Roles of Pt and BaO in the Sulfation of Pt/BaO/Al2O3 Lean NOx Trap Materials: Sulfur K-edge XANES and Pt Llll XAFS Studies

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

Kim,D.; Kwak, J.; Szanyi, J.

2008-01-01

The roles of barium oxide and platinum during the sulfation of Pt-BaO/Al2O3 lean NOx trap catalysts were investigated by S K edge XANES (X-ray absorption near-edge spectroscopy) and Pt LIII XAFS (X-ray absorption fine structure). All of the samples studied [Al2O3, BaO(x; x = 8 or 20 wt %)/Al2O3, Pt(2.5 wt %)/Al2O3, and Pt(2 wt %)-BaO(x; x = 8 or 20 wt %)/Al2O3] were pre-sulfated prior to the X-ray absorption measurements. It was found that barium oxide itself has the ability to directly form barium sulfate even in the absence of Pt and gas-phase oxygen. In the platinum-containing samples, themore » presence of Pt-O species plays an important role in the formation of sulfate species. For the case of the BaO(8)/Al2O3 sample, where the barium coverage is about 0.26 ML, both baria and alumina phases are available for sulfation. S XANES results show that barium sulfates are formed preferentially over aluminum sulfates. When oxygen is absent from the gas phase, the sulfation route that involves Pt-O is eliminated after the initially present Pt-O species are completely consumed. In this case, formation of sulfates is suppressed unless barium oxide is also present. Pt LIII XAFS results show that the first coordination sphere around the Pt atoms in the Pt particles is dependent upon the gas mixture used during the sulfation process. Sulfation under reducing environments (e.g., SO2/H2) leads to formation of Pt-S bonds, while oxidizing conditions (e.g., SO2/O2) continue to show the presence of Pt-O bonds. In addition, a reducing environment was found to cause Pt sintering in greater extent than an oxidizing one. This result explains why samples sulfated under reducing conditions had lower NOx uptakes than those sulfated under oxidizing conditions. Therefore, our results provide needed information for the development of optimum practical operation conditions (e.g., sulfation or desulfation) for lean NOx trap catalysts that minimize deactivation by sulfur.« less

Characterization of NOx, SO2, ethene, and propene from industrial emission sources in Houston, Texas

NASA Astrophysics Data System (ADS)

Washenfelder, R. A.; Trainer, M.; Frost, G. J.; Ryerson, T. B.; Atlas, E. L.; de Gouw, J. A.; Flocke, F. M.; Fried, A.; Holloway, J. S.; Parrish, D. D.; Peischl, J.; Richter, D.; Schauffler, S. M.; Walega, J. G.; Warneke, C.; Weibring, P.; Zheng, W.

2010-08-01

The Houston-Galveston-Brazoria urban area contains industrial petrochemical sources that emit volatile organic compounds and nitrogen oxides, resulting in rapid and efficient ozone production downwind. During September to October 2006, the NOAA WP-3D aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We use measurements of NOx, SO2, and speciated hydrocarbons from industrial sources in Houston to derive source emission ratios and compare these to emission inventories and the first Texas Air Quality Study (TexAQS) in 2000. Between 2000 and 2006, NOx/CO2 emission ratios changed by an average of -29% ± 20%, while a significant trend in SO2/CO2 emission ratios was not observed. We find that high hydrocarbon emissions are routine for the isolated petrochemical facilities. Ethene (C2H4) and propene (C3H6) are the major contributors to ozone formation based on calculations of OH reactivity for organic species including C2-C10 alkanes, C2-C5 alkenes, ethyne, and C2-C5 aldehydes and ketones. Measured ratios of C2H4/NOx and C3H6/NOx exceed emission inventory values by factors of 1.4-20 and 1-24, respectively. We examine trends in C2H4/NOx and C3H6/NOx ratios between 2000 and 2006 for the isolated petrochemical sources and estimate a change of -30% ± 30%, with significant day-to-day and within-plume variability. Median ambient mixing ratios of ethene and propene in Houston show decreases of -52% and -48%, respectively, between 2000 and 2006. The formaldehyde, acetaldehyde, and peroxyacetyl nitrate products produced by alkene oxidation are observed downwind, and their time evolution is consistent with the rapid photochemistry that also produces ozone.

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.

Adsorption of O2, SO2, and SO3 on nickel oxide. Mechanism for sulfate formation

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1985-01-01

Calculations based on the atom superposition and electron delocalization molecular orbital (ASED-MO) technique suggest that O2 will adsorb perferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom is a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the perferred orientation in which the SO3 plane is parallel to the surface. On activation, SO3 adsorbed to an O2(-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Possibilities for alternative mechanisms which require the formation of Ni3(+) or O2(-) are discussed. NiSO4 thus formed leads to the corrosion of Ni at high temperatures in the SO2+O2/SO3 The SO2+O2/SO3 atmosphere, as discussed in the experimental literature.

Angular distributions for the inelastic scattering of NO(X2Π ) with O2(X3Σg-)

NASA Astrophysics Data System (ADS)

Brouard, M.; Gordon, S. D. S.; Nichols, B.; Squires, E.; Walpole, V.; Aoiz, F. J.; Stolte, S.

2017-05-01

The inelastic scattering of NO(X2Π ) by O2(X3Σg-) was studied at a mean collision energy of 550 cm-1 using velocity-map ion imaging. The initial quantum state of the NO(X2Π , v = 0, j = 0.5, Ω =0.5 , 𝜖 = -1 , f) molecule was selected using a hexapole electric field, and specific Λ-doublet levels of scattered NO were probed using (1 +1' ) resonantly enhanced multiphoton ionization. A modified "onion-peeling" algorithm was employed to extract angular scattering information from the series of "pancaked," nested Newton spheres arising as a consequence of the rotational excitation of the molecular oxygen collision partner. The extracted differential cross sections for NO(X) f →f and f →e Λ-doublet resolved, spin-orbit conserving transitions, partially resolved in the oxygen co-product rotational quantum state, are reported, along with O2 fragment pair-correlated rotational state population. The inelastic scattering of NO with O2 is shown to share many similarities with the scattering of NO(X) with the rare gases. However, subtle differences in the angular distributions between the two collision partners are observed.

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

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

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.

1986-01-01

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Rational design of template-free MnOx-CeO2 hollow nanotube as de-NOx catalyst at low temperature

NASA Astrophysics Data System (ADS)

Li, Chenlu; Tang, Xiaolong; Yi, Honghong; Wang, Lifeng; Cui, Xiaoxu; Chu, Chao; Li, Jingying; Zhang, Runcao; Yu, Qingjun

2018-01-01

MnOx-CeO2 hollow nanotube was synthesized for the low temperature selective catalytic reduction (SCR) of NOx with NH3. The nanotube was fabricated firstly through the interfacial oxidation-reduction reaction by dealing the Ce(OH)CO3 intermediate with KMnO4 aqueous solution, then followed by selective wash with HNO3. The catalysts were systematically examined by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, elemental mapping, X-ray photoelectron spectroscopy, NH3 temperature-programmed desorption measurements and catalytic activity test. It was found that the as-prepared MnOx-CeO2-B nanotube exhibited best NOx removal efficiency among the catalysts investigated, where 96% NOx conversion at 100 °C at a space velocity of 30000 h-1 was obtained. Meanwhile, superior resistance to H2O and SO2 was achieved as well as high thermal stability. On the basis of various analysis results, the remarkable de-NOx performance of the MnOx-CeO2-B nanobube could be attributed to the uniform distribution of active species, abundant content of Mn4+ and Oα species, and especially the hollow porous architectures provided huge specific surface area and sufficient acidic sites.

Effect of CO, NOx and SO2 on ROS production, photosynthesis and ascorbate–glutathione pathway to induce Fragaria×annasa as a hyperaccumulator☆

PubMed Central

Muneer, Sowbiya; Kim, Tae Hwan; Choi, Byung Chul; Lee, Beom Seon; Lee, Jeong Hyun

2013-01-01

A study was conducted to determine the effect of carbon monoxide (CO), nitroxide (NOx) and sulfur dioxide (SO2) on ROS production, photosynthesis and ascorbate–glutathione pathway in strawberry plants. The results showed that both singlet oxygen (O2−1) and hydrogen peroxide (H2O2) content increased in CO, NOx and SO2 treated strawberry leaves. A drastic reduction of primary metabolism of plants (photosynthesis), with the closure of stomata, resulted in a reduction of protein, carbohydrate and sucrose content due to production of reactive oxygen species (ROS) under prolonged exposure of gas stress. The resulting antioxidant enzymes were increased under a low dose of gas stress, whereas they were decreased due to a high dose of gas stress. Our results indicate that increased ROS may act as a signal to induce defense responses to CO, NOx and SO2 gas stress. The increased level of antioxidant enzymes plays a significant role in plant protection due to which strawberry plants can be used as a hyperaccumulator to maintain environmental pollution, however, the defense capacity cannot sufficiently alleviate oxidative damage under prolonged exposure of CO, NOx and SO2 stress. PMID:25460723

Effects of NOx and SO2 on the secondary organic aerosol formation from photooxidation of α-pinene and limonene

NASA Astrophysics Data System (ADS)

Zhao, Defeng; Schmitt, Sebastian H.; Wang, Mingjin; Acir, Ismail-Hakki; Tillmann, Ralf; Tan, Zhaofeng; Novelli, Anna; Fuchs, Hendrik; Pullinen, Iida; Wegener, Robert; Rohrer, Franz; Wildt, Jürgen; Kiendler-Scharr, Astrid; Wahner, Andreas; Mentel, Thomas F.

2018-02-01

Anthropogenic emissions such as NOx and SO2 influence the biogenic secondary organic aerosol (SOA) formation, but detailed mechanisms and effects are still elusive. We studied the effects of NOx and SO2 on the SOA formation from the photooxidation of α-pinene and limonene at ambient relevant NOx and SO2 concentrations (NOx: < 1to 20 ppb, SO2: < 0.05 to 15 ppb). In these experiments, monoterpene oxidation was dominated by OH oxidation. We found that SO2 induced nucleation and enhanced SOA mass formation. NOx strongly suppressed not only new particle formation but also SOA mass yield. However, in the presence of SO2 which induced a high number concentration of particles after oxidation to H2SO4, the suppression of the mass yield of SOA by NOx was completely or partly compensated for. This indicates that the suppression of SOA yield by NOx was largely due to the suppressed new particle formation, leading to a lack of particle surface for the organics to condense on and thus a significant influence of vapor wall loss on SOA mass yield. By compensating for the suppressing effect on nucleation of NOx, SO2 also compensated for the suppressing effect on SOA yield. Aerosol mass spectrometer data show that increasing NOx enhanced nitrate formation. The majority of the nitrate was organic nitrate (57-77 %), even in low-NOx conditions (< ˜ 1 ppb). Organic nitrate contributed 7-26 % of total organics assuming a molecular weight of 200 g mol-1. SOA from α-pinene photooxidation at high NOx had a generally lower hydrogen to carbon ratio (H / C), compared to low NOx. The NOx dependence of the chemical composition can be attributed to the NOx dependence of the branching ratio of the RO2 loss reactions, leading to a lower fraction of organic hydroperoxides and higher fractions of organic nitrates at high NOx. While NOx suppressed new particle formation and SOA mass formation, SO2 can compensate for such effects, and the combining effect of SO2 and NOx may have an important

Airborne emission measurements of SO2, NOx and particles from individual ships using sniffer technique

NASA Astrophysics Data System (ADS)

Beecken, J.; Mellqvist, J.; Salo, K.; Ekholm, J.; Jalkanen, J.-P.

2013-12-01

A dedicated system for airborne ship emission measurements of SO2, NOx and particles has been developed and used from several small aircrafts. The system has been adapted for fast response measurements at 1 Hz and the use of several of the instruments is unique. The uncertainty of the given data is about 20.3% for SO2 and 23.8% for NOx emission factors. Multiple measurements of 158 ships measured from the air on the Baltic and North Sea during 2011 and 2012 show emission factors of 18.8 ± 6.5 g kgfuel-1, 66.6 ± 23.4 g kgfuel-1, and 1.8 ± 1.3 × 1016 particles kgfuel-1 for SO2, NOx and particle number respectively. The particle size distributions were measured for particle diameters between 15 and 560 nm. The mean sizes of the particles are between 50 and 62 nm dependent on the distance to the source and the number size distribution is mono-modal. Concerning the sulfur fuel content 85% of the ships comply with the IMO limits. The sulfur emission has decreased compared to earlier measurements from 2007 to 2009. The presented method can be implemented for regular ship compliance monitoring.

Role of lightning phenomenon over surface O3 and NOx at a semi-arid tropical site Hyderabad, India: inter-comparison with satellite retrievals

NASA Astrophysics Data System (ADS)

Venkanna, R.; Nikhil, G. N.; Sinha, P. R.; Siva Rao, T.; Swamy, Y. V.

2016-08-01

The influence of lightning over surface-level trace gases was examined for pre-monsoon and monsoon seasons in the year 2012. Lightning events were measured using ground-based electric field monitor (EFM) and space-based lightning imaging sensor (LIS). The results showed that lightning frequency was higher during pre-monsoon period compared to monsoon, which is in good agreement with the satellite retrievals. The increase in concentration of NOx on lightning event led to a subsequent decrease in surface O3 due to the titration reaction. Source apportionment study of SO2/NOx (S/N) and CO/NOx (C/N) ratios and poor correlation of NOx vs CO and NOx vs SO2 on the lightning day confirmed the emission of NOx from dissimilar sources.

Impact of Ship Emissions on Marine Boundary Layer NO(x) and SO2 Distributions over the Pacific Basin

NASA Technical Reports Server (NTRS)

Davis, D. D.; Grodzinsky, G.; Kasibhatla, P.; Crawford, J.; Chen, G.; Liu, S.; Bandy, A.; Thornton, D.; Guan, H.; Sandholm, S.

2001-01-01

The impact of ship emissions on marine boundary layer (MBL) NO(x) and SO2 levels over the Pacific Ocean has been explored by comparing predictions (with and without ships) from a global chemical transport model (GCTM) against compiled airborne observations of MBL NO(x) and SO2. For latitudes above 15 N, which define that part of the Pacific having the heaviest shipping, this analysis revealed significant model over prediction for NOx and a modest under prediction for SO2 when ship emissions were considered. Possible reasons for the difference in NO(x) and SO2 were explored using a full-chemistry box model. These results revealed that for an actual plume setting the NO(x) lifetime could be greatly shortened by chemical processes promoted by ship plume emissions themselves. Similar chemical behavior was not found for SO2.

Design of multi-shell Fe2O3@MnOx@CNTs for the selective catalytic reduction of NO with NH3: improvement of catalytic activity and SO2 tolerance

NASA Astrophysics Data System (ADS)

Cai, Sixiang; Hu, Hang; Li, Hongrui; Shi, Liyi; Zhang, Dengsong

2016-02-01

Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx performance. Moreover, the Fe2O3 shell could effectively suppress the formation of the surface sulfate species, leading to the desirable SO2 resistance to the multi-shell catalyst. Hence, the synthesis protocol could provide guidance for the preparation and elevation of manganese based catalysts.Manganese based catalysts are highly active in the NH3-SCR reaction for NOx removal. Unfortunately, manganese oxides can be easily deactivated by sulfur dioxide in the flow gas, which has become the main obstacle for their practical applications. To address this problem, we presented a green and facile method for the synthesis of multi-shell Fe2O3@MnOx@CNTs. The morphology and structural properties of the catalysts were systematically investigated. The results revealed that the MnOx@CNT core-shell structure was formed during the chemical bath deposition, while the outermost MnOx species were transformed to Fe2O3 after the galvanic replacement reaction. The formation of the multi-shell structure induced the enhancement of the active oxygen species, reducible species as well as adsorption of the reactants, which brought about excellent de-NOx

Biosphere-Atmosphere Exchange of NOx, CH4, and O3 in Central Amazon

NASA Astrophysics Data System (ADS)

Wiedemann, K. T.; Munger, J. W.; Wofsy, S. C.; Budney, J.; Rizzo, L. V.; Campos, K.; Rocha, H.; Freitas, H.

2016-12-01

Oxidation by OH is the dominant pathway for removing important trace gases such as CH4, CO, CH3Br, and HCFCs. The primary source of atmospheric OH is the photolysis of O3 in the presence of water vapor, and NOx are the main precursors of O3 and OH. Thus, in NOx-rich environments that have both high humidity and high solar radiation, OH concentrations are enhanced, and therefore, tropical forests dominate global oxidation of long-lived gases. The Amazon rain forest has a unique combination of vegetation with diverse characteristics, climate, and a dynamic land use, factors that altogether govern the emission and fate of trace-gases and control particle formation and atmospheric chemistry. Understanding the interactions among the mechanisms that govern local precursor emissions will lead to a better description of the local atmospheric chemistry, which have global impacts. As part of the GoAmazon project, an array of complementary measurements was conducted in a research site in central Amazon, southeast of Santarem (PA, Brazil), situated inside the Tapajos National Forest. The site where the measurements were taken is surrounded by intact rain forest in a 6 km radius, and a 45 m closed canopy. In the east side out of this radius (upwind), some settlements are distributed in a stripe along a road, which were cleared for agriculture and are sparsely populated. The 67 m tower was assembled in the site in 2001 for flux measurements (CO2 and H2O), and included CO in order to assess local and regional biomass burning. In mid 2014 additional instrumentation were added, measuring NOx, O3, CH4, and SO2 fluxes and profiles. The SO2 measurements (until early 2015) showed concentrations up to 0.1 ppb during the peak of the dry season, and a small vertical gradient, suggesting the predominance of biogenic sources. Preliminary results show no significant seasonality in the daytime and nighttime O3 vertical profiles. Occasionally, nighttime profiles showed high concentrations for

COMPARISON OF HISTORIC SO2 AND NOX EMISSION DATA SETS

EPA Science Inventory

The report gives results of a comparison of historic SO2 and NOx emission data sets. During the past few years, several research projects have been conducted to reconstruct historic air pollution emission trends in the U.S. The report compares in detail the emission estimates and...

In-situ functionalization of mesoporous hexagonal ZnO synthesized in task specific ionic liquid as a photocatalyst for elimination of SO2, NOx, and CO

NASA Astrophysics Data System (ADS)

Kowsari, Elaheh; Abdpour, Soheil

2017-12-01

A novel mesoporous structure of zinc oxide was synthesized in hydrothermal autocalve in the presence of a functional ionic liquid (FIL) {[CH2CH2] O2 (mm)2}. This FIL with ether groups was used simultaneously as a designer templating agent and a source of the hydroxyl radical. The presence of this ionic liquid led to producing ethylene glycol in the reaction media, which adsorb on the surface of mesoporous hexagonal ZnO plates. These mesoporous structures can adsorb pollutant gases and increase photocatalytic oxidation of pollutant gases in compare with commercial ZnO nanoparticles and agglomerated nanoparticles synthesized in this work. XPS data confirmed ethylene glycol production by the ionic liquid, which could prove a role for ionic liquids as designers. The estimated BET surface area values of ZnO hexagonal mesoporous plates and agglomerated particles were 84 m2/g and 12 m2/g respectively. Optical properties of the mesoporous structures were analyzed by photoluminescence spectroscopy and diffuse reflectance UV-visible spectroscopy. The performance of these structures as efficient photocatalysts was further demonstrated by their removal of NOx, SO2, and CO under UV irradiation. The removal of NOx, SO2, and CO under UV irradiation was 56%, 81%, and 35% respectively, after 40 min of irradiation time. Reusability of the photocatalyst was determined; the results show no significant decrease of activity of photocatalyst. after five cycles.

Composite TiO2/clays materials for photocatalytic NOx oxidation

NASA Astrophysics Data System (ADS)

Todorova, N.; Giannakopoulou, T.; Karapati, S.; Petridis, D.; Vaimakis, T.; Trapalis, C.

2014-11-01

TiO2 photocatalyst received much attention for air purification applications especially for removal of air pollutants like NOx, VOCs etc. It has been established that the activity of the photocatalyst can be significantly enhanced by its immobilization onto suitable substrates like inorganic minerals, porous silica, hydroxyapatite, adsorbent materials like activated carbon, various co-catalysts such as semiconductors, graphene, reduced graphite oxide, etc. In the present work, photocatalytic composite materials consisted of mineral substrate and TiO2 in weight ratio 1:1 were manufactured and examined for oxidation and removal of nitric oxides NOx (NO and NO2). Commercial titania P25 (Evonik-Degussa) and urea-modified P25 were used as photocatalytically active components. Inorganic minerals, namely kunipia, talk and hydrotalcite were selected as supporting materials due to their layered structure and expected high NOx adsorption capability. Al3+ and Ca2+ intercalation was applied in order to improve the dispersion of TiO2 and its loading into the supporting matrix. The X-ray diffraction analysis and Scanning Electron Microscopy revealed the binary structure of the composites and homogeneous dispersion of the photocatalyst into the substrates. The photocatalytic behavior of the materials in NOx oxidation and removal was investigated under UV and visible light irradiation. The composite materials exhibited superior photocatalytic activity than the bare titania under both types of irradiation. Significant visible light activity was recorded for the composites containing urea-modified titania that was accredited to the N-doping of the semiconductor. Among the different substrates, the hydrotalcite caused highest increase in the NOx removal, while among the intercalation ions the Ca2+ was more efficient. The results were related to the improved dispersion of the TiO2 and the synergetic activity of the substrates as NOx adsorbers.

40 CFR 51.125 - Emissions reporting requirements for SIP revisions relating to budgets for SO2 and NOX emissions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... SIP revisions relating to budgets for SO2 and NOX emissions. 51.125 Section 51.125 Protection of... SIP revisions relating to budgets for SO2 and NOX emissions. (a) For its transport SIP revision under § 51.123 and/or 51.124, each State must submit to EPA SO2 and/or NOX emissions data as described in...

OZONE PRODUCTION EFFICIENCY AND NOX DEPLETION IN AN URBAN PLUME: INTERPRETATION OF FIELD OBSERVATIONS AND IMPLICATIONS FOR EVALUATING O3-NOX-VOC SENSITIVITY

EPA Science Inventory

Ozone production efficiency (OPE) can be defined as the number of ozone (O3) molecules photochemically produced by a molecule of NOx (NO + NO2) before it is lost from the NOx - O3 cycle. Here, we consider observational and modeling techniques to evaluate various operational defi...

The promoting effect of CeO2@Ce-O-P multi-core@shell structure on SO2 tolerance for selective catalytic reduction of NO with NH3 at low temperature

NASA Astrophysics Data System (ADS)

Yao, Weiyuan; Liu, Yue; Wu, Zhongbiao

2018-06-01

A series of CeO2@Ce-O-P "multi-core@shell" catalysts were synthesized in this paper for selective catalytic reduction (SCR) of NO with NH3. The experimental results had showed that CeO2@Ce-O-P-30:3 yielded best SO2 tolerance of an over 70% deNOx efficiency at 250 °C in the presence of 100 ppm SO2 for 20 h, which was much higher compared to pure Ce-O-P and CeO2 samples. Further characterization results indicated that Ce-O-P coating layer could somewhat inhibit sulfur depositing on the catalysts during SCR reaction in the presence of SO2, thereby protecting the active sites from SO2 poisoning. Especially, O2-TPD results illustrated that a great amount of active oxygen species were retained on used CeO2@Ce-O-P catalyst after a long term reaction. The synergetic effect of "multi-core@shell" structure could be attributed to such enhanced performances. The "core" CeO2 devoted abundant active oxygen sites to fulfill the SCR reaction. And the "shell" Ce-O-P could not only provide acid sites, but also protect the active oxygen species by avoiding the over-adsorption of SO2 on the catalyst. This work could provide a new way to increase the sulfur resistance for low temperature SCR catalysts.

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents.

PubMed

Ghorishi, S Behrooz; Singer, Carl F; Jozewicz, Wojciech S; Sedman, Charles B; Srivastava, Ravi K

2002-03-01

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.

Characteristics of Pt-K/MgAl2O4 lean NOx trap catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2012-04-30

We report the various characteristics of Pt-K/MgAl{sub 2}O{sub 4} lean NOx trap (LNT) catalysts including the effect of K loading on nitrate formation/decomposition, NOx storage activity and durability. Upon the adsorption of NO{sub 2} on K/MgAl{sub 2}O{sub 4} samples, potassium nitrates formed on Mg-related sites in MgAl{sub 2}O{sub 4} support are observed, in addition to the typical two potassium nitrates (ionic and bidentate) formed also on Al{sub 2}O{sub 3} supported sample. Based on NO{sub 2} TPD and FTIR results, the Mg-bound KNO{sub 3} thermally decompose at higher temperature than Al-bound KNO{sub 3}, implying its superior thermal stability. At a potassiummore » loading of 5wt%, the temperature of maximum NOx uptake (T{sub max}) is 300 C. Increasing the potassium loading from 5wt% to 10 wt%, the T{sub max} gradually shifted from 300 C to 450 C, indicating the dependence of T{sub max} on the potassium loading. However, increase in potassium loading above 10 wt% only gives rise to the reduction in the overall NOx storage capacity. This work also underlines the obstacles these materials have prior to their practical application (e.g., durability and sulfur poisoning/ removal). This work provides fundamental understanding of Pt-K/MgAl{sub 2}O{sub 4}-based lean NOx trap catalysts, which could be good candidates for high temperature LNT applications.« less

Water-induced morphology changes in BaO/γ-Al2O3 NOx storage materials: an FTIR, TPD, and time-resolved synchrotron XRD study

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

Szanyi, Janos; Kwak, Ja Hun; Kim, Do Heui

2007-03-29

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. This process is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation of nitrites and bulk nitrates exclusively,more » i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

Field test of available methods to measure remotely SO2 and NOx emissions from ships

NASA Astrophysics Data System (ADS)

Balzani Lööv, J. M.; Alfoldy, B.; Beecken, J.; Berg, N.; Berkhout, A. J. C.; Duyzer, J.; Gast, L. F. L.; Hjorth, J.; Jalkanen, J.-P.; Lagler, F.; Mellqvist, J.; Prata, F.; van der Hoff, G. R.; Westrate, H.; Swart, D. P. J.; Borowiak, A.

2013-11-01

Methods for the determination of ship fuel sulphur content and NOx emission factors from remote measurements have been compared in the harbour of Rotterdam and compared to direct stack emission measurements on the ferry Stena Hollandica. The methods were selected based on a review of the available literature on ship emission measurements. They were either optical (LIDAR, DOAS, UV camera), combined with model based estimates of fuel consumption, or based on the so called "sniffer" principle, where SO2 or NOx emission factors are determined from simultaneous measurement of the increase of CO2 and SO2 or NOx concentrations in the plume of the ship compared to the background. The measurements were performed from stations at land, from a boat, and from a helicopter. Mobile measurement platforms were found to have important advantages compared to the landbased ones because they allow to optimize the sampling conditions and to sample from ships on the open sea. Although optical methods can provide reliable results, it was found that at the state of the art, the "sniffer" approach is the most convenient technique for determining both SO2 and NOx emission factors remotely. The average random error on the determination of SO2 emission factors comparing two identical instrumental set-ups was 6%. However, it was found that apparently minor differences in the instrumental characteristics, such as response time, could cause significant differences between the emission factors determined. Direct stack measurements showed that about 14% of the fuel sulphur content was not emitted as SO2. This was supported by the remote measurements and is in agreement with the results of other field studies.

Combined effects Na and SO2 in flue gas on Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO by NH3 simulated by Na2SO4 doping

NASA Astrophysics Data System (ADS)

Zhou, Aiyi; Yu, Danqing; Yang, Liu; Sheng, Zhongyi

2016-08-01

A series of Mn-Ce/TiO2 catalysts were synthesized through an impregnation method and used for low temperature selective catalytic reduction (SCR) of NOx with ammonia (NH3). Na2SO4 was added into the catalyst to simulate the combined effects of alkali metal and SO2 in the flue gas. Experimental results showed that Na2SO4 had strong and fluctuant influence on the activity of Mn-Ce/TiO2, because the effect of Na2SO4 included pore occlusion and sulfation effect simultaneously. When Na2SO4 loading content increased from 0 to 1 wt.%, the SCR activities of Na2SO4-doped catalysts decreased greatly. With further increasing amount of Na2SO4, however, the catalytic activity increased gradually. XRD results showed that Na2SO4 doping could induce the crystallization of MnOx phases, which were also confirmed by TEM and SEM results. BET results showed that the surface areas decreased and a new bimodal mesoporous structure formed gradually with the increasing amount of Na2SO4. XPS results indicated that part of Ce4+ and Mn3+ were transferred to Ce3+ and Mn4+ due to the sulfation after Na2SO4 deposition on the surface of the catalysts. When the doped amounts of Na2SO4 increased, NH3-TPD results showed that the Lewis acid sites decreased and the Brønsted acid sites of Mn-Ce/TiO2 increased quickly, which could be considered as another reason for the observed changes in the catalytic activity. The decreased Mn and Ce atomic concentration, the changes of their oxidative states, and the variation in acidic properties on the surface of Na2SO4-doped catalysts could be the reasons for the fluctuant changes of the catalytic activity.

Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

NASA Technical Reports Server (NTRS)

Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

1995-01-01

Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

Ceramic oxide reactions with V2O5 and SO3

NASA Technical Reports Server (NTRS)

Jones, R. L.; Williams, C. E.

1985-01-01

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Nocturnal Vertical Gradients of O3, NO2, NO3, HONO, HCHO, and SO2 in Los Angeles, CA, during CalNex 2010

NASA Astrophysics Data System (ADS)

Tsai, J.; Pikelnaya, O.; Hurlock, S. C.; Wong, K.; Cheung, R.; Haman, C. L.; Lefer, B. L.; Stutz, J.

2010-12-01

Nocturnal chemistry, through the conversion and removal of air pollutants, plays an important role in determining the initial condition for photochemistry during the following day. In the stable nocturnal boundary layer (NBL) the interplay between suppressed vertical mixing and surface emissions of NOx and VOCs can result in pronounced vertical trace gas profiles. The resulting altitude dependence of nocturnal chemistry makes the interpretation of ground observations challenging. In particular, the quantification of the nocturnal loss of NOx, due to NO3 and N2O5 chemistry, requires observations throughout the entire vertical extent of the NBL. The formation of daytime radical precursors, such as HONO, is also altitude dependent. An accurate assessment of their impact on daytime chemistry requires measurements of their profiles during the night and morning. Here we present observations from the CalNex-LA experiment, which took place from May 15 to June 15, 2010 on the east side of the Los Angeles Basin, CA. A Long-Path Differential Optical Absorption Spectrometer (LP-DOAS) was set up on the roof of the Millikan library (265 m asl, 35m agl) on the campus of the California Institute of Technology. Four retroreflector arrays were mounted about 5 -7 km North-East of the instrument at 310m, 353m, 487m and 788 m asl. The vertical profiles of NO3, HONO, NO2, O3, HCHO, and SO2 were retrieved at altitude intervals of 35-78m, 78-121m, 121-255m and 255-556m above the ground. During many nights vertical gradients were observed, with elevated NO2 and HONO concentrations near the surface and larger ozone and NO3 concentrations aloft. Simultaneous ceilometer observations of the NBL structure show the impact of meteorology on the vertical trace gas distributions. We will discuss the consequences of trace gases gradients on the nocturnal NOx budget.

Implications of near-term coal power plant retirement for SO2 and NOX and life cycle GHG emissions.

PubMed

Venkatesh, Aranya; Jaramillo, Paulina; Griffin, W Michael; Matthews, H Scott

2012-09-18

Regulations monitoring SO(2), NO(X), mercury, and other metal emissions in the U.S. will likely result in coal plant retirement in the near-term. Life cycle assessment studies have previously estimated the environmental benefits of displacing coal with natural gas for electricity generation, by comparing systems that consist of individual natural gas and coal power plants. However, such system comparisons may not be appropriate to analyze impacts of coal plant retirement in existing power fleets. To meet this limitation, simplified economic dispatch models for PJM, MISO, and ERCOT regions are developed in this study to examine changes in regional power plant dispatch that occur when coal power plants are retired. These models estimate the order in which existing power plants are dispatched to meet electricity demand based on short-run marginal costs, with cheaper plants being dispatched first. Five scenarios of coal plant retirement are considered: retiring top CO(2) emitters, top NO(X) emitters, top SO(2) emitters, small and inefficient plants, and old and inefficient plants. Changes in fuel use, life cycle greenhouse gas emissions (including uncertainty), and SO(2) and NO(X) emissions are estimated. Life cycle GHG emissions were found to decrease by less than 4% in almost all scenarios modeled. In addition, changes in marginal damage costs due to SO(2), and NO(X) emissions are estimated using the county level marginal damage costs reported in the Air Pollution Emissions Experiments and Policy (APEEP) model, which are a proxy for measuring regional impacts of SO(2) and NO(X) emissions. Results suggest that location specific parameters should be considered within environmental policy frameworks targeting coal plant retirement, to account for regional variability in the benefits of reducing the impact of SO(2) and NO(X) emissions.

Observed NO/NO2 Ratios in the Upper Troposphere Imply Errors in NO-NO2-O3 Cycling Kinetics or an Unaccounted NOx Reservoir

NASA Astrophysics Data System (ADS)

Silvern, R. F.; Jacob, D. J.; Travis, K. R.; Sherwen, T.; Evans, M. J.; Cohen, R. C.; Laughner, J. L.; Hall, S. R.; Ullmann, K.; Crounse, J. D.; Wennberg, P. O.; Peischl, J.; Pollack, I. B.

2018-05-01

Observations from the SEAC4RS aircraft campaign over the southeast United States in August-September 2013 show NO/NO2 concentration ratios in the upper troposphere that are approximately half of photochemical equilibrium values computed from Jet Propulsion Laboratory (JPL) kinetic data. One possible explanation is the presence of labile NOx reservoir species, presumably organic, decomposing thermally to NO2 in the instrument. The NO2 instrument corrects for this artifact from known labile HNO4 and CH3O2NO2 NOx reservoirs. To bridge the gap between measured and simulated NO2, additional unaccounted labile NOx reservoir species would have to be present at a mean concentration of 40 ppt for the SEAC4RS conditions (compared with 197 ppt for NOx). An alternative explanation is error in the low-temperature rate constant for the NO + O3 reaction (30% 1-σ uncertainty in JPL at 240 K) and/or in the spectroscopic data for NO2 photolysis (20% 1-σ uncertainty). Resolving this discrepancy is important for understanding global budgets of tropospheric oxidants and for interpreting satellite observations of tropospheric NO2 columns.

Thermal decomposition of europium sulfates Eu2(SO4)3·8H2O and EuSO4

NASA Astrophysics Data System (ADS)

Denisenko, Yu. G.; Khritokhin, N. A.; Andreev, O. V.; Basova, S. A.; Sal'nikova, E. I.; Polkovnikov, A. A.

2017-11-01

Reactions of europium sulfates Eu2(SO4)3·8H2O and EuSO4 complete decomposition were studied by Simultaneous Thermal Analysis. It was revealed that one-step dehydratation of Eu2(SO4)3·8H2O crystallohydrate is accompanied by the formation of amorphous anhydrous europium sulfate Eu2(SO4)3. Crystallization of amorphous europium (III) sulfate occurs at 381.1 °C (in argon) and 391.3 °C (in air). The average enthalpy values for dehydratation reaction of Eu2(SO4)3·8H2O (ΔH° = 141.1 kJ/mol), decomposition reactions of Eu2(SO4)3 (ΔH = 463.1 kJ/mol), Eu2O2SO4 (ΔH = 378.4 kJ/mol) and EuSO4 (ΔH = 124.1 kJ/mol) were determined. The step process mechanisms of thermal decomposition of europium (III) sulfate in air and europium (II) sulfate in inert atmosphere were established and justified. The kinetic parameters of complete thermal decomposition of europium (III) sulfate octahydrate were calculated by Kissinger model. The standard enthalpies of compound formation were calculated using thermal effects and formation enthalpy data for binary compounds.

Carbon catalyzed SO2 oxidation by NO2 and O3

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Schryer, D. R.; Rogowski, R. S.

1982-01-01

The oxidation of SO2 to sulfate on carbon particles by trace quantities of NO2 and O3 was studied. Particulate carbon black was either: (1) directly exposed on the pan of a microbalance to various humidified mixtures of SO2 and oxidant gas and the resultant weight gains monitored, or (2) the gas mixtures were bubbled through aqueous suspensions of carbon black and pure water blanks. In each set of experiments the run times were varied appropriately and the yields of sulfate were determined analytically. Conversion of SO2 to sulfate was thus characterized as a function of exposure time and of oxidant gas. Carbon black was determined to be an excellent catalyst for SO2 oxidation to sulfate by both NO2 and O3. No saturation effects were observed in either experimental approach. Conversions of SO2 to sulfate did not appear pH dependent.

JOINT ACTION OF O3 AND SO2 IN MODIFYING PLANT GAS EXCHANGE

EPA Science Inventory

The joint action of O3 and SO2 stress on plants was investigated. Gas exchange measurements of O3, SO2, and H2O vapor were made for garden pea. Plants were grown under controlled environments; O3, SO2, H2O vapor fluxes were evaluated with a whole-plant gas exchange chamber using ...

Airborne emission measurements of SO2 , NOx and particles from individual ships using a sniffer technique

NASA Astrophysics Data System (ADS)

Beecken, J.; Mellqvist, J.; Salo, K.; Ekholm, J.; Jalkanen, J.-P.

2014-07-01

A dedicated system for airborne ship emission measurements of SO2, NOx and particles has been developed and used from several small aircraft. The system has been adapted for fast response measurements at 1 Hz, and the use of several of the instruments is unique. The uncertainty of the given data is about 20% for SO2 and 24% for NOx emission factors. The mean values with one standard deviation for multiple measurements of 158 ships measured from the air on the Baltic and North Sea during 2011 and 2012 show emission factors of 18.8 ± 6.5 g kg3em;">-1 3em;">fuel , 66.6 ± 23.4 g kg3em;">-1 3em;">fuel and 1.8 ± 1.3 1016 particles kg3em;">-1 3em;">fuel for SO2, NOx and particle number, respectively. The particle size distributions were measured for particle diameters between 15 and 560 nm. The mean sizes of the particles are between 45 and 54 nm dependent on the distance to the source, and the number size distribution is monomodal. Concerning the sulfur fuel content, around 85% of the monitored ships comply with the International Maritime Organization (IMO) limits. The reduction of the sulfur emission control area (SECA) limit from 1.5 to 1% in 2010 appears to have contributed to reduction of sulfur emissions that were measured in earlier studies from 2007 to 2009. The presented method can be implemented for regular ship compliance monitoring.

Experimental study on removals of SO2 and NO(x) using adsorption of activated carbon/microwave desorption.

PubMed

Ma, Shuang-Chen; Yao, Juan-Juan; Gao, Li; Ma, Xiao-Ying; Zhao, Yi

2012-09-01

Experimental studies on desulfurization and denitrification were carried out using activated carbon irradiated by microwave. The influences of the concentrations of nitric oxide (NO) and sulfur dioxide (SO2), the flue gas coexisting compositions, on adsorption properties of activated carbon and efficiencies of desulfurization and denitrification were investigated. The results show that adsorption capacity and removal efficiency of NO decrease with the increasing of SO2 concentrations in flue gas; adsorption capacity of NO increases slightly first and drops to 12.79 mg/g, and desulfurization efficiency descends with the increasing SO2 concentrations. Adsorption capacity of SO2 declines with the increasing of O2 content in flue gas, but adsorption capacity of NO increases, and removal efficiencies of NO and SO2 could be larger than 99%. Adsorption capacity of NO declines with the increase of moisture in the flue gas, but adsorption capacity of SO2 increases and removal efficiencies of NO and SO2 would be relatively stable. Adsorption capacities of both NO and SO2 decrease with the increasing of CO2 content; efficiencies of desulfurization and denitrification augment at the beginning stage, then start to fall when CO2 content exceeds 12.4%. The mechanisms of this process are also discussed. The prominent SO2 and NOx treatment techniques in power plants are wet flue gas desulfurization (FGD) and the catalytic decomposition method like selective catalytic reduction (SCR) or nonselective catalytic reduction (NSCR). However, these processes would have some difficulties in commercial application due to their high investment, requirement of expensive catalysts and large-scale equipment, and so on. A simple SO2 and NOx reduction utilizing decomposition by microwave energy method can be used. The pollutants control of flue gas in the power plants by the method of microwave-induced decomposition using adsorption of activated carbon/microwave desorption can meet the

A GdAlO3 Perovskite Oxide Electrolyte-Based NOx Solid-State Sensor

NASA Astrophysics Data System (ADS)

Xiao, Yihong; Wang, Dongmei; Cai, Guohui; Zheng, Yong; Zhong, Fulan

2016-11-01

NOx is a notorious emission from motor vehicles and chemical factories as the precursor of acid rain and photochemical smog. Although zirconia-based NOx sensors have been developed and showed high sensitivity and selectivity at a high temperature of above 800 °C, they fail to show good performance, and even don’t work at the typical work temperature window of the automotive engine (<500 °C). It still is a formidable challenge for development of mild-temperature NOx detector or sensor. Herein, a novel amperometric solid-state NOx sensor was developed using perovskite-type oxide Gd1-xCaxAlO3-δ(GCA) as the electrolyte and NiO as the sensing electrode. NOx sensing properties of the device were investigated at the temperature region of 400-500 °C. The response current value at -300 mV was almost linearly proportional to the NOx concentration between 300 and 500 ppm at 500 °C. At such a temperature, the optimal sensor gave the highest NO2 sensitivity of 20.15 nA/ppm, and the maximum response current value reached 5.57 μA. Furthermore, a 90% response and 90% recover time to 500 ppm NO2 were about 119 and 92 s, respectively. The excellent selectivity and stability towards NOx sensing showed the potential application of the sensor in motor vehicles.

Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

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

Kazmierczak, Karolina; Hoeppe, Henning A., E-mail: henning@ak-hoeppe.d

2011-05-15

The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrationalmore » and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.« less

Airborne Measurements of NOx, NOy, and O3 Using Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Zarzana, K. J.; Wild, R. J.; Thompson, C. R.; Sjostedt, S. J.; Womack, C. C.; Washenfelder, R. A.; Dube, W. P.; Ryerson, T. B.; Brown, S. S.

2015-12-01

NO and NO2 (=NOx) have a large effect on air quality and chemistry. Oxidation reactions transform NOx into other reactive nitrogen species such as PAN, HNO3, organic nitrates and N2O5, which can act either as sinks or reservoirs of NOx. Together with NOx, the sum of these oxidized reactive nitrogen species is termed NOy. Ozone serves as a principal oxidant source for many of these reactions, and it is also produced or destroyed during subsequent chemical cycles. Therefore, simultaneous measurements of all four species (NO, NO2, NOy, and O3) are desirable. Previous measurements of these species have principally been made by converting the compound of interest to NO, which is then detected using chemiluminescence. Alternatively, these species can be converted to NO2, which can then be detected using absorption spectroscopy. The use of a cavity ring down instrument allows for the accurate and rapid detection of NO2 in a compact and robust platform suitable for field deployments on numerous platforms, including vehicles and airplanes. In this work we describe the first aircraft deployment of a four-channel cavity ring-down instrument capable of simultaneously measuring NO2, NO, NOy, and O3. This deployment took place during the 2015 Shale Oil and Natural Gas Nexus (SONGNEX) field campaign in the western United States. The instrument flew in tandem with a chemiluminescence instrument, which measured the same set of compounds. A separate instrument that measured NO2 by a related absorption technique, broadband cavity enhanced spectroscopy (BBCES) was also on board the aircraft. An intercomparison between these instruments will be presented, as well as data from the SONGNEX flights that illustrate the capabilities of the CRDS insrument.

A mitigation strategy for commercial aviation impact on NOx-related O3 change

NASA Astrophysics Data System (ADS)

Wasiuk, D. K.; Khan, M. A. H.; Shallcross, D. E.; Derwent, R. G.; Lowenberg, M. H.

2016-07-01

An operational mitigation strategy for commercial aircraft impact on atmospheric composition, referred to as the turboprop replacement strategy (TRS), is described in this paper. The global air traffic between 2005 and 2011 was modeled with the TRS in which turbofan powered aircraft were replaced with nine chosen turboprop powered aircraft on all routes up to 1700 nautical miles (NM) in range. The results of this TRS double the global number of departures, as well as global mission distance, while global mission time grows by nearly a factor of 3. However, the global mission fuel and the emissions of aviation CO2, H2O, and SOx remain approximately unchanged, and the total global aviation CO, hydrocarbons (HC), and NOx emissions are reduced by 79%, 21%, and 11% on average between 2005 and 2011. The TRS lowers the global mean cruise altitude of flights up to 1700 NM by 2.7 km which leads to a significant decrease in global mission fuel burn, mission time, distance flown, and the aircraft emissions of CO2, CO, H2O, NOx, SOx, and HC above 9.2 km. The replacement of turbofans with turboprops in regional fleets on a global scale leads to an overall reduction in levels of tropospheric O3 at the current estimated mean cruise altitude near the tropopause where the radiative forcing of O3 is strongest. Further, the replacement strategy results in a reduction of ground-level aviation CO and NOx emissions by 33 and 29%, respectively, between 2005 and 2011.

Promotion effect of Pt on a SnO2-WO3 material for NOx sensing

NASA Astrophysics Data System (ADS)

Wang, Chen-Yang; Hong, Zih-Siou; Wu, Ren-Jang

2015-05-01

Metal-oxide nanocomposites were prepared over screen-printed gold electrodes to be used as room-temperature NOx (nitric-oxide (NO) and nitrogen dioxide (NO2)) sensors. Various weight ratios of SnO2-WO3 and Pt loadings were used for NO sensing. The sensing materials were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface analysis. The NO-sensing results indicated that SnO2-WO3 (1:2) was more effective than other materials were. The sensor response (S=resistance of N2/resistance of NO=RN2/RNO) for detecting 1000 ppm of NO at room temperature was 2.6. The response time (T90) and recovery time (TR90) was 40 s and 86 s, respectively. By further loading with 0.5% Pt, the sensor response increased to 3.3. The response and recovery times of 0.5% Pt/SnO2-WO3 (1:2) were 40 s and 206 s, respectively. The linearity of the sensor response for a NO concentration range of 10-1000 ppm was 0.9729. A mechanism involving Pt promotion of the SnO2-WO3 heterojunction was proposed for NO adsorption, surface reaction, and adsorbed NO2 desorption.

Trends of NOx, NO2 and O3 concentrations at three different types of air quality monitoring stations in Athens, Greece

NASA Astrophysics Data System (ADS)

Mavroidis, I.; Ilia, M.

2012-12-01

This work presents a systematic analysis and evaluation of the historic and current levels of atmospheric pollution in the Athens metropolitan region, regarding nitrogen oxides (NOx = NO + NO2), ozone (O3) and the NO2/NOx and NO/NO2 concentration ratios. Hourly, daily, monthly, seasonal and annual pollutant variations are examined and compared, using the results of concentration time series from three different stations of the national network for air pollution monitoring, one urban-traffic, one urban-background and one suburban-background. Concentration data are also related to meteorological parameters. The results show that the traffic affected station of Patission Street presents the higher NOx values and the lower concentrations of O3, while it is the station with the highest number of NO2 limit exceedances. The monitoring data suggest, inter alia, that there is a change in the behaviour of the suburban-background station of Liossia at about year 2000, indicating that the exact location of this station may need to be reconsidered. Comparison of NOx concentrations in Athens with concentrations in urban areas of other countries reveal that the Patission urban-traffic station records very high NOx concentrations, while remarkably high is the ratio of NO2 concentrations recorded at the urban-traffic vs. the urban-background station in Athens, indicating the overarching role of vehicles and traffic congestion on NO2 formation. The NO2/NOx ratio in the urban-traffic station appears to be almost constant with time, while it has been increasing in other urban areas, such as London and Seoul, suggesting an increased effect of primary NO2 in these areas. Diesel passenger cars were only recently allowed in Athens and, therefore, NO2 trends should be carefully monitored since a possible increase in primary NO2 may affect compliance with NO2 air quality standards.

Physical-chemical examination of the N2O3-SO3-H2O system

NASA Technical Reports Server (NTRS)

Linstroem, C.; Malyska, G.

1977-01-01

It was found that when (NO)HSO4 is added to absolute H2SO4, specific conductivity rises sharply, possibly due to an increase in mutual interionic effects and viscosity as the (NO)HSO4 concentration rises. The addition of SO3 to the solution yielded a precipitate; a combination of analysis, IR spectroscopy and X-ray diffraction techniques indicated that this precipitate was (NO)HS2O7.

O3, VOC, NOx, PM2.5 and Meteorological Measurements during an Inversion Episode in Utah's Uinta Basin

NASA Astrophysics Data System (ADS)

Moore, K. D.; Martin, R. S.; Hill, S.; Shorthill, H.

2011-12-01

Recent measurements found high winter ozone (O3) at several locations in northeastern Utah's Uinta Basin. Similar to Wyoming's Upper Green River Basin, the area has seen recent growth in the gas/oil sector. As a part of a more comprehensive project, a study was conducted examining the relationships between O3, volatile organic compounds (VOCs), nitrogen oxides (NOx), fine particulate matter (PM2.5), and meteorology during an inversion episode. The study took place February 21-25, 2011 at the area's population center (Vernal) and at an area within the gas/oil fields (Red Wash). At both sites, O3 and NOx, displayed expected diurnal behaviors. The 1-hr O3 concentrations ranged from 10-90 ppb at Vernal and 34-107 ppb at Red Wash. Average diurnal O3 maximums (±95% CI) were 70.4±12.1 ppb and 76.8±12.6 ppb at Vernal and Red Wash, respectively. The Red Wash average O3 diurnal curve was broader than that at Vernal and did not titrate out as rapidly in the evening and morning hours. In contrast, higher NOx was observed at Vernal, with hourly averaged values ranging from 4.5-80.2 ppb, compared to 1.5-29.7 ppb at Red Wash. The NOx tended to follow traffic patterns at both sites, with morning maximum 1-hr averages of 40.8±12.1 ppb and 20.2±8.7 ppb, respectively. A portable O3 monitor attached to a tethered balloon found high ground level O3 (70-80 ppb) and a decrease to relatively constant levels (50-60 ppb) by 150 m agl. Methane and non-methane hydrocarbons (NHMC) were collected at least twice per day using whole vial and sorbent cartridges, followed by GC-FID and GC-MS analysis. The gas/oil field samples (Red Wash) found significantly higher CH4 levels (2.71±0.32 ppm) compared to the Vernal samples (1.82±0.14 ppm). The NMHC were likewise higher at the Red Wash location. Calculation of the maximum incremental reactivity (MIR) estimated that methane, ethane, propane, acetylene, remaining alkanes, alkenes, and aromatics accounted for 7.9%, 18.5%, 4.7%, 1.0%, 20.6%, 46

Reduction on NOx emissions on urban areas by changing specific vehicle fleets: effects on NO2 and O3 concentration

NASA Astrophysics Data System (ADS)

Goncalves, M.; Jimenez, P.; Baldasano, J.

2007-12-01

The largest amount of NOx emissions in urban areas comes from on-road traffic, which is the largest contributor to urban air pollution (Colvile et al., 2001). Currently different strategies are being tested in order to reduce its effects; many of them oriented to the reduction of the unitary vehicles emissions, by alternative fuels use (such as biofuels, natural gas or hydrogen) or introduction of new technologies (such as hybrid electric vehicles or fuel cells). Atmospheric modelling permits to predict their consequences on tropospheric chemistry (Vautard et al., 2007). Hence, this work assesses the changes on NO2 and O3 concentrations when substituting a 10 per cent of the urban private cars fleets by petrol hybrid electric cars (HEC) or by natural gas cars (NGC) in Madrid and Barcelona urban areas (Spain). These two cities are selected in order to highlight the different patterns of pollutants transport (inland vs. coastal city) and the different responses to emissions reductions. The results focus on a typical summertime episode of air pollution, by means of the Eulerian air quality model ARW- WRF/HERMES/CMAQ, applied with high resolution (1-hr, 1km2) since of the complexity of both areas under study. The detailed emissions scenarios are implemented in the HERMES traffic emissions module, based on the Copert III-EEA/EMEP-CORINAIR (Nztiachristos and Samaras, 2000) methodology. The HEC introduction reduces NOx emissions from on-road traffic in a 10.8 per cent and 8.2 per cent; and the NGC introduction in a 10.3 per cent and 7.8 per cent, for Madrid and Barcelona areas, respectively. The scenarios also affect the NMVOCs reduction (ranging from -3.1 to -6.9 per cent), influencing the tropospheric photochemistry through the NOx/NMVOCs ratio. The abatement of the NO photooxidation but also to the reduction on primary NO2 involves a decrease on NO2 levels centred on urban areas. For example, the NO2 24-hr average concentration in downtown areas reduces up to 8 per

Interaction of SO2 and CO with the Ti2O3(101¯2) surface

NASA Astrophysics Data System (ADS)

Smith, Kevin E.; Henrich, Victor E.

1985-10-01

The interaction of sulfur dioxide with the nearly perfect (101¯2) surface of the corundum transition-metal oxide Ti2O3 has been studied using ultraviolet and x-ray photoemission spectroscopies and low-energy electron diffraction. The reaction of SO2 with Ti2O3 is found to be extremely vigorous, with SO2 adsorbing dissociatively and catalyzing the complete oxidation of the surface to TiO2 and TiS2. This result is significant since exposure to large amounts of O2 does not result in the production of large amounts of TiO2 at the Ti2O3 surface. Dissociative adsorption of SO2 continues for exposures up to at least 104 L (1 L=10-6Torr sec). The reaction is accompanied by large scale surface disorder and by an increase in the work function of 1.32 eV. In contrast, CO adsorbs molecularly for exposures >=105 L, with an extramolecular relaxation-polarization shift of 3.0 eV. For CO exposures <=104 L, the chemisorption mechanism is tentatively identified as dissociative adsorption at defect sites. Inclusive of this study, the interaction of four oxygen-containing molecules (SO2, CO, H2O, and O2) with Ti2O3(101¯2) surfaces has been studied, and their behavior is compared and trends isolated with a view to understanding the oxidation of Ti2O3.

Emissions of NOx, SO2, CO, and HCHO from commercial marine shipping during Texas Air Quality Study (TexAQS) 2006

NASA Astrophysics Data System (ADS)

Williams, E. J.; Lerner, B. M.; Murphy, P. C.; Herndon, S. C.; Zahniser, M. S.

2009-11-01

We report measurements of NOx, SO2, CO, and HCHO mass-based emission factors from more than 200 commercial vessel encounters in the Gulf of Mexico and the Houston-Galveston region of Texas during August and September, 2006. For underway ships, bulk freight carriers have the highest average NOx emissions at ˜87 g NOx (kg fuel)-1, followed by tanker ships at ˜79 g NOx (kg fuel)-1, while container carriers, passenger ships, and tugs all emit an average of about ˜60 g NOx (kg fuel)-1. Emission of NOx from stationary vessels was lower, except for container ships and tugs, and likely reflects use of medium-speed diesel engines. Overall, our mean NOx emission factors are 10-15% lower than published data. Average emission of SO2 was lower for passenger ships and tugs and tows (6-7 g SO2 (kg fuel)-1) than for larger cargo vessels (20-30 g SO2 (kg fuel)-1). Our data for large cargo ships in this region indicate an average residual fuel sulfur content of ˜1.4% which is a factor of two lower than the global average of 2.7%. Emission of CO was low for all categories (7-16 g CO (kg fuel)-1), although our mean overall CO emission factor is about 10% higher than published data. Emission of HCHO was less than 5% that of CO. Despite considerable variability, no functional relationships, such as emissions changes with engine speed or load, could be discerned. Comparison of emission factors from ships to those from other sources suggests ship emissions in this region cannot be ignored.

Comparison and evaluation of anthropogenic emissions of SO2 and NOx over China

NASA Astrophysics Data System (ADS)

Li, Meng; Klimont, Zbigniew; Zhang, Qiang; Martin, Randall V.; Zheng, Bo; Heyes, Chris; Cofala, Janusz; Zhang, Yuxuan; He, Kebin

2018-03-01

Bottom-up emission inventories provide primary understanding of sources of air pollution and essential input of chemical transport models. Focusing on SO2 and NOx, we conducted a comprehensive evaluation of two widely used anthropogenic emission inventories over China, ECLIPSE and MIX, to explore the potential sources of uncertainties and find clues to improve emission inventories. We first compared the activity rates and emission factors used in two inventories and investigated the reasons of differences and the impacts on emission estimates. We found that SO2 emission estimates are consistent between two inventories (with 1 % differences), while NOx emissions in ECLIPSE's estimates are 16 % lower than those of MIX. The FGD (flue-gas desulfurization) device penetration rate and removal efficiency, LNB (low-NOx burner) application rate and abatement efficiency in power plants, emission factors of industrial boilers and various vehicle types, and vehicle fleet need further verification. Diesel consumptions are quite uncertain in current inventories. Discrepancies at the sectorial and provincial levels are much higher than those of the national total. We then examined the impacts of different inventories on model performance by using the nested GEOS-Chem model. We finally derived top-down emissions by using the retrieved columns from the Ozone Monitoring Instrument (OMI) compared with the bottom-up estimates. High correlations were observed for SO2 between model results and OMI columns. For NOx, negative biases in bottom-up gridded emission inventories (-21 % for MIX, -39 % for ECLIPSE) were found compared to the satellite-based emissions. The emission trends from 2005 to 2010 estimated by two inventories were both consistent with satellite observations. The inventories appear to be fit for evaluation of the policies at an aggregated or national level; more work is needed in specific areas in order to improve the accuracy and robustness of outcomes at finer spatial

Effect of Na poisoning catalyst (V2O5-WO3/TiO2) on denitration process and SO3 formation

NASA Astrophysics Data System (ADS)

Xiao, Haiping; Chen, Yu; Qi, Cong; Ru, Yu

2018-03-01

This paper aims to study the effect of alkali metal sodium (Na) poisoning on the performance of the Selective Catalytic Reduction (SCR) catalyst. The result showed that Na2SO4 poisoning leads to a reduced denitration rate of the SCR catalyst and an increase in the SO3 generation rate. Na2O poisoning leads to a significant reduction in the denitration rate of the SCR catalyst and marginally improves the formation of SO3. The maximum of the SO3 generation rate for a Na2SO4-poisoned catalyst reached 1.35%, whereas it was only 0.85% for the SCR catalyst. When the SO2 was contained in flue gas, the denitration rate for the Na2O-poisoned catalyst clearly increased by more than 28%. However, the effect of SO2 on the Na2SO4-poisoned catalyst was very slight. The denitration rate of the SCR catalyst decreased with an increase in the Na content. The BET and XRD results showed that Na poisoning of the catalyst decreased the number of acid sites, the reducibility of the catalyst, the surface area, and pore volume. The H2-TPR and NH3-TPD results show that Na decreases the number of acid sites and the reducibility of the catalyst. The FT-IR and XPS results showed that Na2O poisoning led to the decrease of V5+dbnd O bonds and the consumptions of oxygen atoms. Na2SO4 poisoning can improve surface adsorbed oxygen, which was beneficial for the SO2-SO3 conversion reaction.

Study on the adsorption properties of O{sub 3}, SO{sub 2}, and SO{sub 3} on B-doped graphene using DFT calculations

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

Rad, Ali Shokuhi, E-mail: a.shokuhi@gmail.com; Shabestari, Sahand Sadeghi; Mohseni, Soheil

2016-05-15

We investigated the structure, adsorption, electronic states, and charge transfer of O{sub 3}, SO{sub 2} and SO{sub 3} molecules on the surface of a B-doped graphene using density functional theory (DFT). We found weak physisorption of SO{sub 2} (−10.9 kJ/mole, using B3LYP-D) and SO{sub 3} (−15.7 kJ/mole, using B3LYP-D) on the surface of B-doped graphene while there is strong chemisorption for O{sub 3} (−96.3 kJ/mole, using B3LYP-D ) on this surface. Our results suggest the potential of B-doped graphene as a selective sensor/adsorbent for O{sub 3} molecule. We noticed some change in hybridizing of boron from sp{sup 2} to sp{supmore » 3} upon adsorption of O{sub 3} which cases transformation of the adsorbent from 2D to 3D. - Graphical abstract: The electronic property of B-doped graphene is responsible to highly adsorption of O{sub 3} molecules while the adsorption of SO{sub 2} and SO{sub 3} molecules on this surface exhibits only a weak interaction. - Highlights: • B-doped graphene clearly is n-type semiconductor. • High negatively charge of C-atoms neighboring the boron dopant. • Chemisorption of O{sub 3} and physisorption of SO{sub 2} and SO{sub 3} on the surface of B-doped graphene.« less

DSCOVR_EPIC_L2_O3SO2AI_01

Atmospheric Science Data Center

2018-06-29

... dioxide (SO2) from volcanic plumes, scene reflectivity, and aerosol index (AI), retrieved from the ultraviolet (UV) measurements of DSCOVR ... Access:   Order Data Parameters:  Aerosol Index (AI) Reflectivity at 340 nm Vertical Column of Ozone (O3) ...

NO2-initiated multiphase oxidation of SO2 by O2 on CaCO3 particles

NASA Astrophysics Data System (ADS)

Yu, Ting; Zhao, Defeng; Song, Xiaojuan; Zhu, Tong

2018-05-01

The reaction of SO2 with NO2 on the surface of aerosol particles has been suggested to be important in sulfate formation during severe air pollution episodes in China. However, we found that the direct oxidation of SO2 by NO2 was slow and might not be the main reason for sulfate formation in ambient air. In this study, we investigated the multiphase reaction of SO2 with an O2 / NO2 mixture on single CaCO3 particles using Micro-Raman spectroscopy. The reaction converted the CaCO3 particle to a Ca(NO3)2 droplet, with CaSO4 ⚫ 2H2O solid particles embedded in it, which constituted a significant fraction of the droplet volume at the end of the reaction. The reactive uptake coefficient of SO2 for sulfate formation was on the order of 10-5, which was higher than that for the multiphase reaction of SO2 directly with NO2 by 2-3 orders of magnitude. According to our observations and the literature, we found that in the multiphase reaction of SO2 with the O2 / NO2 mixture, O2 was the main oxidant of SO2 and was necessary for radical chain propagation. NO2 acted as the initiator of radical formation, but not as the main oxidant. The synergy of NO2 and O2 resulted in much faster sulfate formation than the sum of the reaction rates with NO2 and with O2 alone. We estimated that the multiphase oxidation of SO2 by O2 initiated by NO2 could be an important source of sulfate and a sink of SO2, based on the calculated lifetime of SO2 regarding the loss through the multiphase reaction versus the loss through the gas-phase reaction with OH radicals. Parameterization of the reactive uptake coefficient of the reaction observed in our laboratory for further model simulation is needed, as well as an integrated assessment based on field observations, laboratory study results, and model simulations to evaluate the importance of the reaction in ambient air during severe air pollution episodes, especially in China.

Role of plant-generated water vapor and VOC fluxes in shoot chamber measurements of O3 and NOx

NASA Astrophysics Data System (ADS)

Joensuu, J.; Altimir, N.; Raivonen, M.; Kolari, P.; Keronen, P.; Vesala, T.; Bäck, J.; Hari, P.; Järvinen, E.; Nikinmaa, E.

2012-04-01

One of the processes underlying the atmospheric balance of O3 and NOx is their interaction with vegetation. Both are removed, absorbed, and NOx potentially also emitted by foliage. Uncertainties remain on relevant factors controlling O3 and NOx interactions with foliage as well as on including them in large-scale models. One reason for the uncertainty is that chamber measurements of O3 and NOx fluxes are complicated. These reactive gases are adsorbed and desorbed on the chamber walls, depending on the conditions (i.e. humidity). These artefact gas fluxes (chamber blank) must also be quantified and taken into account in the data analysis. Their importance increases when measuring in clean air, where the fluxes are generally small. At near-zero concentrations, the fluxes may not pass the detection limit of the instrumentation, which usually means it is not possible to separate the plant-related fluxes from the chamber blank. The long-term field measurements at the SMEAR II station in Hyytiälä, Southern Finland, have provided valuable insights into O3 and NOx exchange (i.e. Raivonen & al. 2009, Altimir & al. 2006). This project builds up on the expertise and conclusions from these works. The aim of this study was to improve the reliability of the measuring system by checking the role of potential measuring artefact(s). A live shoot, enclosed in a chamber, creates a water vapor in the chamber flux by transpiring. There are also biogenic VOC emissions from the shoot. In principle, these may affect the reactions of O3 and possibly NOx in the chamber. The potential interference of these fluxes created naturally during chamber closure is a main concern. Their effect on the O3 and NOx flux measurements has been tested with field calibrations in 2010-2011. In these calibrations, a controlled water vapor /VOC flux was fed into an empty shoot measurement chamber, and the H2O, CO2, O3 and NOx fluxes created in the chamber were measured. The created water vapor flux pattern

Economics of pollution trading for SO{sub 2} and NOx

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

Dallas Burtraw; David A. Evans; Alan Krupnick

2005-03-15

For years economists have urged policymakers to use market-based approaches such as cap-and-trade programs or emission taxes to control pollution. The sulphur dioxide (SO{sub 2}) allowance market created by Title IV of the 1990 US Clean Air Act Amendments represents the first real test of the wisdom of economists' advice. Subsequent urban and regional applications of NOx emission allowance trading took shape in the 1990s in the United States, culminating in a second large experiment in emission trading in the eastern United States that began in 2003. This paper provides an overview of the economic rationale for emission trading andmore » a description of the major US programs for SO{sub 2} and nitrogen oxides. These programs are evaluated along measures of performance including cost savings, environmental integrity, and incentives for technological innovation. The authors offer lessons for the design of future programs including, most importantly, those reducing carbon dioxide. 128 refs., 1 fig., 1 tab.« less

Synthesis of cationic iridium(I) complexes of water-soluble phosphine ligands, [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3}, and [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} (TPPMS = PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K), TPPTS = P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3})

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

Paterniti, D.P.; Francisco, L.W.; Atwood, J.D.

Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4}more » in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.« less

Current status and future trends of SO2 and NOx pollution during the 12th FYP period in Guiyang city of China

NASA Astrophysics Data System (ADS)

Tian, Hezhong; Qiu, Peipei; Cheng, Ke; Gao, Jiajia; Lu, Long; Liu, Kaiyun; Liu, Xingang

2013-04-01

In order to investigate the future trends of SO2 and NOx pollution in Guiyang city of China, the MM5/CALMET/CALPUFF modeling system is applied to assess the effects of air pollution improvement that would result from reduction targets for SO2 and NOx emissions during the 12th Five-Year Plan (2011-2015). Three scenarios are established for the objective year 2015 based on the reference emissions in base year 2010. Scenario analysis and modeling results show that emissions are projected to increase by 26.5% for SO2 and 138.0% for NOx in 2015 Business-As-Usual (BAU) relative to base year 2010, respectively, which will lead to a substantial worsening tendency of SO2 and NOx pollution. In comparison, both the 2015 Policy Reduction (PR) and 2015 Intensive Policy Reduction (IPR) scenarios would contribute to improve the urban air quality. Under 2015 PR scenario, the maximum annual average concentration of SO2 and NOx will reduce by 54.9% and 31.7%, respectively, relative to the year 2010, with only 2.1% of all individual gridded receptors exceed the national air quality standard limits; while the maximum annual average concentrations of SO2 and NOx can reduce further under 2015 IPR scenario and comply well with standards limits. In view of the technical feasibility and cost-effectiveness, the emission reduction targets set in the 2015 PR scenario are regarded as more reasonable in order to further improve the air quality in Guiyang during the 12th FYP period and a series of comprehensive countermeasures should be effectively implemented.

Oxidation of SO2 by NO2 and O3 on carbon - Implications to tropospheric chemistry

NASA Technical Reports Server (NTRS)

Cofer, W. R., III; Schryer, D. R.; Rogowski, R. S.

1984-01-01

The oxidation of SO2 to sulfate in air at 65 percent relative humidity on carbon particles was investigated gravimetrically in the presence of NO2 and O3. Approximately 1 mg samples of carbon black were exposed to continuously flowing ppbv mixtures of SO2, SO2 + NO2 and SO2 + O3 for prescribed periods of time before desorption into dry N2. Wet chemical analysis of the particles followed desorption. NO2 and O3 were found to have little, if any, effect relative to air on sulfate yields at the concentrations studied.

TRPC3-Nox2 complex mediates doxorubicin-induced myocardial atrophy

PubMed Central

Shimauchi, Tsukasa; Numaga-Tomita, Takuro; Ito, Tomoya; Nishimura, Akiyuki; Matsukane, Ryosuke; Oda, Sayaka; Hoka, Sumio; Ide, Tomomi; Koitabashi, Norimichi; Uchida, Koji; Sumimoto, Hideki; Mori, Yasuo

2017-01-01

Myocardial atrophy is a wasting of cardiac muscle due to hemodynamic unloading. Doxorubicin is a highly effective anticancer agent but also induces myocardial atrophy through a largely unknown mechanism. Here, we demonstrate that inhibiting transient receptor potential canonical 3 (TRPC3) channels abolishes doxorubicin-induced myocardial atrophy in mice. Doxorubicin increased production of ROS in rodent cardiomyocytes through hypoxic stress–mediated upregulation of NADPH oxidase 2 (Nox2), which formed a stable complex with TRPC3. Cardiomyocyte-specific expression of TRPC3 C-terminal minipeptide inhibited TRPC3-Nox2 coupling and suppressed doxorubicin-induced reduction of myocardial cell size and left ventricular (LV) dysfunction, along with its upregulation of Nox2 and oxidative stress, without reducing hypoxic stress. Voluntary exercise, an effective treatment to prevent doxorubicin-induced cardiotoxicity, also downregulated the TRPC3-Nox2 complex and promoted volume load–induced LV compliance, as demonstrated in TRPC3-deficient hearts. These results illustrate the impact of TRPC3 on LV compliance and flexibility and, focusing on the TRPC3-Nox2 complex, provide a strategy for prevention of doxorubicin-induced cardiomyopathy. PMID:28768915

Wetting-induced pulses produced unexpectedly high emissions of N2O and NOx in a desert ecosystem

NASA Astrophysics Data System (ADS)

Eberwein, J. R.; Carey, C.; Aronson, E. L.; Jenerette, D.

2015-12-01

Approximately one third of Earth's land surface is subjected to arid conditions, and aridland soils have the potential for significant feedbacks to global climate change drivers, such as anthropogenic nitrogen deposition. This study examined wetting-induced pulses of N2O and NOx along a nitrogen deposition gradient in the Colorado Desert of southern California. Measurements were made before and following water (to simulate a 2 cm rain event) and nitrogen plus water additions (30 kg NH4NO3 ha-1) at 15 minutes, 12 hours and 24 hours post-wetting. We found nitrogenous fluxes that were substantially higher than expected. N2O fluxes, in particular were remarkably high reaching up to 200 ng N2O-N m-2 s-1, similar to agriculture levels and in the range of peat bog emissions. There was a clear transition between N2O emissions, which peaked 15 minutes after wetting, and NOx emissions, which peaked at the 12 hour timepoint. NOx emissions were also considerable, reaching as high as 350 ng NOx-N m-2 s-1. Both N2O and NOx fluxes responded strongly to water additions, demonstrating a clear wetting-induced pulse response. While N2O was not affected by nitrogen additions, NOx fluxes demonstrated a significant increase with nitrogen plus water over water alone (p=0.016). These results suggest that gaseous nitrogen export, particularly N2O emissions, is a greater form of nitrogen loss in arid systems than is currently assumed. This potential for high nitrogen emissions and the capacity for anthropogenic nitrogen deposition to increase these emissions present serious implications for local air quality and significant soil feedbacks to climate change.

Analysis of Strategies for Multiple Emissions from Electric Power SO2, NOX, CO2, Mercury and RPS

EIA Publications

2001-01-01

At the request of the Subcommittee, the Energy Information Administration prepared an initial report that focused on the impacts of reducing power sector NOx, SO2, and CO2 emissions. The current report extends the earlier analysis to add the impacts of reducing power sector mercury emissions and introducing renewable portfolio standard (RPS) requirements.

Emissions of HC, CO, NOx, CO2, and SO2 from civil aviation in China in 2010

NASA Astrophysics Data System (ADS)

Fan, Weiyi; Sun, Yifei; Zhu, Tianle; Wen, Yi

2012-09-01

Civil aviation in China has developed rapidly in recent years, and the effects of civil aviation emissions on the atmospheric environment should not be neglected. The establishment of emission inventories of atmospheric pollutants from civil aviation contributes to related policy formation and pollution control. According to the 2010's China flight schedules, aircraft/engine combination information and revised emission indices from the International Civil Aviation Organization emission data bank based on meteorological data, the fuel consumption and HC, CO, NOx, CO2, SO2 emissions from domestic flights of civil aviation in China (excluding Taiwan Province) in 2010 are estimated in this paper. The results show that fuel consumption in 2010 on domestic flights in China is 12.12 million tons (metric tons), HC, CO, NOx, CO2 and SO2 emissions are 4600 tons, 39,700 tons, 154,100 tons, 38.21 million tons and 9700 tons, respectively. The fuel consumption and pollutant emissions of China Southern Airline are responsible for the largest national proportion of each, accounting for 27% and 25-28%, respectively.

A study of Pd/SO4/ZrO2/Al2O3 catalysts in n-hexane isomerization

NASA Astrophysics Data System (ADS)

Dzhikiya, O. V.; Smolikov, M. D.; Kazantsev, K. V.; Yablokova, S. S.; Kireeva, T. V.; Paukshtis, E. A.; Gulyaeva, T. I.; Belyi, A. S.

2017-08-01

The effect of palladium concentration in a range from 0.02 to 1.6 wt.% on characteristics of n-hexane isomerization was studied. The (O2-Hchem) titration and O2 chemisorption study revealed that palladium in Pd/SO4/ZrO2/Al2O3 systems adsorbs hydrogen in a ratio H/Pds = 1.13-1.65 at./at. Investigation of the charge state of the metal by IR spectroscopy of adsorbed CO showed the presence of both the metallic (Pd0) and charged palladium species. Pd/SO4/ZrO2/Al2O3 catalysts with charged palladium atoms exhibit high activity and selectivity in n-hexane isomerization.

Polymorphism in Bi2(SO4)3

NASA Astrophysics Data System (ADS)

Subban, Chinmayee V.; Rousse, Gwenaëlle; Courty, Matthieu; Barboux, Philippe; Tarascon, Jean-Marie

2014-12-01

A new polymorph of Bi2(SO4)3 was prepared by reaction of LiBiO2 with H2SO4 and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi2(SO4)3 presents a layered structure made of SO4 sulfate groups and signs of stereochemically active Bi3+ lone pairs. The new Bi2(SO4)3 absorbs water to form Bi2(H2O)2(SO4)2(OH)2 through an intermediate Bi2O(OH)2SO4 phase, and the transition is reversible when heated under vacuum.

40 CFR 75.33 - Standard missing data procedures for SO2, NOX, and flow rate.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 16 2011-07-01 2011-07-01 false Standard missing data procedures for... (CONTINUED) AIR PROGRAMS (CONTINUED) CONTINUOUS EMISSION MONITORING Missing Data Substitution Procedures § 75.33 Standard missing data procedures for SO2, NOX, and flow rate. (a) Following initial certification...

40 CFR 75.33 - Standard missing data procedures for SO2, NOX, and flow rate.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 17 2012-07-01 2012-07-01 false Standard missing data procedures for... (CONTINUED) AIR PROGRAMS (CONTINUED) CONTINUOUS EMISSION MONITORING Missing Data Substitution Procedures § 75.33 Standard missing data procedures for SO2, NOX, and flow rate. (a) Following initial certification...

40 CFR 75.33 - Standard missing data procedures for SO2, NOX, and flow rate.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 17 2013-07-01 2013-07-01 false Standard missing data procedures for... (CONTINUED) AIR PROGRAMS (CONTINUED) CONTINUOUS EMISSION MONITORING Missing Data Substitution Procedures § 75.33 Standard missing data procedures for SO2, NOX, and flow rate. (a) Following initial certification...

40 CFR 75.33 - Standard missing data procedures for SO2, NOX, and flow rate.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 17 2014-07-01 2014-07-01 false Standard missing data procedures for... (CONTINUED) AIR PROGRAMS (CONTINUED) CONTINUOUS EMISSION MONITORING Missing Data Substitution Procedures § 75.33 Standard missing data procedures for SO2, NOX, and flow rate. (a) Following initial certification...

Lightning and anthropogenic NOx sources over the U.S. and the western North Atlantic Ocean: Impact on tropospheric O3 from space-borne observations

NASA Astrophysics Data System (ADS)

Choi, Y.; Eldering, A.; Osterman, G.; Wang, Y.; Cunnold, D.; Yang, Q.; Bucsela, E.; Pickering, K.

2008-12-01

We use the Regional chEmical trAnsport Model (REAM) to analyze the contributions of lightning and anthropogenic NOx on ozone concentrations over the U.S. and the western North Atlantic Ocean from June to August 2005. Tropospheric NO2 columns from OMI, tropospheric O3 columns derived from OMI and MLS measurements, and vertical O3 profiles from TES over the region are used in the analysis. With a 50% reduction in the industrial and electrical power generation NOx emissions in the 23 eastern states over the U.S. from 1999 EPA NEI and a parameterization of lightning-produced NOx based on concurrent NLDN, CAPE, and cloud mass flux data, REAM generally captures the spatial distribution of lightning flash rates and OMI NO2 and OMI-MLS O3 column enhancements with high correlation coefficients (0.6-0.9). The model results show that over the U.S., the contribution of surface NOx emissions to summertime tropospheric O3 declines from 47% to 41% due to the reduced emissions. The contribution of surface NOx emissions becomes similar to that of stratospheric transport over the U.S., with the additional being the dramatic reduction in the relative impact of fossil-fuel NOx emissions over continental outflow regions. In the convective outflow regions over the Gulf of Mexico and the western North Atlantic, the contribution of lightning NOx production on tropospheric O3 in the summer is larger than that of anthropogenic NOx emissions with mean differences of 5% to 25%. The impact of NOx produced by lightning is becoming larger as fossil-fuel combustion NOx emissions decrease. After the onset of the North American monsoon, lightning-derived upper tropospheric O3 enhancements in July and August are shown over the convective outflow regions from REAM simulated and TES measured O3 vertical profiles. This result suggests that TES measurements have a potential to constrain lightning-derived tropospheric O3 enhancements, which may play a critical role in controlling climate.

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.

Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst

USDA-ARS?s Scientific Manuscript database

This paper discusses the potential use of (Fe3O4@SiO2-SO3H) nanoparticle catalyst for the dehydration of glucose into 5-hydroxymethylfurfural (HMF). A magnetically recoverable (Fe3O4@SiO2-SO3H) nanoparticle catalyst was successfully prepared by supporting sulfonic acid groups (SO3H) on the surface o...

Modeling the weekly cycle of NOx and CO emissions and their impacts on O3 in the Los Angeles-South Coast Air Basin during the CalNex 2010 field campaign

NASA Astrophysics Data System (ADS)

Kim, S.-W.; McDonald, B. C.; Baidar, S.; Brown, S. S.; Dube, B.; Ferrare, R. A.; Frost, G. J.; Harley, R. A.; Holloway, J. S.; Lee, H.-J.; McKeen, S. A.; Neuman, J. A.; Nowak, J. B.; Oetjen, H.; Ortega, I.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Scarino, A. J.; Senff, C. J.; Thalman, R.; Trainer, M.; Volkamer, R.; Wagner, N.; Washenfelder, R. A.; Waxman, E.; Young, C. J.

2016-02-01

We developed a new nitrogen oxide (NOx) and carbon monoxide (CO) emission inventory for the Los Angeles-South Coast Air Basin (SoCAB) expanding the Fuel-based Inventory for motor-Vehicle Emissions and applied it in regional chemical transport modeling focused on the California Nexus of Air Quality and Climate Change (CalNex) 2010 field campaign. The weekday NOx emission over the SoCAB in 2010 is 620 t d-1, while the weekend emission is 410 t d-1. The NOx emission decrease on weekends is caused by reduced diesel truck activities. Weekday and weekend CO emissions over this region are similar: 2340 and 2180 t d-1, respectively. Previous studies reported large discrepancies between the airborne observations of NOx and CO mixing ratios and the model simulations for CalNex based on the available bottom-up emission inventories. Utilizing the newly developed emission inventory in this study, the simulated NOx and CO mixing ratios agree with the observations from the airborne and the ground-based in situ and remote sensing instruments during the field study. The simulations also reproduce the weekly cycles of these chemical species. Both the observations and the model simulations indicate that decreased NOx on weekends leads to enhanced photochemistry and increase of O3 and Ox (=O3 + NO2) in the basin. The emission inventory developed in this study can be extended to different years and other urban regions in the U.S. to study the long-term trends in O3 and its precursors with regional chemical transport models.

ROS-induced ROS release orchestrated by Nox4, Nox2, and mitochondria in VEGF signaling and angiogenesis.

PubMed

Kim, Young-Mee; Kim, Seok-Jo; Tatsunami, Ryosuke; Yamamura, Hisao; Fukai, Tohru; Ushio-Fukai, Masuko

2017-06-01

Reactive oxygen species (ROS) derived from NADPH oxidase (NOX) and mitochondria play a critical role in growth factor-induced switch from a quiescent to an angiogenic phenotype in endothelial cells (ECs). However, how highly diffusible ROS produced from different sources can coordinate to stimulate VEGF signaling and drive the angiogenic process remains unknown. Using the cytosol- and mitochondria-targeted redox-sensitive RoGFP biosensors with real-time imaging, here we show that VEGF stimulation in human ECs rapidly increases cytosolic RoGFP oxidation within 1 min, followed by mitochondrial RoGFP oxidation within 5 min, which continues at least for 60 min. Silencing of Nox4 or Nox2 or overexpression of mitochondria-targeted catalase significantly inhibits VEGF-induced tyrosine phosphorylation of VEGF receptor type 2 (VEGFR2-pY), EC migration and proliferation at the similar extent. Exogenous hydrogen peroxide (H 2 O 2 ) or overexpression of Nox4, which produces H 2 O 2 , increases mitochondrial ROS (mtROS), which is prevented by Nox2 siRNA, suggesting that Nox2 senses Nox4-derived H 2 O 2 to promote mtROS production. Mechanistically, H 2 O 2 increases S36 phosphorylation of p66Shc, a key mtROS regulator, which is inhibited by siNox2, but not by siNox4. Moreover, Nox2 or Nox4 knockdown or overexpression of S36 phosphorylation-defective mutant p66Shc(S36A) inhibits VEGF-induced mtROS, VEGFR2-pY, EC migration, and proliferation. In summary, Nox4-derived H 2 O 2 in part activates Nox2 to increase mtROS via pSer36-p66Shc, thereby enhancing VEGFR2 signaling and angiogenesis in ECs. This may represent a novel feed-forward mechanism of ROS-induced ROS release orchestrated by the Nox4/Nox2/pSer36-p66Shc/mtROS axis, which drives sustained activation of angiogenesis signaling program. Copyright © 2017 the American Physiological Society.

Application of V2O5/WO3/TiO2 for Resistive-Type SO2 Sensors

PubMed Central

Izu, Noriya; Hagen, Gunter; Schönauer, Daniela; Röder-Roith, Ulla; Moos, Ralf

2011-01-01

A study on the application of V2O5/WO3/TiO2 (VWT) as the sensitive material for resistive-type SO2 sensor was conducted, based on the fact that VWT is a well-known catalyst material for good selective catalytic nitrogen oxide reduction with a proven excellent durability in exhaust gases. The sensors fabricated in this study are planar ones with interdigitated electrodes of Au or Pt. The vanadium content of the utilized VWT is 1.5 or 3.0 wt%. The resistance of VWT decreases with an increasing SO2 concentration in the range from 20 ppm to 5,000 ppm. The best sensor response to SO2 occurs at 400 °C using Au electrodes. The sensor response value is independent on the amount of added vanadium but dependent on the electrode materials at 400 °C. These results are discussed and a sensing mechanism is discussed. PMID:22163780

Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

USGS Publications Warehouse

Majzlan, J.; Navrotsky, A.; McCleskey, R. Blaine; Alpers, Charles N.

2006-01-01

Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

Effect of H2O on the morphological changes of KNO3 formed on K2O/Al2O3 NOx storage materials: Fourier transform infra-red (FTIR) and time-resolved x-ray diffraction (TR-XRD) studies

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

Based on combined FTIR and XRD studies, we report here that H2O induces a morphological change of KNO3 species formed on model K2O/Al2O3 NOx storage-reduction catalysts. Specifically as evidenced by FTIR, the contact of H2O with NO2 pre-adsorbed on K2O/Al2O3 promotes the transformation from bidentate (surface-like) KNO3 species to ionic (bulk-like) ones irrespective of K loadings. Once H2O is removed from the sample, a reversible transformation into bidentate KNO3 is observed, demonstrating a significant dependence of H2O on such morphological changes. TR-XRD results show the formation of two different types of bulk KNO3 phases (orthorhomobic and rhombohedral) in an as-impregnatedmore » sample. Once H2O begins to desorb above 400 K, the former is transformed into the latter, resulting in the existence of only the rhombohedral KNO3 phase. On the basis of consistent FTIR and TR-XRD results, we propose a model for the morphological changes of KNO3 species with respect to NO2 adsorption/desorption, H2O and/or heat treatments. Compared with the BaO/Al2O3 system, K2O/Al2O3 shows some similarities with respect to the formation of bulk nitrates upon H2O contact. However, there are significant differences that originate from the lower melting temperature of KNO3 relative to Ba(NO3)2.« less

A Comparative Study of N2O Formation during the Selective Catalytic Reduction of NOx with NH3 on Zeolite Supported Cu Catalysts

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

Chen, Hai-Ying; Wei, Zhehao; Kollar, Marton

A comparative study was carried out on a small-pore CHA.Cu and a large-pore BEA.Cu zeolite catalyst to understand the lower N2O formation on small-pore zeolite supported Cu catalysts in the selective catalytic reduction (SCR) of NOx with NH3. On both catalysts, the N2O yield increases with an increase in the NO2/NOx ratios of the feed gas, suggesting N2O formation via the decomposition of NH4NO3. Temperature-programmed desorption experiments reveal that NH4NO3 is more stable on CHA.Cu than on BEA.Cu. In situ FTIR spectra following stepwise (NO2 + O2) and (15NO + NH3 + O2) adsorption and reaction, and product distribution analysismore » using isotope-labelled reactants, unambiguously prove that surface nitrate groups are essential for the formation of NH4NO3. Furthermore, CHA.Cu is shown to be considerably less active than BEA.Cu in catalyzing NO oxidation and the subsequent formation of surface nitrate groups. Both factors, i.e., (1) the higher thermal stability of NH4NO3 on CHA.Cu, and (2) the lower activity for this catalyst to catalyze NO oxidation and the subsequent formation of surface nitrates, likely contribute to the higher SCR selectivity with less N2O formation on this catalyst as compared to BEA.Cu. The latter is determined as the primary reason since surface nitrates are the source that leads to the formation of NH4NO3 on the catalysts.« less

Pilot-scale evaluation of a novel TiO2-supported V2O5 catalyst for DeNOx at low temperatures at a waste incinerator.

PubMed

Jung, Hyounduk; Park, Eunseuk; Kim, Minsu; Jurng, Jongsoo

2017-03-01

The removal of NOx by catalytic technology at low temperatures is significant for treatment of flue gas in waste incineration plants, especially at temperatures below 200°C. A novel highly active TiO 2 -supported vanadium oxide catalyst at low temperatures (200-250°C) has been developed for the selective catalytic reduction (SCR) de-NOx process with ammonia. The catalyst was evaluated in a pilot-scale equipment, and the results were compared with those obtained in our previous work using laboratory scale (small volume test) equipment as well as bench-scale laboratory equipment. In the present work, we have performed our experiments in pilot scale equipment using a part of effluent flue gas that was obtained from flue gas cleaning equipment in a full-scale waste incineration plant in South Korea. Based on our previous work, we have prepared a TiO 2 -supported V 2 O 5 catalyst coated (with a loading of 7wt% of impregnated V 2 O 5 ) on a honeycomb cordierite monolith to remove NOx from a waste incinerator flue gas at low temperatures. The NOx (nitrogen oxides) removal efficiency of the SCR catalyst bed was measured in a catalyst fixed-bed reactor (flow rate: 100m 3 h -1 ) using real exhaust gas from the waste incinerator. The experimental results showed that the V 2 O 5 /TiO 2 SCR catalyst exhibited good DeNOx performance (over 98% conversion at an operating temperature of 300°C, 95% at 250°C, and 70% at 200°C), and was much better than the performance of commercial SCR catalysts (as low as 55% conversion at 250°C) under the same operating conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

The promotional role of Ni in FeVO4/TiO2 monolith catalyst for selective catalytic reduction of NOx with NH3

NASA Astrophysics Data System (ADS)

Wu, Ganxue; Feng, Xi; Zhang, Hailong; Zhang, Yanhua; Wang, Jianli; Chen, Yaoqiang; Dan, Yi

2018-01-01

The promotional effect of nickel additive on the catalytic performance of the representative FeVO4/TiO2 for NH3-SCR reaction is systematically studied for the first time in the present work. The experimental results showed that NOx conversion at low temperature and N2 selectivity could be significantly improved by Ni doping and 0.4Ni-FeV-Ti exhibited the highest NOx removal efficiency. Analysis by XRD, SEM/HR-TEM, Raman, TPD, DRIFTS, TPR and XPS showed that nickel doping effectively promoted the interaction of FeVO4 nanoparticles with TiO2, consequently resulting in an enhanced acidity property, improved redox activity and giving rise to the formation of the surface oxygen vacancies and defect sites.

Permutation-symmetric three-particle hyper-spherical harmonics based on the S3 ⊗ SO(3)rot ⊂ O(2)⊗SO(3)rot ⊂ U(3)⋊S2 ⊂ O(6) subgroup chain

NASA Astrophysics Data System (ADS)

Salom, Igor; Dmitrašinović, V.

2017-07-01

We construct the three-body permutation symmetric hyperspherical harmonics to be used in the non-relativistic three-body Schrödinger equation in three spatial dimensions (3D). We label the state vectors according to the S3 ⊗ SO(3)rot ⊂ O (2) ⊗ SO(3)rot ⊂ U (3) ⋊S2 ⊂ O (6) subgroup chain, where S3 is the three-body permutation group and S2 is its two element subgroup containing transposition of first two particles, O (2) is the ;democracy transformation;, or ;kinematic rotation; group for three particles; SO(3)rot is the 3D rotation group, and U (3) , O (6) are the usual Lie groups. We discuss the good quantum numbers implied by the above chain of algebras, as well as their relation to the S3 permutation properties of the harmonics, particularly in view of the SO(3)rot ⊂ SU (3) degeneracy. We provide a definite, practically implementable algorithm for the calculation of harmonics with arbitrary finite integer values of the hyper angular momentum K, and show an explicit example of this construction in a specific case with degeneracy, as well as tables of K ≤ 6 harmonics. All harmonics are expressed as homogeneous polynomials in the Jacobi vectors (λ , ρ) with coefficients given as algebraic numbers unless the ;operator method; is chosen for the lifting of the SO(3)rot ⊂ SU (3) multiplicity and the dimension of the degenerate subspace is greater than four - in which case one must resort to numerical diagonalization; the latter condition is not met by any K ≤ 15 harmonic, or by any L ≤ 7 harmonic with arbitrary K. We also calculate a certain type of matrix elements (the Gaunt integrals of products of three harmonics) in two ways: 1) by explicit evaluation of integrals and 2) by reduction to known SU (3) Clebsch-Gordan coefficients. In this way we complete the calculation of the ingredients sufficient for the solution to the quantum-mechanical three-body bound state problem.

40 CFR 75.33 - Standard missing data procedures for SO2, NOX, Hg, and flow rate.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 16 2010-07-01 2010-07-01 false Standard missing data procedures for... AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) CONTINUOUS EMISSION MONITORING Missing Data Substitution Procedures § 75.33 Standard missing data procedures for SO2, NOX, Hg, and flow rate. (a) Following initial...

RETROFIT COSTS FOR SO2 AND NOX CONTROL OPTIONS AT 200 COAL-FIRED PLANTS, VOLUME I - INTRODUCTION AND METHODOLOGY

EPA Science Inventory

The report gives results of a study, the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 and NOx controls at 200 large SO2-emitting coal-fired utility plants. To accomplish the object...

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

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

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

Evaluation of the solubility constants of the hydrated solid phases in the H2O-Al2O3-SO3 ternary system

NASA Astrophysics Data System (ADS)

Teyssier, A.; Lagneau, V.; Schmitt, J. M.; Counioux, J. J.; Goutaudier, C.

2017-04-01

During the acid processing of aluminosilicate ores, the precipitation of a solid phase principally consisting of hydrated aluminium hydroxysulfates may be observed. The experimental study of the H2O-Al2O3-SO3 ternary system at 25 ∘C and 101 kPa enabled to describe the solid-liquid equilibra and to identify the nature, the composition and the solubility of the solid phases which may form during the acid leaching. To predict the appearance of these aluminium hydroxysulfates in more complex systems, their solubility constants were calculated by modelling the experimental solubility results, using a geochemical reaction modelling software, CHESS. A model for non-ideality correction, based on the B-dot equation, was used as it was suitable for the considered ion concentration range. The solubility constants of three out of four solid phases were calculated: 104.08 for jurbanite (Al(SO4)(OH).5H2O), 1028.09 for the solid T (Al8(SO4)5(OH)14.34H2O) and 1027.28 for the solid V (Al10(SO4)3(OH)24.20H2O). However the activity correction model was not suitable to determine the solubility constant of alunogen (Al2(SO4)3.15.8H2O), as the ion concentrations of the mixtures were too high and beyond the allowable limits of the model. Another ionic activity correction model, based on the Pitzer equation for example, must be applied to calculate the solubility constant of alunogen.

CARBON NANOTUBES AND NANO-Ce-Zr OXIDES SUPPORTED H3PW12O40 FOR EFFECTIVE ADSORPTION-DECOMPOSITION OF NOx

NASA Astrophysics Data System (ADS)

Cheng, Lin; Wang, Rui

2012-01-01

Surface-modified carbon nanotubes (CNTs) and nano-Ce-Zr mixed oxides (CZO) were prepared and employed initially as supports of H3PW12O40 (HPW) for NOx adsorption-decomposition. Both CNTs and nano-CZO are favorable supports for HPW. After loading with HPW, the NOx adsorption efficiency increases, especially for HPW/CZO in which the highest adsorption efficiency can achieve 98% at the HPW loading of 70%, much higher than that of single HPW. NOx adsorption efficiency can be influenced considerably by catalyst preparing conditions, in particularly, ethyl alcohol is superior to water as solvent for HPW loading onto CNTs; the -OH containing CNTs shows better promotion effect on the adsorption of NOx than that containing -COOH when using absolute ethyl alcohol as solvent; mechanical grinding method is superior to incipient impregnation method in loading HPW onto the support of CZO. For both catalysts of HPW/CNTs and HPW/CZO, with the increase of HPW loading, the NOx adsorption efficiency tends to reach a peak value before dropping down. Heated from 150°C to 450°C at a rate of 50°C/min, the adsorbed NO was found to decompose into N2, O2 and N2O, and yields of N2 being 21.8% and 27.3%, respectively for HPW/CNTs and HPW/CZO were obtained.

40 CFR 97.288 - CAIR SO2 allowance allocations to CAIR SO2 opt-in units.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false CAIR SO2 allowance allocations to CAIR SO2 opt-in units. 97.288 Section 97.288 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS...

40 CFR 96.288 - CAIR SO2 allowance allocations to CAIR SO2 opt-in units.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false CAIR SO2 allowance allocations to CAIR SO2 opt-in units. 96.288 Section 96.288 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR...

Heterogeneous oxidation of SO2 by O3-aged black carbon and its dithiothreitol oxidative potential.

PubMed

Xu, Weiwei; Li, Qian; Shang, Jing; Liu, Jia; Feng, Xiang; Zhu, Tong

2015-10-01

Ozone (O3) is an important atmospheric oxidant. Black carbon (BC) particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere, leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Combined with ion chromatography (IC), DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2. Relative humidity or 254nm UV (ultraviolet) light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol (DTT) assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites. Copyright © 2015. Published by Elsevier B.V.

Reactions of NO2 with BaO/Pt(111) Model Catalysts: The Effects of BaO Film Thickness and NO2 Pressure on the Formation of Ba(NOx)2 Species

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

Mudiyanselage, Kumudu; Yi, Cheol-Woo; Szanyi, Janos

2011-05-31

The adsorption and reaction of NO2 on BaO (<1, ~3, and >20 monolayer equivalent (MLE))/Pt(111) model systems were studied with temperature programmed desorption (TPD), X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRAS) under ultra-high vacuum (UHV) as well as elevated pressure conditions. NO2 reacts with sub-monolayer BaO (<1 MLE) to form nitrites only, whereas the reaction of NO2 with BaO (~3 MLE)/Pt(111) produces mainly nitrites and a small amount of nitrates under UHV conditions (PNO2 ~ 1.0 × 10-9 Torr) at 300 K. In contrast, a thick BaO(>20 MLE) layer on Pt(111) reacts with NO2 to form nitrite-nitratemore » ion pairs under the same conditions. At elevated NO2 pressures (≥ 1.0 × 10-5 Torr), however, BaO layers at all these three coverages convert to amorphous barium nitrates at 300 K. Upon annealing to 500 K, these amorphous barium nitrate layers transform into crystalline phases. The thermal decomposition of the thus-formed Ba(NOx)2 species is also influenced by the coverage of BaO on the Pt(111) substrate: at low BaO coverages, these species decompose at significantly lower temperatures in comparison with those formed on thick BaO films due to the presence of Ba(NOx)2/Pt interface where the decomposition can proceed at lower temperatures. However, the thermal decomposition of the thick Ba(NO3)2 films follows that of bulk nitrates. Results obtained from these BaO/Pt(111) model systems under UHV and elevated pressure conditions clearly demonstrate that both the BaO film thickness and the applied NO2 pressure are critical in the Ba(NOx)2 formation and subsequent thermal decomposition processes.« less

Ce-Sn binary oxide catalyst for the selective catalytic reduction of NOx by NH3

NASA Astrophysics Data System (ADS)

Liu, Zhiming; Feng, Xu; Zhou, Zizheng; Feng, Yongjun; Li, Junhua

2018-01-01

Ce-Sn binary oxide catalysts prepared by the hydrothermal method have been investigated for the selective catalytic reduction (SCR) of NOx with NH3. Compared with pure CeO2 and SnO2, Ce-Sn binary oxide catalyst showed significantly higher NH3-SCR activity. Moreover, Ce-Sn catalyst showed high resistance against H2O and SO2. The high catalytic performance of Ce-Sn binary oxide is attributed to the synergetic effect between Ce and Sn species, which not only enhances the redox property of the catalyst but also increases the Lewis acidity, thus promoting the adsorption and activation of NH3 species, which contributes to improving the NH3-SCR performance.

Photocatalytic degradation of NOx in a pilot street canyon configuration using TiO2-mortar panels.

PubMed

Maggos, Th; Plassais, A; Bartzis, J G; Vasilakos, Ch; Moussiopoulos, N; Bonafous, L

2008-01-01

Titanium dioxide is the most important photocatalysts used for purifying applications. If a TiO2- containing material is left outdoors as a form of flat panels, it is activated by sunlight to remove harmful NOx gases during the day. The photocatalytic efficiency of a TiO2-treated mortar for removal of NOx was investigated in the frame of this work. For this purpose a fully equipped monitoring system was designed at a pilot site. This system allows the in situ evaluation of the de-polluting properties of a photocatalytic material by taking into account the climatologic phenomena in street canyons, accurate measurements of pollution level and full registration of meteorological data The pilot site involved three artificial canyon streets, a pollution source, continuous NOx measurements inside the canyons and the source as well as background and meteorological measurements. Significant differences on the NOx concentration level were observed between the TiO2 treated and the reference canyon. NOx values in TiO2 canyon were 36.7 to 82.0% lower than the ones observed in the reference one. Data arising from this study could be used to assess the impact of the photocatalytic material on the purification of the urban environment.

Effect of reductive treatments on Pt behavior and NOx storage in lean NOx trap catalysts

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

Wang, Xianqin; Kim, Do Heui; Kwak, Ja Hun

2011-10-01

Lean NOx trap (LNT) catalysts represent a promising approach to meet increasingly stringent NOx emission regulations on diesel and other lean-burn engines. Pt material properties, including dispersion and particle size, are known to be important factors in determining NOx uptake performance, since Pt provides active sites for NO oxidation to NO2 necessary for storing NOx as nitrates, and for the reduction of nitrates to N2. In this work, the physicochemical properties of Pt in Pt-BaO/Al2O3 LNT catalysts, such as the Pt accessible surface area and particle size, were investigated by using various tools, such as irreversible volumetric H2 chemisorption, highmore » resolution transmission electron microscopy (HRTEM), and X-ray diffraction (XRD), following successive reductive treatments at elevated temperatures. NOx uptake activities were also measured to establish a relationship between the properties of Pt and NOx storage following identical high-temperature reductive treatments. We find that the reductive treatments of Pt-BaO/Al2O3 lean NOx trap catalysts at temperatures up to 500 ºC promote a significant increase in NOx uptake explained, in part, by an induced close interaction between Pt and BaO phases in the catalyst, thus enabling facilitation of the NOx storage process.« less

Fluidized combustion of coal. [to limit SO2 and NOx emissions

NASA Technical Reports Server (NTRS)

Pope, M.

1978-01-01

A combustion technology that permits the burning of low quality coal, and other fuels, while maintaining stack emissions within State and Federal EPA limits is discussed. Low quality fuels can be burned directly in fluidized beds while taking advantage of low furnace temperatures and chemical activity within the bed to limit SO2 and NOx emissions. The excellent heat transfer characteristics of the fluidized beds also result in a reduction of total heat transfer surface requirements. Tests on beds operating at pressures of one to ten atmospheres, at temperatures as high as 1600 F, and with gas velocities in the vicinity of four to twelve feet per second, have proven the concept. The progress that has been made in the development of fluidized bed combustion technology and work currently underway are discussed.

Promotional effect of Al2O3 on WO3/CeO2-ZrO2 monolithic catalyst for selective catalytic reduction of nitrogen oxides with ammonia after hydrothermal aging treatment

NASA Astrophysics Data System (ADS)

Xu, Haidi; Liu, Shuang; Wang, Yun; Lin, Qingjin; Lin, Chenlu; Lan, Li; Wang, Qin; Chen, Yaoqiang

2018-01-01

Hydrothermal stability of catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) has always been recognized as a challenge in development of candidate catalysts for applications in diesel engine emissions. In this study, Al2O3 was introduced into CeO2-ZrO2 to improve the NH3-SCR activity of WO3/CeO2-ZrO2 after hydrothermal aging (HA) treatment at 800 °C for 12 h. The activity results indicated that the NH3-SCR activity of WO3/CeO2-ZrO2-HA was obviously improved in the whole reaction temperature range after doping Al2O3 into CeO2-ZrO2, for example, the average and maximum NOx conversion were separately increased by ca. 20% and 25% after HA treatment. XRD, Raman, TEM and EDX results revealed that the introduction of Al2O3 inhibited the sintering and agglomeration of CeO2-ZrO2 and WO3 and the formation of Ce2(WO4)3 after HA treatment. Accordingly, WO3/CeO2-ZrO2-Al2O3-HA showed remarkably improved structural stability and reducibility, increased surface acidity, and facilitated the reactivity between adsorbed NH3 and nitrate species, which together contributed to its better catalytic performance after hydrothermal aging treatment.

Processes of Molecular Relaxation in Binary Crystalline Systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4

NASA Astrophysics Data System (ADS)

Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Rabadanov, K. Sh.; Amirov, A. M.

2018-03-01

The processes of molecular relaxation in binary crystalline systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 are studied via differential thermal analysis and Raman spectroscopy. It is found that the relaxation time of the vibrations ν1( A) of anions NO- 3 and CO2- 3 in systems KNO3-KClO4, KNO3-KNO2, and K2CO3-K2SO4 is less than that in KNO3 and K2CO3, respectively. It is shown that the increased rate of relaxation is explained by an additional relaxation mechanism presented in the system. This mechanism is associated with the excitation of vibrations of anions ClO- 4, NO- 2, and SO2- 4 and the lattice phonons that emerge. It is found that this relaxation mechanism requires correspondence of the frequency difference of these vibrations to the region of sufficiently high density of states of the phonon spectrum.

Dry deposition of O3 and SO2 estimated from gradient measurements above a temperate mixed forest.

PubMed

Wu, Zhiyong; Staebler, Ralf; Vet, Robert; Zhang, Leiming

2016-03-01

Vertical profiles of O3 and SO2 concentrations were monitored at the Borden Forest site in southern Ontario, Canada from May 2008 to April 2013. A modified gradient method (MGM) was applied to estimate O3 and SO2 dry deposition fluxes using concentration gradients between a level above and a level below the canopy top. The calculated five-year mean (median) dry deposition velocity (Vd) were 0.35 (0.27) and 0.59 (0.54) cm s(-1), respectively, for O3 and SO2. Vd(O3) exhibited large seasonal variations with the highest monthly mean of 0.68 cm s(-1) in August and the lowest of 0.09 cm s(-1) in February. In contrast, seasonal variations of Vd(SO2) were smaller with monthly means ranging from 0.48 (May) to 0.81 cm s(-1) (December). The different seasonal variations between O3 and SO2 were caused by the enhanced SO2 uptake by snow surfaces in winter. Diurnal variations showed a peak value of Vd in early morning in summer months for both O3 and SO2. Canopy wetness increased the non-stomatal uptake of O3 while decreasing the stomatal uptake. This also applied to SO2, but additional factors such as surface acidity also played an important role on the overall uptake. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Influence of Water on the H2SO4 Yield from the Ozonolysis of 2,3-dimethyl-butene (TME) in Presence of SO2

NASA Astrophysics Data System (ADS)

Véronique, D.; Kukui, A.; Chen, H.; Mellouki, A.

2016-12-01

The influence of the water vapor content on the yield of H2SO4 from the ozonolysis of 2,3-dimethyl-butene (TME) in presence of SO2 was studied using laminar flow reactor coupled with Chemical Ionisation Mass Spectrometer (CIMS) for the H2SO4 monitoring within the range of H2O from 10 ppmv to 3×104 ppmv at different concentrations of TME, O3, SO2. The observed dependences of the H2SO4 yield on H2O concentration can be interpreted by assuming two different paths of the H2SO4 formation: 1) via the formation of SO3 in the reaction of Stabilized Criegee Intermediate (SCI) with SO2 (2a) followed by the reaction of SO3 with H2O (3) and 2) via the formation of stabilized secondary ozonide (SOZ) (2b) producing H2SO4 in the reaction with H2O (4a) in competition with the SOZ decomposition to other products (5): O3+TME => (CH3)2COO (1) (CH3)2COO + SO2 => SO3 (2a) => SOZ (2b) SO3 + H2O => H2SO4 (3) SOZ + H2O => H2SO4 (or SO3) (4a) SOZ + M => products (5) The yield of the SCI, SOZ and the rates of the SCI and SOZ decomposition relative to their reactions with SO2 and H2O, respectively, were estimated from the dependencies of the H2SO4 yield on the concentrations of the reactants.

High-level ab initio studies of NO(X2Π)-O2(X3Σg -) van der Waals complexes in quartet states

NASA Astrophysics Data System (ADS)

Grein, Friedrich

2018-05-01

Geometry optimisations were performed on nine different structures of NO(X2Π)-O2(X3Σg-) van der Waals complexes in their quartet states, using the explicitly correlated RCCSD(T)-F12b method with basis sets up to the cc-pVQZ-F12 level. For the most stable configurations, counterpoise-corrected optimisations as well as extrapolations to the complete basis set (CBS) were performed. The X structure in the 4A‧ state was found to be most stable, with a CBS binding energy of -157 cm-1. The slipped tilted structures with N closer to O2 (Slipt-N), as well as the slipped parallel structure with O of NO closer to O2 (Slipp-O) in 4A″ states have binding energies of about -130 cm-1. C2v and linear complexes are less stable. According to calculated harmonic frequencies, the X isomer is bound. Isotropic hyperfine coupling constants of the complex are compared with those of the monomers.

Preparation of highly active manganese oxides supported on functionalized MWNTs for low temperature NOx reduction with NH3

NASA Astrophysics Data System (ADS)

Pourkhalil, Mahnaz; Moghaddam, Abdolsamad Zarringhalam; Rashidi, Alimorad; Towfighi, Jafar; Mortazavi, Yadollah

2013-08-01

Manganese oxide catalysts (MnOx) supported on functionalized multi-walled carbon nanotubes (FMWNTs) for low temperature selective catalytic reduction (LTSCR) of nitrogen oxides (NOx) with NH3 in the presence of excess O2 were prepared by the incipient wetness impregnation method. These catalysts were characterized by N2 adsorption, Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermal gravimetric analysis (TGA) and H2-temperature programmed reduction (H2-TPR) methods. The effects of reaction temperature, MnOx loading, calcination temperature and calcination time were investigated. The presence of surface nitrate species under moderate calcination conditions may play a favorable role in the LTSCR of NOx with NH3. Under the reaction conditions of 200 °C, 1 bar, NO = NH3 = 900 ppm, O2 = 5 vol%, GHSV = 30,000 h-1 and 12 wt% MnOx, NOx conversion and N2 selectivity were 97% and 99.5%, respectively. The SCR activity was reduced in the presence of 100 ppm SO2 and 2.5 vol% H2O from 97% to 92% within 6 h at 200 °C, however such an effect was shown to be reversible by exposing the catalyst to a helium flow for 2 h at 350 °C due to thermal decomposition of ammonium sulphate salts.

NOx Lifetime During WINTER

NASA Astrophysics Data System (ADS)

Kenagy, H. S.; Sparks, T.; Ebben, C. J.; Wooldridge, P. J.; Lopez-Hilfiker, F.; Lee, B. H.; Thornton, J. A.; McDuffie, E. E.; Fibiger, D. L.; Brown, S. S.; Montzka, D. D.; Weinheimer, A. J.; Apel, E. C.; Jaegle, L.; Cohen, R. C.

2017-12-01

The study of the lifetime and fate of NOx (=NO + NO2) is important for understanding its persistence and distribution. This requires an understanding of the balance of NOx sinks. Although urban NOx lifetimes are relatively well understood during summertime conditions, wintertime NOx chemistry has been comparatively less studied. We used measurements of NOx and its oxidation products from the aircraft-based WINTER (Wintertime INvestigation of Transport, Emissions, and Reactivity) campaign over the northeastern US during February-March 2015 to help constrain NOx lifetime during wintertime conditions when days are shorter, actinic flux is reduced, and temperatures are colder. By analyzing the marine outflow from the NYC-DC corridor, we learn that wintertime NOx has a long lifetime, is much longer-lived during the day than at night, and its lifetime is controlled during both periods by NOx conversion to nitric acid (HNO3) as the primary NOx sink. We also employ a two-box model to constrain the wintertime plume dilution rate and HNO3 deposition rate. Additionally, analysis of the nighttime Ox budget suggests that approximately 10% of O3 is lost overnight through N2O5 dark reactions that produce HNO3.

Sulfate Formation Enhanced by a Cocktail of High NOx, SO2, Particulate Matter, and Droplet pH during Haze-Fog Events in Megacities in China: An Observation-Based Modeling Investigation.

PubMed

Xue, Jian; Yuan, Zibing; Griffith, Stephen M; Yu, Xin; Lau, Alexis K H; Yu, Jian Zhen

2016-07-19

In recent years in a few Chinese megacities, fog events lasting one to a few days have been frequently associated with high levels of aerosol loading characterized by high sulfate (as high as 30 μg m(-3)), therefore termed as haze-fog events. The concomitant pollution characteristics include high gas-phase mixing ratios of SO2 (up to 71 ppbv) and NO2 (up to 69 ppbv), high aqueous phase pH (5-6), and smaller fog droplets (as low as 2 μm), resulting from intense emissions from fossil fuel combustion and construction activities supplying abundant Ca(2+). In this work, we use an observation-based model for secondary inorganic aerosols (OBM-SIA) to simulate sulfate formation pathways under conditions of haze-fog events encountered in Chinese megacities. The OBM analysis has identified, at a typical haze-fogwater pH of 5.6, the most important pathway to be oxidation of S(IV) by dissolved NO2, followed by the heterogeneous reaction of SO2 on the aerosol surface. The aqueous phase oxidation of S(IV) by H2O2 is a very minor formation pathway as a result of the high NOx conditions suppressing H2O2 formation. The model results indicate that the unique cocktail of high fogwater pH, high concentrations of NO2, SO2, and PM, and small fog droplets are capable of greatly enhancing sulfate formation. Such haze-fog conditions could lead to rapid sulfate production at night and subsequently high PM2.5 in the morning when the fog evaporates. Sulfate formation is simulated to be highly sensitive to fogwater pH, PM, and precursor gases NO2 and SO2. Such insights on major contributing factors imply that reduction of road dust and NOx emissions could lessen PM2.5 loadings in Chinese megacities during fog events.

Mortality and Morbidity Due to Exposure to Ambient NO2, SO2, and O3 in Isfahan in 2013-2014.

PubMed

Abdolahnejad, Ali; Jafari, Negar; Mohammadi, Amir; Miri, Mohammad; Hajizadeh, Yaghoub

2018-01-01

The presence of air pollutants such as CO, NO 2 , SO 2 , O 3 , and PM in the ambient air mainly emitted from fossil fuels combustion has become a major health concern. The aims of this study were to estimate the attribution of NO 2 , SO 2 , and O 3 in the premature deaths and prevalence of cardiovascular and respiratory diseases in Isfahan in 2013-2014. In this study, short-term health effects (total mortality, cardiovascular and respiratory mortality, chronic obstructive pulmonary disease, and acute myocardial infarction) of exposure NO 2 , SO 2 , and O 3 on the population of Isfahan were assessed using AirQ 2.2.3 software suggested by the World Health Organization (WHO). The result showed that from nonaccident total mortality in 2013-2014 in Isfahan, the attributable proportion related to NO 2 , SO 2 , and O 3 were 1.03% (109 cases), 3.46% (365 cases), and 1.29% (136 cases), respectively. The percentage of days that people were exposed to the highest concentration of NO 2 (40-49 μg/m 3 ), SO 2 (60-69 μg/m 3 ), and O 3 (40-49 μg/m 3 ) was 34.46%, 16.85%, and 42.74% of a year, respectively. Total mortality attributed to NO 2 , SO 2 , and O 3 exposure was 0.36%, 0.79%, and 0.83%, respectively. The concentrations of NO 2 and SO 2 were upper than the WHO guidelines. The Air-Q software in spite of its limitations can provide useful information regarding the health outcome of the air pollutants. The results estimated in this study were considerable. This information can help the health authorities and policy makers to draw suitable strategies and fulfill effective emission control programs.

Application of banana peels waste as adsorbents for the removal of CO2, NO, NOx, and SO2 gases from motorcycle emissions

NASA Astrophysics Data System (ADS)

Viena, V.; Elvitriana; Wardani, S.

2018-03-01

The aims of the study were to investigate the application of banana peels as adsorbent for the removal of CO, NO, NOx and SO2 gases from motorcycles emissions. The effect of differents thermal activation on the characteristics of banana peels adsorbent (BPA) such as moisture content, ash content, volatile matter and fixed carbon has been studied using proximate analysis. The study of Iodine adsorption capacity of BPA was obtained at 952 mg/g adsorbent. Structure and morphology of BPA were characterized by Fourier transform infrared (FTIR) and field emission scanning electron microscopy (SEM). The results showed that BPA could significantly adsorbed the CO and SO2 gases emissions from motorcycles, but not applicable for NO, NOx gases. After 10 minutes of flue gas analysis at idle mode using BPA adsorption tube, CO gas could be totally removed, from initial 19618 ppm to 0 ppm, while SO2 gas could also be totally removed from 24523 ppm to 0 ppm. SEM test showed that temperature of activation had significant effect on the size of pores of BPA formed. BPA was suitable for application in removing CO and SO2 gases emissions from motorcycles and it helps to reduce the green house gas effects of fossil fuel to the environment.

Magneto-optical investigation of MgSO3·6H2O with polarized light

NASA Astrophysics Data System (ADS)

Petkova, P.

2017-10-01

The crystals of magnesium sulphite hexahydrate (MgSO3·6H2O) belong to point group C3 (no center of symmetry). They possess gyrotropy and nonlinear optical properties. The refractive index no and ne, the angle of Faraday rotation φ(λ), the Verdet constant V(λ), the magneto-optic anomaly factor γ(λ) and the density of oscillators N of MgSO3·6H2O single crystals have been studied in the present work. The investigations were carried out in the spectral range 300 - 800 nm with linear polarized light E ⃗ ⊥ c ̅ , E ⃗ | | c ̅ (c ̅ is the optical axis of MgSO3·6H2O) propagated in the direction (10 1 ̅ 0) .

Mineral dust and NOx promote the conversion of SO2 to sulfate in heavy pollution days

PubMed Central

He, Hong; Wang, Yuesi; Ma, Qingxin; Ma, Jinzhu; Chu, Biwu; Ji, Dongsheng; Tang, Guiqian; Liu, Chang; Zhang, Hongxing; Hao, Jiming

2014-01-01

Haze in China has been increasing in frequency of occurrence as well as the area of the affected region. Here, we report on a new mechanism of haze formation, in which coexistence with NOx can reduce the environmental capacity for SO2, leading to rapid conversion of SO2 to sulfate because NO2 and SO2 have a synergistic effect when they react on the surface of mineral dust. Monitoring data from five severe haze episodes in January of 2013 in the Beijing-Tianjin-Hebei regions agreed very well with the laboratory simulation. The combined air pollution of motor vehicle exhaust and coal-fired flue gases greatly reduced the atmospheric environmental capacity for SO2, and the formation of sulfate was found to be a main reason for the growth of fine particles, which led to the occurrence of haze. These results indicate that the impact of motor vehicle exhaust on the atmospheric environment might be underestimated. PMID:24566871

NoxO1 Controls Proliferation of Colon Epithelial Cells.

PubMed

Moll, Franziska; Walter, Maria; Rezende, Flávia; Helfinger, Valeska; Vasconez, Estefania; De Oliveira, Tiago; Greten, Florian R; Olesch, Catherine; Weigert, Andreas; Radeke, Heinfried H; Schröder, Katrin

2018-01-01

Reactive oxygen species (ROS) produced by enzymes of the NADPH oxidase family serve as second messengers for cellular signaling. Processes such as differentiation and proliferation are regulated by NADPH oxidases. In the intestine, due to the exceedingly fast and constant renewal of the epithelium both processes have to be highly controlled and balanced. Nox1 is the major NADPH oxidase expressed in the gut, and its function is regulated by cytosolic subunits such as NoxO1. We hypothesize that the NoxO1-controlled activity of Nox1 contributes to a proper epithelial homeostasis and renewal in the gut. NoxO1 is highly expressed in the colon. Knockout of NoxO1 reduces the production of superoxide in colon crypts and is not subsidized by an elevated expression of its homolog p47phox. Knockout of NoxO1 increases the proliferative capacity and prevents apoptosis of colon epithelial cells. In mouse models of dextran sulfate sodium (DSS)-induced colitis and azoxymethane/DSS induced colon cancer, NoxO1 has a protective role and may influence the population of natural killer cells. NoxO1 affects colon epithelium homeostasis and prevents inflammation.

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.

Atmospheric isoprene ozonolysis: impacts of stabilised Criegee intermediate reactions with SO2, H2O and dimethyl sulfide

NASA Astrophysics Data System (ADS)

Newland, M. J.; Rickard, A. R.; Vereecken, L.; Muñoz, A.; Ródenas, M.; Bloss, W. J.

2015-08-01

Isoprene is the dominant global biogenic volatile organic compound (VOC) emission. Reactions of isoprene with ozone are known to form stabilised Criegee intermediates (SCIs), which have recently been shown to be potentially important oxidants for SO2 and NO2 in the atmosphere; however the significance of this chemistry for SO2 processing (affecting sulfate aerosol) and NO2 processing (affecting NOx levels) depends critically upon the fate of the SCIs with respect to reaction with water and decomposition. Here, we have investigated the removal of SO2 in the presence of isoprene and ozone, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity, confirming a significant reaction for isoprene-derived SCIs with H2O. Under excess SO2 conditions, the total isoprene ozonolysis SCI yield was calculated to be 0.56 (±0.03). The observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + H2O) / k(SCI + SO2), of 3.1 (±0.5) × 10-5 for isoprene-derived SCIs. The relative rate constant for k(SCI decomposition) / k(SCI+SO2) is 3.0 (±3.2) × 1011 cm-3. Uncertainties are ±2σ and represent combined systematic and precision components. These kinetic parameters are based on the simplification that a single SCI species is formed in isoprene ozonolysis, an approximation which describes the results well across the full range of experimental conditions. Our data indicate that isoprene-derived SCIs are unlikely to make a substantial contribution to gas-phase SO2 oxidation in the troposphere. We also present results from an analogous set of experiments, which show a clear dependence of SO2 removal in the isoprene-ozone system as a function of dimethyl sulfide concentration. We propose that this behaviour arises from a rapid reaction between isoprene-derived SCIs and dimethyl sulfide (DMS); the observed SO2 removal kinetics are consistent with a relative rate constant, k(SCI + DMS

SO2 Adsorption on CeO2(100) and CeO2(111)

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

Mullins, David R.

2016-09-13

The adsorption and reaction of sulfur dioxide, SO2, was studied on oxidized and reduced CeOX(100) and compared to previous results on CeOX(111). SO2 adsorbs on oxidized CeO2(100) as sulfite, SO32-, at 200 K and sulfite is the only adsorbate observed on the surface at any temperature. The sulfite desorbs monotonically from 200 to 700 K. The adsorption and desorption of SO2 does not result in any change in the Ce4+ oxidation state. SO2 also adsorbs as sulfite on reduced CeO1.7(100) at 200 K. There is also a small amount of elemental sulfur, S0, formed. As the sample is heated themore » sulfite decomposes into sulfide, S2-. Roughly 25 % of the adsorbed S either desorbs or diffuses into the bulk of the reduced ceria. The decomposition, and resulting formation of S2- and O2-, re-oxidize some of the Ce3+ to Ce4+. Unlike what has been observed following the adsorption and reaction of many other molecules, the adsorption and reaction of SO2 is virtually identical on CeOX(100) and CeOX(111).« less

High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

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

Gerken, James B.; Stahl, Shannon S.

2015-07-15

Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalystmore » drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Simple analysis of atmospheric NO{sub 2}, SO{sub 2}, and O{sub 3} in mountains by using passive samplers

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

Yamada, Etsu; Kimura, Mitsuo; Tomozawa, Kenichi

1999-12-01

A simple analysis of atmospheric NO{sub 2}, SO{sub 2}, and O{sub 3} in mountains by passive samplers was investigated and applied to the spatial analysis of air pollutants at Mt. Hiei in Kyoto City, Passive samplers were exposed for 30 days. Yanagisawa-type samplers were used for NO{sub 2} determination. The absorbed NO{sub 2} was measured as nitrite ion spectro-photometrically by the Saltzman method. On the other hand, SO{sub 2} samplers comprising an absorbent filter containing sodium carbonate solution were made. The absorbed SO{sub 2} was oxidized to SO{sub 4}{sup 2{minus}} with an H{sub 2}O{sub 2} solution and determined by ionmore » chromatography. For O{sub 3} determination, Ogawa ozone samplers were used. The O{sub 3} reacted with nitrite ion to produce nitrate ion, which was measured by ion chromatography. The relative standard deviations for NO{sub 2}, SO{sub 2}, and O{sub 3} samplers were 1.4%, 3--10%, and 2--5%, respectively. Samplers were set up in 13 locations at Mt. Hiei. The NO{sub 2} concentration and its distribution along the slope of Mt. Hiei changed considerably both daily and seasonally. The seasonal variation of atmospheric NO{sub 2} showed a winter maximum and a summer minimum. The concentration of atmospheric SO{sub 2} at Mt. Hiei was lower than that of NO{sub 2} and scarcely changed. Atmospheric O{sub 3} increased gradually with an increase of the altitude, exhibiting a regular pattern with a maximum in spring and a minimum in winter.« less

Molecular Relaxation in LiNO3-LiClO4 and Li2CO3-Li2SO4 Solid Binary Systems

NASA Astrophysics Data System (ADS)

Aliev, A. R.; Akhmedov, I. R.; Kakagasanov, M. G.; Aliev, Z. A.; Gafurov, M. M.; Amirov, A. M.

2018-06-01

The paper presents spectroscopic combinational scattering investigations of the molecular relaxation in LiNO3-LiClO4 and Li2CO3-Li2SO4 solid binary systems. It is found that the relaxation time for ν1(A) vibrations of NO3 - anion in LiNO3-LiClO4 system is lower than in LiNO3 crystal. And the relaxation time for ν1(A) vibrations of CO3 2- anion in Li2CO3-Li2SO4 system is lower than in Li2CO3 crystal. The increase in the relaxation time is explained by the additional relaxation mechanism of the excited mode of nitrate and carbon ions which is observed in these systems. This mechanism is linked to the vibrations of other anions (ClO4 - or SO4 2-) and a nucleation of the lattice phonon. Experiments show that the additional relaxation mechanism occurs due to the vibration difference which corresponds to the area of rather a high density of states of the phonon spectrum.

Characterization of NOx emission in the suburbs of Tokyo based on simultaneous and real-time observations of atmospheric Ox and NOx

NASA Astrophysics Data System (ADS)

Matsumoto, J.

2013-12-01

Nitrogen oxides, NOx (NO, NO2), and volatile organic compounds, VOCs, are important as precursors of photochemical oxidants (tropospheric ozone, O3). To predict and control photochemical oxidants, NOx emission should be captured precisely. In addition, the ratio of NO2/NOx in the exhaust gas is also important as the initial balance between NO and NO2 in the atmosphere. Monitoring the NO2/NOx ratio in the exhaust gases is essential. Especially, the influence of the NOx emission on the real atmosphere should be explored. However, conversion reactions among NO, NO2 and O3 are typically in the time scale of minutes. The NO2/NOx ratio can change rapidly just after emission. Real-time observations of these compounds in the second time scale are essential. In view of photochemical oxidant, near emission sources of NO, ozone concentration can be easily perturbed by reaction with locally emitted NO. As an index of oxidant, the sum of O3 and NO2 (Ox = O3 + NO2) is useful. In this study, a simultaneous and real-time analyzer of atmospheric Ox and NOx has been developed utilizing the dual NO2 detectors based on laser-induced fluorescence technique (LIF), and characterization of NOx emission was explored through the observations of Ox and NOx in the suburbs of Tokyo. The dual LIF detectors consisted of one laser head, two LIF cells, and one common vacuum pump. As the Ox monitor, the excess NO was added to the sample and O3 was converted to NO2, and then the sum of O3 and NO2 in the sample was quantified at the 1st LIF cell. As the NOx monitor, the excess O3 was added to the sample and NO was converted to NO2, and then the sum of NO and NO2 in the sample was quantified at the 2nd LIF cell. Both the ';Ox' and ';NOx' channels in the dual LIF analyzer were simultaneously monitoring Ox and NOx in the sample air, respectively. The temporal resolution of observed data was 1 s. Typical conversion efficiencies of O3 and NO to NO2 were more than 0.98. The lower detection limits were 0

Effect of K loadings on nitrate formation/decomposition and on NOx storage performance of K-based NOx storage-reduction catalysts

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

Kim, Do Heui; Mudiyanselage, Kumudu K.; Szanyi, Janos

2013-10-25

We have investigated nitrate formation and decomposition processes, and measured NOx storage performance on Pt-K2O/Al2O3 catalysts as a function of potassium loading. After NO2 adsorption at room temperature, ionic and bidentate nitrates were observed by fourier transform infra-red (FTIR) spectroscopy. The ratio of the former to the latter species increased with increasing potassium loading up to 10 wt%, and then stayed almost constant with additional K, demonstrating a clear dependence of loading on the morphology of the K species. Although both K2O(10)/Al2O3 and K2O(20)/Al2O3 samples have similar nitrate species after NO2 adsorption, the latter has more thermally stable nitrate speciesmore » as evidenced by FTIR and NO2 temperature programmed desorption (TPD) results. With regard to NOx storage performance, the temperature of maximum NOx uptake (Tmax) is 573 K up to a potassium loading of 10 wt%. As the potassium loading increases from 10 wt% to 20 wt%, Tmax shifted from 573 K to 723 K. Moreover, the amount of NO uptake (38 cm3 NOx/g catal) at Tmax increased more than three times, indicating that efficiency of K in storing NOx is enhanced significantly at higher temperature, in good agreement with the NO2 TPD and FTIR results. Thus, a combination of characterization and NOx storage performance results demonstrates an unexpected effect of potassium loading on nitrate formation and decomposition processes; results important for developing Pt-K2O/Al2O3 for potential applications as high temperature NOx storage-reduction catalysts.« less

Hilarionite, Fe{2/3+}(SO4)(AsO4)(OH) · 6H2O, a new supergene mineral from Lavrion, Greece

NASA Astrophysics Data System (ADS)

Pekov, I. V.; Chukanov, N. V.; Yapaskurt, V. O.; Rusakov, V. S.; Belakovsky, D. I.; Turchkova, A. G.; Voudouris, P.; Magganas, A.; Katerinopoulos, A.

2014-12-01

A new mineral, hilarionite, ideally Fe{2/3+} (SO4)(AsO4)(OH) · 6H2O, has been found in the Hilarion Mine, Agios Konstantinos, Kamariza, Lavrion district, Attiki Prefecture, Greece. It was formed in the oxidation zone of a sulfide-rich orebody in association with goethite, gypsum, bukovskyite, jarosite, melanterite, chalcanthite, allophane, and azurite. Hilarionite occurs as light green (typically with an olive or grayish tint) to light yellowish green spherulites (up to 1 mm in size) and bunches of prismatic to acicular "individuals" up to 0.5 mm long that are in fact near-parallel or divergent aggregates of very thin, curved fibers up to 0.3 mm long and usually lesser than 2 μm thick. The luster is silky to vitreous. The Mohs' hardness is ca. 2. Hilarionite is ductile, its "individuals" are flexible and inelastic; fracture is uneven or splintery. D(meas) = 2.40(5), D(calc) = 2.486 g/cm3. IR spectrum shows the presence of arsenate and sulfate groups and H2O molecules in significant amounts. The Mössbauer spectrum indicates the presence of Fe3+ at two six-fold coordinated sites and the absence of Fe2+. Hilarionite is optically biaxial (+), α = 1.575(2), γ = 1.64(2), 2 V is large. The chemical composition (electron microprobe, average of 7 point analyses; H2O determined by modified Penfield method) is as follows, wt %: 0.03 MnO, 0.18 CuO, 0.17 ZnO, 33.83 Fe2O3, 0.22 P2O5, 18.92 As2O5, 22.19 SO3, 26.3 H2O, total is 101.82%. The empirical formula calculated on the basis of 15 O is: (Fe{1.90/3+}Cu0.01Zn0.01)Σ1.92[(SO4)1.24(AsO4)0.74(PO4)0.01]Σ1.99(OH)1.01 · 6.03H2O. The X-ray powder diffraction data show close structural relationship of hilarionite and kaňkite, Fe{2/3+}(AsO4)2 · 7H2O. Hilarionite is monoclinic, space group C2/ m, Cm or C2, a = 18.53(4), b = 17.43(3), c = 7.56(1) Å, β = 94.06(15)°, V = 2436(3) Å3, Z = 8. The strongest reflections in the X-ray powder diffraction pattern ( d, Å- I[ hkl]) are: 12.66-100[110], , 5.00-10[22l], , 4

Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

NASA Technical Reports Server (NTRS)

Hwang, S. M.; Cooke, J. A.; De Witt, K. J.; Rabinowitz, M. J.

2010-01-01

Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

What is Eating Ozone? Thermal Reactions between SO2 And O3: Implications for Icy Environments

NASA Technical Reports Server (NTRS)

Loeffler, Mark J.; Hudson, Reggie L.

2016-01-01

Laboratory studies are presented, showing for the first time that thermally driven reactions in solid H2O+SO2+O3 mixtures can occur below 150 K, with the main sulfur-containing product being bisulfate (HSO4(-)). Using a technique not previously applied to the low-temperature kinetics of either interstellar or solar system ice analogs, we estimate an activation energy of 32 kJ per mol for HSO4(-) formation. These results show that at the temperatures of the Jovian satellites, SO2 and O3 will efficiently react making detection of these molecules in the same vicinity unlikely. Our results also explain why O3 has not been detected on Callisto and why the SO2 concentration on Callisto appears to be highest on that world's leading hemisphere. Furthermore, our results predict that the SO2 concentration on Ganymede will be lowest in the trailing hemisphere, where the concentration of O3 is the highest. Our work suggests that thermal reactions in ices play a much more important role in surface and sub-surface chemistry than generally appreciated, possibly explaining the low abundance of sulfur-containing molecules and the lack of ozone observed in comets and interstellar ices.

SO2 and NH3 gas adsorption on a ternary ZnO/CuO/CuCl2 impregnated activated carbon evaluated using combinatorial methods.

PubMed

Romero, Jennifer V; Smith, Jock W H; Sullivan, Braden M; Croll, Lisa M; Dahn, J R

2012-01-09

Ternary libraries of 64 ZnO/CuO/CuCl(2) impregnated activated carbon samples were prepared on untreated or HNO(3)-treated carbon and evaluated for their SO(2) and NH(3) gas adsorption properties gravimetrically using a combinatorial method. CuCl(2) is shown to be a viable substitute for HNO(3) and some compositions of ternary ZnO/CuO/CuCl(2) impregnated carbon samples prepared on untreated carbon provided comparable SO(2) and NH(3) gas removal capacities to the materials prepared on HNO(3)-treated carbon. Through combinatorial methods, it was determined that the use of HNO(3) in this multigas adsorbent formulation can be avoided.

Zincobotryogen, ZnFe3+(SO4)2(OH)ṡ7H2O: validation as a mineral species and new data

NASA Astrophysics Data System (ADS)

Yang, Zhuming; Giester, Gerald; Mao, Qian; Ma, Yuguang; Zhang, Di; Li, He

2017-06-01

Zincobotryogen occurs in the oxidation zone of the Xitieshan lead-zinc deposit, Qinghai, China. The mineral is associated with jarosite, copiapite, zincocopiapite, and quartz. The mineral forms prismatic crystals, 0.05 to 2 mm in size. It is optically positive (2Vcalc = 54.1°), with Z ‖ b and X ∧ c = 10°. The elongation is negative. The refractive indices are n α = 1.542(5), n β = 1.551(5), n γ = 1.587(5). The pleochroism scheme is X = colorless, Y = light yellow, Z = yellow. Microprobe analysis gave (in wt%): SO3 = 38.04, Al2O3 = 0.04, Fe2O3 = 18.46, ZnO = 13.75, MgO = 1.52, MnO = 1.23, H2O = 31.06 (by calculation), Total = 104.10. The simplified formula is (Zn,Mg)Fe3+(SO4)2(OH)ṡ7H2O. The mineral is monoclinic, P121/ n1, a = 10.504(2), b = 17.801(4), c = 7.1263(14) Å, and β = 100.08(3)°, V = 1311.9(5) Å3, Z = 4. The strongest lines in the powder X-ray diffraction pattern d(I)( hkl) are: 8.92 (100)(110), 6.32 (77)(-101), 5.56 (23)(021), 4.08 (22)(-221),3.21 (31)(231), 3.03 (34)(032), 2.77 (22)(042). The crystal structure was refined using 2816 unique reflections to R1( F) = 0.0355 and wR2( F 2) = 0.0651. The refined formula is (Zn0.84Mg0.16)Fe3+(SO4)2(OH)ṡ7H2O. The atomic arrangement is characterized by chains with composition [Fe3+(SO4)2(OH)(H2O)]2- and 7 Å repeat distance running parallel to the c-axis. The chain links to a [ MO(H2O)5] octahedron ( M = Zn, Mg) and an unshared H2O molecule, and forms a larger chain building module with composition [ M 2+Fe3+(SO4)2(OH)(H2O)6(H2O)]. The inter-chain module linkage involves only hydrogen bonding.

Alkali- and Sulfur-Resistant Tungsten-Based Catalysts for NOx Emissions Control.

PubMed

Huang, Zhiwei; Li, Hao; Gao, Jiayi; Gu, Xiao; Zheng, Li; Hu, Pingping; Xin, Ying; Chen, Junxiao; Chen, Yaxin; Zhang, Zhaoliang; Chen, Jianmin; Tang, Xingfu

2015-12-15

The development of catalysts with simultaneous resistance to alkalis and sulfur poisoning is of great importance for efficiently controlling NOx emissions using the selective catalytic reduction of NOx with NH3 (SCR), because the conventional V2O5/WO3-TiO2 catalysts often suffer severe deactivation by alkalis. Here, we support V2O5 on a hexagonal WO3 (HWO) to develop a V2O5/HWO catalyst, which has exceptional resistance to alkali and sulfur poisoning in the SCR reactions. A 350 μmol g(-1) K(+) loading and the presence of 1,300 mg m(-3) SO2 do not almost influence the SCR activity of the V2O5/HWO catalyst, and under the same conditions, the conventional V2O5/WO3-TiO2 catalysts completely lost the SCR activity within 4 h. The strong resistance to alkali and sulfur poisoning of the V2O5/HWO catalysts mainly originates from the hexagonal structure of the HWO. The HWO allows the V2O5 to be highly dispersed on the external surfaces for catalyzing the SCR reactions and has the relatively smooth surfaces and the size-suitable tunnels specifically for alkalis' diffusion and trapping. This work provides a useful strategy to develop SCR catalysts with exceptional resistance to alkali and sulfur poisoning for controlling NOx emissions from the stationary source and the mobile source.

Statistical modeling of O3, NOx, CO, PM2.5, VOCs and noise levels in commercial complex and associated health risk assessment in an academic institution.

PubMed

Singh, Deepak; Kumar, Amit; Kumar, Krishan; Singh, Bupender; Mina, Usha; Singh, Braj Bihari; Jain, Vinod Kumar

2016-12-01

Indoor Air Quality (IAQ) is considered to be of great concern due to its adverse impact on the human health nowadays. The presence of different air pollutants along with noise may aggravate the IAQ. The present study attempts to examine IAQ in terms of major criteria air pollutants (O 3 , NOx=NO+NO 2 , CO and PM 2.5 ) along with total volatile organic compound (TVOC), individual VOC and noise pollution in indoor and outdoor environment of a Commercial Shopping Complex (CSC) in Delhi. Real time measurements have been carried out for O 3 , NOx, CO, PM 2.5 , TVOC and noise while thirteen individual VOCs have been estimated using NIOSH method was performed using Gas Chromatograph. The study also aimed to find out the relationship among VOCs, source estimation using Principal Component Analysis. The observed results for the targeted pollutants were also compared with international and national recommended permissible values. The mean values of O 3 , NOx, CO, PM 2.5 and TVOC are found to be 17.6/(15.0) ppb, 15.8/(14.1) ppb, 8.4/(1.9) ppm, 125.4/(74.6) μg/m 3 and 412.5/(226.5) μg/m 3 for indoor/(outdoor), respectively. Among the individual VOC, toluene was the most abundant followed by xylene-isomers and benzene. The noise pollution level in Indoor/outdoor were found to be 51.5/46.4dB which is below the guideline value (65dB) provided by the WHO. Most of the pollutants were found to have indoor sources. The different kinds of pollutants and noise may have synergistic effect and aggravate the health of the people working and visiting the CSC. Copyright © 2016 Elsevier B.V. All rights reserved.

[{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

PubMed

Botar, Bogdan; Kögerler, Paul; Hill, Craig L

2005-07-07

Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

Emission factors of SO2, NOx and particles from ships in Neva Bay from ground-based and helicopter-borne measurements and AIS-based modeling

NASA Astrophysics Data System (ADS)

Beecken, J.; Mellqvist, J.; Salo, K.; Ekholm, J.; Jalkanen, J.-P.; Johansson, L.; Litvinenko, V.; Volodin, K.; Frank-Kamenetsky, D. A.

2014-10-01

Emission factors of SO2, NOx and size distributed particle numbers were measured for approximately 300 different ships in the Gulf of Finland and Neva Bay area during two campaigns in August/September 2011 and June/July 2012. The measurements were carried out from a harbor vessel and from an MI-8 helicopter downwind of passing ships. Other measurements were carried out from shore sites near the island of Kronstadt and along the river Neva in the city area of Saint Petersburg. Most ships were running at reduced speed (10 knots), i.e. not at their optimal load. Vessels for domestic and international shipping were monitored. It was seen that the distribution of the SO2 emission factors is bi-modal with averages of 4.6 gSO2 kgfuel-1 and 18.2 gSO2 kgfuel-1 for the lower and the higher mode, respectively. The emission factors show compliance with the 1% fuel sulfur content SECA limit for 90% of the vessels in 2011 and 97% in 2012. The distribution of the NOx emission factor is mono-modal with an average of 58 gNOx kgfuel-1. The corresponding emission related to the generated power yields an average of 12.1 gNOx kWh-1. The distribution of the emission factors for particulate number shows that nearly 90% of all particles in the 5.6 nm to 10 μm size range were below 70 nm in diameter. The distribution of the corresponding emission factors for the mass indicates two separated main modes, one for particles between 30 and 300 nm the other above 2 μm. The average particle emission factors were found to be in the range from 0.7 to 2.7 × 1016 particles kgfuel-1 and 0.2 to 3.4 gPM kgfuel-1, respectively. The NOx and particulate emissions are comparable with other studies. The measured emission factors were compared, for individual ships, to modeled ones using the Ship Traffic Emission Assessment Model (STEAM) of the Finnish Meteorological Institute. A reasonably good agreement for gaseous sulfur and nitrogen emissions can be seen for ships in international traffic, but

Catalytic oxidation of Hg(0) by MnOx-CeO2/γ-Al2O3 catalyst at low temperatures.

PubMed

Wang, Pengying; Su, Sheng; Xiang, Jun; You, Huawei; Cao, Fan; Sun, Lushi; Hu, Song; Zhang, Yun

2014-04-01

MnOx-CeO2/γ-Al2O3 (MnCe) selective catalytic reduction (SCR) catalysts prepared by sol-gel method were employed for low-temperature Hg(0) oxidation on a fixed-bed experimental setup. BET, XRD and XPS were used to characterize the catalysts. MnCe catalysts exhibited high Hg(0) oxidation activity at low temperatures (100-250 °C) under the simulated flue gas (O2, CO2, NO, SO2, HCl, H2O and balanced with N2). Only a small decrease in mercury oxidation was observed in the presence of 1200 ppm SO2, which proved that the addition of Ce helped resist SO2 poisoning. An enhancing effect of NO was observed due to the formation of multi-activity NOx species. The presence of HCl alone had excellent Hg(0) oxidation ability, while 10 ppm HCl plus 5% O2 further increased Hg(0) oxidation efficiency to 100%. Hg(0) oxidation on the MnCe catalyst surface followed the Langmiur-Hinshelwood mechanism, where reactions took place between the adsorbed active species and adsorbed Hg(0) to form Hg(2+). NH3 competed with Hg(0) for active sites on the catalyst surface, hence inhibiting Hg(0) oxidation. This study shows the feasibility of a single-step process integrating low-temperature SCR and Hg(0) oxidation from the coal combustion flue gas. Copyright © 2013 Elsevier Ltd. All rights reserved.

Porous sulfated metal oxide SO4 2-/Fe2O3 as an anode material for Li-ion batteries with enhanced electrochemical performance

NASA Astrophysics Data System (ADS)

Li, Zhen; Lv, Qianqian; Huang, Xiaoxiong; Tan, Yueyue; Tang, Bohejin

2017-01-01

Sulfated metal oxide SO4 2-/Fe2O3 was prepared by a novel facile sol-gel method combined with a subsequent heating treatment process. The as-synthesized products were analyzed by XRD, FTIR, and FE-SEM. Compared with the unsulfated Fe2O3, the agglomeration of particles has been alleviated after the incorporation of SO4 2-. Interestingly, the primary particle size of the SO4 2-/Fe2O3 (about 5 nm) is similar to its normal counterparts even after the calcination treatment. More importantly, SO4 2-/Fe2O3 exhibits a porous architecture, which is an intriguing feature for electrode materials. When used as anode materials in Li-ion batteries, SO4 2-/Fe2O3 delivered a higher reversible discharge capacity (992 mAh g-1), with smaller charge transfer resistance, excellent rate performance, and better cycling stability than normal Fe2O3. We believed that the presence of SO4 2- and porous architecture should be responsible for the enhanced electrochemical performance, which could provide more continuous and accessible conductive paths for Li+ and electrons.

Increases to Biogenic Secondary Organic Aerosols from SO2 and NOx in the Southeastern US

NASA Astrophysics Data System (ADS)

Russell, L. M.; Liu, J.; Ruggeri, G.; Takahama, S.; Claflin, M. S.; Ziemann, P. J.; Lee, A.; Murphy, B.; Pye, H. O. T.; Ng, N. L.; McKinney, K. A.; Surratt, J. D.

2017-12-01

During the 2013 Southern Oxidant and Aerosol Study, Fourier Transform Infrared Spectroscopy (FTIR) and Aerosol Mass Spectrometer (AMS) measurements of submicron mass were collected at Look Rock, Tennessee, and Centreville, Alabama. The low NOx, low wind, little rain, and increased daytime isoprene emissions led to multi-day stagnation events at Look Rock that provided clear evidence of particle-phase sulfate enhancing biogenic secondary organic aerosol (bSOA) by selective uptake. Organic mass (OM) sources were apportioned as 42% "vehicle-related" and 54% bSOA, with the latter including "sulfate-related bSOA" that correlated to sulfate (r=0.72) and "nitrate-related bSOA" that correlated to nitrate (r=0.65). Single-particle mass spectra showed three composition types that corresponded to the mass-based factors with spectra cosine similarity of 0.93 and time series correlations of r>0.4. The vehicle-related OM with m/z 44 was correlated to black carbon, "sulfate-related bSOA" was on particles with high sulfate, and "nitrate-related bSOA" was on all particles. The similarity of the m/z spectra (cosine similarity=0.97) and the time series correlation (r=0.80) of the "sulfate-related bSOA" to the sulfate-containing single-particle type provide evidence for particle composition contributing to selective uptake of isoprene oxidation products onto particles that contain sulfate from power plants. Since Look Rock had much less NOx than Centreville, comparing the bSOA at the two sites provides an evaluation of the role of NOx for bSOA. CO and submicron sulfate and OM concentrations were 15-60 % higher at Centreville than at Look Rock but their time series had moderate correlations of r= 0.51, 0.54, and 0.47, respectively. However, NOx had no correlation (r=0.08) between the two sites. OM correlated with the higher NOx levels at Centreville but with O3 at Look Rock. OM sources identified by Positive Matrix Factorization had three very similar factors at both sites from FTIR

Nrf2 mediates redox adaptation in NOX4-overexpressed non-small cell lung cancer cells

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

Wu, Qipeng; Yao, Bei; Li, Ning

The redox adaptation mechanisms in cancer cells are very complex and remain largely unclear. Our previous studies have confirmed that NADPH oxidase 4 (NOX4) is abundantly expressed in non-small cell lung cancer (NSCLC) and confers apoptosis resistance on NSCLC cells. However, the comprehensive mechanisms for NOX4-mediated oxidative resistance of cancer cells remain still undentified. The present study found that NOX4-derived H{sub 2}O{sub 2} enhanced the nuclear factor erythroid 2-related factor 2 (Nrf2) stability via disruption of redox-dependent proteasomal degradation and stimulated its activity through activation of PI3K signaling. Specifically, the results showed that ectopic NOX4 expression did not induce apoptosismore » of A549 cells; however, inhibition of Nrf2 resulted in obvious apoptotic death of NOX4-overexpressed A549 cells, accompanied by a significant increase in H{sub 2}O{sub 2} level and decrease in GSH content. Besides, inhibition of Nrf2 could suppress cell growth and efficiently reverse the enhancement effect of NOX4 on cell growth. The in vivo data confirmed that inhibition of Nrf2 could interfere apoptosis resistance in NOX4-overexpressed A549 tumors and led to cell growth inhibition. In conclusion, these results reveal that Nrf2 is critically involved in redox adaptation regulation in NOX4-overexpressed NSCLC cells. Therefore, NOX4 and Nrf2 may be promising combination targets against malignant progression of NSCLC. - Highlights: • NOX4-derived H{sub 2}O{sub 2} upregulates Nrf2 expression and activity in NSCLC. • Nrf2 confers apoptosis resistance in NOX4-overexpressed NSCLC cells. • Inhibition of Nrf2 reverses the enhancement effect of NOX4 on cell growth.« less

Smog chamber study on aging of combustion soot in isoprene/SO2/NOx system: Changes of mass, size, effective density, morphology and mixing state

NASA Astrophysics Data System (ADS)

Li, Kangwei; Chen, Linghong; Han, Ke; Lv, Biao; Bao, Kaiji; Wu, Xuecheng; Gao, Xiang; Cen, Kefa

2017-02-01

Atmospheric soot aging process is always accompanied by secondary particle formation, which is a comprehensive environmental issue that deserves great attention. On one hand, aging of primary soot could change its own physicochemical properties; on the other hand, complex air pollution caused by pollutant emission from various sources (e.g., vehicle exhausts, coal-fired flue gases and biogenic VOCs emission) may contribute to secondary particle formation onto primary particle surface. In this study, aging of combustion soot in isoprene/SO2/NOx system was investigated under controlled laboratory conditions in several smog chamber experiments. During the evolution of soot, several physical properties such as mass, size, effective density, morphology and mixing state were determined simultaneously by an integrated aerosol analytical system of Scanning Mobility Particle Sizer (SMPS), Differential Mobility Analyzer-Aerosol Particle Mass Analyzer-Condensation Particle Counter (DMA-APM-CPC) and Transmission Electron Microscopy coupled with Energy-dispersive X-ray Spectrometry (TEM/EDX) techniques. Here, based on the experimental results of soot aging under different gas-phase composition and relative humidity (RH), we firstly proposed possible aging pathways of soot in isoprene/SO2/NOx system. A synergetic effect was speculated to exist between SO2 and isoprene on soot aging process, which led to more secondary particle formation. At the same time, TEM/EDX analysis showed that a competitive mechanism between H2SO4(g) and isoprene oxidation vapor may exist: H2SO4(g) firstly condensed onto fresh soot, then an acceleration of isoprene oxidation products formed onto H2SO4 pre-coated soot. In isoprene/SO2/NOx system, high RH conditions could contribute to soot aging and new particle formation. The changes of effective density and dynamic shape factor of soot also indicated that high RH conditions could accelerate soot aging process, and led chain-like soot into more spherical

Sulfation of K-based Lean NOx Trap while Cycling Between Lean and Rich Conditions: I. Microreactor Study

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

Toops, Todd J; Pihl, Josh A

2008-01-01

Exposure of Pt/K/Al{sub 2}O{sub 3} to 15 ppm SO{sub 2} reduces the NOx activity at 200, 300, and 400 C at significantly different rates--1.5, 8.5, and 18.0 {micro}mol NOx/(h g{sub cat}), respectively. During the initial sulfation, NOx conversion is directly linked to lean phase storage capacity, and sulfation does not impact the reduction kinetics since the amount of unconverted NOx was constant or decreased with increasing sulfation time. A portion of sulfur stored at 200 C desorbs upon mild heating to 400 C while cycling between lean and rich conditions. This apparently is a result of sulfur being released frommore » Al{sub 2}O{sub 3}; however, performance is not significantly recovered as much of the sulfur is re-adsorbed on the K-phase. This is apparent from analysis of the NOx storage and release profiles. Additional analysis of these profiles suggests that SO{sub 2} initially adsorbs near Pt before interacting with other sites further away from Pt at 300 C. At 400 C, it appears that SO{sub 2} either preferentially adsorbs near Pt and then quickly diffuses along the surface to other less proximal sites, or it directly adsorbs on sites further away from Pt. De-sulfurization up to 800 C using a temperature programmed reduction (TPR) procedure and rich conditions with both CO{sub 2} and H{sub 2}O restored 73=94% of the LNT performance at 300 and 400 C. However, the recovered performance measured at 200 C was only 34-49% of the original NOx reduction activity. H{sub 2}S and SO{sub 2} were the primary de-sulfurization products with H{sub 2}S having a maximum release between 690 and 755 C, while SO{sub 2} had a peak release between 770 and 785 C. The sulfation temperature does not have a significant impact on the recovered performance, the de-sulfurization products or the sulfur release temperature.« less

Study on room temperature gas-sensing performance of CuO film-decorated ordered porous ZnO composite by In2O3 sensitization

PubMed Central

Li, Tian-tian; Bao, Na; Geng, Ai-fang; Yang, Ying; Dong, Xiang-ting

2018-01-01

For the first time, ordered mesoporous ZnO nanoparticles have been synthesized by a template method. The electroplating after chemical plating method was creatively used to form copper film on the surface of the prepared ZnO, and then a CuO film-decorated ordered porous ZnO composite (CuO/ZnO) was obtained by a high-temperature oxidation method. In2O3 was loaded into the prepared CuO film–ZnO by an ultrasonic-assisted method to sensitize the room temperature gas-sensing performance of the prepared CuO/ZnO materials. The doped In2O3 could effectively improve the gas-sensing properties of the prepared materials to nitrogen oxides (NOx) at room temperature. The 1% In2O3 doped CuO/ZnO sample (1 wt% In2O3–CuO/ZnO) showed the best gas-sensing properties whose response to 100 ppm NOx reached 82%, and the detectable minimum concentration reached 1 ppm at room temperature. The prepared materials had a good selectivity, better response, very low detection limit, and high sensitivity to NOx gas at room temperature, which would have a great development space in the gas sensor field and a great research value. PMID:29515887

Study on room temperature gas-sensing performance of CuO film-decorated ordered porous ZnO composite by In2O3 sensitization

NASA Astrophysics Data System (ADS)

Li, Tian-tian; Bao, Na; Geng, Ai-fang; Yu, Hui; Yang, Ying; Dong, Xiang-ting

2018-02-01

For the first time, ordered mesoporous ZnO nanoparticles have been synthesized by a template method. The electroplating after chemical plating method was creatively used to form copper film on the surface of the prepared ZnO, and then a CuO film-decorated ordered porous ZnO composite (CuO/ZnO) was obtained by a high-temperature oxidation method. In2O3 was loaded into the prepared CuO film-ZnO by an ultrasonic-assisted method to sensitize the room temperature gas-sensing performance of the prepared CuO/ZnO materials. The doped In2O3 could effectively improve the gas-sensing properties of the prepared materials to nitrogen oxides (NOx) at room temperature. The 1% In2O3 doped CuO/ZnO sample (1 wt% In2O3-CuO/ZnO) showed the best gas-sensing properties whose response to 100 ppm NOx reached 82%, and the detectable minimum concentration reached 1 ppm at room temperature. The prepared materials had a good selectivity, better response, very low detection limit, and high sensitivity to NOx gas at room temperature, which would have a great development space in the gas sensor field and a great research value.

Biological removal of NOx from flue gas.

PubMed

Kumaraswamy, R; Muyzer, G; Kuenen, J G; Loosdrecht, M C M

2004-01-01

BioDeNOx is a novel integrated physico-chemical and biological process for the removal of nitrogen oxides (NOx) from flue gas. Due to the high temperature of flue gas the process is performed at a temperature between 50-55 degrees C. Flue gas containing CO2, O2, SO2 and NOx, is purged through Fe(II)EDTA2- containing liquid. The Fe(II)EDTA2- complex effectively binds the NOx; the bound NOx is converted into N2 in a complex reaction sequence. In this paper an overview of the potential microbial reactions in the BioDeNOx process is discussed. It is evident that though the process looks simple, due to the large number of parallel potential reactions and serial microbial conversions, it is much more complex. There is a need for a detailed investigation in order to properly understand and optimise the process.

Laboratory studies of key gas-phase HOx-NOx coupling reactions.

NASA Astrophysics Data System (ADS)

Dillon, Terry J.; Dulitz, Katrin; Crowley, John N.

2013-04-01

The HOx (OH & HO2) and NOx (NO & NO2) families of atmospheric radicals are coupled via a number of gas-phase reactions. These reactions have a substantial impact by controlling radical propagation / termination in catalytic cycles, so modifying the oxidation power of the atmosphere and its rate of O3 production. However, field measurements {1-3} have demonstrated that our understanding of HOx - NOx chemistry is incomplete. We have identified four reactions (R1-R4) where the database is particularly unsatisfactory, leading to large uncertainties in atmospheric models {4-5}. HO2 + NO -> OH + NO2 (R1a) HO2 + NO (+ M) -> HNO3 (+ M) (R1b) NO2* + H2O -> NO2 + H2O (R2a) NO2* + H2O -> OH + HONO (R2b) NO3* + H2O -> NO3 + H2O (R3a) NO3* + H2O -> OH + HNO3 (R3b) OH + HNO3 -> H2O + NO3 (R4) In this experimental work, laser-based kinetic and spectroscopic tools were used to investigate recent observations {6-7} of HNO3 formation from the (otherwise radical propagating) HO2 + NO (R1), and OH formation following absorption of abundant, long wavelength photons by NO2 {8} and NO3 in the presence of water vapour (R2, R3). Uncertainties {9} associated with a classical HOx-NOx coupling reaction (R4) were also addressed. Critical photochemical parameters so derived have included absolute rate coefficients for (R1) and (R4) and product yields (R1b, R2b, R3b). The atmospheric implications of these results will be discussed. References: {1} Faloona, I. et al. J. Geophys. Res., 105, 3771-3783, 2000.; {2} Thakur, A.N. et al., Atmos. Environ., 33, 1403-1422, 1999.; {3} Wennberg, P.O. et al., Geophys. Res. Lett., 26, 1373-1376, 1999.; {4} Cariolle, D. et al., Atmos. Chem. Phys., 8, 4061-4068, 2008.; {5} Wennberg P.O. and Dabdub, D. Science, 319, 2008. ; {6} Butkovskaya, N. et al., J. Phys. Chem. A, 111, 9047-9053, 2007.; {7} Butkovskaya, N. et al., J. Phys. Chem. A, 109, 6509-6520, 2005.; {8} Li, S.P. et al., Science, 319, 1657-1660, 2008. {9} Brown, S.S. et al., J. Phys. Chem., 103, 3031

40 CFR 97.253 - Recordation of CAIR SO2 allowances.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Recordation of CAIR SO2 allowances. 97... (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Allowance Tracking System § 97.253 Recordation of CAIR SO2 allowances. (a)(1) After a compliance account is...

40 CFR 96.253 - Recordation of CAIR SO2 allowances.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Recordation of CAIR SO2 allowances. 96... (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Allowance Tracking System § 96.253 Recordation of CAIR SO2 allowances. (a)(1) After a...

Multiphase oxidation of SO2 by NO2 on CaCO3 particles

NASA Astrophysics Data System (ADS)

Zhao, Defeng; Song, Xiaojuan; Zhu, Tong; Zhang, Zefeng; Liu, Yingjun; Shang, Jing

2018-02-01

Heterogeneous/multiphase oxidation of SO2 by NO2 on solid or aqueous particles is thought to be a potentially important source of sulfate in the atmosphere, for example, during heavily polluted episodes (haze), but the reaction mechanism and rate are uncertain. In this study, in order to assess the importance of the direct oxidation of SO2 by NO2 we investigated the heterogeneous/multiphase reaction of SO2 with NO2 on individual CaCO3 particles in N2 using Micro-Raman spectroscopy. In the SO2 / NO2 / H2O / N2 gas mixture, the CaCO3 solid particle was first converted to the Ca(NO3)2 droplet by the reaction with NO2 and the deliquescence of Ca(NO3)2, and then NO2 oxidized SO2 in the Ca(NO3)2 droplet forming CaSO4, which appeared as needle-shaped crystals. Sulfate was mainly formed after the complete conversion of CaCO3 to Ca(NO3)2, that is, during the multiphase oxidation of SO2 by NO2. The precipitation of CaSO4 from the droplet solution promoted sulfate formation. The reactive uptake coefficient of SO2 for sulfate formation is on the order of 10-8, and RH enhanced the uptake coefficient. We estimate that the direct multiphase oxidation of SO2 by NO2 is not an important source of sulfate in the ambient atmosphere compared with the SO2 oxidation by OH in the gas phase and is not as important as other aqueous-phase pathways, such as the reactions of SO2 with H2O2, O3, and O2, with or without transition metals.

Relationship of peroxyacetyl nitrate to active and total odd nitrogen at northern high latitudes: influence of reservoir species on NOx and O3

NASA Technical Reports Server (NTRS)

Singh, H. B.; Herlth, D.; O'Hara, D.; Zahnle, K.; Bradshaw, J. D.; Sandholm, S. T.; Talbot, R.; Crutzen, P. J.; Kanakidou, M.

1992-01-01

Measurements of peroxyacetyl nitrate (PAN), NO, NO2, HNO3, NOy (total odd nitrogen), and O3 were made in the high-latitude troposphere over North America and Greenland (35 degrees to 82 degrees N) during the Arctic Boundary Layer Expedition (ABLE 3A) (July-August 1988) throughout 0-to 6-km altitudes. These data are analyzed to quantitatively describe the relationships between various odd nitrogen species and assess their significance to global tropospheric chemistry. In the free troposphere, PAN was as much as 25 times more abundant than NOx. PAN to NOx ratio increased with increasing altitude and latitude. PAN was found to be the single most abundant reactive nitrogen species in the free troposphere and constituted a major fraction of NOy, PAN to NOy ratios were about 0.1 in the boundary layer and increased to 0.4 in the free troposphere. A 2-D global photochemical model with C1-C3 hydrocarbon chemistry is used to compare model predictions with measured results. A sizable portion (approximately 50%) of the gaseous reactive nitrogen budget is unaccounted for, and unknown organic nitrates and pernitrates are expected to be present. Model calculations (August 1, 70 degrees N) show that a major fraction of the observed NOx (50 to 70% of median) may find its source in the available PAN reservoir. PAN and the unknown reservoir species may have the potential to control virtually the entire NOx availability of the high latitude troposphere. It is predicted that the summer NOx and O3 mixing ratios in the Arctic/sub-Arctic troposphere would be considerably lower in the absence of the ubiquitous PAN reservoir. Conversely, this PAN reservoir may be responsible for the observed temporal increase in tropospheric O3 at high latitudes.

Factors associated with NO2 and NOX concentration gradients near a highway

NASA Astrophysics Data System (ADS)

Richmond-Bryant, J.; Snyder, M. G.; Owen, R. C.; Kimbrough, S.

2018-02-01

The objective of this research is to learn how the near-road gradient, in which NO2 and NOX (NO + NO2) concentrations are elevated, varies with changes in meteorological and traffic variables. Measurements of NO2 and NOX were obtained east of I-15 in Las Vegas and fit to functions whose slopes (dCNO2/dx and dCNOX/dx, respectively) characterize the size of the near-road zone where NO2 and NOX concentrations from mobile sources on the highway are elevated. These metrics were used to learn about the near-road gradient by modeling dCNO2/dx and dCNOX/dx as functions of meteorological variables (e.g., wind direction, wind speed), traffic (vehicle count), NOX concentration upwind of the road, and O3 concentration at two fixed-site ambient monitors. Generalized additive models (GAM) were used to model dCNO2/dx and dCNOX/dx versus the independent variables because they allowed for nonlinearity of the variables being compared. When data from all wind directions were included in the analysis, variability in O3 concentration comprised the largest proportion of variability in dCNO2/dx, followed by variability in wind direction. In a second analysis constrained to winds from the west, variability in O3 concentration remained the largest contributor to variability in dCNO2/dx, but the relative contribution of variability in wind speed to variability in dCNO2/dx increased relative to its contribution for the all-wind analysis. When data from all wind directions were analyzed, variability in wind direction was by far the largest contributor to variability in dCNOX/dx, with smaller contributions from hour of day and upwind NOX concentration. When only winds from the west were analyzed, variability in upwind NOX concentration, wind speed, hour of day, and traffic count all were associated with variability in dCNOX/dx. Increases in O3 concentration were associated with increased magnitude near-road dCNO2/dx, possibly shrinking the zone of elevated concentrations occurring near roads

The reactions of SO3 with HO2 radical and H2O...HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4.

PubMed

Gonzalez, Javier; Torrent-Sucarrat, Miquel; Anglada, Josep M

2010-03-07

The influence of a single water molecule on the gas-phase reactivity of the HO(2) radical has been investigated by studying the reactions of SO(3) with the HO(2) radical and with the H(2)O...HO(2) radical complex. The naked reaction leads to the formation of the HSO(5) radical, with a computed binding energy of 13.81 kcal mol(-1). The reaction with the H(2)O...HO(2) radical complex can give two different products, namely (a) HSO(5) + H(2)O, which has a binding energy that is computed to be 4.76 kcal mol(-1) more stable than the SO(3) + H(2)O...HO(2) reactants (Delta(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol(-1) below the energy of the reactants (Delta(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H(2)SO(4) may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO(2), HSO(5), the HSO(5)...H(2)O hydrogen bonded complex, H(2)SO(4), and two H(2)SO(4)...H(2)O complexes, in order to help with the possible experimental identification of some of these species.

Emission factors of SO2, NOx and particles from ships in Neva Bay from ground-based and helicopter-borne measurements and AIS-based modeling

NASA Astrophysics Data System (ADS)

Beecken, J.; Mellqvist, J.; Salo, K.; Ekholm, J.; Jalkanen, J.-P.; Johansson, L.; Litvinenko, V.; Volodin, K.; Frank-Kamenetsky, D. A.

2015-05-01

Emission factors of SO2, NOx and size-distributed particle numbers were measured for approximately 300 different ships in the Gulf of Finland and Neva Bay area during two campaigns in August/September 2011 and June/July 2012. The measurements were carried out from a harbor vessel and from an Mi-8 helicopter downwind of passing ships. Other measurements were carried out from shore sites near the island of Kronstadt and along the Neva River in the urban area of Saint Petersburg. Most ships were running at reduced speed (10 kn), i.e., not at their optimal load. Vessels for domestic and international shipping were monitored. It was seen that the distribution of the SO2 emission factors is bi-modal, with averages of 4.6 and 18.2 gSO2 kgfuel-1 for the lower and the higher mode, respectively. The emission factors show compliance with the 1% fuel sulfur content Sulfur Emission Control Areas (SECA) limit for 90% of the vessels in 2011 and 97% in 2012. The distribution of the NOx emission factor is mono-modal, with an average of 58 gNOx kgfuel-1. The corresponding emission related to the generated power yields an average of 12.1 gNOx kWh-1. The distribution of the emission factors for particulate number shows that nearly 90% of all particles in the 5.6 nm to 10 μm size range were below 70 nm in diameter. The distribution of the corresponding emission factors for the mass indicates two separated main modes, one for particles between 30 and 300 nm and the other for above 2 μm. The average particle emission factors were found to be in the range from 0.7 to 2.7 × 1016 particles kgfuel-1 and 0.2 to 3.4 gPM kgfuel-1, respectively. The NOx and particulate emissions are comparable with other studies. The measured emission factors were compared, for individual ships, to modeled ones using the Ship Traffic Emission Assessment Model (STEAM) of the Finnish Meteorological Institute. A reasonably good agreement for gaseous sulfur and nitrogen emissions can be seen for ships in

Towards Ideal NOx and CO2 Emission Control Technology for Bio-Oils Combustion Energy System Using a Plasma-Chemical Hybrid Process

NASA Astrophysics Data System (ADS)

Okubo, M.; Fujishima, H.; Yamato, Y.; Kuroki, T.; Tanaka, A.; Otsuka, K.

2013-03-01

A pilot-scale low-emission boiler system consisting of a bio-fuel boiler and plasma-chemical hybrid NOx removal system is investigated. This system can achieve carbon neutrality because the bio-fuel boiler uses waste vegetable oil as one of the fuels. The plasma-chemical hybrid NOx removal system has two processes: NO oxidation by ozone produced from plasma ozonizers and NO2 removal using a Na2SO3 chemical scrubber. Test demonstrations of the system are carried out for mixed oils (mixture of A-heavy oil and waste vegetable oil). Stable combustion is achieved for the mixed oil (20 - 50% waste vegetable oil). Properties of flue gas—e.g., O2, CO2 and NOx—when firing mixed oils are nearly the same as those when firing heavy oil for an average flue gas flow rate of 1000 Nm3/h. NOx concentrations at the boiler outlet are 90 - 95 ppm. Furthermore, during a 300-min continuous operation when firing 20% mixed oil, NOx removal efficiency of more than 90% (less than 10 ppm NOx emission) is confirmed. In addition, the CO2 reduction when heavy oil is replaced with waste vegetable oil is estimated. The system comparison is described between the plasma-chemical hybrid NOx removal and the conventional technology.

Elevated O3 in Fresh and Aged Lightning-NOx Plumes Interacting with Biomass Burning Plumes over the Central U.S. during DC3 (Invited)

NASA Astrophysics Data System (ADS)

Huntrieser, H.; Lichtenstern, M.; Scheibe, M.; Aufmhoff, H.; Schlager, H.; Pucik, T.; Minikin, A.; Weinzierl, B.; Heimerl, K.; Fütterer, D.; Rappenglück, B.; Ackermann, L.; Pickering, K. E.; Cummings, K.; Barth, M. C.

2013-12-01

During the Deep Convective Clouds and Chemistry Experiment (DC3) in summer 2012 a variety of different thunderstorm systems were investigated over the Central U.S. by the DLR research aircraft Falcon together with the NCAR GV and NASA DC-8 aircraft. In addition, the complete DC3 field phase was characterized by a number of extended wildfires burning in the surroundings of the thunderstorms. Here we mainly focus on trace gas in situ measurements, such as NOx, CO, O3, CH4, SO2, NMHC, and a variety of aerosol measurements carried out by the Falcon in the fresh (~0-6 h) and aged (~12-24 h) anvil outflow at ~10-12 km altitude. It is well-known that thunderstorms modify the trace gas composition in the upper troposphere (UT) and may affect O3 mixing ratios, an important greenhouse gas in the UT. However, a complete picture of the different processes affecting the UT-O3 composition in vicinity of thunderstorms and its large-scale effects is still missing. From the DC3 data set we present an example of small-scale effects on the O3 composition in the anvil outflow, such as immediate O3 production by an aircraft-induced flash. But we also show how the efficient convective transport that extended over the whole updraft region may transport O3-poorer air masses from the, in general, rather unpolluted inflow region (with regard to anthropogenic emissions) over the Central U.S. directly to the UT. However, in a few cases enhanced O3 mixing ratios were observed in the anvil outflow attributed to different chemical and dynamical processes. In the two most powerful convective systems, an intense MCS over Missouri/Arkansas and a supercell over Texas, extended biomass burning (BB) plumes from New Mexico interacted with the thunderstorms. Ozone production was obvious in the BB plumes transported mainly in the lower troposphere at ~2-5 km altitude (ΔO3/ΔCO=0.1). However, if these air masses affected by BB emissions (containing high amounts of O3 precursors such as CH4 and NMHC) were

A comparative investigation of SO2 oxidative transfer over CuO with a CeO2 surface

NASA Astrophysics Data System (ADS)

Liu, Yifeng; Shen, Benxian; Pi, Zhipeng; Chen, Hua; Zhao, Jigang

2017-04-01

To further improve the catalytic desulfurization function of the Mg-Al spinel sulfur transfer agent in a fluid catalytic cracking (FCC) unit, the reaction paths of SO2 oxidation by O2 over the metal oxide surface of CuO (111) and CeO2 (111) were investigated. In reference to the fact that SO2 reacting with O2 over CuO was a Mars-van Krevelen cycle, a similar reaction law for SO2 oxidation over CeO2 was also verified by characterization methods (e.g., IR, XPS). Meanwhile, the molecular simulation results indicated that the rate-control step of SO2 oxidation over CeO2 (111) and CuO (111) was a SO3 desorption step. The lower energy barrier in the rate-control step corresponded to better catalytic performance; hence, it could explain the reason that CeO2 had a better sulfur oxidization transfer performance than CuO.

Allocating emissions to 4 km and 1 km horizontal spatial resolutions and its impact on simulated NOx and O3 in Houston, TX

NASA Astrophysics Data System (ADS)

Pan, Shuai; Choi, Yunsoo; Roy, Anirban; Jeon, Wonbae

2017-09-01

A WRF-SMOKE-CMAQ air quality modeling system was used to investigate the impact of horizontal spatial resolution on simulated nitrogen oxides (NOx) and ozone (O3) in the Greater Houston area (a non-attainment area for O3). We employed an approach recommended by the United States Environmental Protection Agency to allocate county-based emissions to model grid cells in 1 km and 4 km horizontal grid resolutions. The CMAQ Integrated Process Rate analyses showed a substantial difference in emissions contributions between 1 and 4 km grids but similar NOx and O3 concentrations over urban and industrial locations. For example, the peak NOx emissions at an industrial and urban site differed by a factor of 20 for the 1 km and 8 for the 4 km grid, but simulated NOx concentrations changed only by a factor of 1.2 in both cases. Hence, due to the interplay of the atmospheric processes, we cannot expect a similar level of reduction of the gas-phase air pollutants as the reduction of emissions. Both simulations reproduced the variability of NASA P-3B aircraft measurements of NOy and O3 in the lower atmosphere (from 90 m to 4.5 km). Both simulations provided similar reasonable predictions at surface, while 1 km case depicted more detailed features of emissions and concentrations in heavily polluted areas, such as highways, airports, and industrial regions, which are useful in understanding the major causes of O3 pollution in such regions, and to quantify transport of O3 to populated communities in urban areas. The Integrated Reaction Rate analyses indicated a distinctive difference of chemistry processes between the model surface layer and upper layers, implying that correcting the meteorological conditions at the surface may not help to enhance the O3 predictions. The model-observation O3 bias in our studies (e.g., large over-prediction during the nighttime or along Gulf of Mexico coastline), were due to uncertainties in meteorology, chemistry or other processes. Horizontal grid

Insights into the Electronic Structure of Ozone and Sulfur Dioxide from Generalized Valence Bond Theory: Bonding in O3 and SO2.

PubMed

Takeshita, Tyler Y; Lindquist, Beth A; Dunning, Thom H

2015-07-16

There are many well-known differences in the physical and chemical properties of ozone (O3) and sulfur dioxide (SO2). O3 has longer and weaker bonds than O2, whereas SO2 has shorter and stronger bonds than SO. The O-O2 bond is dramatically weaker than the O-SO bond, and the singlet-triplet gap in SO2 is more than double that in O3. In addition, O3 is a very reactive species, while SO2 is far less so. These disparities have been attributed to variations in the amount of diradical character in the two molecules. In this work, we use generalized valence bond (GVB) theory to characterize the electronic structure of ozone and sulfur dioxide, showing O3 does indeed possess significant diradical character, whereas SO2 is effectively a closed shell molecule. The GVB results provide critical insights into the genesis of the observed difference in these two isoelectronic species. SO2 possesses a recoupled pair bond dyad in the a"(π) system, resulting in SO double bonds. The π system of O3, on the other hand, has a lone pair on the central oxygen atom plus a pair of electrons in orbitals on the terminal oxygen atoms that give rise to a relatively weak π interaction.

RETROFIT COSTS FOR SO2 AND NOX CONTROL OPTIONS AT 200 COAL-FIRED PLANTS, VOLUME II - SITE SPECIFIC STUDIES FOR AL, DE. FL, GA, IL

EPA Science Inventory

The report gives results of a study, the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 and NOx controls at 200 large SO2-emitting coal-fired utility plants. To accomplish the object...

High surface O3 episodes in Seoul under different meteorological regimes during KORUS-AQ campaign.

NASA Astrophysics Data System (ADS)

Kim, H.; Lee, M.; Jung, J.; Cho, S.; Shin, H.; Lee, G.; Park, M.; Hong, J.

2017-12-01

To examine chemical characteristics of ozone (O3) formation in Seoul Metropolitan Area (SMA), H2O2, PAN, and HONO were measured in conjunction with O3 and its precursors. The experiment was conducted at Olympic Park in Seoul during May 12 June 15, 2016. For the entire experiment period, the high O3 episodes of hourly mean concentration over 100 ppbv occurred on May 20, 23, 25, 29, and 30 and June 10 and 14. These episodes were different in meteorological conditions, precursor strengths, and chemical characteristics. The local influence was dominant under stagnant condition on May 20, 23 and June 10. When stagnant conditions developed over the Korean peninsula, the PBL (Planetary Boundary Layer) height often changed rapidly, leading to abrupt change in O3 and NOx. Particularly the nighttime concentrations of reactive gases such as O3 and NOx were sensitive to the change in PBL height. It is thought to be driven by land-sea breeze circulation. During May 25 28 when air was coming from the Eastern China, O3 was enhanced with aerosols and high SO2 and CO but low NOx concentration. Odd-Oxygen (O3+NO2, OX) ratio indicates the different chemical regimes, particularly at night(8PM - 7AM). O3/OX ratio was close to zero when local influence was dominant due to O3-titration by NOx. In contrast, this ratio was high over 0.6 in Chinese outflow plumes.

High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

PubMed Central

2015-01-01

Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

40 CFR 97.260 - Submission of CAIR SO2 allowance transfers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Submission of CAIR SO2 allowance... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Allowance Transfers § 97.260 Submission of CAIR SO2 allowance transfers. (a) A CAIR authorized account...

40 CFR 97.254 - Compliance with CAIR SO2 emissions limitation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Compliance with CAIR SO2 emissions... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Allowance Tracking System § 97.254 Compliance with CAIR SO2 emissions limitation. (a) Allowance transfer...

40 CFR 96.254 - Compliance with CAIR SO2 emissions limitation.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Compliance with CAIR SO2 emissions... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Allowance Tracking System § 96.254 Compliance with CAIR SO2 emissions limitation...

Wall shear stress promotes intimal hyperplasia through the paracrine H2O2-mediated NOX-AKT-SVV axis.

PubMed

Zhang, Haolong; Yang, Zhipeng; Wang, Jing; Wang, Xuehu; Zhao, Yu; Zhu, Fangyu

2018-05-27

Oscillatory wall shear stress (WSS)-linked oxidative stress promotes intimal hyperplasia (IH) development, but the underlying mechanisms are not completely understood. We used an in vivo rabbit carotid arterial stenosis model representing different levels of WSS and found that WSS was increased at 1 month with 50% stenosis and was accompanied by VSMCs proliferation and interstitial collagen accumulation. Increased WSS promoted the expression of NOX, AKT, and survivin (SVV) and the proliferation/migration of VSMCs and reduced apoptosis. Our in vitro study suggested that H 2 O 2 promoted proliferation and migration while suppressing apoptosis in cultured human umbilical vascular endothelial cells. We demonstrated that the elevation of WSS promotes VSMC proliferation and migration through the H 2 O 2 -mediated NOX-AKT-SVV axis, thereby accelerating IH development. Copyright © 2017. Published by Elsevier Inc.

PAN and O3 enhancement at Taehwa Research Forest in Korea

NASA Astrophysics Data System (ADS)

Gil, J.; Lee, M.; Rhee, H.; Lee, Y.; Park, H.; Kim, S.

2017-12-01

PAN (Peroxyacetyl Nitrate) is one of the most important secondary pollutant produced by the reaction of NOx (= NO + NO2) and oxygenated VOCs (Volatile Organic Compounds). It is considered more reliable indicator of photochemical pollution than O3 in urban area. To observe the evolution of biogenic emission being mixed with urban pollutants, measurement was conducted at TRF (Taehwa Research Forest) near SMA (Seoul Metropolitan Area) in Korea during 2012, and 2013. PAN with reactive gases (O3, NOx, CO, SO2) were measured at six heights (4.1, 9.5, 15, 20, 31, 39 m) of a 41m tower along with BVOCs (Biogenic Volatile Organic Compounds). PAN was measured using a fast GC-LCD (Gas Chromatography with Luminol-based Chemiluminescence Detection). For PAN and O3, the 5%ile, 50%ile, and 95%ile were 0.12 ppbv, 0.46 ppbv, and 2.09 ppbv, and 18.4 ppbv, 44.7 ppbv, and 66.6 ppbv respectively. PAN was visibly higher during warm seasons (0.69 ppbv) than cold seasons (0.35 ppbv) and their monthly mean concentrations were the highest in June. The PAN maxima (7.78 ppbv) was observed in August 2013 with the elevation of O3 and NOx. It is noteworthy that there were enhancement of PAN and O3 around 6 PM, along with isoprene emission and a sudden increase of NO2 near the time for enhancement. A F0AM (Framework for 0-D Atmospheric Modeling) was used to identify the contribution of BVOCs and NOx to PAN and O3 enhancement.

Resonance Raman spectra of an O2-binding H-NOX domain reveal heme relaxation upon mutation.

PubMed

Tran, Rosalie; Boon, Elizabeth M; Marletta, Michael A; Mathies, Richard A

2009-09-15

Resonance Raman spectra were measured for the wild type Heme-Nitric oxide/OXygen binding domain from Thermoanaerobacter tengcongensis (Tt H-NOX WT) and three other Tt H-NOX proteins containing mutations at key conserved residues to determine the heme conformation in solution. The most dramatic changes in heme conformation occurred in the O2-bound forms, and the single Tt H-NOX P115A mutation was sufficient to generate a significant relaxation of the chromophore. Clear evidence of heme relaxation in the Tt H-NOX I5L, P115A, and I5L/P115A mutants in solution is demonstrated by the observation of reduced resonance Raman intensities for several out-of-plane low frequency modes (e.g., gamma11, gamma12, gamma13, and gamma15) in the 400-750 cm(-1) region known to be sensitive to ruffling and saddling deformations, as well as increased vibrational frequencies for the core heme skeletal stretching modes, nu3, nu2, and nu10. In addition, all three mutants exhibited some degree of heme conformational heterogeneity based on several broad skeletal markers (e.g., nu10) in the high frequency region. These results are comparable to those observed by Olea et al. for Tt H-NOX P115A in crystal form, where four different heme structures were determined from a single unit cell. On the basis of the resonance Raman spectra, it is clear that the actual heme conformation for Tt H-NOX P115A in solution is considerably more relaxed than that of the WT protein, with increased flexibility within the protein pocket, allowing for rapid sampling of alternate conformations.

Effect of water on sulfur dioxide (SO2) and nitrogen oxides (NOx) removal from flue gas in a direct current corona discharge reactor

NASA Astrophysics Data System (ADS)

Yang, Jiaxiang; Chi, Xiaochun; Dong, Limin

2007-05-01

A direct current (dc) corona discharge reactor composed of needle-plate electrodes in a glass container filled with flue gas was designed. To clarify the influence of water on discharge characteristics, water was introduced in the plasma reactor as electrode where plate electrode is immersed, under the application of dc voltage. Experiment results show that (1) corona wind forming between high-voltage needle electrode and water by corona discharge enhances the cleaning efficiency of flue gas due to the existence of water and the cleaning efficiency will increase with the increase of applied dc voltage within definite range and (2) both removal efficiencies of NOx and SO2 increased in the presence of water, which reach up to 98% for SO2, and about 85% for NOx under suitable conditions. These results play an important role in flue gas cleanup research.

Rate constant for the reaction SO + BrO yields SO2 + Br

NASA Technical Reports Server (NTRS)

Brunning, J.; Stief, L.

1986-01-01

The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.

Total OH reactivity as a constraint of model calculated peroxy radical production, and the catalytic efficiency of NOx in O3 production in a boreal forest environment.

NASA Astrophysics Data System (ADS)

Javed, M. U.; Hens, K.; Martinez, M.; Kubistin, D.; Novelli, A.; Beygi, Z. H.; Axinte, R.; Nölscher, A. C.; Sinha, V.; Song, W.; Johnson, A. M.; Auld, J.; Bohn, B.; Sander, R.; Taraborrelli, D.; Williams, J.; Fischer, H.; Lelieveld, J.; Harder, H.

2016-12-01

Peroxy radicals play a key role in ozone (O3) production and hydroxyl (OH) recycling influencing the self-cleansing capacity and air quality. Organic peroxy radical (RO2) concentrations are estimated by three different approaches for a boreal forest, based on the field campaign HUMPPA-COPEC 2010 in Southern Finland. RO2 concentrations were simulated by a box model constrained by the comprehensive dataset from the campaign and cross-checked against the photostationary state (PSS) of NOx [= nitric oxide (NO) + nitrogen dioxide (NO2)] calculations. The model simulated RO2 concentrations appear too low to explain the measured PSS of NOx. As the atmospheric RO2 production is proportional to OH loss, the total OH loss rate frequency (total OH reactivity) in the model is underestimated compared to the measurements. The total OH reactivity of the model is tuned to match the observed total OH reactivity by increasing the biogenic volatile organic compound (BVOCs) concentrations for the model simulations. The new-found simulated RO2 concentrations based on the tuned OH reactivity explain the measured PSS of NOx reasonably well. Furthermore, the sensitivity of the NOx lifetime and the catalytic efficiency of NOx (CE) in O3 production, in the context of organic alkyl nitrate (RONO2) formation, was also investigated. Based on the campaign data, it was found that the lifetime of NOx and the CE are reduced and are sensitive to the RONO2 formation under low-NOx conditions, which matches a previous model-based study.

Synthesis of Pt/K2CO3/MgAlOx–reduced graphene oxide hybrids as promising NOx storage–reduction catalysts with superior catalytic performance

PubMed Central

Mei, Xueyi; Yan, Qinghua; Lu, Peng; Wang, Junya; Cui, Yuhan; Nie, Yu; Umar, Ahmad; Wang, Qiang

2017-01-01

Pt/K2CO3/MgAlOx–reduced graphene oxide (Pt/K/MgAlOx–rGO) hybrids were synthesized, characterized and tested as a promising NOx storage and reduction (NSR) catalyst. Mg–Al layered double hydroxides (LDHs) were grown on rGO via in situ hydrothermal crystallization. The structure and morphology of samples were thoroughly characterized using various techniques. Isothermal NOx adsorption tests indicated that MgAlOx–rGO hybrid exhibited better NOx trapping performance than MgAlOx, from 0.44 to 0.61 mmol · g−1, which can be attributed to the enhanced particle dispersion and stabilization. In addition, a series of MgAlOx–rGO loaded with 2 wt% Pt and different loadings (5, 10, 15, and 20 wt%) of K2CO3 (denoted as Pt/K/MgAlOx–rGO) were obtained by sequential impregnation. The influence of 5% H2O on the NOx storage capacity of MgAlOx–rGO loaded with 2 wt% Pt and 10% K2CO3 (2Pt/10 K/MgAlOx–rGO) catalyst was also evaluated. In all, the 2Pt/10 K/MgAlOx–rGO catalyst not only exhibited high thermal stability and NOx storage capacity of 1.12 mmol · g−1, but also possessed excellent H2O resistance and lean–rich cycling performance, with an overall 78.4% of NOx removal. This work provided a new scheme for the preparation of highly dispersed MgAlOx–rGO hybrid based NSR catalysts. PMID:28205630

New family of lanthanide-based inorganic-organic hybrid frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and their derivatives.

PubMed

Liang, Jianbo; Ma, Renzhi; Ebina, Yasuo; Geng, Fengxia; Sasaki, Takayoshi

2013-02-18

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

40 CFR 96.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Opt-in Units § 96.286 Withdrawal from CAIR SO2 Trading Program. Except as provided...

40 CFR 96.260 - Submission of CAIR SO2 allowance transfers.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Submission of CAIR SO2 allowance... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Allowance Transfers § 96.260 Submission of CAIR SO2 allowance transfers. (a) A CAIR...

40 CFR 96.286 - Withdrawal from CAIR SO 2 Trading Program.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Withdrawal from CAIR SO 2 Trading... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO 2 Opt-in Units § 96.286 Withdrawal from CAIR SO 2 Trading Program. Except as...

40 CFR 96.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Opt-in Units § 96.286 Withdrawal from CAIR SO2 Trading Program. Except as provided...

40 CFR 96.286 - Withdrawal from CAIR SO 2 Trading Program.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Withdrawal from CAIR SO 2 Trading... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO 2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO 2 Opt-in Units § 96.286 Withdrawal from CAIR SO 2 Trading Program. Except as...

40 CFR 96.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS CAIR SO2 Opt-in Units § 96.286 Withdrawal from CAIR SO2 Trading Program. Except as provided...

Evaluation of the SO(2) and NH(3) gas adsorption properties of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO ternary impregnated activated carbon using combinatorial materials science methods.

PubMed

Romero, Jennifer V; Smith, Jock W H; Sullivan, Braden M; Macdonald, Landan; Croll, Lisa M; Dahn, J R

2013-02-11

Impregnated activated carbons (IAC) are widely used materials for the removal of toxic gases in personal respiratory protection applications. The combinatorial method has been employed to prepare IACs containing different types of metal oxides in various proportions and evaluate their adsorption performance for low molecular weight gases, such as SO(2) and NH(3), under dry conditions. Among the metal oxides used for the study, Mn(3)O(4) was found to have the highest capacity for retaining SO(2) gas under dry conditions. NiO and ZnO were found to have similar NH(3) adsorption capacities which are higher than the NH(3) capacities observed for the other metal oxide impregnants used in the study. Although Cu- or Zn-based impregnants and their combinations have been extensively studied and used as gas adsorbents, neither Mn(3)O(4) nor NiO have been incorporated in the formulations used. In this study, ternary libraries of IACs with various combinations of CuO/ZnO/Mn(3)O(4) and CuO/ZnO/NiO were studied and evaluated for their adsorption of SO(2) and NH(3) gases. Combinations of CuO, ZnO, and Mn(3)O(4) were found to have the potential to be multigas adsorbents compared to formulations that contain NiO.

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.

40 CFR 97.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Opt-in Units § 97.286 Withdrawal from CAIR SO2 Trading Program. Except as provided under paragraph (g) of...

40 CFR 97.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Opt-in Units § 97.286 Withdrawal from CAIR SO2 Trading Program. Except as provided under paragraph (g) of...

40 CFR 97.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Opt-in Units § 97.286 Withdrawal from CAIR SO2 Trading Program. Except as provided under paragraph (g) of...

40 CFR 97.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Opt-in Units § 97.286 Withdrawal from CAIR SO2 Trading Program. Except as provided under paragraph (g) of...

40 CFR 97.286 - Withdrawal from CAIR SO2 Trading Program.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Withdrawal from CAIR SO2 Trading... PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS CAIR SO2 Opt-in Units § 97.286 Withdrawal from CAIR SO2 Trading Program. Except as provided under paragraph (g) of...

DEPOSITION VELOCITIES OF SO2 AND O3 OVER AGRICULTURAL AND FOREST ECOSYSTEMS

EPA Science Inventory

The results of field studies that measured the flux and deposition velocity of SO2 and O3 are reported. Three of the studies were over agricultural crops (pasture, corn, and soybean), and two were over forest (a deciduous forest and a mixed coniferous - deciduous forest). In al...

Dosimeter-Type NOx Sensing Properties of KMnO4 and Its Electrical Conductivity during Temperature Programmed Desorption

PubMed Central

Groβ, Andrea; Kremling, Michael; Marr, Isabella; Kubinski, David J.; Visser, Jacobus H.; Tuller, Harry L.; Moos, Ralf

2013-01-01

An impedimetric NOx dosimeter based on the NOx sorption material KMnO4 is proposed. In addition to its application as a low level NOx dosimeter, KMnO4 shows potential as a precious metal free lean NOx trap material (LNT) for NOx storage catalysts (NSC) enabling electrical in-situ diagnostics. With this dosimeter, low levels of NO and NO2 exposure can be detected electrically as instantaneous values at 380 °C by progressive NOx accumulation in the KMnO4 based sensitive layer. The linear NOx sensing characteristics are recovered periodically by heating to 650 °C or switching to rich atmospheres. Further insight into the NOx sorption-dependent conductivity of the KMnO4-based material is obtained by the novel eTPD method that combines electrical characterization with classical temperature programmed desorption (TPD). The NOx loading amount increases proportionally to the NOx exposure time at sorption temperature. The cumulated NOx exposure, as well as the corresponding NOx loading state, can be detected linearly by electrical means in two modes: (1) time-continuously during the sorption interval including NOx concentration information from the signal derivative or (2) during the short-term thermal NOx release. PMID:23549366

RETROFIT COSTS FOR SO2 AND NOX CONTROL OPTIONS AT 200 COAL-FIRED PLANTS, VOLUME V - SITE SPECIFIC STUDIES FOR PA, SC, TN, VA, WI, WV

EPA Science Inventory

The report gives results of a study, the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 and NOx controls at 200 large SO2-emitting coal-fired utility plants. To accomplish the object...

RETROFIT COSTS FOR SO2 AND NOX CONTROL OPTIONS AT 200 COAL-FIRED PLANTS, VOLUME III - SITE SPECIFIC STUDIES FOR IN, KY, MA, MD, MI, MN

EPA Science Inventory

The report gives results of a study, the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 and NOx controls at 200 large SO2-emitting coal-fired utility plants. To accomplish the object...

Coupling catalytic hydrolysis and oxidation on Mn/TiO2-Al2O3 for HCN removal

NASA Astrophysics Data System (ADS)

Wang, Langlang; Wang, Xueqian; Cheng, Jinhuan; Ning, Ping; Lin, Yilong

2018-05-01

The manganese-modified titania-alumina (Mn/TiO2-Al2O3) catalyst synthesized by sol-gol method was used to remove hydrogen cyanide (HCN) from simulated flue gas. Further, effects of the mass ratios of Ti/Al, Mn loading, calcination temperature, and relative humidity on HCN conversion efficiency and catalytic activity were systematically investigated. The results indicated that the Mn/TiO2-Al2O3 catalyst exhibited significantly enhanced HCN removal efficiency, and the maximum yield of N2 increased to 68.02% without the participation of water vapor. When water vapor was added into the flue gas, the yield of N2 decreased and the formation of NOx was also inhibited. The XRD and XPS results indicated that Mn was mainly present in the form of Mn2+, Mn3+, and Mn4+ on the surface of catalyst and chemisorbed oxygen played a major role in the HCN catalytic oxidation process. The results of DSC-TGA analysis and H2-TPR indicated that the catalyst also exhibited a good thermal and chemical stability. NH3-TPD and CO2-TPD indicated that the surface of the catalyst mainly contained acidic sites. During the reaction, part of NH3 was adsorbed by Brönsted and Lewis acid sites. NH3 adsorbed on Lewis acid sites participated in NH3-SCR, which reduced the amount of NOx produced and resulted in a high N2 yield.

Variation of radiative forcings and global warming potentials from regional aviation NOx emissions

NASA Astrophysics Data System (ADS)

Skowron, Agnieszka; Lee, David S.; De León, Ruben R.

2015-03-01

The response to hemispherical and regional aircraft NOx emissions is explored by using two climate metrics: radiative forcing (RF) and Global Warming Potential (GWP). The global chemistry transport model, MOZART-3 CTM, is applied in this study for a series of incremental aircraft NOx emission integrations to different regions. It was found that the sensitivity of chemical responses per unit emission rate from regional aircraft NOx emissions varies with size of aircraft NOx emission rate and that climate metric values decrease with increasing aircraft NOx emission rates, except for Southeast Asia. Previous work has recognized that aircraft NOx GWPs may vary regionally. However, the way in which these regional GWPs are calculated are critical. Previous studies have added a fixed amount of NOx to different regions. This approach can heavily bias the results of a regional GWP because of the well-established sensitivity of O3 production to background NOx whereby the Ozone Production Efficiency (OPE) is greater at small background NOx. Thus, even a small addition of NOx in a clean-air area can produce a large O3 response. Using this 'fixed addition' method of 0.035 Tg(N) yr-1, results in the greatest effect observed for North Atlantic and Brazil, ∼10.0 mW m-2/Tg(N) yr-1. An alternative 'proportional approach' is also taken that preserves the subtle balance of local NOx-O3-CH4 systems with the existing emission patterns of aircraft and background NOx, whereby a proportional amount of aircraft NOx, 5% (N) yr-1, is added to each region in order to determine the response. This results in the greatest effect observed for North Pacific that with its net NOx RF of 23.7 mW m-2/Tg(N) yr-1 is in contrast with the 'fixed addition' method. For determining regional NOx GWPs, it is argued that the 'proportional' approach gives more representative results. However, a constraint of both approaches is that the regional GWP determined is dependent on the relative global emission pattern

Simulation of the diurnal variations of the isotope anomaly (?17O) of reactive trace gases (NOx, HOx) and implications for the ?17O of nitrate.

NASA Astrophysics Data System (ADS)

Morin, Samuel; Sander, Rolf; Savarino, Joël.

2010-05-01

The isotope anomaly of secondary atmospheric species such as nitrate (NO3-) has potential to provide useful constrains on their formation pathways. Indeed, the ?17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero ?17O in the atmosphere. Interpreting variations of ?17O in nitrate requires an in-depth understanding of the ?17O of its precursors taking into account non-linear chemical regimes operating under various environmental settings. In addition, the role of isotope exchange reactions must be carefully accounted for. To investigate the relevance of various assessments of the isotopic signature of nitrate production pathways that have recently been proposed in the literature, an atmospheric chemistry box model (MECCA, Sander et al., 2005, ACP)) was used to explicitly compute the diurnal variations of the isotope anomaly of NOx, HOx under several conditions prevailing in the marine boundary layer. ?17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation applied at each time step of the model (30 seconds typically). The model confirms that diurnal variations in ?17O of NOx are well predicted by the photochemical steady-state relationship introduced by Michalski et al. (2003, GRL) during the day, but that at night a different approach must be employed (e.g. « fossilization » of the ?17O of NOx as soon as the photochemical lifetime of NOx drops below ca. 5 minutes). The model also allows to evaluate the impact on ?17O of NOx and nitrate of the frequently made simplifying assumption that ?17O(HOx)=0 permil, with and without mass-independent fractionation during the H+O2-HO2 reaction. Recommendations for the modeling of ?17O of nitrate will be given, based on the extensive model work carried out. In addition, the link between diurnal variations of the ?17O of nitrate precursors and seasonal

Cyclic Nanostructures of Tungsten Oxide (WO3)n  (n = 2–6) as NOx Gas Sensor: A Theoretical Study

PubMed Central

Izadyar, Mohammad; Jamsaz, Azam

2014-01-01

Today's WO3-based gas sensors have received a lot of attention, because of important role as a sensitive layer for detection of the small quantities of  NOx. In this research, a theoretical study has been done on the sensing properties of different cyclic nanoclusters of (WO3)n  (n = 2–6) for NOx  (x = 1,2) gases. Based on the calculated adsorption energies by B3LYP and X3LYP functionals, from the different orientations of  NOx molecule on the tungsten oxide clusters, O–N⋯W was preferred. Different sizes of the mentioned clusters have been analyzed and W2O6 cluster was chosen as the best candidate for NOx detection from the energy viewpoint. Using the concepts of the chemical hardness and electronic charge transfer, some correlations between the energy of adsorption and interaction energy have been established. These analyses confirmed that the adsorption energy will be boosted with charge transfer enhancement. However, the chemical hardness relationship is reversed. Finally, obtained results from the natural bond orbital and electronic density of states analysis confirmed the electronic charge transfer from the adsorbates to WO3 clusters and Fermi level shifting after adsorption, respectively. The last parameter confirms that the cyclic clusters of tungsten oxide can be used as NOx gas sensors. PMID:25544841

EMISSIONS AND COST ESTIMATES FOR GLOBALLY SIGNIFICANT ANTHROPOGENIC COMBUSTION SOURCES OF NOX, N2O, CH4, CO AND CO2

EPA Science Inventory

The report discusses the development of emission factors for CO2, CO, CH4, NOx, and N2O for about 80 globally significant combustion sources in seven source categories: utility, industrial, fuel production, transportation, residential, commercial, and kilns/ovens/dryers. ecause o...

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.

Modeling atmospheric mineral aerosol chemistry to predict heterogeneous photooxidation of SO2

NASA Astrophysics Data System (ADS)

Yu, Zechen; Jang, Myoseon; Park, Jiyeon

2017-08-01

The photocatalytic ability of airborne mineral dust particles is known to heterogeneously promote SO2 oxidation, but prediction of this phenomenon is not fully taken into account by current models. In this study, the Atmospheric Mineral Aerosol Reaction (AMAR) model was developed to capture the influence of air-suspended mineral dust particles on sulfate formation in various environments. In the model, SO2 oxidation proceeds in three phases including the gas phase, the inorganic-salted aqueous phase (non-dust phase), and the dust phase. Dust chemistry is described as the absorption-desorption kinetics of SO2 and NOx (partitioning between the gas phase and the multilayer coated dust). The reaction of absorbed SO2 on dust particles occurs via two major paths: autoxidation of SO2 in open air and photocatalytic mechanisms under UV light. The kinetic mechanism of autoxidation was first leveraged using controlled indoor chamber data in the presence of Arizona Test Dust (ATD) particles without UV light, and then extended to photochemistry. With UV light, SO2 photooxidation was promoted by surface oxidants (OH radicals) that are generated via the photocatalysis of semiconducting metal oxides (electron-hole theory) of ATD particles. This photocatalytic rate constant was derived from the integration of the combinational product of the dust absorbance spectrum and wave-dependent actinic flux for the full range of wavelengths of the light source. The predicted concentrations of sulfate and nitrate using the AMAR model agreed well with outdoor chamber data that were produced under natural sunlight. For seven consecutive hours of photooxidation of SO2 in an outdoor chamber, dust chemistry at the low NOx level was attributed to 55 % of total sulfate (56 ppb SO2, 290 µg m-3 ATD, and NOx less than 5 ppb). At high NOx ( > 50 ppb of NOx with low hydrocarbons), sulfate formation was also greatly promoted by dust chemistry, but it was suppressed by the competition between NO2 and SO2

Environmental assessment of an enhanced-oil-recovery steam generator equipped with a low-NOx burner. Volume 1. Technical results. Final report, January 1984-January 1985

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

Castaldini, C.; Waterland, L.R.; Lips, H.I.

1986-02-01

The report discusses results from sampling flue gas from an enhanced-oil-recovery steam generator (EOR steamer) equipped with an MHI PM low-NOx burner. The tests included burner performance/emission mapping tests, comparative testing of an identical steamer equipped with a conventional burner, and comprehensive testing of the low-NOx-burner-equipped steamer. Comprehensive test measurements included continuous flue-gas monitoring; source assessment sampling system testing with subsequent laboratory analysis to give total flue-gas organics in two boiling point ranges and specific quantitation on the semivolatile organic priority pollutants; C1 to C6 hydrocarbon sampling; Methods 5/8 sampling for particulate and SO/sub 2/ and SO/sub 3/ emissions; andmore » emitted particle size distribution tests using Andersen impactors. Full-load NOx emissions of 110 ppm (3% O/sub 2/) could be maintained from the low-NOx burner at acceptable CO and smoke emissions, compared to about 300 ppm (3% O/sub 2/) from the conventional-burner-equipped steamer. At the low-NOx condition, CO, SO/sub 2/, and SO/sub 3/ emissions were 93, 594, and 3.1 ppm, respectively. Particulate emissions were 39 mg/dscm with a mean particle diameter of 3 to 4 micrometers. Total organic emissions were 11.1 mg/dscm, almost exclusively volatile (C1 to C6) organics. Three PAHs were detected at from 0.1 to 1.4 micrograms/dscm.« less

40 CFR 97.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Permits § 97.220 General CAIR SO2 Trading Program permit requirements. (a) For each CAIR SO2 source...

40 CFR 97.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Permits § 97.220 General CAIR SO2 Trading Program permit requirements. (a) For each CAIR SO2 source...

40 CFR 97.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Permits § 97.220 General CAIR SO2 Trading Program permit requirements. (a) For each CAIR SO2 source...

40 CFR 97.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Permits § 97.220 General CAIR SO2 Trading Program permit requirements. (a) For each CAIR SO2 source...

40 CFR 97.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) FEDERAL NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS Permits § 97.220 General CAIR SO2 Trading Program permit requirements. (a) For each CAIR SO2 source...

Stereochemical and electronic control of M-SO/sub 2/ bonding geometry in d/sup 6/ molybdenum and tungsten SO/sub 2/ complexes: novel n/sup 1/reverse arrown/sup 2/ SO/sub 2/ linkage isomerization in Mo(CO)/sub 2/(PPh/sub 3/)/sub 2/(CNR)(SO/sub 2/) and structures of Mo(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(SO/sub 2/) and (Mo(CO)/sub 2/(py)(PPh/sub 3/)(. mu. -SO/sub 2/))/sub 2/

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

Kubas, G.J.; Jarvinen, G.D.; Ryan, R.R.

1983-04-06

New complexes, mer,trans,M(CO)/sub 3/(PR/sub 3/)/sub 2/(SO/sub 2/) (M = Mo,W; R = Ph,Cy,i-Pr) (I), cis,trans-Mo(CO)/sub 2/-(PPh/sub 3/)/sub 2/(SO/sub 2/)(L) (L = NCMe,py,CNCy,CN-t-Bu and CN(p-tolyl))(II), and (Mo(CO)/sub 2/(py)(PPh/sub 3/)(..mu..-SO/sub 2/))/sub 2/, have been prepared and characterized by infrared spectroscopy, /sup 17/O and /sup 31/P NMR spectroscopy, and X-ray crystallography. Syntheses for fac-Mo(CO)/sub 3/(n/sup 2/-SO/sub 2/)(LL) (LL = dppe,bpy,phen,2 py) have also been developed. Depending upon L, II has been found to coordinate SO/sub 2/ either in the S-bonded (n/sup 1/ planar) or O,S-bonded (n/sup 2/) geometries. Remarkably, for L = CNCy or CN-t-Bu, II has been found to contain, in themore » solid state, an apparent equimixture of both coordination types. Isomerization of fac-M(CO)/sub 3/(dppe)(n/sup 2/-SO/sub 2/) (M=Mo,w; dppe = 1,2-bis(diphenylphosphino)ethane) to an n/sup 1/-planar SO/sub 2/ form, mer-M(CO)/sub 3/(dppe)(SO/sub 2/), has also been found to occur. Thus, control of the SO/sub 2/ coordination geometry has been achieved by varying either the electronic properties of the ancillary ligands or their disposition with respect to the SO/sub 2/. The X-ray crystal structure of mer,trans-Mo(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(SO/sub 2/) revealed n/sup 1/-planar SO/sub 2/ binding, the first example of this geometry for group 6 metals. The M-S distance, 2.239 (3) angstrom, is the longest such distance for this geometry recorded to date. Crystal data: Pbca, Z=8, a=24.712(8) angstrom, b=16.033(6) angstrom, c=14.058(5) angstrom, R=0.079 for 2934 reflections with Igreater than or equal to2sigma(I). The structure of (Mo(CO)/sub 2/(py)(PPh/sub 3/)(..mu..-SO/sub 2/))/sub 2/ showed a novel SO/sub 2/ bridging geometry in which all three atoms of SO/sub 2/ are metal coordinated. Crystal data: P1, Z=1, a=14.883(4) angstrom, b=9.264(2) angstrom, c=10.808(2) angstrom, R=0.039 for 3282 reflections with Igreater than or equal to2sigma(I).« less

The Role of NOX4 and TRX2 in Angiogenesis and Their Potential Cross-Talk

PubMed Central

Chen, Chaofei; Li, Li; Zhou, Huanjiao Jenny; Min, Wang

2017-01-01

The nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX) family is the major source of reactive oxygen species (ROS) in the vascular system. In this family, NOX4, a constitutive active form of NOXs, plays an important role in angiogenesis. Thioredoxin 2 (TRX2) is a key mitochondrial redox protein that maintains normal protein function and also provides electrons to peroxiredoxin 3 (PRX3) to scavenge H2O2 in mitochondria. Angiogenesis, a process of new blood vessel formation, is involved in a variety of physiological processes and pathological conditions. It seems to be paradoxical for ROS-producing NOX4 and ROS-scavenging TRX2 to have a similar role in promoting angiogenesis. In this review, we will focus on data supporting the role of NOX4 and TRX2 in angiogenesis and their cross-talks and discuss how ROS can positively or negatively regulate angiogenesis, depending on their species, levels and locations. NOX4 and TRX2-mediated ROS signaling could be promising targets for the treatment of angiogenesis-related diseases. PMID:28594389

Novel Co- or Ni-Mn binary oxide catalysts with hydroxyl groups for NH3-SCR of NOx at low temperature

NASA Astrophysics Data System (ADS)

Gao, Fengyu; Tang, Xiaolong; Yi, Honghong; Zhao, Shunzheng; Wang, Jiangen; Shi, Yiran; Meng, Xiaomi

2018-06-01

Novel hydroxyl-containing Me-Mn binary oxides (Me = Co, Ni) were prepared for the selective catalytic reduction of NOx with NH3 by a combined complexation-esterification method. The binary oxides of Co-MnOx and Ni-MnOx with mixed crystal phases of Mn3O4 and Co3O4, Mn2O3 and NiMnO3 were obtained at 550 °C. SCR activity decreased in the order of Mn3O4-Co3O4-OH > Mn2O3-NiMnO3-OH > Mn2O3-OH > Mn3O4-OH, benefiting from the high concentration of chemisorbed oxygen and effective electron transformation of cations. Mn2O3-containing catalysts had better selectivity to N2 than those containing Mn3O4. Higher selectivity to N2O over Mn3O4-containing catalysts was attributed to the depth dehydrogenation of coordinated NH3 by the active oxygen species with lower Mnsbnd O band energy. The typical Eley-Rideal mechanism over Mn3O4-OH and Mn3O4-Co3O4-OH, and the additional formation pathway of NH4NO3 species over Mn2O3-OH and Mn2O3-NiMnO3-OH catalysts were proposed via the in-situ DRIFTS experiments. Although the Co and Ni elements had a good role in delaying the poisoning of SO2, these catalysts were eventually sulfated by SO2 over the postponement, which might due to the metal sulfate and ammonia hydrogensulfite species.

Modeling the effects of changes in New Source Review on national SO{sub 2} and NOx emissions from electricity-generating units

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

David A. Evans; Benjamin F. Hobbs; Craig Oren

2007-03-15

The Clean Air Act establishes New Source Review (NSR) programs that apply to the construction or modification of major stationary emissions sources. In 2002 and 2003, the U.S. Environmental Protection Agency revised its rules to narrow the applicability of NSR to facility renovations. Congress then mandated a National Research Council study of the effects of the rules. An electricity-sector model - the Integrated Planning Model (IPM) - was used to explore the possible effects of the equipment replacement provision (ERP), the principal NSR change that was to affect the power-generation industry. The studies focused in particular on coal-fired electricity generatingmore » units, EGUs, for two reasons. First, coal-fired EGUs are important contributors of these pollutants, accounting for approximately 70 and 20% of nations SO{sub 2} and NOx emissions in 2004, respectively. Second, the shares of total capacity of large coal-fired EGUs that lack flue-gas desulfurization to control SO{sub 2} and selective catalytic reduction to reduce NOx emissions are 62 and 63% respectively. Although the analysis cannot predict effects on local emissions, assuming that the Clean Air Interstate Rule (CAIR) is implemented, we find that stringent enforcement of the previous NSR rules would likely lead to no or limited decreases in national emissions compared to policies such as ERP. Our results indicate that tighter emissions caps could achieve further decreases in national emissions more cost-effectively than NSR programs. 15 refs., 3 figs., 1 tab.« less

The interaction of NO2 with BaO: from cooperative adsorption to Ba(NO3)2 formation

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

Yi, Cheol-Woo W.; Kwak, Ja Hun; Szanyi, Janos

2007-10-25

The effect of water on the morphology of BaO/Al2O3-based NOx storage materials was investigated using Fourier transform infrared spectroscopy, temperature programmed desorption, and time-resolved synchrotron X-ray diffraction techniques. The results of this multi-spectroscopy study reveal that, in the presence of water, surface Ba-nitrates convert to bulk nitrates, and water facilitates the formation of large Ba(NO3)2 particles. The conversion of surface to bulk Ba-nitrates is completely reversible, i.e. after the removal of water from the storage material a significant fraction of the bulk nitrates re-convert to surface nitrates. NO2 exposure of a H2O-containing (wet) BaO/Al2O3 sample results in the formation ofmore » nitrites and bulk nitrates exclusively, i.e. no surface nitrates form. After further exposure to NO2, the nitrites completely convert to bulk nitrates. The amount of NOx taken up by the storage material is, however, essentially unaffected by the presence of water, regardless of whether the water was dosed prior to or after NO2 exposure. Based on the results of this study we are now able to explain most of the observations reported in the literature on the effect of water on NOx uptake on similar storage materials.« less

Quantification of the enhanced effectiveness of NOx control from simultaneous reductions of VOC and NH3 for reducing air pollution in the Beijing-Tianjin-Hebei region, China

NASA Astrophysics Data System (ADS)

Xing, Jia; Ding, Dian; Wang, Shuxiao; Zhao, Bin; Jang, Carey; Wu, Wenjing; Zhang, Fenfen; Zhu, Yun; Hao, Jiming

2018-06-01

As one common precursor for both PM2.5 and O3 pollution, NOx gains great attention because its controls can be beneficial for reducing both PM2.5 and O3. However, the effectiveness of NOx controls for reducing PM2.5 and O3 are largely influenced by the ambient levels of NH3 and VOC, exhibiting strong nonlinearities characterized as NH3-limited/NH3-poor and NOx-/VOC-limited conditions, respectively. Quantification of such nonlinearities is a prerequisite for making suitable policy decisions but limitations of existing methods were recognized. In this study, a new method was developed by fitting multiple simulations of a chemical transport model (i.e., Community Multiscale Air Quality Modeling System, CMAQ) with a set of polynomial functions (denoted as pf-RSM) to quantify responses of ambient PM2.5 and O3 concentrations to changes in precursor emissions. The accuracy of the pf-RSM is carefully examined to meet the criteria of a mean normalized error within 2 % and a maximal normalized error within 10 % by using 40 training samples with marginal processing. An advantage of the pf-RSM method is that the nonlinearity in PM2.5 and O3 responses to precursor emission changes can be characterized by quantitative indicators, including (1) a peak ratio (denoted as PR) representing VOC-limited or NOx-limited conditions, (2) a suggested ratio of VOC reduction to NOx reduction to avoid increasing O3 under VOC-limited conditions, (3) a flex ratio (denoted as FR) representing NH3-poor or NH3-rich conditions, and (4) enhanced benefits in PM2.5 reductions from simultaneous reduction of NH3 with the same reduction rate of NOx. A case study in the Beijing-Tianjin-Hebei region suggested that most urban areas present strong VOC-limited conditions with a PR from 0.4 to 0.8 in July, implying that the NOx emission reduction rate needs to be greater than 20-60 % to pass the transition from VOC-limited to NOx-limited conditions. A simultaneous VOC control (the ratio of VOC reduction

An Alternative to NOx Cap-and-Trade Programs: An Exploratory Analysis of Charging NOx Emitters for Health Damages

NASA Astrophysics Data System (ADS)

Mauzerall, D. L.; Sultan, B.; Kim, N.; Bradford, D.

2003-12-01

To address the problem of elevated O3 concentrations throughout the northeastern United States in summer, a NOx cap-and-trade program was implemented that reduced NOx emissions from large point sources by nearly 50%. To determine whether this program has been successful, we examine O3, NO and temperature measurements collected in the EPA-AIRS network prior to and after the cap-and-trade program went into effect in 1999. Ambient NO concentrations as measured in the EPA-AIRS network are lower in the post-cap period in all months except July. We find that the upper half of the distribution of O3 concentrations within the region is essentially unchanged (or slightly higher) in May and June, modestly reduced in July and August (except the highest concentrations which are larger in August), and significantly lower in September (ranging from 0-20 ppb lower between the mean and highest concentrations) in the 1999-2001 post-cap period relative to the 1995-1998 pre-cap period. Except for September, the frequency with which the 80ppb 8-hour NAAQS standard for O3 is exceeded has not decreased. Temperatures during the post-cap period were slightly higher in June, July and August, and slightly lower in September - likely contributing to reduced O3 levels during September in the post-cap period. To explore the possibility that trading, or selective emissions over the course of the summer, could influence regional O3 concentrations, we conduct chemical transport modeling experiments using the CAMx regional model. Even within May-September for a single year, demands for electrical power and hence NOx emissions are greater during hot than cool periods. We demonstrate that substantially more O3 is produced from identical NOx emissions from a single power plant on high temperature than on low temperature days in July 1995. Thus a lack of temporal restrictions on when in a single summer month NOx emissions may occur can result in higher O3 levels. We also demonstrate that identical NOx

O3, SO2, NO2, and UVB measurements in Beijing and Baseline Station of northwestern part of China

NASA Technical Reports Server (NTRS)

Guo, Song; Zhou, Xiuji; Zhang, Xiachun

1994-01-01

A MKII Brewer ozone spectrometer was used in Beijing from Oct. 1990 to June 1991 to measure O3, SO2 and UVB radiation. And since Nov. 1991 a new MKIV Brewer spectrometer, which can take the measurements of O3, SO2, NO2 and UVB radiation, has been set up in Beijing. The MKII Brewer spectrometer was moved to Qinghai baseline station which is on the Qinghai-tibetean plateau in the northwestern part of China. Both the data in Beijing and Qinghai baseline station has been analyzed and some results will be shown here along with the ozone profiles botained through the Umkehr program given by AES of Canada for the Brewer ozone spectrometer.

RETROFIT COSTS FOR SO2 AND NOX CONTROL OPTIONS AT 200 COAL-FIRED PLANTS, VOLUME IV - SITE SPECIFIC STUDIES FOR MO, MS, NC, NH, NJ, NY, OH

EPA Science Inventory

The report gives results of a study, the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 and NOx controls at 200 large SO2-emitting coal-fired utility plants. To accomplish the object...

The role of Nox1 and Nox2 in GPVI-dependent platelet activation and thrombus formation☆

PubMed Central

Walsh, T.G.; Berndt, M.C.; Carrim, N.; Cowman, J.; Kenny, D.; Metharom, P.

2014-01-01

Background Activation of the platelet-specific collagen receptor, glycoprotein (GP) VI, induces intracellular reactive oxygen species (ROS) production; however the relevance of ROS to GPVI-mediated platelet responses remains unclear. Objective The objective of this study was to explore the role of the ROS-producing NADPH oxidase (Nox)1 and 2 complexes in GPVI-dependent platelet activation and collagen-induced thrombus formation. Methods and results ROS production was measured by quantitating changes in the oxidation-sensitive dye, H2DCF-DA, following platelet activation with the GPVI-specific agonist, collagen related peptide (CRP). Using a pharmacological inhibitor specific for Nox1, 2-acetylphenothiazine (ML171), and Nox2 deficient mice, we show that Nox1 is the key Nox homolog regulating GPVI-dependent ROS production. Nox1, but not Nox2, was essential for CRP-dependent thromboxane (Tx)A2 production, which was mediated in part through p38 MAPK signaling; while neither Nox1 nor Nox2 was significantly involved in regulating CRP-induced platelet aggregation/integrin αIIbβ3 activation, platelet spreading, or dense granule and α-granule release (ATP release and P-selectin surface expression, respectively). Ex-vivo perfusion analysis of mouse whole blood revealed that both Nox1 and Nox2 were involved in collagen-mediated thrombus formation at arterial shear. Conclusion Together these results demonstrate a novel role for Nox1 in regulating GPVI-induced ROS production, which is essential for optimal p38 activation and subsequent TxA2 production, providing an explanation for reduced thrombus formation following Nox1 inhibition. PMID:24494191

40 CFR 96.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS Permits § 96.220 General CAIR SO2 Trading Program permit requirements. (a...

40 CFR 96.220 - General CAIR SO 2 Trading Program permit requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false General CAIR SO 2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS Permits § 96.220 General CAIR SO 2 Trading Program permit requirements. (a...

40 CFR 96.220 - General CAIR SO2 Trading Program permit requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false General CAIR SO2 Trading Program... (CONTINUED) AIR PROGRAMS (CONTINUED) NOX BUDGET TRADING PROGRAM AND CAIR NOX AND SO2 TRADING PROGRAMS FOR STATE IMPLEMENTATION PLANS Permits § 96.220 General CAIR SO2 Trading Program permit requirements. (a...