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In this work, the influence of varying mixing ratios of O-2 on positive streamer initiation in supercritical (SC) CO2 at different applied voltages was investigated using a 3-D particle model. Zener's model was included in the 3-D particle model to calculate the field ionization rate during streamer formation and propagation. The evolution of positive streamer was classified into three main stages namely inception cloud, primary streamer channels, and successive streamer branching. The effect of O-2 with different mixing ratios (2%, 10%, and 20%) on the morphology, average electron density, electric field distribution, streamer length, and electron energy distribution function (EEDF) for positive streamer in SC-CO2 at four different voltages (12, 12.5, 13, and 13.5 kV) is then investigated. The 2-D cross sections of the initial stage of the streamer and the electric field distribution are presented in detail. At the same applied voltage, the size of inception cloud, average electron density, electric field, and streamer length with the maximum electric field decreased with increasing oxygen concentration in SC-CO2. With increasing applied voltage, the apparent size of inception cloud, primary streamer channels, successive streamer branching, average electron density, electric field, and streamer length increased. The simulation results showed that adding O-2 to SC-CO2 can significantly affect the streamer initiation and propagation.

Energy-Efficient Ammonia Production from Air and Water Using Electrocatalysts with Limited Faradaic Efficiency

Coastal environments are nitrogen (N) removal hot spots, which regulate the amount of land-derived N reaching the open sea. However, mixing between freshwater and seawater creates gradients of inorganic N and bioavailable organic matter, which affect N cycling. In this study, we compare nitrate reduction processes between estuary and offshore archipelago environments in the coastal Baltic Sea. Denitrification rates were similar in both environments, despite lower nitrate and carbon concentrations in the offshore archipelago. However, DNRA (dissimilatory nitrate reduction to ammonium) rates were higher at the offshore archipelago stations, with a higher proportion of autochthonous carbon. The production rate and concentrations of the greenhouse gas nitrous oxide (N2O) were higher in the estuary, where nitrate concentrations and allochthonous carbon inputs are higher. These results indicate that the ratio between nitrate and autochthonous organic carbon governs the balance between N-removing denitrification and N-recycling DNRA, as well as the end-product of denitrification. As a result, a significant amount of the N removed in the estuary is released as N2O, while the offshore archipelago areas are characterized by efficient internal recycling of N. Our results challenge the current understanding of the role of these regions as filters of land-to-sea transfer of N.

Mechanisms of alloy degradation in a fireside N-S-O-C-H-Cl-Na-K atmosphere at 880 degrees C were elucidated using SEM-EDS, chemical equilibrium calculations, and XRD. Alloys 310S, 800H/HT, and 600 were studied after 0, 8000, and 16,000 h exposure in a boiler co-firing biomass waste. For 310S and 800H/HT it was shown that nitrogen formed internal Cr nitrides lowering the Cr activity and inhibiting internal alloy Cr permeation, and that NaCl and Na2SO4 reacted with Cr oxide to form chromate and to accelerate the S and the Cl pickup. Alloy 600 showed no nitride or major chromate formation. Bio4Energy

The dissociation process of hydrogen molecules on W(110) was studied using density functional theory and classical molecular dynamics. We have calculated the dissociation probability for molecules with energies below 300 meV and analyzed the dynamics of the adsorption process. Our results show that the fate of each trajectory is determined at distances relatively far from the surface, at roughly 2–2.5 Å. This distance varies slightly with the initial kinetic energy of the molecule. Part of our simulations include van der Waals dispersion effects in the interaction between molecule and surface. We present a comparison between these results and other theoretical and experimental results previously published. The inclusion of the van der Waals term provokes an increase in the far-distance attraction that is compensated by a stronger repulsion at short distances. The combination of both effects appreciably decreases the value of the dissociation probability. The successful comparison of our results with experimental information confirms that the methodology employed can be considered as a rich and accurate instrument to study the dissociation of hydrogen on surfaces., A. R. F. acknowledges financial support by the University of Bordeaux. This work was conducted in the scope of the transborder joint Laboratory “QuantumChemPhys: Theoretical Chemistry and Physics at the Quantum Scale” (ANR-10-IDEX-03-02). This work has been supported in part by the Basque Departamento de Educación, Universidades e Investigación, the University of the Basque Country UPV/EHU (Grant No. IT1246-19) and the Spanish Ministerio de Ciencia e Innovación (PID2019-107396GB-I00/AEI/10.13039/501100011033).

Waste scrap tyres were thermally decomposed at the temperature of 600 &deg, C and heating rate of 10 &deg, C&middot, min&minus, 1. Decomposition was followed by the TG analysis. The resulting pyrolytic carbon black was chemically activated by a KOH solution at 800 &deg, C. Activated and non-activated carbon black were investigated using high pressure thermogravimetry, where adsorption isotherms of N2, CO2, and cyclohexane were determined. Isotherms were determined over a wide range of pressure, 0.03&ndash, 4.5 MPa for N2 and 0.03&ndash, 2 MPa for CO2. In non-activated carbon black, for the same pressure and temperature, a five times greater gas uptake of CO2 than N2 was determined. Contrary to non-activated carbon black, activated carbon black showed improved textural properties with a well-developed irregular mesoporous-macroporous structure with a significant amount of micropores. The sorption capacity of pyrolytic carbon black was also increased by activation. The uptake of CO2 was three times and for cyclohexane ten times higher in activated carbon black than in the non-activated one. Specific surface areas evaluated from linearized forms of Langmuir isotherm and the BET isotherm revealed that for both methods, the values are comparable for non-activated carbon black measured by CO2 and for activated carbon black measured by cyclohexane. It was found out that the N2 sorption capacity of carbon black depends only on its specific surface area size, contrary to CO2 sorption capacity, which is affected by both the size of specific surface area and the nature of carbon black.

Nutrient export from agricultural landscapes is a water quality concern and the cause of mitigation activities worldwide. Climate change impacts hydrology and nutrient cycling by changing soil moisture, stoichiometric nutrient ratios, and soil temperature, potentially complicating mitigation measures. This research quantifies the impact of climate change and climate anomalies on hydrology, nutrient cycling, and greenhouse gas emissions in an agricultural catchment of the Chesapeake Bay watershed. We force a calibrated model with seven downscaled and bias-corrected regional climate models and derived climate anomalies to assess their impact on hydrology and the export of nitrate (NO3-), phosphorus (P), and sediment, and emissions of nitrous oxide (N2O) and di-nitrogen (N-2). Modelaverage (+/- standard deviation) results indicate that climate change, through an increase in precipitation and temperature, will result in substantial increases in winter/spring flow (10.6 +/- 12.3%), NO3-(17.3 +/- 6.4%), dissolved P (32.3 +/- 18.4%), total P (24.8 +/- 16.9%), and sediment (25.2 +/- 16.6%) export, and a slight increases in N2O (0.3 +/- 4.8%) and N-2 (0.2 +/- 11.8%) emissions. Conversely, decreases in summer flow (-29.1 +/- 24.6%) and the export of dissolved P (-15.5 +/- 26.4%), total P (-16.3 +/- 20.7%), sediment (-20.7 +/- 18.3%), and NO3-(-29.1 +/- 27.8%) are driven by greater evapotranspiration from increasing summer temperatures. Decreases in N2O (-26.9 +/- 15.7%) and N-2 (-36.6 +/- 22.9%) are predicted in the summer and driven by drier soils. While the changes in flow are related directly to changes in precipitation and temperature, the changes in nutrient and sediment export are, to some extent, driven by changes in agricultural management that climate change induces, such as earlier spring tillage and altered nutrient application timing and by alterations to nutrient cycling in the soil. (C) 2018 Elsevier B.V. All rights reserved. National Science FoundationNational Science Foundation (NSF) [1360415, 1343802]; USDAUnited States Department of Agriculture (USDA) [2012-67019-19434] We would like to acknowledge high-performance computing support from Yellowstone (http://n2t.net/ark:/85065/d7wd3xhc) provided by NCAR's Computational and Information Systems Laboratory, support from the National Science Foundation under award numbers 1360415 and 1343802, and funding support from the USDA under project number 2012-67019-19434. All data, methods, and code used in this manuscript are available upon request. Public domain – authored by a U.S. government employee

Nuclear and electronic dynamics in a wavepacket comprising bound Rydberg and valence electronic states of nitrogen from 12 to 15 eV are investigated using attosecond transient absorption. Vibrational quantum beats with a fundamental period of 50 femtoseconds persist for a picosecond in the b′ 1Σ+u valence state. Multi-state calculations show that these coherences result primarily from near infrared-induced coupling between the inner and outer regions of the b′ 1Σ+u state potential and the dark a″ 1Σ+g state. The excellent spectral and temporal resolution of this technique allows measurement of the anharmonicity of the b′ 1Σ+u potential directly from the observed quantum beats.

Continuous nitrogen gas (N-2) flushing extends the shelf life of raw milk (RM) during cold storage. The effect of N-2 treatment on the total antioxidant capacity (TAC) and ascorbic acid (AA) content of RM was determined during cold storage. TAC of RM or deproteinized RM was determined by ABTS and DPPH methods, while L(+)-AA content of RM was determined chromatographically on days 0, 4 and 7 during storage at 6 +/- 1 degrees C. With the ABTS method, the TAC of RM decreased from 472.33 +/- 16.70 to 369.47 +/- 62.06 mu M TEAC while it reduced from 13.30 +/- 0.84 to 8.20 +/- 0.66 mu M TEAC with DPPH method during cold storage. TAC of RM determined with ABTS method decreased after 4 day-storage; however, they remained statistically similar for N-2-treated samples during 7 day-storage. The AA content of RM ranged from 14.06 to 10.76 mg/L during storage but N-2-treatment did not influence AA content significantly. Deproteinization reduced TAC values of milk samples significantly, and the reduction with the ABTS method was about 47.50 % for control samples cold-stored for four days, while it was 11.67 % for N-2-treated deproteinized RM. In conclusion, N-2-flushing through the headspace of milk containing vessels showed a significant protective effect on the antioxidant components of RM during cold storage.

It has been discussed that lightning flashes emit high-energy electrons, positrons, photons, and neutrons with single energies of several tens of MeV. In the first part of this paper we study the absorption of neutron beams in the atmosphere. We initiate neutron beams of initial energies of 350 keV, 10 MeV, and 20 MeV at source altitudes of 4 km and 16 km upward and downward and see that in all these cases neutrons reach ground altitudes and that the cross-section areas extend to several km(2). We estimate that for terrestrial gamma-ray flashes approximately between 10 and 2000 neutrons per ms and m(2) are possibly detectable at ground, at 6 km, or at 500 km altitude. In the second part of the paper we discuss a feedback model involving the generation and motion of electrons, positrons, neutrons, protons, and photons close to the vicinity of lightning leaders. In contrast to other feedback models, we do not consider large-scale thundercloud fields but enhanced fields of lightning leaders. We launch different photon and electron beams upward at 4 km altitude. We present the spatial and energy distribution of leptons, hadrons, and photons after different times and see that leptons, hadrons, and photons with energies of at least 40 MeV are produced. Because of their high rest mass hadrons are measurable on a longer time scale than leptons and photons. The feedback mechanism together with the field enhancement by lightning leaders yields particle energies even above 40 MeV measurable at satellite altitudes.

The electrochemical synthesis of ammonia from nitrogen under mild conditions using renewable electricity is an attractive alternative1–4 to the energy-intensive Haber–Bosch process, which dominates industrial ammonia production. However, there are considerable scientific and technical challenges5,6 facing the electrochemical alternative, and most experimental studies reported so far have achieved only low selectivities and conversions. The amount of ammonia produced is usually so small that it cannot be firmly attributed to electrochemical nitrogen fixation7–9 rather than contamination from ammonia that is either present in air, human breath or ion-conducting membranes9, or generated from labile nitrogen-containing compounds (for example, nitrates, amines, nitrites and nitrogen oxides) that are typically present in the nitrogen gas stream10, in the atmosphere or even in the catalyst itself. Although these sources of experimental artefacts are beginning to be recognized and managed11,12, concerted efforts to develop effective electrochemical nitrogen reduction processes would benefit from benchmarking protocols for the reaction and from a standardized set of control experiments designed to identify and then eliminate or quantify the sources of contamination. Here we propose a rigorous procedure using 15N2 that enables us to reliably detect and quantify the electrochemical reduction of nitrogen to ammonia. We demonstrate experimentally the importance of various sources of contamination, and show how to remove labile nitrogen-containing compounds from the nitrogen gas as well as how to perform quantitative isotope measurements with cycling of 15N2 gas to reduce both contamination and the cost of isotope measurements. Following this protocol, we find that no ammonia is produced when using the most promising pure-metal catalysts for this reaction in aqueous media, and we successfully confirm and quantify ammonia synthesis using lithium electrodeposition in tetrahydrofuran13. The use of this rigorous protocol should help to prevent false positives from appearing in the literature, thus enabling the field to focus on viable pathways towards the practical electrochemical reduction of nitrogen to ammonia. A protocol for the electrochemical reduction of nitrogen to ammonia enables isotope-sensitive quantification of the ammonia produced and the identification and removal of contaminants.

Because of the limited number and size of the oil extraction opportunities, olives are generally piled and stored at ambient temperatures for weeks before processing. Under these conditions biochemical changes could result a negative affect on the olive quality. The changes in the olive result poor stability in olive oil because of the oxidation and decomposition of bioactive compounds such as phenolic substances. Indeed, it is known that polyphenols are a large family of compounds found in plant tissues, which show strong antioxidant activity. The healthy characteristic of the phenolic compounds is associated to their radical scavenging activities. In this study, Gemlik olives cultivated from Osmaniye area were stored for 25 days at 5 °C under three different conditions (20 kPa CO 2 atmosphere, 20 kPa N 2 atmosphere and air). Olive oil was extracted following of 0, 5, 15 and 25 days of olive fruits storage. Qualtiy markers (free fatty acidity, peroxide value, K 270 and K 232 ) together with the phenolic compounds and fatty acid compositions of oils were determined. The physical properties of olives (flesh/pit ratio, average weight and fruit firmness) were well-preserved under CO 2 and N 2 atmospheres. The phenolics (tyrosol, syringic acid, vanilin, p-coumaric acid, oleuropein, cinnamic acid and luteolin) and fatty acids (palmitic, palmiteloic, heptadecanoic, heptadecenoic, stearic, oleic, linoleic, linolenic, arachidic, behenic, docosadienoic and lignoceric acids) composition were generally unchanged during storage. Oleuropein, the bitter principle of olives disapperead faster in the oils obtained through storage under N 2 than other storage conditions. © 2018, Springer Science+Business Media, LLC, part of Springer Nature. OKÜBAP-2015-PT3-011 ?Each data point represents mean of three replicates ± SD aSmall letters indicate significance for olive storage duration within each treatment (p < 0.05) ACapital letters indicate significance at a given storage time between treatments (p < 0.05) Acknowledgements Many thanks to Osmaniye Korkut Ata University Research Council for funding this research (OKÜBAP-2015-PT3-011). Many thanks also go to Prof. Ziya Günata for proofreading the manuscript.

We employ a synergistic material and process development strategy to improve the performance of a single-cycle vacuum pressure swing adsorption (VPSA) process for the hydrogen purification and the CO2 separation from reforming-based hydrogen synthesis. Based on process-informed adsorbent selection criteria, including high CO2 cyclic capacity and selective uptake of impurities like CO, N2, and CH4 over H2, a metal organic framework (MOF), Cu-TDPAT, is selected. First, adsorption isotherms of CO2, CO, CH4, N2 and H2 are measured. Subsequently, a column model is used for optimization-based analysis of the VPSA cycle with Cu-TDPAT as the adsorbent to assess both the separation performance, and the process performance in terms of energy consumption and productivity. The adsorption characteristics of Cu-TDPAT require an adaptation of the original VPSA process to increase the CO2 separation performance of the process. After this adaptation, Cu-TDPAT clearly outperforms the benchmark material, zeolite 13X, in several metrics including higher H2 purities and recoveries and fewer columns needed for a continuous separation process. Most importantly, Cu-TDPAT offers a two-fold improvement in CO2 productivities when compared to zeolite 13X, thus substantially decreasing the bed size required to achieve the same throughput. However, zeolite 13X remains the better adsorbent for reaching high CO2 purities and recoveries due to its higher selectivity for CO2 over all other components in the gas stream, which leads to an overall lower energy consumption. The obtained results show that the final performance strongly depends on an interplay of various factors related to both material and process. Hence, an integrated process and material design approach should be the new paradigm for developing novel gas separation processes., Chemical Engineering Journal, 414, ISSN:0300-9467, ISSN:1385-8947, ISSN:1873-3212, ISSN:0923-0467

The compression of ammonium azide (AA) has been considered to be a promising route for producing high energy-density polynitrogen compounds. So far though, there is no experimental evidence that pure AA can be transformed into polynitrogen materials under high pressure at room temperature. We report here on high pressure (P) and temperature (T) experiments on AA embedded in N2 and on pure AA in the range 0–30 GPa, 300–700 K. The decomposition of AA into N2 and NH3 was observed in liquid N2 around 15 GPa–700 K. For pressures above 20 GPa, our results show that AA in N2 transforms into a new crystalline compound and solid ammonia when heated above 620 K. This compound is stable at room temperature and on decompression down to at least 7.0 GPa. Pure AA also transforms into a new compound at similar P–T conditions, but the product is different. The newly observed phases are studied by Raman spectroscopy and X-ray diffraction and compared to nitrogen and hydronitrogen compounds that have been predicted in the literature. While there is no exact match with any of them, similar vibrational features are found between the product that was obtained in AA + N2 with a polymeric compound of N9H formula.

Nanoporous materials used in industrial applications (e.g., catalysis and separations) draw their functionality from properties at the nanoscale (1 – 10 Å). When shaped into a technical form these solids reveal spatial variations in the same properties over much larger length scales (1 µm – 1 cm). The multiscale characterization of these systems is impaired by the trade‐off between sample size and image resolution that is bound to the use of most imaging techniques. We show here the application of X‐ray computed tomography for the non‐invasive spatial characterization of a zeolite/activated carbon adsorbent bed across three orders of magnitude in scale. Through the unique combination of gas adsorption isotherms measured locally and their interpretation by physisorption analysis, we determine three‐dimensional maps of the specific surface area and micropore volume. We further use machine learning to identify and locate the materials within the packed bed. This novel ability to reveal the extent of heterogeneity in technical porous solids will enable a deeper understanding of their function in industrial reactors. Such developments are essential towards bridging the gap between material research and process design.

The preparation and reactivity of a novel molybdenum dinitrogen complex supported by a nitrogen-centred tripodal phosphine ligand (N-triphos, N(CH2PPh2)3, NP3Ph) are reported. Reaction of N-triphos with [MoX3(THF)3] (X = Cl, Br, I) gave the Mo(III) complex [MoX3(κ2-NP3Ph)(THF)] (1), where bidentate N-triphos coordination was observed. Reduction of this complex in the presence of dppm (bis(diphenylphosphino)methane) gave the dinitrogen complex [Mo(N2)(dppm)(κ3-NP3Ph)] (2), which exhibits moderate dinitrogen activation. An additional hydride complex, [Mo(H)2(dppm)(κ3-NP3Ph)] (4), was produced either as a minor side product during the reduction step, or as a major product by direct hydrogenation of the dinitrogen complex 2. The reactivity of the dinitrogen complex 2 with a range of Lewis acids was also investigated. At low temperatures, protic or borane Lewis acids (H+, BBr3 and tris(pentafluorophenyl)borane (BCF)) were found to coordinate to the apical nitrogen atom of the N-triphos ligand, with no conclusive evidence of any functionalisation of the dinitrogen ligand. Alkali metal Lewis acid addition to 2 resulted in the unexpected rearrangement of the N-triphos ligand to form [Mo(dppm)(PMePh2)(PCP)][B(C6F5)4] (7), where PCP, [Ph2PCNHCH2PPh2] is the carbenic ligand formed upon rearrangement from the reaction of 2 with M[B(C6F5)4] (M = Li, Na or K). Single crystal X-ray diffraction of complexes 1, 2, 4 and 7 provided structural confirmation of the N-triphos molybdenum complexes described.

This article presents gas hydrate experimental measurements for mixtures containing methane (CH 4 ), carbon dioxide (CO 2 ) and nitrogen (N 2 ) with the aim to better understand the impact of water (H 2 O) on the phase equilibrium. Some of these phase equilibrium experiments were carried out with a very high water-to-gas ratio that shifts the gas hydrate dissociation points to higher pressures. This is due to the significantly different solubilities of the different guest molecules in liquid H 2 O. A second experiment focused on CH 4 -CO 2 exchange between the hydrate and the vapor phases at moderate pressures. The results show a high retention of CO 2 in the gas hydrate phase with small pressure variations within the first hours. However, for our system containing 10.2 g of H 2 O full conversion of the CH 4 hydrate grains to CO 2 hydrate is estimated to require 40 days. This delay is attributed to the shrinking core effect, where initially an outer layer of CO 2 -rich hydrate is formed that effectively slows down the further gas exchange between the vapor phase and the inner core of the CH 4 -rich hydrate grain.

High harmonic spectroscopy gives access to molecular structure with Angström resolution. Such information is encoded in the destructive interferences occurring between the harmonic emissions from the different parts of the molecule. By solving the time-dependent Schrödinger equation, either numerically or with the molecular strong-field approximation, we show that the electron dynamics in the emission process generally results in a strong spectral smoothing of the interferences, blurring the structural information. However we identify specific generation conditions where they are unaffected. These findings have important consequences for molecular imaging and orbital tomography using high harmonic spectroscopy.

Physical review / A 95(4), 043419(2017). doi:10.1103/PhysRevA.95.043419, By theoretical calculation, we demonstrate the possibility to control and partially suppress the Coulomb explosion of N$_2$ molecules after core-level photoionization by an x-ray laser and subsequent Auger decay. This is achieved by means of a femtosecond infrared laser pulse interacting with the N$_{2}$$^{2+}$ dication produced by the x-ray pulse. Suppression of molecular fragmentation requires few-femtosecond IR pulses interacting with the system either during or shortly after the arrival of the x-ray pulse. The IR pulse suppresses fragmentation mostly by optically coupling the electronic routes to ultrafast molecular dissociation with electronic channels able to support long-lived vibrational resonances. The effect is strongly dependent on the orientation of the molecule with respect to the polarization axis of the IR field. Our calculations are motivated by x-ray pump–IR probe experiments performed at an x-ray free-electron laser [J. M. Glownia et al., Opt. Express 18, 17620 (2010)], where only enhancement of N$_{2}$$^{2+}$ fragmentation as a function of the pump-probe delay time was reported. The opposite effect reported here becomes apparent when the various electronic channels are considered separately. In practice, this corresponds to a coincident measurement of the energy of the ejected Auger electron., Published by APS, Woodbury, NY

It has been discussed that lightning flashes emit high-energy electrons, positrons, photons, and neutrons with single energies of several tens of MeV. In the first part of this paper we study the absorption of neutron beams in the atmosphere. We initiate neutron beams of initial energies of 350 keV, 10 MeV, and 20 MeV at source altitudes of 4 km and 16 km upward and downward and see that in all these cases neutrons reach ground altitudes and that the cross-section areas extend to several km(2). We estimate that for terrestrial gamma-ray flashes approximately between 10 and 2000 neutrons per ms and m(2) are possibly detectable at ground, at 6 km, or at 500 km altitude. In the second part of the paper we discuss a feedback model involving the generation and motion of electrons, positrons, neutrons, protons, and photons close to the vicinity of lightning leaders. In contrast to other feedback models, we do not consider large-scale thundercloud fields but enhanced fields of lightning leaders. We launch different photon and electron beams upward at 4 km altitude. We present the spatial and energy distribution of leptons, hadrons, and photons after different times and see that leptons, hadrons, and photons with energies of at least 40 MeV are produced. Because of their high rest mass hadrons are measurable on a longer time scale than leptons and photons. The feedback mechanism together with the field enhancement by lightning leaders yields particle energies even above 40 MeV measurable at satellite altitudes.

Among microporous adsorbents, zeolites constitute the reference materials in CO2-capture technologies, because of their high CO2 affinity, high chemical and thermal stability, and low cost. Being synthesized in powder form, they need to be shaped in pellets or monolith to be suitable for real applications. The process has a direct effect on CO2-capture properties of the material creating, in this sense, substantial differences between lab-scale (adsorbents) and plant-scale systems (adsorbers). The ability of the honeycomb monolith to efficiently separate gases of interest arises from the properties of its single components such as an active phase and a phase resulting from the decomposition of a binder. Moreover, the textural (i.e., pore distribution and exposed surface) and structural properties (e.g., amorphization) of the active phase can be modified in the conditions adopted during the process that leads to the final artifact. These modifications can affect the CO2-capture performances of the active p...

Sulfur dioxide (SO2) is a molecule of considerable interest for both atmospheric chemistry and astrophysics. In the Earth’s atmosphere, it enters in the sulfur cycle and it is ubiquitous present in polluted atmospheres, where it is responsible for acid rains. It is also of astrophysical and planetological importance, being present on Venus and in interstellar clouds. In this work the collisional broadening of a number of ν1 ro-vibrational lines of SO2 perturbed by N2, O2 and He are investigated at room temperature in the 9 μm atmospheric region by means of high resolution tunable diode laser (TDL) infrared spectroscopy. From N2- and O2-broadening coefficients, the broadening parameters of sulfur dioxide in air, useful for atmospheric applications, are derived as well. From the present measurements some conclusions on the quantum number dependence of the N2-, O2- and He-broadening coefficients are drawn. While the J dependence is weak for all the perturbers investigated, different trends with Ka are reported. N2-broadening coefficients show a slight decrease with increasing values of Ka, whereas O2 and He broadening cross sections first increase up to K a ″ ≈ 6 and then they keep a nearly constant value. A comparison and a brief discussion on the efficiency of self-, N2-, O2- and He-collisional dynamics are given. The data obtained represent a significant analysis on foreign broadening of SO2 useful for atmospheric remote sensing and astrophysical applications.

N-doped and N, S-codoped titania powders were prepared applying simple chemical treatment with various modifiers. The N and S were introduced preserving the crystalline structure, morphology and specific surface area of the initial TiO2. The level of N, S doping varied depending on the modifier two of which were structural isomers. In all samples, N was found interstitially incorporated in the TiO2 lattice. S was recorded in ionic states S6+ and S4+. All modified powders exhibited enhanced visible light absorption and narrower energy band gap in comparison to the initial titania. Except for the N-doped titania, the photocatalytic activity in NOx oxidation under UV light decreased after doping, while the activity under visible light did not increase for all modified samples. This outcome was related to the high level of N and S doping and intense e(-)-h(+) recombination on dopants' sites. The activity of the photocatalysts in NOx oxidation processes was also connected to the type of non-metal dopant in the lattice of TiO2. The beneficial effect of N-doping was ascribed to the preferential formation of center dot OH species on N-doped surface, whereas the detrimental effect of N, S-codoping was credited to the suppressed center dot OH production on S-doped surface. (C) 2012 Elsevier B.V. All rights reserved. Catalysis Today

Outlier diagnostic in phase equilibrium data of binary clathrate hydrates containing CO 2 is the main aim of the present work. The treated experimental data are concerning the clathrate hydrates of CO 2 + CH 4 /N 2 in the presence of water. The utilized algorithm applies the basis of a mathematical approach, in which the statistical Hat matrix, Williams plot, and the residuals of two models results bring about the probable outliers detection. The range of applicability of the applied models and quality of the existing experimental data are also investigated. The van der Waals and Platteeuw (vdW–P) solid solution theory is used to model the hydrate phase, and the Valderrama–Patel–Teja equation of state (VPT-EoS) along with the non-density dependent (NDD) mixing rules is applied to deal with the fluid phases in the first model. The compositions of the vapor phase in equilibrium with gas hydrate and liquid water as well as the equilibrium pressures are predicted through the mentioned model. The second model includes a correlation proposed by Adisasmito et al., which is utilized to represent the hydrate dissociation pressures for three-phase equilibrium conditions (liquid water–vapor–hydrate). It is interpreted from the obtained results that the applied models for calculation/estimation of the phase behavior of the investigated binary clathrate hydrate systems have wide ranges of applicability. Consequently, we may, with high confidence level, say that among all data treated, one experimental equilibrium pressure value and four experimental hydrate dissociation values are probable doubtful ones.

Soils can be a source and sink for atmospheric nitrous oxide (N2O). Consumption of N2O has been reported for anoxic soils and sediments rich in organic matter and depleted in nitrates ( NO 3 − ), and also for some dry, oxic soils. However, the mechanisms and controls of N2O consumption in dry soil are not clear. Here, we report on a field study in China (Taihang mountain region, Shijiazhuang), in which N2O uptake by a sandy loam soil was measured for the greater part of the season (from April to October in 2011), and on four incubation experiments, in which we tried to reveal the roles of water content and oxygen (O2) concentrations on N2O consumption. Flux measurements in the field were made bi-weekly on unfertilized cropped land with static flux chambers (5 replicates) for 6 months. The results show that N2O–N fluxes ranged from −26.0 to −726.6 μg m−2 h−1. Consumption of N2O was largest when the soil was dry (5–20% soil water filled pore space). In the incubation experiments, N2O consumption and N2 production were measured in (an)aerobic soil with soil moisture content ranging from 1% to 50% (wt/wt) and with N2O addition, using a thermostatic, robotized incubation system. Under anaerobic conditions, N2O was rapidly consumed at water content of >10% (wt/wt). However, a significant consumption also occurred at 1% soil moisture. Under aerobic conditions, N2O consumption increased with increasing soil moisture content, but significant consumption was still measured at 2% moisture. Sterilization of oxic soil completely blocked N2O consumption, suggesting that the consumption had a biological nature. In conclusion, the steady N2O consumption measured in the field was confirmed by the laboratory experiments, but the relationship with soil moisture content was reversed. Further studies are required to understand this apparent anomaly.

Atomically detailed simulations were used to examine CO2/N-2 separation potential of metal organic framework- (MOF-) based mixed matrix membranes (mmms) in this study. Gas permeability and selectivity of 700 new mmms composed of 70 different mofs and 10 different polymers were calculated for CO2/N-2 separation. This is the largest number of MOF-based mmms for which computational screening is done to date. Selecting the appropriate mofs as filler particles in polymers resulted in mmms that have higher CO2/N-2 selectivities and higher CO2 permeabilities compared to pure polymer membranes. We showed that, for polymers that have low CO2 permeabilities but high CO2 selectivities, the identity of the MOF used as filler is not important. All mofs enhanced the CO2 permeabilities of this type of polymers without changing their selectivities. Several MOF-based mmms were identified to exceed the upper bound established for polymers. The methods we introduced in this study will create many opportunities to select the MOF/polymer combinations with useful properties for CO2 separation applications., Scientific and Technological Research Council of Turkey (TÜBİTAK)

Adsorption, 18 (1), ISSN:0929-5607, ISSN:1572-8757

Hydrofluorocarbons have been used as replacement gases of chlorofluorocarbons, since the latter have been phased out by the Montreal Protocol due to their environmental hazardous ozone-depleting effects. This is also the case of difluoromethane (CH2F2, HFC-32), which nowadays is widely used in refrigerant mixtures together with CF3CH3, CF3CH2F, and CF3CHF2. Due to its commercial use, in the last years, the atmospheric concentration of HFC-32 has increased significantly. However, this molecule presents strong absorptions within the 8–12 μm atmospheric window, and hence it is a greenhouse gas which contributes to global warming. Although over the years several experimental and theoretical investigations dealt with the spectroscopic properties of CH2F2, up to now pressure broadening coefficients have never been determined. In the present work, the line-by-line parameters of CH2F2 are retrieved for either ground state or ν7 band transitions by means of microwave (MW) and infrared (IR) absorption spectroscopy, respectively. In particular, laboratory experiments are carried out on 9 pure rotational transitions of the ground state and 26 ro-vibrational transitions belonging to the ν7 band lying around 8.2 μm within the atmospheric region. Measurements are carried out at room temperature on self-perturbed CH2F2 as well as on CH2F2 perturbed by N2 and O2. The line shape analysis leads to the first determination of self-, N2-, O2-, and air-broadening coefficients, and also of line intensities (IR). Upon comparison, broadening coefficients of ground state transitions are larger than those of the ν7 band, and no clear dependence on the rotational quantum numbers can be reported. The obtained results represent basic information for the atmospheric modelling of this compound as well as for remote sensing applications.

Molecular dynamics simulations have been used to study the effects of the corrugation in the holding potential of nitrogen molecules on the structure of fluid monolayer and submonolayer films of the molecules on a solid substrate. Structures of monolayer and submonolayer fluid films of nitrogen molecules adsorbed on graphite and on a model uncorrugated “smooth” graphite surface are compared. For films on the “smooth” graphite surface the melting temperature is lowered by 7 K. Contrary to what is found for films on the corrugated surface, the simulations show that there is a region of liquid–gas coexistence, demonstrating that this is a normal triple point system. A discrepancy between calculated and experimental melting temperatures of submonolayer films was traced to the intermolecular potentials. These have been tested by comparing molecular dynamics simulations of isosteric heats of adsorption in fluid films with experimental measurements. The establishment of the effects of the corrugation in the hold...

0953-4075; A coherent rotational superposition state is produced in the ground vibronic level of N2 through the interaction of the molecule with the electric field vector of a nonresonant laser pulse. This rotational wavepacket is shaped with a linear frequency chirp of the laser field. The structural shape of the rotational coherences shows a strong dependence with the frequency-chirp amplitude. A comparison with a theoretical model allows the interpretation of the observed effects in terms of dephasing of the wavepacket induced by the laser phase distortion. Application of the presented results to the phase characterization of short XUV pulses is suggested.

The Short Wavelength Spectrometer (SWS) onboard the Infrared Space Observatory (ISO) has been used to search for solid O-2 in cold dense clouds at 6.45 mu m. Additional constraints on the O-2 abundance are obtained from analysis of the 4.67 mu m solid CO absorption profile observed from the ground. We derive upper limits of 50% and 100% of solid O-2 relative to solid CO toward the protostellar sources R CrA IRS2 and NGC 7538 IRS9 respectively, corresponding to abundances of 30 x 10(-6) and 15 x 10(-6) relative to n(H). These results indicate that the abundance of solid O-2 in dense clouds accounts for less than 6% of the total oxygen budget in the interstellar medium. The reservoirs of oxygen in dense clouds are discussed, taking into account recent measurements of oxygen-bearing species.

The melting mechanism in submonolayer films of ${\mathrm{N}}_{2}$ molecules adsorbed on the basal planes of graphite is studied using molecular-dynamics simulations. The melting is strongly correlated with the formation of vacancies in the films. As the temperature increases, the edges of the submonolayer patch become atomically rough and vacancies are first created there. Then there is an onset temperature at which the vacancies penetrate into the patch. At an intermediate region of coverages \ensuremath{\sim}0.3\char21{}0.8 commensurate layers, there is sufficient free volume for the film to melt at that temperature. At higher coverages, \ensuremath{\sim}0.8\char21{}1.0 layers, a solid with defects is formed, and additional free volume must be created by higher energy mechanisms such as layer promotion for melting to occur; thus, the melting temperature rises with coverage. In contrast, for very small patches, the atomically rough zone penetrates the entire patch at a lower temperature where the film melts. The calculated melting temperatures are significantly lower than observed experimentally, indicating a severe fault in the potential model. A possible source of the discrepancy is identified.