Br9-x.

    PubMed

    Zuo, Chuantian; Ding, Liming

    2017-06-01

    A family of perovskite light absorbers (NH 4 ) 3 Sb 2 I x Br 9-x (0≤x≤9) was prepared. These materials show good solubility in ethanol, a low-cost, hypotoxic, and environmentally friendly solvent. The light absorption of (NH 4 ) 3 Sb 2 I x Br 9-x films can be tuned by adjusting I and Br content. The absorption onset for (NH 4 ) 3 Sb 2 I x Br 9-x films changes from 558 nm to 453 nm as x changes from 9 to 0. (NH 4 ) 3 Sb 2 I 9 single crystals were prepared, exhibiting a hole mobility of 4.8 cm 2  V -1  s -1 and an electron mobility of 12.3 cm 2  V -1  s -1 . (NH 4 ) 3 Sb 2 I 9 solar cells gave an open-circuit voltage of 1.03 V and a power conversion efficiency of 0.51 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Effects of gaseous ammonia on intracellular pH values in leaves of C 3- and C 4-plants

    NASA Astrophysics Data System (ADS)

    Yin, Zu-Hua; Kaiser, Werner; Heber, Ulrich; Raven, John A.

    Responses of cytosolic and vacuolar pH to different concentrations (1.3-5.4 μmol NH 3 mol -1 gas or 0.940-3.825 mg NH 3 m -3 gas) of gaseous NH 3 were studied in experiments of 3 h duration by recording changes in fluorescence of pyranine and esculin in leaves of C 3 and C 4 plants. After a lag phase of 0.5-4 min, the uptake of NH 3 at 50-200 nmol m -2 leaf area s -1 increased pyranine fluorescence, indicating cytosolic alkalinization in leaves of Pelargonium zonale L. (C 3) and Amaranthus caudatus L. (C 4). A smaller increase in esculin fluorescence induced by NH 3 indicated some vacuolar alkalization in a Spinacia oleracea L. leaf. Photosynthesis and transpiration remained unchanged during exposure of illuminated leaves to NH 3 for up to 30 min (the maximum tested). CO 2 concentrations influenced the extent of cytosolic alkalinization. 500 μmol CO 2 mol -1 gas suppressed the NH 3-induced cytosolic alkalinization relative to that found in 16 μmol CO 2 mol -1 gas. The suppressing effect of CO 2 on NH 3-induced alkalization was larger in illuminated leaves of the C 4Amaranthus than the C 3Pelargonium. These results indicate that the alkaline pH shift caused by solution and protonation of NH 3 in aqueous leaf compartments is affected by assimilation of NH 3.

  8. Alternative E ammonia feedstock

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

    Lentz, M.J.; Wright, R.A.

    1999-07-01

    Power plants are using more Ammonia for increasing precipitator and baghouse efficiency, for SCR and SNCR processes, and for controlling acid stack plumes and dewpoint corrosion. These simple systems inject ammonia and air into the furnace or the precipitator or baghouse inlet ductwork. The common feedstocks in use today are Anhydrous ammonia [NH{sub 3}] and Aqueous ammonia [NH{sub 4}OH], both defined as poison gases by US authorities and most Western nations. Storage and handling procedures for these products are strictly regulated. Wilhelm Environmental Technologies Inc. is developing use of solid, formed or prilled Urea [CO(NH{sub 2}){sub 2}] as the feedstock.more » When heated in moist air, Urea sublimes to ammonia [NH{sub 3}] and carbon dioxide [CO{sub 2}]. Urea is stored and handled without restrictions or environmental concerns. Urea is a more expensive feedstock than NH{sub 3}, but much less expensive than [NH{sub 4}OH]. The design, and operating results, of a pilot system at Jacksonville Electric St. John's River Plant [Unit 2] are described. The pilot plant successfully sublimed Urea up to 100 pounds/hour. Further testing is planned. Very large ammonia use may favor NH{sub 3}, but smaller quantities can be produced at attractive prices with Urea based ammonia systems. Storage costs are far less. Many fluidized-bed boilers can use pastille or solid urea metered directly into the existing cyclones for NO{sub x} control. This is more economical than aqueous ammonia or aqueous urea based technology.« less

  9. Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

    NASA Astrophysics Data System (ADS)

    Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

    2017-12-01

    Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially

  10. Kinetics of NH3 -oxidation, NO-turnover, N2 O-production and electron flow during oxygen depletion in model bacterial and archaeal ammonia oxidisers.

    PubMed

    Hink, Linda; Lycus, Pawel; Gubry-Rangin, Cécile; Frostegård, Åsa; Nicol, Graeme W; Prosser, James I; Bakken, Lars R

    2017-12-01

    Ammonia oxidising bacteria (AOB) are thought to emit more nitrous oxide (N 2 O) than ammonia oxidising archaea (AOA), due to their higher N 2 O yield under oxic conditions and denitrification in response to oxygen (O 2 ) limitation. We determined the kinetics of growth and turnover of nitric oxide (NO) and N 2 O at low cell densities of Nitrosomonas europaea (AOB) and Nitrosopumilus maritimus (AOA) during gradual depletion of TAN (NH 3  + NH4+) and O 2 . Half-saturation constants for O 2 and TAN were similar to those determined by others, except for the half-saturation constant for ammonium in N. maritimus (0.2 mM), which is orders of magnitudes higher than previously reported. For both strains, cell-specific rates of NO turnover and N 2 O production reached maxima near O 2 half-saturation constant concentration (2-10 μM O 2 ) and decreased to zero in response to complete O 2 -depletion. Modelling of the electron flow in N. europaea demonstrated low electron flow to denitrification (≤1.2% of the total electron flow), even at sub-micromolar O 2 concentrations. The results corroborate current understanding of the role of NO in the metabolism of AOA and suggest that denitrification is inconsequential for the energy metabolism of AOB, but possibly important as a route for dissipation of electrons at high ammonium concentration. © 2017 Society for Applied Microbiology and John Wiley & Sons Ltd.

  11. Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

    NASA Astrophysics Data System (ADS)

    Murape, D. M.; Eassa, N.; Nyamhere, C.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

    2012-05-01

    Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH4)2S/(NH4)2SO4) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (ϕb) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at -0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb-O, present on the as-received material is effectively removed on treating with ([(NH4)2S/(NH4)2SO4]+S) and (NH4)2S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.

  12. Formation of amino acids from NH3 /NO2, CO2 and H2O: implications for the prebiotic origin of biomolecules.

    PubMed

    Singh, Amrinder; Nisha; Singh, Palwinder

    2015-11-15

    The search for the conditions which must have prevailed in the long-distant past during the conversion of inanimate matter into animate matter is a fascinating area of research and it continues to draw the attention of the scientific community. The initiation of life on this planet must have been preceded by the development of biomolecules, amongst which amino acids have unique importance. Formation of amino acids under a certain set of conditions is shown in the present experiments. Solutions of ammonium carboxylates or the mixture of two such salts were prepared in 3:6.9:0.1 (v/v/v) acetonitrile/water/formic acid at a concentration of 50 μM. The studies were performed using a quadrupole time-of-flight (QqTOF) mass spectrometer. The formation of different amino acids was detected with high-resolution mass spectrometry. Here, we show the formation of amino acids when a solution of ammonium salts was injected into an electrospray ionization (ESI)-QqTOF-MS instrument. The ammonium salts were the source of NH3 and CO2 and H2 O was available in the medium. It seems that the combination of NH3 , CO2 , and H2 O leads to the formation of amino acids. Further to the literature reports of formation of amino acids under the reduced atmosphere represented by gases such as NH3 , CH4 , H2 and H2 O, here we demonstrate the formation of amino acids by the combination of NH3 /NO2 , CO2 and water vapours in the ESI source of the mass spectrometer. Copyright © 2015 John Wiley & Sons, Ltd.

  13. Lethal and sublethal effects of ammonia to juvenile Lampsilis mussels (Unionidae) in sediment and water-only exposures

    USGS Publications Warehouse

    Newton, T.J.; Bartsch, M.R.

    2007-01-01

    We compared the sensitivity of two juvenile unionid mussels (Lampsilis cardium and Lampsilis higginsii) to ammonia in 96-h water-only and sediment tests by use of mortality and growth measurements. Twenty mussels were placed in chambers buried 2.5 cm into reference sediments to approximate pore-water exposure (sediment tests) or elevated above the bottom of the experimental units (water-only tests). In the sediment tests, a pH gradient existed between the overlying water (mean 8.0), sediment-water interface (mean 7.7), and 2.5 cm depth (mean 7.4). We assumed that mussels were exposed to ammonia in pore water and report effect concentrations in pore water, but if they were exposed to the higher pH water, more of the ammonia would be in the toxic un-ionized (NH 3) form. The only differences in toxicity and growth between mussel species occurred in some of the water-only tests. In sediment tests, median lethal concentrations (LC50s) ranged from 124 to 125 ??g NH3-N/L. In water-only tests, LC50s ranged from 157 to 372 ??g NH3-N/L. In sediment tests, median effective concentrations (EC50s based on growth) ranged from 30 to 32 ??g NH3-N/L. Juvenile mussels in the water-only tests grew poorly and did not exhibit a dose-response relation. These data demonstrate that growth is a sensitive and valuable endpoint for studies on ammonia toxicity with juvenile freshwater mussels and that growth should be measured via sediment tests. ?? 2007 SETAC.

  14. The role of unstable NH3 in the formation of nitrogen-rich alpha-U2N(3+x) by the reaction of UC or U with NH3

    NASA Astrophysics Data System (ADS)

    Katsura, Masahiro; Hirota, Masayuki; Miyake, Masanobu

    1994-10-01

    Reactions of U or UC with a stream of NH3 or N2 were carried out at 600 and 900 C. It has been found that in high temperature reactions of U or UC with flowing NH3, the catalytic decomposition of NH3 proceeds in parallel with the nitridation reaction of U or UC by action of NH3, which leads to the formation alpha-U2N(3+x), and eventually a steady state is established where the partial pressures of NH3, H2 and N2 (PNH3, PH2, and PN2) in the flowing gas and the N:U ratio of alpha-U2N(3+x) are all uniquely determined. The nitrogen activity a(sub N) of the flowing gas may be increased by suppressing the decomposition of NH3 into H2 and N2. The N:U ratio of alpha-U2N(3+x) increases as the extent of dissociation of NH3, alpha, decreases.

  15. Indoor, outdoor, and regional summer and winter concentrations of PM10, PM2.5, SO4(2)-, H+, NH4+, NO3-, NH3, and nitrous acid in homes with and without kerosene space heaters.

    PubMed Central

    Leaderer, B P; Naeher, L; Jankun, T; Balenger, K; Holford, T R; Toth, C; Sullivan, J; Wolfson, J M; Koutrakis, P

    1999-01-01

    Twenty-four-hour samples of PM10 (mass of particles with aerodynamic diameter < or = 10 microm), PM2.5, (mass of particles with aerodynamic diameter < or = 2.5 microm), particle strong acidity (H+), sulfate (SO42-), nitrate (NO3-), ammonia (NH3), nitrous acid (HONO), and sulfur dioxide were collected inside and outside of 281 homes during winter and summer periods. Measurements were also conducted during summer periods at a regional site. A total of 58 homes of nonsmokers were sampled during the summer periods and 223 homes were sampled during the winter periods. Seventy-four of the homes sampled during the winter reported the use of a kerosene heater. All homes sampled in the summer were located in southwest Virginia. All but 20 homes sampled in the winter were also located in southwest Virginia; the remainder of the homes were located in Connecticut. For homes without tobacco combustion, the regional air monitoring site (Vinton, VA) appeared to provide a reasonable estimate of concentrations of PM2.5 and SO42- during summer months outside and inside homes within the region, even when a substantial number of the homes used air conditioning. Average indoor/outdoor ratios for PM2.5 and SO42- during the summer period were 1.03 +/- 0.71 and 0.74 +/- 0.53, respectively. The indoor/outdoor mean ratio for sulfate suggests that on average approximately 75% of the fine aerosol indoors during the summer is associated with outdoor sources. Kerosene heater use during the winter months, in the absence of tobacco combustion, results in substantial increases in indoor concentrations of PM2.5, SO42-, and possibly H+, as compared to homes without kerosene heaters. During their use, we estimated that kerosene heaters added, on average, approximately 40 microg/m3 of PM2.5 and 15 microg/m3 of SO42- to background residential levels of 18 and 2 microg/m3, respectively. Results from using sulfuric acid-doped Teflon (E.I. Du Pont de Nemours & Co., Wilmington, DE) filters in homes with

  16. Ammonia concentrations at a site in Southern Scotland from 2 yr of continuous measurements

    NASA Astrophysics Data System (ADS)

    Burkhardt, J.; Sutton, M. A.; Milford, C.; Storeton-West, R. L.; Fowler, D.

    Atmospheric ammonia (NH 3) concentrations were measured using a continuous-flow annular denuder over a period of 2 yr at a rural site near Edinburgh, Scotland. Meteorological parameters as well as sulphur dioxide (SO 2) concentrations were also recorded. The overall arithmetic mean NH 3 concentration was 1.4 μg m -3. Although an annual cycle with largest NH 3 concentrations in summer was apparent for seasonal geometric mean concentrations, arithmetic mean concentrations were largest in the spring and autumn, indicating the increased importance of occasional high concentration events in these seasons. The NH 3 concentrations were influenced by local sources as well as by background concentrations, dependent on wind direction, whereas SO 2 geometric standard deviations indicated more distant sources. The daily cycle of NH 3 and SO 2 concentrations was dependent on wind speed ( u). At u<1 m s -1, NH 3 concentrations were smallest and SO 2 concentrations were largest around noon, whereas at u>1 m s -1 this cycle was less pronounced for both gases and NH 3 concentrations were largest around 1800 hours. These opposite diurnal cycles may be explained by the interaction of boundary layer mixing with local sources for NH 3 and remote sources for SO 2. Comparing the ammonia data with critical levels and critical loads shows that the critical level is not exceeded at this site over any averaging time. In contrast, the N critical load would probably be exceeded for moorland vegetation near this site, showing that the contribution of atmospheric NH 3 to nitrogen deposition in the long term is a more significant issue than exceedance of critical levels.

  17. Semiconducting perovskites (2-XC6H4C2H4NH3)2SnI4 (X = F, Cl, Br): steric interaction between the organic and inorganic layers.

    PubMed

    Xu, Zhengtao; Mitzi, David B; Dimitrakopoulos, Christos D; Maxcy, Karen R

    2003-03-24

    Two new semiconducting hybrid perovskites based on 2-substituted phenethylammonium cations, (2-XC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) (X = Br, Cl), are characterized and compared with the previously reported X = F compound, with a focus on the steric interaction between the organic and inorganic components. The crystal structure of (2-ClC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) is solved in a disordered subcell [C2/m, a = 33.781(7) A, b = 6.178(1) A, c = 6.190(1) A, beta = 90.42(3)(o), and Z = 2]. The structure is similar to the known (2-FC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) structure with regard to both the conformation of the organic cations and the bonding features of the inorganic sheet. The (2-BrC(6)H(4)C(2)H(4)NH(3))(2)SnI(4) system adopts a fully ordered monoclinic cell [P2(1)/c, a = 18.540(2) A, b = 8.3443(7) A, c = 8.7795(7) A, beta = 93.039(1)(o), and Z = 2]. The organic cation adopts the anti conformation, instead of the gauche conformation observed in the X = F and Cl compounds, apparently because of the need to accommodate the additional volume of the bromo group. The steric effect of the bromo group also impacts the perovskite sheet, causing notable distortions, such as a compressed Sn-I-Sn bond angle (148.7(o), as compared with the average values of 153.3 and 154.8(o) for the fluoro and chloro compounds, respectively). The optical absorption features a substantial blue shift (lowest exciton peak: 557 nm, 2.23 eV) relative to the spectra of the fluoro and chloro compounds (588 and 586 nm, respectively). Also presented are transport properties for thin-film field-effect transistors (TFTs) based on spin-coated films of the two hybrid semiconductors.

  18. Lithium amide (LiNH2) under pressure.

    PubMed

    Prasad, Dasari L V K; Ashcroft, N W; Hoffmann, Roald

    2012-10-11

    Static high pressure lithium amide (LiNH(2)) crystal structures are predicted using evolutionary structure search methodologies and intuitive approaches. In the process, we explore the relationship of the structure and properties of solid LiNH(2) to its molecular monomer and dimer, as well as its valence-isoelectronic crystalline phases of methane, water, and ammonia all under pressure. A NaNH(2) (Fddd) structure type is found to be competitive for the ground state of LiNH(2) above 6 GPa with the P = 1 atm I4[overline] phase. Three novel phases emerge at 11 (P4[overline]2(1)m), 13 (P4(2)/ncm), and 46 GPa (P2(1)2(1)2(1)), still containing molecular amide anions, which begin to form N-H···N hydrogen bonds. The P2(1)2(1)2(1) phase remains stable over a wide pressure range. This phase and another Pmc2(1) structure found at 280 GPa have infinite ···(H)N···H···N(H)···H polymeric zigzag chains comprising symmetric N···H···N hydrogen bonds with one NH bond kept out of the chain, an interesting general feature found in many of our high pressure (>280 GPa) LiNH(2) structures, with analogies in high pressure H(2)O-ices. All the predicted low enthalpy LiNH(2) phases are calculated to be enthalpically stable with respect to their elements but resist metallization with increasing pressure up to several TPa. The possibility of Li sublattice melting in the intermediate pressure range structures is raised.

  19. High Pressure Cosmochemistry of Major Planetary Interiors: Laboratory Studies of the Water-rich Region of the System Ammonia-water

    NASA Technical Reports Server (NTRS)

    Nicol, M.; Johnson, M.; Koumvakalis, A. S.

    1985-01-01

    The behavior of gas-ice mixtures in major planets at very high pressures was studied. Some relevant pressure-temperature-composition (P-T-X) regions of the hydrogen (H2)-helium (He)-water (H2O-ammonia (NH3)-methane (CH4) phase diagram were determined. The studies, and theoretical model, of the relevant phases, are needed to interpret the compositions of ice-gas systems at conditions of planetary interest. The compositions and structures of a multiphase, multicomponent system at very high pressures care characterized, and the goal is to characterize this system over a wide range of low and high temperatures. The NH3-H2O compositions that are relevant to planetary problems yet are easy to prepare were applied. The P-T surface of water was examined and the corresponding surface for NH3 was determined. The T-X diagram of ammonia-water at atmospheric pressure was studied and two water-rich phases were found, NH3-2H2O (ammonia dihydrate), which melts incongruently, and NH3.H2O (ammonia monohydrate), which is nonstoichiometric and melts at a higher temperature than the dihydrate. It is suggested that a P-T surface at approximately the monohydrate composition and the P-X surface at room temperature is determined.

  20. An ammonia-stabilized mixed-cation borohydride: synthesis, structure and thermal decomposition behavior.

    PubMed

    Yang, Yanjing; Liu, Yongfeng; Wu, Hui; Zhou, Wei; Gao, Mingxia; Pan, Hongge

    2014-01-07

    We demonstrate the synthesis, crystal structure and thermal decomposition behavior of a novel ammonia-stabilized mixed-cation borohydride where the NH3 groups enable the coexistence of Li and Mg cations as an "assistant". Li2Mg(BH4)4·6NH3, which is comprised of orderly arranged Mg[NH3]6(2+) ammine complexes and Li2[BH4]4(2-) complex anions, was synthesized by the mechanochemical reaction between Mg(BH4)2·6NH3 and LiBH4. This novel compound crystallizes in a tetragonal P4(3)2(1)2 (No. 96) structure with lattice parameters a = b = 10.7656(8) Å and c = 13.843(1) Å with very short dihydrogen bonds, which determine a very low onset temperature of 80 °C for hydrogen release and are also responsible for the nucleation of Li2Mg(BH4)4·3NH3 as a decomposition intermediate. Mechanistic investigations on the thermal decomposition showed that the H(δ+)-H(δ-) combination in the ammonia-stabilized mixed-cation borohydride was significantly enhanced due to the strengthened Mg-N bonds. Upon heating, 11.02 moles of H2 (equivalent to 11.1 wt%) and 3.07 moles of NH3 are evolved from one mole of Li2Mg(BH4)4·6NH3 with a three-step reaction. The insights into the formation mechanism of ammonia-stabilized mixed-cation borohydride and the role played by NH3 group are very useful as a guideline for the design and synthesis of novel B-N-based materials with high hydrogen content.

  1. Hidden cost of U.S. agricultural exports: particulate matter from ammonia emissions.

    PubMed

    Paulot, Fabien; Jacob, Daniel J

    2014-01-21

    We use a model of agricultural sources of ammonia (NH3) coupled to a chemical transport model to estimate the impact of U.S. food export on particulate matter concentrations (PM2.5). We find that food export accounts for 11% of total U.S. NH3 emissions (13% of agricultural emissions) and that it increases the population-weighted exposure of the U.S. population to PM2.5 by 0.36 μg m(-3) on average. Our estimate is sensitive to the proper representation of the impact of NH3 on ammonium nitrate, which reflects the interplay between agricultural (NH3) and combustion emissions (NO, SO2). Eliminating NH3 emissions from food export would achieve greater health benefits than the reduction of the National Ambient Air Quality Standards for PM2.5 from 15 to 12 μg m(-3). Valuation of the increased premature mortality associated with PM2.5 from food export (36 billion US$ (2006) per year) amounts to 50% of the gross food export value. Livestock operations in densely populated areas have particularly large health costs. Decreasing SO2 and NOx emissions will indirectly reduce health impact of food export as an ancillary benefit.

  2. Thermally-induced first-order phase transition in the (FC6H4C2H4NH3)2[PbI4] photoluminescent organic-inorganic material

    NASA Astrophysics Data System (ADS)

    Koubaa, M.; Dammak, T.; Garrot, D.; Castro, M.; Codjovi, E.; Mlayah, A.; Abid, Y.; Boukheddaden, K.

    2012-03-01

    The thermal properties of the perovskite slab alkylammonium lead iodide (FC6H4C2H4NH3)2[PbI4] are investigated using spectroscopic ellipsometry, differential scanning calorimetry, photoluminescence, and Raman spectroscopy. The spectroscopic ellipsometry, performed in the heating mode, clearly evidenced the presence of a singularity at 375 K. This is corroborated by the temperature dependence of the photoluminescence, which pointed out a first-order order-disorder phase transition at ˜375 K, with a hysteresis loop of 40 K width. Raman spectroscopy data suggest that this transition arises from a dynamic rotational disordering of the ammonium headgroups of the alkylammonium chain. In contrast, differential scanning calorimetry measurements on a pellet sample led to an entropy change value ΔS ≈0.39 J/K/mol at the transition, suggesting the existence of a residual short-range order of the NH3+ on cooling from the high temperature phase.

  3. Characterization of an Fe≡N–NH 2 intermediate relevant to catalytic N 2 reduction to NH 3

    DOE PAGES

    Anderson, John S.; Cutsail, III, George E.; Rittle, Jonathan; ...

    2015-05-22

    The ability of certain transition metals to mediate the reduction of N 2 to NH 3 has attracted broad interest in the biological and inorganic chemistry communities. Early transition metals such as Mo and W readily bind N 2 and mediate its protonation at one or more N atoms to furnish M(N xH y) species that can be characterized and, in turn, extrude NH 3. By contrast, the direct protonation of Fe–N 2 species to Fe(N xH y) products that can be characterized has been elusive. In this paper, we show that addition of acid at low temperature to [(TPB)Fe(Nmore » 2)][Na(12-crown-4)] results in a new S = 1/2 Fe species. EPR, ENDOR, Mössbauer, and EXAFS analysis, coupled with a DFT study, unequivocally assign this new species as [(TPB)Fe≡N–NH 2] +, a doubly protonated hydrazido(2–) complex featuring an Fe-to-N triple bond. This unstable species offers strong evidence that the first steps in Fe-mediated nitrogen reduction by [(TPB)Fe(N 2)][Na(12-crown-4)] can proceed along a distal or “Chatt-type” pathway. Finally, a brief discussion of whether subsequent catalytic steps may involve early or late stage cleavage of the N–N bond, as would be found in limiting distal or alternating mechanisms, respectively, is also provided.« less

  4. Physiological and molecular responses of the spiny dogfish shark (Squalus acanthias) to high environmental ammonia: scavenging for nitrogen.

    PubMed

    Nawata, C Michele; Walsh, Patrick J; Wood, Chris M

    2015-01-15

    In teleosts, a branchial metabolon links ammonia excretion to Na(+) uptake via Rh glycoproteins and other transporters. Ureotelic elasmobranchs are thought to have low branchial ammonia permeability, and little is known about Rh function in this ancient group. We cloned Rh cDNAs (Rhag, Rhbg and Rhp2) and evaluated gill ammonia handling in Squalus acanthias. Control ammonia excretion was <5% of urea-N excretion. Sharks exposed to high environmental ammonia (HEA; 1 mmol(-1) NH4HCO3) for 48 h exhibited active ammonia uptake against partial pressure and electrochemical gradients for 36 h before net excretion was re-established. Plasma total ammonia rose to seawater levels by 2 h, but dropped significantly below them by 24-48 h. Control ΔP(NH3) (the partial pressure gradient of NH3) across the gills became even more negative (outwardly directed) during HEA. Transepithelial potential increased by 30 mV, negating a parallel rise in the Nernst potential, such that the outwardly directed NH4(+) electrochemical gradient remained unchanged. Urea-N excretion was enhanced by 90% from 12 to 48 h, more than compensating for ammonia-N uptake. Expression of Rhp2 (gills, kidney) and Rhbg (kidney) did not change, but branchial Rhbg and erythrocytic Rhag declined during HEA. mRNA expression of branchial Na(+)/K(+)-ATPase (NKA) increased at 24 h and that of H(+)-ATPase decreased at 48 h, while expression of the potential metabolon components Na(+)/H(+) exchanger2 (NHE2) and carbonic anhydrase IV (CA-IV) remained unchanged. We propose that the gill of this nitrogen-limited predator is poised not only to minimize nitrogen loss by low efflux permeability to urea and ammonia but also to scavenge ammonia-N from the environment during HEA to enhance urea-N synthesis. © 2015. Published by The Company of Biologists Ltd.

  5. Analogues of Cis- and Transplatin with a Rich Solution Chemistry: cis-[PtCl2 (NH3 )(1-MeC-N3)] and trans-[PtI2 (NH3 )(1-MeC-N3)].

    PubMed

    Siebel, Sabine; Dammann, Claudia; Sanz Miguel, Pablo J; Drewello, Thomas; Kampf, Gunnar; Teubner, Natascha; Bednarski, Patrick J; Freisinger, Eva; Lippert, Bernhard

    2015-12-01

    Mono(nucleobase) complexes of the general composition cis-[PtCl2 (NH3 )L] with L=1-methylcytosine, 1-MeC (1 a) and L=1-ethyl-5-methylcytosine, as well as trans-[PtX2 (NH3 )(1-MeC)] with X=I (5 a) and X=Br (5 b) have been isolated and were characterized by X-ray crystallography. The Pt coordination occurs through the N3 atom of the cytosine in all cases. The diaqua complexes of compounds 1 a and 5 a, cis-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) and trans-[Pt(H2 O)2 (NH3 )(1-MeC)](2+) , display a rich chemistry in aqueous solution, which is dominated by extensive condensation reactions leading to μ-OH- and μ-(1-MeC(-) -N3,N4)-bridged species and ready oxidation of Pt to mixed-valence state complexes as well as diplatinum(III) compounds, one of which was characterized by X-ray crystallography: h,t-[{Pt(NH3 )2 (OH)(1-MeC(-) -N3,N4)}2 ](NO3 )22 [NH4 ](NO3 )⋅2H2 O. A combination of (1) H NMR spectroscopy and ESI mass spectrometry was applied to identify some of the various species present in solution and the gas phase, respectively. As it turned out, mass spectrometry did not permit an unambiguous assignment of the structures of +1 cations due to the possibilities of realizing multiple bridging patterns in isomeric species, the occurrence of different tautomers, and uncertainties regarding the Pt oxidation states. Additionally, compound 1 a was found to have selective and moderate antiproliferative activity for a human cervix cancer line (SISO) compared to six other human cancer cell lines. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Constraining U.S. ammonia emissions using TES remote sensing observations and the GEOS-Chem adjoint model

    EPA Science Inventory

    Ammonia (NH(3)has significant impacts on biodiversity, eutrophication, and acidification. Widespread uncertainty in the magnitude and seasonality of NH3 emissions hinders efforts to address these issues. In this work, we constrain U.S. NH3 sources using obse...

  7. Ortho-to-para abundance ratios of NH2 in 26 comets: implications for the real meaning of OPRs

    NASA Astrophysics Data System (ADS)

    Shinnaka, Yoshiharu; Kawakita, Hideyo; Jehin, Emmanuël; Decock, Alice; Hutsemékers, Damien; Manfroid, Jean

    2016-11-01

    Abundance ratios of nuclear-spin isomers for cometary molecules having identical protons, such as water and ammonia, have been measured and discussed from the viewpoint that they are primordial characters in comet. In the case of ammonia, its ortho-to-para abundance ratio (OPR) is usually estimated from OPRs of NH2 because of difficulty in measuring OPR of ammonia directly. We report our survey for OPRs of NH2 in 26 comets. A weighted mean of ammonia OPRs for the comets is 1.12 ± 0.01 and no significant difference is found between the Oort Cloud comets and the Jupiter-family comets. These values correspond to ˜30 K as nuclear-spin temperatures. The OPRs of ammonia in comets probably reflect the physicochemical conditions in coma, rather than the conditions for the molecular formation or condensation in the pre-solar molecular cloud/the solar nebula, based on comparison of OPRs (and nuclear-spin temperatures) of ammonia with those of water, 14N/15N ratios in ammonia, and D/H ratios in water. The OPRs could be reset to a nuclear-spin weights ratio in solid phase and modified by interactions with protonated ions like H3O+, water clusters (H2O)n, ice grains, and paramagnetic impurities (such as O2 molecules and grains) in the inner coma gas. Relationship between the OPRs of ammonia and water is a clue to understanding the real meaning of the OPRs.

  8. Formation of uranium and cerium nitrides by the reaction of carbides with NH 3 and N 2/H 2 stream

    NASA Astrophysics Data System (ADS)

    Nakagawa, Takashi; Matsuoka, Hirotaka; Sawa, Masaji; Hirota, Masayuki; Miyake, Masanobu; Katsura, Masahiro

    1997-08-01

    UC or CeC 2 were converted into U 2N 3 or CeN by the use of NH 3 or an N 2/H 2 gas mixture. A stream of NH 3 works not only as a nitriding agent but also as a carbon clearing agent due to its high nitriding and hydriding activities. When the carbide is converted into nitride, carbon is liberated. Some experiments were performed in order to examine the role of the carbon activity of carbon materials (amorphous carbon or graphite) in the formation of CH 4.

  9. Elevated Blood Ammonia Level Is a Potential Biological Risk Factor of Behavioral Disorders in Prisoners

    PubMed Central

    Duan, Yunfeng; Wu, Xiaoli; Liang, Shan; Jin, Feng

    2015-01-01

    Hydrothion (H2S) and ammonia (NH3) can be toxic for the human central nervous system and cause psychological disturbances and behavioral disorders. In order to evaluate the association between the two potential toxicants and mental health, in this study, we compare a male prisoner and control population. Forty-nine male prisoners and 52 control volunteers took part in the study. An aggressive behavior assessment, the Self-Rating Depression Scale (SDS), and the State-Trait Anxiety Inventory (STAI) were used to characterize the participants' mental health status. Venous blood was collected for detection of H2S and NH3. The results indicated that blood NH3 was significantly higher in male prisoners than in controls. However, blood H2S was significantly lower. Blood NH3 was also significantly and positively correlated with prisoners. In the multivariate adjusted models, after controlling for age, education, marital status, and BMI, we found a positive association between NH3 and prisoners, but not blood H2S. While the functions of the two toxicants were quite different, blood NH3 may be a potential biological risk factor for behavioral disorders and blood H2S showed neuroprotection. Additionally, the impact of other factors such as diet and gut bacteria should be considered when evaluating risk for behavioral disorders. PMID:26457003

  10. Synthesis and molecular structure of [Cu(NH3)4][Ni(CN)4]: A missing piece in the [Cu(NH3)n][Ni(CN)4] story

    NASA Astrophysics Data System (ADS)

    Solanki, Dina; Hogarth, Graeme

    2015-11-01

    Reaction of CuCl2·2H2O and K2[Ni(CN)4]·2H2O in aqueous ammonia gave blue rod-like crystals of [Cu(NH3)4][Ni(CN)4]. An X-ray crystallographic reveals that square-planar anions and cations are weakly associated through coordination of a cis pair of cyanide ligands to copper, with one short and one long contact and thus the copper centre is best described as a square-based pyramid. Crystals lose ammonia readily upon removal from the solvent and this has been probed by TGA and DSC measurements. For comparison we have also re-determined the structure of the related ethylenediamine (en) complex [Cu(en)2][Ni(CN)4] at 150 K. This consists of a 1D chain in which a trans pair of cyanide ligands bind to copper such that the latter has an overall tetragonally distorted octahedral coordination geometry.

  11. In-situ DRIFTS investigation on the selective catalytic reduction of NO with NH3 over the sintered ore catalyst

    NASA Astrophysics Data System (ADS)

    Chen, Wangsheng; Li, Ze; Hu, Fali; Qin, Linbo; Han, Jun; Wu, Gaoming

    2018-05-01

    In this study, the sintered ore used as catalysts for the selective catalytic reduction (SCR) of NOX with NH3 from the sintering flue gas was investigated. The experimental results demonstrated that the maximum denitration efficiency, about 61.64%, occurred at 300 °C, 1.0 NH3/NO ratio, and 1000 h-1 gas hourly space velocity (GHSV). In order to understand the SCR denitration mechanism, the catalyst was characterized by DRIFTS, XPS, H2-TPR, BET and ICP-MS. It was found that there were Lewis and Brønsted acid sites at the surface of the sintered ore, which lead to the appearance of amide species (sbnd NH2), NH4+ intermediates, gaseous or weakly adsorbed NO2 and nitrite species. Hence, it was concluded that the reaction of the amide species (sbnd NH2) with gaseous NO (E-R mechanism) and the reaction of absorbed NO2 with the coordinated ammonia (L-H mechanism) were attributed to NOx reduction.

  12. Photocrystallographic structure determination of a new geometric isomer of [Ru(NH3)4(H2O)(eta1-OSO)][MeC6H4SO3]2.

    PubMed

    Bowes, Katharine F; Cole, Jacqueline M; Husheer, Shamus L G; Raithby, Paul R; Savarese, Teresa L; Sparkes, Hazel A; Teat, Simon J; Warren, John E

    2006-06-21

    The structure of a new metastable geometric isomer of [Ru(NH3)4(H2O)(SO2)][MeC6H4SO3]2 in which the SO2 group is coordinated through a single oxygen in an eta1-OSO bonding mode has been determined at 13 K; the new isomer was obtained as a 36% component of the structure within a single crystal upon irradiation using a tungsten lamp.

  13. Solvent-Dependent Delamination, Restacking, and Ferroelectric Behavior in a New Charge-Separated Layered Compound: [NH4 ][Ag3 (C9 H5 NO4 S)2 (C13 H14 N2 )2 ]⋅8 H2 O.

    PubMed

    Sushrutha, Sringeri Ramesh; Mohana, Shivanna; Pal, Somnath; Natarajan, Srinivasan

    2017-01-03

    A new anionic coordination polymer, [NH 4 ][Ag 3 (C 9 H 5 NO 4 S) 2 (C 13 H 14 N 2 ) 2 ]⋅8 H 2 O, with a two-dimensional structure, has been synthesized by a reaction between silver nitrate, 8-hydroxyquinoline-5-sulfonic acid (HQS), and 4,4'-trimethylene dipyridine (TMDP). The compound stabilizes in a noncentrosymmetric space group, and the lattice water molecules and the charge-compensating [NH 4 ] + group occupy the inter-lamellar spaces. The lattice water molecules can be fully removed and reinserted, which is accompanied by a crystalline-amorphous-crystalline transformation. This transformation resembles the collapse/delamination and restacking of the layers. To the best of our knowledge, this is the first observation of delamination and restacking in an inorganic coordination polymer that contains silver. The presence of a natural dipole (the anionic framework and cationic ammonium ions) along with the noncentrosymmetric space group gives rise to the room-temperature ferroelectric behavior of the compound. The ferroelectric behavior is also water-dependent and exhibits a ferroelectric-paraelectric transformation. The temperature-dependent dielectric measurements indicate that the ferroelectric/ paraelectric transformation occurs at 320 K. This transformation has also been investigated by using in-situ IR spectroscopy and PXRD studies. The second-harmonic generation (SHG) study indicated values that are comparable to some of the known SHG solids, such as potassium dihydrogen phosphate (KDP) and urea. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Inhibition of ammonia poisoning by addition of platinum to Ru/α-Al2 O3 for preferential CO oxidation in fuel cells.

    PubMed

    Sato, Katsutoshi; Yagi, Sho; Zaitsu, Shuhei; Kitayama, Godai; Kayada, Yuto; Teramura, Kentaro; Takita, Yusaku; Nagaoka, Katsutoshi

    2014-12-01

    In polymer electrolyte fuel cell (PEFC) systems, small amounts of ammonia (NH3 ) present in the reformate gas deactivate the supported ruthenium catalysts used for preferential oxidation (PROX) of carbon monoxide (CO). In this study, we investigated how the addition of a small amount of platinum to a Ru/α-Al2 O3 catalyst (Pt/Ru=1:9 w/w) affected the catalyst's PROX activity in both the absence and the presence of NH3 (130 ppm) under conditions mimicking the reformate conditions during steam reforming of natural gas. The activity of undoped Ru/α-Al2 O3 decreased sharply upon addition of NH3 , whereas Pt/Ru/α-Al2 O3 exhibited excellent PROX activity even in the presence of NH3 . Ruthenium K-edge X-ray absorption near-edge structure (XANES) spectra indicated that in the presence of NH3 , some of the ruthenium in the undoped catalyst was oxidized in the presence of NH3 , whereas ruthenium oxidation was not observed with Pt/Ru/α-Al2 O3 . These results suggest that ruthenium oxidation is retarded by the platinum, so that the catalyst shows high activity even in the presence of NH3 . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The catalytic role of water in the photochemistry of ammonia ice: from diluted to concentrated phase

    NASA Astrophysics Data System (ADS)

    Jonusas, Mindaugas; Krim, Lahouari

    2017-10-01

    Using infrared spectroscopy as an in situ probe for reactions occurring in the solid phase, we investigated the influence of water molecules on the photochemistry of ammonia ices. Experiments were carried out in diluted and concentrated phases and between 3 and 130 K. We showed that the photolysis of NH3-H2O (2 per cent of H2O) ices using continuous radiation from 115 to 400 nm produces NH2OH as the main photoproduct, but also that such a photoinduced reaction strongly depends on both the initial ice temperature and the environment where the primary reactants NH3 and H2O are trapped. Our experimental results highlight the catalytic role played by H2O molecules in enhancing the formation yield of NH2 during the photolysis process through the NH3 + OH → NH2 + H2O hydrogen abstraction reaction, which is only favored at low temperatures in the range of 3-60 K. During heating of such irradiated ammonia-water ices, the amount of NH2OH keeps rising while that of NH2, is greatly reduced only from 70 K onwards. These behaviours are attributed to the competition that occurs between NH2 formation from the NH3 + OH reaction and its consumption from the NH2 + OH radical recombination. These results might explain the variable abundances of NH2 and NH3 provided by previous astronomical observations, where the NH2/NH3 ratio ranges from 0.02 to 0.5 depending on the regions of the interstellar medium that were analysed.

  16. A neodymium(III)-ammonium complex involving oxalate and carbonate ligands: (NH4)2[Nd2(C2O4)3(CO3)(H2O)].H2O.

    PubMed

    Trombe, Jean-Christian; Galy, Jean; Enjalbert, Renée

    2002-10-01

    The title compound, diammonium aqua-mu-carbonato-tri-mu-oxalato-dineodymium(III) hydrate, (NH(4))(2)[Nd(2)(CO(3))(C(2)O(4))(3)(H(2)O)].H(2)O, involving the two ligands oxalate and carbonate, has been prepared hydrothermally as single crystals. The Nd atoms form a tetranuclear unit across the inversion centre at (1/2, 1/2, 1/2). Starting from this tetranuclear unit, the oxalate ligands serve to develop a three-dimensional network. The carbonate group acts as a bis-chelating ligand to two Nd atoms, and is monodentate to a third Nd atom. The oxalate groups are all bis-chelating. The two independent Nd atoms are ninefold coordinated and the coordination polyhedron of these atoms is a distorted monocapped antiprism.

  17. Theoretical study on the spectroscopic properties of CO3(*-).nH2O clusters: extrapolation to bulk.

    PubMed

    Pathak, Arup K; Mukherjee, Tulsi; Maity, Dilip K

    2008-10-24

    Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO(3)(*-).nH(2)O (n=1-8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second-order Moller-Plesset perturbation (MP2) and coupled cluster theory using the 6-311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO(3)(*-).nH(2)O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time-dependent density functional theory using the Becke three-parameter nonlocal exchange and the Lee-Yang-Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO(3)(*-).8H(2)O cluster is in excellent agreement with the reported experimental spectrum for CO(3)(*-) (aq), obtained based on pulse radiolysis experiments.

  18. Ammonia volatilization from farm tanks containing anaerobically digested animal slurry

    NASA Astrophysics Data System (ADS)

    Sommer, S. G.

    Ammonia (NH 3) volatilization from three full-scale tanks containing anaerobically digested animal slurry from one biogas plant was determined with a meteorological mass balance technique. No surface crust developed on the slurry. This provided an ideal system for analysing loss patterns from slurries without cover and to study the effect of a cover of straw and air-filled clay granules. Ammonia volatilization from uncovered slurry ranged from zero at subzero temperatures to 30 g N m -2 d -1 during summer. The high volatilization rate was attributed to a lack of surface cover, high slurry pH and high TAN (NH 3 + NH 4+) concentration. Ammonia volatilization from the covered slurry was insignificant. From the uncovered slurry the annual loss of NH3 was 3.3 kg N m -2 There was a significant effect of incident global radiation (ICR), air temperature at 20 cm (T_20) and rain on NH3 volatilization from the uncovered slurry. The straw covered slurry was significantly affected by T_20.

  19. Variation of Ambient Ammonia Pollution in Relation With PM2.5 Characteristics in Winter of Delhi, India

    NASA Astrophysics Data System (ADS)

    S., Sr.; Saxena, M., , Dr; Mandal, T. K., , Dr; Kotnala, R. K.; Sharma, S. K., , Dr

    2017-12-01

    Ambient ammonia, SO2 and NOx are primary precursor gases for the formation of particulate matter (PM2.5) which result in photochemical smog and haze formation specifically in winter season. The ambient ammonia, other trace gases and fine particles were monitored in winter season from Jan 2013 to Dec 2015 at CSIR-NPL, Delhi. The average mixing ratios of ambient NH3, NO, NO2 and SO2 over the entire period of winter season were recorded as 25.3±4.6 (ppb), 21.4±7.2 (ppb), 20.8±5.9 (ppb) and 1.9±0.5 (ppm), respectively. The NH4+ and other ionic species in PM2.5 were also simultaneously observed at the the study site to see the transformation of NH3 and NH4+. The results indicated that the concentration level of NH3 and NH4+/NH3 ratios grew simultaneously with the increase of PM2.5 levels. NH3 enhanced the formation of ammonium sulphate and ammonium nitrate and exert a significant impact on ion chemistry of PM2.5. In the wintertime atmosphere of urban Delhi, NH3 was sufficient in fully neutralizing the fine particulates. The important role of ammonia is recognized in increasing PM2.5 mass concentration as it help in formation of ammonium aerosol due to reaction with acid gases. Keywords: Air quality, Ammonia, Trace Gases, Particulates

  20. Photoacoustic measurement of ammonia in the atmosphere: influence of water vapor and carbon dioxide

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

    Rooth, R.A.; Verhage, A.J.L.; Wouters, L.W.

    1990-09-01

    The photoacoustic determination of the ammonia concentration in atmospheric air by absorption of CO{sub 2} laser radiation at 9.22 {mu}m is influenced by the presence of H{sub 2}O and CO{sub 2}. Kinetic cooling due to the coupling of excited CO{sub 2} and N{sub 2} levels causes important changes in phase and amplitude of the photoacoustic signal. Theoretical background is presented to deduce the correct NH{sub 3} concentration from the signal. The experimental setup used to perform field measurements is described. Adhesion of NH{sub 3} to the walls of the resonant photoacoustic cell was investigated. Temperature effects are treated. Field datamore » of NH{sub 3} and H{sub 2}O concentrations are presented. Key words: Photoacoustics, ammonia, kinetic cooling, trace gas measurements, ammonia adhesion, acoustic resonance, CO{sub 2} laser radiation, water vapor absorption, carbon dioxide absorption.« less

  1. Metal-Borohydride-Modified Zr(BH4 )4 ⋅8 NH3 : Low-Temperature Dehydrogenation Yielding Highly Pure Hydrogen.

    PubMed

    Huang, Jianmei; Ouyang, Liuzhang; Gu, Qinfen; Yu, Xuebin; Zhu, Min

    2015-10-12

    Due to its high hydrogen density (14.8 wt %) and low dehydrogenation peak temperature (130 °C), Zr(BH4 )4 ⋅8 NH3 is considered to be one of the most promising hydrogen-storage materials. To further decrease its dehydrogenation temperature and suppress its ammonia release, a strategy of introducing LiBH4 and Mg(BH4 )2 was applied to this system. Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 composites showed main dehydrogenation peaks centered at 81 and 106 °C as well as high hydrogen purities of 99.3 and 99.8 mol % H2 , respectively. Isothermal measurements showed that 6.6 wt % (within 60 min) and 5.5 wt % (within 360 min) of hydrogen were released at 100 °C from Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 and Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , respectively. The lower dehydrogenation temperatures and improved hydrogen purities could be attributed to the formation of the diammoniate of diborane for Zr(BH4 )4 ⋅8 NH3 -4 LiBH4 , and the partial transfer of NH3 groups from Zr(BH4 )4 ⋅8 NH3 to Mg(BH4 )2 for Zr(BH4 )4 ⋅8 NH3 -2 Mg(BH4 )2 , which result in balanced numbers of BH4 and NH3 groups and a more active H(δ+) ⋅⋅⋅(-δ) H interaction. These advanced dehydrogenation properties make these two composites promising candidates as hydrogen-storage materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enhanced ammonia removal at room temperature by pH controlled partial nitrification and subsequent anaerobic ammonium oxidation.

    PubMed

    Durán, U; del Val Río, A; Campos, J L; Mosquera-Corral, A; Méndez, R

    2014-01-01

    The Anammox-based processes are suitable for the treatment of wastewaters characterized by a low carbon to nitrogen (C/N) ratio. The application of the Anammox process requires the availability of an effluent with a NO2- -N/NH4+ -N ratio composition around 1 g g-1, which involves the necessity of a previous step where the partial nitrification is performed. In this step, the inhibition of the nitrite-oxidizing bacteria (NOB) is crucial. In the present work, a combined partial nitrification-ANaerobic AMmonia OXidation (Anammox) two-units system operated at room temperature (20 degreeC) has been tested for the nitrogen removal of pre-treated pig slurry. To achieve the successful partial nitrification and inhibit the NOB activity, different ammonium/inorganic carbon (NH4+/IC) ratios were assayed from 1.19 to 0.82g NH4+-Ng-1 HCO3-C. This procedure provoked a decrease of the pH value to 6.0 to regulate the inhibitory effect over ammonia-oxidizing bacteria caused by free ammonia. Simultaneously, the NOB experienced the inhibitory effect of free nitrous acid which avoided the presence of nitrate in the effluent. The NH4+/IC ratio which allowed the obtaining of the desired effluent composition (50% of both ammonium and nitrite) was 0.82 +/- 0.02 g NH4+-N g-1 HCO3- -C. The Anammox reactor was fed with the effluent of the partial nitrification unit containing a NO2 -N/NH4+ -N ratio of 1 g g-1' where a nitrogen loading rate of 0.1 g N L-1 d-1 was efficiently removed.

  3. Synthetic, Infrared, 1Hand 13CNMR Spectral Studies on N-(p-Substituted Phenyl)-p-Substituted Benzenesulphonamides, p-X'C6H4SO2NH- (p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br

    NASA Astrophysics Data System (ADS)

    Gowda, B. Thimme; Jayalakshmi, K. L.; Shetty, Mahesha

    2004-05-01

    Thirty N-(p-substituted phenyl)-p-substituted benzenesulphonamides of the general formula, p-X'C6H4SO2NH(p-XC6H4), where X' or X = H, CH3, C2H5, F, Cl or Br, are synthesised and their infrared spectra in the solid state and 1H and 13C NMR spectra in solution are measured. The N-H stretching vibrational frequencies, νN-H vary in the range 3334 - 3219 cm-1, while the asymmetric and symmetric SO2 vibrations appear in the ranges 1377 - 1311 cm-1 and 1182 - 1151 cm-1, respectively. The compounds exhibit S-N and C-N stretching vibrational absorptions in the ranges 937 - 898 cm-1 and 1310 - 1180 cm-1, respectively. There are no particular trends in the variation of these frequencies on substitution with either electron withdrawing or electron donating groups. The 1H and 13C chemical shifts of N-(p-substituted phenyl)-p-substituted benzenesulphonamides, are assigned to various protons and carbons of the two benzene rings. Further, incremental shifts of the ring protons and carbons due to -SO2NH(p-XC6H4) groups in the compounds of the formula, C6H5SO2NH(p-XC6H4), and p-X'C6H4SO2- and p-X'C6H4SO2NH- groups in the compounds of the formula, p-X'C6H4SO2NH(C6H5) are computed and used to calculate the 1H and 13C chemical shifts of the parallely substituted compounds of the general formula p-X'C6H4SO2NH(p-XC6H4). The computed values agree well with the observed chemical shifts. The above incremental shifts are found to correlate with the Hammett substituent parameters.

  4. Environmental assessment of NH3 injection for an industrial package boiler. Volume 2. Data supplement. Final report, January 1983-January 1984

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

    Castaldini, C.; DeRosier, R.; Waterland, L.R.

    1986-02-01

    The report discusses emission results from comprehensive flue-gas sampling of a gas- and oil-fired industrial boiler equipped with Exxon's Thermal DeNOx Ammonia Injection Process for NOx reduction. Comprehensive emission measurements included continuous monitoring of flue gas emissions; source assessment sampling system (SASS) tests; EPA Method 5/17 for solid and condensible particulate emissions and ammonia emissions; controlled condensation system for SO2 and SO3; and N2O emission sampling. Ammonia injection at a NH3/NO molar ratio of 2.52 gave a NOx reduction of 41% from an uncontrolled level of 234 ppm to a controlled level of 137 ppm. NH3 emissions increased from 11more » ppm for the baseline to an average of 430 ppm for ammonia injection. Nitrous oxide, N2O, was reduced 68% from a 50 ppm baseline level to a 17 ppm controlled level. Total particulate emissions increased by an order of magnitude from a baseline of 17.7 ng/J to a controlled level of 182 ng/J.« less

  5. Nitrogen metabolism, acid-base regulation, and molecular responses to ammonia and acid infusions in the spiny dogfish shark (Squalus acanthias).

    PubMed

    Nawata, C Michele; Walsh, Patrick J; Wood, Chris M

    2015-07-01

    Although they are ureotelic, marine elasmobranchs express Rh glycoproteins, putative ammonia channels. To address questions raised by a recent study on high environmental ammonia (HEA) exposure, dogfish were intravascularly infused for 24 h at 3 ml kg(-1) h(-1) with isosmotic NaCl (500 mmol l(-1), control), NH4HCO3 (500 mmol l(-1)), NH4Cl (500 mmol l(-1)), or HCl (as 125 mmol l(-1) HCl + 375 mmol l(-1) NaCl). While NaCl had no effect on arterial acid-base status, NH4HCO3 caused mild alkalosis, NH4Cl caused strong acidosis, and HCl caused lesser acidosis, all predominantly metabolic in nature. Total plasma ammonia (T(Amm)) and excretion rates of ammonia (J(Amm)) and urea-N (J(Urea-N)) were unaffected by NaCl or HCl. However, despite equal loading rates, plasma T(Amm) increased to a greater extent with NH4Cl, while J(Amm) increased to a greater extent with NH4HCO3 due to much greater increases in blood-to-water PNH3 gradients. As with HEA, both treatments caused large (90%) elevations of J(Urea-N), indicating that urea-N synthesis by the ornithine-urea cycle (OUC) is driven primarily by ammonia rather than HCO3(-). Branchial mRNA expressions of Rhbg and Rhp2 were unaffected by NH4HCO3 or NH4Cl, but v-type H(+)-ATPase was down-regulated by both treatments, and Rhbg and Na(+)/H(+) exchanger NHE2 were up-regulated by HCl. In the kidney, Rhbg was unresponsive to all treatments, but Rhp2 was up-regulated by HCl, and the urea transporter UT was up-regulated by HCl and NH4Cl. These responses are discussed in the context of current ideas about branchial, renal, and OUC function in this nitrogen-limited predator.

  6. Synthesis, characterization, and application of Zn(NH 3)(CO3) for selective adsorptive separation of CO2

    NASA Astrophysics Data System (ADS)

    Khazeni, Naasser

    This study explores the potential of Zn(NH3)(CO3) for selective CO2 separation. It develops a novel, highly controllable, single-pot synthesis approach based on urea hydrolysis and solvothermal aging to increase the feasibility of synthesizing Zn(NH3)(CO3), determines the structure of Zn(NH3)(CO3) in detail through single crystal X-ray diffraction and powder X-ray diffraction analyses, and performs adsorption analyses for the compound using CO2, N 2, H2, O2, and CH4 as adsorptives. Through adsorptive characterization, a systematic adsorbent selection screening is performed to assess the potential application of Zn(NH3)(CO 3) for adsorptive separation of CO2 from an upstream gas mixture of power generation, hydrogen production, and natural gas industries. Structural analysis shows Zn(NH3)(CO3) to have an inorganic helical framework that consists of a small helix of (ZnOCO) 2 and a large helix of (ZnOCO)4 with two ammines (NH 3) pendant from every other zinc. In terms of adsorption capacity and CO2 selectivity, Zn(NH3)(CO3) adsorbed 0.550 mmole/g CO2 at 293 K and 4500 mmHg, but only 0.047 mmole/g N 2, 0.084 mmole/g H2, 0.207 mmole/g 02, and 0.060 mmole/g CH4 at the same temperature and pressure. This behavior demonstrates considerable equilibrium selectivities - 36, 31, 63, and 11 - for separating CO2 from CH4, CO2 from H 2, CO2 from N2, and CO2 from 02, respectively. During adsorption, the pendant ammines act as the gates of check-valves: applied pressure opens the gates for adsorption; and during desorption, the gates are closed, trapping the adsorbates, until a reduction of pressure to near-atmospheric levels. Therefore, Zn(NH3)(CO3) exhibits low-pressure H3 or H4 hysteresis, indicating that the Zn(NH3)(CO3) framework can achieve gas storage at near-atmospheric pressures. Additionally, the compound proves structurally stable, with an adsorption decrease of 0.8% after 20 adsorption/desorption cycles - a factor that, considered with the other characteristics of Zn(NH

  7. Specific heat of (C 6H 11NH 3) CuCl 3 (CHAC), a system of ferromagnetic chains

    NASA Astrophysics Data System (ADS)

    Schouten, J. C.; van der Geest, G. J.; de Jonge, W. J. M.; Kopinga, K.

    1980-08-01

    The heat capacity of (C 6H 11NH 3) CuCl 3 (CHAC) has been measured for 0.45 < T < 60 K. Three-dimensional ordering is observed at T = 2.214 K. The data in the paramagnetic region can be described by a ferromagnetic S = {1}/{2} Heisenberg linear chain model system with J/ k = +45 ± 5K.

  8. Support effects in single atom iron catalysts on adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S)

    NASA Astrophysics Data System (ADS)

    Gao, Zhengyang; Yang, Weijie; Ding, Xunlei; Lv, Gang; Yan, Weiping

    2018-04-01

    The effects of support on gas adsorption is crucial for single atom catalysts design and optimization. To gain insight into support effects on gas adsorption characteristics, a comprehensive theoretical study was performed to investigate the adsorption characteristics of toxic gases (NO2, NH3, SO3 and H2S) by utilizing single atom iron catalysts with three graphene-based supports. The adsorption geometry, adsorption energy, electronic and magnetic properties of the adsorption system have been explored. Additionally, the support effects have been analyzed through d-band center and Fermi softness, and thermodynamic analysis has been performed to consider the effect of temperature on gas adsorption. The support effects have a remarkable influence on the adsorption characteristics of four types of toxic gases which is determined by the electronic structure of graphene-based support, and the electronic structure can be characterized by Fermi softness of catalysts. Fermi softness and uplift height of Fe atom could be good descriptors for the adsorption activity of single atom iron catalysts with graphene-based supports. The findings can lay a foundation for the further study of graphene-based support effects in single atom catalysts and provide a guideline for development and design of new graphene-based support materials utilizing the idea of Fermi softness.

  9. Contribution to the Study of Ammonia Removal from Digestate by Struvite Precipitation

    NASA Astrophysics Data System (ADS)

    Vidlarova, P.; Heviankova, S.; Kyncl, M.

    2017-10-01

    This study deals with an issue of ammonia removal from anaerobic digestion’s by-product - digestate. The aim of the research is ammonia removal by chemical precipitation using the combination of Mg2+, NH4+ and PO43-ions in struvite (MgNH4PO4 . 6 H2O). Laboratory tests were carried out using the sample of digestate liquor. The final product of the treatment may have the potential to be used as a fertilizer.

  10. Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture.

    PubMed

    Malhautier, Luc; Gracian, Catherine; Roux, Jean-Claude; Fanlo, Jean-Louis; Le Cloirec, Pierre

    2003-01-01

    The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.

  11. Ice chemistry of acetaldehyde reveals competitive reactions in the first step of the Strecker synthesis of alanine: formation of HO-CH(CH3)-NH2 vs. HO-CH(CH3)-CN

    NASA Astrophysics Data System (ADS)

    Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Duvernay, Fabrice; Theulé, Patrice; Chiavassa, Thierry

    2015-08-01

    The understanding of compound formation in laboratory simulated astrophysical environments is an important challenge in obtaining information on the chemistry occurring in these environments. We here investigate by means of both laboratory experiments and quantum chemical calculations the ice-based reactivity of acetaldehyde (CH3CHO) with ammonia (NH3) and hydrogen cyanide (HCN) in excess of water (H2O) promoted by temperature. A priori, this study should give information on alanine (2HN-CH(CH3)-COOH) formation (the simplest chiral amino acid detected in meteorites), since these reactions concern the first steps of its formation through the Strecker synthesis. However, infrared spectroscopy, mass spectrometry with HC14N or HC15N isotopologues and B3LYP-D3 results converge to indicate that an H2O-dominated ice containing CH3CHO, NH3 and HCN not only leads to the formation of α-aminoethanol (2HN-CH(CH3)-OH, the product compound of the first step of the Strecker mechanism) and its related polymers (2HN-(CH(CH3)-O)n-H) due to reaction between CH3CHO and NH3, but also to the 2-hydroxypropionitrile (HO­-CH(CH3)-CN) and its related polymers (H-(O-CH(CH3))n-CN) from direct reaction between CH3CHO and HCN. The ratio between these two species depends on the initial NH3/HCN ratio in the ice. Formation of α-aminoethanol is favoured when the NH3 concentration is larger than HCN. We also show that the presence of water is essential for the formation of HO­-CH(CH3)-CN, contrarily to 2HN-CH(CH3)-OH whose formation also takes place in absence of H2O ice. As in astrophysical ices NH3 is more abundant than HCN, formation of α-aminoethanol should consequently be favoured compared to 2-hydroxypropionitrile, thus pointing out α-aminoethanol as a plausible intermediate species for alanine synthesis through the Strecker mechanism in astrophysical ices.

  12. Study on structures and properties of ammonia clusters (NH3)n (n=1-5) and liquid ammonia in terms of ab initio method and atom-bond electronegativity equalization method ammonia-8P fluctuating charge potential model.

    PubMed

    Yu, Ling; Yang, Zhong-Zhi

    2010-05-07

    Structures, binding energies, and vibrational frequencies of (NH(3))(n) (n=2-5) isomers and dynamical properties of liquid ammonia have been explored using a transferable intermolecular potential eight point model including fluctuating charges and flexible body based on a combination of the atom-bond electronegativity equalization and molecular (ABEEM) mechanics (ABEEM ammonia-8P) in this paper. The important feature of this model is to divide the charge sites of one ammonia molecule into eight points region containing four atoms, three sigma bonds, and a lone pair, and allows the charges in system to fluctuate responding to the ambient environment. Due to the explicit descriptions of charges and special treatment of hydrogen bonds, the results of equilibrium geometries, dipole moments, cluster interaction energies, vibrational frequencies for the gas phase of small ammonia clusters, and radial distribution function for liquid ammonia calculated with the ABEEM ammonia-8P potential model are in good agreement with those measured by available experiments and those obtained from high level ab initio calculations. The properties of ammonia dimer are studied in detail involving the structure and one-dimensional, two-dimensional potential energy surface. As for interaction energies, the root mean square deviation is 0.27 kcal/mol, and the linear correlation coefficient reaches 0.994.

  13. Separating methane emissions from agricultural sources and natural gas: direct measurements of excess columns of CH4, C2H6 and NH3 in the Colorado Front Range

    NASA Astrophysics Data System (ADS)

    Kille, N.; Chiu, R.; Frey, M.; Hase, F.; Kumar Sha, M.; Blumenstock, T.; Hannigan, J. W.; Volkamer, R. M.

    2017-12-01

    Methane (CH4) is a major greenhouse gas emitted from biogenic, thermogenic, and pyrogenic sources. Here we demonstrate a novel approach to separate sources of CH4 emissions based on a network of small portable sensors performing column measurements in the Northern Colorado Front Range (NCFR). In the study area CH4 is emitted from biogenic sources such as concentrated animal feeding operations (CAFOs) and natural gas production and storage. In March 2015 we deployed a network of five Fourier Transform Spectrometers (FTS) to characterize the regional scale methane dome in Colorado's Denver-Julesburg Basin based on excess vertical column measurements (the column enhancement inside the dome over background). Three EM27sun FTS measured CH4, oxygen (O2) and water vapor (H2O) columns at Eaton, CO (inside the dome) and at two boundary sites; the CU mobile SOF (Solar Occultation Flux) measured ethane (C2H6), ammonia (NH3), and H2O at Eaton, CO. The column averaged dry air mole fractions XCH4, XC2H6, and XNH3 were determined using O2 columns for air mass factor normalization, and background column was subtracted to derive excess vertical columns of DXCH4, DXC2H6, DXNH3 at Eaton, CO. Eaton is located both near CAFOs and at the northern edge of oil and natural gas production wells. Our approach for source apportioning methane employs a linear regression analysis that explains DXCH4 in terms of DXC2H6 as tracer for natural gas sources, and DXNH3 as tracer for CAFO emissions. The results of the source apportionment are compared with literature values of the NH3/CH4 and C2H6/CH4 ratio to evaluate the method of excess columns, which is independent of boundary layer height.

  14. The reaction of NH2 with NO2

    NASA Technical Reports Server (NTRS)

    Jayanty, R. K. M.; Simonaitis, R.; Heicklen, J.

    1976-01-01

    Ammonia (NH3) was photolyzed at 213.9 nm in the presence of NO2 at 25 C in order to study the reactions of NH2 with NO2. The products included NO, with a quantum yield of 1.0. The other measured products of the reaction were N2 and N2O with respective quantum yields of 0.94 plus or minus 0.10 and 0.3 in the presence of small amounts of He and 0.65 plus or minus 0.15 and 0.13 in the presence of a large excess of He. The quantum yield for NO2 consumption was 6.0 plus or minus 2.0 in the absence of He. These results are explained in terms of various reactions.

  15. Trends of NO-, NO 2-, and NH 3-emissions from gasoline-fueled Euro-3- to Euro-4-passenger cars

    NASA Astrophysics Data System (ADS)

    Heeb, Norbert V.; Saxer, Christian J.; Forss, Anna-Maria; Brühlmann, Stefan

    Vehicular emissions of reactive nitrogen compounds (RNCs) such as nitric oxide (NO), nitrogen dioxide (NO 2), and ammonia (NH 3) have a substantial impact on urban air quality. NO and NO 2 support the photochemical formation of ozone, and NH 3 is involved in the atmospheric formation of secondary aerosols. Vehicular NO is mainly formed during combustion, whereas NO 2 and NH 3 are both secondary pollutants of the catalytic converter systems. Herein we report on tail-pipe RNC emissions of gasoline-fueled Euro-3- and Euro-4-passenger cars at transient driving from 0 to 150 km h -1. Two sets of 10 in-use vehicles with comparable engine size and mileage were studied with time-resolved chemical ionization-mass spectrometry (CI-MS). Each vehicle was tested in 7 different driving cycles including the legislative European (EDC) and the US FTP-75 driving cycles. Mean emission factors (EFs) for different traffic situations are reported and effects of cold start, velocity, acceleration, and deceleration are discussed. Furthermore, critical operating conditions supporting the de novo formation of NH 3 have been identified. In the EDC, mean NO- and NH 3-EFs of 57±26 and 16±12 mg km -1 were obtained for Euro-3-vehicles; those of the Euro-4-technology were lower by about 25% and 33% at the levels of 43±46 and 10±7 mg km -1, respectively. NO 2 emissions of the investigated three-way catalyst (TWC) vehicles accounted for <1% of the detected RNCs, whereas NH 3 was found to be the dominant RNC for most vehicle conditions. Molar NH 3 proportions varied from about 0.4-0.8, as soon as catalyst light-off occurred. NO was found in large excess only during the cold-start period. Catalyst light-off is indicated by a fast transition from NO- to NH 3-rich exhaust. Velocity and acceleration had pronounced effects on the RNC emission characteristics. Mean velocity-dependent EFs for NO and NH 3 varied by about one order of magnitude from 10 to 74 and 15 to 161 mg km -1 for Euro-3-vehicles and

  16. Bulk Kosterlitz-Thouless Type Molecular Superconductor β″-(BEDT-TTF)2[(H2O)(NH4)2Cr(C2O4)3]·18-crown-6.

    PubMed

    Martin, Lee; Lopez, Jordan R; Akutsu, Hiroki; Nakazawa, Yasuhiro; Imajo, Shusaku

    2017-11-20

    A new molecular superconductor, β″-(BEDT-TTF) 2 [(H 2 O)(NH 4 ) 2 Cr(C 2 O 4 ) 3 ]·18-crown-6, has been synthesized from the organic donor molecule BEDT-TTF with the anion Cr(C 2 O 4 ) 3 3- . The crystal structure consists of conducting organic layers of BEDT-TTF molecules which adopt the β″ packing motif (layer A), layers of NH 4 + and Λ-Cr(C 2 O 4 ) 3 3- (layer B), layers of (H 2 O)(NH 4 )18-crown-6 (layer C), and layers of NH 4 + and Δ-Cr(C 2 O 4 ) 3 3- (layer D) which produce a superstructure with a repeating pattern of ABCDABCDA. As a result of this packing arrangement, this is the 2D superconductor with the widest gap between conducting layers where only a single donor packing motif is present (β″). Superconducting critical temperatures at ambient pressure observed by electrical transport and magnetic measurements are 4.0-4.9 and 2.5 K, respectively. The strong 2D nature of this system, the broad transition to T zero at 1.8K, and the transition of α of V ∝ I α from 1 to 3 on I-V curves strongly suggest that the superconducting transition is very close to a Kosterlitz-Thouless transition. The magnetic field dependence of the superconducting critical temperature parallel to the conducting plane gives an upper critical field μ 0 H c2∥ > 8 T, which is over the calculated Pauli-Clogston limit for this material.

  17. Ammonia Excretion in an Osmoregulatory Syncytium Is Facilitated by AeAmt2, a Novel Ammonia Transporter in Aedes aegypti Larvae

    PubMed Central

    Durant, Andrea C.; Donini, Andrew

    2018-01-01

    The larvae of the mosquito Aedes aegypti inhabit ammonia rich septic tanks in tropical regions of the world that make extensive use of these systems, explaining the prevalence of disease during dry seasons. Since ammonia (NH3/NH4+) is toxic to animals, an understanding of the physiological mechanisms of ammonia excretion permitting the survival of A. aegypti larvae in high ammonia environments is important. We have characterized a novel ammonia transporter, AeAmt2, belonging to the Amt/MEP/Rh family of ammonia transporters. Based on the amino acid sequence, the predicted topology of AeAmt2 consists of 11 transmembrane helices with an extracellular N-terminus and a cytoplasmic C-terminus region. Alignment of the predicted AeAmt2 amino acid sequence with other Amt/MEP proteins from plants, bacteria, and yeast highlights the presence of conserved residues characteristic of ammonia conducting channels in this protein. AeAmt2 is expressed in the ionoregulatory anal papillae of A. aegypti larvae where it is localized to the apical membrane of the epithelium. dsRNA-mediated knockdown of AeAmt2 results in a significant decrease in NH4+ efflux from the anal papillae, suggesting a key role in facilitating ammonia excretion. The effect of high environmental ammonia (HEA) on expression of AeAmt2, along with previously characterized AeAmt1, AeRh50-1, and AeRh50-2 in the anal papillae was investigated. We show that changes in expression of ammonia transporters occur in response to acute and chronic exposure to HEA, which reflects the importance of these transporters in the physiology of life in high ammonia habitats. PMID:29695971

  18. Ammonia in Jupiter’s troposphere from high-resolution 5-micron spectroscopy

    NASA Astrophysics Data System (ADS)

    Giles, Rohini; Fletcher, Leigh; Irwin, Patrick; Orton, Glenn S.; Sinclair, James Andrew

    2017-10-01

    Jupiter's tropospheric ammonia (NH3) abundance is studied using spatially-resolved 5-micron observations from CRIRES, a high-resolution spectrometer at the Very Large Telescope in 2012. The high resolving power (R=96,000) allows the line shapes of three NH3 absorption features to be resolved. These three absorption features have different line strengths and probe slightly different pressure levels, and they can therefore be used to constrain the vertical profile of NH3 in the 1-4 bar pressure range. The instrument slit was aligned north-south along Jupiter's central meridian, allowing us to search for latitudinal variability. The CRIRES observations do not provide evidence for belt-zone variability in NH3, as any spectral differences can be accounted for by the large differences in cloud opacity between the cloudy zones and the cloud-free belts. However, we do find evidence for localised small-scale variability in NH3. Specifically, we detect a strong enhancement in NH3 on the southern edge of the North Equatorial Belt (4-6°N). This is consistent with the ‘ammonia plumes’ observed by Fletcher et al. (2016, doi:10.1016/j.icarus.2016.06.008) at the 500-mbar level using 10-micron observations from TEXES/IRTF, as well as with measurements by Juno’s Microwave Radiometer (Li et al. 2017, doi:10.1002/2017GL073159).

  19. Graphene assisted effective hole-extraction on In2O3:H/CH3NH3PbI3 interface: Studied by modulated surface spectroscopy

    NASA Astrophysics Data System (ADS)

    Vinoth Kumar, Sri Hari Bharath; Muydinov, Ruslan; Kol'tsova, Tat‘yana; Erfurt, Darja; Steigert, Alexander; Tolochko, Oleg; Szyszka, Bernd

    2018-01-01

    Charge separation in CH3NH3PbI3 (MAPbI3) films deposited on a hydrogen doped indium oxide (In2O3:H) photoelectrode was investigated by modulated surface photovoltage (SPV) spectroscopy in a fixed capacitor arrangement. It was found that In2O3:H reproducibly extracts photogenerated-holes from MAPbI3 films. The oxygen-plasma treatment of the In2O3:H surface is suggested to be a reason for this phenomenon. Introducing graphene interlayer increased charge separation nearly 6 times as compared to that on the In2O3:H/MAPbI3 interface. Furthermore, it is confirmed by SPV spectroscopy that the defects of the MAPbI3 interface are passivated by graphene.

  20. Marine, freshwater and aerially acclimated mangrove rivulus (Kryptolebias marmoratus) use different strategies for cutaneous ammonia excretion

    PubMed Central

    Cooper, Christopher A.; Wilson, Jonathan M.

    2013-01-01

    Rhesus (Rh) glycoproteins are ammonia gas (NH3) channels known to be involved in ammonia transport in animals. Because of the different osmoregulatory and ionoregulatory challenges faced by teleost fishes in marine and freshwater (FW) environments, we hypothesized that ammonia excretion strategies would differ between environments. Also, we hypothesized that cutaneous NH3 volatilization in air-acclimated fish is facilitated by base secretion. To test these hypotheses, we used the skin of the euryhaline amphibious mangrove rivulus (Kryptolebias marmoratus). The skin excretes ammonia and expresses Rh glycoproteins. Serosal-to-mucosal cutaneous ammonia flux was saturable (0–16 mmol/l ammonia, Km of 6.42 mmol/l). In FW, ammonia excretion increased in response to low mucosal pH but decreased with pharmacological inhibition of Na+/H+ exchangers (NHE) and H+ ATPase. Conversely, in brackish water (BW), lowering the mucosal pH significantly decreased ammonia excretion. Inhibitors of NHE also decreased ammonia excretion in BW fish. Immunofluorescence microscopy demonstrated that both the Rh isoform, Rhcg1, and NHE3 proteins colocalized in Na+/K+ ATPase expressing mitochondrion-rich cells in the gills, kidney, and skin. We propose that the mechanisms of cutaneous ammonia excretion in FW K. marmoratus are consistent with the model for branchial ammonia excretion in FW teleost fish. NH4+ excretion appeared to play a stronger role in BW. NH4+ excretion in BW may be facilitated by apical NHE and/or diffuse through paracellular pathways. In aerially acclimated fish, inhibition of NHE and H+ ATPase, but not the Cl−/HCO3− exchanger, significantly affected cutaneous surface pH, suggesting that direct base excretion is not critical for NH3 volatilization. Overall, K. marmoratus use different strategies for excreting ammonia in three different environments, FW, BW, and air, and Rh glycoproteins and NHE are integral to all. PMID:23389109

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

    PubMed

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

    2014-03-01

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

  2. Experimental investigation of nitrogen isotopic effects associated with ammonia degassing at 0-70 °C

    NASA Astrophysics Data System (ADS)

    Deng, Yuying; Li, Yingzhou; Li, Long

    2018-04-01

    Ammonia degassing is a common process in natural alkaline waters and in the atmosphere. To quantitatively assess the nitrogen cycle in these systems, the essential parameter of nitrogen isotope fractionation factors associated with ammonia degassing is required, but still not constrained yet. In this study, we carried out laboratory experiments to examine the nitrogen isotope behavior during ammonia degassing in alkaline conditions. The experiments started with ammonium sulfate solution with excess sodium hydroxide. The reaction can be described as: NH4+ + OH- (excess) → NH3·nH2O → NH3 (g)↑. Two sets of experiments, one with ammonia degassing under static conditions and the other with ammonia degassing by bubbling of N2 gas, were carried out at 2, 21, 50, and 70 °C. The results indicate that kinetic isotopic effects are dominated during efficient degassing of ammonia in the bubbling experiments, which yielded kinetic nitrogen isotope fractionation factors αNH3(g)-NH3(aq) of 0.9898 at 2 °C, 0.9918 at 21 °C, 0.9935 at 50 °C and 0.9948 at 70 °C. These values show a good relationship with temperature as 103lnαNH3(g)-NH3(aq) = 14.6 - 6.8 × 1000/T. In contrast, isotopic effects during less efficient degassing of ammonia in the static experiments are more complicated. The results do not match either kinetic isotope fractionation or equilibrium isotope fractionation but sit between these two. The most likely cause is that back dissolution of the degassed ammonia occurred in these experiments and consequently shifted kinetic isotope fractionation toward equilibrium isotope fractionation. Our experimental results highlight complicated isotopic effects may occur in natural environments, and need to be fully considered in the interpretation of field data.

  3. [Comparing the ammonia volatilization characteristic of two typical paddy soil with total wheat straw returning in Taihu Lake region].

    PubMed

    Wang, Jun; Wang, De-Jian; Zhang, Gang; Wang, Yuan

    2013-01-01

    An experiment using monolith lysimeter was conducted to compare the characteristic of N loss by ammonia (NH3) volatilization between the gleyed paddy soil (G soil) and hydromorphic paddy soil (H soil) the Changshu National Agro-ecological Experimental Station of the Chinese Academy of Sciences(31 degrees 33' N, 123 degrees 38' E). Three treatments were designed for each soil type, i. e. control (no urea and straw applied), nitrogen solely and nitrogen plus wheat straw. Ammonia volatilization, flood water NH4(+) -N concentration, pH and top soil Eh were measured during the rice-growing season. Results showed that the NH3 volatilization flux and cumulative N losses by NH3 volatilization from G soil were significantly higher than those from H soil, the average cumulative N losses being about 41.8 kg x hm(-2) and 11.2 kg x hm(-2), or 15.2% and 3.8% of the fertilizer N, respectively. The average N loss by NH3 volatilization during the tillering stage was the highest among the three fertilization stages, accounting for 29.4% and 8.3% of the fertilizer N for G soil and H soil, respectively. Wheat straw returning significantly increased paddy filed NH3 volatilization losses. Comparing with the sole application of fertilizer-N, the cumulative N loss by NH3 volatilization of fertilizer-N in combination with wheat straw was increased by 19.8% and 20.6% for G soil and H soil, respectively. In addition, ammonia volatilization fluxes showed a positive relationship with the flood water NH4(+) -N concentration and pH for both soils, but the relationship with top soil Eh still needs further study.

  4. Synthesis and Evaluation of Cu/SAPO-34 Catalysts for NH3-SCR 2: Solid-state Ion Exchange and One-pot Synthesis

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

    Gao, Feng; Walter, Eric D.; Washton, Nancy M.

    2015-01-01

    Cu-SAPO-34 catalysts are synthesized using two methods: solid-state ion exchange (SSIE) and one-pot synthesis. SSIE is conducted by calcining SAPO-34/CuO mixtures at elevated temperatures. For the one-pot synthesis method, Cu-containing chemicals (CuO and CuSO4) are added during gel preparation. A high-temperature calcination step is also needed for this method. Catalysts are characterized with surface area/pore volume measurements, temperature programmed reduction (TPR), electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies, and scanning electron microscopy (SEM). Catalytic properties are examined using standard ammonia selective catalytic reduction (NH3-SCR) and ammonia oxidation reactions. In Cu-SAPO-34 samples formed using SSIE, Cu presents bothmore » as isolated Cu2+ ions and unreacted CuO. The former is highly active and selective in NH3-SCR, while the latter catalyzes a side reaction; notably, the non-selective oxidation of NH3 above 350 ºC. Using the one-pot method followed by a high-temperature aging treatment, it is possible to form Cu SAPO-34 samples with predominately isolated Cu2+ ions at low Cu loadings. However at much higher Cu loadings, isolated Cu2+ ions that bind weakly with the CHA framework and CuO clusters also form. These Cu moieties are very active in catalyzing non-selective NH3 oxidation above 350 ºC. Low-temperature reaction kinetics indicate that Cu-SAPO-34 samples formed using SSIE have core-shell structures where Cu is enriched in the shell layers; while Cu is more evenly distributed within the one-pot samples. Reaction kinetics also suggest that at low temperatures, the local environment next to Cu2+ ion centers plays little role on the overall catalytic properties. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed at the

  5. ISO ammonia line absorption reveals a layer of hot gas veiling Sgr B2

    NASA Astrophysics Data System (ADS)

    Ceccarelli, C.; Baluteau, J.-P.; Walmsley, M.; Swinyard, B. M.; Caux, E.; Sidher, S. D.; Cox, P.; Gry, C.; Kessler, M.; Prusti, T.

    2002-02-01

    We report the first results of the unbiased spectral high resolution survey obtained towards Sgr B2 with the Long Wavelength Spectrometer on board ISO. The survey detected more than one hundreds lines from several molecules. Ammonia is the molecule with the largest number (21) of detected lines in the survey. We detected NH3 transitions from levels with energies from 45 to 500 cm-1. The detected transitions are from both para and ortho ammonia and metastable and non-metastable levels. All the ammonia lines are in absortion against the FIR continuum of Sgr B2. With such a large number of detected lines in such a large range of energy levels, we could very efficiently constrain the main parameters of the absorbing gas layer. The gas is at (700 +/- 100) K and has a density lower than 104 cm-3. The total NH3 column density in the layer is (3+/- 1) x 1016 cm-2, equally shared between ortho and para ammonia. Given the derived relatively high gas temperature and ammonia column density, our observations support the hypothesis previously proposed of a layer of shocked gas between us and Sgr B2. We also discuss previous observations of far infrared line absorption from other molecules, like H2O and HF, in the light of this hot absorbing layer. If the absorption is done by the hot absorbing layer rather than by the warm envelope surrounding Sgr B2, as was previously supposed in order to interpret the mentioned observations, the derived H2O and HF abundances are one order of magitude larger than previously estimated. Yet, the present H2O and HF observations do not allow one to disentangle the absorption from the hot layer against the warm envelope. Our conclusions are hence that care should be applied when interpreting the absorption observations in Sgr B2, as the hot layer clearly seen in the ammonia transitions may substantially contribute to the absorption. ISO is an ESA project with instruments funded by ESA Member States (especially the PI countries: France, Germany, The

  6. Ammonia excretion in Caenorhabditis elegans: mechanism and evidence of ammonia transport of the Rhesus protein CeRhr-1

    PubMed Central

    Adlimoghaddam, Aida; Boeckstaens, Mélanie; Marini, Anna-Maria; Treberg, Jason R.; Brassinga, Ann-Karen C.; Weihrauch, Dirk

    2015-01-01

    ABSTRACT The soil-dwelling nematode Caenorhabditis elegans is a bacteriovorous animal, excreting the vast majority of its nitrogenous waste as ammonia (25.3±1.2 µmol gFW−1 day−1) and very little urea (0.21±0.004 µmol gFW−1 day−1). Although these roundworms have been used for decades as genetic model systems, very little is known about their strategy to eliminate the toxic waste product ammonia from their bodies into the environment. The current study provides evidence that ammonia is at least partially excreted via the hypodermis. Starvation reduced the ammonia excretion rates by more than half, whereas mRNA expression levels of the Rhesus protein CeRhr-2, V-type H+-ATPase (subunit A) and Na+/K+-ATPase (α-subunit) decreased correspondingly. Moreover, ammonia excretion rates were enhanced in media buffered to pH 5 and decreased at pH 9.5. Inhibitor experiments, combined with enzyme activity measurements and mRNA expression analyses, further suggested that the excretion mechanism involves the participation of the V-type H+-ATPase, carbonic anhydrase, Na+/K+-ATPase, and a functional microtubule network. These findings indicate that ammonia is excreted, not only by apical ammonia trapping, but also via vesicular transport and exocytosis. Exposure to 1 mmol l−1 NH4Cl caused a 10-fold increase in body ammonia and a tripling of ammonia excretion rates. Gene expression levels of CeRhr-1 and CeRhr-2, V-ATPase and Na+/K+-ATPase also increased significantly in response to 1 mmol l−1 NH4Cl. Importantly, a functional expression analysis showed, for the first time, ammonia transport capabilities for CeRhr-1 in a phylogenetically ancient invertebrate system, identifying these proteins as potential functional precursors to the vertebrate ammonia-transporting Rh-glycoproteins. PMID:25740900

  7. Soil-plant-atmosphere ammonia exchange associated with calluna vulgaris and deschampsia flexuosa

    NASA Astrophysics Data System (ADS)

    Schjoerring, Jan K.; Husted, Søren; Poulsen, Mette M.

    Ammonia fluxes and compensation points at atmospheric NH 3 concentrations corresponding to those occurring under natural growth conditions (0-26 nmol NH 3 mol air -1) were measured for canopies of two species native to heathland in N.W. Europe, viz. Calluna vulgaris (L.) Hull and Deschampsia flexuosa (L.) Trin. The NH 3 compensation point in 2 yr-old C. vulgaris plants, in which current year's shoots had just started growing, was below the detection limit (0.1 nmol mol -1 at 8°C). Fifty days later, when current year's shoots were elongating and flowers developed, the NH 3 compensation point was approximately 6±2.0 nmol mol -1 at 22°C (0.8±0.3 nmol mol -1 at 8°C). The plants in which the shoot tips had just started growing were characterized by a low N concentration in the shoot dry matter (5.8 mg N g -1 shoot dry weight) and a low photosynthetic CO 2 assimilation compared to the flowering plants in which the average dry matter N concentration in old shoots and woody stems was 7.4 and in new shoots 9.5 mg N g -1 shoot dry weight. Plant-atmosphere NH 3 fluxes in C. vulgaris responded approximately linearly to changes in the atmospheric NH 3 concentration. The maximum net absorption rate at 26 nmol NH 3 mol -1 air was 12 nmol NH 3 m -2 ground surface s -1 (equivalent to 13.3 pmol NH 3 g -1 shoot dry matter s -1). Ammonia absorption in Deschampsia flexuosa plants increased approximately linearly with increasing NH 3 concentrations up to 20 nmol mol -1. The maximum NH 3 absorption was 8.5 nmol m -2 ground surface s -1 (30.4 pmol g -1 shoot dry weight s -1). The NH 3 compensation point at 24°C was 3.0±1.1, and at 31°C 7.5±0.6 nmol mol air -1. These values correspond to a NH 3 compensation point of 0.45±0.15 at 8°C. The soil used for cultivation of C. vulgaris (peat soil with pH 6.9) initially adsorbed NH 3 at a rate which exceeded the absorption by the plant canopy. During a 24 d period following the harvest of the plants soil NH 3 adsorption declined and the

  8. Hydrothermal Synthesis of PbTiO3 Nanocrystals with a pH-Adjusting Agent of Ammonia Solution

    NASA Astrophysics Data System (ADS)

    Li, Xinyi; Huang, Zhixiong; Zhang, Lianmeng; Guo, Dongyun

    2018-05-01

    The PbTiO3 nanocrystals were synthesized by a hydrothermal method, and ammonia solution was firstly used as a pH-adjusting agent. The effect of ammonia concentration on formation and morphologies of PbTiO3 nanocrystals was investigated. At low ammonia concentration (0-2.2 mol/L), no perovskite PbTiO3 phase was formed. When the ammonia concentration was 4.4 mol/L, the rod-like PbTiO3 nanocrystals with highly crystalline were successfully synthesized. As the ammonia concentration further increased to 13.2 mol/L, the flake-like PbTiO3 nanocrystals were formed.

  9. Short-term effect of ammonia concentration and salinity on activity of ammonia oxidizing bacteria.

    PubMed

    Claros, J; Jiménez, E; Borrás, L; Aguado, D; Seco, A; Ferrer, J; Serralta, J

    2010-01-01

    A continuously aerated SHARON (single reactor high activity ammonia removal over nitrite) system has been operated to achieve partial nitritation. Two sets of batch experiments were carried out to study the effect of ammonia concentration and salinity on the activity of ammonia-oxidizing bacteria (AOB). Activity of AOB raised as free ammonia concentration was increased reaching its maximum value at 4.5 mg NH3-N l(-1). The half saturation constant for free ammonia was determined (K(NH3)=0.32 mg NH3-N l(-1)). Activity decreased at TAN (total ammonium-nitrogen) concentration over 2,000 mg NH4-N l(-1). No free ammonia inhibition was detected. The effect of salinity was studied by adding different concentrations of different salts to the biomass. No significant differences were observed between the experiments carried out with a salt containing or not containing NH4. These results support that AOB are inhibited by salinity, not by free ammonia. A mathematical expression to represent this inhibition is proposed. To compare substrate affinity and salinity inhibitory effect on different AOB populations, similar experiments were carried out with biomass from a biological nutrient removal pilot plant. The AOB activity reached its maximum value at 0.008 mg NH3-N l(-1) and decreased at TAN concentration over 400 mg NH4-N l(-1). These differences can be explained by the different AOB predominating species: Nitrosomonas europaea and N. eutropha in the SHARON biomass and Nitrosomonas oligotropha in the pilot plant.

  10. Stabilities of protonated water-ammonia clusters

    NASA Astrophysics Data System (ADS)

    Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

    2018-05-01

    Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

  11. Reaction of Si(100) with NH3: Rate-limiting steps and reactivity enhancement via electronic excitation

    NASA Astrophysics Data System (ADS)

    Bozso, F.; Avouris, Ph.

    1986-09-01

    We report on the low-temperature reaction of ammonia with Si(100)-(2×1). The dangling bonds in the clean Si surface promote NH3 dissociation even at temperatures as low as 90 K. The N atoms thus produced occupy subsurface sites, while the H atoms bind to surface Si atoms, tie up the dangling bonds, and inactivate the surface. Thermal or electronic-excitation-induced hydrogen desorption restores the dangling bonds and the reactivity of the surface. Silicon nitride film growth is achieved at 90 K by simultaneous exposure of the Si surface to NH3 and an electron beam.

  12. 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.

  13. Water-Ammonia Ionic Ocean on Uranus and Neptune-Clue from Tropospheric Hydrogen Sulfide Clouds

    NASA Astrophysics Data System (ADS)

    Atreya, S. K.; Egeler, P. A.; Wong, A.

    2005-12-01

    Interior models of the ice-giants, Uranus and Neptune, predict a water-ammonia ionic ocean at tens of kilobar pressure [1,2]. If correct, its implication for planetary formation models is profound. In this presentation we demonstrate that the existence of an ionic ocean will manifest itself in the planets' tropospheric cloud structure, particularly in the form of a hydrogen sulfide, i.e. H2S-ice, cloud. In fact, an H2S cloud was introduced ad hoc in the 3-5 bar region to explain microwave absorption [3] and the methane [4] observations, but its presence cannot be proved in the absence of entry probes. Our equilibrium cloud condensation model (ECCM) shows that an H2S-ice cloud does not form when conventional enrichment factors (20-30× solar at Uranus, and 30-50× solar at Neptune) are employed for all heavy elements (mass >4) [5]. However, a deep ``cloud'' composed of a weak solution of ammonia and water forms, and its base is at 370 and 500 bars, respectively, for 30× solar and 50× solar enrichment factors. If an ionic ``ocean'' exists much deeper, water vapor, as well as ammonia dissolved in it, would be severely depleted at levels above this ocean. The consequences of such water vapor and ammonia depletions are that (1) clouds of water and ammonia, if present, are much less prominent; (2) only small amount of H2S vapor is removed by NH3, to form an NH4SH cloud; so that (3) a cloud of H2S-ice can now form; and (4) an H2O ``ocean'' in the 1-kilobar region [6] does not form. This scenario has important implications for the design of entry probe missions, as measurements to only 10-20 bars, rather than kilobar levels, will need to be made. The heavy elements, Ar, Kr, Xe, Ne, C, and S, as well as He, D/H, GeH4, AsH3, PH3, and CO can all be accessed at pressures less than 20 bars. These measurements are critical for constraining the formation models [5,7,8]. Measurement of water in the well-mixed region of Uranus and Neptune is technologically highly challenging

  14. Measurement of ammonia emissions from temperate and sub-polar seabird colonies

    NASA Astrophysics Data System (ADS)

    Riddick, S. N.; Blackall, T. D.; Dragosits, U.; Daunt, F.; Newell, M.; Braban, C. F.; Tang, Y. S.; Schmale, J.; Hill, P. W.; Wanless, S.; Trathan, P.; Sutton, M. A.

    2016-06-01

    The chemical breakdown of marine derived reactive nitrogen transported to the land as seabird guano represents a significant source of ammonia (NH3) in areas far from other NH3 sources. Measurements made at tropical and temperate seabird colonies indicate substantial NH3 emissions, with emission rates larger than many anthropogenic point sources. However, several studies indicate that thermodynamic processes limit the amount of NH3 emitted from guano, suggesting that the percentage of guano volatilizing as NH3 may be considerably lower in colder climates. This study undertook high resolution temporal ammonia measurements in the field and coupled results with modelling to estimate NH3 emissions at a temperate puffin colony and two sub-polar penguin colonies (Signy Island, South Orkney Islands and Bird Island, South Georgia) during the breeding season. These emission rates are then compared with NH3 volatilization rates from other climates. Ammonia emissions were calculated using a Lagrangian atmospheric dispersion model, resulting in mean emissions of 5 μg m-2 s-1 at the Isle of May, 12 μg m-2 s-1 at Signy Island and 9 μg m-2 s-1 at Bird Island. The estimated percentage of total guano nitrogen volatilized was 5% on the Isle of May, 3% on Signy and 2% on Bird Island. These values are much smaller than the percentage of guano nitrogen volatilized in tropical contexts (31-65%). The study confirmed temperature, wind speed and water availability have a significant influence on the magnitude of NH3 emissions, which has implications for reactive nitrogen in both modern remote regions and pre-industrial atmospheric composition and ecosystem interactions.

  15. Nucleobases and Prebiotic Molecules in Organic Residues Produced from the Ultraviolet Photo-Irradiation of Pyrimidine in NH3 and H2O+NH3 Ices

    NASA Technical Reports Server (NTRS)

    Nuevo, Michel; Milam, Stefanie N.; Sandford, Scott

    2012-01-01

    Although not yet identified in the interstellar medium (ISM), N-heterocycles including nucleobases the information subunits of DNA and RNA are present in carbonaceous chondrites, which indicates that molecules of biological interest can be formed in non-terrestrial environments via abiotic pathways. Recent laboratory experiments and ab-initio calculations have already shown that the irradiation of pyrimidine in pure H2O ices leads to the formation of a suite of oxidized pyrimidine derivatives, including the nucleobase uracil. In the present work, NH3:pyrimidine and H2O:NH3:pyrimidine ice mixtures with different relative proportions were irradiated with UV photons under astrophysically relevant conditions. Liquid- and gas-chromatography analysis of the resulting organic residues has led to the detection of the nucleobases uracil and cytosine, as well as other species of prebiotic interest such as urea and small amino acids. The presence of these molecules in organic residues formed under abiotic conditions supports scenarios in which extraterrestrial organics that formed in space and were subsequently delivered to telluric planets via comets and meteorites could have contributed to the inventory of molecules that triggered the first biological reactions on their surfaces.

  16. Photodissociation dynamics of gaseous CpCo(CO)2 and ligand exchange reactions of CpCoH2 with C3H4, C3H6, and NH3.

    PubMed

    Oana, Melania; Nakatsuka, Yumiko; Albert, Daniel R; Davis, H Floyd

    2012-05-31

    The photodissociation dynamics of CpCo(CO)(2) was studied in a molecular beam using photofragment translational energy spectroscopy with 157 nm photoionization detection of the metallic products. At 532 and 355 nm excitation, the dominant one-photon channel involved loss of a single CO ligand producing CpCoCO. The product angular distributions were isotropic, and a large fraction of excess energy appeared as product vibrational excitation. Production of CpCO + 2CO resulted from two-photon absorption processes. The two-photon dissociation of mixtures containing CpCo(CO)(2) and H(2) at the orifice of a pulsed nozzle was used to produce a novel 16-electron unsaturated species, CpCoH(2). Transition metal ligand exchange reactions, CpCoH(2) + L → CpCoL + H(2) (L = propyne, propene, or ammonia), were studied under single-collision conditions for the first time. In all cases, ligand exchange occurred via 18-electron association complexes with lifetimes comparable to their rotational periods. Although ligand exchange reactions were not detected from CpCoH(2) collisions with methane or propane (L = CH(4) or C(3)H(8)), a molecular beam containing CpCoCH(4) was produced by photolysis of mixtures containing CpCo(CO)(2) and CH(4).

  17. Imaging a multidimensional multichannel potential energy surface: Photodetachment of H{sup −}(NH{sub 3}) and NH{sub 4}{sup −}

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

    Hu, Qichi; Johnson, Christopher J.; Continetti, Robert E., E-mail: hguo@umn.edu, E-mail: rcontinetti@ucsd.edu

    2016-06-28

    Probes of the Born-Oppenheimer potential energy surfaces governing polyatomic molecules often rely on spectroscopy for the bound regions or collision experiments in the continuum. A combined spectroscopic and half-collision approach to image nuclear dynamics in a multidimensional and multichannel system is reported here. The Rydberg radical NH{sub 4} and the double Rydberg anion NH{sub 4}{sup −} represent a polyatomic system for benchmarking electronic structure and nine-dimensional quantum dynamics calculations. Photodetachment of the H{sup −}(NH{sub 3}) ion-dipole complex and the NH{sub 4}{sup −} DRA probes different regions on the neutral NH{sub 4} PES. Photoelectron energy and angular distributions at photon energiesmore » of 1.17, 1.60, and 2.33 eV compare well with quantum dynamics. Photoelectron-photofragment coincidence experiments indicate dissociation of the nascent NH{sub 4} Rydberg radical occurs to H + NH{sub 3} with a peak kinetic energy of 0.13 eV, showing the ground state of NH{sub 4} to be unstable, decaying by tunneling-induced dissociation on a time scale beyond the present scope of multidimensional quantum dynamics.« less

  18. A Feasibility Study of Ammonia Recovery from Coking Wastewater by Coupled Operation of a Membrane Contactor and Membrane Distillation

    PubMed Central

    Horng, Ren-Yang; Hsu, Shu-Fang; Chen, Shiao-Shing; Ho, Chia-Hua

    2018-01-01

    More than 80% of ammonia (NH3) in the steel manufacturing process wastewater is contributed from the coking wastewater, which is usually treated by biological processes. However, the NH3 in the coking wastewater is typically too high for biological treatment due to its inhibitory concentration. Therefore, a two-stage process including a hollow fiber membrane contactor (HFMC) and a modified membrane distillation (MD) system was developed and applied to reduce and recover NH3 from coking wastewater. The objectives of this paper are to evaluate different membrane materials, receiving solutions, and operation parameters for the system, remove NH3 from the coking wastewater to less than 300 mg N/L, which is amenable to the biological process, and recover ammonia solution for reuse. As a result, the polytetrafluoroethylene (PTFE) HFMC using sulfuric acid as a receiving solution can achieve a maximum NH3-N transmembrane flux of 1.67 g N/m2·h at pH of 11.5 and reduce NH3 in the coking wastewater to less than 300 mg N/L. The NH3 in the converted ammonium sulfate ((NH4)2SO4) was then recovered by the modified MD using ice water as the receiving solution to produce ≥3% of ammonia solution for reuse. PMID:29510505

  19. Effects of chronic ammonia exposure on ammonia metabolism and excretion in marine medaka Oryzias melastigma.

    PubMed

    Gao, Na; Zhu, Limei; Guo, Zhiqiang; Yi, Meisheng; Zhang, Li

    2017-06-01

    Ammonia is highly toxic to aquatic organisms, but whether ammonia excretion or ammonia metabolism to less toxic compounds is the major strategy for detoxification in marine fish against chronic ammonia exposure is unclear to date. In this study, we investigated the metabolism and excretion of ammonia in marine medaka Oryzias melastigma during chronic ammonia exposure. The fish were exposed to 0, 0.1, 0.3, 0.6, and 1.1 mmol l -1  NH 4 Cl spiked seawater for 8 weeks. Exposure of 0.3-1.1 mmol l -1  NH 4 Cl had deleterious effects on the fish, including significant reductions in growth, feed intake, and total protein content. However, the fish could take strategies to detoxify ammonia. The tissue ammonia (T Amm ) in the 0.3-1.1 mmol l -1  NH 4 Cl treatments was significantly higher than those in the 0 and 0.1 mmol l -1  NH 4 Cl treatments after 2 weeks of exposure, but it recovered with prolonged exposure time, ultimately reaching the control level after 8 weeks. The amino acid catabolic rate decreased to reduce the gross ammonia production with the increasing ambient ammonia concentration. The concentrations of most metabolites remained constant in the 0-0.6 mmol l -1  NH 4 Cl treatments, whereas 5 amino acids and 3 energy metabolism-related metabolites decreased in the 1.1 mmol l -1  NH 4 Cl treatment. J Amm steadily increased in ambient ammonia from 0 to 0.6 mmol l -1 and slightly decreased when the ambient ammonia concentration increased to 1.1 mmol l -1 . Overall, marine medaka cope with sublethal ammonia environment by regulating the tissue T Amm via reducing the ammonia production and increasing ammonia excretion. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Ices on Charon: Distribution of H2O and NH3 from New Horizons LEISA observations

    NASA Astrophysics Data System (ADS)

    Dalle Ore, C. Morea; Protopapa, S.; Cook, J. C.; Grundy, W. M.; Cruikshank, D. P.; Verbiscer, A. J.; Ennico, K.; Olkin, C. B.; Stern, S. A.; Weaver, H. A.; Young, L. A.; New Horizons Science Team

    2018-01-01

    Charon, the largest moon of Pluto, appeared as a fairly homogeneous, gray, icy world to New Horizons during closest approach on July 14th, 2015. Charon's sub-Pluto hemisphere was scanned by the Ralph/LEISA near-IR spectrograph providing an unprecedented opportunity to measure its surface composition. We apply a statistical clustering tool to identify spectrally distinct terrains and a radiative transfer approach to study the variations of the 2.0-μm H2O ice band. We map the distribution of the ices previously reported to be present on Charon's surface, namely H2O and the products of NH3 in H2O. We find that H2O ice is mostly in the crystalline phase, confirming previous studies. The regions with the darkest albedos show the strongest signature of amorphous-phase ice, although the crystalline component is still strong. The brighter albedo regions, often corresponding to crater ejecta blankets, are characterized by larger H2O grains, possibly an indication of a younger age. We observe two different behaviors for the two absorption bands representing NH3 in H2O. The 2.21-μm band tends to cluster more in the northern areas compared to the ∼2.01-μm band. Both bands are present in the brighter crater rays, but not all craters show both bands. The 2.21-μm band is also clearly present on the smaller moons Hydra and Nix. These results hint that different physical conditions may determine the appearance or absence of these two different forms of NH3 in H2O ice in the Pluto system. We also investigate the blue slope affecting the spectrum at wavelengths longer than ∼1.8 μm previously reported by several authors. We find that the slope is common among the objects in the Pluto system, Charon, the smaller moons Nix and Hydra, and the darkest terrains on Pluto. It also characterizes the analog ice tholin obtained from irradiation of Pluto-specific materials (a mixture of N2, CH4, and CO ices) in the laboratory. Our modeling results show that Pluto ice tholins are

  1. Vibrational spectroscopic analysis of taranakite (K,NH 4)Al 3(PO 4) 3(OH)·9(H 2O) from the Jenolan Caves, Australia

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Palmer, Sara J.; Pogson, Ross E.

    2011-12-01

    Many phosphate containing minerals are found in the Jenolan Caves. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the mineral taranakite (K,NH 4)Al 3(PO 4) 3(OH)·9(H 2O) which has been identified by X-ray diffraction. Jenolan Caves taranakite has been characterised by Raman spectroscopy. Raman and infrared bands are assigned to H 2PO 4, OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of taranakite in the caves has been proven.

  2. Rapid measurement of 3J(H N-H alpha) and 3J(N-H beta) coupling constants in polypeptides.

    PubMed

    Barnwal, Ravi Pratap; Rout, Ashok K; Chary, Kandala V R; Atreya, Hanudatta S

    2007-12-01

    We present two NMR experiments, (3,2)D HNHA and (3,2)D HNHB, for rapid and accurate measurement of 3J(H N-H alpha) and 3J(N-H beta) coupling constants in polypeptides based on the principle of G-matrix Fourier transform NMR spectroscopy and quantitative J-correlation. These experiments, which facilitate fast acquisition of three-dimensional data with high spectral/digital resolution and chemical shift dispersion, will provide renewed opportunities to utilize them for sequence specific resonance assignments, estimation/characterization of secondary structure with/without prior knowledge of resonance assignments, stereospecific assignment of prochiral groups and 3D structure determination, refinement and validation. Taken together, these experiments have a wide range of applications from structural genomics projects to studying structure and folding in polypeptides.

  3. Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

    PubMed

    Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

    2015-01-06

    The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

  4. Accurate coupled cluster reaction enthalpies and activation energies for X+H2 --> XH+H (X=F, OH, NH2, and CH3)

    NASA Astrophysics Data System (ADS)

    Kraka, Elfi; Gauss, Jürgen; Cremer, Dieter

    1993-10-01

    Coupled cluster calculations at the CCSD(T)/[5s4p3d/4s3p] and CCSD(T)/[5s4p3d2 f1g/4s3p2d] level of theory are reported for reactions X+H2→XH+H [X=F (1a), OH (1b), NH2 (1c), and CH3 (1d)] utilizing analytical energy gradients for geometry, frequency, charge distribution, and dipole moment calculations of reactants, transition states, and products. A careful analysis of vibrational corrections leads to reaction enthalpies at 300 K, which are within 0.04, 0.15, 0.62, and 0.89 kcal/mol of experimental values. For reaction (1a) a bent transition state and for reactions (1b) and (1c) transition states with a cis arrangement of the reactants are calculated. The cis forms of transition states (1b) and (1c) are energetically favored because of electrostatic interactions, in particular dipole-dipole attraction as is revealed by calculated charge distributions. For reactions (1a)-(1d), the CCSD(T)/[5s4p3d2 f1g/4s3p2d] activation energies at 300 K are 1.1, 5.4, 10.8, and 12.7 kcal/mol which differ by just 0.1, 1.4, 2.3, and 1.8 kcal/mol, respectively, from the corresponding experimental values of 1±0.1, 4±0.5, 8.5±0.5, and 10.9±0.5 kcal/mol. For reactions (1), this is the best agreement between experiment and theory that has been obtained from ab initio calculations not including any empirically based corrections. Agreement is achieved after considering basis set effects, basis set superposition errors, spin contamination, tunneling effect and, in particular, zero-point energies as well as temperature corrections. Net corrections for the four activation energies are -1.05, -0.2, 1.25, and 0.89 kcal/mol, which shows that for high accuracy calculations a direct comparison of classical barriers and activation energies is misleading.

  5. Solid-State Synthesis and Structure of the Enigmatic Ammonium Octaborate: (NH4)2[B7O9(OH)5]·3/4B(OH)3·5/4H2O.

    PubMed

    Neiner, Doinita; Sevryugina, Yulia V; Schubert, David M

    2016-09-06

    The compound known since the 19th century as ammonium octaborate was structurally characterized revealing the ammonium salt of the ribbon isomer of the heptaborate anion, [B7O9(OH)5](2-), with boric acid and water molecules. Of composition (NH4)2B7.75O12.63·4.88H2O, it approximates the classical ammonium octaborate composition (NH4)2B8O13·6H2O and has the structural formula {(NH4)2[B7O9(OH)5]}4·3B(OH)3·5H2O. It spontaneously forms at room temperature in solid-state mixtures of ammonium tetraborate and ammonium pentaborate. It crystallizes in the monoclinic space group P21/c with a = 11.4137(2) Å, b = 11.8877(2) Å, c = 23.4459(3) Å, β = 90.092(1)°, V = 3181.19(8) Å(3), and Z = 2 and contains well-ordered ammonium cations and [B7O9(OH)5](2-) anions and disordered B(OH)3 and H2O molecules linked by extensive H bonding. Expeditious solid-state formation of the heptaborate anion under ambient conditions has important implications for development of practical syntheses of industrially useful borates.

  6. Process-based modelling of NH3 exchange with grazed grasslands

    NASA Astrophysics Data System (ADS)

    Móring, Andrea; Vieno, Massimo; Doherty, Ruth M.; Milford, Celia; Nemitz, Eiko; Twigg, Marsailidh M.; Horváth, László; Sutton, Mark A.

    2017-09-01

    In this study the GAG model, a process-based ammonia (NH3) emission model for urine patches, was extended and applied for the field scale. The new model (GAG_field) was tested over two modelling periods, for which micrometeorological NH3 flux data were available. Acknowledging uncertainties in the measurements, the model was able to simulate the main features of the observed fluxes. The temporal evolution of the simulated NH3 exchange flux was found to be dominated by NH3 emission from the urine patches, offset by simultaneous NH3 deposition to areas of the field not affected by urine. The simulations show how NH3 fluxes over a grazed field in a given day can be affected by urine patches deposited several days earlier, linked to the interaction of volatilization processes with soil pH dynamics. Sensitivity analysis showed that GAG_field was more sensitive to soil buffering capacity (β), field capacity (θfc) and permanent wilting point (θpwp) than the patch-scale model. The reason for these different sensitivities is dual. Firstly, the difference originates from the different scales. Secondly, the difference can be explained by the different initial soil pH and physical properties, which determine the maximum volume of urine that can be stored in the NH3 source layer. It was found that in the case of urine patches with a higher initial soil pH and higher initial soil water content, the sensitivity of NH3 exchange to β was stronger. Also, in the case of a higher initial soil water content, NH3 exchange was more sensitive to the changes in θfc and θpwp. The sensitivity analysis showed that the nitrogen content of urine (cN) is associated with high uncertainty in the simulated fluxes. However, model experiments based on cN values randomized from an estimated statistical distribution indicated that this uncertainty is considerably smaller in practice. Finally, GAG_field was tested with a constant soil pH of 7.5. The variation of NH3 fluxes simulated in this way

  7. Synthesis and structure of heptaaqua(nitrilotris(methylenephosphonato))(dibarium)sodium monohydrate [Na(H{sub 2}O){sub 3}(μ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(μ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O

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

    Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: xps@ftiudm.ru; Zakirova, R. M., E-mail: ftt@udsu.ru

    Crystals of the monohydrate form of heptaaqua(nitrilotris(methylenephosphonato))(dibarium) sodium [Na(H{sub 2}O{sub )3}(µ{sup 6}-NH(CH{sub 2}PO{sub 3}){sub 3})(µ-H{sub 2}O){sub 3}Ba{sub 2}(H{sub 2}O)] · H{sub 2}O are obtained; space group P2{sub 1}/c, Z = 4; a = 13.9117(10) Å, b = 11.54030(10) Å, and c = 24.1784(17) Å, ß = 148.785(18)°. The Na atom is coordinated octahedrally by one oxygen atom of a phosphonate group and five water molecules, including two bridging molecules. Ba atoms occupy two inequivalent crystallographic positions with coordination number eight and nine. The coordination spheres of both Ba atoms include two water molecules. Each ligand is bound to one Namore » atom and five Ba atoms forming three Ba–O–P–O and five Ba–O–P–C–N–C–P–O chelate cycles. In addition to the coordination bonds, molecules, including the solvate water molecule, are involved in hydrogen bonds in the crystal packing.« less

  8. Sulfonyl chlorides as an efficient tool for the postsynthetic modification of Cr-MIL-101-SO3H and CAU-1-NH2.

    PubMed

    Klinkebiel, Arne; Reimer, Nele; Lammert, Martin; Stock, Norbert; Lüning, Ulrich

    2014-08-25

    Postsynthetic modification can be used to introduce sulfonamide functionalities into MOF frameworks. Using sulfonyl chlorides as reactive intermediates, Cr-MIL-SO3H and CAU-1-NH2 have been further modified to give hitherto unknown functionalized MOFs in which a sulfonamide group is bound to the framework either by its N or its S atom.

  9. Endohedral complexes of fullerene-like silica molecules with H2O, CH4, and CH3NH2 molecules

    NASA Astrophysics Data System (ADS)

    Filonenko, O. V.; Lobanov, V. V.

    2013-07-01

    The possibility of formation of (SiO2)60@H2O, (SiO2)60@CH4, and (SiO2)60@CH3NH2 endohedral complexes was studied by the density functional (DFT) method (B3LYP exchange correlation functional, 6-31G** basis). The penetration of these molecules into the cavity of fullerene-like silica molecules is hindered by high activation barriers, which ensures the stability of the complexes formed during the synthesis of these molecules.

  10. A highly stable two-dimensional copper(II)-organic framework for proton conduction and ammonia impedance sensing.

    PubMed

    Sun, Zhibing; Yu, Shihang; Zhao, Lili; Wang, Jifeng; Li, Zifeng; Li, Gang

    2018-05-22

    This work reports on the design and fabrication of a proton conductive 2D MOF, [Cu(p-IPhHIDC)]n (1) (p-IPhH3IDC = 2-(p-N-imidazol-1-yl)-phenyl-1H-imidazole-4,5dicarboxylic acid) as an advanced ammonia impedance sensor at room temperature and 68-98% RHs. MOF 1 shows the optimized proton conductivity value of 1.51 × 10-3 S·cm-1 at 100 C and 98% RH. Its temperature-dependent and humidity-dependent proton conduction properties have been explored. The large amount of uncoordinated carboxylate groups between the layers play a vital role in the resultant conductivity. Distinctly, the fabricated MOF-based sensor displays the required stability to NH3, enhanced sensitivity and notable selectivity to NH3 gas. At room temperature and 68% RH, it indicates a remarkable gas response of 8620% to 130 ppm of NH3 gas and lower detection limit (2 ppm) towards NH3 gas. It is also found that the gas response of the ammonia sensor increases linearly with the increase of NH3 gas concentration under 68-98% RHs and room temperature. Moreover, the sensor indicates excellent reversibility and selectivity toward NH3 vs N2, H2, O2, CO, CO2, benzene and MeOH. Based on structural analyses, activation energy calculations, water and NH3 vapor absorptions, and PXRD determinations, the proton conduction and NH3 sensing mechanisms are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Combining anti-cancer drugs with artificial sweeteners: synthesis and anti-cancer activity of saccharinate (sac) and thiosaccharinate (tsac) complexes cis-[Pt(sac)2(NH3)2] and cis-[Pt(tsac)2(NH3)2].

    PubMed

    Al-Jibori, Subhi A; Al-Jibori, Ghassan H; Al-Hayaly, Lamaan J; Wagner, Christoph; Schmidt, Harry; Timur, Suna; Baris Barlas, F; Subasi, Elif; Ghosh, Shishir; Hogarth, Graeme

    2014-12-01

    The new platinum(II) complexes cis-[Pt(sac)2(NH3)2] (sac=saccharinate) and cis-[Pt(tsac)2(NH3)2] (tsac=thiosaccharinate) have been prepared, the X-ray crystal structure of cis-[Pt(sac)2(NH3)2] x H2O reveals that both saccharinate anions are N-bound in a cis-arrangement being inequivalent in both the solid-state and in solution at room temperature. Preliminary anti-cancer activity has been assessed against A549 human alveolar type-II like cell lines with the thiosaccharinate complex showing good activity. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. A robust viologen and Mn-based porous coordination polymer with two types of Lewis acid sites providing high affinity for H2O, CO2 and NH3.

    PubMed

    Leblanc, A; Mercier, N; Allain, M; Dul, M-C; Weber, G; Geoffroy, N; Bellat, J-P; Bezverkhyy, I

    2017-11-21

    A novel porous coordination polymer [Mn(pc3)(H 2 O) 2 ]·xH 2 O (3 < x < 4) is synthesized in water at pH = 7 using the anionic viologen-carboxylate ligand 4,4'-bipyridinium,1,1'-bis-(2,4-dicarboxyphenyl) (pc3 2- ). Dehydration of the material results in the formation of open pores containing two types of accessible Lewis acid sites: exposed Mn 2+ cations and N + atoms of viologen units. Due to this property the PCP shows high affinity and capacity in the adsorption of H 2 O, CO 2 and NH 3 . Despite the presence of strong adsorption sites this material is stable in liquid water and in gaseous NH 3 .

  13. Experimental ammonia-free phosphate-bonded investments using Mg(H2PO4)2 solution.

    PubMed

    Takashiba, Shigeyuki; Zhang, Zutai; Tamaki, Yukimichi

    2002-12-01

    In our previous study, we investigated ammonia-free phosphate-bonded investments using Mg (H2PO4)2 powder. The purpose of the present study was to attempt usage of 50 wt% Mg (H2PO4)2 solution instead of powder. Magnesium oxide (MgO) was prepared as a binder and cristobalite was selected as a refractory. After arranging six kinds of experimental investments (A-F) with different cristobalite/MgO ratios, the fundamental properties of the dental investments were examined. The properties of the molds were influenced by the amount of MgO. Decreases in MgO showed lower mold strengths, longer setting time and larger setting expansion. According to XRD analysis, the peaks of MgH(PO4)3 x 3H2O newly formed, cristobalite and MgO were detected in the A set, but MgO peaks in F set were reduced. On the other hand, the surface of F was entirely covered by phosphorus. From these results, it was found that the usage of Mg(H2PO4)2 solution was possible for ammonia-free investments.

  14. Ammonia Vapor Removal by Cu3(BTC)2 and Its Characterization by MAS NMR

    DTIC Science & Technology

    2009-01-01

    Experimental Section Materials. Cu(acetate)2(H2O), Cu(L-tartrate)3(H2O)3, Cu( CO3 )- Cu(OH)2, 1,3,5-benzenetricarboxylic acid, NH4HCO3, and N,N...for 3 days. The crystals were activated under high vacuum at a temperature of 170 °C. Nitrogen Adsorption Equilibria. Nitrogen adsorption equi- libria...solid (NH4)3BTC. 13C CP-MAS NMR confirmed the identity and purity of the trisubstituted material. BTC-Cu( CO3 )Cu(OH)2-NH4HCO3 Reaction. BTC (100 mg, 480

  15. A photochemical study of the kinetics of the reactions of NH2 with phosphine, ethylene, and acetylene using flash photolysis-laser induced fluorescence. Ph.D. Thesis Catholic Univ. of America; [ammonia in the atmosphere of Jupiter

    NASA Technical Reports Server (NTRS)

    Bosco, S. R.

    1982-01-01

    The photochemistry of the reactions of NH2 was investigated in an attempt to explain the existence of an abundance of ammonia in the Jovian atmosphere. The production of ammonia reservoirs from the coupling of ammonia with other atmospheric constituents was considered. The rate constants for the reactions of NH2 radicals with phosphine, acetylene, and ethylene were measured. Flash photolysis was used for the production of NH2 radicals and laser induced fluorescence was employed for radical detection. It was determined that the rates of the reactions were too slow to be significant as a source of ammonia reservoirs in the Jovian atmosphere.

  16. Controlled precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3

    NASA Astrophysics Data System (ADS)

    Wang, Yong; Li, Zhibao; Demopoulos, George P.

    2008-03-01

    In this study, homogeneous (unseeded) precipitation of nesquehonite (MgCO 3·3H 2O) by the reaction of MgCl 2 with (NH 4) 2CO 3 in supersaturated solutions was investigated. Factors that influence the precipitation of MgCO 3·3H 2O, such as reaction temperature, initial concentration, stirring speed, titration speed, equilibration time, have been studied. SEM images and particle size distribution show that the temperature, initial concentration and titration speed have significant effect on nesquehonite's crystal morphology and particle size. In addition, stirring speed and equilibration time also have some influence on its properties. X-ray powder diffraction (XRD) results show that the obtained crystals compositions are greatly affected by the reaction temperature. With the morphological transformation, their corresponding composition also change from MgCO 3· xH 2O to Mg 5(CO 3) 4(OH) 2·4H 2O in the interval of 288-333 K. With the optimization of operating conditions, the crystals can grow up to a length of about 40 μm and a width of 5 μm, indicating good filtration properties. High-purity nesquehonite obtained in this study was calcined to produce highly pure MgO at 1073 K as shown by XRD results.

  17. Catalytic Silylation of N 2 and Synthesis of NH 3 and N 2H 4 by Net Hydrogen Atom Transfer Reactions Using a Chromium P 4 Macrocycle

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

    Kendall, Alexander J.; Johnson, Samantha I.; Bullock, R. Morris

    We report the first discrete molecular Cr-based catalysts for the reduction of N2. This study is focused on the reactivity of the Cr-N2 complex, trans-[Cr(N2)2(PPh4NBn4)] P4Cr(N2)2, bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-PPh4NBn4 ligand is critical to preserve the structural integrity of the catalyst. P4Cr(N2)2 was found to mediate the reduction of N2 by three complementary reaction pathways: (1) Cr-catalyzed reduction of N2 to N(SiMe3)3 by Na and Me3SiCl affording up to 34 equiv N(SiMe3)3; (2) stoichiometric reduction of N2 by protons and electrons. For example, the reaction of cobaltocene (CoCp2) and collidinium triflate (ColH[OTf]) at roommore » temperature to afforded 1.9 equiv of NH3, or at -78 °C to afforded a mixture of NH3 and N2H4; (3) the first example of NH3 formation from the reaction of a terminally bound N2 ligand with a traditional H atom source, TEMPOH, (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr(15N2)2(PPh4NBn4)] reacts with excess TEMPOH to afford a 1.4 equiv of 15NH3.« less

  18. Study of the structural phase transitions of (CH 3NH 3) 3Sb 2Cl 9 (MACA) and (CH 3NH 3) 3Bi 2Cl 9 (MACB) by infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Bator, G.; Jakubas, R.; Malarski, Z.

    1991-06-01

    Infrared spectra of polycrystalline (CH 3NH 3) 3Sb 2Cl 9 and (CH 3NH 3) 3Bi 2Cl 9 have been studied in the temperature range 90-300 K. A systematic temperature dependence study of the internal modes has been carried out. We discuss the effects of the dynamic state of methylammonium (MA) cations on their vibrational spectra. The results show that the dynamics of MA cations in both compounds is similar in higher (about 300 K) and lower temperature (in the vicinity of 100 K) regions. Substantial differences are revealed in the intermediate temperature interval. The results are in good agreement with earlier dielectric, calorimetric and 1H NMR studies.

  19. Biochar-induced concomitant decrease in ammonia volatilization and increase in nitrogen use efficiency by wheat.

    PubMed

    Mandal, Sanchita; Thangarajan, Ramya; Bolan, Nanthi S; Sarkar, Binoy; Khan, Naser; Ok, Yong Sik; Naidu, Ravi

    2016-01-01

    Ammonia (NH3) volatilization is a major nitrogen (N) loss from the soil, especially under tropical conditions, NH3 volatilization results in low N use efficiency by crops. Incubation experiments were conducted using five soils (pH 5.5-9.0), three N sources such as, urea, di-ammonium phosphate (DAP), and poultry manure (PM) and two biochars such as, poultry litter biochar (PL-BC) and macadamia nut shell biochar (MS-BC). Ammonia volatilization was higher at soil with higher pH (pH exceeding 8) due to the increased hydroxyl ions. Among the N sources, urea recorded the highest NH3 volatilization (151.6 mg kg(-1)soil) followed by PM (124.2 mg kg(-1)soil) and DAP (99 mg kg(-1)soil). Ammonia volatilization was reduced by approximately 70% with PL-BC and MS-BC. The decreased NH3 volatilization with biochars is attributed to multiple mechanisms such as NH3 adsorption/immobilization, and nitrification. Moreover, biochar increased wheat dry weight and N uptake as high as by 24.24% and 76.11%, respectively. This study unravels the immense potential of biochar in decreasing N volatilization from soils and simultaneously improving use efficiency by wheat. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).

    PubMed

    Wu, Xiao-Peng; Sun, Xiao-Ming; Wei, Xi-Guang; Ren, Yi; Wong, Ning-Bew; Li, Wai-Kee

    2009-06-09

    The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.

  1. Myocardial perfusion quantification using simultaneously acquired 13 NH3 -ammonia PET and dynamic contrast-enhanced MRI in patients at rest and stress.

    PubMed

    Kunze, Karl P; Nekolla, Stephan G; Rischpler, Christoph; Zhang, Shelley HuaLei; Hayes, Carmel; Langwieser, Nicolas; Ibrahim, Tareq; Laugwitz, Karl-Ludwig; Schwaiger, Markus

    2018-04-19

    Systematic differences with respect to myocardial perfusion quantification exist between DCE-MRI and PET. Using the potential of integrated PET/MRI, this study was conceived to compare perfusion quantification on the basis of simultaneously acquired 13 NH 3 -ammonia PET and DCE-MRI data in patients at rest and stress. Twenty-nine patients were examined on a 3T PET/MRI scanner. DCE-MRI was implemented in dual-sequence design and additional T 1 mapping for signal normalization. Four different deconvolution methods including a modified version of the Fermi technique were compared against 13 NH 3 -ammonia results. Cohort-average flow comparison yielded higher resting flows for DCE-MRI than for PET and, therefore, significantly lower DCE-MRI perfusion ratios under the common assumption of equal arterial and tissue hematocrit. Absolute flow values were strongly correlated in both slice-average (R 2  = 0.82) and regional (R 2  = 0.7) evaluations. Different DCE-MRI deconvolution methods yielded similar flow result with exception of an unconstrained Fermi method exhibiting outliers at high flows when compared with PET. Thresholds for Ischemia classification may not be directly tradable between PET and MRI flow values. Differences in perfusion ratios between PET and DCE-MRI may be lifted by using stress/rest-specific hematocrit conversion. Proper physiological constraints are advised in model-constrained deconvolution. © 2018 International Society for Magnetic Resonance in Medicine.

  2. Was early Mars warmed by ammonia?

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.; Brown, L. L.; Acord, J. M.; Pollack, J. B.

    1992-01-01

    Runoff channels and valley networks present on ancient, heavily cratered Martian terrain suggests that the climate of Mars was originally warm and wet. One explanation for the formation of these channels is that the surface was warmed by the greenhouse effect of a dense, CO2 atmosphere. However, recent work shows that this theory is not consistent for the early period of the solar system. One way to increase the surface temperature predicted is to assume that other greenhouse gases were present in Mars' atmosphere in addition to CO2 and H2O. This possible gas is ammonia, NH3. If ammonia was present in sufficient quantities, it could have raised the surface temperature to 273 K. An adequate source would have been volcanic outgassing if the NH3 produced was shielded from photolysis by an ultraviolet light absorber.

  3. Air-stable hydrogen generation materials and enhanced hydrolysis performance of MgH2-LiNH2 composites

    NASA Astrophysics Data System (ADS)

    Ma, Miaolian; Ouyang, Liuzhang; Liu, Jiangwen; Wang, Hui; Shao, Huaiyu; Zhu, Min

    2017-08-01

    Hydrolysis of materials in water can be a promising solution of onsite hydrogen generation for realization of hydrogen economy. In this work, it was the first time that the MgH2-LiNH2 composites were explored as air-stable hydrolysis system for hydrogen generation. The MgH2-LiNH2 composites with different composition ratios were synthesized by ball milling with various durations and the hydrogen generation performances of the composite samples were investigated and compared. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy techniques were adopted to elucidate the performance improvement mechanisms. The hydrolysis properties of MgH2 were found to be significantly enhanced by the introduction of LiNH2. The 4MgH2-LiNH2 composite ball milled for 5 h can generate 887.2 mL g-1 hydrogen in 1 min and 1016 mL g-1 in 50 min, one of the best results so far for Mg based hydrolysis materials. The LiOH·H2O and NH4OH phases of hydrolysis products from LiNH2 may prevent formation of Mg(OH)2 passivation layer on the surface and supply enough channels for hydrolysis of MgH2. The MgH2-LiNH2 composites appeared to be very stable in air and no obvious negative effect on kinetics and hydrogen generation yield was observed. These good performances demonstrate that the studied MgH2-LiNH2 composites can be a promising and practicable hydrogen generation system.

  4. Tuneable diode laser spectroscopy correction factor investigation on ammonia measurement

    NASA Astrophysics Data System (ADS)

    Li, Nilton; El-Hamalawi, Ashraf; Baxter, Jim; Barrett, Richard; Wheatley, Andrew

    2018-01-01

    Current diesel engine aftertreatment systems, such as Selective Catalyst Reduction (SCR) use ammonia (NH3) to reduce Nitrogen Oxides (NOx) into Nitrogen (N2) and water (H2O). However, if the reaction between NH3 and NOx is unbalanced, it can lead either NH3 or NOx being released into the environment. As NH3 is classified as a dangerous compound in the environment, its accurate measurement is essential. Tuneable Diode Laser (TDL) spectroscopy is one of the methods used to measure raw emissions inside engine exhaust pipes, especially NH3. This instrument requires a real-time exhaust temperature, pressure and other interference compounds in order to adjust itself to reduce the error in NH3 readings. Most researchers believed that exhaust temperature and pressure were the most influential factors in TDL when measuring NH3 inside exhaust pipes. The aim of this paper was to quantify these interference effects on TDL when undertaking NH3 measurement. Surprisingly, the results show that pressure was the least influential factor when compared to temperature, H2O, CO2 and O2 when undertaking NH3 measurement using TDL.

  5. Ammonia-water mixtures at high pressures - Melting curves of ammonia dihydrate and ammonia monohydrate and a revised high-pressure phase diagram for the water-rich region. [in primordial solar system ices

    NASA Technical Reports Server (NTRS)

    Boone, S.; Nicol, M. F.

    1991-01-01

    The phase relations of some mixtures of ammonia and water are investigated to create a phase diagram in pressure-temperature-composition space relevant to the geophysical study of bodies in the outer solar system. The mixtures of NH3(x)H2O(1-x), where x is greater than 0.30 but less than 0.51, are examined at pressures and temperatures ranging from 0-6.5 GPa and 125-400 K, respectively. The ruby luminescence technique monitors the pressure and a diamond-anvil cell compresses the samples, and the phases are identified by means of normal- and polarized-light optical microscopy. The melting curve for NH3H2O(2) is described by the equation T = 176 + 60P - 8.5P squared for the ranges of 0.06-1.4 GPa and 179-243 K. The equation for NH3H2O is T = 194 + 37P - P squared, which represents a minor correction of a previous description by Johnson et al. (1985). Observed phase transitions are consistent with the high-pressure stability limit of NH3H2O(2), and the transition boundary is found to be linear.

  6. Biogas upgrading by chemical absorption using ammonia rich absorbents derived from wastewater.

    PubMed

    McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

    2014-12-15

    The use of ammonia (NH3) rich wastewaters as an ecological chemical absorption solvent for the selective extraction of carbon dioxide (CO2) during biogas upgrading to 'biomethane' has been studied. Aqueous ammonia absorbents of up to 10,000 gNH3 m(-3) demonstrated CO2 absorption rates higher than recorded in the literature for packed columns using 20,000-80,000 g NH3 m(-3) which can be ascribed to the process intensification provided by the hollow fibre membrane contactor used in this study to support absorption. Centrifuge return liquors (2325 g m(-3) ionised ammonium, NH4(+)) and a regenerant (477 gNH4(+) m(-3)) produced from a cationic ion exchanger used to harvest NH4(+) from crude wastewater were also tested. Carbon dioxide fluxes measured for both wastewaters compared reasonably with analogue ammonia absorption solvents of equivalent NH3 concentration. Importantly, this demonstrates that ammonia rich wastewaters can facilitate chemically enhanced CO2 separation which eliminates the need for costly exogenic chemicals or complex chemical handling which are critical barriers to implementation of chemical absorption. When testing NH3 analogues, the potential to recover the reaction product ammonium bicarbonate (NH4HCO3) in crystalline form was also illustrated. This is significant as it suggests a new pathway for ammonia separation which avoids biological nitrification and produces ammonia stabilised into a commercially viable fertiliser (NH4HCO3). However, in real ammonia rich wastewaters, sodium bicarbonate and calcium carbonate were preferentially formed over NH4HCO3 although it is proposed that NH4HCO3 can be preferentially formed by manipulating both ion exchange and absorbent chemistry. Copyright © 2014. Published by Elsevier Ltd.

  7. Processing of ammonia-containing ices by heavy ions and its relevance to outer Solar System surfaces

    NASA Astrophysics Data System (ADS)

    Pilling, Sergio; Seperuelo Duarte, Eduardo; da Silveira, Enio F.; Domaracka, Alicja; Balanzat, Emmanuel; Rothard, Hermann; Boduch, Philippe

    Ammonia-containing ices have been detected or postulated as important components of the icy surfaces of planetary satellites (e.g. Enceladus, Miranda), in the outer Solar System objects (e.g. Charon, Quaoar) and in Oort cloud comets. We present experimental studies of the interaction of heavy, highly-charged, and energetic ions with ammonia-containing ices (pure NH3 ; NH3 :CO; NH3 :H2 O and NH3 :H2 O:CO) in an attempt to simulate the physical chemistry induced by heavy-ion cosmic rays and heavy-ion solar wind particles at outer Solar System surfaces. The measurements were performed inside a high vacuum chamber at the heavy-ion accelerator GANIL (Grand Accelerateur National d'Ions Lourds) in Caen, France. The gas samples were deposited onto a polished CsI substrate previously cooled to 13 K. In-situ analysis was performed by a Fourier transform infrared spectrometer (FTIR) at different ion fluences. The dissociation cross-section and sputtering yield of ammonia and other ice compounds have been determined. Half-life of frozen ammonia due to heavy ion bombardment at different Solar System surfaces has been estimated. Radiolysis products have been identified and their implications for the chemistry on outer Solar System surfaces are discussed.

  8. Ammonia as a Temperature Tracer in the Ultraluminous Galaxy Merger Arp 220

    NASA Astrophysics Data System (ADS)

    Ott, Jürgen; Henkel, Christian; Braatz, James A.; Weiß, Axel

    2011-12-01

    We present Australia Telescope Compact Array (ATCA) and Robert C. Byrd Green Bank Telescope (GBT) observations of ammonia (NH3) and the 1.2 cm radio continuum toward the ultraluminous infrared galaxy merger Arp 220. We detect the NH3(1,1), (2,2), (3,3), (4,4), (5,5), and (6,6) inversion lines in absorption against the unresolved, (62 ± 9) mJy continuum source at 1.2 cm. The peak apparent optical depths of the ammonia lines range from ~0.05 to 0.18. The absorption lines are well described by single-component Gaussians with central velocities in between the velocities of the eastern and western cores of Arp 220. Therefore, the ammonia likely traces gas that encompasses both cores. The absorption depth of the NH3(1,1) line is significantly shallower than expected based on the depths of the other transitions. The shallow (1,1) profile may be caused by contamination from emission by a hypothetical, cold (lsim 20 K) gas layer with an estimated column density of <~ 2 × 1014 cm-2. This layer would have to be located behind or away from the radio continuum sources to produce the contaminating emission. The widths of the ammonia absorption lines are ~120-430 km s-1, in agreement with those of other molecular tracers. We cannot confirm the extremely large line widths of up to ~1800 km s-1 previously reported for this galaxy. Using all of the ATCA detections except for the shallow (1,1) line, we determine a rotational temperature of (124 ± 19) K, corresponding to a kinetic temperature of T kin = (186 ± 55) K. Ammonia column densities depend on the excitation temperature. For excitation temperatures of 10 K and 50 K, we estimate N(NH3) = (1.7 ± 0.1) × 1016 cm-2 and (8.4 ± 0.5) × 1016 cm-2, respectively. The relation scales linearly for possible higher excitation temperatures. Our observations are consistent with an ortho-to-para-ammonia ratio of unity, implying that the ammonia formation temperature exceeds ~30 K. In the context of a model with a molecular ring that

  9. Catalytic Silylation of N2 and Synthesis of NH3 and N2H4 by Net Hydrogen Atom Transfer Reactions Using a Chromium P4 Macrocycle.

    PubMed

    Kendall, Alexander J; Johnson, Samantha I; Bullock, R Morris; Mock, Michael T

    2018-02-21

    We report the first discrete molecular Cr-based catalysts for the reduction of N 2 . This study is focused on the reactivity of the Cr-N 2 complex, trans-[Cr(N 2 ) 2 (P Ph 4 N Bn 4 )] (P 4 Cr(N 2 ) 2 ), bearing a 16-membered tetraphosphine macrocycle. The architecture of the [16]-P Ph 4 N Bn 4 ligand is critical to preserve the structural integrity of the catalyst. P 4 Cr(N 2 ) 2 was found to mediate the reduction of N 2 at room temperature and 1 atm pressure by three complementary reaction pathways: (1) Cr-catalyzed reduction of N 2 to N(SiMe 3 ) 3 by Na and Me 3 SiCl, affording up to 34 equiv N(SiMe 3 ) 3 ; (2) stoichiometric reduction of N 2 by protons and electrons (for example, the reaction of cobaltocene and collidinium triflate at room temperature afforded 1.9 equiv of NH 3 , or at -78 °C afforded a mixture of NH 3 and N 2 H 4 ); and (3) the first example of NH 3 formation from the reaction of a terminally bound N 2 ligand with a traditional H atom source, TEMPOH (2,2,6,6-tetramethylpiperidine-1-ol). We found that trans-[Cr( 15 N 2 ) 2 (P Ph 4 N Bn 4 )] reacts with excess TEMPOH to afford 1.4 equiv of 15 NH 3 . Isotopic labeling studies using TEMPOD afforded ND 3 as the product of N 2 reduction, confirming that the H atoms are provided by TEMPOH.

  10. Recovery of ammonia from swine manure using gas-permeable membranes: effect of aeration.

    PubMed

    García-González, M C; Vanotti, M B; Szogi, A A

    2015-04-01

    The gas-permeable membrane process can recover ammonia from manure, reducing pollution whilst converting ammonia into an ammonium salt fertilizer. The process involves manure pH control to increase ammonium (NH4(+)) recovery rate that is normally carried out using an alkali. In this study a new strategy to avoid the use of alkali was tested applying low-rate aeration and nitrification inhibition. The wastewater used was raw swine manure with 2390 mg NH4(+)-N/L. Results showed that aeration increased pH above 8.5 allowing quick transformation of NH4(+) into gaseous ammonia (NH3) and efficient recovery by permeation through the submerged membrane. The overall NH4(+) recovery obtained with aeration was 98% and ammonia emissions losses were less than 1.5%. The new approach can substitute large amounts of alkali chemicals needed to obtain high NH4(+) recovery with important economic and environmental savings. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Atmospheric ammonia and its impacts on regional air quality over the megacity of Shanghai, China

    PubMed Central

    Wang, Shanshan; Nan, Jialiang; Shi, Chanzhen; Fu, Qingyan; Gao, Song; Wang, Dongfang; Cui, Huxiong; Saiz-Lopez, Alfonso; Zhou, Bin

    2015-01-01

    Atmospheric ammonia (NH3) has great environmental implications due to its important role in ecosystem and global nitrogen cycle, as well as contribution to secondary particle formation. Here, we report long-term continuous measurements of NH3 at different locations (i.e. urban, industrial and rural) in Shanghai, China, which provide an unprecedented portrait of temporal and spatial characteristics of atmospheric NH3 in and around this megacity. In addition to point emission sources, air masses originated from or that have passed over ammonia rich areas, e.g. rural and industrial sites, increase the observed NH3 concentrations inside the urban area of Shanghai. Remarkable high-frequency NH3 variations were measured at the industrial site, indicating instantaneous nearby industrial emission peaks. Additionally, we observed strong positive exponential correlations between NH4+/(NH4++NH3) and sulfate-nitrate-ammonium (SNA) aerosols, PM2.5 mass concentrations, implying a considerable contribution of gas-to-particle conversion of ammonia to SNA aerosol formation. Lower temperature and higher humidity conditions were found to favor the conversion of gaseous ammonia to particle ammonium, particularly in autumn. Although NH3 is currently not included in China’s emission control policies of air pollution precursors, our results highlight the urgency and importance of monitoring gaseous ammonia and improving its emission inventory in and around Shanghai. PMID:26514559

  12. Branchial ammonia excretion in the Asian weatherloach Misgurnus anguillicaudatus.

    PubMed

    Moreira-Silva, J; Tsui, T K N; Coimbra, J; Vijayan, M M; Ip, Y K; Wilson, J M

    2010-01-01

    The weatherloach, Misgurnus anguillicaudatus, is a freshwater, facultative air-breathing fish that lives in streams and rice paddy fields, where it may experience drought and/or high environmental ammonia (HEA) conditions. The aim of this study was to determine what roles branchial Na(+)/K(+)-ATPase, H(+)-ATPase, and Rhcg have in ammonia tolerance and how the weatherloach copes with ammonia loading conditions. The loach's high ammonia tolerance was confirmed as was evident from its high 96 h LC(50) value and high tissue tolerance to ammonia. The weatherloach does not appear to make use of Na(+)/NH(4)(+)-ATPase facilitated transport to excrete ammonia when exposed to HEA or to high environmental pH since no changes in activity were observed. Using immunofluorescence microscopy, distinct populations of vacuolar (V)-type H(+)-ATPase and Na(+)/K(+)-ATPase immunoreactive cells were identified in branchial epithelia, with apical and basolateral staining patterns, respectively. Rhesus C glycoprotein (Rhcg1), an ammonia transport protein, immunoreactivity was also found in a similar pattern as H(+)-ATPase. Rhcg1 (Slc42a3) mRNA expression also increased significantly during aerial exposure, although not significantly under ammonia loading conditions. The colocalization of H(+)-ATPase and Rhcg1 to the similar non-Na(+)/K(+)-ATPase immunoreactive cell type would support a role for H(+)-ATPase in ammonia excretion via Rhcg by NH(4)(+) trapping. The importance of gill boundary layer acidification in net ammonia excretion was confirmed in this fish; however, it was not associated with an increase in H(+)-ATPase expression, since tissue activity and protein levels did not increase with high environmental pH and/or HEA. However the V-ATPase inhibitor, bafilomycin, did decrease net ammonia flux whereas other ion transport inhibitors (amiloride, SITS) had no effect. H(+)-ATPase inhibition also resulted in a consequent elevation in plasma ammonia levels and a decrease in the net acid

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

    NASA Astrophysics Data System (ADS)

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

    1983-12-01

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

  14. Ammonia blood test

    MedlinePlus

    Serum ammonia; Encephalopathy - ammonia; Cirrhosis - ammonia; Liver failure - ammonia ... Ammonia (NH3) is produced by cells throughout the body, especially the intestines, liver, and kidneys. Most of ...

  15. Conformational Isomerism of trans-[Pt(NH2C6H11)2I2] and the Classical Wernerian Chemistry of [Pt(NH2C6H11)4]X2 (X = Cl, Br, I)1

    PubMed Central

    Johnstone, Timothy C.; Lippard, Stephen J.

    2012-01-01

    X-ray crystallographic analysis of the compound trans-[Pt(NH2C6H11)2I2] revealed the presence of two distinct conformers within one crystal lattice. This compound was studied by variable temperature NMR spectroscopy to investigate the dynamic interconversion between these isomers. The results of this investigation were interpreted using physical (CPK) and computational (molecular mechanics and density functional theory) models. The conversion of the salts [Pt(NH2C6H11)4]X2 into trans-[Pt(NH2C6H11)2X2] (X = Cl, Br, I) was also studied and is discussed here with an emphasis on parallels to the work of Alfred Werner. PMID:23554544

  16. A periodic DFT study of ammonia adsorption on the V2O5 (001), V2O5 (010) and V2O5 (100) surfaces: Lewis versus Brönsted acid sites

    NASA Astrophysics Data System (ADS)

    Yao, Huichao; Chen, Yu; Wei, Yuechang; Zhao, Zhen; Liu, Zhichang; Xu, Chunming

    2012-11-01

    The adsorption of ammonia at Brönsted and Lewis acid sites on three low-index (001), (010) and (100) surfaces of V2O5 catalyst was investigated using density functional theory (DFT) method. Three levels of surface relaxation periodic models including top single layer relaxation (S-model), moderately deeper relaxation (M-model) and full relaxation model (F-model) were applied to examine the effect of the surface relaxation on the binding structures and adsorption energies. The results of calculations showed that on the saturated basal plane V2O5 (001), ammonia adsorption at the Brönsted acid sites (VOH) is energetically more favorable. On unsaturated (010) and (100) surfaces, ammonia is adsorbed strongly on both Brönsted (VOH) and Lewis acid sites (V). Surface relaxations have no influence on ammonia adsorption on saturated (001) surface, while a strong dependence on the relaxation models is observed for NH3-adsorption energies on (010) and (100) surfaces, especially at the Lewis acid sites of both side planes. When complete relaxation considered (F-model), ammonia adsorption on the Lewis acid sites (V) dominates for side planes (010) and (100). In the presence of VOH as neighbor, the ammonia adsorption at V sites is however weakened significantly due to steric hindrance. Hydrogen bonds may play a role, although not determining one, in the respect of the adsorption of ammonia on (010) and (100) surfaces. Moderate relaxation and full relaxation are absolutely necessary for the description of both H and NH3 adsorption on unsaturated (100) and (010) surfaces, respectively.

  17. Effectiveness and reaction networks of H2O2 vapor with NH3 gas for decontamination of the toxic warfare nerve agent, VX on a solid surface.

    PubMed

    Gon Ryu, Sam; Wan Lee, Hae

    2015-01-01

    The nerve agent, O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) must be promptly eliminated following its release into the environment because it is extremely toxic, can cause death within a few minutes after exposure, acts through direct skin contact as well as inhalation, and persists in the environment for several weeks after release. A mixture of hydrogen peroxide vapor and ammonia gas was examined as a decontaminant for the removal of VX on solid surfaces at ambient temperature, and the reaction products were analyzed by gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance spectrometry (NMR). All the VX on glass wool filter disks was found to be eliminated after 2 h of exposure to the decontaminant mixtures, and the primary decomposition product was determined to be non-toxic ethyl methylphosphonic acid (EMPA); no toxic S-[2-(diisopropylamino)ethyl] methylphosphonothioic acid (EA-2192), which is usually produced in traditional basic hydrolysis systems, was found to be formed. However, other by-products, such as toxic O-ethyl S-vinyl methylphosphonothioate and (2-diisopropylaminoethyl) vinyl disulfide, were detected up to 150 min of exposure to the decontaminant mixture; these by-products disappeared after 3 h. The two detected vinyl byproducts were identified first in this study with the decontamination system of liquid VX on solid surfaces using a mixture of hydrogen peroxide vapor and ammonia gas. The detailed decontamination reaction networks of VX on solid surfaces produced by the mixture of hydrogen peroxide vapor and ammonia gas were suggested based on the reaction products. These findings suggest that the mixture of hydrogen peroxide vapor and ammonia gas investigated in this study is an efficient decontaminant mixture for the removal of VX on solid surfaces at ambient temperature despite the formation of a toxic by-product in the reaction process.

  18. Recovery of valuable metals from waste diamond cutters through ammonia-ammonium sulfate leaching

    NASA Astrophysics Data System (ADS)

    Xue, Ping; Li, Guang-qiang; Yang, Yong-xiang; Qin, Qin-wei; Wei, Ming-xing

    2017-12-01

    Copper and zinc were recovered from waste diamond cutters through leaching with an ammonia-ammonium sulfate system and air as an oxidant. The effects of experimental parameters on the leaching process were investigated, and the potential-pH ( E-pH) diagrams of Cu-NH3-SO4 2--H2O and Zn-NH3-SO4 2--H2O at 25°C were drawn. Results showed that the optimal parameters for the leaching reaction are as follows: reaction temperature, 45°C; leaching duration, 3 h; liquid-to-solid ratio, 50:1 (mL/g); stirring speed, 200 r/min; ammonia concentration, 4.0 mol/L; ammonium sulfate concentration, 1.0 mol/L; and air flow rate, 0.2 L/min. The results of the kinetics study indicated that the leaching is controlled by the surface chemical reaction at temperatures below 35°C, and the leaching is controlled by diffusion through the product layer at temperatures above 35°C.

  19. Demonstrating hydrogen production from ammonia using lithium imide - Powering a small proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Hunter, Hazel M. A.; Makepeace, Joshua W.; Wood, Thomas J.; Mylius, O. Simon; Kibble, Mark G.; Nutter, Jamie B.; Jones, Martin O.; David, William I. F.

    2016-10-01

    Accessing the intrinsic hydrogen content within ammonia, NH3, has the potential to play a very significant role in the future of a CO2-free sustainable energy supply. Inexpensive light metal imides and amides are effective at decomposing ammonia to hydrogen and nitrogen (2NH33H2 + N2), at modest temperatures, and thus represent a low-cost approach to on-demand hydrogen production. Building upon this discovery, this paper describes the integration of an ammonia cracking unit with a post-reactor gas purification system and a small-scale PEM fuel cell to create a first bench-top demonstrator for the production of hydrogen using light metal imides.

  20. Effective identification of (NH4)2CO3 and NH4HCO3 concentrations in NaHCO3 regeneration process from desulfurized waste.

    PubMed

    Govindan, Muthuraman; Karunakaran, Kannan; Nallasamy, Palanisami; Moon, Il Shik

    2015-01-01

    This work describes the quantitative analysis of (NH4)2CO3 and NH4HCO3 using a simple solution phase titration method. Back titration results at various (NH4)2CO3-NH4HCO3 ratios demonstrated that 6:4 ratio caused a 3% error in their differentiation, but very high errors were found at other ratios. A similar trend was observed for the double indicator method, especially when strong acid HCl was used as a titrant, where still less errors (2.5%) at a middle ratio of (NH4)2CO3-NH4HCO3 was found. Remaining ratios with low (NH4)2CO3 (2:8, 4:6) show high +ve error (found concentration is less) and high (NH4)2CO3 (7:3, 8:2, and 9:1) show high -ve error (found concentration is higher) and vice versa for NH4HCO3. In replacement titration using Na2SO4, at both higher end ratios of (NH4)2CO3-NH4HCO3 (2:8 and 9:1), both -ve and +ve errors were minimized to 75% by partial equilibrium arrest between (NH4)2CO3 and NH2COONH4, instead of more than 100% observed in back titration and only double indicator methods. In the presence of (NH4)2SO4 both -ve and +ve error% are completely reduced to 3±1 at ratios 2:8, 4:6, and 6:4 of (NH4)2CO3-NH4HCO3, which demonstrates that the equilibrium transformation between NH2COONH4 and (NH4)2CO3 is completely controlled. The titration conducted at lower temperature (5 °C) in the presence of (NH4)2SO4 at higher ratios of (NH4)2CO3-NH4HCO3 (7:3, 8:2,and 9:1) shows complete minimization of both -ve and +ve errors to 2±1%, which explains the complete arresting of equilibrium transformation. Finally, the developed method shows 2±1% error in differentiation of CO3(2-) and HCO3(-) in the regeneration process of NaHCO3 from crude desulfurized sample. The developed method is more promising to differentiate CO3(2-) and HCO3(-) in industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Modelling ammonia volatilization from animal slurry applied with trail hoses to cereals

    NASA Astrophysics Data System (ADS)

    Sommer, S. G.; Olesen, J. E.

    In Europe ammonia (NH 3), volatilization from animal manure is the major source of NH 3 in the atmosphere. From March to July 1997, NH 3 volatilization from trail hose applied slurry was measured for seven days after application in six experiments. A statistical analysis of data showed that NH 3 volatilization rate during the first 4-5 h after slurry application increased significantly ( P<5%) with wind speed and soil slurry surface water content. NH 3 volatilization in the six measuring periods during the experiments increased significantly ( P<5%) with relative water content of the soil slurry surface, global radiation, pH, and decreased with increasing rainfall during each measuring period and rainfall accumulated from onset of each experiment. A mechanistic model of NH 3 volatilization was developed. Model inputs are climate variables, soil characteristics and total ammoniacal nitrogen (TAN=ammonium+ammonia) in the soil surface layer. A pH submodel for predicting pH at the surface of the soil slurry liquid was developed. The measured NH 3 volatilization was compared with model simulations. The simulated results explained 27% of the variation in measured NH 3 volatilization rates during all seven days, but 48% of measured volatilization rates during the first 24 h. Calculations with the model showed that applying slurry in the morning or in the afternoon reduced volatilization by 50% compared with a noon application. Spreading the slurry with trail hoses to a 60 cm high crop reduced losses by 75% compared with a spreading onto bare soil. Ammonia volatilization was 50% lower when the soil had dried out after slurry application compared with a wet slurry surface.

  2. Evidence of amino acid precursors: C-N bond coupling in simulated interstellar CO2/NH3 ices

    NASA Astrophysics Data System (ADS)

    Esmaili, Sasan

    2015-08-01

    Low energy secondary electrons are abundantly produced in astrophysical or planetary ices by the numerous ionizing radiation fields typically encountered in space environments and may thus play a role in the radiation processing of such ices [1]. One approach to determine their chemical effect is to irradiate nanometer thick molecular solids of simple molecular constituents, with energy selected electron beams and to monitor changes in film chemistry with the surface analytical techniques [2].Of particular interest is the formation of HCN, which is a signature of dense gases in interstellar clouds, and is ubiquitous in the ISM. Moreover, the chemistry of HCN radiolysis products such as CN- may be essential to understand of the formation of amino acids [3] and purine DNA bases. Here we present new results on the irradiation of multilayer films of CO2 and NH3 with 70 eV electrons, leading to CN bond formations. The electron stimulated desorption (ESD) yields of cations and anions are recorded as a function of electron fluence. The prompt desorption of cationic reaction/scattering products [4], is observed at low fluence (~4x1013 electrons/cm2). Detected ions include C2+, C2O2+, C2O+, CO3+, C2O3+ or CO4+ from pure CO2, and N+, NH+, NH2+, NH3+, NH4+, N2+, N2H+ from pure NH3, and NO+, NOH+ from CO2/NH3 mixtures. Most saliently, increasing signals of negative ion products desorbing during prolonged irradiation of CO2/NH3 films included C2-, C2H-, C2H2-, as well as CN-, HCN- and H2CN-. The identification of particular product ions was accomplished by using 13CO2 and 15NH3 isotopes. The chemistry induced by electrons in pure films of CO2 and NH3 and mixtures with composition ratios (3:1), (1:1), and (1:3), was also studied by X-ray photoelectron spectroscopy (XPS). Irradiation of CO2/NH3 mixed films at 22 K produces species containing the following bonds/functional groups identified by XPS: C=O, O-H, C-C, C-O, C=N and N=O. (This work has been funded by NSERC).

  3. Does ammonia trigger hyperventilation in the elasmobranch, Squalus acanthias suckleyi?

    PubMed

    De Boeck, Gudrun; Wood, Chris M

    2015-01-15

    We examined the ventilatory response of the spiny dogfish, to elevated internal or environmental ammonia. Sharks were injected via arterial catheters with ammonia solutions or their Na salt equivalents sufficient to increase plasma total ammonia concentration [TAmm]a by 3-5 fold from 145±21μM to 447±150μM using NH4HCO3 and a maximum of 766±100μM using (NH4)2SO4. (NH4)2SO4 caused a small increase in ventilation frequency (+14%) and a large increase in amplitude (+69%), while Na2SO4 did not. However, CO2 partial pressure (PaCO2) also increased and arterial pHa and plasma bicarbonate concentration ([HCO3(-)]a) decreased. NH4HCO3 caused a smaller increase in plasma ammonia resulting in a smaller but significant, short lived increases in ventilation frequency (+6%) and amplitude (36%), together with a rise in PaCO2 and [HCO3(-)]a. Injection with NaHCO3 which increased pHa and [HCO3(-)]a did not change ventilation. Plasma ammonia concentration correlated significantly with ventilation amplitude, while ventilation frequency showed a (negative) correlation with pHa. Exposure to high environmental ammonia (1500μM NH4HCO3) did not induce changes in ventilation until plasma [TAmm]a increased and ventilation amplitude (but not frequency) increased in parallel. We conclude that internal ammonia stimulates ventilation in spiny dogfish, especially amplitude or stroke volume, while environmental ammonia only stimulates ventilation after ammonia diffuses into the bloodstream. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Pilot-scale testing of renewable biocatalyst for swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions

    USDA-ARS?s Scientific Manuscript database

    Comprehensive control of odors, hydrogen sulfide (H2S), ammonia (NH3), and greenhouse gas (GHG) emissions associated with swine production is a critical need. A pilot-scale experiment was conducted to evaluate the topical application of soybean peroxidase (SBP) and calcium peroxide (CaO2) as a manu...

  5. Renewable biocatalyst for swine manure treatment and mitigation of odorous VOCs, ammonia and hydrogen sulfide emissions: Review

    USDA-ARS?s Scientific Manuscript database

    Comprehensive control of odors, hydrogen sulfide (H2S), ammonia (NH3), and greenhouse gas (GHG) emissions associated with swine production is a critical need. The objective of this paper is to review the use of soybean peroxidase (SBP) and peroxides as a manure additive to mitigate emissions of odor...

  6. Measurement of ammonia emissions from tropical seabird colonies

    NASA Astrophysics Data System (ADS)

    Riddick, S. N.; Blackall, T. D.; Dragosits, U.; Daunt, F.; Braban, C. F.; Tang, Y. S.; MacFarlane, W.; Taylor, S.; Wanless, S.; Sutton, M. A.

    2014-06-01

    The excreta (guano) of seabirds at their breeding colonies represents a notable source of ammonia (NH3) emission to the atmosphere, with effects on surrounding ecosystems through nitrogen compounds being thereby transported from sea to land. Previous measurements in temperate UK conditions quantified emission hotspots and allowed preliminary global upscaling. However, thermodynamic processes and water availability limit NH3 formation from guano, which suggests that the proportion of excreted nitrogen that volatilizes as NH3 may potentially be higher at tropical seabird colonies than similar colonies in temperate or sub-polar regions. To investigate such differences, we measured NH3 concentrations and environmental conditions at two tropical seabird colonies during the breeding season: a colony of 20,000 tern spp. and noddies on Michaelmas Cay, Great Barrier Reef, and a colony of 200,000 Sooty terns on Ascension Island, Atlantic Ocean. At both sites time-integrated NH3 concentrations and meteorological parameters were measured. In addition, at Ascension Island, semi-continuous hourly NH3 concentrations and micrometeorological parameters were measured throughout the campaign. Ammonia emissions, quantified using a backwards Lagrangian atmospheric dispersion model, were estimated at 21.8 μg m-2 s-1 and 18.9 μg m-2 s-1 from Michaelmas Cay and Ascension Island, respectively. High temporal resolution NH3 data at Ascension Island estimated peak hourly emissions up to 377 μg NH3 m2 s-1. The estimated percentage fraction of total guano nitrogen volatilized was 67% at Michaelmas Cay and 32% at Ascension Island, with the larger value at the former site attributed to higher water availability. These values are much larger than published data for sub-polar locations, pointing to a substantial climatic dependence on emission of atmospheric NH3 from seabird colonies.

  7. EPR/ENDOR and Theoretical Study of the Jahn-Teller-Active [HIPTN3N]MoVL Complexes (L = N-, NH).

    PubMed

    Sharma, Ajay; Roemelt, Michael; Reithofer, Michael; Schrock, Richard R; Hoffman, Brian M; Neese, Frank

    2017-06-19

    The molybdenum trisamidoamine (TAA) complex [Mo] {[3,5-(2,4,6-i-Pr 3 C 6 H 2 ) 2 C 6 H 3 NCH 2 CH 2 N]Mo} carries out catalytic reduction of N 2 to ammonia (NH 3 ) by protons and electrons at room temperature. A key intermediate in the proposed [Mo] nitrogen reduction cycle is nitridomolybdenum(VI), [Mo(VI)]N. The addition of [e - /H + ] to [Mo(VI)]N to generate [Mo(V)]NH might, in principle, follow one of three possible pathways: direct proton-coupled electron transfer; H + first and then e - ; e - and then H + . In this study, the paramagnetic Mo(V) intermediate {[Mo]N} - and the [Mo]NH transfer product were generated by irradiating the diamagnetic [Mo]N and {[Mo]NH} + Mo(VI) complexes, respectively, with γ-rays at 77 K, and their electronic and geometric structures were characterized by electron paramagnetic resonance and electron nuclear double resonance spectroscopies, combined with quantum-chemical computations. In combination with previous X-ray studies, this creates the rare situation in which each one of the four possible states of [e - /H + ] delivery has been characterized. Because of the degeneracy of the electronic ground states of both {[Mo(V)]N} - and [Mo(V)]NH, only multireference-based methods such as the complete active-space self-consistent field (CASSCF) and related methods provide a qualitatively correct description of the electronic ground state and vibronic coupling. The molecular g values of {[Mo]N} - and [Mo]NH exhibit large deviations from the free-electron value g e . Their actual values reflect the relative strengths of vibronic and spin-orbit coupling. In the course of the computational treatment, the utility and limitations of a formal two-state model that describes this competition between couplings are illustrated, and the implications of our results for the chemical reactivity of these states are discussed.

  8. Bond-selective photodissociation of partially deuterated ammonia molecules: Photodissociations of vibrationally excited NHD2 in the 5νNH state and NH2D in the 5νND state

    NASA Astrophysics Data System (ADS)

    Akagi, Hiroshi; Yokoyama, Keiichi; Yokoyama, Atsushi

    2004-03-01

    Ultraviolet photodissociation of NHD2 excited to the fourth overtone state of the NH stretching mode (5νNH) and NH2D excited to that of the ND stretching mode (5νND) has been investigated by using a crossed laser and molecular beams method. Branching ratio between the NH and ND bond dissociations has been determined by utilizing a (2+1) resonance enhanced multiphoton ionization scheme of H and D atoms. For the photolysis of NHD2 in the 5νNH state, the NH dissociation cross section is 5.1±1.4 times as large as the ND dissociation cross section per bond. On the other hand, for the photolysis of NH2D in the 5νND state, the ratio of the NH dissociation cross section per bond to the ND dissociation cross section decreases to 0.68±0.16. In comparison with the branching ratios for the photolysis of vibrationally unexcited NH2D and NHD2 [Koda and Back, Can. J. Chem. 55, 1380 (1977)], the present results indicate that the excitation of the NH stretching mode enhances the NH dissociation with ca. two times larger NH/ND branching ratio, whereas the excitation of the ND stretching mode results in the preferential ND dissociation with ca. 3-4 times larger ND/NH branching ratio than that for the vibrational ground states. The mechanism of the bond-selective enhancement has been discussed in terms of the energetics and dynamics of wave packet.

  9. Top-Down Constraints on Air Quality Model Emissions of NH3, NOx, and SO2 using Surface, Aircraft, and Satellite Data

    NASA Astrophysics Data System (ADS)

    Alvarado, M. J.; Lonsdale, C. R.; Winijkul, E.; Brodowski, C. M.; Cady-Pereira, K.; Henze, D. K.; Capps, S.

    2016-12-01

    Accurate modeling of the formation of ozone (O3) and fine particulate matter (PM2.5) requires accurate estimates of the emissions of precursor species such as ammonia (NH3), nitrogen oxides (NOx = NO+NO2) and sulfur dioxide (SO2). Here we present an evaluation of the 2011 EPA National Emission Inventory for NH3, NOx, and SO2 using CMAQv5.0.2 and data from the 2013 NOAA Southeast Nexus (SENEX) field campaign. Model results are compared to surface and aircraft measurements during each campaign, as well as satellite NH3 observations from the NOAA Cross-track Infrared Sounder (CrIS) and satellite observations of NO2 and SO2 from the NASA Ozone Monitoring Instrument (OMI). We also present an evaluation of the California Air Resources Board (CARB) NH3 emissions for 2012 using CMAQ and the CrIS NH3 observations. We discuss the lessons learned in using CrIS NH3 observations in the southeast US, where CMAQ predicts most of the gas-phase NH3 is very close to the surface, and contrast this with the use of CrIS NH3 observations over California. We discuss the use of two methods - a mass balance approach and an approach using the CMAQ adjoint - to optimize these emissions and evaluate the improvement in model performance for gas-phase NH3, NOx, and SO2, as well as for the formation of O3 and PM2.5.

  10. Survey for Ortho-to-Para Abundance Ratios (OPRs) of NH2 in Comets: Revisit to the Meaning of OPRs of Cometary Volatiles

    NASA Astrophysics Data System (ADS)

    Kawakita, Hideyo; Shinnaka, Yoshiharu; Jehin, Emmanuel; Decock, Alice; Hutsemekers, Damien; Manfroid, Jean

    2016-10-01

    Since molecules having identical protons can be classified into nuclear-spin isomers (e.g., ortho-H2O and para-H2O for water) and their inter-conversions by radiative and non-destructive collisional processes are believed to be very slow, the ortho-to-para abundance ratios (OPRs) of cometary volatiles such as H2O, NH3 and CH4 in coma have been considered as primordial characters of cometary molecules [1]. Those ratios are usually interpreted as nuclear-spin temperatures although the real meaning of OPRs is in strong debate. Recent progress in laboratory studies about nuclear-spin conversion in gas- and solid-phases [2,3] revealed short-time nuclear-spin conversions for water, and we have to reconsider the interpretation for observed OPRs of cometary volatiles. We have already performed the survey for OPRs of NH2 in more than 20 comets by large aperture telescopes with high-resolution spectrographs (UVES/VLT, HDS/Subaru, etc.) in the optical wavelength region [4]. The observed OPRs of ammonia estimated from OPRs of NH2, cluster around ~1.1 (cf. 1.0 as a high-temperature limit), indicative of ~30 K as nuclear-spin temperatures. We present our latest results for OPRs of cometary NH2 and discuss about the real meaning of OPRs of cometary ammonia, in relation to OPRs of water in cometary coma. Chemical processes in the inner coma may play an important role to achieve un-equilibrated OPRs of cometary volatiles in coma.This work was financially supported by MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018 (No. S1411028) (HK) and by Graint-in-Aid for JSPS Fellows, 15J10864 (YS).References:[1] Mumma & Charnley, 2011, Annu. Rev. Astro. Astrophys. 49, 471.[2] Hama & Watanabe, 2013, Chem. Rev. 113, 8783.[3] Hama et al., 2008, Science 351, 6268.[4] Shinnaka et al., 2011, ApJ 729, 81.

  11. High-efficiency perovskite solar cells based on the black polymorph of HC(NH2)2 PbI3.

    PubMed

    Lee, Jin-Wook; Seol, Dong-Jin; Cho, An-Na; Park, Nam-Gyu

    2014-08-06

    Perovskite solar cells with power conversion efficiencies exceeding 16% at AM 1.5 G one sun illumination are developed using the black polymorph of formamidnium lead iodide, HC(NH2)2 PbI3 . Compared with CH3 NH3 PbI3 , HC(NH2 )2 PbI3 extends its absoprtion to 840 nm and shows no phase transition between 296 and 423 K. Moreover, a solar cell based on HC(NH2 )2 PbI3 exhibits photostability and little I-V hysteresis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Ammonium stability and nitrogen isotope fractionations for NH4+-NH3(aq)-NH3(gas) systems at 20-70 °C and pH of 2-13: Applications to habitability and nitrogen cycling in low-temperature hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Li, Long; Lollar, Barbara Sherwood; Li, Hong; Wortmann, Ulrich G.; Lacrampe-Couloume, Georges

    2012-05-01

    Ammonium/ammonia is an essential nutrient and energy source to support life in oceanic and terrestrial hydrothermal systems. Thus the stability of ammonium is crucial to determine the habitability or ecological structure in hydrothermal environments, but still not well understood. To date, the lack of constraints on nitrogen isotope fractionations between ammonium and ammonia has limited the application of nitrogen isotopes to trace (bio)geochemical processes in such environments. In this study, we carried out laboratory experiments to (1) examine the stability of ammonium in an ammonium sulfate solution under temperature conditions from 20 to 70 °C and pH from 2.1 to 12.6 and (2) determine nitrogen isotope fractionation between ammonium and ammonia. Our experimental results show that ammonium is stable under the experimental temperatures when pH is less than 6. In experiments with starting pH greater than 8, significant ammonium was lost as a result of dissociation of ammonium and degassing of ammonia product. Nitrogen concentrations in the fluids decreased by more than 50% in the first two hours, indicating extremely fast effusion rates of ammonia. This implies that ammonium at high pH fluids (e.g., Lost City Hydrothermal Vents, Oman ophiolite hyperalkaline springs) may not be stable. Habitable environments may be more favorable at the leading edge of a pH gradient toward more acidic conditions, where the fluid can efficiently trap any ammonia transferred from a high pH vent. Although modeling shows that high temperature, low pH hydrothermal vents (e.g., Rainbow hydrothermal vent) may have the capability to retain ammonium, their high temperatures may limit habitability. The habitable zone associated with such a hydrothermal vent is likely at the lower front of a temperature gradient. In contrast, modeling of ammonium in deep terrestrial systems, suggests that saline fracture waters in crystalline rocks such as described in the Canadian Shield and in the

  13. Structural determinants of NH3 and NH4+ transport by mouse Rhbg, a renal Rh glycoprotein.

    PubMed

    Abdulnour-Nakhoul, Solange; Le, Trang; Rabon, Edd; Hamm, L Lee; Nakhoul, Nazih L

    2016-12-01

    Renal Rhbg is localized to the basolateral membrane of intercalated cells and is involved in NH 3 /NH 4 + transport. The structure of Rhbg is not yet resolved; however, a high-resolution crystal structure of AmtB, a bacterial homolog of Rh, has been determined. We aligned the sequence of Rhbg to that of AmtB and identified important sites of Rhbg that may affect transport. Our analysis positioned three conserved amino acids, histidine 183 (H183), histidine 342 (H342), and tryptophan 230 (W230), within the hydrophobic pore where they presumably serve to control NH 3 transport. A fourth residue, phenylalanine 128 (F128) was positioned at the upper vestibule, presumably contributing to recruitment of NH 4 + We generated three mutations each of H183, H342, W230, and F128 and expressed them in frog oocytes. Immunolabeling showed that W230 and F128 mutants were localized to the cell membrane, whereas H183 and H342 staining was diffuse and mostly intracellular. To determine function, we compared measurements of NH 3 /NH 4 + and methyl amine (MA)/methyl ammonium (MA + )-induced currents, intracellular pH, and surface pH (pHs) among oocytes expressing the mutants, Rhbg, or injected with H 2 O. In H183 and W230 mutants, NH 4 + -induced current and intracellular acidification were inhibited compared with that of Rhbg, and MA-induced intracellular alkalinization was completely absent. Expression of H183A or W230A mutants inhibited NH 3 /NH 4 + - and MA/MA + -induced decrease in pHs to the level observed in H 2 O-injected oocytes. Mutations of F128 did not significantly affect transport of NH 3 or NH 4 + These data demonstrated that mutating H183 or W230 caused loss of function but not F128. H183 and H342 may affect membrane expression of the transporter.

  14. Structural determinants of NH3 and NH4+ transport by mouse Rhbg, a renal Rh glycoprotein

    PubMed Central

    Abdulnour-Nakhoul, Solange; Le, Trang; Rabon, Edd; Hamm, L. Lee

    2016-01-01

    Renal Rhbg is localized to the basolateral membrane of intercalated cells and is involved in NH3/NH4+ transport. The structure of Rhbg is not yet resolved; however, a high-resolution crystal structure of AmtB, a bacterial homolog of Rh, has been determined. We aligned the sequence of Rhbg to that of AmtB and identified important sites of Rhbg that may affect transport. Our analysis positioned three conserved amino acids, histidine 183 (H183), histidine 342 (H342), and tryptophan 230 (W230), within the hydrophobic pore where they presumably serve to control NH3 transport. A fourth residue, phenylalanine 128 (F128) was positioned at the upper vestibule, presumably contributing to recruitment of NH4+. We generated three mutations each of H183, H342, W230, and F128 and expressed them in frog oocytes. Immunolabeling showed that W230 and F128 mutants were localized to the cell membrane, whereas H183 and H342 staining was diffuse and mostly intracellular. To determine function, we compared measurements of NH3/NH4+ and methyl amine (MA)/methyl ammonium (MA+)-induced currents, intracellular pH, and surface pH (pHs) among oocytes expressing the mutants, Rhbg, or injected with H2O. In H183 and W230 mutants, NH4+-induced current and intracellular acidification were inhibited compared with that of Rhbg, and MA-induced intracellular alkalinization was completely absent. Expression of H183A or W230A mutants inhibited NH3/NH4+- and MA/MA+-induced decrease in pHs to the level observed in H2O-injected oocytes. Mutations of F128 did not significantly affect transport of NH3 or NH4+. These data demonstrated that mutating H183 or W230 caused loss of function but not F128. H183 and H342 may affect membrane expression of the transporter. PMID:27681563

  15. Effect of different ammonia sources on aceticlastic and hydrogenotrophic methanogens.

    PubMed

    Tian, Hailin; Fotidis, Ioannis A; Kissas, Konstantinos; Angelidaki, Irini

    2018-02-01

    Ammonium chloride (NH 4 Cl) was usually used as a model ammonia source to simulate ammonia inhibition during anaerobic digestion (AD) of nitrogen-rich feedstocks. However, ammonia in AD originates mainly from degradation of proteins, urea and nucleic acids, which is distinct from NH 4 Cl. Thus, in this study, the inhibitory effect of a "natural" ammonia source (urea) and NH 4 Cl, on four pure methanogenic strains (aceticlastic: Methanosarcina thermophila, Methanosarcina barkeri; hydrogenotrophic: Methanoculleus bourgensis, Methanoculleus thermophilus), was assessed under mesophilic (37 °C) and thermophilic (55 °C) conditions. The results showed that urea hydrolysis increased pH significantly to unsuitable levels for methanogenic growth, while NH 4 Cl had a negligible effect on pH. After adjusting initial pH to 7 and 8, urea was significantly stronger inhibitor with longer lag phases to methanogenesis compared to NH 4 Cl. Overall, urea seems to be more toxic on both aceticlastic and hydrogenotrophic methanogens compared to NH 4 Cl under the same total and free ammonia levels. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst.

    PubMed

    Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

    2017-04-01

    Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O 2 at room temperature to an acidic RuO 2 /γ-Al 2 O 3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO 2 and acidic sites on the γ-Al 2 O 3 and with physisorption of multiple ammonia molecules.

  17. Carbon-free H2 production from ammonia triggered at room temperature with an acidic RuO2/γ-Al2O3 catalyst

    PubMed Central

    Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma; Tasaki, Ryo; Honda, Kyoko; Imamura, Kazuya; Sato, Katsutoshi

    2017-01-01

    Ammonia has been suggested as a carbon-free hydrogen source, but a convenient method for producing hydrogen from ammonia with rapid initiation has not been developed. Ideally, this method would require no external energy input. We demonstrate hydrogen production by exposing ammonia and O2 at room temperature to an acidic RuO2/γ-Al2O3 catalyst. Because adsorption of ammonia onto the catalyst is exothermic, the catalyst bed is rapidly heated to the catalytic ammonia autoignition temperature, and subsequent oxidative decomposition of ammonia produces hydrogen. A differential calorimeter combined with a volumetric gas adsorption analyzer revealed a large quantity of heat evolved both with chemisorption of ammonia onto RuO2 and acidic sites on the γ-Al2O3 and with physisorption of multiple ammonia molecules. PMID:28508046

  18. Outdoor, indoor, and human breath content measurements of ammonia by tunable diode laser spectroscopy technique

    NASA Astrophysics Data System (ADS)

    Moskalenko, Konstantin L.; Nadezhdinskii, Alexander I.

    1996-10-01

    Trace contents of ammonia in outdoor, indoor and exhaled air were measured on the base of high resolution absorption spectra. Tunable diode laser system developed for this purpose possesses approximately one second time constant, approximately 200 cm3 sample volume, 5 ppb sensitivity. The calibration of unit was based on measurements of relative intensities of sQ(3,1)...sQ(3,3) absorption lines of v2s and following calculation on the base of a priori data on strength and broadening coefficients of detected lines. Measured indoor contents of ammonia was in 5-10 times higher than outdoor contents. Approximately two times drop in NH3 room content after 6 p.m. was detected. Obtained behavior of ammonia content in respiration right after the smoking demonstrates that the removing of ammonia from lungs has the ventilation character. Measured contents of NH3 in human respiration was ranged between 120 and 220 ppb. The absence of ammonia content differences from respiration of smoking and non smoking persons demonstrates that the accumulation of NH3 by human organism seems to be rather negligible for a short time exposure, e.g. like smoking.

  19. Identification of Major Sources of Atmospheric NH3 in an Urban Environment in Northern China During Wintertime.

    PubMed

    Teng, Xiaolin; Hu, Qingjing; Zhang, Leiming; Qi, Jiajia; Shi, Jinhui; Xie, Huan; Gao, Huiwang; Yao, Xiaohong

    2017-06-20

    To assess the relative contributions of traffic emission and other potential sources to high levels of atmospheric ammonia (NH 3 ) in urban areas in the wintertime, atmospheric NH 3 and related pollutants were measured at an urban site, ∼300 m from a major traffic road, in northern China in November and December 2015. Hourly average NH 3 varied from 0.3 to 10.8 ppb with an average of 2.4 ppb during the campaign. Contrary to the common perspective in literature, traffic emission was demonstrated to be a negligible contributor to atmospheric NH 3 . Atmospheric NH 3 correlated well with ambient water vapor during many time periods lasting from tens of hours to several days, implying NH 3 released from water evaporation is an important source. Emissions from local green space inside the urban areas were identified to significantly contribute to the observed atmospheric NH 3 during ∼60% of the sampling times. Evaporation of predeposited NH x through wet precipitation combined with emissions from local green space likely caused the spikes of atmospheric NH 3 mostly occurring 1-4 h after morning rush hours or after and during slight shower events. There are still ∼30% of the data samples with appreciable NH 3 level for which major contributors are yet to be identified.

  20. Synthesis of NH4-Substituted Muscovite at 6.3 GPa and 1000°C: Implications for Nitrogen Transport to the Earth's Mantle

    NASA Astrophysics Data System (ADS)

    Sokol, A. G.; Sokol, E. V.; Kupriyanov, I. N.; Sobolev, N. V.

    2018-03-01

    The synthesis of NH4-bearing muscovite at P = 6.3 GPa and T = 1000°C in equilibrium with NH3-H2O fluid is performed. It is determined that the newly formed muscovite is enriched in celadonite minal and contains 370 ppm of NH4. The obtained data make it possible to conclude that ammonium-bearing micas have sufficient thermal stability and can transport crustal nitrogen to the mantle in the presence of a reduced water-ammonia fluid at fO2 less than the values of IW + 2 log units even in the regime of "hot" subduction. The key parameter that determines the efficiency of this mechanism for the deep nitrogen cycle is redox stability of NH4-bearing muscovite at the mantle PT-parameters.

  1. Estimation of NH3 Bi-Directional Flux from Managed Agricultural Soils

    EPA Science Inventory

    The Community Multi-Scale Air Quality model (CMAQ v4.7) contains a bi-directional ammonia (NH3) flux option that computes emission and deposition of ammonia derived from commercial fertilizer via a temperature dependent parameterization of canopy and soil compensation ...

  2. The effect of nitrification inhibitors on NH3 and N2O emissions in highly N fertilized irrigated Mediterranean cropping systems.

    PubMed

    Recio, Jaime; Vallejo, Antonio; Le-Noë, Julia; Garnier, Josette; García-Marco, Sonia; Álvarez, José Manuel; Sanz-Cobena, Alberto

    2018-09-15

    There is an increasing concern about the negative impacts associated to the release of reactive nitrogen (N) from highly fertilized agro-ecosystems. Ammonia (NH 3 ) and nitrous oxide (N 2 O) are harmful N pollutants that may contribute both directly and indirectly to global warming. Surface applied manure, urea and ammonium (NH 4 + ) based fertilizers are important anthropogenic sources of these emissions. Nitrification inhibitors (NIs) have been proposed as a useful technological approach to reduce N 2 O emission although they can lead to large NH 3 losses due to increasing NH 4 + pool in soils. In this context, a field experiment was carried out in a maize field with aiming to simultaneously quantify NH 3 volatilization and N 2 O emission, assessing the effect of two NIs 3,4‑dimethilpyrazol phosphate (DMPP) and 3,4‑dimethylpyrazole succinic acid (DMPSA). The first treatment was pig slurry (PS) before seeding (50 kg N ha -1 ) and calcium ammonium nitrate (CAN) at top-dressing (150 kg N ha -1 ), and the second was DMPP diluted in PS (PS + DMPP) (50 kg N ha -1 ) and CAN + DMPSA (150 kg N ha -1 ) also before seeding and at top-dressing, respectively. Ammonia emissions were quantified by a micrometeorological method during 20 days after fertilization and N 2 O emissions were assessed using manual static chambers during all crop period. The treatment with NIs was effective in reducing c. 30% cumulative N 2 O losses. However, considering only direct N 2 O emissions after second fertilization event, a significant reduction was not observed using CAN+DMPSA, probably because high WFPS of soil, driven by irrigation, favored denitrification. Cumulative NH 3 losses were not significantly affected by NIs. Indeed, NH 3 volatilization accounted 14% and 10% of N applied in PS + DMPP and PS plots, respectively and c. 2% of total N applied in CAN+DMPSA and CAN plots. Since important NH 3 losses still exist even although abating strategies

  3. Phase diagram for ammonia-water mixtures at high pressures - Implications for icy satellites

    NASA Technical Reports Server (NTRS)

    Cynn, H. C.; Boone, S.; Koumvakalis, A.; Nicol, M.; Stevenson, D. J.

    1989-01-01

    The (NH3)x(H2O)1-x phase diagram for X from 0 to 0.50 has been reexamined at temperatures from 125 K to 400 K and at pressures from 6.0 GPa using diamond anvil cells, and the implications of the findings for icy satellites are addressed. Titan is likely to have a thicker NH3-H2O ocean than previously suspected, because the stability field of NH3-H2O is found to be smaller than previously supposed. The implications for methane and ammonia volcanism on Titan are briefly discussed. The experimentally observed reactivity between the liquid and iron may also have implications for planetary and satellite evolution.

  4. Are the 'cave' minerals archerite (K,NH 4)H 2PO 4 and biphosphammite (K,NH 4)H 2PO 4 identical? A molecular structural study

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Xi, Yunfei; Palmer, Sara J.

    2011-08-01

    The molecular structure of the mineral archerite ((K,NH 4)H 2PO 4) has been determined and compared with that of biphosphammite ((NH 4,K)H 2PO 4). Raman spectroscopy and infrared spectroscopy has been used to characterise these 'cave' minerals. Both minerals originated from the Murra-el-elevyn Cave, Eucla, Western Australia. The mineral is formed by the reaction of the chemicals in bat guano with calcite substrates. Raman and infrared bands are assigned to HPO4-, OH and NH stretching vibrations. The Raman band at 981 cm -1 is assigned to the HOP stretching vibration. Bands in the 1200-1800 cm -1 region are associated with NH4+ bending modes. The molecular structure of the two minerals appear to be very similar, and it is therefore concluded that the two minerals are identical.

  5. Synthesis, Resistivity, and Thermal Properties of the Cubic Perovskite NH 2CH=NH 2SnI 3and Related Systems

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Liang, K.

    1997-12-01

    Combining concentrated hydriodic acid solutions of tin(II) iodide and formamidine acetate in an inert atmosphere results in the precipitation of a new conducting organic-inorganic compound, NH 2CH=NH 2SnI 3, which at room temperature adopts a cubic perovskite structure. The lattice constant for NH 2CH=NH 2SnI 3is found to be a=6.316(1) Å, which is approximately 1.2% larger than that for the isostructural compound CH 3NH 3SnI 3. The electrical resistivity of a pressed pellet of the new compound exhibits semimetallic temperature dependence from 10 to 300 K, with evidence of a structural transition at approximately 75 K. NH 2CH=NH 2SnI 3begins to slowly decompose in an inert atmosphere at temperatures as low as 200°C, with bulk decomposition/melting occurring above 300°C. The properties of the formamidinium-based perovskite are compared with those of the related cubic (at room temperature) perovskite CH 3NH 3SnI 3and the mixed-cation system (CH 3NH 3) 1- x(NH 2CH=NH 2) xSnI 3.

  6. [Effects of superphosphate addition on NH3 and greenhouse gas emissions during vegetable waste composting].

    PubMed

    Yang, Yan; Sun, Qin-ping; Li, Ni; Liu, Chun-sheng; Li, Ji-jin; Liu, Ben-sheng; Zou, Guo-yuan

    2015-01-01

    To study the effects of superphosphate (SP) on the NH, and greenhouse gas emissions, vegetable waste composting was performed for 27 days using 6 different treatments. In addition to the controls, five vegetable waste mixtures (0.77 m3 each) were treated with different amounts of the SP additive, namely, 5%, 10%, 15%, 20% and 25%. The ammonia volatilization loss and greenhouse gas emissions were measured during composting. Results indicated that the SP additive significantly decreased the ammonia volatilization and greenhouse gas emissions during vegetable waste composting. The additive reduced the total NH3 emission by 4.0% to 16.7%. The total greenhouse gas emissions (CO2-eq) of all treatments with SP additives were decreased by 10.2% to 20.8%, as compared with the controls. The NH3 emission during vegetable waste composting had the highest contribution to the greenhouse effect caused by the four different gases. The amount of NH3 (CO2-eq) from each treatment ranged from 59.90 kg . t-1 to 81.58 kg . t-1; NH3(CO2-eq) accounted for 69% to 77% of the total emissions from the four gases. Therefore, SP is a cost-effective phosphorus-based fertilizer that can be used as an additive during vegetable waste composting to reduce the NH3 and greenhouse gas emissions as well as to improve the value of compost as a fertilizer.

  7. Back Propagation Neural Network Model for Predicting the Performance of Immobilized Cell Biofilters Handling Gas-Phase Hydrogen Sulphide and Ammonia

    PubMed Central

    Rene, Eldon R.; López, M. Estefanía; Kim, Jung Hoon; Park, Hung Suck

    2013-01-01

    Lab scale studies were conducted to evaluate the performance of two simultaneously operated immobilized cell biofilters (ICBs) for removing hydrogen sulphide (H2S) and ammonia (NH3) from gas phase. The removal efficiencies (REs) of the biofilter treating H2S varied from 50 to 100% at inlet loading rates (ILRs) varying up to 13 g H2S/m3 ·h, while the NH3 biofilter showed REs ranging from 60 to 100% at ILRs varying between 0.5 and 5.5 g NH3/m3 ·h. An application of the back propagation neural network (BPNN) to predict the performance parameter, namely, RE (%) using this experimental data is presented in this paper. The input parameters to the network were unit flow (per min) and inlet concentrations (ppmv), respectively. The accuracy of BPNN-based model predictions were evaluated by providing the trained network topology with a test dataset and also by calculating the regression coefficient (R 2) values. The results from this predictive modeling work showed that BPNNs were able to predict the RE of both the ICBs efficiently. PMID:24307999

  8. New evidence for chemical depletion of ammonia in the 1 to 2 bar region of Jupiter's atmosphere

    NASA Astrophysics Data System (ADS)

    Wong, M. H.; Atreya, S. K.; Romani, P. N.; De Pater, I.; Kuhn, W. R.; Kalogerakis, K. S.

    2014-12-01

    It has long been known that the vertical profile of ammonia within Jupiter's cloud layers is not well-described by a simple equilibrium profile, with saturated vapor above the cloud base and the well-mixed deep abundance below the cloud base. An additional depletion of ammonia by a factor of 4-10 is required by global microwave spectra at p < 6 bar [e.g., 1]. Dynamical effects, ranging from cloud layer circulation between belts and zones [2] to molecular differentiation following convective activity [3] might be sufficient to explain the global microwave data. However, in situ cloud density measurements by the Galileo Probe [4] suggest a large gap in our understanding of cloud chemistry in Jupiter, especially when combined with other tracers such as volatile mixing ratios [5] and static stability [6]. Using the "fresh clouds" method of modeling cloud density [7], and assuming that cloud-forming advection was weak at all levels in the probe site, we find that NH4SH formation cannot explain cloud densities between 1 and 1.4 bar in situ. The composition of additional chemical species, or adsorption of ammonia on other ices, are candidate processes that strongly require further laboratory study of the H2O-NH3-H2S volatile system at temperatures of 150 to 300 K [1]. Spectral features near 3 microns suggest widespread NH4SH in the visible cloud decks of Jupiter [8], but additional species may also contribute to absorption at these wavelengths. Infrared spectroscopy at high angular resolution in the future---performed by Juno, JWST, or 30-m class ground-based telescopes---may be able to observe ammonia depletion mechanisms in action. References:[1] de Pater et al. (2001), Icarus 149, 66-78.[2] Showman and de Pater (2005), Icarus 174, 192-204.[3] Sugiyama et al. (2011), GRL 38, L13201.[4] Ragent et al. (1998), JGR 103, 22891-22909.[5] Wong et al. (2004), Icarus 171, 153-170.[6] Magalhães, Seiff, and Young (2002), Icarus 158, 410-433.[7] Wong et al. (2014), Icarus

  9. Studies on the use of supercritical ammonia for ceramic nitride synthesis and fabrication

    NASA Technical Reports Server (NTRS)

    Cornell, Linda; Lin, Y. C.; Philipp, Warren H.

    1990-01-01

    The extractability of ammonia halides (including ammonium thiocyanate) formed as byproducts from the synthesis of Si(NH)2 via ammonolysis of the corresponding silicon tetrahalides using supercritical NH3 as the extraction medium was investigated. It was found that the NH4SCN byproduct of ammonolysis of Si(SCN)4 can be almost completely extracted from the insoluble Si(NH)2 forming a promising system for the synthesis of pure Si(NH)2, one of the best precursors for Si3N4. In addition it was found that Si3N4, AlN, BN, and Si(NH)2 are insoluble in SC ammonia. Also discussed are design considerations for a supercritical ammonia extraction unit.

  10. Ammonia Volatilization Loss from Surface Applied Livestock Manure

    USDA-ARS?s Scientific Manuscript database

    Ammonia (NH3) emission from livestock manures used in agriculture reduces N uptake by crops and negatively impacts air quality. This laboratory study was conducted to evaluate NH3 emission from different livestock manures applied to two soils: Candler fins sand (CFS; light-textured soil, pH 6.8 and...

  11. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  12. Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst.

    PubMed

    Chen, Shiming; Perathoner, Siglinda; Ampelli, Claudio; Mebrahtu, Chalachew; Su, Dangsheng; Centi, Gabriele

    2017-03-01

    Ammonia is synthesized directly from water and N 2 at room temperature and atmospheric pressure in a flow electrochemical cell operating in gas phase (half-cell for the NH 3 synthesis). Iron supported on carbon nanotubes (CNTs) was used as the electrocatalyst in this half-cell. A rate of ammonia formation of 2.2×10 -3  gNH3  m -2h -1 was obtained at room temperature and atmospheric pressure in a flow of N 2 , with stable behavior for at least 60 h of reaction, under an applied potential of -2.0 V. This value is higher than the rate of ammonia formation obtained using noble metals (Ru/C) under comparable reaction conditions. Furthermore, hydrogen gas with a total Faraday efficiency as high as 95.1 % was obtained. Data also indicate that the active sites in NH 3 electrocatalytic synthesis may be associated to specific carbon sites formed at the interface between iron particles and CNT and able to activate N 2 , making it more reactive towards hydrogenation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. NH4(+) Resides Inside the Water 20-mer Cage As Opposed to H3O(+), Which Resides on the Surface: A First Principles Molecular Dynamics Simulation Study.

    PubMed

    Willow, Soohaeng Yoo; Singh, N Jiten; Kim, Kwang S

    2011-11-08

    Experimental vibrational predissociation spectra of the magic NH4(+)(H2O)20 clusters are close to those of the magic H3O(+)(H2O)20 clusters. It has been assumed that the geometric features of NH4(+)(H2O)20 clusters might be close to those of H3O(+)(H2O)20 clusters, in which H3O(+) resides on the surface. Car-Parrinello molecular dynamics simulations in conjunction with density functional theory calculations are performed to generate the infrared spectra of the magic NH4(+)(H2O)20 clusters. In comparison with the experimental vibrational predissociation spectra of NH4(+)(H2O)20, we find that NH4(+) is inside the cage structure of NH4(+)(H2O)20 as opposed to on the surface structure. This shows a clear distinction between the structures of NH4(+)(H2O)20 and H3O(+)(H2O)20 as well as between the hydration phenomena of NH4(+) and H3O(+).

  14. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    NASA Astrophysics Data System (ADS)

    Venterea, R. T.; Sadowsky, M.; Breuillin-Sessoms, F.; Wang, P.; Clough, T. J.; Coulter, J. A.

    2015-12-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted 'hot spots' and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils ('L' and 'W') having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3-) levels than soil L, but was more resistant to nitrite (NO2-) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2- oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2- was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2-. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2- oxidization leading to greater NO2- levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2-, N2O and nitrifier genes, and the first to show how ASC can regulate NO2- levels and N2O production.

  15. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production.

    PubMed

    Venterea, Rodney T; Clough, Timothy J; Coulter, Jeffrey A; Breuillin-Sessoms, Florence; Wang, Ping; Sadowsky, Michael J

    2015-07-16

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted 'hot spots' and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils ('L' and 'W') having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4(+)) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3(-)) levels than soil L, but was more resistant to nitrite (NO2(-)) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2(-) oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2(-) was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2(-). Differences between soils were explained by greater slNH3 in soil L which inhibited NO2(-) oxidization leading to greater NO2(-) levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2(-), N2O and nitrifier genes, and the first to show how ASC can regulate NO2(-) levels and N2O production.

  16. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    NASA Astrophysics Data System (ADS)

    Venterea, Rodney T.; Clough, Timothy J.; Coulter, Jeffrey A.; Breuillin-Sessoms, Florence

    2015-07-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils (‘L’ and ‘W’) having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3-) levels than soil L, but was more resistant to nitrite (NO2-) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2- oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2- was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2-. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2- oxidization leading to greater NO2- levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2-, N2O and nitrifier genes, and the first to show how ASC can regulate NO2- levels and N2O production.

  17. Infrared spectra of the ammonium ion in ammonium metavanadate NH 4VO 3

    NASA Astrophysics Data System (ADS)

    de Waal, D.; Heyns, A. M.; Range, K.-J.; Eglmeier, C.

    The ND stretching modes of isotopically dilute NH 3D + ions in NH 4VO 3 are in agreement with the predicted splitting into C s, C s and C1(2) components under C s site symmetry for the NH +4 ion. The three bands observed represent the three NH bonding distances in the crystal, and the position, shape and low temperature behaviour of each band confirms the existence of two types of hydrogen bonding in NH 4VO 3. The low temperature infrared modes of NH +4 and ND +4 in NH 4VO 3 and ND 4VO 3, respectively, can be assigned under space group Pbcm. Temperature dependence of these modes also reflects the presence of both normal and bifurcated hydrogen bonds in NH 4VO 3.

  18. Sawdust biochar application to rice paddy field: reduced nitrogen loss in floodwater accompanied with increased NH3 volatilization.

    PubMed

    Feng, Yanfang; Sun, Haijun; Xue, Lihong; Wang, Yueman; Yang, Linzhang; Shi, Weiming; Xing, Baoshan

    2018-03-01

    Sawdust biochar (SDB) was for the first time applied to rice paddy field to evaluate its effects on potential nitrogen (N) runoff and ammonia (NH 3 ) volatilization losses in a soil column experimental system. Results showed that total N concentration of surface floodwater under SDB treatments was reduced by 7.29-35.16, 16.34-32.35, and 12.21-28.12% after three split N fertilizations, respectively. Particularly, NH 4 + -N was decreased by 11.84-27.08, 14.29-36.50, and 2.97-19.64%, respectively. However, SDB addition has no significant influence on NO 3 - -N concentration. Meanwhile, SDB application increased NH 4 + -N and total N content of top (0-15 cm) soil. Furthermore, these SDB-induced influences were more pronounced for 3 wt% SDB treatments. SDB treatments recorded 3.56-5.78 kg ha -1 higher NH 3 volatilization than urea control treatment, which was attributed to the elevated pH values of floodwater and top soil induced by SDB. Fortunately, the yield-scale NH 3 volatilization was not increased dramatically.

  19. Ammonia biofiltration and nitrous oxide generation during the start-up of gas-phase compost biofilters

    NASA Astrophysics Data System (ADS)

    Maia, Guilherme D. N.; Day V, George B.; Gates, Richard S.; Taraba, Joseph L.

    2012-01-01

    Gas-Phase Biofiltration technology is widely utilized for treating ammonia gas (NH 3) with one of its potential detrimental by-products being nitrous oxide (N 2O), a potent greenhouse gas (100-y radiative forcing 298 times greater than carbon dioxide). The present work was conducted to investigate the relation between NH 3 removal during biofiltration and N 2O generation as a product of incomplete denitrification during the start-up of gas-phase compost biofilters. Four laboratory scale tubular biofilters in up flow mode (20 s residence-time) were studied for 21 days: 3 replicates were subjected to 16 ppm v (0.78 g m -2 h -1) of NH 3 and a statistical control not subjected to NH 3. Ammonia concentration differences between biofilter inlet (Bottom = 16 ppm v) and outlet (Top) and N 2O concentration differences between biofilter outlet (Top) and biofilter inlet (background concentrations at the bottom) were used to determine the extent of the correlation between NH 3 removal and N 2O generation. Correlations with CH 4 and CO 2 were also reported. The high Spearman correlation coefficients for the three replicates ( ρ = -0.845, -0.820, and -0.841, with P ≤ 0.0001 for replications A, B and C, respectively) suggested that availability of nitrate/nitrite owing to NH 3 nitrification favored conditions for N 2O generation as a sub-product of denitrification. The statistical control received no NH 3 inputs and did not generate N 2O. Therefore, the results indicated that the process of NH 3 removal was a trigger for N 2O production. Carbon dioxide and N 2O were moderately correlated. Methane and N 2O were weakly correlated and only for replicate C. No significant correlation was found for the Statistical Control between N 2O and CH 4.

  20. Fast Magic-Angle Spinning Three-Dimensional NMR Experiment for Simultaneously Probing H-H and N-H Proximities in Solids.

    PubMed

    Reddy, G N Manjunatha; Malon, Michal; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

    2016-12-06

    A fast magic-angle spinning (MAS, 70 kHz) solid-state NMR experiment is presented that combines 1 H Double-Quantum (DQ) and 14 N- 1 H HMQC (Heteronuclear Multiple-Quantum Coherence) pulse-sequence elements, so as to simultaneously probe H-H and N-H proximities in molecular solids. The proposed experiment can be employed in both two-dimensional (2D) and three-dimensional (3D) versions: first, a 2D 14 N HMQC-filtered 1 H-DQ experiment provides specific DQ-SQ correlation peaks for proton pairs that are in close proximities to the nitrogen sites, thereby achieving spectral filtration. Second, a proton-detected three-dimensional (3D) 1 H(DQ)- 14 N(SQ)- 1 H(SQ) experiment correlates 1 H(DQ)- 1 H(SQ) chemical shifts with 14 N shifts such that longer range N···H-H correlations are observed between protons and nitrogen atoms with internuclear NH distances exceeding 3 Å. Both 2D and 3D versions of the proposed experiment are demonstrated for an amino acid hydrochloride salt, l-histidine·HCl·H 2 O, and a DNA nucleoside, guanosine·2H 2 O. In the latter case, the achieved spectral filtration ensures that DQ cross peaks are only observed for guanine NH and CH8 1 H resonances and not ribose and water 1 H resonances, thus providing insight into the changes in the solid-state structure of this hydrate that occur over time; significant changes are observed in the NH and NH 2 1 H chemical shifts as compared to the freshly recrystallized sample previously studied by Reddy et al., Cryst. Growth Des. 2015, 15, 5945.

  1. Formation of Nitrogen and Hydrogen-bearing Molecules in Solid Ammonia and Implications for Solar System and Interstellar Ices

    NASA Astrophysics Data System (ADS)

    Zheng, Weijun; Jewitt, David; Osamura, Yoshihiro; Kaiser, Ralf I.

    2008-02-01

    We irradiated solid ammonia (NH3) in the temperature range of 10-60 K with high-energy electrons to simulate the processing of ammonia-bearing ices in the interstellar medium and in the solar system. By monitoring the newly formed molecules online and in situ, the synthesis of hydrazine (N2H4), diazene (N2H2 isomers), hydrogen azide (HN3), the amino radical (NH2), molecular hydrogen (H2), and molecular nitrogen (N2) has been confirmed. Our results show that the production rates of hydrazine, diazene, hydrogen azide, molecular hydrogen, and molecular nitrogen are higher in amorphous ammonia than those in crystalline ammonia; this behavior is similar to the production of molecular hydrogen, molecular oxygen, and hydrogen peroxide found in electron-irradiated water ices. However, the formation of hydrazine in crystalline ammonia does not show any temperature dependence. Our experimental results give hints to the origin of molecular nitrogen in the Saturnian system and possibly in the atmospheres of proto-Earth and Titan; our research may also guide the search of hitherto unobserved nitrogen-bearing molecules in the interstellar medium and in our solar system.

  2. Fluorographene based Ultrasensitive Ammonia Sensor

    PubMed Central

    Tadi, Kiran Kumar; Pal, Shubhadeep; Narayanan, Tharangattu N.

    2016-01-01

    Single molecule detection using graphene can be brought by tuning the interactions via specific dopants. Electrostatic interaction between the most electronegative element fluorine (F) and hydrogen (H) is one of the strong interactions in hydrogen bonding, and here we report the selective binding of ammonia/ammonium with F in fluorographene (FG) resulting to a change in the impedance of the system. Very low limit of detection value of ~0.44 pM with linearity over wide range of concentrations (1 pM–0.1 μM) is achieved using the FG based impedance sensor, andthisscreen printed FG sensor works in both ionized (ammonium) and un-ionized ammonia sensing platforms. The interaction energies of FG and NH3/NH4+ are evaluated using density functional theory calculations and the interactions are mapped. Here FGs with two different amounts of fluorinecontents −~5 atomic% (C39H16F2) and ~24 atomic% (C39H16F12) - are theoretically and experimentally studied for selective, high sensitive and ultra-low level detection of ammonia. Fast responding, high sensitive, large area patternable FG based sensor platform demonstrated here can open new avenues for the development of point-of-care devices and clinical sensors. PMID:27142522

  3. Infrared spectra of the 1-pyridinium (C5H5NH+) cation and pyridinyl (C5H5NH and 4-C5H6N) radicals isolated in solid para-hydrogen.

    PubMed

    Golec, Barbara; Das, Prasanta; Bahou, Mohammed; Lee, Yuan-Pern

    2013-12-19

    Protonated pyridine and its neutral counterparts (C5H6N) are important intermediates in organic and biological reactions and in the atmosphere. We have recorded the IR absorption spectra of the 1-pyridinium (C5H5NH(+)) cation, 1-pyridinyl (C5H5NH), and 4-pyridinyl (4-C5H6N) produced on electron bombardment during matrix deposition of a mixture of pyridine (C5H5N) and p-H2 at 3.2 K; all spectra were previously unreported. The IR features of C5H5NH(+) diminished in intensity after the matrix was maintained in darkness for 15 h, whereas those of C5H5NH and 4-C5H6N radicals increased. Irradiation of this matrix with light at 365 nm diminished lines of C5H5NH(+) and C5H5NH but enhanced lines of 4-C5H6N slightly, whereas irradiation at 405 nm diminished lines of 4-C5H6N significantly. Observed wavenumbers and relative intensities of these species agree satisfactorily with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3LYP/6-31++G(d,p) method. Assignments of C5H5NH and 4-C5H6N radicals were further supported by the observation of similar spectra when a Cl2/C5H5N/p-H2 matrix was irradiated first at 365 nm and then with IR light to generate H atoms to induce the H + C5H5N reaction.

  4. Photochemical Generation of H_{2}NCNX, H_{2}NNCX, H_{2}NC(NX) (x = O, s) in Low-Temperature Matrices

    NASA Astrophysics Data System (ADS)

    Voros, Tamas; Lajgut, Gyozo Gyorgy; Magyarfalvi, Gabor; Tarczay, Gyorgy

    2017-06-01

    The [NH_{2}, C, N, O] and the [NH_{2}, C, N, S] systems were investigated by quantum-chemical computations and matrix-isolation spectroscopic methods. The equilibrium structures of the isomers and their relative energies were determined by CCSD(T) method. This was followed by the computation of the harmonic and anharmonic vibrational wavenumbers, infrared intensities, relative Raman activities and UV excitation energies. These computed data were used to assist the identification of products obtained by UV laser photolysis of 3,4-diaminofurazan, 3,4-diaminothiadiazole and 1,2,4-thiadiazole-3,5-diamine in low-temperature Ar and Kr matrices. Experimentally, first the precursors were studied by matrix-isolation IR and UV spectroscopic methods. Based on these UV spectra, different wavelengths were selected for photolysis. The irradiations, carried out by a tunable UV laser-light source, resulted in the decomposition of the precursors, and in the appearance of new bands in the IR spectra. Some of these bands were assigned to cyanamide (H_{2}NCN) and its isomer, the carbodiimide molecule (HNCNH), generated from H_{2}NCN. By the analysis of the relative absorbance vs. photolysis time curves, the other bands were grouped to three different species both for the O- and the S-containing systems. In the case of the O-containing isomers, these bands were assigned to the H_{2}NNCO:H_{2}NCN, and H_{2}NCNO:H_{2}NCN complexes, and to the ring-structure H_{2}NC(NO) isomer. In a similar way, the complexes of H_{2}NNCS and H_{2}NCNS with the H_{2}NCN, and H_{2}NC(NS) were also identified. 1,2,4-thiadiazole-3,5-diamine was also investigated in similar way like the above mentioned precursors. The results of this study also support the identification of the new S-containing isomers. Except for H_{2}NNCO and H_{2}NCNS, these molecules were not identified previously. It is expected that at least some of these species, like the methyl isocyanate (CH_{3}CNO) isomer, are present and could be

  5. Self-Consistent Charge Density Functional Tight-Binding Study of Poly(3,4-ethylenedioxythiophene): Poly(styrenesulfonate) Ammonia Gas Sensor.

    PubMed

    Marutaphan, Ampaiwan; Seekaew, Yotsarayuth; Wongchoosuk, Chatchawal

    2017-12-01

    Geometric and electronic properties of 3,4-ethylenedioxythiophene (EDOT), styrene sulfonate (SS), and EDOT: SS oligomers up to 10 repeating units were studied by the self-consistent charge density functional tight-binding (SCC-DFTB) method. An application of PEDOT:PSS for ammonia (NH 3 ) detection was highlighted and investigated both experimentally and theoretically. The results showed an important role of H-bonds in EDOT:SS oligomers complex conformation. Electrical conductivity of EDOT increased with increasing oligomers and doping SS due to enhancement of π conjugation. Printed PEDOT:PSS gas sensor exhibited relatively high response and selectivity to NH 3 . The SCC-DFTB calculation suggested domination of direct charge transfer process in changing of PEDOT:PSS conductivity upon NH 3 exposure at room temperature. The NH 3 molecules preferred to bind with PEDOT:PSS via physisorption. The most favorable adsorption site for PEDOT:PSS-NH 3 interaction was found to be at the nitrogen atom of NH 3 and hydrogen atoms of SS with an average optimal binding distance of 2.00 Å.

  6. Improvements in the hydrogen storage properties of the Mg(NH2)2-LiH composite by KOH addition.

    PubMed

    Amica, G; Enzo, S; Larochette, P Arneodo; Gennari, F C

    2018-06-06

    Potassium-containing compounds, such as KH, KOH, KNH2 and different potassium halides, have shown positive effects on the dehydrogenation properties of the Li-Mg-N-H system. However, it is still discussed whether the K-compounds modify the thermodynamics of the system or if they have only a catalytic effect. In this work the impact of the addition of two K-containing compounds (0.08 mol% of KCl and KOH) on the hydrogen storage performance of the Mg(NH2)2-LiH composite was studied. The KOH incorporation reduced the dehydrogenation temperature from 197 °C to 154 °C, beginning the process at low temperature (∼70 °C). The doped sample was able to reversibly absorb and desorb 4.6 wt% of hydrogen with improved kinetics; dehydrogenation rates were increased four times, whereas absorptions required 20% less time to be completed in comparison to the pristine material. The thermodynamic destabilization of the Mg(NH2)2-2LiH composite by the addition of a small amount of KOH was demonstrated by an increment of 30% in the dehydrogenation equilibrium pressure. According to detailed structural investigations, the KH formed by the KOH decomposition through milling and thermal treatment, can replace LiH and react with Mg(NH2)2 to produce a mixed potassium-lithium amide (Li3K(NH2)4). The KH role is not limited to catalysis, but rather it is responsible for the thermodynamic destabilization of the Mg(NH2)2-LiH composite and it is actively involved in the dehydrogenation process.

  7. Cell-mediated T lymphocyte responses against syngeneic cells modified with amino-reactive hapten (AED-NH2): H-2Dk serves as an element for cell-mediated lympholysis to amino-reactive hapten (AED-NH2)-modified self.

    PubMed

    Mizuochi, T; Fujiwara, H; Takai, Y; Hamaoka, T

    1985-02-01

    Spleen cells from C3H/He mice immunized to the newly synthesized amino-reactive hapten, 5-sulfo-1-naphthoxy acetic acid N-hydroxysuccinimide (AED-NH2), were stimulated in vitro with AED-NH2 modified syngeneic cells. After 5 days of culture, effector cells were assayed for their cytotoxic activity against AED-NH2-modified target blast cells. In contrast to other amino-reactive haptens reported so far, a strong cytotoxic activity against AED-NH2-modified syngeneic cells was found in H-2b mice as well as in H-2k mice. Furthermore, Dk-restricted anti-AED-NH2 CTL recognition was observed in H-2k mice as shown by cold target inhibition. Previous studies have demonstrated the predominant influence of K over D region self determinants, and of the chemical reactivity of the haptenic reagent in Ir gene control of CTL response to hapten-self. The present report illustrates the importance of the hapten itself in genetic regulation of these CTL responses.

  8. Toxic effects and possible mechanisms of hydrogen sulfide and/or ammonia on porcine oocyte maturation in vitro.

    PubMed

    Yang, Lei-Lei; Zhao, Yong; Luo, Shi-Ming; Ma, Jun-Yu; Ge, Zhao-Jia; Shen, Wei; Yin, Shen

    2018-03-15

    Previous studies suggest that hydrogen sulfide (H 2 S) and ammonia (NH 3 ) are two major air pollutants which can cause damage to porcine health. However, the mechanisms underlying toxic effects of these compounds on porcine oocyte maturation are not clear. To clarify the mechanism, we evaluated the oocyte quality by detecting some events during oocytes maturation. In our study, porcine oocytes were cultured with different concentrations of Na 2 S and/or NH 4 Cl in vitro and the rate of the first polar body extrusion decreased significantly. Also, actin filament was seriously disrupted to damage the cytoskeleton which resulted in reduced rate of oocyte maturation. We explored the reactive oxygen species (ROS) generation and found that the ROS level was increased significantly after Na 2 S treatment but not after NH 4 Cl treatment. Moreover, early stage apoptosis rate was significantly increased and autophagy protein LC3 B expression level was higher in oocytes treated with Na 2 S and/or NH 4 Cl, which might be caused by ROS elevation. Additionally, exposure to Na 2 S and/or NH 4 Cl also caused ROS generation and early apoptosis in cumulus cells, which might further affect oocyte maturation in vitro. In summary, our data suggested that exposure to H 2 S and/or NH 3 decreased porcine oocyte maturation in vitro, which might be caused by actin disruption, ROS generation, early apoptosis and autophagy. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiter's Great Red Spot

    NASA Astrophysics Data System (ADS)

    Carlson, R. W.; Baines, K. H.; Anderson, M. S.; Filacchione, G.; Simon, A. A.

    2016-08-01

    The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

  10. Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiters Great Red Spot

    NASA Technical Reports Server (NTRS)

    Carlson, Robert W.; Baines, Kevin H.; Anderson, M. S.; Filacchione, G.; Simon, A. A.

    2016-01-01

    The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3 ) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2 ). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

  11. Development and evaluation of optical fiber NH3 sensors for application in air quality monitoring

    NASA Astrophysics Data System (ADS)

    Huang, Yu; Wieck, Lucas; Tao, Shiquan

    2013-02-01

    Ammonia is a major air pollutant emitted from agricultural practices. Sources of ammonia include manure from animal feeding operations and fertilizer from cropping systems. Sensor technologies with capability of continuous real time monitoring of ammonia concentration in air are needed to qualify ammonia emissions from agricultural activities and further evaluate human and animal health effects, study ammonia environmental chemistry, and provide baseline data for air quality standard. We have developed fiber optic ammonia sensors using different sensing reagents and different polymers for immobilizing sensing reagents. The reversible fiber optic sensors have detection limits down to low ppbv levels. The response time of these sensors ranges from seconds to tens minutes depending on transducer design. In this paper, we report our results in the development and evaluation of fiber optic sensor technologies for air quality monitoring. The effect of change of temperature, humidity and carbon dioxide concentration on fiber optic ammonia sensors has been investigated. Carbon dioxide in air was found not interfere the fiber optic sensors for monitoring NH3. However, the change of humidity can cause interferences to some fiber optic NH3 sensors depending on the sensor's transducer design. The sensitivity of fiber optic NH3 sensors was found depends on temperature. Methods and techniques for eliminating these interferences have been proposed.

  12. Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O.

    PubMed

    Babić-Ivancić, Vesna; Kontrec, Jasminka; Brecević, Ljerka; Kralj, Damir

    2006-10-01

    The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.

  13. Manure fertilization alters the population of ammonia-oxidizing bacteria rather than ammonia-oxidizing archaea in a paddy soil.

    PubMed

    Wang, Yu; Zhu, Guibing; Song, Liyan; Wang, Shanyun; Yin, Chengqing

    2014-03-01

    Manure fertilizers are widely used in agriculture and highly impacted the soil microbial communities such as ammonia oxidizers. However, the knowledge on the communities of archaeal versus bacterial ammonia oxidizers in paddy soil affected by manure fertilization remains largely unknown, especially for a long-term influence. In present work, the impact of manure fertilization on the population of ammonia oxidizers, related potential nitrification rates (PNRs) and the key factors manipulating the impact were investigated through studying two composite soil cores (long-term fed with manure fertilization versus undisturbed). Moreover, soil incubated with NH(4)(+) for 5 weeks was designed to verify the field research. The results showed that the copy numbers of bacterial amoA gene in the manure fed soil were significant higher than those in the unfed soil (p < 0.05), suggesting a clear stimulating effect of long-term manure fertilization on the population of ammonia-oxidizing bacteria (AOB). The detected PNRs in the manure fed soil core (14-218 nmol L(-1)  N g(-1)  h(-1)) were significant higher than those in the unfed soil core (5-72 nmol L(-1)  N g(-1)  h(-1) ; p < 0.05). Highly correlations between the PNRs and the bacterial amoA gene copies rather than archaeal amoA gene were observed, indicating strong nitrification capacity related to bacterial ammonia oxidizers. The NH(4)(+) -N significantly correlated to the abundance of AOB (p < 0.01) and explained 96.1% of the environmental variation, showing the NH(4)(+) -N was the main factor impacting the population of AOB. The incubation experiment demonstrated a clear increase of the bacterial amoA gene abundance (2.0 × 10(6) to 8.4 × 10(6)  g(-1) d.w.s. and 1.6 × 10(4) to 4.8 × 10(5)  g(-1) d.w.s.) in both soil but not for the archaeal amoA gene, in agreement with the field observation. Overall, our results suggested that manure fertilization promoted the

  14. Electronic, magnetic and transport properties of transition metal-doped holely C2N-h2D nanoribbons

    NASA Astrophysics Data System (ADS)

    He, Jing-Jing; Guo, Yan-Dong; Yan, Xiao-Hong; Zeng, Hong-Li

    2018-01-01

    A novel layered two-dimensional graphene-like material C2N-h2D with evenly distributed holes and nitrogen atoms has been synthesized via a bottom-up wet-chemical reaction [Nat. Commun. 6, 6486 (2015)]. The presence of holes provides a ground for further functionalization by doping. By performing a first-principles study, we have doped transition metals at the center of the holes of C2N-h2D nanoribbons and explored their doping effects on electronic, magnetic and transport properties. It is found that the doping can essentially regulate the electronic properties of C2N-h2D nanoribbons. The metallic zigzag ribbon is tuned into a semiconductor for Mn, Fe and Co-doped cases, but half-metal for Ni-doping. This transition is derived from the peculiar band morphology which has a big band gap between the edge state and the higher band, so when the energy of the edge state is reduced by the impurity state, the band gap falls too and crosses the Fermi level. In contrast, the pristine semiconducting armchair C2N-h2D nanoribbon is changed into metallic. Different from the zigzag case, its physical mechanism originates from the hybridization of 3 d orbitals of transition metal atoms and the p orbitals of carbon and nitrogen atoms which introduces several resonant peaks at the Fermi level in the density of states. Furthermore, the magnetic moments of all doped materials are enhanced compared to the pristine structures but decrease as the atomic number of the transition metal atom increases. And the spin polarization of armchair C2N-h2D nanoribbon is increased, while that of the zigzag structure is decreased except the Ni-doped one which is completely spin-polarized suggesting great prospects in the future of spintronics and nanoelectronics.

  15. High-level ab initio predictions for the ionization energies and heats of formation of five-membered-ring molecules: thiophene, furan, pyrrole, 1,3-cyclopentadiene, and borole, C4H4X/C4H4X+ (X = S, O, NH, CH2, and BH).

    PubMed

    Lo, Po-Kam; Lau, Kai-Chung

    2011-02-10

    The ionization energies (IEs) and heats of formation (ΔH°(f0)/ΔH°(f298)) for thiophene (C(4)H(4)S), furan (C(4)H(4)O), pyrrole (C(4)H(4)NH), 1,3-cyclopentadiene (C(4)H(4)CH(2)), and borole (C(4)H(4)BH) have been calculated by the wave function-based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled-cluster level with single and double excitations plus a quasi-perturbative triple excitation [CCSD(T)]. Where appropriate, the zero-point vibrational energy correction (ZPVE), the core-valence electronic correction (CV), and the scalar relativistic effect (SR) are included in these calculations. The respective CCSD(T)/CBS predictions for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), being 8.888, 8.897, 8.222, and 8.582 eV, are in excellent agreement with the experimental values obtained from previous photoelectron and photoion measurements. The ΔH°(f0)/ΔH°(f298) values for the aforementioned molecules and their corresponding cations have also been predicted by the CCSD(T)/CBS method, and the results are compared with the available experimental data. The comparisons between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2) suggest that the CCSD(T)/CBS procedure is capable of predicting reliable IE values for five-membered-ring molecules with an uncertainty of ±13 meV. In view of the excellent agreements between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), the similar CCSD(T)/CBS IE and ΔH°(f0)/ΔH°(f298) predictions for C(4)H(4)BH, whose thermochemical data are not readily available due to its reactive nature, should constitute a reliable data set. The CCSD(T)/CBS IE(C(4)H(4)BH) value is 8.868 eV, and ΔH°(f0)/ΔH°(f298) values for C(4)H(4)BH and C(4)H(4)BH(+) are 269.5/258.6 and 1125.1/1114.6 kJ/mol, respectively. The highest occupied molecular orbitals

  16. The H2SO4-HNO3-NH3 system at high humidities and in fogs: 1. Spatial and temporal patterns in the San Joaquin Valley of California

    NASA Astrophysics Data System (ADS)

    Jacob, Daniel J.; Munger, J. William; Waldman, Jed M.; Hoffmann, Michael R.

    1986-01-01

    A systematic characterization of the atmospheric H2SO4-HNO3-NH3 system was conducted in the fog water, the aerosol, and the gas phase at a network of sites in the San Joaquin Valley of California. Spatial patterns of concentrations were established that reflect the distribution of SO2, NOx, and NH3 emissions within the valley. The concept of atmospheric alkalinity was introduced to interpret these concentrations in terms of the buffering capacity of the atmosphere with respect to inputs of strong acids. Regions of predominantly acidic and alkaline fog water were identified. Fog water was found to be alkaline in most of the valley, but small changes in emission budgets could lead to widespread acid fog. An extended stagnation episode was studied in detail: progressive accumulation of H2SO4-HNO3-NH3 species was documented over the course of the episode and interpreted in terms of production and removal mechanisms. Secondary production of strong acids H2SO4 and HNO3 under stagnant conditions resulted in a complete titration of available alkalinity at the sites farthest from NH3 sources. A steady SO2 conversion rate of 0.4-1.1% h-1 was estimated in the stagnant mixed layer under overcast conditions and was attributed to nonphotochemical heterogeneous processes. Removal of SO2 was enhanced in fog, compared to nonfoggy conditions. Conversion of NOx to HNO3 slowed down during the stagnation episode because of reduced photochemical activity; fog did not appear to enhance conversion of NOx. Decreases in total HNO3 concentrations were observed upon acidification of the atmosphere and were attributed to displacement of NO3- by H2SO4 in the aerosol, followed by rapid deposition of HNO3(g). The occurrence of fog was associated with general decreases of aerosol concentrations due to enhanced removal by deposition.

  17. Multiple Condensation Reactions Involving Pt(II) /Pd(II) -OH2 , Pt-NH3 , and Cytosine-NH2 Groups: New Twists in Cisplatin-Nucleobase Chemistry.

    PubMed

    Yin-Bandur, Lu; Sanz Miguel, Pablo J; Rodríguez-Santiago, Luis; Sodupe, Mariona; Berghaus, Melanie; Lippert, Bernhard

    2016-09-12

    The coordination chemistry of the antitumor agent cisplatin and related complexes with DNA and its constituents, that is, the nucleobases, appears to be dominated by 1:1 and 1:2 adducts of the types cis-[Pta2 (nucleobase)X] and cis-[Pta2 (nucleobase)2 ] (a=NH3 or amine; a2 =diamine or diimine; X=Cl, OH or OH2 ). Here, we have studied the interactions of the putative 1:1 adducts cis-[Pta2 (1-MeC-N3)(OH2 )](2+) (with a=NH3 , a2 =2,2'-bpy (2,2'-bipyridine), 1-MeC=model nucleobase 1-methylcytosine) with additional cis-[Pt(NH3 )2 (OH2 )2 ](2+) or its kinetically superior analogues [Pd(en)(OH2 )2 ](2+) (en=ethylenediamine) and [Pd(2,2'-bpy)(OH2 )2 ](2+) . Depending upon the conditions applied different compounds of different nuclearity are formed. Without exception they represent condensation products of the components, containing μ-1-MeC-H , μ-OH(-) , as well as μ-NH2 (-) bridges. In the presence of Ag(+) ions, the isolated products in several cases display additionally Pt→Ag dative bonds. On the basis of the cytosine-containing structures established by X-ray crystallography, it is proposed that any of the feasible initial 1:1 nucleobase adducts of cisplatin could form dinuclear Pt complexes upon reaction with additional hydrolyzed cisplatin, thereby generating nucleobase adducts other than the presently established ones. Two findings appear to be of particular significance: First, hydrolyzed cisplatin can have a moderately accelerating effect on the formation of a secondary nucleobase product. Second, NH3 ligands of the cisplatin moiety can be converted into bridging amido ligands following condensation with the diaqua species of cisplatin. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Effect of fertilizer application on ammonia emission and concentration levels of ammonium, nitrate, and nitrite ions in a rice field.

    PubMed

    Das, Piw; Sa, Jae-Hwan; Kim, Ki-Hyun; Jeon, Eui-Chan

    2009-07-01

    The concentrations of ammonium NH4+, nitrate NO3-, and nitrite NO2- ions were recorded along with ammonia (NH(3)) emission from a fertilized rice field located in the Kwangju province in South Korea over a period of 4 months (June to October 2006). The highest magnitude of NH(3) flux was 20,754 microg m(-2) h(-1), while the average flux value over the entire sampling period was 2,395 microg m(-2) h(-1). The highest ionic concentrations were 1.67, 0.44, and 0.71 ppm for NH4+, NO3-, and NO2- ions, respectively. Possible effects of soil pH on NH(3) fluxes were detected, as they concurrently exhibited a gradual and periodic change during the sampling period. Positive correlations existed between concentrations of NH4+ and NO2- ions and the soil pH. Positive correlations also existed between NH(3) emission flux and ambient (and water) temperatures. Results indicated that fertilizer application to rice can lead to significant emission of NH(3) along with NH4+ and NO3- ions.

  19. Ammonia volatilization loss from surface applied livestock manure.

    PubMed

    Paramasivam, S; Jayaraman, K; Wilson, Takela C; Alva, Ashok K; Kelson, Luma; Jones, Leandra B

    2009-03-01

    Ammonia (NH(3)) emission from livestock manures used in agriculture reduces N uptake by crops and negatively impacts air quality. This laboratory study was conducted to evaluate NH(3)emission from different livestock manures applied to two soils: Candler fins sand (CFS; light-textured soil, pH 6.8 and field capacity soil water content of 70 g kg(-1)) from Lake Alfred, Florida and Ogeechee loamy sand (OLS; medium-textured soil, pH 5.2 and field capacity soil water content of 140 g kg(-1)) from Savannah, Georgia. Poultry litter (PL) collected from a poultry farm near Douglas, Georgia, and fresh solid separate of swine manure (SM) collected from a farm near Clinton, North Carolina were used. Each of the soil was weighed in 100 g sub samples and amended with either PL or SM at rates equivalent to either 0, 2.24, 5.60, 11.20, or 22.40 Mg ha(-1) in 1L Mason jars and incubated in the laboratory at field capacity soil water content for 19 days to monitor NH(3) volatilization. Results indicated a greater NH(3) loss from soils amended with SM compared to that with PL. The cumulative NH(3)volatilization loss over 19 days ranged from 4 to 27% and 14 to 32% of total N applied as PL and SM, respectively. Volatilization of NH(3) was greater from light-textured CFS than that from medium-textured OLS. Volatilization loss increased with increasing rates of manure application. Ammonia volatilization was lower at night time than that during the day time. Differences in major factors such as soil water content, temperature, soil type and live stock manure type influenced the diurnal variation in volatilization loss of NH(3) from soils. A significant portion (> 50%) of cumulative NH(3) emission over 19 d occurred during the first 5-7 d following the application of livestock manures. Results of this study demonstrate that application of low rates of livestock manure (< or = 5.60 Mg ha(-1)) is recommended to minimize NH(3) emissions.

  20. Flow of ices in the Ammonia-Water System

    NASA Technical Reports Server (NTRS)

    Durham, W. B.; Kirby, S. H.; Stern, L. A.

    1993-01-01

    We have fabricated in the laboratory and subsequently deformed crystalline hydrates and partial melts of the water-rich end of the NH3-H2O system, with the aim of improving our understanding of physical processes occurring in icy moons of the outer solar system. Deformation experiments were carried out at constant strain rate. The range of experimental variables are given. Phase relationships in the NH3-H2O system indicate that water ice and ammonia dihydrate, NH3-2H2O, are the stable phases under our experiment conditions. X-ray diffraction of our samples usually revealed these as the dominant phases, but we have also observed an amorphous phase (in unpressurized samples only) and occasionally significant ammonia monohydrate, NH3-H2O. The onset of partial melting at the peritectic temperature at about 176 K appeared as a sharp transition in strength observed in samples of x(sub NH3) = 0.05 and 0.01, the effect of melt was less pronounced. For any given water ice + dihydrate alloy in the subsolidus region, we observed one rheological law over the entire temperature range from 175 K to about 140 K. Below 140 K, a shear instability similar to that occurring in pure water ice under the same conditions limited our ability to measure ductile flow. The rheological laws for the several alloys vary systematically from that of pure ice to that of dihydrate. Pure dihydrate is about 4 orders of magnitude less viscous than water ice just below the peritectic temperature, but because of a very pronounced temperature dependence in dihydrate (100 kJ/mol versus 43 kJ/mol for water ice) the viscosity of dihydrate equals or exceeds that of water ice at T less than 140 K. The large variation in viscosity of dihydrate with relatively small changes in temperature may be helpful in explaining the rich variety of tectonic and volcanic features seen on the surfaces of icy moons in the outer solar system.

  1. Radio-Frequency-Controlled Urea Dosing for NH3-SCR Catalysts: NH3 Storage Influence to Catalyst Performance under Transient Conditions

    PubMed Central

    Dietrich, Markus; Hagen, Gunter; Reitmeier, Willibald; Burger, Katharina; Hien, Markus; Grass, Philippe; Kubinski, David; Visser, Jaco; Moos, Ralf

    2017-01-01

    Current developments in exhaust gas aftertreatment led to a huge mistrust in diesel driven passenger cars due to their NOx emissions being too high. The selective catalytic reduction (SCR) with ammonia (NH3) as reducing agent is the only approach today with the capability to meet upcoming emission limits. Therefore, the radio-frequency-based (RF) catalyst state determination to monitor the NH3 loading on SCR catalysts has a huge potential in emission reduction. Recent work on this topic proved the basic capability of this technique under realistic conditions on an engine test bench. In these studies, an RF system calibration for the serial type SCR catalyst Cu-SSZ-13 was developed and different approaches for a temperature dependent NH3 storage were determined. This paper continues this work and uses a fully calibrated RF-SCR system under transient conditions to compare different directly measured and controlled NH3 storage levels, and NH3 target curves. It could be clearly demonstrated that the right NH3 target curve, together with a direct control on the desired level by the RF system, is able to operate the SCR system with the maximum possible NOx conversion efficiency and without NH3 slip. PMID:29182589

  2. Rapid Ammonia Gas Transport Accounts for Futile Transmembrane Cycling under NH3/NH4+ Toxicity in Plant Roots1[C][W

    PubMed Central

    Coskun, Devrim; Britto, Dev T.; Li, Mingyuan; Becker, Alexander; Kronzucker, Herbert J.

    2013-01-01

    Futile transmembrane NH3/NH4+ cycling in plant root cells, characterized by extremely rapid fluxes and high efflux to influx ratios, has been successfully linked to NH3/NH4+ toxicity. Surprisingly, the fundamental question of which species of the conjugate pair (NH3 or NH4+) participates in such fluxes is unresolved. Using flux analyses with the short-lived radioisotope 13N and electrophysiological, respiratory, and histochemical measurements, we show that futile cycling in roots of barley (Hordeum vulgare) seedlings is predominately of the gaseous NH3 species, rather than the NH4+ ion. Influx of 13NH3/13NH4+, which exceeded 200 µmol g–1 h–1, was not commensurate with membrane depolarization or increases in root respiration, suggesting electroneutral NH3 transport. Influx followed Michaelis-Menten kinetics for NH3 (but not NH4+), as a function of external concentration (Km = 152 µm, Vmax = 205 µmol g–1 h–1). Efflux of 13NH3/13NH4+ responded with a nearly identical Km. Pharmacological characterization of influx and efflux suggests mediation by aquaporins. Our study fundamentally revises the futile-cycling model by demonstrating that NH3 is the major permeating species across both plasmalemma and tonoplast of root cells under toxicity conditions. PMID:24134887

  3. The Transition from Hydrogen Bonding to Ionization in (HCI)n(NH3)n and (HCI)n(H2O)n Clusters: Consequences for Anharmonic Vibrational Spectroscopy

    NASA Technical Reports Server (NTRS)

    Chaban, Galina M.; Gerber, R. Benny; Janda, Kenneth C.; Kwak, Dochan (Technical Monitor)

    2001-01-01

    Anharmonic vibrational frequencies and intensities are calculated for 1:1 and 2:2 (HCl)(sub n)(NH3)(sub n) and (HCl)(sub n)(H2O)(sub n) complexes, employing the correlation-corrected vibrational self-consistent field method with ab initio potential surfaces at the MP2/TZP computational level. In this method, the anharmonic coupling between all vibrational modes is included, which is found to be important for the systems studied. For the 4:4 (HCl)(sub n)(H2O)(sub n) complex, the vibrational spectra are calculated at the harmonic level, and anharmonic effects are estimated. Just as the (HCl)(sub n)(NH3)(sub n) structure switches from hydrogen-bonded to ionic for n=2, the (HCl)(sub n)(H2O)(sub n) switches to ionic structure for n=4. For (HCl)2(H2O)2, the lowest energy structure corresponds to the hydrogen-bonded form. However, configurations of the ionic form are separated from this minimum by a barrier of less than an O-H stretching quantum. This suggests the possibility of experiments on ionization dynamics using infrared excitation of the hydrogen-bonded form. The strong cooperative effects on the hydrogen bonding, and concomitant transition to ionic bonding, makes an accurate estimate of the large anharmonicity crucial for understanding the infrared spectra of these systems. The anharmonicity is typically of the order of several hundred wave numbers for the proton stretching motions involved in hydrogen or ionic bonding, and can also be quite large for the intramolecular modes. In addition, the large cooperative effects in the 2:2 and higher order (HCl(sub n)(H2O)(sub n) complexes may have interesting implications for solvation of hydrogen halides at ice surfaces.

  4. Fabrication and Electromagnetic Properties of Conjugated NH2-CuPc@Fe3O4

    NASA Astrophysics Data System (ADS)

    Yan, Liang; Pu, Zejun; Xu, Mingzhen; Wei, Renbo; Liu, Xiaobo

    2017-10-01

    Conjugated amino-phthalocyanine copper containing carboxyl groups/magnetite (NH2-CuPc@Fe3O4) has been fabricated from FeCl3·6H2O and NH2-CuPc via a simple solvothermal method and its electromagnetic properties investigated. Scanning electron microscopy and transmission electron microscopy revealed that the NH2-CuPc@Fe3O4 was a waxberry-like nanomaterial with NH2-CuPc molecules effectively embedded in the interior of Fe3O4 particles in the form of beads. Introduction of NH2-CuPc effectively improved the complementarity between the dielectric and magnetic losses of the system, resulting in excellent electromagnetic performance. The minimum reflection loss of the as-prepared composite reached -33.4 dB at 7.0 GHz for coating layer thickness of 4.0 mm and bandwidth below -10.0 dB (90% absorption) of up to 3.8 GHz. These results indicate that introduction of NH2-CuPc results in a composite with potential for use as an electromagnetic microwave absorption material.

  5. Physiological plasticity of the thermophilic ammonia oxidizing archaeon Nitrosocaldus yellowstonii in response to a changing environment

    NASA Astrophysics Data System (ADS)

    Jewell, T.; Johnson, A.; Gelsinger, D.; de la Torre, J. R.

    2012-12-01

    Our understanding of nitrogen biogeochemical cycling in high temperature environments underwent a dramatic revision with the discovery of ammonia oxidizing archaea (AOA). The importance of AOA to the global nitrogen cycle came to light when recent studies of marine AOA demonstrated the dominance of these organisms in the ocean microbiome and their role as producers of the greenhouse gas nitrous oxide (N2O). Understanding how AOA respond to fluctuating environments is crucial to fully comprehending their contribution to global biogeochemical cycling and climate change. In this study we use the thermophilic AOA Nitrosocaldus yellowstonii strain HL72 to explore the physiological plasticity of energy metabolism in these organisms. Previous studies have shown that HL72 grows autotrophically by aerobically oxidizing ammonia (NH3) to nitrite (NO2-). Unlike studies of marine AOA, we find that HL72 can grow over a wide ammonia concentration range (0.25 - 10 mM NH4Cl) with comparable generation times when in the presence of 0.25 to 4 mM NH4Cl. However, preliminary data indicate that amoA, the alpha subunit of ammonia monooxygenase (AMO), is upregulated at low ammonia concentrations (<50 μM) compared to growth at 1 mM. Although the ammonia oxidation pathway has not been fully elucidated, we have shown that nitric oxide (NO) appears to be a key intermediate: exponentially growing HL72 produces significant NO and the removal of NO using a scavenger reversibly inhibits growth. In addition to AMO, the HL72 genome also contains sequences for a urease encoded by subunits ureABC and an active urea transporter. Urea ((NH2)2CO) is an organic compound ubiquitous to aquatic and soil habitats that, when hydrolyzed, forms NH3 and CO2. We examined urea as an alternate source of ammonia for the ammonia oxidation pathway. HL72 grows over a wide range of urea concentrations (0.25 - 10 mM) at rates comparable to growth on ammonia. In a substrate competition experiment HL72 preferentially

  6. AMBIENT AMMONIA AND AMMONIUM AEROSOL ACROSS A REGION OF VARIABLE AMMONIA EMISSION DENSITY

    EPA Science Inventory

    The paper presents one year of ambient ammonia (NH3), ammonium (NH4+), hydrochloric acid (HCI), chloride (CI¯), nitric acid (HNO3), nitrate (NO3¯), nitrous acid (HONO), sulfur dioxide (SO2), and sulfate (SO4

  7. ZnO nanowires: Synthesis and charge transfer mechanism in the detection of ammonia vapour

    NASA Astrophysics Data System (ADS)

    Nancy Anna Anasthasiya, A.; Ramya, S.; Rai, P. K.; Jeyaprakash, B. G.

    2018-01-01

    ZnO nanowires with hexagonal wurtzite structure were grown on the glass substrate using Successive Ionic Layer Adsorption and Reaction (SILAR) method. Both experimental and theoretical studies demonstrated that NH3 chemisorbed and transferred the charge to the surface of the nanowire via its nitrogen site to the zinc site of ZnO nanowires, leading to the detection of NH3 vapour. The adsorbed ammonia dissociated into NH2 and H due to steric repulsion, and then into N2 and H2 gas. The formation of the N2 gas during the desorption process confirmed by observing peak at 14 and 28 m/z in the GC-MS spectrum.

  8. Na+/H+ and Na+/NH4+ exchange activities of zebrafish NHE3b expressed in Xenopus oocytes

    PubMed Central

    Ito, Yusuke; Kato, Akira; Hirata, Taku; Hirose, Shigehisa

    2014-01-01

    Zebrafish Na+/H+ exchanger 3b (zNHE3b) is highly expressed in the apical membrane of ionocytes where Na+ is absorbed from ion-poor fresh water against a concentration gradient. Much in vivo data indicated that zNHE3b is involved in Na+ absorption but not leakage. However, zNHE3b-mediated Na+ absorption has not been thermodynamically explained, and zNHE3b activity has not been measured. To address this issue, we overexpressed zNHE3b in Xenopus oocytes and characterized its activity by electrophysiology. Exposure of zNHE3b oocytes to Na+-free media resulted in significant decrease in intracellular pH (pHi) and intracellular Na+ activity (aNai). aNai increased significantly when the cytoplasm was acidified by media containing CO2-HCO3− or butyrate. Activity of zNHE3b was inhibited by amiloride or 5-ethylisopropyl amiloride (EIPA). Although the activity was accompanied by a large hyperpolarization of ∼50 mV, voltage-clamp experiments showed that Na+/H+ exchange activity of zNHE3b is electroneutral. Exposure of zNHE3b oocytes to medium containing NH3/NH4+ resulted in significant decreases in pHi and aNai and significant increase in intracellular NH4+ activity, indicating that zNHE3b mediates the Na+/NH4+ exchange. In low-Na+ (0.5 mM) media, zNHE3b oocytes maintained aNai of 1.3 mM, and Na+-influx was observed when pHi was decreased by media containing CO2-HCO3− or butyrate. These results provide thermodynamic evidence that zNHE3b mediates Na+ absorption from ion-poor fresh water by its Na+/H+ and Na+/NH4+ exchange activities. PMID:24401990

  9. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    PubMed Central

    Venterea, Rodney T.; Clough, Timothy J.; Coulter, Jeffrey A.; Breuillin-Sessoms, Florence

    2015-01-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils (‘L’ and ‘W’) having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3−) levels than soil L, but was more resistant to nitrite (NO2−) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2− oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2− was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2−. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2− oxidization leading to greater NO2− levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2−, N2O and nitrifier genes, and the first to show how ASC can regulate NO2− levels and N2O production. PMID:26179972

  10. CO 2 Absorption and Magnesium Carbonate Precipitation in MgCl 2NH 3NH 4Cl Solutions: Implications for Carbon Capture and Storage

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

    Zhu, Chen; Wang, Han; Li, Gen

    CO 2 absorption and carbonate precipitation are the two core processes controlling the reaction rate and path of CO 2 mineral sequestration. Whereas previous studies have focused on testing reactive crystallization and precipitation kinetics, much less attention has been paid to absorption, the key process determining the removal efficiency of CO 2. In this study, adopting a novel wetted wall column reactor, we systematically explore the rates and mechanisms of carbon transformation from CO 2 gas to carbonates in MgCl 2NH 3NH 4Cl solutions. We find that reactive diffusion in liquid film of the wetted wall column is the rate-limitingmore » step of CO 2 absorption when proceeding chiefly through interactions between CO 2(aq) and NH 3(aq). We further quantified the reaction kinetic constant of the CO 2NH 3 reaction. Our results indicate that higher initial concentration of NH 4Cl ( ≥2mol∙L -1) leads to the precipitation of roguinite [(NH 4) 2Mg(CO 3) 2∙4H 2O], while nesquehonite appears to be the dominant Mg-carbonate without NH 4Cl addition. We also noticed dypingite formation via phase transformation in hot water. This study provides new insight into the reaction kinetics of CO 2 mineral carbonation that indicates the potential of this technique for future application to industrial-scale CO 2 sequestration.« less

  11. CO 2 Absorption and Magnesium Carbonate Precipitation in MgCl 2NH 3NH 4Cl Solutions: Implications for Carbon Capture and Storage

    DOE PAGES

    Zhu, Chen; Wang, Han; Li, Gen; ...

    2017-09-19

    CO 2 absorption and carbonate precipitation are the two core processes controlling the reaction rate and path of CO 2 mineral sequestration. Whereas previous studies have focused on testing reactive crystallization and precipitation kinetics, much less attention has been paid to absorption, the key process determining the removal efficiency of CO 2. In this study, adopting a novel wetted wall column reactor, we systematically explore the rates and mechanisms of carbon transformation from CO 2 gas to carbonates in MgCl 2NH 3NH 4Cl solutions. We find that reactive diffusion in liquid film of the wetted wall column is the rate-limitingmore » step of CO 2 absorption when proceeding chiefly through interactions between CO 2(aq) and NH 3(aq). We further quantified the reaction kinetic constant of the CO 2NH 3 reaction. Our results indicate that higher initial concentration of NH 4Cl ( ≥2mol∙L -1) leads to the precipitation of roguinite [(NH 4) 2Mg(CO 3) 2∙4H 2O], while nesquehonite appears to be the dominant Mg-carbonate without NH 4Cl addition. We also noticed dypingite formation via phase transformation in hot water. This study provides new insight into the reaction kinetics of CO 2 mineral carbonation that indicates the potential of this technique for future application to industrial-scale CO 2 sequestration.« less

  12. Raman studies of phase transitions in ferroelectric [C2H5NH3]2ZnCl4

    NASA Astrophysics Data System (ADS)

    Ben Mohamed, C.; Karoui, K.; Bulou, A.; Ben Rhaiem, A.

    2017-03-01

    The present paper accounted for the synthesis, differential scanning calorimetric and vibrational spectroscopy of [C2H5NH3]2ZnCl4grown at room temperature. Differential scanning calorimetric (DSC) disclosed five phase transitions at T1=231 K, T2=234 K, T3=237 K, T4=247 K and T5=312 K. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 238 K. Raman spectra as function temperature have been used to characterize these transitions and their nature, which indicates a change of the some peak near the transitions phase. The analysis of the wavenumber and the line width based on the order-disorder model allowed to obtain information relative to the thermal coefficient and the activation energy near the transitions phase.

  13. High transport and excellent optical property of a two-dimensional single-layered hybrid perovskite (C4H9NH3)2PbBr4: a theoretical study.

    PubMed

    Lei, Jun-Hui; Zhao, Yu-Qing; Tang, Qiong; Lin, Jian-Guo; Cai, Meng-Qiu

    2018-05-16

    Organic-inorganic hybrid perovskites are developed to pursue high charge carrier mobility and light absorption coefficient. In this study, we present a detailed comparative research of the atomic and electronic structures of single-layered perovskites (C4H9NH3)2PbBr4 with two-dimensional/three-dimensional (2D/3D) spatial arrangement to predict the in plane charge carrier mobility along with the charge effective mass, elastic constant, and deformation potential. The calculated results reveal that the intrinsic in plane carrier mobilities of 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 along the 100 and 010 directions are superior to those of the 3D structure. Furthermore, the optical properties are calculated from the electronic structure; it is found that the light absorption spectrum of 2D single-layered perovskite (C4H9NH3)2PbBr4 with a high absorption coefficient is wider than that of the 3D phase. We speculate that the superior mobility and wider absorption spectrum of the 2D mono-layered perovskite are due to high charge density and ferroelectricity originating from structure distortion upon 3D-to-2D structure transformation. These results indicate that the 2D single-layered hybrid perovskite (C4H9NH3)2PbBr4 is a potential candidate for application in the optoelectronic and photovoltaic fields.

  14. A theoretical study of hydrogen- and lithium-bonded complexes of F-H∕Li and Cl-H∕Li with NF3, NH3, and NH2(CH3).

    PubMed

    McDowell, Sean A C; St Hill, Janine A S

    2011-10-28

    Hydrogen- and lithium-bonded complexes of A-H∕Li (A = F, Cl) with the amine analogues NF(3), NH(3), and NH(2)(CH(3)) were studied at the MP2∕6-311++G(d,p) level of theory. Bond extensions and redshifts were obtained for the H-bonded complexes, while bond extensions and blueshifts were obtained for the Li-bonded species. The variation of these and other properties with the basicity of the amines was investigated and rationalized by comparing the ab initio results with predictions from a model derived from perturbation theory.

  15. On the Surface Formation of NH3 and HNCO in Dark Molecular Clouds - Searching for Wöhler Synthesis in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Fedoseev, Gleb; Lamberts, Thanja; Linnartz, Harold; Ioppolo, Sergio; Zhao, Dongfeng

    Despite its potential to reveal the link between the formation of simple species and more complex molecules (e.g., amino acids), the nitrogen chemistry of the interstellar medium (ISM) is still poorly understood. Ammonia (NH _{3}) is one of the few nitrogen-bearing species that have been observed in interstellar ices toward young stellar objects (YSOs) and quiescent molecular clouds. The aim of the present work is to experimentally investigate surface formation routes of NH _{3} and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant cryogenic temperatures. This study focuses on the formation of NH _{3} and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing start to become predominant. Our work confirms the surface formation of ammonia through the sequential addition of three hydrogen/deuterium atoms to a single nitrogen atom at low temperature. The H/D fractionation of the formed ammonia is also shown. Furthermore, we show the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH _{3}. Finally, we discuss the implications of HNCO in astrobiology, as a possible starting point for the formation of more complex prebiotic species.

  16. The influence of NH3 on NO2 conversion in a dc corona discharge in N2:O2:CO2:NO2:NH3 mixture

    NASA Astrophysics Data System (ADS)

    Dors, Mirosław; Mizeraczyk, Jerzy; Czech, Tadeusz; Konieczka, Jerzy

    1996-10-01

    The aim of this paper is to investigate the influence of NH3 additive (540-1470 ppm) on the conversion of NO2 and the creation of NO and N2O in a mixture of N2:O2:CO2: NO2:NH3 subjected to the so-called direct current (dc) corona discharge. The dc corona discharge was generated in a needle-to-plate reactor. Seven positively polarized needles were used as one electrode and a stainless steel plate as the other. The time-averaged discharge current was varied from 0 to 7 mA. It was found that the dc corona discharge decomposed NO2 and produced NO and N2O. The reduction of NO2 was higher without NH3 additive if the residence time of the operating gas was relatively short. However, in a longer corona discharge processing the NH3 additive may be useful for reduction of NO2.

  17. [The Research for Trace Ammonia Escape Monitoring System Based on Tunable Diode Laser Absorption Spectroscopy].

    PubMed

    Zhang, Li-fang; Wang, Fei; Yu, Li-bin; Yan, Jian-hua; Cen, Ke-fa

    2015-06-01

    In order to on-line measure the trace ammonia slip of the commercial power plant in the future, this research seeks to measure the trace ammonia by using tunable diode laser absorption spectroscopy under ambient temperature and pressure, and at different temperatures, and the measuring temperature is about 650 K in the power plant. In recent years lasers have become commercially available in the near-infrared where the transitions are much stronger, and ammonia's spectroscopy is pretty complicated and the overlapping lines are difficult to resolve. A group of ammonia transitions near 4 433.5 cm(-1) in the v2 +v3 combination band have been thoroughly selected for detecting lower concentration by analyzing its absorption characteristic and considering other absorption interference in combustion gases where H2O and CO2 mole fraction are very large. To illustrate the potential for NH3 concentration measurements, predictions for NH3, H2O and CO2 are simultaneously simulated, NH3 absorption lines near 4 433.5 cm(-1) wavelength meet weaker H2O absorption than the commercial NH3 lines, and there is almost no CO2 absorption, all the parameters are based on the HITRAN database, and an improved detection limit was obtained for interference-free NH3 monitoring, this 2.25 μm band has line strengths several times larger than absorption lines in the 1.53 μm band which was often used by NH3 sensors for emission monitoring and analyzing. The measurement system was developed with a new Herriott cell and a heated gas cell realizing fast absorption measurements of high resolution, and combined with direct absorption and wavelenguh modulation based on tunable diode laser absorption spectroscopy at different temperatures. The lorentzian line shape is dominant at ambient temperature and pressure, and the estimated detectivity is approximately 0.225 x 10(-6) (SNR = 1) for the directed absorption spectroscopy, assuming a noise-equivalent absorbance of 1 x 10(-4). The heated cell

  18. On-board Measurement of HCN and NH3 Emissions from Vehicles During Real-World Driving

    NASA Astrophysics Data System (ADS)

    Moss, J. A.; Baum, M. M.

    2013-12-01

    Emission control systems in light-duty motor vehicles have played an important role in improving regional air quality by dramatically reducing the concentration of criteria pollutants (carbon monoxide, hydrocarbons, and nitrogen oxides) in exhaust emissions. Unintended side-reactions occurring on the surface of three-way catalysts can, however, lead to emission of non-criteria pollutants such as ammonia (NH3) and hydrogen cyanide (HCN). A pair of spectrometers based on tunable diode lasers (TDL) emitting in the near-infrared (1529 nm) and mid-infrared (2975 nm) have been developed for determination of HCN and acetylene (C2H2) emission rates from light-duty motor vehicles in real-time, while driving. Both spectrometers have been evaluated extensively using standard gas mixtures in the laboratory and exhaust from idling and moving vehicles. The TDL spectrometers were incorporated into an on-board instrument suite containing instrumentation for measurement of CO2, HCN, C2H2, NH3 and amines, and exhaust flow rate. On-board measurements were carried out on a fleet of ten vehicles driving a 30 minute circuit representative of real-world urban driving conditions. These measurements afforded emission factors for NH3 (194 × 147 mg km-1) and HCN (3.33 × 3.61 mg km-1), as well as the first report of methylamine emission factors, 0.70 × 0.61 mg km-1. Emissions of both amines were highly correlated (R2 = 0.95). The temporally-resolved TDL spectrometer measurements indicate that the highest HCN and C2H2 emissions occur during specific emission modes that are a function of driving conditions.

  19. Ammonia formation from NO reaction with surface hydroxyls on rutile TiO2 (110) - 1×1

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

    Kim, Boseong; Kay, Bruce D.; Dohnalek, Zdenek

    2015-01-15

    The reaction of NO with hydroxylated rutile TiO2(110)-1×1 surface (h-TiO2) was investigated as a function of NO coverage using temperature-programmed desorption. Our results show that NO reaction with h-TiO2 leads to formation of NH3 which is observed to desorb at ~ 400 K. Interestingly, the amount of NH3 produced depends nonlinearly on the coverage of NO. The yield increases up to a saturation value of ~1.3×1013 NH3/cm2 at a NO dose of 5×1013 NO/cm2, but subsequently decreases at higher NO doses. Preadsorbed H2O is found to have a negligible effect on the NH3 desorption yield. Additionally, no NH3 is formedmore » in the absence of surface hydroxyls (HOb’s) upon coadsorption of NO and H2O on a stoichiometric TiO2(110) (s-TiO2(110)). Based on these observations, we conclude that nitrogen from NO has a strong preference to react with HOb’s on the bridge-bonded oxygen rows (but not with H2O) to form NH3. The absolute NH3 yield is limited by competing reactions of HOb species with titanium-bound oxygen adatoms to form H2O. Our results provide new mechanistic insight about the interactions of NO with hydroxyl groups on TiO2(110) .« less

  20. Bluish-white-light-emitting diodes based on two-dimensional lead halide perovskite (C6H5C2H4NH3)2PbCl2Br2

    NASA Astrophysics Data System (ADS)

    Cai, Peiqing; Wang, Xiangfu; Seo, Hyo Jin; Yan, Xiaohong

    2018-04-01

    Bluish-white-light-emitting diodes (BWLEDs) are designed based on the two-dimensional mixed halide perovskite (C6H5C2H4NH3)2PbCl2Br2 at room temperature. Bluish-white electroluminescence devices were fabricated by a spin-coating method. The BWLEDs can be turned on at 4.9 V and depict a maximum luminance of ˜70 cd/m2 at 7 V. Low and room temperature photoluminescence spectra show the coexistence of free exciton and self-trapped exciton luminescence in a deformable lattice. The strategy of achieving white electroluminescence (EL) from mixed halide perovskite reported here can be applied to other two-dimensional perovskites to increase the optoelectronic efficiency of the device in the future.

  1. 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.

  2. Variation in the Water and Ammonia Abundance in Jupiter’s North Equatorial Belt

    NASA Astrophysics Data System (ADS)

    Bjoraker, Gordon L.; de Pater, Imke; Wong, Michael H.; Adamkovics, Mate; Hewagama, Tilak; Orton, Glenn

    2017-10-01

    We used iSHELL on NASA’s Infrared Telescope Facility and NIRSPEC on the Keck telescope concurrent with Juno perijoves 4-6 between February and May 2017 to obtain 5-micron spectra of Jupiter. Here we will focus on observations of the North Equatorial Belt. Spectrally resolved line profiles of CH3D, NH3, and H2O probe the 1 to 8-bar level of Jupiter’s troposphere. This overlaps with the weighting functions for several channels of Juno’s microwave radiometer. The profile of the CH3D lines at 4.66 microns is very broad in Hot Spots due to collisions with up to 8 bars of H2, where unit optical depth occurs due to collision-induced H2 opacity. The extreme width of these CH3D features implies that the Hot Spots that we observed do not have significant cloud opacity for P > 2 bars. We will discuss the abundance of NH3 and gaseous H2O within Hot Spots and other regions near the longitude of perijove for each Juno encounter. We had dry nights on Mauna Kea and a sufficient Doppler shift to detect H2O. We will compare line wings to derive H2O profiles in the 2 to 6-bar region. NEB Hot Spots are depleted in NH3 with respect to adjacent regions, especially for P < 2 bars. NEB Hot Spots are highly depleted in H2O for P < 5 bars.

  3. Ammonia losses and nitrogen partitioning at a southern High Plains open lot dairy

    NASA Astrophysics Data System (ADS)

    Todd, Richard W.; Cole, N. Andy; Hagevoort, G. Robert; Casey, Kenneth D.; Auvermann, Brent W.

    2015-06-01

    Animal agriculture is a significant source of ammonia (NH3). Cattle excrete most ingested nitrogen (N); most urinary N is converted to NH3, volatilized and lost to the atmosphere. Open lot dairies on the southern High Plains are a growing industry and face environmental challenges as well as reporting requirements for NH3 emissions. We quantified NH3 emissions from the open lot and wastewater lagoons of a commercial New Mexico dairy during a nine-day summer campaign. The 3500-cow dairy consisted of open lot, manure-surfaced corrals (22.5 ha area). Lactating cows comprised 80% of the herd. A flush system using recycled wastewater intermittently removed manure from feeding alleys to three lagoons (1.8 ha area). Open path lasers measured atmospheric NH3 concentration, sonic anemometers characterized turbulence, and inverse dispersion analysis was used to quantify emissions. Ammonia fluxes (15-min) averaged 56 and 37 μg m-2 s-1 at the open lot and lagoons, respectively. Ammonia emission rate averaged 1061 kg d-1 at the open lot and 59 kg d-1 at the lagoons; 95% of NH3 was emitted from the open lot. The per capita emission rate of NH3 was 304 g cow-1 d-1 from the open lot (41% of N intake) and 17 g cow-1 d-1 from lagoons (2% of N intake). Daily N input at the dairy was 2139 kg d-1, with 43, 36, 19 and 2% of the N partitioned to NH3 emission, manure/lagoons, milk, and cows, respectively.

  4. Ammonia gas sensors based on poly (3-hexylthiophene)-molybdenum disulfide film transistors.

    PubMed

    Xie, Tao; Xie, Guangzhong; Su, Yuanjie; Hongfei, Du; Ye, Zongbiao; Jiang, Yadong

    2016-02-12

    In this work, in order to enhance the recovery performance of organic thin film transistors (OTFTs) ammonia (NH3) sensors, poly (3-hexylthiophene) (P3HT) and molybdenum disulfide (MoS2) were combined as sensitive materials. Different sensitive film structures as active layers of OTFTs, i.e., P3HT-MoS2 composite film, P3HT/MoS2 bilayer film and MoS2/P3HT bilayer film were fabricated by spray technology. OTFT gas sensors based on P3HT-MoS2 composite film showed a shorter recovery time than others when the ammonia concentration changed from 4 to 20 ppm. Specifically, x-ray diffraction (XRD), Raman and UV-visible absorption were employed to explore the interface properties between P3HT and single-layer MoS2. Through the complementary characterization, a mechanism based on charge transfer is proposed to explain the physical originality of these OTFT gas sensors: closer interlayer d-spacing and better π-π stacking of the P3HT chains in composite film have ensured a short recovery time of OTFT gas sensors. Moreover, sensing mechanisms of OTFTs were further studied by comparing the device performance in the presence of nitrogen or dry air as a carrier gas. This work not only strengthens the fundamental understanding of the sensing mechanism, but provides a promising approach to optimizing the OTFT gas sensors.

  5. Selective Catalytic Reduction of NO by NH 3 with WO 3-TiO 2 Catalysts: Influence of Catalyst Synthesis Method

    DOE PAGES

    He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

    2016-02-02

    A series of supported WO 3/TiO 2 catalysts was prepared by a new synthesis procedure involving co-precipitation of an aqueous TiO(OH) 2 and (NH 4) 10W 12O 41*5H 2O slurry under controlled pH conditions. The morphological properties, molecular structures, surface acidity and surface chemistry of the supported WO 3/TiO 2 catalysts were determined with BET, in situ Raman, in situ IR and temperature-programmed surface reaction (TPSR) spectroscopy, respectively. Isotopic 18O- 16O exchange demonstrated that tungsten oxide was exclusively present as surface WO x species on the TiO 2 support with mono-oxo W=O coordination. In contrast to previous studies employing impregnationmore » synthesis that found only surface one mono-oxo O=WO 4 site on TiO 2, the co-precipitation procedure resulted in the formation of two distinct surface WO x species: mono-oxo O=WO 4 (~1010-1017 cm -1) on low defect density patches of TiO 2 and a second mono-oxo O=WO 4 (~983-986 cm -1) on high defect density patches of TiO 2. The concentration of the second WO x surface species increases as a function of solution pH. Both surface WOx sites, however, exhibited the same NO/NH 3 SCR reactivity. The co-precipitated WO 3-TiO 2 catalysts synthesized in alkaline solutions exhibited enhanced performance for the NO/NH 3 SCR reaction that is ascribed to the greater number of surface defects on the resulting TiO2 support. For the co-precipitated catalyst prepared at pH10, surface NH 4 + species on Br nsted acid sites were found to be more reactive than surface NH 3* species on Lewis acid sites for SCR of NO with NH 3.« less

  6. H2(15)O or 13NH3 PET and electromagnetic tomography (LORETA) during partial status epilepticus.

    PubMed

    Zumsteg, D; Wennberg, R A; Treyer, V; Buck, A; Wieser, H G

    2005-11-22

    The authors evaluated the feasibility and source localization utility of H2(15)O or 13NH3 PET and low-resolution electromagnetic tomography (LORETA) in three patients with partial status epilepticus (SE). Results were correlated with findings from intraoperative electrocorticographic recordings and surgical outcomes. PET studies of cerebral blood flow and noninvasive source modeling with LORETA using statistical nonparametric mapping provided useful information for localizing the ictal activity in patients with partial SE.

  7. Condensation and Vaporization Studies of CH3OH and NH3 Ices: Major Implications for Astrochemistry

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1993-01-01

    In an extension of previously reported work on ices containing H20, CO, CO2, SO2, H2S, and H2, We present measurements of the physical and infrared spectral properties of ices containing CH30H and NH3.The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed 87 of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

  8. Ammonia Inactivation of Ascaris Ova in Ecological Compost by Using Urine and Ash

    PubMed Central

    Parzen, Rebecca E.; Mercado Guzmán, Álvaro

    2012-01-01

    Viable ova of Ascaris lumbricoides, an indicator organism for pathogens, are frequently found in feces-derived compost produced from ecological toilets, demonstrating that threshold levels of time, temperature, pH, and moisture content for pathogen inactivation are not routinely met. Previous studies have determined that NH3 has ovicidal properties for pathogens, including Ascaris ova. This research attempted to achieve Ascaris inactivation via NH3 under environmental conditions commonly found in ecological toilets and using materials universally available in an ecological sanitation setting, including compost (feces and sawdust), urine, and ash. Compost mixed with stored urine and ash produced the most rapid inactivation, with significant inactivation observed after 2 weeks and with a time to 99% ovum inactivation (T99) of 8 weeks. Compost mixed with fresh urine and ash achieved a T99 of 15 weeks, after a 4-week lag phase. Both matrices had relatively high total-ammonia concentrations and pH values of >9.24 (pKa of ammonia). In compost mixed with ash only, and in compost mixed with fresh urine only, inactivation was observed after an 11-week lag phase. These matrices contained NH3 concentrations of 164 to 173 and 102 to 277 mg/liter, respectively, when inactivation occurred, which was below the previously hypothesized threshold for inactivation (280 mg/liter), suggesting that a lower threshold NH3 concentration may be possible with a longer contact time. Other significant results include the hydrolysis of urea to ammonia between pH values of 10.4 and 11.6, above the literature threshold pH of 10. PMID:22582051

  9. Ammonia inactivation of Ascaris ova in ecological compost by using urine and ash.

    PubMed

    McKinley, James W; Parzen, Rebecca E; Mercado Guzmán, Álvaro

    2012-08-01

    Viable ova of Ascaris lumbricoides, an indicator organism for pathogens, are frequently found in feces-derived compost produced from ecological toilets, demonstrating that threshold levels of time, temperature, pH, and moisture content for pathogen inactivation are not routinely met. Previous studies have determined that NH(3) has ovicidal properties for pathogens, including Ascaris ova. This research attempted to achieve Ascaris inactivation via NH(3) under environmental conditions commonly found in ecological toilets and using materials universally available in an ecological sanitation setting, including compost (feces and sawdust), urine, and ash. Compost mixed with stored urine and ash produced the most rapid inactivation, with significant inactivation observed after 2 weeks and with a time to 99% ovum inactivation (T(99)) of 8 weeks. Compost mixed with fresh urine and ash achieved a T(99) of 15 weeks, after a 4-week lag phase. Both matrices had relatively high total-ammonia concentrations and pH values of >9.24 (pK(a) of ammonia). In compost mixed with ash only, and in compost mixed with fresh urine only, inactivation was observed after an 11-week lag phase. These matrices contained NH(3) concentrations of 164 to 173 and 102 to 277 mg/liter, respectively, when inactivation occurred, which was below the previously hypothesized threshold for inactivation (280 mg/liter), suggesting that a lower threshold NH(3) concentration may be possible with a longer contact time. Other significant results include the hydrolysis of urea to ammonia between pH values of 10.4 and 11.6, above the literature threshold pH of 10.

  10. The Jovian atmospheric window at 2.7 microns: A search for H2S

    NASA Technical Reports Server (NTRS)

    Larson, H. P.; Davis, D. S.; Hofmann, R.; Bjoraker, G. L.

    1984-01-01

    The atmospheric transmission window at 2.7 microns in Jupiter's atmosphere was observed at a spectral resolution of 0.1/cm from the Kuiiper Airborne Observatory. From an analysis of the CH4 abundance (80 m-am) and the H2O abundance ( 0.0125 cm-am) it was determined that the penetration depth of solar flux at 2.7 microns is near the base of the NH3 cloud layer. The upper limit to H2O at 2.7 microns and other results suggest that photolytic reactions in Jupiter's lower troposphere may not be as significant as was previously thought. A search for H2S in Jupiter's atmosphere yielded an upper limit of 0.1 cm-am. The corresponding limit to the element abundance ratio S/H was approx. 1.7x10(-8), about 10(-3) times the solar value. Upon modeling the abundance and distribution of H2S in Jupiter's atmosphere it was concluded that, contrary to expectations, sulfur-bearing chromophores are not present in significant amounts in Jupiter's visible clouds. Rather, it appears that most of Jupiter's sulfur is locked up as NH4SH in a lower cloud layer. Alternatively, the global abundance of sulfur in Jupiter may be significantly depleted.

  11. The C( 3P) + NH 3 reaction in interstellar chemistry. I. Investigation of the product formation channels

    DOE PAGES

    Bourgalais, Jeremy; Capron, Michael; Kailasanathan, Ranjith Kumar Abhinavam; ...

    2015-10-13

    The product formation channels of ground state carbon atoms, C( 3P), reacting with ammonia, NH3, have been investigated using two complementary experiments and electronic structure calculations. Reaction products are detected in a gas flow tube experiment (330 K, 4 Torr) using tunable vacuum-ultraviolet (VUV) photoionization coupled with time of flight mass spectrometry. Temporal profiles of the species formed and photoionization spectra are used to identify primary products of the C + NH 3 reaction. In addition, H-atom formation is monitored by VUV laser induced fluorescence (LIF) from room temperature to 50 K in a supersonic gas flow generated by themore » Laval nozzle technique. Electronic structure calculations are performed to derive intermediates, transition states, and complexes formed along the reaction coordinate. The combination of photoionization and LIF experiments supported by theoretical calculations indicate that in the temperature and pressure range investigated, the H + H 2CN production channel represents 100% of the product yield for this reaction. As a result, kinetics measurements of the title reaction down to 50 K and the effect of the new rate constants on interstellar nitrogen hydride abundances using a model of dense interstellar clouds are reported in Paper II.« less

  12. Diffusive and rotational dynamics of condensed n-H2 confined in MCM-41

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

    Prisk, Timothy R; Bryan, Matthew; Sokol, Paul E

    2014-01-01

    In this paper, we report an inelastic neutron scattering study of liquid and solid n-H2 confined within MCM-41. This is a high surface area, mesoporous silica glass with a narrow pore size distribution centered at 3.5 nm. The scattering data provides information about the diffusive and rotational dynamics of the adsorbed n-H2 at low temperatures. In the liquid state, the neutron scattering data demonstrates that only a fraction of the adsorbed o-H2 is mobile on the picosecond time scale. This mobile fraction undergoes liquid-like jump diffusion, and values for the residence time t and effective mean-squared displacement hu2i are reportedmore » as a function of pore filling. In the solid state, the rotational energy levels of adsorbed H2 are strongly perturbed from their free quantum rotor behavior in the bulk solid. The underlying orientational potential of the hindered rotors is due to the surface roughness and heterogeneity of the MCM-41 pore walls. This potential is compared to the hindering potential of other porous silicas, such as Vycor. Strong selective adsorption makes the interfacial layer rich in o-H2, leaving the inner core volume consisting of a depleted mixture of o-H2 and p-H2.« less

  13. Tungsten phosphanylarylthiolato complexes [W{PhP(2-SC6H4)2-kappa3S,S',P} 2] and [W{P(2-SC6H4)3-kappa4S,S',S",P}2]: synthesis, structures and redox chemistry.

    PubMed

    Hildebrand, Alexandra; Lönnecke, Peter; Silaghi-Dumitrescu, Luminita; Hey-Hawkins, Evamarie

    2008-09-14

    PhP(2-SHC6H4)2 (PS2H2) reacts with WCl6 with reduction of tungsten to give the air-sensitive tungsten(IV) complex [W{PhP(2-SC6H4)2-kappa(3)S,S',P}2] (1). 1 is oxidised in air to [WO{PhPO(2-SC6H4)2-kappa(3)S,S',O}{PhP(2-SC6H4)2-kappa(3)S,S',P}] (2). The attempted synthesis of 2 by reaction of 1 with iodosobenzene as oxidising agent was unsuccessful. [W{P(2-SC6H4)3-kappa(4)S,S',S",P}2] (3) was formed in the reaction of P(2-SHC6H4)3 (PS3H3) with WCl6. The W(VI) complex 3 contains two PS3(3-) ligands, each coordinated in a tetradentate fashion resulting in a tungsten coordination number of eight. The reaction of 3 with AgBF4 yields the dinuclear tungsten complex [W2{P(2-SC6H4)3-kappa(4)S,S',S",P}3]BF4 (4). Complexes 1-4 were characterised by spectral methods and X-ray structure determination.

  14. Physiology, biochemistry, and specific inhibitors of CH4, NH4+, and CO oxidation by methanotrophs and nitrifiers.

    PubMed Central

    Bédard, C; Knowles, R

    1989-01-01

    Ammonia oxidizers (family Nitrobacteraceae) and methanotrophs (family Methylococcaceae) oxidize CO and CH4 to CO2 and NH4+ to NO2-. However, the relative contributions of the two groups of organisms to the metabolism of CO, CH4, and NH4+ in various environments are not known. In the ammonia oxidizers, ammonia monooxygenase, the enzyme responsible for the conversion of NH4+ to NH2OH, also catalyzes the oxidation of CH4 to CH3OH. Ammonia monooxygenase also mediates the transformation of CH3OH to CO2 and cell carbon, but the pathway by which this is done is not known. At least one species of ammonia oxidizer, Nitrosococcus oceanus, exhibits a Km for CH4 oxidation similar to that of methanotrophs. However, the highest rate of CH4 oxidation recorded in an ammonia oxidizer is still five times lower than rates in methanotrophs, and ammonia oxidizers are apparently unable to grow on CH4. Methanotrophs oxidize NH4+ to NH2OH via methane monooxygenase and NH4+ to NH2OH via methane monooxygenase and NH2OH to NO2- via an NH2OH oxidase which may resemble the enzyme found in ammonia oxidizers. Maximum rates of NH4+ oxidation are considerably lower than in ammonia oxidizers, and the affinity for NH4+ is generally lower than in ammonia oxidizers. NH4+ does not apparently support growth in methanotrophs. Both ammonia monooxygenase and methane monooxygenase oxidize CO to CO2, but CO cannot support growth in either ammonia oxidizers or methanotrophs. These organisms have affinities for CO which are comparable to those for their growth substrates and often higher than those in carboxydobacteria. The methane monooxygenases of methanotrophs exist in two forms: a soluble form and a particulate form. The soluble form is well characterized and appears unrelated to the particulate. Ammonia monooxygenase and the particulate methane monooxygenase share a number of similarities. Both enzymes contain copper and are membrane bound. They oxidize a variety of inorganic and organic compounds, and

  15. Use of dilute ammonia gas for treatment of 1,2,3-trichloropropane and explosives-contaminated soils.

    PubMed

    Coyle, Charles G; Waisner, Scott A; Medina, Victor F; Griggs, Chris S

    2017-12-15

    Laboratory studies were performed to test a novel reactive gas process for in-situ treatment of soils containing halogenated propanes or explosives. A soil column study, using a 5% ammonia-in-air mixture, established that the treatment process can increase soil pH from 7.5 to 10.2. Batch reactor experiments were performed to demonstrate contaminant destruction in sealed jars exposed to ammonia. Comparison of results from batch reactors that were, and were not, exposed to ammonia demonstrated reductions in concentrations of 1,2,3-trichloropropane (TCP), 1,3-dichloropropane (1,3-DCP), 1,2-dicholoropropane (1,2-DCP) and dibromochloropropane (DBCP) that ranged from 34 to 94%. Decreases in TCP concentrations at 23° C ranged from 37 to 65%, versus 89-94% at 62° C. A spiked soil column study was also performed using the same set of contaminants. The study showed a pH penetration distance of 30 cm in a 2.5 cm diameter soil column (with a pH increase from 8 to > 10), due to treatment via 5% ammonia gas at 1 standard cubic centimeter per minute (sccm) for 7 days. Batch reactor tests using explosives contaminated soils exhibited a 97% decrease in 2,4,6-trinitrotoluene (TNT), an 83% decrease in nitrobenzene, and a 6% decrease in hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). A biotransformation study was also performed to investigate whether growth of ammonia-oxidizing microorganisms could be stimulated via prolonged exposure of soil to ammonia. Over the course of the 283 day study, only a very small amount of nitrite generation was observed; indicating very limited ammonia monooxygenase activity. Overall, the data indicate that ammonia gas addition can be a viable approach for treating halogenated propanes and some types of explosives in soils. Published by Elsevier Ltd.

  16. Archaea produce lower yields of N2 O than bacteria during aerobic ammonia oxidation in soil.

    PubMed

    Hink, Linda; Nicol, Graeme W; Prosser, James I

    2017-12-01

    Nitrogen fertilisation of agricultural soil contributes significantly to emissions of the potent greenhouse gas nitrous oxide (N 2 O), which is generated during denitrification and, in oxic soils, mainly by ammonia oxidisers. Although laboratory cultures of ammonia oxidising bacteria (AOB) and archaea (AOA) produce N 2 O, their relative activities in soil are unknown. This work tested the hypothesis that AOB dominate ammonia oxidation and N 2 O production under conditions of high inorganic ammonia (NH 3 ) input, but result mainly from the activity of AOA when NH 3 is derived from mineralisation. 1-octyne, a recently discovered inhibitor of AOB, was used to distinguish N 2 O production resulting from archaeal and bacterial ammonia oxidation in soil microcosms, and specifically inhibited AOB growth, activity and N 2 O production. In unamended soils, ammonia oxidation and N 2 O production were lower and resulted mainly from ammonia oxidation by AOA. The AOA N 2 O yield relative to nitrite produced was half that of AOB, likely due to additional enzymatic mechanisms in the latter, but ammonia oxidation and N 2 O production were directly linked in all treatments. Relative contributions of AOA and AOB to N 2 O production, therefore, reflect their respective contributions to ammonia oxidation. These results suggest potential mitigation strategies for N 2 O emissions from fertilised agricultural soils. © 2016 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

  17. The Relationship of the Silicon Surface Roughness and Gate Oxide Integrity in NH4OH/H2O2 Mixtures

    NASA Astrophysics Data System (ADS)

    Meuris, M.; Verhaverbeke, S.; Mertens, P. W.; Heyns, M. M.; Hellemans, L.; Bruynseraede, Y.; Philipossian, A.

    1992-11-01

    In this study some recent findings on the cleaning action of the NH4OH/H2O2 (SC1) step in a pre-gate oxidation cleaning (RCA cleaning) are given. An important parameter in this mixture is the NH4OH/H2O2 ratio. The Fe contamination on the silicon surface after this cleaning step is found to increase upon decreasing the NH4OH/H2O2 ratio. This can be attributed to the incorporation of Fe in the chemical oxide, grown by the hydrogen peroxide. The particle removal efficiency of the cleaning step is found to decrease upon decreasing the NH4OH/H2O2 ratio. On the other hand, using a lower NH4OH concentration results in a less severe silicon surface roughening. It is demonstrated in this study that the NH4OH/H2O2 ratio during the SC1 step of the cleaning is the determining parameter for the breakdown properties of a gate oxide. A (0.25/1/5) NH4OH/H2O2/H2O mixture at 75°C in our experimental conditions is suggested to be the best compromise between particle removal and surface roughness during the SC1 step.

  18. Evaluating the Thermodynamics of Electrocatalytic N 2 Reduction in Acetonitrile

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

    Lindley, Brian M.; Appel, Aaron M.; Krogh-Jespersen, Karsten

    The synthesis of ammonia by proton-coupled electroreduction of dinitrogen (N2) represents a sustainable alternative to currently practiced hydrogenation methods. Developments in this area require knowledge of the standard reduction potentials that describe the thermodynamics of N2 reduction. The first collection of N2 reduction standard potentials in organic solvent are reported here. The potentials for reduction of N2 to ammonia (NH3), hydrazine (N2H4), and diazene (N2H2) in acetonitrile (MeCN) solution are derived using thermochemical cycles. Ammonia is the thermodynamically favored product, with a 0.43 V difference between NH3 and N2H4 and a 1.26 V difference between NH3 and N2H2. The thermodynamicsmore » for reduction of N2 to the protonated products ammonium (NH4+) and hydrazinium (N2H5+) under strongly acidic conditions are also presented. Comparison with previously determined values for the H+/H2 potential in MeCN reveals a 63 mV thermodynamic preference for N2 reduction to NH3 over H2 production. Combined with knowledge of the kinetics of electrode-catalyzed H2 evolution, a wide working region is identified to guide future electrocatalytic studies.« less

  19. Different transport behaviors of NH4 (+) and NH3 in transmembrane cyclic peptide nanotubes.

    PubMed

    Zhang, Mingming; Fan, Jianfen; Xu, Jian; Weng, Peipei; Lin, Huifang

    2016-10-01

    Two water-filled transmembrane cyclic peptide nanotubes (CPNTs) of 8×cyclo-(WL)n=4,5/POPE were chosen to investigate the dependences of the transport properties of the positive NH4 (+) and neutral NH3 on the channel radius. Molecular dynamic simulations revealed that molecular charge, size, ability to form H-bonds and channel radius all significantly influence the behaviors of NH4 (+) and NH3 in a CPNT. Higher electrostatic interactions, more H-bonds, and water-bridges were found in the NH4 (+) system, resulting in NH4 (+) meeting higher energy barriers, while NH3 can enter, exit and permeate the channels effortlessly. This work sheds a first light on the differences between the mechanisms of NH4 (+) and NH3 moving in a CPNT at an atomic level. Graphical Abstract Snapshot of the simulation system of NH4 (+)_octa-CPNT with an NH4 (+) initially positioned at one mouth of the tube, PMF profiles for single NH4 (+) ion and NH3 molecule moving through water-filled transmembrane CPNTs of 8×cyclo-(WL)n=4,5/POPE and sketch graphs of the possible H-bond forms of NH3 and NH4 (+) with the neighboring water.

  20. Mechanisms of ammonia and ammonium transport by rhesus-associated glycoproteins

    PubMed Central

    Caner, Tolga; Abdulnour-Nakhoul, Solange; Brown, Karen; Islam, M. Toriqul; Hamm, L. Lee

    2015-01-01

    In this study we characterized ammonia and ammonium (NH3/NH4+) transport by the rhesus-associated (Rh) glycoproteins RhAG, Rhbg, and Rhcg expressed in Xenopus oocytes. We used ion-selective microelectrodes and two-electrode voltage clamp to measure changes in intracellular pH, surface pH, and whole cell currents induced by NH3/NH4+ and methyl amine/ammonium (MA/MA+). These measurements allowed us to define signal-specific signatures to distinguish NH3 from NH4+ transport and to determine how transport of NH3 and NH4+ differs among RhAG, Rhbg, and Rhcg. Our data indicate that expression of Rh glycoproteins in oocytes generally enhanced NH3/NH4+ transport and that cellular changes induced by transport of MA/MA+ by Rh proteins were different from those induced by transport of NH3/NH4+. Our results support the following conclusions: 1) RhAG and Rhbg transport both the ionic NH4+ and neutral NH3 species; 2) transport of NH4+ is electrogenic; 3) like Rhbg, RhAG transport of NH4+ masks NH3 transport; and 4) Rhcg is likely to be a predominantly NH3 transporter, with no evidence of enhanced NH4+ transport by this transporter. The dual role of Rh proteins as NH3 and NH4+ transporters is a unique property and may be critical in understanding how transepithelial secretion of NH3/NH4+ occurs in the renal collecting duct. PMID:26354748

  1. A Three-Step Atomic Layer Deposition Process for SiN x Using Si2Cl6, CH3NH2, and N2 Plasma.

    PubMed

    Ovanesyan, Rafaiel A; Hausmann, Dennis M; Agarwal, Sumit

    2018-06-06

    We report a novel three-step SiN x atomic layer deposition (ALD) process using Si 2 Cl 6 , CH 3 NH 2 , and N 2 plasma. In a two-step process, nonhydrogenated chlorosilanes such as Si 2 Cl 6 with N 2 plasmas lead to poor-quality SiN x films that oxidize rapidly. The intermediate CH 3 NH 2 step was therefore introduced in the ALD cycle to replace the NH 3 plasma step with a N 2 plasma, while using Si 2 Cl 6 as the Si precursor. This three-step process lowers the atomic H content and improves the film conformality on high-aspect-ratio nanostructures as Si-N-Si bonds are formed during a thermal CH 3 NH 2 step in addition to the N 2 plasma step. During ALD, the reactive surface sites were monitored using in situ surface infrared spectroscopy. Our infrared spectra show that, on the post-N 2 plasma-treated SiN x surface, Si 2 Cl 6 reacts primarily with the surface -NH 2 species to form surface -SiCl x ( x = 1, 2, or 3) bonds, which are the reactive sites during the CH 3 NH 2 cycle. In the N 2 plasma step, reactive -NH 2 surface species are created because of the surface H available from the -CH 3 groups. At 400 °C, the SiN x films have a growth per cycle of ∼0.9 Å with ∼12 atomic percent H. The films grown on high-aspect-ratio nanostructures have a conformality of ∼90%.

  2. Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH 3 with V 2O 5-WO 3/TiO 2 catalysts

    DOE PAGES

    He, Yuanyuan; Ford, Michael E.; Zhu, Minghui; ...

    2016-04-14

    We compared the molecular structures, surface acidity and catalytic activity for NO/NH 3/O 2 SCR of V 2O 5-WO 3/TiO 2 catalysts for two different synthesis methods: co-precipitation of aqueous vanadium and tungsten oxide precursors with TiO(OH) 2 and by incipient wetness impregnation of the aqueous precursors on a reference crystalline TiO 2 support (P25; primarily anatase phase). Bulk analysis by XRD showed that co-precipitation results in small and/or poorly ordered TiO 2(anatase) particles and that VO x and WO x do not form solid solutions with the bulk titania lattice. Surface analysis of the co-precipitated catalyst by High Sensitivity-Lowmore » Energy Ion Scattering (HS-LEIS) confirms that the VO x and WO x are surface segregated for the co-precipitated catalysts. In situ Raman and IR spectroscopy revealed that the vanadium and tungsten oxide components are present as surface mono-oxo O = VO 3 and O = WO 4 sites on the TiO 2 supports. Co-precipitation was shown for the first time to also form new mono-oxo surface VO 4 and WO 4 sites that appear to be anchored at surface defects of the TiO 2 support. IR analysis of chemisorbed ammonia showed the presence of both surface NH 3 * on Lewis acid sites and surface NH 4 +* on Brønsted acid sites. TPSR spectroscopy demonstrated that the specific SCR kinetics was controlled by the redox surface VO 4 species and that the surface kinetics was independent of TiO 2 synthesis method or presence of surface WO 5 sites. SCR reaction studies revealed that the surface WO5 sites possess minimal activity below ~325 °C and their primary function is to increase the adsorption capacity of ammonia. A relationship between the SCR activity and surface acidity was not found. The SCR reaction is controlled by the surface VO 4 sites that initiate the reaction at ~200 °C. The co-precipitated catalysts were always more active than the corresponding impregnated catalysts. Finally, we ascribe the higher activity of the co

  3. Theoretical study of geometry relaxation following core excitation: H2O, NH3, and CH4

    NASA Astrophysics Data System (ADS)

    Takahashi, Osamu; Kunitake, Naoto; Takaki, Saya

    2015-10-01

    Single core-hole (SCH) and double core-hole excited state molecular dynamics (MD) calculations for neutral and cationic H2O, NH3, and CH4 have been performed to examine geometry relaxation after core excitation. We observed faster X-H (X = C, N, O) bond elongation for the core-ionized state produced from the valence cationic molecule and the double-core-ionized state produced from the ground and valence cationic molecules than for the first resonant SCH state. Using the results of SCH MD simulations of the ground and valence cationic molecules, Auger decay spectra calculations were performed. We found that fast bond scission leads to peak broadening of the spectra.

  4. Condensation and vaporization studies of CH3OH and NH3 ices: Major implications for astrochemistry

    NASA Technical Reports Server (NTRS)

    Sandford, Scott A.; Allamandola, Louis J.

    1993-01-01

    In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.

  5. Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic

    NASA Astrophysics Data System (ADS)

    Li, Yang; Li, Ying; Wang, Baomin; Luo, Yi; Yang, Dawei; Tong, Peng; Zhao, Jinfeng; Luo, Lun; Zhou, Yuhan; Chen, Si; Cheng, Fang; Qu, Jingping

    2013-04-01

    Although nitrogenase enzymes routinely convert molecular nitrogen into ammonia under ambient temperature and pressure, this reaction is currently carried out industrially using the Haber-Bosch process, which requires extreme temperatures and pressures to activate dinitrogen. Biological fixation occurs through dinitrogen and reduced NxHy species at multi-iron centres of compounds bearing sulfur ligands, but it is difficult to elucidate the mechanistic details and to obtain stable model intermediate complexes for further investigation. Metal-based synthetic models have been applied to reveal partial details, although most models involve a mononuclear system. Here, we report a diiron complex bridged by a bidentate thiolate ligand that can accommodate HN=NH. Following reductions and protonations, HN=NH is converted to NH3 through pivotal intermediate complexes bridged by N2H3- and NH2- species. Notably, the final ammonia release was effected with water as the proton source. Density functional theory calculations were carried out, and a pathway of biological nitrogen fixation is proposed.

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

    NASA Astrophysics Data System (ADS)

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

    1996-11-01

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

  7. Oxidation of ammonia and methane in an alkaline, saline lake

    USGS Publications Warehouse

    Joye, S.B.; Connell, T.L.; Miller, L.G.; Oremland, R.S.; Jellison, R.S.

    1999-01-01

    The oxidation of ammonia (NH3) and methane (CH4) was investigated in an alkaline saline lake, Mono Lake, California (U.S.A.). Ammonia oxidation was examined in April and July 1995 by comparing dark 14CO2 fixation rates in the presence or absence of methyl fluoride (MeF), an inhibitor of NH3 oxidation. Ammonia oxidizer-mediated dark 14CO2 fixation rates were similar in surface (5-7 m) and oxycline (11-15 m) waters, ranging between 70-340 and 89-186 nM d-1, respectively, or 1-7% of primary production by phytoplankton. Ammonia oxidation rates ranged between 580-2,830 nM d-1 in surface waters and 732-1,548 nM d-1 in oxycline waters. Methane oxidation was examined using a 14CH4 tracer technique in July 1994, April 1995, and July 1995. Methane oxidation rates were consistently higher in July, and rates in oxycline and anaerobic bottom waters (0.5-37 and 7-48 nM d-1, respectively) were 10-fold higher than those in aerobic surface waters (0.04-3.8 nM d-1). The majority of CH4 oxidation, in terms of integrated activity, occurred within anoxic bottom waters. Water column oxidation reduced the potential lake-atmosphere CH4 flux by a factor of two to three. Measured oxidation rates and water column concentrations were used to estimate the biological turnover times of NH3 and CH4. The NH3 pool turns over rapidly, on time scales of 0.8 d in surface waters and 10 d within the oxycline, while CH4 is cycled on 103-d time scales in surface waters and 102-d time scales within oxycline and bottom waters. Our data suggest an important role for NH3 oxidation in alkaline, saline lakes since the process converts volatile NH3 to soluble NO2-, thereby reducing loss via lake-atmosphere exchange and maintaining nitrogen in a form that is readily available to phytoplankton.

  8. Thermal decomposition of sodium amide, NaNH2, and sodium amide hydroxide composites, NaNH2-NaOH.

    PubMed

    Jepsen, Lars H; Wang, Peikun; Wu, Guotao; Xiong, Zhitao; Besenbacher, Flemming; Chen, Ping; Jensen, Torben R

    2016-09-14

    Sodium amide, NaNH 2 , has recently been shown to be a useful catalyst to decompose NH 3 into H 2 and N 2 , however, sodium hydroxide is omnipresent and commercially available NaNH 2 usually contains impurities of NaOH (<2%). The thermal decomposition of NaNH 2 and NaNH 2 -NaOH composites is systematically investigated and discussed. NaNH 2 is partially dissolved in NaOH at T > 100 °C, forming a non-stoichiometric solid solution of Na(OH) 1-x (NH 2 ) x (0 < x < ∼0.30), which crystallizes in an orthorhombic unit cell with the space group P2 1 2 1 2 1 determined by synchrotron powder X-ray diffraction. The composite xNaNH 2 -(1 - x)NaOH (∼0.70 < x < 0.72) shows a lowered melting point, ∼160 °C, compared to 200 and 318 °C for neat NaNH 2 and NaOH, respectively. We report that 0.36 mol of NH 3 per mol of NaNH 2 is released below 400 °C during heating in an argon atmosphere, initiated at its melting point, T = 200 °C, possibly due to the formation of the mixed sodium amide imide solid solution. Furthermore, NaOH reacts with NaNH 2 at elevated temperatures and provides the release of additional NH 3 .

  9. A detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds

    NASA Technical Reports Server (NTRS)

    Herbst, Eric; Defrees, D. J.; Mclean, A. D.

    1987-01-01

    The initial reactions of the Herbst and Klemperer (1973) and the Dalgarno (1974) schemes (I and II, respectively) for the gas-phase synthesis of ammonia in dense interstellar clouds were investigated. The rate of the slightly endothermic reaction between N(+) and H2 to yield NH(+) and H (scheme I) under interstellar conditions was reinvestigated under thermal and nonthermal conditions based on laboratory data. It was found that the relative importance of this reaction in synthesizing ammonia is determined by how the laboratory data at low temperature are interpreted. On the other hand, the exothermic reaction between N and H3(+) to form NH2(+) + H (scheme II) was calculated to possess significant activation energy and, therefore, to have a negligible rate coefficient under interstellar conditions. Consequently, this reaction cannot take place appreciably in interstellar clouds.

  10. Reversible flexible structural changes in multidimensional MOFs by guest molecules (I{sub 2}, NH{sub 3}) and thermal stimulation

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

    Chen, Yang; Li, Libo; Yang, Jiangfeng

    Three metal–organic frameworks (MOFs), [Cu(INA){sub 2}], [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}], were synthesized with 3D, 2D, and 0D structures, respectively. Reversible flexible structural changes of these MOFs were reported. Through high temperature (60–100 °C) stimulation of I{sub 2} or ambient temperature stimulation of NH{sub 3}, [Cu(INA){sub 2}] (3D) converted to [Cu(INA){sub 2}I{sub 2}] (2D) and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] (0D); as the temperature increased to 150 °C, the MOFs changed back to their original form. In this way, this 3D MOF has potential application in the capture of I{sub 2} and NH{sub 3}more » from polluted water and air. XRD, TGA, SEM, NH{sub 3}-TPD, and the measurement of gas adsorption were used to describe the changes in processes regarding the structure, morphology, and properties. - Graphical abstract: Through I{sub 2}, NH{sub 3} molecules and thermal stimulation, the three MOFs can achieve reversible flexible structural changes. Different methods were used to prove the flexible reversible changes. - Highlights: • [Cu(INA){sub 2}] can flexible transform to [Cu(INA){sub 2}I{sub 2}] and [Cu(INA){sub 2}(H{sub 2}O){sub 2}(NH{sub 3}){sub 2}] by adsorbing I{sub 2} or NH{sub 3}. • The reversible flexible transformation related to material source, temperature and concentration. • Potential applications for the capture of I{sub 2} and NH{sub 3} from polluted water or air.« less

  11. Simultaneous Graphite Exfoliation and N Doping in Supercritical Ammonia.

    PubMed

    Sasikala, Suchithra Padmajan; Huang, Kai; Giroire, Baptiste; Prabhakaran, Prem; Henry, Lucile; Penicaud, Alain; Poulin, Philippe; Aymonier, Cyril

    2016-11-16

    We report the exfoliation of graphite and simultaneous N doping of graphene by two methods: supercritical ammonia treatment and liquid-phase exfoliation with NH 4 OH. While the supercritical ammonia allowed N doping at a level of 6.4 atom % in 2 h, the liquid-phase exfoliation with NH 4 OH allowed N doping at a level of 2.7 atom % in 6 h. The N doped graphene obtained via the supercritical ammonia route had few layers (<5) and showed large lateral flake size (∼8 μm) and low defect density (I D /I G < 0.6) in spite of their high level of N doping. This work is the first demonstration of supercritical ammonia as an exfoliation agent and N doping precursor for graphene. Notably, the N doped graphene showed electrocatalytic activity toward oxygen reduction reaction with high durability and good methanol tolerance compared to those of commercial Pt/C catalyst.

  12. Synthesis and hydriding properties of Li 2Mg(NH) 2

    NASA Astrophysics Data System (ADS)

    Markmaitree, Tippawan; Shaw, Leon L.

    The phase pure Li 2Mg(NH) 2 has been synthesized via a dehydriding treatment of a ball milled 2LiNH 2 + MgH 2 mixture. This phase pure Li 2Mg(NH) 2 has been utilized to investigate its hydriding kinetics at the temperature range 180-220 °C. It is found that the hydriding process of Li 2Mg(NH) 2 is very sluggish even though it has favorable thermodynamic properties for near the ambient temperature operation. Holding at 200 °C for 10 h only results in 3.75 wt.% H 2 uptake. The detailed kinetic analysis reveals that the hydriding process of Li 2Mg(NH) 2 is diffusion-controlled. Thus, this study unambiguously indicates that the future direction to enhance the hydriding kinetics of this promising hydrogen storage material system should be to minimize the diffusion distance and increase the diffusion rate.

  13. Search for ammonia in comet C/2012 S1 (ISON)

    NASA Astrophysics Data System (ADS)

    Faggi, S.; Codella, C.; Tozzi, G.; Comoretto, G.; Crovisier, J.; Nesti, R.; Panella, D.; Boissier, J.; Bolli, P.; Brucato, J.; Massi, F.; Tofani, G.

    2014-07-01

    Comets are pristine bodies of the Solar System and their studies can give precious hints on the formation of the Solar System itself. New comets, coming form the Oort Colud at their first passage close to the Sun, are particularly important, because they are not differentiated by the Solar radiation and they are supposed to have a large quantity of organic matter close to the surface. Here we report the results of a search for NH_3(1,1) emission at 23.7 GHz in comet C/2012 S1 ISON using a new dual-feed K-band receiver mounted on the Medicina 32-m antenna. We observed the comet once close to its perihelion, from 2013 Nov. 25 to Nov. 28, when its heliocentric distance changed from 0.25 au to 0.03 au. We integrated about 6 hrs per day, obtaining high-spectral-resolution (1 km/s) spectra with a typical rms noise of 10 mK. Such sensitivity allowed us to derive an upper limit of Q(NH_3) of about 2.5 ×10^{29} mol/s on November 26. This upper limit would correspond to a Q(H_2O) of about 2.5 ×10^{31} mol/s, assuming the typical Q(H_2O)/Q(NH_3) ratio of 100. These findings confirm that no significant Q(H_2O) enhancement happened near the perihelion, consistent with a definitive decrease of molecules production rate.

  14. ORTHO-PARA SELECTION RULES IN THE GAS-PHASE CHEMISTRY OF INTERSTELLAR AMMONIA

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

    Faure, A.; Hily-Blant, P.; Le Gal, R.

    The ortho-para chemistry of ammonia in the cold interstellar medium is investigated using a gas-phase chemical network. Branching ratios for the primary reaction chain involved in the formation and destruction of ortho- and para-NH{sub 3} were derived using angular momentum rules based on the conservation of the nuclear spin. We show that the 'anomalous' ortho-to-para ratio of ammonia ({approx}0.7) observed in various interstellar regions is in fact consistent with nuclear spin selection rules in a para-enriched H{sub 2} gas. This ratio is found to be independent of temperature in the range 5-30 K. We also predict an ortho-to-para ratio ofmore » {approx}2.3 for NH{sub 2}. We conclude that a low ortho-to-para ratio of H{sub 2} naturally drives the ortho-to-para ratios of nitrogen hydrides below the statistical values.« less

  15. Removal of ammonia solutions used in catalytic wet oxidation processes.

    PubMed

    Hung, Chang Mao; Lou, Jie Chung; Lin, Chia Hua

    2003-08-01

    Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.

  16. Summer ammonia measurements in a densely populated Mediterranean city

    NASA Astrophysics Data System (ADS)

    Pandolfi, M.; Amato, F.; Reche, C.; Alastuey, A.; Otjes, R. P.; Blom, M. J.; Querol, X.

    2012-04-01

    Real-time measurements of ambient concentrations of gas-phase ammonia were performed in Barcelona (NE Spain) in summer between May and September 2011. Two measurement sites were selected: one in an urban background traffic-influenced area (UB) and the other in the historical city centre (CC). Levels of ammonia were higher at CC (5.6 ± 2.1 μg m-3 or 7.5 ± 2.8 ppbv) compared with UB (2.2 ± 1.0 μg m-3 or 2.9 ± 1.3 ppbv). This difference is attributed to the contribution from non-traffic sources such as waste containers, sewage systems, humans and open markets more dense in the densely populated historical city centre. Under high temperatures in summer these sources had the potential to increase the ambient levels of ammonia well above the urban-background-traffic-influenced UB measurement station. Measurements were used to assess major local emissions, sinks and diurnal evolution of NH3. The measured levels of NH3, especially high in the old city, may contribute to the high mean annual concentrations of secondary sulfate and nitrate measured in Barcelona compared with other cities in Spain affected by high traffic intensity. Ancillary measurements, including PM10, PM2.5, PM1 levels (Particulate Matter with aerodynamic diameter smaller than 10 μm, 2.5 μm, and 1 μm), gases and black carbon concentrations and meteorological data, were performed during the measurement campaign. The analysis of specific periods (3 special cases) during the campaign revealed that road traffic was a significant source of NH3. However, its effect was more evident at UB compared with CC where it was masked given the high levels of NH3 from non-traffic sources measured in the old city. The relationship between SO42- daily concentrations and gas-fraction ammonia (NH3/(NH3+NH4+)) revealed that the gas-to-phase partitioning (volatilization or ammonium salts formation) also played an important role in the evolution of NH3 concentration in summer in Barcelona.

  17. Chemi-luminescence measurements of hyperthermal Xe{sup +}/Xe{sup 2+}+ NH{sub 3} reactions

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

    Prince, Benjamin D.; Steiner, Colby P.; Chiu, Yu-Hui

    2012-04-14

    Luminescence spectra are recorded for the reactions of Xe{sup +}+ NH{sub 3} and Xe{sup 2+}+ NH{sub 3} at energies ranging from 11.5 to 206 eV in the center-of-mass (E{sub cm}) frame. Intense features of the luminescence spectra are attributed to the NH (A {sup 3}{Pi}{sub i}-X {sup 3}{Sigma}{sup -}), hydrogen Balmer series, and Xe I emission observable for both primary ions. Evidence for charge transfer products is only found through Xe I emission for both primary ions and NH{sup +} emission for Xe{sup 2+} primary ions. For both primary ions, the absolute NH (A-X) cross section increases with collision energymore » before leveling off at a constant value, approximately 9 x 10{sup -18} cm{sup 2}, at about 50 eV while H-{alpha} emission increases linearly with collision energy. The nascent NH (A) populations derived from the spectral analysis are found to be independent of collision energy and have a constant rotational temperature of 4200 K.« less

  18. Simultaneous stabilization/solidification of Mn2+ and NH4+-N from electrolytic manganese residue using MgO and different phosphate resource.

    PubMed

    Shu, Jiancheng; Wu, Haiping; Liu, Renlong; Liu, Zuohua; Li, Bing; Chen, Mengjun; Tao, Changyuan

    2018-02-01

    This study examined simultaneous stabilization and solidification (S/S) of Mn 2+ and NH 4 + -N from electrolytic manganese residue (EMR) using MgO and different phosphate resource. The characteristics of EMR NH 4 + -N and Mn 2+ S/S behavior, S/S mechanisms, leaching test and economic analysis, were investigated. The results show that the S/S efficiency of Mn 2+ and NH 4 + -N could reach 91.58% and 99.98%, respectively, and the pH value is 8.75 when the molar ratio of Mg:P is 3:1 and the dose of PM (MgO and Na 3 PO 4 ·12H 2 O) is 8wt%. In this process, Mn 2+ could mainly be stabilized in the forms of Mn(H 2 PO 4 ) 2 ·2H 2 O, Mn 3 (PO 4 ) 2 ·3H 2 O, Mn(OH) 2 , and MnOOH, and NH 4 + -N in the form of NH 4 MgPO 4 ·6H 2 O. Economic evaluation indicates that using PM process has a lower cost than HPM and HOM process for the S/S of Mn 2+ and NH 4 + -N from EMR at the same stabilization agent dose. Leaching test values of all the measured metals are within the permitted level for the GB8978-1996 test suggested when the dose of PM, HPM and HOM is 8wt%. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Estimating the agricultural fertilizer NH3 emission in China based on the bi-directional CMAQ model and an agro-ecosystem model

    NASA Astrophysics Data System (ADS)

    Wang, S.

    2014-12-01

    Atmospheric ammonia (NH3) plays an important role in fine particle formation. Accurate estimates of ammonia can reduce uncertainties in air quality modeling. China is one of the largest countries emitting ammonia with the majority of NH3 emissions coming from the agricultural practices, such as fertilizer applications and animal operations. The current ammonia emission estimates in China are mainly based on pre-defined emission factors. Thus, there are considerable uncertainties in estimating NH3 emissions, especially in time and space distribution. For example, fertilizer applications vary in the date of application and amount by geographical regions and crop types. In this study, the NH3 emission from the agricultural fertilizer use in China of 2011 was estimated online by an agricultural fertilizer modeling system coupling a regional air-quality model and an agro-ecosystem model, which contains three main components 1) the Environmental Policy Integrated Climate (EPIC) model, 2) the meso-scale meteorology Weather Research and Forecasting (WRF) model and 3) the CMAQ air quality model with bi-directional ammonia fluxes. The EPIC output information about daily fertilizer application and soil characteristics would be the input of the CMAQ model. In order to run EPIC model, much Chinese local information is collected and processed. For example, Crop land data are computed from the MODIS land use data at 500-m resolution and crop categories at Chinese county level; the fertilizer use rate for different fertilizer types, crops and provinces are obtained from Chinese statistic materials. The system takes into consideration many influencing factors on agriculture ammonia emission, including weather, the fertilizer application method, timing, amount, and rate for specific pastures and crops. The simulated fertilizer data is compared with the NH3 emissions and fertilizer application data from other sources. The results of CMAQ modeling are also discussed and analyzed with

  20. Ammonia as a respiratory gas in water and air-breathing fishes.

    PubMed

    Randall, David J; Ip, Yuen K

    2006-11-01

    Ammonia is produced in the liver and excreted as NH(3) by diffusion across the gills. Elevated ammonia results in an increase in gill ventilation, perhaps via stimulation of gill oxygen chemo-receptors. Acidification of the water around the fish by carbon dioxide and acid excretion enhances ammonia excretion and constitutes "environmental ammonia detoxification". Fish have difficulties in excreting ammonia in alkaline water or high concentrations of environmental ammonia, or when out of water. The mudskipper, Periphthalmodon schlosseri, is capable of active NH(4)(+) transport, maintaining low internal levels of ammonia. To prevent a back flux of NH(3), these air-breathing fish can increase gill acid excretion and reduce the membrane NH(3) permeability by modifying the phospholipid and cholesterol compositions of their skin. Several air-breathing fish species can excrete ammonia into air through NH(3) volatilization. Some fish detoxify ammonia to glutamine or urea. The brains of some fish can tolerate much higher levels of ammonia than other animals. Studies of these fish may offer insights into the nature of ammonia toxicity in general.

  1. CFD modelling of a membrane reactor for hydrogen production from ammonia

    NASA Astrophysics Data System (ADS)

    Shwe Hla, San; Dolan, Michael D.

    2018-01-01

    Despite the growing use of hydrogen (H2) as a transport fuel, one of the major barriers still remaining is efficient and inexpensive fuel distribution and storage. Current approaches, such as compression, liquefaction or metal hydride formation, incur a significant energy penalty. Ammonia (NH3) has long been considered a prospective H2 medium, exhibiting a higher volumetric H2 density than liquid H2, through liquid-phase storage at mild pressure. Decomposition of NH3 into H2 and N2 can be achieved via use of catalytic reactors and fuel-cell-grade H2 can be produced using metal membranes at H2 distribution sites.In this study, a 3-Dimensional (3D) Computational Fluid Dynamics (CFD) model has been developed to understand the performance of the H2 separation process in gas mixtures derived from an NH3-cracking reaction. The reactor consists of 19 tubular membrane tubes, each 470 mm long, inside a tubular shell with an inner diameter of 130 mm. Standard transport and energy equations governing a 3D, pressure-based, steady-state model were derived from the laws of conservation of mass, momentum and energy. The governing equations were solved using commercial CFD software ANSYS Fluent 18.0. Gas flow and mixing were modelled by the two-equation standard k-epsilon model for closure. Coupled solver was used for pressure-velocity coupling, enabling a pseudo-transient option with pseudo time steps of 0.01 s. To estimate H2 permeation through the metal membrane, a constant H2 permeability of 3.0E-07 mol.m-1 s-1 Pa-0.5 derived from series of experiments tested under a range of industrial conditions, was used. Model simulations were conducted for an adiabatic temperature of 300 °C, a feed-side pressure of 7.8 bara and a permeate side pressure of 0.1 bara. A parametric analysis was carried out to explore the effects of variation in total feed-gas flow and effects of changes in NH3-cracking efficiency on H2 production rates and H2 yields. The model estimated that 4.6-11.6 kg H2

  2. Dewetting behavior of polystyrene film filled with (C6H5C2H4NH3)2PbI4

    NASA Astrophysics Data System (ADS)

    Xue, Longjian; Cheng, Ziyong; Fu, Jun; Han, Yanchun

    2008-08-01

    The dewetting behavior of thin (about 30 nm) polystyrene (PS) films filled with different amount of (C6H5C2H4NH3)2PbI4 (PhE-PbI4) on the silicon substrate with a native oxide layer was investigated. For different additive concentrations, PhE-PbI4 showed different spatial distributions in the PS films, which had a strong influence on the film wettability, dewetting dynamics, and mechanism. With 0.5 wt % additive, PhE-PbI4 formed a noncontinuous diffusion layer, which caused a continuous hole nucleation in the film. With about 1 wt % additive, a continuous gradient distribution layer of PhE-PbI4 formed in the film, which inhibited the dewetting. When the concentration is higher (2 wt %), large PhE-PbI4 aggregates, in addition to the PhE-PbI4 continuous layer, formed in the film. These large aggregates (larger than radius of gyration of PS) migrated to the interface, resulting in the hole nucleation and eventually the complete dewetting of the film.

  3. Emission factors and characteristics of ammonia, hydrogen sulfide, carbon dioxide, and particulate matter at two high-rise layer hen houses

    NASA Astrophysics Data System (ADS)

    Ni, Ji-Qin; Liu, Shule; Diehl, Claude A.; Lim, Teng-Teeh; Bogan, Bill W.; Chen, Lide; Chai, Lilong; Wang, Kaiying; Heber, Albert J.

    2017-04-01

    Air pollutants emitted from confined animal buildings can cause environmental pollution and ecological damage. Long-term (>6 months) and continuous (or high frequency) monitoring that can reveal seasonal and diurnal variations is needed to obtain emission factors and characteristics about these pollutants. A two-year continuous monitoring of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2) and particulate matter (PM10) emissions from two 218,000-hen high-rise layer houses (H-A and H-B) in Indiana, USA was conducted from June 2007 to May 2009. Gaseous pollutant concentrations were measured with two gas analyzers and PM10 concentrations were measured with three Tapered Element Oscillating Microbalances. The operation and performance of ventilation fans were continuously monitored with multiple methods. Only the emission rates calculated with valid data days (days with more than 18 h, or 75%, of valid data) are reported in this paper. The two-house and two-year mean ± standard deviation emissions per day per hen for NH3, H2S, CO2, and PM10 were 1.08 ± 0.42 g, 1.37 ± 0.83 mg, 76.7 ± 14.6 g, and 20.6 ± 22.5 mg, respectively. Seasonal emission variations were demonstrated for NH3 and CO2, but not evident for H2S and PM10. Ammonia and CO2 emissions were higher in winter than in summer. Significant daily mean emission variations were observed for all four pollutants between the two houses (P < 0.05), and between the two years from the same house (P < 0.01) except for CO2 at one house. Carbon dioxide originated from manure decomposition was >9% of that from bird respiration. Emissions of CO2 during molting were about 80% of those during normal egg production days. Emissions of H2S were not a major concern due to their very low quantities. Emissions of PM10 were more variable than other pollutants. However, not all of the emission statistics are explainable.

  4. SEASONAL NH 3 EMISSIONS FOR ANNUAL 2001 CMAQ SIMULATION: INVERSE MODEL ESTIMATION AND EVALUATION

    EPA Science Inventory

    The formation of ammonium nitrate aerosols is often limited by ammonia (NH3), and sulfate aerosols are predominantly in the form of ammonium sulfate. While NH3plays a central role in the prediction of nitrate and sulfate aerosols, inherent uncertainty exist...

  5. Removal of triclosan in nitrifying activated sludge: effects of ammonia amendment and bioaugmentation.

    PubMed

    Lee, Do Gyun; Cho, Kun-Ching; Chu, Kung-Hui

    2015-04-01

    This study investigated two possible strategies, increasing ammonia oxidation activity and bioaugmenting with triclosan-degrader Sphingopyxis strain KCY1, to enhance triclosan removal in nitrifying activated sludge (NAS). Triclosan (2 mg L(-1)) was removed within 96-h in NAS bioreactors amended with 5, 25 and 75 mg L(-1) of ammonium (NH4-N). The fastest triclosan removal was observed in 25 mg NH4-NL(-1) amended-bioreactors where high ammonia oxidation occurred. Inhibition of ammonia oxidation and slower triclosan removal were observed in 75 mg NH4-NL(-1) amended-bioreactors. Triclosan removal was correlated to the molar ratio of the amount of nitrate produced to the amount of ammonium removed. Bioaugmentation with strain KCY1 did not enhance triclosan removal in the bioreactors with active ammonia oxidation. Approximately 36-42% and 59% of triclosan added were removed within 24-h by ammonia-oxidizing bacteria and unknown triclosan-degrading heterotrophs, respectively. The results suggested that increasing ammonia oxidation activity can be an effective strategy to enhance triclosan removal in NAS. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Spirodi(iminohydantoin) Products from Oxidation of 2′-Deoxyguanosine in the Presence of NH4Cl in Nucleoside and Oligodeoxynucleotide Contexts

    PubMed Central

    2015-01-01

    Upon oxidation of the heterocyclic ring in 2′-deoxyguanosine (dG), the initial electrophilic intermediate displays a wide range of reactivities with nucleophiles leading to many downstream products. In the present study, the product profiles were mapped when aqueous solutions of dG were allowed to react with NH4Cl in the presence of the photooxidants riboflavin and Rose Bengal as well as the diffusible one-electron oxidant Na2IrCl6. Product characterization identified the 2′-deoxyribonucleosides of spiroiminodihydantoin, 5-guanidinohydantoin, and oxazolone resulting from H2O as the nucleophile. When NH3 was the nucleophile, a set of constitutional isomers that are diastereotopic were also observed, giving characteristic masses of dG + 31. ESI+-MS/MS of these NH3 adducts identified them to be spirocycles with substitution of either the C5 or C8 carbonyl with an amine. The NH3 adducts exhibit acid-catalyzed hydrolysis to spiroiminodihydantoin. Quantification of the NH3 and H2O adducts resulting from oxidation of dG in the nucleoside, single-stranded, and duplex oligodeoxynucleotide contexts were monitored allowing mechanisms for product formation to be proposed. These data also provide a cautionary note to those who purify their oligonucleotide samples with ammonium salts before oxidation because this will lead to unwanted side reactions in which ammonia participates in product formation. PMID:25539403

  7. An experimental and numerical study of nitrogen oxide formation mechanisms in ammonia-hydrogen-air flames

    NASA Astrophysics Data System (ADS)

    Kumar, Praveen

    The demand for sustainable alternative fuels is ever-increasing in the power generation, transportation, and energy sectors due to the inherent non-sustainable characteristics and political constraints of current energy resources. A number of alternative fuels derived from cellulosic biomass, algae, or waste are being considered, along with the conversion of electricity to non-carbon fuels such as hydrogen or ammonia (NH3). The latter is receiving attention recently because it is a non-carbon fuel that is readily produced in large quantities, stored and transported with current infrastructure, and is often a byproduct of biomass or waste conversion processes. However, pure or anhydrous ammonia combustion is severely challenging due to its high auto-ignition temperature (650 °C), low reactivity, and tendency to promote NOx formation. As such, the present study focuses on two major aspects of the ammonia combustion. The first is an applied investigation of the potential to achieve pure NH3 combustion with low levels of emissions in flames of practical interest. In this study, a swirl-stabilized flame typically used in fuel-oil home-heating systems is optimized for NH3 combustion, and measurements of NO and NH3 are collected for a wide range of operating conditions. The second major focus of this work is on fundamental investigation of NO x formation mechanisms in flames with high levels of NH3 in H2. For laminar premixed and diffusion jet flames, experimental measurements of flame speeds, exhaust-gas sampling, and in-situ NO measurements (NO PLIF) are compared with numerically predicted flames using complex chemical kinetics within CHEMKIN and reacting CFD codes i.e., UNICORN. From the preliminary testing of the NOx formation mechanisms, (1) Tian (2) Konnov and (3) GRI-Mech3.0 in laminar premixed H2/NH 3 flames, the Tian and Konnov mechanisms are found to capture the reduction in measured flame speeds with increasing NH3 in the fuel mixture, both qualitatively and

  8. Effects of Si/Al Ratio on Cu/SSZ-13 NH3-SCR Catalysts: Implications for the active Cu species and the Roles of Brønsted Acidity

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

    Gao, Feng; Washton, Nancy M.; Wang, Yilin

    2015-09-03

    Cu/SSZ-13 catalysts with three Si/Al ratios of 6, 12 and 35 were synthesized with Cu incorporation via solution ion exchange. The implications of varying Si/Al ratios on the nature of the multiple Cu species that can be present in the SSZ-13 zeolite are a major focus of this work, as highlighted by the results of a variety of catalyst characterization and reaction kinetics measurements. Specifically, catalysts were characterized with surface area/pore volume measurements, temperature programmed reduction by H2 (H2-TPR), NH3 temperature programmed desorption (NH3-TPD), and DRIFTS and solid-state nuclear magnetic resonance (NMR) spectroscopies. Catalytic properties were examined using NO oxidation,more » ammonia oxidation, and standard ammonia selective catalytic reduction (NH3-SCR) reactions on selected catalysts under differential conditions. Besides indicating possible variably active multiple Cu species for these reactions, the measurements are also used to untangle some of the complexities caused by the interplay between redox of Cu ion centers and Brønsted acidity. All three reactions appear to follow a redox reaction mechanism, yet the roles of Brønsted acidity are quite different. For NO oxidation, increasing Si/Al ratio lowers Cu redox barriers, thus enhancing reaction rates. Brønsted acidity appears to play essentially no role for this reaction. For standard NH3-SCR, residual Brønsted acidity plays a significant beneficial role at both low- and high-temperature regimes. For NH3 oxidation, no clear trend is observed suggesting both Cu ion center redox and Brønsted acidity play important and perhaps competing roles. The authors gratefully acknowledge the US Department of Energy (DOE), Energy Efficiency and Renewable Energy, Vehicle Technologies Office for the support of this work. The research described in this paper was performed in the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s

  9. Ammonia chemistry in a flameless jet

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

    Zieba, Mariusz; Schuster, Anja; Scheffknecht, Guenter

    2009-10-15

    In this paper, the nitrogen chemistry in an ammonia (NH{sub 3}) doped flameless jet is investigated using a kinetic reactor network model. The reactor network model is used to explain the main differences in ammonia chemistry for methane (CH{sub 4})-containing fuels and methane-free fuels. The chemical pathways of nitrogen oxides (NO{sub x}) formation and destruction are identified using rate-of-production analysis. The results show that in the case of natural gas, ammonia reacts relatively late at fuel lean condition leading to high NO{sub x} emissions. In the pre-ignition zone, the ammonia chemistry is blocked due to the absence of free radicalsmore » which are consumed by methane-methyl radical (CH{sub 3}) conversion. In the case of methane-free gas, the ammonia reacted very rapidly and complete decomposition was reached in the fuel rich region of the jet. In this case the necessary radicals for the ammonia conversion are generated from hydrogen (H{sub 2}) oxidation. (author)« less

  10. A neuronal disruption in redox homeostasis elicited by ammonia alters the glycine/glutamate (GABA) cycle and contributes to MMA-induced excitability.

    PubMed

    Royes, Luiz Fernando Freire; Gabbi, Patrícia; Ribeiro, Leandro Rodrigo; Della-Pace, Iuri Domingues; Rodrigues, Fernanda Silva; de Oliveira Ferreira, Ana Paula; da Silveira Junior, Mauro Eduardo Porto; da Silva, Luís Roberto Hart; Grisólia, Alan Barroso Araújo; Braga, Danielle Valente; Dobrachinski, Fernando; da Silva, Anderson Manoel Herculano Oliveira; Soares, Félix Alexandre Antunes; Marchesan, Sara; Furian, Ana Flavia; Oliveira, Mauro Schneider; Fighera, Michele Rechia

    2016-06-01

    Hyperammonemia is a common finding in children with methylmalonic acidemia. However, its contribution to methylmalonate-induced excitotoxicty is poorly understood. The aim of this study was to evaluate the mechanisms by which ammonia influences in the neurotoxicity induced by methylmalonate (MMA) in mice. The effects of ammonium chloride (NH4Cl 3, 6, and 12 mmol/kg; s.c.) on electroencephalographic (EEG) and behavioral convulsions induced by MMA (0.3, 0.66, and 1 µmol/2 µL, i.c.v.) were observed in mice. After, ammonia, TNF-α, IL1β, IL-6, nitrite/nitrate (NOx) levels, mitochondrial potential (ΔΨ), reactive oxygen species (ROS) generation, Methyl-Tetrazolium (MTT) reduction, succinate dehydrogenase (SDH), and Na(+), K(+)-ATPase activity levels were measured in the cerebral cortex. The binding of [(3)H]flunitrazepam, release of glutamate-GABA; glutamate decarboxylase (GAD) and glutamine synthetase (GS) activity and neuronal damage [opening of blood brain barrier (BBB) permeability and cellular death volume] were also measured. EEG recordings showed that an intermediate dose of NH4Cl (6 mmol/kg) increased the duration of convulsive episodes induced by MMA (0.66 μmol/2 μL i.c.v). NH4Cl (6 mmol/kg) administration also induced neuronal ammonia and NOx increase, as well as mitochondrial ROS generation throughout oxidation of 2,7-dichlorofluorescein diacetate (DCFH-DA) to DCF-RS, followed by GS and GAD inhibition. The NH4Cl plus MMA administration did not alter cytokine levels, plasma fluorescein extravasation, or neuronal damage. However, it potentiated DCF-RS levels, decreased the ΔΨ potential, reduced MTT, inhibited SDH activity, and increased Na(+), K(+)-ATPase activity. NH4Cl also altered the GABA cycle characterized by GS and GAD activity inhibition, [(3)H]flunitrazepam binding, and GABA release after MMA injection. On the basis of our findings, the changes in ROS and reactive nitrogen species (RNS) levels elicited by ammonia alter the glycine

  11. Enhancing the Performance of Perovskite Solar Cells by Hybridizing SnS Quantum Dots with CH3 NH3 PbI3.

    PubMed

    Han, Jianhua; Yin, Xuewen; Nan, Hui; Zhou, Yu; Yao, Zhibo; Li, Jianbao; Oron, Dan; Lin, Hong

    2017-08-01

    The combination of perovskite solar cells and quantum dot solar cells has significant potential due to the complementary nature of the two constituent materials. In this study, solar cells (SCs) with a hybrid CH 3 NH 3 PbI 3 /SnS quantum dots (QDs) absorber layer are fabricated by a facile and universal in situ crystallization method, enabling easy embedding of the QDs in perovskite layer. Compared with SCs based on CH 3 NH 3 PbI 3 , SCs using CH 3 NH 3 PbI 3 /SnS QDs hybrid films as absorber achieves a 25% enhancement in efficiency, giving rise to an efficiency of 16.8%. The performance improvement can be attributed to the improved crystallinity of the absorber, enhanced photo-induced carriers' separation and transport within the absorber layer, and improved incident light utilization. The generality of the methods used in this work paves a universal pathway for preparing other perovskite/QDs hybrid materials and the synthesis of entire nontoxic perovskite/QDs hybrid structure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Toward a chemiresistive ammonia (NH3) gas sensor based on viral-templated gold nanoparticles embedded in polypyrrole nanowires

    NASA Astrophysics Data System (ADS)

    Yan, Yiran; Zhang, Miluo; Su, Heng Chia; Myung, Nosang V.; Haberer, Elaine D.

    2014-08-01

    Preliminary studies toward the assembly of a gold-polypyrrole (PPy) peapod-like chemiresistive ammonia (NH3) gas sensors are presented. The proposed synthesis process will use electropolymerization to embed gold nanoparticles in polypyrrole nanowires. Viral-templating of gold nanoparticles and PPy electrodeposition via cyclic voltammetry are the focus of this investigation. A gold-binding M13 bacteriophage was used as a bio-template to assemble continuous chains of gold nanoparticles on interdigitated Pt working electrodes. The dimensions of the resulting nanowire-like structures were examined and the electrical resistance measured. PPy films were electropolymerized using an interdigitated planar, Pt electrode integrated counter and reference electrode. Morphological characterization of the polymer films was completed.

  13. Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

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

    Bertrand, Guy

    2012-06-29

    The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry”more » since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH 3 and NH 2NH 2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH 3- and NH 2NH 2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require high temperatures and long reaction times. To address

  14. The effect of oxygen vacancies on the binding interactions of NH3 with rutile TiO2(110) -1×1

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

    Kim, Boseong; Li, Zhenjun; Kay, Bruce D.

    2012-11-21

    A series of NH3 temperature-programmed desorption (TPD) spectra was taken after the NH3 dose at 70 K on rutile TiO2(110)-1×1 surfaces with the oxygen vacancy (VO) concentrations of ~0% (p-TiO2) and 5% (r-TiO2), respectively, to study the effect of VO’s on the desorption energy of NH3 as a function of the coverage, θ. Our results show that at zero coverage limit, the desorption energy of NH3 on r-TiO2 is 115 kJ/mol, which is 10 kJ/mol less than that on p-TiO2. The desorption energy from the Ti4+ sites decreases with increasing θ due to the repulsive NH3 - NH3 interactions andmore » approaches ~ 55 kJ/mol upon the saturation of Ti4+ sites (θ = 1 monolayer, ML) on both p- and r-TiO2. The absolute saturation coverage is determined to be about 10% smaller on r-TiO2 than that on p-TiO2. Further, the trailing edges of the NH3 TPD spectra on the hydroxylated TiO2(110) (h-TiO2) appear to be the same as that on r-TiO2 while those on oxidized TiO2(110) (o-TiO2) shift to higher temperatures. We present the detailed analysis of the results and reconcile the observed differences based on the repulsive adsorbate-adsorbate interactions between neighboring NH3 molecules and the surface charge associated with the presence of VO’s. Besides NH3, no other reaction products are observed in the TPD spectra.« less

  15. The Green Bank Ammonia Survey: Observations of Hierarchical Dense Gas Structures in Cepheus-L1251

    NASA Astrophysics Data System (ADS)

    Keown, Jared; Di Francesco, James; Kirk, Helen; Friesen, Rachel K.; Pineda, Jaime E.; Rosolowsky, Erik; Ginsburg, Adam; Offner, Stella S. R.; Caselli, Paola; Alves, Felipe; Chacón-Tanarro, Ana; Punanova, Anna; Redaelli, Elena; Seo, Young Min; Matzner, Christopher D.; Chun-Yuan Chen, Michael; Goodman, Alyssa A.; Chen, How-Huan; Shirley, Yancy; Singh, Ayushi; Arce, Hector G.; Martin, Peter; Myers, Philip C.

    2017-11-01

    We use Green Bank Ammonia Survey observations of NH3 (1, 1) and (2, 2) emission with 32″ FWHM resolution from a ˜10 pc2 portion of the Cepheus-L1251 molecular cloud to identify hierarchical dense gas structures. Our dendrogram analysis of the NH3 data results in 22 top-level structures, which reside within 13 lower-level parent structures. The structures are compact (0.01 {pc}≲ {R}{eff}≲ 0.1 {pc}) and are spatially correlated with the highest H2 column density portions of the cloud. We also compare the ammonia data to a catalog of dense cores identified by higher-resolution (18.″2 FWHM) Herschel Space Observatory observations of dust continuum emission from Cepheus-L1251. Maps of kinetic gas temperature, velocity dispersion, and NH3 column density, derived from detailed modeling of the NH3 data, are used to investigate the stability and chemistry of the ammonia-identified and Herschel-identified structures. We show that the dust and dense gas in the structures have similar temperatures, with median T dust and T K measurements of 11.7 ± 1.1 K and 10.3 ± 2.0 K, respectively. Based on a virial analysis, we find that the ammonia-identified structures are gravitationally dominated, yet may be in or near a state of virial equilibrium. Meanwhile, the majority of the Herschel-identified dense cores appear to be not bound by their own gravity and instead confined by external pressure. CCS (20 - 10) and HC5N (9-8) emission from the region reveal broader line widths and centroid velocity offsets when compared to the NH3 (1, 1) emission in some cases, likely due to these carbon-based molecules tracing the turbulent outer layers of the dense cores.

  16. Reinterpretation of the Vibrational Spectroscopy of the Medicinal Bioinorganic Synthon c,c,t-[Pt(NH3)2Cl2(OH)2]†

    PubMed Central

    Johnstone, Timothy C.

    2014-01-01

    The Pt(IV) complex c,c,t-[Pt(NH3)2Cl2(OH)2] is an important intermediate in the synthesis of Pt(IV) anticancer prodrugs and has been investigated as an anticancer agent in its own right. An analysis of the vibrational spectroscopy of this molecule was previously reported [Faggiani et al., 1982, Can. J. Chem. 60, 529] in which crystallographic determination of the structure of the complex permitted a site group approach. The space group, however, was incorrectly assigned. In the present study we have redetermined at high resolution crystal structures of c,c,t-[Pt(NH3)2Cl2(OH)2] and c,c,t-[Pt(NH3)2Cl2(OH)2H2O2, which enable discussion of the effect of hydrogen bonding on the N–H and O–H vibrational bands. The correct crystallographic site symmetry of the platinum complex in the c,c,t-[Pt(NH3)2Cl2(OH)2] structure is employed to conduct a new vibrational analysis using both group theoretical and modern DFT methods. This analysis reveals the nature and symmetry of the “missing band” described in the original publication and suggests a possible explanation for its disappearance. PMID:24515615

  17. Titan's Ammonia Feature

    NASA Technical Reports Server (NTRS)

    Smythe, W.; Nelson, R.; Boryta, M.; Choukroun, M.

    2011-01-01

    NH3 has long been considered an important component in the formation and evolution of the outer planet satellites. NH3 is particularly important for Titan, since it may serve as the reservoir for atmospheric nitrogen. A brightening seen on Titan starting in 2004 may arise from a transient low-lying fog or surface coating of ammonia. The spectral shape suggests the ammonia is anhydrous, a molecule that hydrates quickly in the presence of water.

  18. Sensing Parts per Million Level Ammonia and Parts per Billion Level Acetic Acid in the Gas Phase by Common Black Film with a Fluorescent pH Probe.

    PubMed

    Fu, Jingni; Zhang, Luning

    2018-01-16

    Relying on the nanometer-thick water core and large surface area-to-volume ratio (∼2 × 10 8 m -1 ) of common black film (CBF), we are able to use a pH-sensitive dye (carboxy-seminaphthorhodafluor-1, SNARF-1) to detect ammonia and acetic acid gas adsorption into the CBF, with the limit of detection reaching 0.8 ppm for NH 3 gas and 3 ppb for CH 3 COOH gas in the air. Data analysis reveals that fluorescence signal change is linearly proportional to the gas concentration up to 15 ppm and 65 ppb for NH 3 and CH 3 COOH, respectively.

  19. Biochar application reduce ammonia volatilization in a soil-plant system: A closed chamber experiment

    NASA Astrophysics Data System (ADS)

    Mandal, Sanchita; Donner, Erica; Smith, Euan; Lombi, Enzo

    2017-04-01

    Ammonia (NH3) volatilization is considered as one of the major mechanisms responsible for the loss of nitrogen (N) from soil-plant systems worldwide. About 10-30% of N can be lost as NH3 volatilization, which constitutes a significant economic loss. In recent years carbon-based materials such as biochar have created a great research interest because of their ability to increase soil fertility by reducing nutrient loss and pollutants bioavailability in soil. Most of the studies so far have investigated how biochar addition can reduce NH3 volatilization from soils but less information is available for soil-plant systems. In this research, wheat plants (Triticum aestivum, variety: Calingiri) were grown in a calcareous soil (pH 8, calcarosol) inside a closed chamber system to assess both ammonia volatilization and plant N uptake. In this specialized glass chamber air was passed through an inlet where the flow rate was maintained using an air pump (3.5 L min-1). The air outlet was passed through a sulphuric acid trap which was used to capture the volatilized NH3 from the chamber. Plants were watered using the inlet to maintain 50% field capacity throughout the incubation. Two different biochar samples were used in this study: a poultry manure biochar (PM-BC) and a green waste compost biochar (GW-BC) produced at 250 ˚C. Five different application rates were tested (0, 0.5, 1, 1.5, and 2%). The soil was mixed with biochar samples, water, N, P, K, Ca, Mg, and S for one week before sowing. After one week of germination, plants were transferred to the chamber for further three weeks incubation for NH3 volatilization measurement. The study identified that biochar application reduced the NH3 volatilization and increase the plant biomass. Biochar application at 0.5 and 2% decreased the NH3 volatilization by 36 and 48% respectively. The N uptake of the plants also increased from 2.9 to 28% at 0.5 and 2% application rates respectively. The dry biomass of the plant also increased

  20. Pnicogen bonds between X═PH3 (X = O, S, NH, CH2) and phosphorus and nitrogen bases.

    PubMed

    Alkorta, Ibon; Sánchez-Sanz, Goar; Elguero, José; Del Bene, Janet E

    2014-02-27

    Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the pnicogen bonded complexes formed between the acids O═PH3, S═PH3, HN═PH3, and H2C═PH3 and the bases NH3, NCH, N2, PH3, and PCH. All nitrogen and phosphorus bases form complexes in which the bases are lone pair electron donors. The binding energies of complexes involving the stronger bases NH3, NCH, and PH3 differentiate among the acids, but the binding energies of complexes with the weaker bases do not. These complexes are stabilized by charge transfer from the lone pair orbital of N or P to the σ*P═A orbital of X═PH3, where A is the atom of X directly bonded to P. PCH also forms complexes with the X═PH3 acids as a π electron donor to the σ*P═A orbital. The binding energies and the charge-transfer energies of the π complexes are greater than those of the complexes in which PCH is a lone pair donor. Whether the positive charge on P increases, decreases, or remains the same upon complex formation, the chemical shieldings of (31)P decrease in the complexes relative to the corresponding monomers. (1p)J(P-N) and (1p)J(P-P) values correlate best with the corresponding P-N and P-P distances as a function of the nature of the base. (1)J(P-A) values do not correlate with P-A distances. Rather, the absolute values of (1)J(P-O), (1)J(P-S), and (1)J(P-N) decrease upon complexation. Decreasing (1)J(P-A) values correlate linearly with increasing complex binding energies. In contrast, (1)J(P-C) values increase upon complexation and correlate linearly with increasing binding energies.

  1. Comparison of atmospheric reactions of NH3 and NH2 with hydroxyl radical on the singlet, doublet and triplet potential energy surfaces, kinetic and mechanistic study

    NASA Astrophysics Data System (ADS)

    Vahedpour, Morteza; Douroudgari, Hamed; Afshar, Sheida; Asgharzade, Somaie

    2018-05-01

    The NH2 + OH and NH3 + OH reactions on the singlet, doublet and triplet potential energy surfaces carry out using MP2, QCISD, G3MP2, M06-2X, B3LYP, and CCSD(T)//MP2 levels. Three pre-reactive complexes, 1C1, 3C1 and 3C2 were formed among amidogen and hydroxyl radicals. From variety of the 1C1, four types of products are obtained that 1HNO + H2 is thermodynamically stable and three others are being stable after relaxation to triplet state. On the triplet state, five types of adducts are obtained that four of them have enough thermodynamic stability. Two intersystem crossing are presented among triplet and singlet states of the NH2 + OH reaction. 3NH + H2O adduct is spontaneous and exothermic in standard condition. Results lead to different adducts which are playing significant role in the atmospheric and combustion chemistry. The rate constants of selected pathways are calculated at the 300-2500 K temperature range at M06-2X/aug-ccpvqz and CCSD(T)/6-311++G(3df, 3pd) levels of theory.

  2. Determination of the rate constant for the NH2(X2B1) + NH2(X2B1) recombination reaction with collision partners He, Ne, Ar, and N2 at low pressures and 296 K. Part 1.

    PubMed

    Altinay, Gokhan; Macdonald, R Glen

    2012-02-09

    The recombination rate constant for the NH(2)(X(2)B(1)) + NH(2)(X(2)B(1)) → N(2)H(4)(X(1)A(1)) reaction in He, Ne, Ar, and N(2) was measured over the pressure range 1-20 Torr at a temperature of 296 K. The NH(2) radical was produced by 193 nm laser photolysis of NH(3) dilute in the third-body gas. The production of NH(2) and the loss of NH(3) were monitored by high-resolution continuous-wave absorption spectroscopy: NH(2) on the (1)2(21) ← (1)3(31) rotational transition of the (0,7,0)A(2)A(1) ← (0,0,0) X(2)B(1) vibronic band and NH(3) on either inversion doublet of the (q)Q(3)(3) rotational transition of the ν(1) fundamental. Both species were detected simultaneously following the photolysis laser pulse. The broader Doppler width of the NH(2) spectral transition allowed temporal concentration measurements to be extended up to 20 Torr before pressure broadening effects became significant. Fall-off behavior was identified and the bimolecular rate constants for each collision partner were fit to a simple Troe form defined by the parameters, k(0), k(inf), and F(cent). This work is the first part of a two part series in which part 2 will discuss the measurements with more efficient energy transfer collision partners CH(4), C(2)H(6), CO(2), CF(4), and SF(6). The pressure range was too limited to extract any new information on k(inf), and k(inf) was taken from the theoretical calculations of Klippenstein et al. (J. Phys. Chem A 2009, 113, 10241) as k(inf) = 7.9 × 10(-11) cm(3) molecule(-1) s(-1) at 296 K. The individual Troe parameters were: He, k(0) = 2.8 × 10(-29) and F(cent) = 0.47; Ne, k(0) = 2.7 × 10(-29) and F(cent) = 0.34; Ar, k(0) = 4.4 × 10(-29) and F(cent) = 0.41; N(2), k(0) = 5.7 × 10(-29) and F(cent) = 0.61, with units cm(6) molecule(-2) s(-1) for k(0). In the case of N(2) as the third body, it was possible to measure the recombination rate constant for the NH(2) + H reaction near 20 Torr total pressure. The pure three-body recombination rate

  3. Understanding Gas-Phase Ammonia Chemistry in Protoplanetary Disks

    NASA Astrophysics Data System (ADS)

    Chambers, Lauren; Oberg, Karin I.; Cleeves, Lauren Ilsedore

    2017-01-01

    Protoplanetary disks are dynamic regions of gas and dust around young stars, the remnants of star formation, that evolve and coagulate over millions of years in order to ultimately form planets. The chemical composition of protoplanetary disks is affected by both the chemical and physical conditions in which they develop, including the initial molecular abundances in the birth cloud, the spectrum and intensity of radiation from the host star and nearby systems, and mixing and turbulence within the disk. A more complete understanding of the chemical evolution of disks enables a more complete understanding of the chemical composition of planets that may form within them, and of their capability to support life. One element known to be essential for life on Earth is nitrogen, which often is present in the form of ammonia (NH3). Recent observations by Salinas et al. (2016) reveal a theoretical discrepancy in the gas-phase and ice-phase ammonia abundances in protoplanetary disks; while observations of comets and protostars estimate the ice-phase NH3/H2O ratio in disks to be 5%, Salinas reports a gas-phase NH3/H2O ratio of ~7-84% in the disk surrounding TW Hydra, a young nearby star. Through computational chemical modeling of the TW Hydra disk using a reaction network of over 5000 chemical reactions, I am investigating the possible sources of excess gas-phase NH3 by determining the primary reaction pathways of NH3 production; the downstream chemical effects of ionization by ultraviolet photons, X-rays, and cosmic rays; and the effects of altering the initial abundances of key molecules such as N and N2. Beyond providing a theoretical explanation for the NH3 ice/gas discrepancy, this new model may lead to fuller understanding of the gas-phase formation processes of all nitrogen hydrides (NHx), and thus fuller understanding of the nitrogen-bearing molecules that are fundamental for life as we know it.

  4. Total cross sections of electron scattering by molecules NF3, PF3, N(CH3)3, P(CH3)3, NH(CH3)2, PH(CH3)2, NH2CH3 and PH2CH3 at 30-5000 eV

    NASA Astrophysics Data System (ADS)

    Shi, D. H.; Sun, J. F.; Zhu, Z. L.; Liu, Y. F.

    2010-04-01

    Total cross sections of electron scattering by eight molecules NF3, PF3, N(CH3)3, P(CH3)3, NH(CH3)2, PH(CH3)2, NH2CH3 and PH2CH3, which have some structural similarities, are calculated at the Hartree-Fork level by the modified additivity rule approach [D.H. Shi, J.F. Sun, Z.L. Zhu, H. Ma, Y.F. Liu, Eur. Phys. J. D 45, 253 (2007); D.H. Shi, J.F. Sun, Y.F. Liu, Z.L. Zhu, X.D. Yang, Chin. Opt. Lett. 4, 192 (2006)]. The modified additivity rule approach takes into considerations that the contributions of the geometric shielding effect vary as the energy of incident electrons, the dimension of target molecule, the number of electrons in the molecule and the number of atoms constituting the molecule. The present investigations cover the impact energy range from 30 to 5000 eV. The quantitative total cross sections are compared with those obtained by experiments and other theories. Excellent agreement is observed even at energies of several tens of eV. It shows that the modified additivity rule approach is applicable to carry out the total cross section calculations of electron scattering by these molecules at intermediate and high energies, in particular over the energy range above 80 eV or so. It proves that the microscopic molecular properties, such as the geometrical size of the target and the number of atoms constituting the molecule, are of crucial importance in the TCS calculations. The new results for PH(CH3)2 and PH2CH3 are also presented at energies from 30 to 5000 eV, although no experimental and theoretical data are available for comparison. In the present calculations, the atoms are still represented by the spherical complex optical potential, which is composed of static, exchange, polarization and absorption terms.

  5. Competition Between Co(NH3)63+ and Inner Sphere Mg2+ Ions in the HDV Ribozyme

    PubMed Central

    Gong, Bo; Chen, Jui-Hui; Bevilacqua, Philip C.; Golden, Barbara L.; Carey, Paul R.

    2009-01-01

    Divalent cations play critical structural and functional roles in many RNAs. While the hepatitis delta virus (HDV) ribozyme can undergo self-cleavage in the presence of molar concentrations of monovalent cations, divalent cations such as Mg2+ are required for efficient catalysis under physiological conditions. Moreover, the cleavage reaction can be inhibited with Co(NH3)63+, an analog of Mg(H2O)62+. Here, the binding of Mg2+ and Co(NH3)63+ to the HDV ribozyme are studied by Raman microscopic analysis of crystals. Raman difference spectra acquired at different metal ion conditions reveal changes in the ribozyme. When Mg2+ alone is introduced to the ribozyme, inner sphere coordination of Mg(H2O)x2+ (x≤5) to non-bridging PO2− oxygen, and changes in base stretches and phosphodiester group conformation are observed. In addition, binding of Mg2+ induces deprotonation of a cytosine assigned to the general acid C75, consistent with solution studies. When Co(NH3)63+ alone is introduced, deprotonation of C75 is again observed, as are distinctive changes in base vibrational ring modes and phosphodiester backbone conformation. In contrast to Mg2+ binding, Co(NH3)63+ binding does not perturb PO2− group vibrations, consistent with its ability to make only outer sphere contacts. Surprisingly, competitive binding studies reveal that Co(NH3)63+ ions displace some inner sphere-coordinated magnesium species, including ions coordinated to PO2− groups or the N7 of a guanine, likely G1 at the active site. These observations contrast with the tenet that Co(NH3)63+ ions displace only outer sphere magnesium ions. Overall, our data support two classes of inner sphere Mg2+-PO2− binding sites: sites that Co(NH3)63+ can displace, and others it cannot. PMID:19888753

  6. Double-walled structure of anodic TiO2 nanotubes in H3PO4/NH4F mixed electrolyte

    NASA Astrophysics Data System (ADS)

    Chen, Siyu; Chen, Ying; Li, Chengyuan; Ouyang, Huijun; Qin, Shuai; Song, Ye

    2018-04-01

    Normally, the well-ordered anodic TiO2 nanotubes (ATNTs) are obtained in NH4F electrolyte, after annealing, the double-walled structure of nanotubes will appear. Here, after adding H3PO4 into NHF4 electrolyte, we got the double-walled structure of nanotubes by anodizing without annealing, which means the direct existence of anion-contaminated layer in ATNTs. Influence of H3PO4 content on anodizing voltage and morphology of ATNTs were compared in detail. The XRD pattern illustrated that the crystallinity decreases with increasing H3PO4 concentration, and the anion-contaminated layer thickens with the increase of H3PO4 concentration. Meanwhile, the existence of the anion-contaminated layer also proved the limitations of the filed-assisted dissolution theory, while the double-walled structure can be explained by oxygen bubble model and plastic flow model.

  7. Diverse microbial species survive high ammonia concentrations

    NASA Astrophysics Data System (ADS)

    Kelly, Laura C.; Cockell, Charles S.; Summers, Stephen

    2012-04-01

    Planetary protection regulations are in place to control the contamination of planets and moons with terrestrial micro-organisms in order to avoid jeopardizing future scientific investigations relating to the search for life. One environmental chemical factor of relevance in extraterrestrial environments, specifically in the moons of the outer solar system, is ammonia (NH3). Ammonia is known to be highly toxic to micro-organisms and may disrupt proton motive force, interfere with cellular redox reactions or cause an increase of cell pH. To test the survival potential of terrestrial micro-organisms exposed to such cold, ammonia-rich environments, and to judge whether current planetary protection regulations are sufficient, soil samples were exposed to concentrations of NH3 from 5 to 35% (v/v) at -80°C and room temperature for periods up to 11 months. Following exposure to 35% NH3, diverse spore-forming taxa survived, including representatives of the Firmicutes (Bacillus, Sporosarcina, Viridibacillus, Paenibacillus, Staphylococcus and Brevibacillus) and Actinobacteria (Streptomyces). Non-spore forming organisms also survived, including Proteobacteria (Pseudomonas) and Actinobacteria (Arthrobacter) that are known to have environmentally resistant resting states. Clostridium spp. were isolated from the exposed soil under anaerobic culture. High NH3 was shown to cause a reduction in viability of spores over time, but spore morphology was not visibly altered. In addition to its implications for planetary protection, these data show that a large number of bacteria, potentially including spore-forming pathogens, but also environmentally resistant non-spore-formers, can survive high ammonia concentrations.

  8. The physics and chemistry of small molecular clouds in the galactic plane. 3: NH3

    NASA Astrophysics Data System (ADS)

    Turner, B. E.

    1995-05-01

    We have made extensive observations of the (1, 1) and (2, 2) lines of NH3 in all 27 of the Clemens-Barvainis small molecular clouds for which several structural models including hydrostatic equilibrium polytropes were developed in an earlier paper based on CO-18 and (13)CO observations. As with the 11 cirrus cores earlier studied in CO-18, (13)CO, H2CO, and NH3, the NH3 lines in CB objects are well fitted by both polytropic models and ad hoc n is approximately 1/r models, using the external UV fields derived in the earlier papers. The reanalysis of the cirrus cores, which now includes the C-12/C-13 ratio as a variable, yields the same NH3 fractional abundances as the earlier analysis, and reaffirms a strong preference for centrally condensed abundance profiles. The same preference is found, but somewhat less decisively, for the CB objects. As before, the NH3 analyses give no clear preference for polytropic or 1/r structures. The large central NH3 abundances (0.4-3.2 x10-8 for cirrus cores; a factor 1.8 times smaller for CB objects) are much too large is these translucent objects to be explained by the standard gas-phase reaction N(+) + H2 approaches NH(+), but may be explained by the reaction N + H3(+) approaches NH2(+) provided it has no activation barrier. Various arguments are advanced against photcatalysis of NH3 on grains. By including consistently the effects of UV radiation fields and electron excitation, our models have now fitted accurately all four lines of CO-18 and (13)CO, three lines of H2CO, and two lines of NH3 so far observed. With the possible exception of the (average) NH3 abundances, the CB objects and cirrus cores are indistinguishable physically or chemically, and the properties we have found for them seem to represent the conditions in all small, low-mass moleculra clouds regardless of galactic latitude.

  9. Recovery of ammonia and phosphate minerals from swine wastewater using gas-permeable membranes.

    PubMed

    Vanotti, M B; Dube, P J; Szogi, A A; García-González, M C

    2017-04-01

    Gas-permeable membrane technology is useful to recover ammonia (NH 3 ) from liquid manures. In this study, phosphorus (P) recovery via MgCl 2 precipitation was enhanced by combining it with NH 3 recovery through gas-permeable membranes. Anaerobically digested swine wastewater containing approximately 2300 mg NH 4 + -N L -1 and 450 mg P L -1 was treated using submerged membranes plus low-rate aeration to recover the NH 3 from within the liquid and MgCl 2 to precipitate the P. The experiments included a first configuration where N and P were recovered sequentially and a second configuration with simultaneous recovery. The low-rate aeration reduced the natural carbonate, increased pH and accelerated NH 3 uptake by the gas-permeable membrane system, which in turn benefited P recovery. Phosphorus removal efficiency was >90% and P recovery efficiency was about 100%. With higher NH 3 capture, the recovered P contained higher P 2 O 5 content (37-46%, >98% available), similar to the composition of the biomineral newberyite (MgHPO 4 ·3H 2 O). Published by Elsevier Ltd.

  10. EMRP JRP MetNH3: Towards a Consistent Metrological Infrastructure for Ammonia Measurements in Ambient Air

    NASA Astrophysics Data System (ADS)

    Leuenberger, Daiana; Balslev-Harder, David; Braban, Christine F.; Ebert, Volker; Ferracci, Valerio; Gieseking, Bjoern; Hieta, Tuomas; Martin, Nicholas A.; Pascale, Céline; Pogány, Andrea; Tiebe, Carlo; Twigg, Marsailidh M.; Vaittinen, Olavi; van Wijk, Janneke; Wirtz, Klaus; Niederhauser, Bernhard

    2016-04-01

    Measuring ammonia in ambient air is a sensitive and priority issue due to its harmful effects on human health and ecosystems. In addition to its acidifying effect on natural waters and soils and to the additional nitrogen input to ecosystems, ammonia is an important precursor for secondary aerosol formation in the atmosphere. The European Directive 2001/81/EC on "National Emission Ceilings for Certain Atmospheric Pollutants (NEC)" regulates ammonia emissions in the member states. However, there is a lack of regulation regarding certified reference material (CRM), applicable analytical methods, measurement uncertainty, quality assurance and quality control (QC/QA) procedures as well as in the infrastructure to attain metrological traceability. As shown in a key comparison in 2007, there are even discrepancies between reference materials provided by European National Metrology Institutes (NMIs) at amount fraction levels up to three orders of magnitude higher than ambient air levels. MetNH3 (Metrology for ammonia in ambient air), a three-year project that started in June 2014 in the framework of the European Metrology Research Programme (EMRP), aims to reduce the gap between requirements set by the European emission regulations and state-of-the-art of analytical methods and reference materials. The overarching objective of the JRP is to achieve metrological traceability for ammonia measurements in ambient air from primary certified reference material CRM and instrumental standards to the field level. This requires the successful completion of the three main goals, which have been assigned to three technical work packages: To develop improved reference gas mixtures by static and dynamic gravimetric generation methods Realisation and characterisation of traceable preparative calibration standards (in pressurised cylinders as well as mobile generators) of ammonia amount fractions similar to those in ambient air based on existing methods for other reactive analytes. The

  11. The ALFAM2 database on ammonia emission from field-applied manure: description and illustrative analysis

    USDA-ARS?s Scientific Manuscript database

    Ammonia (NH3) emission from animal manure contributes to air pollution and ecosystem degradation, and is a loss of reactive nitrogen (N) from agricultural systems. Estimates of NH3 emission are necessary for national inventories and nutrient management. Many studies have made measurements of NH3 emi...

  12. New Insight into SO2 Poisoning and Regeneration of CeO2-WO3/TiO2 and V2O5-WO3/TiO2 Catalysts for Low-Temperature NH3-SCR.

    PubMed

    Xu, Liwen; Wang, Chizhong; Chang, Huazhen; Wu, Qingru; Zhang, Tao; Li, Junhua

    2018-06-19

    In this study, the poisoning effects of SO 2 on the V 2 O 5 -WO 3 /TiO 2 (1%VWTi) and CeO 2 -WO 3 /TiO 2 (5%CeWTi) selective catalytic reduction (SCR) catalysts were investigated in the presence of steam, and also the regeneration of deactivated catalysts was studied. After pretreating the catalysts in a flow of NH 3 + SO 2 + H 2 O + O 2 at 200 °C for 24 h, it was observed that the low-temperature SCR (LT-SCR) activity decreased significantly over the 1%VWTi and 5%CeWTi catalysts. For 1%VWTi, NH 4 HSO 4 (ABS) was the main product detected after the poisoning process. Both of NH 4 HSO 4 and cerium sulfate species were formed on the poisoned 5%CeWTi catalyst, indicating that SO 2 reacted with Ce 3+ /Ce 4+ , even in the presence of high concentration of NH 3 . The decrease of BET specific surface area, NO x adsorption capacity, the ratio of chemisorbed oxygen, and reducibility were responsible for the irreversible deactivation of the poisoned 5%CeWTi catalyst. Meanwhile, the LT-SCR activity could be recovered over the poisoned 1%VWTi after regeneration at 400 °C, but not for the 5%CeWTi catalyst. For industrial application, it is suggested that the regeneration process can be utilized for 1%VWTi catalysts after a period of time after NH 4 HSO 4 accumulated on the catalysts.

  13. VERIFICATION OF AMBIENT MONITORING TECHNOLOGIES FOR AMMONIA AND HYDROGEN SULFIDE AT ANIMAL FEEDING OPERATIONS

    EPA Science Inventory

    The increasing concentration of livestock agriculture into animal feeding operations (AFOs) has raised concerns about the environmental and potential health impact of the emissions from AFOs into the atmosphere. Gaseous ammonia (NH3) and hydrogen sulfide (H2...

  14. Influence of Starvation on Potential Ammonia-Oxidizing Activity and amoA mRNA Levels of Nitrosospira briensis

    PubMed Central

    Bollmann, Annette; Schmidt, Ingo; Saunders, Aaron M.; Nicolaisen, Mette H.

    2005-01-01

    The effect of short-term ammonia starvation on Nitrosospira briensis was investigated. The ammonia-oxidizing activity was determined in a concentrated cell suspension with a NOx biosensor. The apparent half-saturation constant [Km(app)] value of the NH3 oxidation of N. briensis was 3 μM NH3 for cultures grown both in continuous and batch cultures as determined by a NOx biosensor. Cells grown on the wall of the vessel had a lower Km(app) value of 1.8 μM NH3. Nonstarving cultures of N. briensis showed potential ammonia-oxidizing activities of between 200 to 250 μM N h−1, and this activity decreased only slowly during starvation up to 10 days. Within 10 min after the addition of fresh NH4+, 100% activity was regained. Parallel with activity measurements, amoA mRNA and 16S rRNA were investigated. No changes were observed in the 16S rRNA, but a relative decrease of amoA mRNA was observed during the starvation period. During resuscitation, an increase in amoA mRNA expression was detected simultaneously. The patterns of the soluble protein fraction of a 2-week-starved culture of N. briensis showed only small differences in comparison to a nonstarved control. From these results we conclude that N. briensis cells remain in a state allowing fast recovery of ammonia-oxidizing activity after addition of NH4+ to a starved culture. Maintaining cells in this kind of active state could be the survival strategy of ammonia-oxidizing bacteria in nature under fluctuating NH4+ availability. PMID:15746329

  15. Enhanced low-temperature NH3-SCR performance of MnOx/CeO2 catalysts by optimal solvent effect

    NASA Astrophysics Data System (ADS)

    Yao, Xiaojiang; Kong, Tingting; Chen, Li; Ding, Shimin; Yang, Fumo; Dong, Lin

    2017-10-01

    A series of MnOx/CeO2 catalysts were prepared by modulating the solvents (deionized water (DW), anhydrous ethanol (AE), acetic acid (AA), and oxalic acid (OA) solution) with the purpose of improving the low-temperature NH3-SCR performance, broadening the operating temperature window, and enhancing the H2O + SO2 resistance. The synthesized catalysts were characterized by means of N2-physisorption, XRD, EDS mapping, Raman, XPS, H2-TPR, NH3-TPD, and in situ DRIFTS technologies. Furthermore, the catalytic performance and H2O + SO2 resistance were evaluated by NH3-SCR model reaction. The obtained results indicate that MnOx/CeO2 catalyst prepared with oxalic acid solution as a solvent exhibits the best catalytic performance among these catalysts, which shows above 80% NO conversion during a wide operating temperature range of 100-250 °C and good H2O + SO2 resistance for low-temperature NH3-SCR reaction. This is related to that oxalic acid solution can promote the dispersion of MnOx and enhance the electron interaction between MnOx and CeO2, which are beneficial to improving the physicochemical property of MnOx/CeO2 catalyst, and further lead to the enhancement of catalytic performance and good H2O + SO2 resistance.

  16. Preparation, Characterization, and Structure of Two Layered Molybdenum(VI) Phosphates: KMo(H 2O)O 2PO 4 and NH 4Mo(H 2O)O 2PO 4

    NASA Astrophysics Data System (ADS)

    Millini, Roberto; Carati, Angela

    1995-08-01

    New layered Mo(VI) compounds, KMo(H 2O)O 2PO 4 (I) and NH 4Mo(H 2O)O 2PO 4 (II), were synthesized hydrothermally and their structures were determined from single-crystal X-ray analysis. Compounds (I) and (II) are isostructural and crystallize in the monoclinic P2 1/ n space group with a = 12.353(3), b = 8.623(2), c = 5.841(1) Å, β = 102.78(1)°, V = 606.8(2) Å 3, Z = 4, and R = 0.027 ( Rw = 0.030) for compound (I) and a = 12.435(3), b = 8.761(2), c = 6.015(1), β = 103.45(1)°, V = 637.3(2) Å 3, Z = 4, and R = 0.040 ( Rw = 0.041) for compound (II). The structure consists of layers built up of eight- and four-membered rings resulting from the alternation of corner-sharing [MoO 6] octahedra and [PO 4] tetrahedra. The layers stack along the (1¯01) direction by intercalating K and NH 4 ions.

  17. Facile Uptake and Release of Ammonia by Nickel Halide Ammines.

    PubMed

    Breternitz, Joachim; Vilk, Yury E; Giraud, Elsa; Reardon, Hazel; Hoang, Tuan K A; Godula-Jopek, Agata; Gregory, Duncan H

    2016-06-08

    Although major difficulties are experienced for hydrogen- storage materials to meet performance requirements for mobile applications, alternative fuel cell feedstocks such as ammonia can be stored in the solid state safely at high capacity. We herein describe the NiX2 -NH3 (X=Cl, Br, I) systems and demonstrate their exceptional suitability for NH3 storage (up to 43 wt % NH3 with desorption that begins at 400 K). The structural effects that result from the uptake of NH3 were studied by powder X-ray diffraction (PXD), FTIR spectroscopy and SEM. NH3 release at elevated temperatures was followed by in situ PXD. The cycling capabilities and air stability of the systems were also explored. NH3 is released from the hexaammines in a three-step process to yield the diammine, monoammine and NiX2 dihalides respectively and (re)ammoniation occurs readily at room temperature. The hexaammines do not react with air after several hours of exposure. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Biochar applied at an appropriate rate can avoid increasing NH3 volatilization dramatically in rice paddy soil.

    PubMed

    Feng, Yanfang; Sun, Haijun; Xue, Lihong; Liu, Yang; Gao, Qian; Lu, Kouping; Yang, Linzhang

    2017-02-01

    Biochar application can increase carbon sequestration and reduce greenhouse gases emissions in paddy soils. However, its influence on ammonia (NH 3 ) volatilization is neglected. This soil column study was conducted using two biochars (wheat straw pyrolyzed at 500 °C and 700 °C) with two application rates (0.5 wt% and 3 wt%) to evaluate their impact on NH 3 volatilization from rice paddy. Results showed that biochar application did not change NH 3 volatilization fluxes pattern after N fertilization. Four biochar treatments recorded higher NH 3 volatilization (20.50-31.88 kg N ha -1 ) compared with the control (18.65 kg N ha -1 ). Especially, two 3 wt% biochar treatments had significantly 40.8-70.9% higher NH 3 volatilization than control. After the basal and first supplementary fertilization, the floodwater pH values were 7.61-7.79 and 7.51-7.76 under biochar treatments, higher than control (7.37 and 7.16, respectively). Meanwhile, after three split N fertilizations, the pH of surface soil received biochar increased by 0.19-0.45, 0.19-0.39, and 0.01-0.21 units, in comparison with the control soil. Furthermore, 3 wt% biochar treatments had higher floodwater and surface soil pH values than 0.5 wt% biochar treatments. Higher NH 4 + -N and lower NO 3 - -N concentrations of surface soil under biochar application were observed compared with control at tillering stage, whereas they were at similar level at jointing stage. The increased NH 3 volatilization at 3 wt% biochar treatments is attributed to increased pH of surface floodwater and soil, and reduced nitrification processes induced by biochar application. Biochar should be applied at lower rate to rice paddy soil, considering the NH 3 volatilization. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Catalysts for selective hydrogenation of furfural derived from the double complex salt [Pd(NH 3 ) 4 ](ReO 4 ) 2 on γ-Al 2 O 3

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

    Thompson, Simon T.; Lamb, H. Henry

    The double complex salt [Pd(NH3)4](ReO4)2 was employed as precursor of supported bimetallic catalysts for selective hydrogenation of furfural. Direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 in flowing H2 at 400 °C yields bimetallic nanoparticles 1–2 nm in size that exhibit significant interaction between the metals, as evidenced by temperature-programmed hydride decomposition (complete suppression of β-PdHx formation), extended X-ray absorption fine structure spectroscopy at the Pd K and Re LIII edges (PdRe distance = 2.72 Å), and scanning transmission electron microscopy with energy dispersive X-ray analysis. In contrast, calcination of [Pd(NH3)4](ReO4)2 on γ-Al2O3 at 350 °C in air and subsequent reduction inmore » H2 at 400 °C results in metal segregation and formation of large (>50 nm) supported Pd particles; Re species cover the Pd particles and γ-Al2O3 support. A PdRe 1:2 catalyst prepared by sequential impregnation and calcination using HReO4 and [Pd(NH3)4](NO3)2 has a similar morphology. The catalyst derived by direct reduction of [Pd(NH3)4](ReO4)2 on γ-Al2O3 exhibits remarkably high activity for selective hydrogenation of furfural to furfuryl alcohol (FAL) at 150 °C and 1 atm. Suppression of H2 chemisorption via elimination of Pd threefold sites, as evidenced by CO diffuse-reflectance infrared Fourier transform spectroscopy, correlates with increased FAL selectivity.« less

  20. Electric conductivity analysis and dielectric relaxation behavior of the hybrid polyvanadate (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}

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

    Nefzi, H.; Sediri, F., E-mail: faouzi.sediri@ipeit.rnu.tn; Faculté des Sciences de Tunis, Université Tunis El Manar, 2092 El Manar, Tunis

    2013-05-15

    Highlights: ► Plate-like crystals (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}] were synthesized. ► Frequency and temperature dependence of AC conductivity indicate CBH model. ► The temperature dependence of DC conductivity exhibits two conduction mechanisms. - Abstract: Layered hybrid compound (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}] has been synthesized via hydrothermal method. Techniques X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and impedance spectroscopy have been used to characterize the hybrid material. Electrical and dielectric properties dependence on both temperature and frequency of the compound have been reported. The direct current conductivity process is thermally activated andmore » it is found to be 12.67 × 10{sup −4} Ω{sup −1} m{sup −1} at 523 K. The spectra follow the Arrhenius law with two activation energy 0.25 eV for T < 455 K and 0.5 eV for T > 455 K.« less

  1. Three-dimensional characterization of the ammonia plume from a beef cattle feedlot

    NASA Astrophysics Data System (ADS)

    Staebler, Ralf M.; McGinn, Sean M.; Crenna, Brian P.; Flesch, Thomas K.; Hayden, Katherine L.; Li, Shao-Meng

    2009-12-01

    In Canada approximately 45% of ammonia (NH 3) emissions are attributed to dairy and beef cattle industries. The present study focused on NH 3 emissions from a beef feedlot with a one-time capacity of 17,220 head. The aim was to improve the Canadian NH 3 emission inventories and air quality forecasting capabilities. A Cessna 207, equipped with a fast-response NH 3/NO y detector and a quadrupole aerosol mass spectrometer, was flown in a grid pattern covering an area of 8 × 8 km centered on a feedlot (800 × 800 m) at altitudes ranging from 30 to 300 m above ground. Stationary ground measurements of NH 3 concentration and turbulence parameters were made downwind of the feedlot. Three flights were conducted under varying meteorological conditions, ranging from very calm to windy with near-neutral stratification. NH 3 mixing ratios up to 100 ppbv were recorded on the calm day, up to 300 m above ground. An average feedlot NH 3 emission rate of 76 ± 4 μg m -2 s -1 (equivalent to 10.2 g head -1 h -1) was estimated. Characteristics of the measured NH 3 plume were compared to those predicted by a Lagrangian dispersion model. The spatially integrated pattern of NH 3 concentrations predicted and measured agreed but the measured was often more complex than the predicted spatial distribution. The study suggests that the export of NH 3 through advection accounted for about 90% of the emissions from the feedlot, chemical transformation was insignificant, and dry deposition accounted for the remaining 10%.

  2. Impact of substrates acclimation strategy on simultaneous biodegradation of hydrogen sulfide and ammonia.

    PubMed

    Jiang, Xia; Luo, Yiqun; Yan, Rong; Tay, Joo Hwa

    2009-12-01

    Three columns were differentiated with feeding mixture of H(2)S and NH(3) (MFC), feeding NH(3) followed by H(2)S (NFC), and feeding H(2)S followed by NH(3) (SFC). Removal performance, biodegradation capacity and microbial community structures in the three columns were compared. The results show that NFC has a shorter acclimation period for the removal of NH(3) gas and nitrification than MFC. Under the high loading of H(2)S and NH(3) at 164 and 82 gm(-3) h(-1), respectively, NFC exhibited high removal efficiency of NH(3) (>95%) while the removal efficiencies were obtained at 63 and 75% in MFC and SFC, respectively. The removal of NH(3) gas in NFC was significantly attributed to nitrification (over 50%), while adsorption and chemical reaction contributed to the removal of NH(3) in MFC and SFC. The different biodegradation capacities of NH(3) could be due to the dissimilarity in the microbial population presented in each column.

  3. Atmospheric ammonia and its impacts on regional air quality over the megacity of Shanghai, China.

    PubMed

    Wang, Shanshan; Nan, Jialiang; Shi, Chanzhen; Fu, Qingyan; Gao, Song; Wang, Dongfang; Cui, Huxiong; Saiz-Lopez, Alfonso; Zhou, Bin

    2015-10-30

    Atmospheric ammonia (NH3) has great environmental implications due to its important role in ecosystem and global nitrogen cycle, as well as contribution to secondary particle formation. Here, we report long-term continuous measurements of NH3 at different locations (i.e. urban, industrial and rural) in Shanghai, China, which provide an unprecedented portrait of temporal and spatial characteristics of atmospheric NH3 in and around this megacity. In addition to point emission sources, air masses originated from or that have passed over ammonia rich areas, e.g. rural and industrial sites, increase the observed NH3 concentrations inside the urban area of Shanghai. Remarkable high-frequency NH3 variations were measured at the industrial site, indicating instantaneous nearby industrial emission peaks. Additionally, we observed strong positive exponential correlations between NH4(+)/(NH4(+)+NH3) and sulfate-nitrate-ammonium (SNA) aerosols, PM2.5 mass concentrations, implying a considerable contribution of gas-to-particle conversion of ammonia to SNA aerosol formation. Lower temperature and higher humidity conditions were found to favor the conversion of gaseous ammonia to particle ammonium, particularly in autumn. Although NH3 is currently not included in China's emission control policies of air pollution precursors, our results highlight the urgency and importance of monitoring gaseous ammonia and improving its emission inventory in and around Shanghai.

  4. Effect of cationic substitution on the double-well hydrogen-bond potential in [K1-x(NH4)x]3H(SO4)2 proton conductors: a single-crystal neutron diffraction study.

    PubMed

    Choudhury, R R; Chitra, R; Selezneva, E V; Makarova, I P

    2017-10-01

    The structure of the mixed crystal [K 1-x (NH 4 ) x ] 3 H(SO 4 ) 2 as obtained from single-crystal neutron diffraction is compared with the previously reported room-temperature neutron structure of crystalline K 3 H(SO 4 ) 2 . The two structures are very similar, as indicated by the high value of their isostructurality index (94.8%). It was found that the replacement of even a small amount (3%) of K + with NH 4 + has a significant influence on the short strong hydrogen bond connecting the two SO 4 2- ions. Earlier optical measurements had revealed that the kinetics of the superionic transition in the solid solution [K 1-x (NH 4 ) x ] 3 H(SO 4 ) 2 are much faster than in K 3 H(SO 4 ) 2 ; this reported difference in the kinetics of the superionic phase transition in this class of crystal is explained on the basis of the difference in strength of the hydrogen-bond interactions in the two structures.

  5. Submersible microbial desalination cell for simultaneous ammonia recovery and electricity production from anaerobic reactors containing high levels of ammonia.

    PubMed

    Zhang, Yifeng; Angelidaki, Irini

    2015-02-01

    High ammonia concentration in anaerobic reactors can seriously inhibit the anaerobic digestion process. In this study, a submersible microbial desalination cell (SMDC) was developed as an innovative method to lower the ammonia level in a continuous stirred tank reactor (CSTR) by in situ ammonia recovery and electricity production. In batch experiment, the ammonia concentration in the CSTR decreased from 6 to 0.7 g-N/L during 30 days, resulting in an average recovery rate of 80 g-N/m(2)/d. Meanwhile, a maximum power density of 0.71±0.5 W/m(2) was generated at 2.85 A/m(2). Both current driven NH4(+) migration and free NH3 diffusion were identified as the mechanisms responsible for the ammonia transportation. With an increase in initial ammonia concentration and a decrease in external resistance, the SMDC performance was enhanced. In addition, the coexistence of other cations in CSTR or cathode had no negative effect on the ammonia transportation. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Photocopy of Photograph, 14th ND PHOG No. N.H.82816 U.S. Navy ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Photocopy of Photograph, 14th ND PHOG No. N.H.82816 U.S. Navy photograph, circa 1945. AERIAL OF MAKALAPA ADMINISTRATION ARE IN WORLD WAR II, from National Park Service, U.S.S. Arizona Memorial, 14th Naval District Photograph Collection. - U.S. Naval Base, Pearl Harbor, Makalapa Support Facilities, Makalapa Administration Area, Pearl City, Honolulu County, HI

  7. The international research progress of Ammonia(NH3) emissions and emissions reduction technology in farmland ecosystem

    NASA Astrophysics Data System (ADS)

    Yang, W. Z.; Jiao, Y.

    2017-03-01

    NH3 is the important factor leading to the grey haze, and one of the main causes of environmental problems of serious ecological imbalance, such as acid rain and air quality deterioration. The fertilizer excessive application of the current farmland results NH3 emissions intensity greatly. In order to clear the farmland NH3 emissions research status and achievements, the literature of farmland NH3 emission related were retrievaled by the SCI journals and Chinese science citation database. Some factors of NH3 emission were analyzed such as soil factors, climate factors and farmland management measures. The research progress was inductived on farmland NH3 emission reduction technology. The results will help to clarify farmland NH3 emissions research progress. The theoretical guidance was provided on the future of farmland NH3 emissions research.

  8. Ammonia volatilization from a paddy field following applications of urea: rice plants are both an absorber and an emitter for atmospheric ammonia.

    PubMed

    Hayashi, Kentaro; Nishimura, Seiichi; Yagi, Kazuyuki

    2008-02-15

    Ammonia (NH(3)) volatilization from a paddy field following applications of urea was measured. Two lysimeters of Gray Lowland soil with a pH (H(2)O) of 5.7 were used for the experiment. Urea was applied at a rate of 50 kg N ha(-1) by incorporation as the basal fertilization (BF) and at rates of 30 and 10 kg N ha(-1) by top-dressing as the first (SF1) and second (SF2) supplemental fertilizations, respectively. Two wind tunnels per lysimeter were installed just after BF; one was transplanted with rice plants (PR plot), and the other was without rice plants (NR plot). Weak volatilization was observed at the PR plots after BF. By contrast, strong volatilization was observed at the PR plots after SF1 with a maximum flux of 150 g N ha(-1) h(-1); however, almost no volatilization was observed after SF2. The NH(3) volatilization loss accounted for 2.1%, 20.9%, 0.5%, and 8.2% of the applied urea at each application, BF, SF1, SF2, and the total application, respectively, for which only the net fluxes as volatilization were accumulated. The NH(3) volatilization fluxes from the paddy water surface (F(vol)) at the NR plots were estimated using a film model for its verification. After confirmation of good correlation, the film model was applied to estimate F(vol) at the PR plots. The NH(3) exchange fluxes by rice plants (F(ric)) were obtained by subtracting F(vol) from the observed net NH(3) flux. The derived F(ric) showed that the rice plants emitted NH(3) remarkably just after SF1 when a relatively high rate of urea was applied, although they absorbed atmospheric NH(3) in the other periods. In conclusion, rice plants are essentially an absorber of atmospheric NH(3); however, they turn into an emitter of NH(3) under excess nutrition of ammoniacal nitrogen.

  9. Movement of NH3 through the human urea transporter B: a new gas channel

    PubMed Central

    Musa-Aziz, Raif; Enkavi, Giray; Mahinthichaichan, P.; Tajkhorshid, Emad; Boron, Walter F.

    2013-01-01

    Aquaporins and Rh proteins can function as gas (CO2 and NH3) channels. The present study explores the urea, H2O, CO2, and NH3 permeability of the human urea transporter B (UT-B) (SLC14A1), expressed in Xenopus oocytes. We monitored urea uptake using [14C]urea and measured osmotic water permeability (Pf) using video microscopy. To obtain a semiquantitative measure of gas permeability, we used microelectrodes to record the maximum transient change in surface pH (ΔpHS) caused by exposing oocytes to 5% CO2/33 mM HCO3− (pHS increase) or 0.5 mM NH3/NH4+ (pHS decrease). UT-B expression increased oocyte permeability to urea by >20-fold, and Pf by 8-fold vs. H2O-injected control oocytes. UT-B expression had no effect on the CO2-induced ΔpHS but doubled the NH3-induced ΔpHS. Phloretin reduced UT-B-dependent urea uptake (Jurea*) by 45%, Pf* by 50%, and (−ΔpHS*)NH3 by 70%. p-Chloromercuribenzene sulfonate reduced Jurea* by 25%, Pf* by 30%, and (ΔpHS*)NH3 by 100%. Molecular dynamics (MD) simulations of membrane-embedded models of UT-B identified the monomeric UT-B pores as the main conduction pathway for both H2O and NH3 and characterized the energetics associated with permeation of these species through the channel. Mutating each of two conserved threonines lining the monomeric urea pores reduced H2O and NH3 permeability. Our data confirm that UT-B has significant H2O permeability and for the first time demonstrate significant NH3 permeability. Thus the UTs become the third family of gas channels. Inhibitor and mutagenesis studies and results of MD simulations suggest that NH3 and H2O pass through the three monomeric urea channels in UT-B. PMID:23552862

  10. Depletion of the heaviest stable N isotope is associated with NH4+/NH3 toxicity in NH4+-fed plants

    PubMed Central

    2011-01-01

    Background In plants, nitrate (NO3-) nutrition gives rise to a natural N isotopic signature (δ15N), which correlates with the δ15N of the N source. However, little is known about the relationship between the δ15N of the N source and the 14N/15N fractionation in plants under ammonium (NH4+) nutrition. When NH4+ is the major N source, the two forms, NH4+ and NH3, are present in the nutrient solution. There is a 1.025 thermodynamic isotope effect between NH3 (g) and NH4+ (aq) which drives to a different δ15N. Nine plant species with different NH4+-sensitivities were cultured hydroponically with NO3- or NH4+ as the sole N sources, and plant growth and δ15N were determined. Short-term NH4+/NH3 uptake experiments at pH 6.0 and 9.0 (which favours NH3 form) were carried out in order to support and substantiate our hypothesis. N source fractionation throughout the whole plant was interpreted on the basis of the relative transport of NH4+ and NH3. Results Several NO3--fed plants were consistently enriched in 15N, whereas plants under NH4+ nutrition were depleted of 15N. It was shown that more sensitive plants to NH4+ toxicity were the most depleted in 15N. In parallel, N-deficient pea and spinach plants fed with 15NH4+ showed an increased level of NH3 uptake at alkaline pH that was related to the 15N depletion of the plant. Tolerant to NH4+ pea plants or sensitive spinach plants showed similar trend on 15N depletion while slight differences in the time kinetics were observed during the initial stages. The use of RbNO3 as control discarded that the differences observed arise from pH detrimental effects. Conclusions This article proposes that the negative values of δ15N in NH4+-fed plants are originated from NH3 uptake by plants. Moreover, this depletion of the heavier N isotope is proportional to the NH4+/NH3 toxicity in plants species. Therefore, we hypothesise that the low affinity transport system for NH4+ may have two components: one that transports N in the

  11. Depletion of the heaviest stable N isotope is associated with NH4+/NH3 toxicity in NH4+-fed plants.

    PubMed

    Ariz, Idoia; Cruz, Cristina; Moran, Jose F; González-Moro, María B; García-Olaverri, Carmen; González-Murua, Carmen; Martins-Loução, Maria A; Aparicio-Tejo, Pedro M

    2011-05-16

    In plants, nitrate (NO3-) nutrition gives rise to a natural N isotopic signature (δ15N), which correlates with the δ15N of the N source. However, little is known about the relationship between the δ15N of the N source and the 14N/15N fractionation in plants under ammonium (NH4+) nutrition. When NH4+ is the major N source, the two forms, NH4+ and NH3, are present in the nutrient solution. There is a 1.025 thermodynamic isotope effect between NH3 (g) and NH4+ (aq) which drives to a different δ15N. Nine plant species with different NH4+-sensitivities were cultured hydroponically with NO3- or NH4+ as the sole N sources, and plant growth and δ15N were determined. Short-term NH4+/NH3 uptake experiments at pH 6.0 and 9.0 (which favours NH3 form) were carried out in order to support and substantiate our hypothesis. N source fractionation throughout the whole plant was interpreted on the basis of the relative transport of NH4+ and NH3. Several NO3--fed plants were consistently enriched in 15N, whereas plants under NH4+ nutrition were depleted of 15N. It was shown that more sensitive plants to NH4+ toxicity were the most depleted in 15N. In parallel, N-deficient pea and spinach plants fed with 15NH4+ showed an increased level of NH3 uptake at alkaline pH that was related to the 15N depletion of the plant. Tolerant to NH4+ pea plants or sensitive spinach plants showed similar trend on 15N depletion while slight differences in the time kinetics were observed during the initial stages. The use of RbNO3 as control discarded that the differences observed arise from pH detrimental effects. This article proposes that the negative values of δ15N in NH4+-fed plants are originated from NH3 uptake by plants. Moreover, this depletion of the heavier N isotope is proportional to the NH4+/NH3 toxicity in plants species. Therefore, we hypothesise that the low affinity transport system for NH4+ may have two components: one that transports N in the molecular form and is associated with

  12. Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

    NASA Astrophysics Data System (ADS)

    Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

    1991-03-01

    The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

  13. Understanding of ammonia transport in PEM fuel cells

    NASA Astrophysics Data System (ADS)

    Jung, Myunghee

    This dissertation investigates ammonia (NH3) as a fuel contaminant to the anode in Proton Exchange Membrane Fuel Cells (PEMFCs). Since NH 3 is fed to the anode in a gas phase and transferred to the cathode, the effect of a contaminant is distributed through MEA and quite complicated. This study is focused on the investigation of mechanism of NH3 transport and the isolation of multiple effects to degrade the performance of fuel cell. An External Reference Electrode (ERE) was employed to decouple the effect of individual electrode and explain the mechanism of NH3 contamination. A mechanism of NH3 transport is proposed and supported by data for various inlet conditions in a N2/N2 laboratory-scale fuel cell at Open Circuit Conditions (OCC). With a commercialized GORE(TM) PRIMEA RTM 5631 MEAs at 70°C, data were obtained utilizing a material balance technique, which uses an ion selective electrode (ISE) to determine the concentration of ammonium ion in the process streams. The results indicate that ammonia is not transported across the membrane when the feeds to both electrodes are dry. However, with humidified feeds ammonia was transported from the anode to the cathode. The data also indicate the water content of in the MEA is the critical factor that causes NH3 crossover in the MEA. Diffusion coefficients of NH3 in MEA are also calculated at different relative humilities. An ERE was developed for PEM fuel cell by using a NafionRTM strip which was used to understand contamination mechanism. The voltage of anode electrode relative to ERE was measured during a polarization curve. The data showed the measurement of individual electrode potential was extremely affected by the misalignment between two electrodes. We compare the overpotential measured from the reference electrode and the calculated overpotential from subtracting the cell voltages between neat hydrogen and a 25 ppm CO in H 2 stream at same current. The studies indicated that the overpotentials obtained from

  14. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2

    NASA Astrophysics Data System (ADS)

    Wilzewski, Jonas S.; Gordon, Iouli E.; Kochanov, Roman V.; Hill, Christian; Rothman, Laurence S.

    2016-01-01

    To increase the potential for use of the HITRAN database in astronomy, experimental and theoretical line-broadening coefficients, line shifts and temperature-dependence exponents of molecules of planetary interest broadened by H2, He, and CO2 have been assembled from available peer-reviewed sources. The collected data were used to create semi-empirical models so that every HITRAN line of the studied molecules has corresponding parameters. Since H2 and He are major constituents in the atmospheres of gas giants, and CO2 predominates in atmospheres of some rocky planets with volcanic activity, these spectroscopic data are important for remote sensing studies of planetary atmospheres. In this paper we make the first step in assembling complete sets of these parameters, thereby creating datasets for SO2, NH3, HF, HCl, OCS and C2H2.

  15. Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

    NASA Astrophysics Data System (ADS)

    Shi, Qihua; Zhang, Yimin; Liu, Tao; Huang, Jing

    2018-03-01

    In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V2O5; therefore, wastewater containing a high level of NH4 + is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH4 + concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH4 + was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.

  16. The Effects of Acute Copper and Ammonia Challenges on Ammonia and Urea Excretion by the Blue Crab Callinectes sapidus.

    PubMed

    Zimmer, Alex M; Jorge, Marianna Basso; Wood, Chris M; Martins, Camila M G; Bianchini, Adalto

    2017-04-01

    Copper (Cu) is a persistent environmental contaminant that elicits several physiological disturbances in aquatic organisms, including a disruption in ammonia regulation. We hypothesized that exposure to Cu in a model crustacean (blue crab, Callinectes sapidus) acclimated to brackish water (2 ppt) would lead to hyperammonemia by stimulating an increase in ammonia production and/or by inhibiting ammonia excretion. We further hypothesized that urea production would represent an ammonia detoxification strategy in response to Cu. In a pilot experiment, exposure to 0, 100, and 200 µg/L Cu for 6 h caused significant concentration-dependent increases in ammonia excretion (J amm ). Based on these results, an acute 24-h 100 µg/L Cu exposure was conducted and this similarly caused an overall stimulation of J amm during the 24-h period, indicative of an increase in ammonia production. Terminal haemolymph total ammonia content (T amm ) was unchanged, suggesting that while ammonia production was increased, there was no inhibition of the excretion mechanism. In support of our second hypothesis, urea excretion (J urea ) increased in response to Cu exposure; haemolymph [urea] was unaffected. This suggested that urea production also was increased. To further test the hypothesis that J urea increased to prevent hyperammonemia during Cu exposure, crabs were exposed to high environmental ammonia (HEA; 2.5 mmol/L NH 4 HCO 3 ) for 12 h in a separate experiment. This led to a fourfold increase in haemolymph T amm , whereas J urea increased only transiently and haemolymph [urea] was unchanged, indicating that urea production likely does not contribute to the attenuation of hyperammonemia in blue crabs. Overall, Cu exposure in blue crabs led to increased ammonia and urea production, which were both eliminated by excretion. These results may have important implications in aquaculture systems where crabs may be exposed to elevated Cu and/or ammonia.

  17. Etude des mécanismes d'ionisation de H{2}O par interaction He^{*}(2 ^1S, 2 ^3S)/Ne^{*}(^3P{0}, ^3P{2})+H{2}O

    NASA Astrophysics Data System (ADS)

    Le Nadan, André; Sinou, Guillaume; Tuffin, Firmin

    1993-06-01

    Experimental observations of Penning ionisation of H{2}O by the helium metastables 21S and 23S and by the neon metastables ^3P{0} and ^3P{2} are reported. The kinetic energies of the ions created during the collision process (both parent and fragment) are analysed. Certain particularities of the experimental results are explained by involving the hypothesis of transfers of vibrational energy to kinetic energy. Furthermore, the forms of the energy distributions of the fragment ions are explained by th predissociation of the ^2B{2} state of H{2}O+. Nous avons étudié l'ionisation Penning de H{2}O par des métastables 21S et 23S de l'hélium, ainsi que ^3P{0} et ^3P{2} du néon. Nous avons analysé l'énergie cinétique des ions créés au cours de la collision (parents et fragments). Afin d'interpréter certaines particularités expérimentales, l'hypothèse de transferts d'énergie de vibration en énergie cinétique est proposées. Par ailleurs, les caractéristiques des distributions en énergie des ions fragments sont expliquées par la prédissociation de l'état ^2B{2} de H{2}O+.

  18. SEASONAL NH3 EMISSION ESTIMATES FOR THE EASTERN UNITED STATES BASED ON AMMONIUM WET CONCENTRATIONS AND AN INVERSE MODELING METHOD

    EPA Science Inventory

    Significant uncertainty exists in the magnitude and variability of ammonia (NH3) emissions. NH3 emissions are needed as input for air quality modeling of aerosols and deposition of nitrogen compounds. Approximately 85% of NH3 emissions are estimated to come from agricultural ...

  19. Effect of the SiCl4 Flow Rate on SiBN Deposition Kinetics in SiCl4-BCl3-NH3-H2-Ar Environment

    PubMed Central

    Li, Jianping; Qin, Hailong; Liu, Yongsheng; Ye, Fang; Li, Zan; Cheng, Laifei; Zhang, Litong

    2017-01-01

    To improve the thermal and mechanical stability of SiCf/SiC or C/SiC composites with SiBN interphase, SiBN coating was deposited by low pressure chemical vapor deposition (LPCVD) using SiCl4-BCl3-NH3-H2-Ar gas system. The effect of the SiCl4 flow rate on deposition kinetics was investigated. Results show that deposition rate increases at first and then decreases with the increase of the SiCl4 flow rate. The surface of the coating is a uniform cauliflower-like structure at the SiCl4 flow rate of 10 mL/min and 20 mL/min. The surface is covered with small spherical particles when the flow rate is 30 mL/min. The coatings deposited at various SiCl4 flow rates are all X-ray amorphous and contain Si, B, N, and O elements. The main bonding states are B-N, Si-N, and N-O. B element and B-N bonding decrease with the increase of SiCl4 flow rate, while Si element and Si-N bonding increase. The main deposition mechanism refers to two parallel reactions of BCl3+NH3 and SiCl4+NH3. The deposition process is mainly controlled by the reaction of BCl3+NH3. PMID:28772986

  20. 1H NMR relaxometry and quadrupole relaxation enhancement as a sensitive probe of dynamical properties of solids—[C(NH2)3]3Bi2I9 as an example

    NASA Astrophysics Data System (ADS)

    Florek-Wojciechowska, M.; Wojciechowski, M.; Jakubas, R.; Brym, Sz.; Kruk, D.

    2016-02-01

    1H nuclear magnetic resonance relaxometry has been applied to reveal information on dynamics and structure of Gu3Bi2I9 ([Gu = C(NH2)3] denotes guanidinium cation). The data have been analyzed in terms of a theory of quadrupole relaxation enhancement, which has been extended here by including effects associated with quadrupole (14N) spin relaxation caused by a fast fluctuating component of the electric field gradient tensor. Two motional processes have been identified: a slow one occurring on a timescale of about 8 × 10-6 s which has turned out to be (almost) temperature independent, and a fast process in the range of 10-9 s. From the 1H-14N relaxation contribution (that shows "quadrupole peaks") the quadrupole parameters, which are a fingerprint of the arrangement of the anionic network, have been determined. It has been demonstrated that the magnitude of the quadrupole coupling considerably changes with temperature and the changes are not caused by phase transitions. At the same time, it has been shown that there is no evidence of abrupt changes in the cationic dynamics and the anionic substructure upon the phase transitions.

  1. Ammonia emissions in Europe, part II: How ammonia emission abatement strategies affect secondary aerosols

    NASA Astrophysics Data System (ADS)

    Backes, Anna M.; Aulinger, Armin; Bieser, Johannes; Matthias, Volker; Quante, Markus

    2016-02-01

    In central Europe, ammonium sulphate and ammonium nitrate make up a large fraction of fine particles which pose a threat to human health. Most studies on air pollution through particulate matter investigate the influence of emission reductions of sulphur- and nitrogen oxides on aerosol concentration. Here, we focus on the influence of ammonia (NH3) emissions. Emission scenarios have been created on the basis of the improved ammonia emission parameterization implemented in the SMOKE for Europe and CMAQ model systems described in part I of this study. This includes emissions based on future European legislation (the National Emission Ceilings) as well as a dynamic evaluation of the influence of different agricultural sectors (e.g. animal husbandry) on particle formation. The study compares the concentrations of NH3, NH4+, NO3 -, sulphur compounds and the total concentration of particles in winter and summer for a political-, technical- and behavioural scenario. It was found that a reduction of ammonia emissions by 50% lead to a 24% reduction of the total PM2.5 concentrations in northwest Europe. The observed reduction was mainly driven by reduced formation of ammonium nitrate. Moreover, emission reductions during winter had a larger impact than during the rest of the year. This leads to the conclusion that a reduction of the ammonia emissions from the agricultural sector related to animal husbandry could be more efficient than the reduction from other sectors due to its larger share in winter ammonia emissions.

  2. Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California.

    PubMed

    Cisneros, Ricardo; Bytnerowicz, Andrzej; Schweizer, Donald; Zhong, Sharon; Traina, Samuel; Bennett, Deborah H

    2010-10-01

    Two-week average concentrations of ozone (O3), nitric acid vapor (HNO3) and ammonia (NH3) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O3, 1.0-3.8 microg m(-3) for HNO3, and 2.6-5.2 microg m(-3) for NH3. Calculated O3 exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha(-1) for maximum values, and 0.4-8 kg N ha(-1) for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O3 human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O3.

  3. The abundance of ammonia in Comet P/Halley derived from ultraviolet spectrophotometry of NH by ASTRON and IUE

    NASA Technical Reports Server (NTRS)

    Feldman, P. D.; Fournier, K. B.; Grinin, V. P.; Zvereva, A. M.

    1993-01-01

    From an analysis of the spatial profiles of both the NH and OH UV emissions observed by the ASTRON satellite, the ratio of ammonia-to-water production rates in Comet Halley on April 9, 1986 is derived and found to lie in the range of 0.44-0.94 percent. In order to compare this result with those based on both ground-based and in situ observations made on other dates during the 1985-1986 apparition of the comet, the IUE observational data base for December 1985 and March-April 1986 is used to evaluate the ratio of NH to OH column density in the IUE field of view and thus constrain the long-term behavior of this ratio. The IUE data base indicates that, to within a factor of 2, the ammonia-to-water production rate ratio is the same for a small sample of moderately bright comets observed recently.

  4. Color-Changing Microfiber-Based Multifunctional Window Screen for Capture and Visualized Monitoring of NH3.

    PubMed

    Wang, Zhen; Yuan, Xinxin; Cong, Shan; Chen, Zhigang; Li, Qingwen; Geng, Fengxia; Zhao, Zhigang

    2018-05-02

    Air pollution is one of the most serious issues affecting the world today. Instead of expensive and energy-intensive air filtering devices, a fiber-based transparent air filter coated on a window screen is seen as one of the state-of-the-art filtration technologies to combat the seriously growing problem, delivering the advantages of simplicity, convenience, and high filtering efficiency. However, such a window screen is currently limited to particulate matter (PM) filtration and ineffective with other air pollutants. Here, we report the use of a newfangled type of color-changing fibers, porous Prussian blue analogues (CuHCF)/polymer composite microfibers, for transparent window screens toward air pollutant filtration. To increase pollution filtration, pores and dimples are purposely introduced to the fibers using binary solvent systems through a nonsolvent-induced phase separation mechanism. Such composite microfibers overcome some of the limitations of those previously used fibers and could simultaneously capture PM 2.5 , PM 10 , and NH 3 with high efficiency. More interestingly, a distinct color change is observed upon exposure to air pollutants in such window screens, which provides multifunctional capability of simultaneous pollutant capture and naked eye screening of the pollutant amount. Specifically, in the case of long-term exposure to low-concentration NH 3 , the symbol displayed in such window screens changes from yellow color to brown and the coloration rate is directly controlled by the NH 3 concentration, which may serve as a careful reminder for those people who are repeatedly exposed to low-concentration ammonia gas (referred to as chronic poisoning). In contrast, after short-term exposure to a high concentration of ammonia gas, the yellow symbol immediately becomes blackened, which provides timely information about the risk of acute ammonia poisoning or even ammonia explosion. Further spectroscopic results show that the chromatic behaviors in

  5. A modified biotrickling filter for nitrification-denitrification in the treatment of an ammonia-contaminated air stream.

    PubMed

    Raboni, Massimo; Torretta, Vincenzo

    2016-12-01

    A conventional biotrickling filter for airborne ammonia nitrification has been modified, by converting the liquid sump into a biological denitrifying reactor. The biotrickling filter achieves an average ammonia removal efficiency of 92.4 %, with an empty bed retention time (EBRT) equal to 36 s and an average ammonia concentration of 54.7 mg Nm -3 in the raw air stream. The denitrification reactor converts ammonia into inert gas N 2 , in addition to other important advantages connected to the alkaline character of the biochemical pathway of the denitrifying bacteria. Firstly, the trickling water crossing the denitrification reactor underwent a notable pH increase from 7.3 to 8.0 which prevented the acidic inhibition of the nitrifying bacteria due to the buildup of nitric and nitrous acids. Secondly, the pH increase created the ideal conditions for the autotrophic nitrifying bacteria. The tests proved that an ammonia removal efficiency of above 90 % can be achieved with an EBRT greater than 30 s and a volumetric load lower than 200 g NH 3  m -3  day -1 . The results of the biofilm observation by using a scanning confocal laser microscope are reported together with the identification of degrading bacteria genera in the biotrickling filter. The efficiency of the plant and its excellent operational stability highlight the effectiveness of the synergistic action between the denitrification reactor and the biotrickling filter in removing airborne ammonia.

  6. Ammonia formation by the reduction of nitrite/nitrate by FeS: ammonia formation under acidic conditions.

    PubMed

    Summers, David P

    2005-08-01

    One issue for the origin of life under a non-reducing atmosphere is the availability of the reduced nitrogen necessary for amino acids, nucleic acids, etc. One possible source of this nitrogen is the formation of ammonia from the reduction of nitrates and nitrites produced by the shock heating of the atmosphere and subsequent chemistry. Ferrous ions will reduce these species to ammonium, but not under acidic conditions. We wish to report results on the reduction of nitrite and nitrate by another source of iron (II), ferrous sulfide, FeS. FeS reduces nitrite to ammonia at lower pHs than the corresponding reduction by aqueous Fe+ 2. The reduction follows a first order decay, in nitrite concentration, with a half-life of about 150 min (room temperature, CO2, pH 6.25). The highest product yield of ammonia measured was 53%. Under CO2, the product yield decreases from pH 5.0 to pH 6.9. The increasing concentration of bicarbonate, at higher pH, interferes with the reaction. Comparing experiments under N2 CO2 shows the interference of bicarbonate. The reaction proceeds well in the presence of such species as chloride, sulfate, and phosphate, though the yield drops significantly with phosphate. FeS also reduces nitrate and, unlike with Fe+ 2, the reduction shows more reproducibility. Again, the product yield decreases with increasing pH, from 7% at pH 4.7 to 0% at pH 6.9. It appears that nitrate is much more sensitive to the presence of added species, perhaps not competing as well for binding sites on the FeS surface. This may be the cause of the lack of reproducibility of nitrate reduction by Fe+ 2 (which also can be sensitive to binding by certain species).

  7. First-principles investigation on defect-induced silicene nanoribbons - A superior media for sensing NH3, NO2 and NO gas molecules

    NASA Astrophysics Data System (ADS)

    Walia, Gurleen Kaur; Randhawa, Deep Kamal Kaur

    2018-04-01

    In this paper, the electronic and transport properties of armchair silicene nanoribbons (ASiNRs) are analyzed for their application as highly selective and sensitive gas molecule sensors. The study is focused on sensing three nitrogen based gases; ammonia (NH3), nitrogen dioxide (NO2) and nitric oxide (NO), which depending upon their adsorption energy and charge transfer, form bonds of varying strength with ASiNRs. The negligible band gap of ASiNRs is tuned by adding a defect in ASiNRs. Adsorption of NH3 leads to the opening of band gap whereas on adsorption of NO2 and NO, ASiNRs exhibit metallic nature. Distinctly divergent electronic and transport properties of ASiNRs are observed and on adsorption of NH3, NO2 and NO, renders them suitable for sensing them. All gas molecules show stronger adsorption on defective ASiNRs (D-ASiNRs) as compared to pristine ASiNRs (P-ASiNRs). The work reveals that introduction of defect can drastically improve the sensitivity of ASiNRs.

  8. MOFs for the Sensitive Detection of Ammonia: Deployment of fcu-MOF Thin Films as Effective Chemical Capacitive Sensors.

    PubMed

    Assen, Ayalew H; Yassine, Omar; Shekhah, Osama; Eddaoudi, Mohamed; Salama, Khaled N

    2017-09-22

    This work reports on the fabrication and deployment of a select metal-organic framework (MOF) thin film as an advanced chemical capacitive sensor for the sensing/detection of ammonia (NH 3 ) at room temperature. Namely, the MOF thin film sensing layer consists of a rare-earth (RE) MOF (RE-fcu-MOF) deposited on a capacitive interdigitated electrode (IDE). Purposely, the chemically stable naphthalene-based RE-fcu-MOF (NDC-Y-fcu-MOF) was elected and prepared/arranged as a thin film on a prefunctionalized capacitive IDE via the solvothermal growth method. Unlike earlier realizations, the fabricated MOF-based sensor showed a notable detection sensitivity for NH 3 at concentrations down to 1 ppm, with a detection limit appraised to be around 100 ppb (at room temperature) even in the presence of humidity and/or CO 2 . Distinctly, the NDC-Y-fcu-MOF based sensor exhibited the required stability to NH 3 , in contrast to other reported MOFs, and a remarkable detection selectivity toward NH 3 vs CH 4 , NO 2 , H 2 , and C 7 H 8 . The NDC-Y-fcu-MOF based sensor exhibited excellent performance for sensing ammonia for simulated breathing system in the presence of the mixture of carbon dioxide and/or humidity (water vapor), with no major alteration in the detection signal.

  9. Insertion of bentonite with Organometallic [Fe3O(OOC6H5)6(H2O)3(NO3).nH2O] as Adsorbent of Congo Red

    NASA Astrophysics Data System (ADS)

    Said, Muhammad; Paluta Utami, Hasja; Hayati, Ferlina

    2018-01-01

    The adsorption of Congo red using bentonite inserted organometallic has been investigated. The insertion bentonite was characterized using FT-IR Spectrophotometer, XRD and XRF analysis. The FT-IR characterization showed the higher intensity of peak wavenumber at 470.6 cm-1 for Fe3O on the ratio 1:3. While the XRD characterization showed the shift of diffraction angle of 2θ was 5.2° and has a basal spacing of 16.8 Å. In the XRF characterization, the insertion process of organometallic occurred optimally with the percentage of metal oxide reached 71.75 %. The adsorption process of bentonite inserted organometallic compound [Fe3O(OOC6H5)6(H2O)3(NO3)·nH2O] showed the adsorption rate (k) is 0.050 min-1, the largest adsorption capacity (b) at 70°C is 4.48 mol/g, the largest adsorption energy at temperature 30°C which is 6.4 kJ/mol Organometallic compounds. The value of the enthalpy (ΔH) and entropy (ΔS) decreased with increasing concentrations of the Congo red. Effect of pH on the adsorption on at pH 3 shows the biggest of number Congo red absorbed is 19.52 mg/L for insertion of bentonite.

  10. Response characteristics of stable mixed-potential NH 3 sensors in diesel engine exhaust

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

    Brosha, Eric L.; Prikhodko, Vitaly Y.; Kreller, Cortney R.

    Here, a mixed-potential, electrochemical sensor platform is extended to NH 3 sensing by the introduction of a new gold alloy working electrode. A planar, pre-commercial NH 3 sensor utilized LANL’s controlled interface approach, and a Pd-Au alloy working electrode was tested in exhaust of a GM 1.9 L diesel engine downstream of a diesel oxidation catalyst through a slipstream arrangement. A fraction of the exhaust was pulled across the sensor with a pump at 20 L/min. In order to simulate NH 3 slip inside of a full SCR emissions control system, NH 3 was injected immediately upstream of the sensormore » using a calibrated mass flow controller. The sensor response quantitatively tracked the NH 3 as measured via Fourier transform infrared (FTIR) analyzer. A calibration curve was obtained in the exhaust from an ammonia staircase response with the engine running at steady-state engine conditions resulting in low background concentrations of NO x and HC (<20 ppm) during calibration. Exhaust gas recirculation (EGR) switching and sweeps were used to evaluate the NH 3 sensor response under different amounts of total background NO x. The calibration curve was used to directly compare the [NH 3] calculated from sensor response to the gas phase composition measured via FTIR. In general, there was excellent quantitative agreement between the sensor response and the actual NH 3 in the exhaust gas, and fast response time such that transients (<5 ppm) could be easily discerned from baseline. A LANL pre-commercial NO x sensor was tested simultaneously with the NH 3 sensor and the extent of cross-sensitivity between the two sensors will be discussed.« less

  11. Response characteristics of stable mixed-potential NH 3 sensors in diesel engine exhaust

    DOE PAGES

    Brosha, Eric L.; Prikhodko, Vitaly Y.; Kreller, Cortney R.; ...

    2016-10-20

    Here, a mixed-potential, electrochemical sensor platform is extended to NH 3 sensing by the introduction of a new gold alloy working electrode. A planar, pre-commercial NH 3 sensor utilized LANL’s controlled interface approach, and a Pd-Au alloy working electrode was tested in exhaust of a GM 1.9 L diesel engine downstream of a diesel oxidation catalyst through a slipstream arrangement. A fraction of the exhaust was pulled across the sensor with a pump at 20 L/min. In order to simulate NH 3 slip inside of a full SCR emissions control system, NH 3 was injected immediately upstream of the sensormore » using a calibrated mass flow controller. The sensor response quantitatively tracked the NH 3 as measured via Fourier transform infrared (FTIR) analyzer. A calibration curve was obtained in the exhaust from an ammonia staircase response with the engine running at steady-state engine conditions resulting in low background concentrations of NO x and HC (<20 ppm) during calibration. Exhaust gas recirculation (EGR) switching and sweeps were used to evaluate the NH 3 sensor response under different amounts of total background NO x. The calibration curve was used to directly compare the [NH 3] calculated from sensor response to the gas phase composition measured via FTIR. In general, there was excellent quantitative agreement between the sensor response and the actual NH 3 in the exhaust gas, and fast response time such that transients (<5 ppm) could be easily discerned from baseline. A LANL pre-commercial NO x sensor was tested simultaneously with the NH 3 sensor and the extent of cross-sensitivity between the two sensors will be discussed.« less

  12. Broadening of spectral lines of CO2, N2O , H2CO, HCN, and H2S by pressure of gases dominant in planetary atmospheres (H2, He and CO2)

    NASA Astrophysics Data System (ADS)

    Samuels, Shanelle; Gordon, Iouli; Tan, Yan

    2018-01-01

    HITRAN1,2 is a compilation of spectroscopic parameters that a variety of computer codes use to predict and simulate the transmission and emission of light in planetary atmospheres. The goal of this project is to add to the potential of the HITRAN database towards the exploration of the planetary atmospheres by including parameters describing broadening of spectral lines by H2, CO2, and He. These spectroscopic data are very important for the study of the hydrogen and helium-rich atmospheres of gas giants as well as rocky planets with volcanic activities, including Venus and Mars, since their atmospheres are dominated by CO2. First step in this direction was accomplished by Wilzewski et al.3 where this was done for SO2, NH3, HF, HCl, OCS and C2H2. The molecules investigated in this work were CO2, N2O, H2CO, HCN and H2S. Line-broadening coefficients, line shifts and temperature-dependence exponents for transitions of these molecules perturbed by H2, CO2 and He have been assembled from available peer-reviewed experimental and theoretical sources. The data was evaluated and the database was populated with these data and their extrapolations/interpolations using semi-empirical models that were developed to this end.Acknowledgements: Financial support from NASA PDART grant NNX16AG51G and the Smithsonian Astrophysical Observatory Latino Initiative Program from the Latino Initiatives Pool, administered by the Smithsonian Latino Center is gratefully acknowledged.References: 1. HITRAN online http://hitran.org/2. Gordon, I.E., Rothman, L.S., Hill, C., Kochanov, R.V., Tan, Y., et al., 2017. The HITRAN2016 Molecular Spectroscopic Database. J. Quant. Spectrosc. Radiat. Transf. doi:10.1016/j.jqsrt.2017.06.0383. Wilzewski, J.S., Gordon, I.E., Kochanov, R. V., Hill, C., Rothman, L.S., 2016. H2, He, and CO2 line-broadening coefficients, pressure shifts and temperature-dependence exponents for the HITRAN database. Part 1: SO2, NH3, HF, HCl, OCS and C2H2. J. Quant. Spectrosc. Radiat

  13. Ammonia emissions, transport, and deposition downwind of agricultural areas at local to regional scales

    NASA Astrophysics Data System (ADS)

    Zondlo, Mark; Pan, Da; Golston, Levi; Sun, Kang; Tao, Lei

    2016-04-01

    Ammonia (NH3) emissions from agricultural areas show extreme spatiotemporal variations, yet agricultural emissions dominate the global NH3 budget and ammoniated aerosols are a dominant component of unhealthy fine particulate matter. The emissions of NH3 and their deposition near and downwind of agricultural areas is complex. As part of a multi-year field intensive along the Colorado Front Range (including the NASA DISCOVER-AQ and NSF FRAPPE field experiments), we have examined temporal emissions of NH3 from feedlots, regional transport of ammonia and ammoniated aerosols from the plains to relatively pristine regions in Rocky Mountain National Park, and dry deposition and re-emission of grassland NH3 in the park. Eddy covariance measurements at feedlots and natural grasslands in the mountains were conducted with newly-developed open-path, eddy covariance laser-based sensors for NH3 (0.7 ng NH3/m2/s detection limit at 10 Hz). These measurements were coupled with other NH3/NHx measurements from mobile laboratories, aircraft, and satellite to examine the transport of NH3 from agricultural areas to cleaner regions downwind. At the farm level, eddy covariance NH3 fluxes showed a strong diurnal component correlated with temperature regardless of the season but with higher absolute emissions in summer than winter. While farm-to-farm variability (N=62 feedlots) was high, similar diurnal trends were observed at all sites regardless of individual farm type (dairy, beef, sheep, poultry, pig). Deposition at scales of several km showed relatively small deposition (10% loss) based upon NH3/CH4 tracer correlations, though the NH3 concentrations were so elevated (up to ppmv) that these losses should not be neglected when considering near-farm deposition. Ammonia was efficiently transported at least 150 km during upslope events to the Colorado Front Range (ele. 3000-4000 m) based upon aircraft, mobile laboratory, and model measurements. The gas phase lifetime of NH3 was estimated to

  14. The effect of temperature on post-feeding ammonia excretion and oxygen consumption in the southern catfish.

    PubMed

    Luo, Yiping; Xie, Xiaojun

    2009-08-01

    The post-prandial rates of ammonia excretion (TAN) and oxygen consumption MO2 in the southern catfish (Silurus meridionalis) were assessed at 2 h intervals post-feeding until the rates returned to those of the fasting rates, at 17.5, 22.5, 27.5, and 32.5 degrees C, respectively. Both fasting TAN and MO2 increased with temperature, and were lower than those previously reported for many fish species. The relationship between fasting TAN (mmol NH(3)-N kg(-1) h(-1)) and temperature (T, degrees C) was described as: fasting TAN = 0.144e (0.0266T) (r = 0.526, n = 27, P < 0.05). The magnitude of ammonia excretion and its ratio to total N intake EXNH3-N during the specific dynamic action (SDA) tended to increase initially, and then decrease with increasing temperature. The ammonia quotient (AQ), calculated as mol NH(3)-N/mol O(2), following feeding decreased as temperature increased. The relationship between AQ during SDA and temperature was described as: AQ(during SDA) = 0.303e (-0.0143T) (r = 0.739, n = 21, P < 0.05). Our results suggest that ammonia excretion and oxygen consumption post-feeding are operating independently of each other. Furthermore, it appears that the importance of protein as a metabolic substrate in postprandial fish decreases with temperature.

  15. REVIEW OF EMISSION FACTORS AND METHODOLOGIES TO ESTIMATE AMMONIA EMISSIONS FROM ANIMAL WASTE HANDLING

    EPA Science Inventory

    Currently, approximately 80% of ammonia (NH3) emissions in the United States (U.S.) originate from livestock waste. This report summarizes and discusses recent available U.S. and European information on NH3 emissions from swine farms and assesses the applicability for general use...

  16. EFFECTIVE HYPERFINE-STRUCTURE FUNCTIONS OF AMMONIA

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

    Augustovičová, L.; Soldán, P.; Špirko, V., E-mail: spirko@marge.uochb.cas.cz

    The hyperfine structure of the rotation-inversion ( v {sub 2} = 0{sup +}, 0{sup −}, 1{sup +}, 1{sup −}) states of the {sup 14}NH{sub 3} and {sup 15}NH{sub 3} ammonia isotopomers is rationalized in terms of effective (ro-inversional) hyperfine-structure (hfs) functions. These are determined by fitting to available experimental data using the Hougen’s effective hyperfine-structure Hamiltonian within the framework of the non-rigid inverter theory. Involving only a moderate number of mass independent fitting parameters, the fitted hfs functions provide a fairly close reproduction of a large majority of available experimental data, thus evidencing adequacy of these functions for reliable prediction.more » In future experiments, this may help us derive spectroscopic constants of observed inversion and rotation-inversion transitions deperturbed from hyperfine effects. The deperturbed band centers of ammonia come to the forefront of fundamental physics especially as the probes of a variable proton-to-electron mass ratio.« less

  17. Elevated production of NH4NO3 from the photochemical processing of vehicle exhaust: Implications for air quality in the Seoul Metropolitan Region

    NASA Astrophysics Data System (ADS)

    Link, Michael F.; Kim, Jounghwa; Park, Gyutae; Lee, Taehyoung; Park, Taehyun; Babar, Zaeem Bin; Sung, Kijae; Kim, Pilho; Kang, Seokwon; Kim, Jeong Soo; Choi, Yongjoo; Son, Jihawn; Lim, Ho-Jin; Farmer, Delphine K.

    2017-05-01

    A vehicle fleet representative of passenger vehicles driven in the Seoul Metropolitan Region was investigated for primary emissions and secondary chemistry. Exhaust was photochemically oxidized in a flow reactor to determine the ammonium nitrate (NH4NO3) aerosol formation potential from vehicles of gasoline, diesel and liquid petroleum gasoline (LPG) fuel types. Secondary formation of aerosol NH4NO3, was larger than primary emissions for all vehicle fuel types except diesel, for which negligible secondary NH4NO3 production was observed. Although diesel vehicles emitted more primary nitrogen oxides than other vehicle types, ammonia emitted from gasoline and liquid petroleum gasoline fuels types limited the secondary production of NH4NO3. The results suggest that gasoline and liquid petroleum gasoline vehicles with three-way catalysts could be an important source of ammonia for NH4NO3 aerosol formation in ammonia-limited environments, including the Seoul Metropolitan Region.

  18. Reversible intercalation of ammonia molecules into a layered double hydroxide structure without exchanging nitrate counter-ions

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

    Carbajal Arizaga, Gregorio Guadalupe, E-mail: gregoriocarbajal@yahoo.com.m; Wypych, Fernando; Castillon Barraza, Felipe

    2010-10-15

    A zinc/aluminum LDH was precipitated with recycled ammonia from a chemical vapor deposition reaction. The LDH presented a crystalline phase with basal distance of 8.9 A, typical for nitrate-containing LDHs, and another phase with a basal distance of 13.9 A. Thermal treatment at 150 {sup o}C eliminated the phase with the bigger basal distance leaving only the anhydrous nitrate-intercalated LDH structure with 8.9 A. Intense N-H stretching modes in the FTIR spectra suggested that the expansion was due to intercalation of ammonia in the form of [NH{sub 4}(NH{sub 3}){sub n}]{sup +} species. When additional samples were precipitated with pure ammonia,more » the conventional LDH nitrate structure was obtained (8.9 A basal distance) at pH=7, as well as a pure crystalline phase with 13.9 A basal distance at pH=10 due to ammonia intercalation that can be removed by heating at 150 {sup o}C or by stirring in acetone, confirming a unusual sensu stricto intercalation process into a LDH without exchanging nitrate ions. - Graphical abstract: LDH-nitrate precipitated with ammonia expands the interlayer space if ammonia is bubbled up to pH 10. The basal distance decreased when the compound was heated at 150 {sup o}C or stirred in acetone. Nitrate ions are not exchanged.« less

  19. Growth and optical, magnetic and transport properties of (C4H9NH3)2MCl4 organic-inorganic hybrid films (M = Cu, Sn)

    NASA Astrophysics Data System (ADS)

    Aruta, C.; Licci, F.; Zappettini, A.; Bolzoni, F.; Rastelli, F.; Ferro, P.; Besagni, T.

    2005-10-01

    Films of (C4H9NH3)2MCl4 (M=Cu and Sn) organic-inorganic hybrid perovskites have been deposited in-situ by a single-source thermal ablation technique on glassy, crystalline and polymeric substrates. Independently of the substrate, the films were well crystallized, c-axis oriented and with a narrow rocking curve of the (0010) reflection (full width at half maximum <1°). The (0 0 ℓ) reflections were consistent with those of the bulk orthorhombic phases and the “c” lattice parameters were 30.85±0.05 and 32.35±0.05 Å, for the Cu- and the Sn-compound, respectively. (C4H9NH3)2CuCl4 films had an optical absorption peak at 375 nm at room temperature. From the magnetic point of view they act as layered nanocomposites with a dominant ferromagnetic component localized in planes (2D magnetism). Tc was 7.3±0.1 K and a moderate easy-plane anisotropy was observed. The photoluminescence spectra of typical (C4H9NH3)2SnCl4 films at 12 K had a broad yellow band, which did not correspond to any significant peak in the absorption spectrum. The films were semiconducting down to 250 K or, in the case of the best samples, down to 200 K and became insulating at lower temperature. The resistivity of the best films was (5±1) 104 Ω cm at 300 K, and the energy gap was 1.11 eV.

  20. Ammonia Formation by the Reduction of Nitrite/Nitrate by FeS: Ammonia Formation Under Acidic Conditions

    NASA Technical Reports Server (NTRS)

    Summers, David P.; DeVincenzi, Donald (Technical Monitor)

    2000-01-01

    FeS reduces nitrite to, ammonia at pHs lower than the corresponding reduction by aqueous Fe+2. The reduction follows a reasonable first order decay, in nitrite concentration, with a half life of about 150 min (room temperature, CO2, pH 6.25). The highest ammonia product yield measured was 53%. Under CO2, the product yield decreases from pH 5.0 to pH 6.9. The increasing concentration of bicarbonate at higher pH interferes with the reaction. Bicarbonate interference is shown by comparing runs under N2 and CO2. The reaction proceeds well in the presence of such species as chloride, sulfate, and phosphate though the yield drops significantly with phosphate. FeS also reduces nitrate and, unlike with Fe+2, the reduction shows more reproducibility. Again, the product yield decreases with increasing pH, from 7% at pH 4.7 to 0% at pH 6.9. It appears as if nitrate is much more sensitive to the presence of added species, perhaps not competing as well for binding sites on the FeS surface. This may be the cause of the lack of reproducibility of nitrate reduction by Fe+2 (which also can be sensitive to binding by certain species).

  1. Tolerance to Ammonia of Thulinius ruffoi (Bertolani, 1981), a Tardigrade Isolated from a Sewage Treatment Plant.

    PubMed

    Sobczyk, Mateusz; Michno, Klaudia; Kosztyła, Paulina; Stec, Daniel; Michalczyk, Łukasz

    2015-12-01

    The acute toxicity of ammonia on Thulinius ruffoi (Bertolani, 1981), a eutardigrade isolated from a small waste water treatment plant (WWTP) in Poland, was estimated. Our results show that no active individuals survived a 24 h exposure to solutions equal to or higher than 125 mg/L of total ammonia nitrogen (NH3-N + NH4 (+)-N), which, under the conditions in our experiment, was equivalent to 1.17 mg/L of un-ionised ammonia (NH3). The LC50 concentration of total ammonia nitrogen was equal to 52 mg/L (or 0.65 mg/L un-ionised ammonia). Given that the norms for the concentration of ammonia in treated waters leaving WWTPs are usually several times lower than the LC50 for T. ruffoi, this species does not seem to be a good bioindicator candidate for WWTPs. In this paper we also note that various ecotoxicological studies use different methodological approaches and we suggest that a more uniform methodology may aid interspecific comparisons of LC50 values.

  2. A three-dimensional model of the global ammonia cycle

    NASA Astrophysics Data System (ADS)

    Dentener, Frank J.; Crutzen, Paul J.

    1994-11-01

    Using a three-dimensional (3-D) transport model of the troposphere, we calculated the global distributions of ammonia (NH3) and ammonium (NH4(+)), taking into account removal of NH3 on acidic aerosols, in liquid water clouds and by reaction with OH. Our estimated global 10 deg x 10 deg NH3 emission inventory of 45 Tg N-NH3/yr provides a reasonable agreement between calculated wet NH4(+) deposition and measurements and of measured and modeled NH4(+) in aerosols, although in Africa and Asia especially discrepancies exist. NH3 emissions from natural continental ecosystems were calculated applying a canopy compensation point and oceanic NH3 emissions were related to those of DMS (dimethylsulfide). In many regions of the earth, the pH found in rain and cloud water can be attributed to acidity derived from NO, SO2 and DMS emissions and alkalinity from NH3. In the remote lower troposphere, sulfate aerosols are calculated to be almost neutralized to ammonium sulfate (NH4)2SO4, whereas in the middle and upper troposphere, according to our calculations, the aerosol should be more acidic, as a result of the oxidation of DMS and SO2 throughout the troposphere and removal of NH3 on acidic aerosols at lower heights. Although the removal of NH3 by reaction with the OH radical is relatively slow, the intermediate NH2 radical can provide a substantial annual N2O source of 0.9(+0.9/-0.4) Tg, thus contributing by about 5% to estimated global N2O production. The oxidation by OH of NH3 from anthropogenic sources accounts for 10% of the estimated total anthropogenic sources of N2O. This source was not accounted for in previous studies, and is mainly located in the tropics, which have high NH3 and OH concentrations. Biomass burning plumes, containing high NO(x) and NH3 concentrations provide favorable conditions for gas phase N2O production. This source is probably underestimated in this model study, due to the coarse resolution of the 3-D model, and the rather low biomass burning NH3

  3. Increased atmospheric ammonia over the world’s major agricultural areas detected from space

    PubMed Central

    Warner, J. X.; Dickerson, R. R.; Wei, Z.; Strow, L. L.; Wang, Y.; Liang, Q.

    2018-01-01

    This study provides evidence of substantial increases in atmospheric ammonia (NH3) concentrations (14-year) over several of the worlds major agricultural regions, using recently available retrievals from the Atmospheric Infrared Sounder (AIRS) aboard NASA's Aqua satellite. The main sources of atmospheric NH3 are farming and animal husbandry involving reactive nitrogen ultimately derived from fertilizer use; rates of emission are also sensitive to climate change. Significant increasing trends are seen over the US (2.61% yr−1), the European Union (EU) (1.83% yr−1), and China (2.27% yr−1). Over the EU, the trend results from decreased scavenging by acid aerosols. Over the US, the increase results from a combination of decreased chemical loss and increased soil temperatures. Over China, decreased chemical loss, increasing temperatures, and increased fertilizer use all play a role. Over South Asia, increased NH3 emissions are masked by increased SO2 and NOx emissions, leading to increased aerosol loading and adverse health effects. PMID:29657344

  4. Densities and apparent molar volumes of atmospherically important electrolyte solutions. 1. The solutes H2SO4, HNO3, HCl, Na2SO4, NaNO3, NaCl, (NH4)2SO4, NH4NO3, and NH4Cl from 0 to 50 °C, including extrapolations to very low temperature and to the pure liquid state, and NaHSO4, NaOH, and NH3 at 25 °C.

    PubMed

    Clegg, S L; Wexler, A S

    2011-04-21

    Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer

  5. Determination of the rate constant for the NH2(X(2)B1) + NH2(X(2)B1) reaction at low pressure and 293 K.

    PubMed

    Bahng, Mi-Kyung; Macdonald, R Glen

    2008-12-25

    The rate constant for the reaction NH(2)(X(2)B(1)) + NH(2)(X(2)B(1)) --> products was measured in CF(4), N(2) and Ar carrier gases at 293 +/- 2 K over a pressure range from 2 to 10 Torr. The NH(2) radical was produced by the 193 nm photolysis of NH(3) dilute in the carrier gas. Both the loss of NH(3) and its subsequent recovery and the production of NH(2) and subsequent reaction were monitored simultaneously following the photolysis laser pulse. Both species were detected using quantitative time-resolved high-resolution absorption spectroscopy. The NH(3) molecule was monitored in the NIR using a rotation transition of the nu(1) + nu(3) first combination band near 1500 nm, and the NH(2) radical was monitored using the (1)2(21) <-- (1)3(31) rotational transition of the (0,7,0)A(2)A(1) <-- (0,0,0) X(2)B(1) band near 675 nm. The low-pressure rate constant showed a linear dependence on pressure. The slope of the pressure dependence was dominated by a recombination rate constant for NH(2) + NH(2) given by (8.0 +/- 0.5) x 10(-29), (5.7 +/- 0.7) x 10(-29), and (3.9 +/- 0.4) x 10(-29) cm(6) molecule(-2) s(-1) in CF(4), N(2), and Ar bath gases, respectively, where the uncertainties are +/-2sigma in the scatter of the measurements. The average of the three independent measurements of the sum of the disproportionation rate constants (the zero pressure rate constant) was (3.4 +/- 6) x 10(-13) cm(3) molecule(-1) s(-1), where the uncertainty is +/-2sigma in the scatter of the measurements.

  6. Phase transition in organic-inorganic perovskite (C9H19NH3)2 PbI2Br2 of long-chain alkylammonium

    NASA Astrophysics Data System (ADS)

    Abid, H.; Trigui, A.; Mlayah, A.; Hlil, E. K.; Abid, Y.

    2012-01-01

    Single perovskite slab alkylammonium lead iodides bromides (C9H19NH3)2PbI2Br2 is a new member of the family of hybrid organic-inorganic perovskite compounds. It exhibits a single structural phase transition with changes in the conformation of alkylammonium chains below room temperature. Differential scanning calorimetry (DSC), powder X-ray diffraction and FT-Raman spectroscopy were used to investigate this phase transition. These changes were characterized by a decreased conformational disorder of the methylene units of the alkyl chains. Phase transition was examined in light of the interesting optical properties of this material, as well as the relevance of this system as models for phase transitions in lipid bilayers.

  7. Ammonia 15N/14N Isotope Ratio in the Jovian Atmosphere

    NASA Technical Reports Server (NTRS)

    Mahaffy, P.R.; Niemann, H. B.; Atreya, S. K.; Wong, M. H.; Owen, T. C; Einaudi, Franco (Technical Monitor)

    2000-01-01

    Data from the Galileo Probe Mass Spectrometer has been used to derive the N-15/N-14 isotope ratio in ammonia at Jupiter. Although the mass spectral interference from the water contribution to 18 amu makes an accurate derivation of the (N-15)H3/(N-14)H3 ratio difficult from measurements of the singly ionized signals at 18 and 17 amu, this interference is not present in the doubly charged 8.5 and 9.0 amu signals from (N-14)H3++ and (N-15)H3++ respectively. Although the count rate from the 9 amu signal is low during the direct sampling of the atmosphere, the ammonia signal was considerably enhanced during the first enrichment cell (EC1) experiment that measured gas sampled between 0.8 and 2.8 bar. Count rates at 9 amu in the EC1 experiment reach 60/second and measure ammonia sampled from 0.88 to 2.8 bar. In the EC1 measurements the 8.5 amu signal is not measured directly, but can be calculated from the ammonia contribution to 17 amu and the ratio of NH3 ions of a double to single charged observed during a high resolution mass scan taken near the end of the descent. The high resolution scan gives this ratio from ammonia sampled much deeper in the atmosphere. These results are described and compared with Infrared Space Observatory-Short Wavelength Spectrometer (ISO-SWS) observations that give this ratio at 400 mbar.

  8. Version 2 of the IASI NH3 neural network retrieval algorithm: near-real-time and reanalysed datasets

    NASA Astrophysics Data System (ADS)

    Van Damme, Martin; Whitburn, Simon; Clarisse, Lieven; Clerbaux, Cathy; Hurtmans, Daniel; Coheur, Pierre-François

    2017-12-01

    Recently, Whitburn et al.(2016) presented a neural-network-based algorithm for retrieving atmospheric ammonia (NH3) columns from Infrared Atmospheric Sounding Interferometer (IASI) satellite observations. In the past year, several improvements have been introduced, and the resulting new baseline version, Artificial Neural Network for IASI (ANNI)-NH3-v2.1, is documented here. One of the main changes to the algorithm is that separate neural networks were trained for land and sea observations, resulting in a better training performance for both groups. By reducing and transforming the input parameter space, performance is now also better for observations associated with favourable sounding conditions (i.e. enhanced thermal contrasts). Other changes relate to the introduction of a bias correction over land and sea and the treatment of the satellite zenith angle. In addition to these algorithmic changes, new recommendations for post-filtering the data and for averaging data in time or space are formulated. We also introduce a second dataset (ANNI-NH3-v2.1R-I) which relies on ERA-Interim ECMWF meteorological input data, along with surface temperature retrieved from a dedicated network, rather than the operationally provided Eumetsat IASI Level 2 (L2) data used for the standard near-real-time version. The need for such a dataset emerged after a series of sharp discontinuities were identified in the NH3 time series, which could be traced back to incremental changes in the IASI L2 algorithms for temperature and clouds. The reanalysed dataset is coherent in time and can therefore be used to study trends. Furthermore, both datasets agree reasonably well in the mean on recent data, after the date when the IASI meteorological L2 version 6 became operational (30 September 2014).

  9. Far-UV, visible, and near-IR reflectance spectra of frosts of H2O, CO2, NH3 and SO2

    NASA Technical Reports Server (NTRS)

    Hapke, B.; Wells, E.; Wagner, J.; Partlow, W.

    1981-01-01

    Measurements in the 0.1-2.5 micron range are presented for the reflectance spectra of the frosts of several volatiles pertinent to the study of comet nuclei. The frost spectra have distinctive features permitting their identification by spectroscopic reflectance remote sensing, notably in the far UV. It is found that: (1) H2O has a minimum at 0.16 microns and a maximum at 0.13 microns; (2) CO2 has minima near 0.21, 0.18 and 0.125 microns, with maxima at 0.19, 0.135 and 0.120 microns; (3) NH3 is bright at wavelengths longer than 0.21 microns, where reflectance drops to a value of only a few per cent at shorter wavelengths; (4) SO2 has a sharp drop at 0.32 microns, with a minimum at 0.18 microns and a maximum at 0.13 microns. The features in the frost spectra largely correspond to absorption line bands in the gas phase.

  10. Interfacial Interactions in Monolayer and Few-Layer SnS/CH3 NH3 PbI3 Perovskite van der Waals Heterostructures and Their Effects on Electronic and Optical Properties.

    PubMed

    Li, Jian-Cai; Wei, Zeng-Xi; Huang, Wei-Qing; Ma, Li-Li; Hu, Wangyu; Peng, Ping; Huang, Gui-Fang

    2018-02-05

    A high light-absorption coefficient and long-range hot-carrier transport of hybrid organic-inorganic perovskites give huge potential to their composites in solar energy conversion and environmental protection. Understanding interfacial interactions and their effects are paramount for designing perovskite-based heterostructures with desirable properties. Herein, we systematically investigated the interfacial interactions in monolayer and few-layer SnS/CH 3 NH 3 PbI 3 heterostructures and their effects on the electronic and optical properties of these structures by density functional theory. It was found that the interfacial interactions in SnS/CH 3 NH 3 PbI 3 heterostructures were van der Waals (vdW) interactions, and they were found to be insensitive to the layer number of 2D SnS sheets. Interestingly, although their band gap decreased upon increasing the layer number of SnS, the near-gap electronic states and optical absorption spectra of these heterostructures were found to be strikingly similar. This feature was determined to be critical for the design of 2D layered SnS-based heterostructures. Strong absorption in the ultraviolet and visible-light regions, type II staggered band alignment at the interface, and few-layer SnS as an active co-catalyst make 2D SnS/CH 3 NH 3 PbI 3 heterostructures promising candidates for photocatalysis, photodetectors, and solar energy harvesting and conversion. These results provide first insight into the nature of interfacial interactions and are useful for designing hybrid organic-inorganic perovskite-based devices with novel properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Evaluation of a regional air-quality model with bidirectional NH3 exchange coupled to an agroecosystem modelecosystem model

    EPA Science Inventory

    Atmospheric ammonia (NH3) is the primary atmospheric base and an important precursor for inorganic particulate matter and when deposited NH3 contributes to surface water eutrophication, soil acidification and decline in species biodiversity. Flux measurement...

  12. Trapping in water - an important prerequisite for complex reactivity in astrophysical ices: the case of acetone (CH3)2C = O and ammonia NH3

    NASA Astrophysics Data System (ADS)

    Fresneau, Aurélien; Danger, Grégoire; Rimola, Albert; Theule, Patrice; Duvernay, Fabrice; Chiavassa, Thierry

    2014-10-01

    Water is the most abundant compound in interstellar and cometary ices. Laboratory experiments on ice analogues have shown that water has a great influence on the chemical activity of these ices. In this study, we investigated the reactivity of acetone-ammonia ices, showing that water is an essential component in chemical reactions with high activation energies. In a water-free binary ice, acetone and ammonia do not react due to high activation energy, as the reactants desorb before reacting (at 120 and 140 K, respectively). By contrast, our study shows that under experimental conditions of ˜150 K, this reaction does occur in the presence of water. Here, water traps reactants in the solid phase above their desorption temperatures, allowing them to gather thermal energy as the reaction proceeds. Using infrared spectroscopy and mass spectrometry associated with isotopic labelling, as well as quantum chemical calculations, 2-aminopropan-2-ol (2HN-C(CH3)2-OH) was identified as the acetone-ammonia reaction product. The formation of this product may represent the first step towards formation of 2-aminoisobutyric acid (AIB) in the Strecker synthesis. The activation energy for the formation of 2-aminopropan-2-ol was measured to be 42 ± 3 kJ mol-1, while its desorption energy equalled 61.3 ± 0.1 kJ mol-1. Our work demonstrates that astrophysical water, rather than being a non-thermally reactive species, is crucial for the evolution of complex chemistry occurring in the Universe.

  13. High-sensitivity in situ QCLAS-based ammonia concentration sensor for high-temperature applications

    NASA Astrophysics Data System (ADS)

    Peng, W. Y.; Sur, R.; Strand, C. L.; Spearrin, R. M.; Jeffries, J. B.; Hanson, R. K.

    2016-07-01

    A novel quantum cascade laser (QCL) absorption sensor is presented for high-sensitivity in situ measurements of ammonia (hbox {NH}_3) in high-temperature environments, using scanned wavelength modulation spectroscopy (WMS) with first-harmonic-normalized second-harmonic detection (scanned WMS-2 f/1 f) to neutralize the effect of non-absorption losses in the harsh environment. The sensor utilized the sQ(9,9) transition of the fundamental symmetric stretch band of hbox {NH}_3 at 10.39 {\\upmu }hbox {m} and was sinusoidally modulated at 10 kHz and scanned across the peak of the absorption feature at 50 Hz, leading to a detection bandwidth of 100 Hz. A novel technique was used to select an optimal WMS modulation depth parameter that reduced the sensor's sensitivity to spectral interference from hbox {H}_2hbox {O} and hbox {CO}_2 without significantly sacrificing signal-to-noise ratio. The sensor performance was validated by measuring known concentrations of hbox {NH}_3 in a flowing gas cell. The sensor was then demonstrated in a laboratory-scale methane-air burner seeded with hbox {NH}_3, achieving a demonstrated detection limit of 2.8 ± 0.26 ppm hbox {NH}_3 by mole at a path length of 179 cm, equivalence ratio of 0.6, pressure of 1 atm, and temperatures of up to 600 K.

  14. Environmental assessment of NH/sub 3/ injection for an industrial package boiler. Volume 1. Technical results. Final report, January 1983-January 1984

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

    Castaldini, C.; DeRosier, R.; Waterland, L.R.

    1986-02-01

    The report discusses emission results from comprehensive flue gas sampling of a gas- and oil-fired industrial boiler equipped with Exxon's Thermal DeNO/sub x/ Ammonia Injection Process for NO/sub x/ reduction. Comprehensive emission measurements included continuous monitoring of flue gas emissions; source assessment sampling system (SASS) tests; EPA Method 5/17 for solid and condensible particulate emissions and ammonia emissions; controlled condensation system for SO/sub 2/ and SO/sub 3/; and N/sub 2/O emission sampling. Ammonia injection at a NH/sub 3//NO molar ratio of 2.52 gave a NO/sub x/ reduction of 41% from an uncontrolled level of 234 ppm to a controlled levelmore » of 137 ppm. NH/sub 3/ emissions increased from 11 ppm for the baseline to an average of 430 ppm for ammonia injection. Nitrous oxide, N/sub 2/O was reduced 68% from a 50 ppm baseline level to a 17 ppm controlled level. Total particulate emissions increased by an order of magnitude from a baseline of 17.7 ng/J to a controlled level of 182 ng/J. The increase is in part attributed to formation of ammonia sulfate and bisulfate from residual ammonia and SO/sub x/. Total organic emissions were at a moderate level and showed a relative concentration in the nonvolatile category. Organic emissions of CO and trace inorganic elements were not significantly affected by ammonia injection.« less

  15. UV photoprocessing of NH3 ice: photon-induced desorption mechanisms

    NASA Astrophysics Data System (ADS)

    Martín-Doménech, R.; Cruz-Díaz, G. A.; Muñoz Caro, G. M.

    2018-01-01

    Ice mantles detected on the surface of dust grains towards the coldest regions of the interstellar medium can be photoprocessed by the secondary ultraviolet (UV) field present in dense cloud interiors. In this work, we present UV-irradiation experiments under astrophysically relevant conditions of pure NH3 ice samples in an ultra-high vacuum chamber where solid samples were deposited on to a substrate at 8 K. The ice analogues were subsequently photoprocessed with a microwave-discharged hydrogen-flow lamp. The induced radiation and photochemistry led to the production of H2, N2 and N2H4. In addition, photodesorption to the gas phase of the original ice component, NH3, and two of the three detected photoproducts, H2 and N2, was observed thanks to a quadrupole mass spectrometer (QMS). Calibration of the QMS allowed quantification of the photodesorption yields, leading to Ypd (NH3) = 2.1^{+2.1}_{-1.0} × 10-3 molecules/{incident photon}, which remained constant during the whole experiments, while photodesorption of H2 and N2 increased with fluence, pointing towards an indirect photodesorption mechanism involving energy transfer for these species. Photodesorption yield of N2 molecules after a fluence equivalent to that experienced by ice mantles in space was similar to that of the NH3 molecules (Ypd (N2) = 1.7^{+1.7}_{-0.9} × 10-3 molecules/{incident photon}).

  16. Negative differential resistance and bias-modulated metal-to-insulator transition in zigzag C2N-h2D nanoribbon

    NASA Astrophysics Data System (ADS)

    He, Jing-Jing; Guo, Yan-Dong; Yan, Xiao-Hong

    2017-04-01

    Motivated by the fabrication of layered two-dimensional material C2N-h2D [Nat. Commun. 6, 6486 (2015)], we cut the single-layer C2N-h2D into a zigzag nanoribbon and perform a theoretical study. The results indicate that the band structure changes from semiconducting to metallic and a negative differential resistance effect occurs in the I-V curve. Interestingly, the current can be reduced to zero and this insulator-like state can be maintained as the bias increases. We find this unique property is originated from a peculiar band morphology, with only two subbands appearing around the Fermi level while others being far away. Furthermore the width and symmetry of the zigzag C2N-h2D nanoribbon can be used to tune the transport properties, such as cut-off bias and the maximum current. We also explore the electron transport property of an aperiodic model composed of two nanoribbons with different widths and obtain the same conclusion. This mechanism can be extended to other systems, e.g., hybrid BCN nanoribbons. Our discoveries suggest that the zigzag C2N-h2D nanoribbon has great potential in nanoelectronics applications.

  17. 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.

  18. Theoretical kinetics study of the F((2)P) + NH3 hydrogen abstraction reaction.

    PubMed

    Espinosa-Garcia, J; Fernandez-Ramos, A; Suleimanov, Y V; Corchado, J C

    2014-01-23

    The hydrogen abstraction reaction of fluorine with ammonia represents a true chemical challenge because it is very fast, is followed by secondary abstraction reactions, which are also extremely fast, and presents an experimental/theoretical controversy about rate coefficients. Using a previously developed full-dimensional analytical potential energy surface, we found that the F + NH3 → HF + NH2 system is a barrierless reaction with intermediate complexes in the entry and exit channels. In order to understand the reactivity of the title reaction, thermal rate coefficidents were calculated using two approaches: ring polymer molecular dynamics and quasi-classical trajectory calculations, and these were compared with available experimental data for the common temperature range 276-327 K. The theoretical results obtained show behavior practically independent of temperature, reproducing Walther-Wagner's experiment, but in contrast with Persky's more recent experiment. However, quantitatively, our results are 1 order of magnitude larger than those of Walther-Wagner and reasonably agree with the Persky at the lowest temperature, questioning so Walther-Wagner's older data. At present, the reason for this discrepancy is not clear, although we point out some possible reasons in the light of current theoretical calculations.

  19. Ammonia emissions from a U.S. broiler house--comparison of concurrent measurements using three different technologies

    EPA Science Inventory

    There is a need for robust and accurate techniques for the measurement of ammonia (NH3) and other atmospheric pollutant emissions from poultry production facilities. Reasonable estimates of ammonia emission rate (ER) from poultry facilities are needed to guide discussions about t...

  20. Emissions of NO and NH3 from a typical vegetable-land soil after the application of chemical N fertilizers in the Pearl River Delta.

    PubMed

    Li, Dejun

    2013-01-01

    Cropland soil is an important source of atmospheric nitric oxide (NO) and ammonia (NH3). Chinese croplands are characterized by intensive management, but limited information is available with regard to NO emissions from croplands in China and NH3 emissions in south China. In this study, a mesocosm experiment was conducted to measure NO and NH3 emissions from a typical vegetable-land soil in the Pearl River Delta following the applications of 150 kg N ha(-1) as urea, ammonium nitrate (AN) and ammonium bicarbonate (ABC), respectively. Over the sampling period after fertilization (72 days for NO and 39 days for NH3), mean NO fluxes (± standard error of three replicates) in the control and urea, AN and ABC fertilized mesocosms were 10.9±0.9, 73.1±2.9, 63.9±1.8 and 66.0±4.0 ng N m(-2) s(-1), respectively; mean NH3 fluxes were 8.9±0.2, 493.6±4.4, 144.8±0.1 and 684.7±8.4 ng N m(-2) s(-1), respectively. The fertilizer-induced NO emission factors for urea, AN and ABC were 2.6±0.1%, 2.2±0.1% and 2.3±0.2%, respectively. The fertilizer-induced NH3 emission factors for the three fertilizers were 10.9±0.2%, 3.1±0.1% and 15.2±0.4%, respectively. From the perspective of air quality protection, it would be better to increase the proportion of AN application due to its lower emission factors for both NO and NH3.