WorldWideScience

Sample records for atmospheric oxidation by-products

  1. Atmospheric oxidation of selected hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Olariu, R.I.

    2002-02-01

    This work presents investigations on the gas-phase chemistry of phenol and the cresol isomers performed in a 1080 l quartz glass reactor in Wuppertal and in a large-volume outdoor photoreactor EUPHORE in Valencia, Spain. The studies aimed at clarifying the oxidation mechanisms of the reactions of these compounds with OH and NO{sub 3} radicals. Product investigations on the oxidation of phenol and the cresol isomers initiated by OH radicals were performed in the 1080 l quartz glass reactor with analyses by in situ FT-IR absorption spectroscopy. The primary focus of the investigations was on the determination of product yields. This work represents the first determination and quantification of 1,2-dihydroxybenzenes in the OH oxidation of phenolic compounds. Possible reaction pathways leading to the observed products have been elucidated. (orig.)

  2. Atmospheric oxidation of selected alcohols and esters

    Energy Technology Data Exchange (ETDEWEB)

    Becker, K.H.; Cavalli, F.

    2001-03-01

    The decision whether it is appropriate and beneficial for the environment to deploy specific oxygenated organic compounds as replacements for traditional solvent types requires a quantitative assessment of their potential atmospheric impacts including tropospheric ozone and other photooxidant formation. This involves developing chemical mechanisms for the gasphase atmospheric oxidation of the compounds which can be reliably used in models to predict their atmospheric reactivity under a variety of environmental conditions. Until this study, there was very little information available concerning the atmospheric fate of alcohols and esters. The objectives of this study were to measure the atmospheric reaction rates and to define atmospheric reaction mechanisms for the following selected oxygenated volatile organic compounds: the alcohols, 1-butanol and 1-pentanol, and the esters, methyl propionate and dimethyl succinate. The study has successfully addressed these objectives. (orig.)

  3. Greenhouse effect due to atmospheric nitrous oxide

    Science.gov (United States)

    Yung, Y. L.; Wang, W. C.; Lacis, A. A.

    1976-01-01

    The greenhouse effect due to nitrous oxide in the present atmosphere is about 0.8 K. Increase in atmospheric N2O due to perturbation of the nitrogen cycle by man may lead to an increase in surface temperature as large as 0.5 K by 2025, or 1.0 K by 2100. Other climatic effects of N2O are briefly discussed.

  4. Primary atmospheric oxidation mechanism for toluene.

    Science.gov (United States)

    Baltaretu, Cristian O; Lichtman, Eben I; Hadler, Amelia B; Elrod, Matthew J

    2009-01-08

    The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique at temperatures ranging from 228 to 298 K. A major dienedial-producing pathway was detected for the first time for toluene oxidation, and glyoxal and methylglyoxal were found to be minor primary oxidation products. The results suggest that secondary oxidation processes involving dienedial and epoxide primary products are likely responsible for previous observations of glyoxal and methylglyoxal products from toluene oxidation. Because the dienedial-producing pathway is a null cycle for tropospheric ozone production and glyoxal and methylglyoxal are important secondary organic aerosol precursors, these new findings have important implications for the modeling of toluene oxidation in the atmosphere.

  5. Oxidation kinetics of aluminum nitride at different oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Hou Xinmei [Metallurgical and Ecological Engineering School, University of Science and Technology Beijing, Beijing 100083 (China); Chou, K.-C. [Metallurgical and Ecological Engineering School, University of Science and Technology Beijing, Beijing 100083 (China)], E-mail: kcc126@126.com; Zhong Xiangchong [High Temperature Ceramics Institute, Zhengzhou University, Henan Province 450052 (China); Seetharaman, Seshadri [Department of Materials Science and Engineering, Royal Institute of Technology, Stockholm (Sweden)

    2008-10-06

    In the present work, the oxidation kinetics of AlN powder was investigated by using thermogravimetric analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The experiments were carried out both in isothermal as well as non-isothermal modes under two different oxidizing atmospheres. The results showed that the oxidation reaction started at around 1100 K and the rate increased significantly beyond 1273 K forming porous aluminum oxide as the reaction product. The oxidation rate was affected by temperature and oxygen partial pressure. A distinct change in the oxidation mechanism was noticed in the temperature range 1533-1543 K which is attributed to the phase transformation in oxidation product, viz. alumina. Diffusion is the controlling step during the oxidation process. Based on the experimental data, a new model for predicting the oxidation process of AlN powder had been developed, which offered an analytic form expressing the oxidation weight increment as a function of time, temperature and oxygen partial pressure. The application of this new model to this system demonstrated that this model could be used to describe the oxidation behavior of AlN powder.

  6. Atmospheric oxidation of carbon disulfide (CS2)

    Science.gov (United States)

    Zeng, Zhe; Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z.

    2017-02-01

    This contribution investigates primary steps governing the OH-initiated atmospheric oxidation of CS2. Our approach comprises high-level density functional theory calculation of energies and optimisation of molecular structures as well as RRKM-ME analysis for estimating pressure-dependent reaction rate constants. We find the overall reaction OH + CS2 → OCS + SH too slow to account for the formation of the reported experimental products. The initial reaction of OH with CS2 proceeds to produce an S-adduct, SCS(OH). Species-formation history for the system OH + CS2 indicates that, the S-adduct represents the most plausible product with a barrier-less addition process and a stability amounting to 48.5 kJ/mol, in reference to the separated reactants. This adduct then undergoes a bimolecular reaction with atmospheric O2 yielding OCS and HOSO, rather than dissociating back into its separated reactants. We also find that further atmospheric oxidation of the C-adduct (if formed) yields two of the major experimental products namely OCS and SO2. The kinetic analysis provided in this study explains the atmospheric fate of reduced sulfur species, an important S-bearing group in the global cycle of sulfur.

  7. A new method for quantitatively characterizing atmospheric oxidation capacity

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Based on atmospheric chemical kinetics, the rate constant of overall pseudo-first order oxidation re-moval of gaseous pollutants (Kpor,T) is proposed to characterize the atmospheric oxidation capacity in troposphere. Being a quantitative parameter, Kpor,T can be used to address the issues related to at-mospheric oxidation capacity. By applying this method, the regional oxidation capacity of the atmos-phere in Pearl River Delta (PRD) is numerically simulated based on CBM-IV chemical mechanism. Re-sults show the significant spatio-temporal variation of the atmospheric oxidation capacity in PRD. It is found that OH initiated oxidations, heterogeneous oxidation of SO2, and photolysis of aldehydes are the three most important oxidation processes influencing the atmospheric oxidation capacity in PRD.

  8. Formation of disinfection by-products after pre-oxidation with chlorine dioxide or ferrate.

    Science.gov (United States)

    Yang, Xin; Guo, Wanhong; Zhang, Xing; Chen, Feng; Ye, Tingjin; Liu, Wei

    2013-10-01

    The effect of pre-oxidation with chlorine dioxide (ClO2) or ferrate (Fe(VI)) on the formation of disinfection by-products (DBPs) during chlorination or chloramination was tested with natural waters from 12 sources (9 surface waters, 1 groundwater, and 2 wastewater effluents). DBPs investigated included trihalomethanes (THM), chloral hydrate (CH), haloketones (HK), haloacetonitriles (HAN) and trichloronitromethane (TCNM), chlorite and chlorate. Chlorite and chlorate were found in the ClO2-treated waters. Application of 1 mg/L ClO2 ahead of chlorination reduced the formation potential for THM by up to 45% and the formation of HK, HAN and TCNM in most of the samples. The CH formation results were mixed. The formation of CH and HK was enhanced with low doses of Fe(VI) (1 mg/L as Fe), but was greatly reduced at higher doses (20 mg/L Fe). Fe(VI) reduced the formation of THM, HAN and TCNM in most of the samples. Reduced potential for the formation of NDMA was observed in most of the samples after both ClO2 and Fe(VI) pre-oxidation.

  9. High Performance Nitrous Oxide Analyzer for Atmospheric Research Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This project targets the development of a highly sensitive gas sensor to monitor atmospheric nitrous oxide. Nitrous oxide is an important species in Earth science...

  10. Formation of disinfection by-products in the ultraviolet/chlorine advanced oxidation process.

    Science.gov (United States)

    Wang, Ding; Bolton, James R; Andrews, Susan A; Hofmann, Ron

    2015-06-15

    Disinfection by-product (DBP) formation may be a concern when applying ultraviolet light and free chlorine (UV/chlorine) as an advanced oxidation process (AOP) for drinking water treatment, due to typically large chlorine doses (e.g. 5-10 mg L(-1) as free chlorine). A potential mitigating factor is the low chlorine contact times for this AOP treatment (e.g. seconds). Full-scale and pilot-scale test results showed minimal trihalomethane (THM) and haloacetic acid (HAA) formation during UV/chlorine treatment, while dichloroacetonitrile (DCAN) and bromochloroacetonitrile (BCAN) were produced rapidly. Adsorbable organic halide (AOX) formation was significant when applying the UV/chlorine process in water that had not been previously chlorinated, while little additional formation was observed in prechlorinated water. Chlorine photolysis led to chlorate and bromate formation, equivalent to approximately 2-17% and 0.01-0.05% of the photolyzed chlorine, respectively. No perchlorate or chlorite formation was observed. During simulated secondary disinfection of AOP-treated water, DBP formation potential for THMs, HAAs, HANs, and AOX was observed to increase approximately to the same extent as was observed for pretreatment using the more common AOP of UV combined with hydrogen peroxide (UV/H2O2).

  11. Removal of disinfection by-product precursors with ozone-UV advanced oxidation process.

    Science.gov (United States)

    Chin, A; Bérubé, P R

    2005-05-01

    The efficacy of using ozone (O3), ultraviolet irradiation (UV) and the combined O3-UV advanced oxidation process (AOP) to remove 2 classes of disinfection by-product (DBP) precursors from raw surface water samples have been evaluated and compared. In particular, trihalomethane and haloacetic acids formation potentials were measured. Laboratory batch scale experiments were carried out as a function of ozone and UV dosage in order to study the removal kinetics. It is concluded that the combined O3-UV AOP is more effective than either the ozone or UV treatment alone. Ozone-UV AOP is capable of mineralizing up to 50% of the total organic carbon from the raw source water at an ozone dose of 0.62+/-0.019 mg O3/mL and a UV dose of 1.61 W s/cm2. In addition, O3-UV AOP can reduce trihalomethane formation potential by roughly 80% and haloacetic acids formation potential by roughly 70% at the same ozone and UV dosage.

  12. Atmospheric oxidation capacity sustained by a tropical forest.

    Science.gov (United States)

    Lelieveld, J; Butler, T M; Crowley, J N; Dillon, T J; Fischer, H; Ganzeveld, L; Harder, H; Lawrence, M G; Martinez, M; Taraborrelli, D; Williams, J

    2008-04-10

    Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere, which are removed by oxidation reactions and deposition of reaction products. The oxidation is mainly initiated by hydroxyl radicals (OH), primarily formed through the photodissociation of ozone. Previously it was thought that, in unpolluted air, biogenic VOCs deplete OH and reduce the atmospheric oxidation capacity. Conversely, in polluted air VOC oxidation leads to noxious oxidant build-up by the catalytic action of nitrogen oxides (NO(x) = NO + NO2). Here we report aircraft measurements of atmospheric trace gases performed over the pristine Amazon forest. Our data reveal unexpectedly high OH concentrations. We propose that natural VOC oxidation, notably of isoprene, recycles OH efficiently in low-NO(x) air through reactions of organic peroxy radicals. Computations with an atmospheric chemistry model and the results of laboratory experiments suggest that an OH recycling efficiency of 40-80 per cent in isoprene oxidation may be able to explain the high OH levels we observed in the field. Although further laboratory studies are necessary to explore the chemical mechanism responsible for OH recycling in more detail, our results demonstrate that the biosphere maintains a remarkable balance with the atmospheric environment.

  13. Synthesis by-products from the Wacker oxidation of safrole in methanol using rho-benzoquinone and palladium chloride.

    Science.gov (United States)

    Cox, M; Klass, G

    2006-12-20

    This paper reports the identification of a number of by-products, which are produced during the Wacker oxidation of safrole to 3,4-methylenedioxyphenyl-2-propanone (MDP2P) using rho-benzoquinone and palladium chloride when methanol is utilised as the solvent. Also described is the retrieval of these compounds from illicit samples from a clandestine laboratory, which was uncovered in South Australia in September 2003.

  14. Atmospheric oxidation capacity sustained by a tropical forest

    NARCIS (Netherlands)

    Lelieveld, J.; Butler, T.; Crowley, J.N.; Dillon, T.J.; Fischer, H.; Ganzeveld, L.N.; Harder, H.; Lawrence, M.G.; Martinez, M.; Taraborelli, D.; Williams, J.

    2008-01-01

    Terrestrial vegetation, especially tropical rain forest, releases vast quantities of volatile organic compounds (VOCs) to the atmosphere1, 2, 3, which are removed by oxidation reactions and deposition of reaction products4, 5, 6. The oxidation is mainly initiated by hydroxyl radicals (OH), primarily

  15. Chemically bonded cements formulated with by-products of magnesium oxide

    OpenAIRE

    2008-01-01

    The casting of magnesium and potassium phosphate (KMgPO4•6H2O; K-struvite) cements becomes possible after the aqueous reaction between magnesium oxide and potassium dihydrogen phosphate. This reaction is quite exothermic and allows the resulting paste setting in just few minutes. Those cements, when are cast with magnesium oxides of high purity, are used to retain and encapsulate special residues and as repairing concrete mortar, as it is described in the bibliography. However, it is also pos...

  16. OXIDATION BEHAVIOR OF KOVAR ALLOY IN CONTROLLED ATMOSPHERE

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Controlled oxidation experiments were performed on Kovar alloy by changing oxi-dation atmosphere, temperature, and exposure time to produce films with different oxide type and thickness. The results indicated that single Fe3O4 and single FeO were respectively obtained when Kovar alloy was oxidized in N2-2.31%H2O-0.95%H2 at 500℃ and in N2-2.31%H2O-O.5%H2 at 1000℃, and all kinetic curves followed linear relation; mixed oxides of FeO and Fe3O4 formed when Kovar was oxidized in N2-2.31%H2O at 1000℃, and parabolic kinetics were obeyed. Analysis of metal-lographic cross section of oxides indicated that oxygen diffusion inward through the oxide scale is responsible for intergranular oxide, which had formed beneath the oxide scales when the oxide products were mixed oxides of FeO and Fe3O4, and which did not occur when the oxide was single FeO or Fe3O4. The oxidation model was also established.

  17. Heterogeneous Photocatalytic Oxidation of Atmospheric Trace Contaminants

    Science.gov (United States)

    Ollis, David F.

    1996-01-01

    Heterogeneous photocatalysis involves the use of a light-activated catalyst at room temperature in order to carry out a desired reaction. In the presence of molecular oxygen, illumination of the n-type semiconductor oxide titanium dioxide (TiO2) provides for production of highly active forms of oxygen, such as hydroxyl radicals, which are able to carry out the complete oxidative destruction of simple hydrocarbons such as methane, ethane, ethylene, propylene, and carbon monoxide. This broad oxidation potential, coupled with the ability with sufficient residence time to achieve complete oxidation of simple hydrocarbon contaminants to carbon dioxide and water, indicated that heterogeneous photocatalysis should be examined for its potential for purification of spacecraft air. If a successful catalyst and photoreactor could be demonstrated at the laboratory level, such results would allow consideration of photocatalysts as a partial or complete replacement of adsorption systems, thereby allowing for reduction in lift-off weight of a portion of the life support system for the spacecraft, or other related application such as a space station or a conventional commercial aircraft. The present research was undertaken to explore this potential through achievement of the following plan of work: (a) ascertain the intrinsic kinetics of conversion of pollutants of interest in spacecraft, (b) ascertain the expected lifetime of catalysts through examination of most likely routes of catalyst deactivation and regeneration (c) model and explore experimentally the low pressure drop catalytic monolith, a commercial configuration for automotive exhaust control (d) examine the kinetics of multicomponent conversions. In the recent course of this work, we have also discovered how to increase catalyst activity via halide promotion which has allowed us to achieve approximately 100% conversion of an aromatic contaminant (toluene) in a very short residence time of 5-6 milliseconds.

  18. Control of disinfection by-product formation using ozone-based advanced oxidation processes.

    Science.gov (United States)

    Chen, Kuan-Chung; Wang, Yu-Hsiang

    2012-01-01

    The effects of ozone dosage, water temperature and catalyst addition in an ozonation-fluidized bed reactor (O3/FBR) on treated water quality and on the control of chlorinated and ozonated disinfection by-products (DBPs) were investigated. A biofiltration column was used to evaluate its removal efficiency on biodegradable organic matter and to reduce DBP formation. The Dong-Gang River, polluted by agricultural and domestic wastewater in Pingtung, Taiwan, was used as the water source. The treated water quality in terms of dissolved organic carbon (DOC), biodegradable DOC, ultraviolet absorbance at 254 nm (UV254) and specific UV absorbance (SUVA) improved with increasing ozone and catalyst dosages. Catalytic ozonation was more effective than ozonation alone at reducing the formation of DBPs at a given dosage. Experimental results show that water temperature had little effect on the treated water quality with the O3/FBR system used in this study (p > 0.05). The combination of O3/FBR and the biofiltration process effectively decreased the amount ofDBP precursors. The concentration of total trihalomethanes (TTHMs) was less than the maximum contaminant level (MCL) requirement, which is 80 microg/L, for all treated waters and the concentration of five haloacetic acids (HAA5) fell below 60 microg/L with an ozone dosage higher than 2.5 mg/L.

  19. Formation of iodinated disinfection by-products during oxidation of iodide-containing water with potassium permanganate.

    Science.gov (United States)

    Ye, Tao; Xu, Bin; Lin, Yi-Li; Hu, Chen-Yan; Xia, Sheng-Ji; Lin, Lin; Mwakagenda, Seleli Andrew; Gao, Nai-Yun

    2012-11-30

    This study shows that iodinated disinfection by-products (I-DBPs) including iodoform (IF), iodoacetic acid (IAA) and triiodoacetic acid (TIAA) can be produced when iodide-containing waters are in contact with potassium permanganate. IF was found as the major I-DBP species during the oxidation. Iodide was oxidized to HOI, I(2) and I(3)(-), consequently, which led to the formation of iodinated organic compounds. I-DBPs varied with reaction time, solution pH, initial concentrations of iodide and potassium permanganate. Yields of IF, IAA and TIAA increased with reaction time and considerable I-DBPs were formed within 12 h. Peak IF yields were found at circumneutral pH range. However, formation of IAA and TIAA was favored under acidic conditions. Molar ratio of iodide to potassium permanganate showed significant influence on formation of IF, IAA and TIAA. The formation of IF, IAA and TIAA also depended on the characteristics of the waters.

  20. Explosion characteristics of flammable organic vapors in nitrous oxide atmosphere.

    Science.gov (United States)

    Koshiba, Yusuke; Takigawa, Tomihisa; Matsuoka, Yusaku; Ohtani, Hideo

    2010-11-15

    Despite unexpected explosion accidents caused by nitrous oxide have occurred, few systematic studies have been reported on explosion characteristics of flammable gases in nitrous oxide atmosphere compared to those in air or oxygen. The objective of this paper is to characterize explosion properties of mixtures of n-pentane, diethyl ether, diethylamine, or n-butyraldehyde with nitrous oxide and nitrogen using three parameters: explosion limit, peak explosion pressure, and time to the peak explosion pressure. Then, similar mixtures of n-pentane, diethyl ether, diethylamine, or n-butyraldehyde with oxygen and nitrogen were prepared to compare their explosion characteristics with the mixtures containing nitrous oxide. The explosion experiments were performed in a cylindrical vessel at atmospheric pressure and room temperature. The measurements showed that explosion ranges of the mixtures containing nitrous oxide were narrow compared to those of the mixtures containing oxygen. On the other hand, the maximum explosion pressures of the mixtures containing nitrous oxide were higher than those of the mixtures containing oxygen. Moreover, our experiments revealed that these mixtures differed in equivalence ratios at which the maximum explosion pressures were observed: the pressures of the mixtures containing nitrous oxide were observed at stoichiometry; in contrast, those of the mixtures containing oxygen were found at fuel-rich area. Chemical equilibrium calculations confirmed these behaviors.

  1. The Mantle-Atmosphere Connection: Oxidation of the Atmosphere through Mantle Convection

    Science.gov (United States)

    Lee, K. K. M.; Gu, T.; Li, M.; McCammon, C. A.

    2015-12-01

    Earth's mantle connects the surface with the deep interior through convection, and the evolution of its redox state will affect the distribution of siderophile elements1, recycling of refractory isotopes2 and the oxidation state of the atmosphere through volcanic outgassing3. The rise of oxygen in atmosphere, i.e., the Great Oxidation Event (G.O.E.) occurred ~2.4 billion years ago (Ga)4. However, multiple lines of evidence point to biological oxygen production well before 2.4 Ga5; while chromium isotopes in iron formations indicates a decline of atmospheric oxygen about 1.88 Ga6. In contrast to the fluctuation of atmospheric oxygen, vanadium in Archean mantle lithosphere suggests that the mantle redox state has been constant for ~3.5 Ga7. Indeed, the redox state of the deep Earth's interior is not well constrained8 and its effect on mantle dynamics is unknown. Here we show a redox-induced density difference affects mantle convection and may potentially cause the oxidation of the upper mantle. From two synthetic enstatite chondritic samples with identical bulk compositions but formed under different oxygen fugacities (fO2) compressed to lower mantle pressures and temperatures, we find Al2O3 forms its own phase separate from the dominant Mg-silicate perovskite phase (i.e., bridgmanite9) in the more reduced composition, in contrast to a more Al-rich, bridgmanite-dominated assemblage for a more oxidized starting composition. As a result, the reduced material is ~1-1.5% denser than the oxidized material. Geodynamical numerical simulations show that the redox-induced density difference could lead to an increased oxidation of Earth's upper mantle but is buffered by slow mixing with more reduced material through hot upwellings, which will potentially affect mantle redox and rise of oxygen in atmosphere.

  2. The oxidation and surface speciation of indium and indium oxides exposed to atmospheric oxidants

    Science.gov (United States)

    Detweiler, Zachary M.; Wulfsberg, Steven M.; Frith, Matthew G.; Bocarsly, Andrew B.; Bernasek, Steven L.

    2016-06-01

    Metallic indium and its oxides are useful in electronics applications, in transparent conducting electrodes, as well as in electrocatalytic applications. In order to understand more fully the speciation of the indium and oxygen composition of the indium surface exposed to atmospheric oxidants, XPS, HREELS, and TPD were used to study the indium surface exposed to water, oxygen, and carbon dioxide. Clean In and authentic samples of In2O3 and In(OH)3 were examined with XPS to provide standard spectra. Indium was exposed to O2 and H2O, and the ratio of O2 - to OH- in the O1s XPS region was used to monitor oxidation and speciation of the surface. HREELS and TPD indicate that water dissociates on the indium surface even at low temperature, and that In2O3 forms at higher temperatures. Initially, OH- is the major species at the surface. Pure In2O3 is also OH- terminated following water exposure. Ambient pressure XPS studies of water exposure to these surfaces suggest that high water pressures tend to passivate the surface, inhibiting extensive oxide formation.

  3. UV-based advanced oxidation processes for the treatment of odour compounds: efficiency and by-product formation.

    Science.gov (United States)

    Zoschke, Kristin; Dietrich, Norman; Börnick, Hilmar; Worch, Eckhard

    2012-10-15

    The occurrence of the taste and odour compounds geosmin and 2-methyl isoborneol (2-MIB) affects the organoleptic quality of raw waters from drinking water reservoirs worldwide. UV-based oxidation processes for the removal of these substances are an alternative to adsorption and biological processes, since they additionally provide disinfection of the raw water. We could show that the concentration of geosmin and 2-MIB could be reduced by VUV irradiation and the combination of UV irradiation with ozone and hydrogen peroxide in pure water and water from a drinking water reservoir. The figure of merit EE/O is an appropriate tool to compare the AOPs and showed that VUV and UV/O(3) yielded the lowest treatment costs for the odour compounds in pure and raw water, respectively. Additionally, VUV irradiation with addition of ozone, generated by the VUV lamp, was evaluated. The generation of ozone and the irradiation were performed in a single reactor system using the same low-pressure mercury lamp, thereby reducing the energy consumption of the treatment process. The formation of the undesired by-products nitrite and bromate was investigated. The combination of VUV irradiation with ozone produced by a VUV lamp avoided the formation of relevant concentrations of the by-products. The internal generation of ozone is capable to produce ozone concentrations sufficient to reduce EE/O below 1 kWh m(-3) and without the risk of the formation of nitrite or bromate above the maximum contaminant level.

  4. Degradation of carbamazepine by UV/chlorine advanced oxidation process and formation of disinfection by-products.

    Science.gov (United States)

    Zhou, Shiqing; Xia, Ying; Li, Ting; Yao, Tian; Shi, Zhou; Zhu, Shumin; Gao, Naiyun

    2016-08-01

    Pharmaceuticals in water are commonly found and are not efficiently removed by current treatment processes. Degradation of antiepileptic drug carbamazepine (CBZ) by UV/chlorine advanced oxidation process was systematically investigated in this study. The results showed that the UV/chlorine process was more effective at degrading CBZ than either UV or chlorination alone. The CBZ degradation followed pseudo-first order reaction kinetics, and the degradation rate constants (kobs) were affected by the chlorine dose, solution pH, and natural organic matter concentration to different degrees. Degradation of CBZ greatly increased with increasing chlorine dose and decreasing solution pH during the UV/chlorine process. Additionally, the presence of natural organic matter in the solution inhibited the degradation of CBZ. UV photolysis, chlorination, and reactive species (hydroxyl radical •OH and chlorine atoms •Cl) were identified as responsible for CBZ degradation in the UV/chlorine process. Finally, a degradation pathway for CBZ in the UV/chlorine process was proposed and the formation potentials of carbonaceous and nitrogenous disinfection by-products were evaluated. Enhanced formation of trichloroacetic acid, dichloroacetonitrile, and trichloronitromethane precursors should be considered when applying UV/chlorine advanced oxidation process to drinking water.

  5. Application of effect-directed analysis to identify mutagenic nitrogenous disinfection by-products of advanced oxidation drinking water treatment.

    Science.gov (United States)

    Vughs, D; Baken, K A; Kolkman, A; Martijn, A J; de Voogt, P

    2016-07-22

    Advanced oxidation processes are important barriers for organic micropollutants in (drinking) water treatment. It is however known that medium pressure UV/H2O2 treatment may lead to mutagenicity in the Ames test, which is no longer present after granulated activated carbon (GAC) filtration. Many nitrogen-containing disinfection by-products (N-DBPs) result from the reaction of photolysis products of nitrate with (photolysis products of) natural organic material (NOM) during medium pressure UV treatment of water. Identification of the N-DBPs and the application of effect-directed analysis to combine chemical screening results with biological activity would provide more insight into the relation of specific N-DBPs with the observed mutagenicity and was the subject of this study. To this end, fractions of medium pressure UV-treated and untreated water extracts were prepared using preparative HPLC and tested using the Ames fluctuation test. In addition, high-resolution mass spectrometry was performed on all fractions to assess the presence of N-DBPs. Based on toxicity data and read across analysis, we could identify five N-DBPs that are potentially genotoxic and were present in relatively high concentrations in the fractions in which mutagenicity was observed. The results of this study offer opportunities to further evaluate the identity and potential health concern of N-DBPs formed during advanced oxidation UV drinking water treatment.

  6. Removal of precursors for disinfection by-products (Dbps)--differences between ozone- and OH-radical-induced oxidation.

    Science.gov (United States)

    Kleiser, G; Frimmel, F H

    2000-06-22

    Pre-oxidation is often applied to reduce the formation of disinfection by-products (DBPs). The aim of pre-oxidation is to remove the centers of natural organic matter (NOM) which are responsible for the formation of DBPs. In this paper, the differences between ozone- and OH-radical-induced oxidation to remove DBP-precursors are compared. The experiments were done with water of the River Ruhr (Germany) with a concentration of dissolved organic carbon (DOC) of 2 mg/l. Ozonation was able to remove DBP precursors selectively. After application of an absorbed ozone mass of 1.5 mg/mg DOC, a reduction in the formation potential for (THM-FP) and in the formation potential for organic halogen adsorbable on activated carbon (AOX-FP) down to 68 and 73% of the initial concentration was achieved, respectively. A removal of NOM was not achieved using absorbed ozone masses between 0.5 and 1.5 mg/mg DOC. In the hydrogen peroxide/UV process, in which OH-radicals are the reactive species, an increase in the THM concentration was measured after application of this process with short irradiation times. The maximum value of the THM-FP was 20% higher than the initial THM-FP. After an irradiation time of 1,050 min and a hydrogen peroxide consumption of 5.6 mg/l, the THM-FP and AOX-FP decreased to 75 and 71% of the initial formation potential, respectively. There was no selective removal of DBP precursors because the DOC concentration decreased also to 75% of the initial DOC-concentration after 1,050 min of irradiation.

  7. Atmospheric Oxidation Mechanisms for Diethyl Ether and its Oxidation Products, Ethyl Formate and Ethyl Acetate.

    Science.gov (United States)

    Orlando, J. J.; Tyndall, G. S.

    2006-12-01

    Carbon-containing compounds are present in the earth's atmosphere as the result of emissions from natural and anthropogenic sources. Their oxidation in the atmosphere, initiated by such oxidants as OH, ozone, and nitrate radicals, leads to potentially harmful secondary pollutants such as ozone, carbonyl species, organic acids and aerosols. Ethers and esters are two classes of compounds that contribute to the complex array of organic compounds found in anthropogenically-influenced air. Additional ester is present as a result of the oxidation of the ethers. In this paper, the oxidation of diethyl ether and its two main oxidation products, ethyl formate and ethyl acetate, are studied over ranges of temperature, oxygen partial pressure, and NOx concentration, using an environmental chamber / FTIR absorption technique. Major end-products (the esters from diethyl ether; organic acids and anhydrides from the esters) are quantified, and these data are interpreted in terms of the chemistry of the various alkoxy and peroxy radicals generated. Emphasis is placed on the effects of chemical activation on the behavior of the alkoxy radicals, as well as on a novel peroxy radical rearrangement that may contribute to the observed products of ether oxidation under some conditions. Finally, the data are used, in conjunction with data on similar species, to provide a general representation of ether and ester oxidation in the atmosphere.

  8. Atmospheric Hydroperoxides in West Antarctica: Links to Stratospheric Ozone and Atmospheric Oxidation Capacity

    Science.gov (United States)

    Frey, Markus M.; Stewart, Richard W.; McConnell, Joseph R.; Bales, Roger C.

    2005-01-01

    The troposphere above the West Antarctic Ice Sheet (WAIS) was sampled for hydroperoxides at 21 locations during 2-month-long summer traverses from 2000 to 2002, as part of US ITASE (International Transantarctic Scientific Expedition). First time quantitative measurements using an HPLC method showed that methylhydroperoxide (MHP) is the only important organic hydroperoxide occurring in the Antarctic troposphere, and that it is found at levels ten times those previously predicted by photochemical models. During three field seasons, means and standard deviations for hydrogen peroxide (H2O2) were 321+/-158 pptv, 650+/-176 pptv and 330+/-147 pptv. While MHP was detected, but not quantified in December 2000, levels in summer 2001 and 2002 were 317+128 pptv and 304+/-172.2 pptv. Results from firn air experiments and diurnal variability of the two species showed that atmospheric H2O2 is significantly impacted by a physical snow pack source between 76 and 90degS, whereas MHP is not. We show strong evidence of a positive feedback between stratospheric ozone and H2O2 at the surface. Between November-27 and December-12 in 2001, when ozone column densities dropped below 220 DU (means in 2000 and 2001 were 318 DU and 334 DU, respectively), H2O2 was 1.7 times that observed in the same period in 2000 and 2002, while MHP was only 80% of the levels encountered in 2002. Photochemical box model runs suggest that NO and OH levels on WAIS are closer to coastal values, while Antarctic Plateau levels are higher, confirming that region to be a highly oxidizing environment. The modeled sensitivity of H2O2 and particularly MHP to NO offers the potential to use atmospheric hydroperoxides to constrain the NO background and thus estimate the past oxidation capacity of the remote atmosphere. Index Terms: 0365 Atmospheric Composition and Structure: Troposphere: composition and chemistry; 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 1610 Global Change: Atmosphere (03

  9. Photo-Fenton oxidation of 3-amino-5-methylisoxazole: a by-product from biological breakdown of some pharmaceutical compounds.

    Science.gov (United States)

    Souza, Bianca M; Marinho, Belisa A; Moreira, Francisca C; Dezotti, Márcia W C; Boaventura, Rui A R; Vilar, Vítor J P

    2015-11-10

    The present study aims to assess the removal of 3-amino-5-methylisoxazole (AMI), a recalcitrant by-product resulting from the biological breakdown of some pharmaceuticals, applying a solar photo-Fenton process assisted by ferrioxalate complexes (SPFF) (Fe(3+)/H2O2/oxalic acid/UVA-Vis) and classical solar photo-Fenton process (SPF) (Fe(2+)/H2O2/UVA-Vis). The oxidation ability of SPFF was evaluated at different iron/oxalate molar ratios (1:3, 1:6, and 1:9, with [total iron] = 3.58 × 10(-2) mM and [oxalic acid] = 1.07 × 10(-1), 2.14 × 10(-1) and 3.22 × 10(-1) mM, respectively) and pH values (3.5-6.5), using low iron contents (2.0 mg Fe(3+) L(-1)). Additionally, the use of other organic ligands such as citrate and ethylenediamine-N,N'-disuccinic acid (EDDS) was tested. The oxidation power of the classical SPF was assessed at different pH values (2.8-4.0) using 2.0 mg Fe(2+) per liter. Furthermore, the effect of AMI concentration (2-20 mg L(-1)), presence of inorganic ions (Cl(-), SO4(2-), NO3(-), HCO3(-), NH4(+)), and radical scavengers (sodium azide and D-mannitol) on the SPF method at pH 3.5 was also assessed. Experiments were done using a lab-scale photoreactor with a compound parabolic collector (CPC) under simulated solar radiation. A pilot-scale assay was conducted using the best operation conditions. While at near neutral pH, an iron/oxalate molar ratio of 1:9 led to the removal of 72 % of AMI after 90 min of SPFF, at pH 3.5, an iron/oxalate molar ratio of 1:3 was enough to achieve complete AMI degradation (below the detection limit) after 30 min of reaction. The SPF process at pH 3.5 underwent a slower AMI degradation, reaching total AMI degradation after 40 min of reaction. The scale up of SPF process showed a good reproducibility. Oxalic and oxamic acids were identified as the main low-molecular-weight carboxylic acids detected during the pilot-scale SPF reaction. Graphical abstract ᅟ.

  10. Formation of iodinated disinfection by-products during oxidation of iodide-containing waters with chlorine dioxide.

    Science.gov (United States)

    Ye, Tao; Xu, Bin; Lin, Yi-Li; Hu, Chen-Yan; Lin, Lin; Zhang, Tian-Yang; Gao, Nai-Yun

    2013-06-01

    This study was to explore the formation of iodinated disinfection by-products (I-DBPs), including iodoform (CHI3), iodoacetic acid (IAA) and triiodoacetic acid (TIAA), when iodide-containing artificial synthesized waters and raw waters are in contact with chlorine dioxide (ClO2). Among the investigated I-DBPs, CHI3 was the major species during ClO2 oxidation in artificial synthesized waters. Impact factors were evaluated, including the concentrations of ClO2, iodide (I(-)), dissolved organic carbon (DOC) and pH. Formation of CHI3, IAA and TIAA followed an increasing and then decreasing pattern with increased ClO2 or DOC concentration. I-DBPs yield was significantly affected by solution pH. High concentrations of I-DBPs were generated under circumneutral conditions with the maximum formation at pH 8. The increase of I(-) concentration can increase I-DBPs yields, but the increment was suppressed when I(-) concentration was higher than 50 μM. When 100 μg/L I(-)and ClO2 (7.5-44.4 μM) were spiked to the raw water samples from Yangshupu and Minhang drinking water treatment plant, certain amounts of CHI3 and IAA were found under pH 7 and the concentrations were strongly correlated with ClO2 dosage and water qualities, however, no TIAA was detected. Finally, we investigated I-DBPs formation of 18 model compounds, including 4 carboxylic acids, 5 phenols and 8 amino acids, treating with ClO2 when I(-) was present. Results showed that most of these model compounds could form a considerable amount of I-DBPs, especially for propanoic acid, butanoic acid, resorcinol, hydroquinone, alanine, glutamic acid, phenylalanine and serine.

  11. Pathways for the Oxidation of Sarin in Urban Atmospheres

    Energy Technology Data Exchange (ETDEWEB)

    Gerald E. Streit; James E. Bossert; Jeffrey S. Gaffney; Jon Reisner; Laurie A. McNair; Michael Brown; Scott Elliott

    1998-11-01

    Terrorists have threatened and carried out chemicalhiological agent attacks on targets in major cities. The nerve agent sarin figured prominently in one well-publicized incident. Vapors disseminating from open containers in a Tokyo subway caused thousands of casualties. High-resolution tracer transport modeling of agent dispersion is at hand and will be enhanced by data on reactions with components of the urban atmosphere. As a sample of the level of complexity currently attainable, we elaborate the mechanisms by which sarin can decompose in polluted air. A release scenario is outlined involving the passage of a gas-phase agent through a city locale in the daytime. The atmospheric chemistry database on related organophosphorus pesticides is mined for rate and product information. The hydroxyl,radical and fine-mode particles are identified as major reactants. A review of urban air chernistry/rnicrophysics generates concentration tables for major oxidant and aerosol types in both clean and dirty environments. Organic structure-reactivity relationships yield an upper limit of 10-1' cm3 molecule-' S-* for hydrogen abstraction by hydroxyl. The associated midday loss time scale could be as little as one hour. Product distributions are difficult to define but may include nontoxic organic oxygenates, inorganic phosphorus acids, sarin-like aldehydes, and nitrates preserving cholinergic capabilities. Agent molecules will contact aerosol surfaces in on the order of minutes, with hydrolysis and side-chain oxidation as likely reaction channels.

  12. Can Highly Oxidized Organics Contribute to Atmospheric New Particle Formation?

    Science.gov (United States)

    Ortega, Ismael K; Donahue, Neil M; Kurtén, Theo; Kulmala, Markku; Focsa, Cristian; Vehkamäki, Hanna

    2016-03-10

    Highly oxidized organic molecules may play a critical role in new-particle formation within Earth's atmosphere along with sulfuric acid, which has long been considered as a key compound in this process. Here we explore the interactions of these two partners, using quantum chemistry to find the formation free energies of heterodimers and trimers as well as the fastest evaporation rates of (2,2) tetramers. We find that the heterodimers are more strongly bound than pure sulfuric acid dimers. Their stability correlates well with the oxygen to carbon ratio of the organics, their volatility, and the number of hydrogen bonds formed. Most of the stable trimers contain one sulfuric acid and two organics (1,2), whereas many (2,2) tetramers evaporate quickly, probably due to the stability of (1,2) clusters. This finding agrees with recent experimental studies that show how new-particle formation involving oxidized organics and sulfuric acid may be rate-limited by activation of (1,2) trimers, confirming the importance of this process in the atmosphere.

  13. Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants.

    Science.gov (United States)

    Zhang, Yang; Shu, Jinian; Zhang, Yuanxun; Yang, Bo

    2013-09-01

    The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10-dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

  14. Homogeneous and heterogeneous reactions of anthracene with selected atmospheric oxidants

    Institute of Scientific and Technical Information of China (English)

    Yang Zhang; Jinian Shu; Yuanxun Zhang; Bo Yang

    2013-01-01

    The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber,respectively.The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed.Meanwhile,the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes.The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr,respectively.The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUVATOFMS).Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions.Anthrone,anthraquinone,9,10-dihydroxyanthracene,and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene,while anthrone,anthraquinone,9-nitroanthracene,and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.

  15. Kinetics of the oxidation of Zn foils in air atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Baca, R; Martinez, J [Centro de Investigacion de Dispositivos Semiconductores, BUAP, Puebla. C.P. 72570 (Mexico); Kryshtab, T [Departamento de Ciencias de Materiales, ESFM - IPN, Mexico D.F (Mexico); Juarez, G; Solache, H; Andraca, J; Garcia, O; Pena-Sierra, R, E-mail: rbaca02006@yahoo.com.mx

    2010-02-15

    The formation kinetics of ZnO thin films grown by oxidation of polycrystalline Zn foils in air atmosphere at temperatures below the melting point is reported. Previous to the oxidation process the Zn foils were polished to produce mirror-like finished surfaces. The growth rate of the ZnO films was monitored by ellipsometric measurements. The growth rate of the ZnO films under 100 nm follows a linear and parabolic behavior in accordance with previously reported studies. The thicknesses of the films strongly influence the appearance of the final produced ZnO surface. The ZnO films surfaces with thicknesses less than 100 nm resulted uniform with low rms roughness. However as the films become thicker the rms roughness increased and a uniform distribution of whiskers was observed. X-ray diffraction and photoluminescence (PL) studies were done on the ZnO films to find out their structural and optical characteristics. PL spectra on the films are composed by two main bands; a weak near-band gap in the ultraviolet region and a strong but well defined green band. A discussion is included on the origins of the observed PL spectra.

  16. Combined atmospheric oxidant capacity and increased levels of exhaled nitric oxide

    Science.gov (United States)

    Yang, Changyuan; Li, Huichu; Chen, Renjie; Xu, Wenxi; Wang, Cuicui; Tse, Lap Ah; Zhao, Zhuohui; Kan, Haidong

    2016-07-01

    Nitrogen dioxide and ozone are two interrelated oxidative pollutants in the atmosphere. Few studies have evaluated the health effects of combined oxidant capacity (O x ). We investigated the short-term effects of O x on fractional exhaled nitric oxide (FeNO), a well-established biomarker for airway inflammation, in a group of chronic obstructive pulmonary disease patients. Real-time concentrations of O x were obtained by calculating directly the sum of nitrogen dioxide and ozone. Linear mixed-effect models were applied to explore the acute effects of O x on FeNO levels. Short-term exposure to Ox was significantly associated with elevated FeNO. This effect was strongest in the first 24 h after exposure, and was robust to the adjustment of PM2.5. A 10 μg m-3 increase in 24 h average concentrations of O x was associated with 4.28% (95% confidence interval: 1.19%, 7.37%) increase in FeNO. The effect estimates were statistically significant only among males, elders, and those with body mass index ≥24 kg m-2, a comorbidity, higher educational attainment, or moderate airflow limitation. This analysis demonstrated an independent effect of O x on respiratory inflammation, and suggested that a single metric O x might serve as a preferable indicator of atmospheric oxidative capacity in further air pollution epidemiological studies.

  17. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-12-01

    Full Text Available Global models of atmospheric mercury generally assume that gas-phase OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming gas-phase Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux to the Arctic of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by

  18. Global atmospheric model for mercury including oxidation by bromine atoms

    Directory of Open Access Journals (Sweden)

    C. D. Holmes

    2010-08-01

    Full Text Available Global models of atmospheric mercury generally assume that OH and ozone are the main oxidants converting Hg0 to HgII and thus driving mercury deposition to ecosystems. However, thermodynamic considerations argue against the importance of these reactions. We demonstrate here the viability of atomic bromine (Br as an alternative Hg0 oxidant. We conduct a global 3-D simulation with the GEOS-Chem model assuming Br to be the sole Hg0 oxidant (Hg + Br model and compare to the previous version of the model with OH and ozone as the sole oxidants (Hg + OH/O3 model. We specify global 3-D Br concentration fields based on our best understanding of tropospheric and stratospheric Br chemistry. In both the Hg + Br and Hg + OH/O3 models, we add an aqueous photochemical reduction of HgII in cloud to impose a tropospheric lifetime for mercury of 6.5 months against deposition, as needed to reconcile observed total gaseous mercury (TGM concentrations with current estimates of anthropogenic emissions. This added reduction would not be necessary in the Hg + Br model if we adjusted the Br oxidation kinetics downward within their range of uncertainty. We find that the Hg + Br and Hg + OH/O3 models are equally capable of reproducing the spatial distribution of TGM and its seasonal cycle at northern mid-latitudes. The Hg + Br model shows a steeper decline of TGM concentrations from the tropics to southern mid-latitudes. Only the Hg + Br model can reproduce the springtime depletion and summer rebound of TGM observed at polar sites; the snowpack component of GEOS-Chem suggests that 40% of HgII deposited to snow in the Arctic is transferred to the ocean and land reservoirs, amounting to a net deposition flux of 60 Mg a−1. Summertime events of depleted Hg0 at Antarctic sites due to subsidence are much better simulated by the Hg + Br model. Model

  19. Nitrous oxide and carbon dioxide emissions during initial decomposition of animal by-products applied as fertilisers to soils.

    NARCIS (Netherlands)

    Cayuela, M.L.; Velthof, G.L.; Mondini, C.; Sinicco, T.; Groenigen, van J.W.

    2010-01-01

    The recycling of organic wastes as soil amendments is notably promoted in sustainable agricultural systems. However, for many animal by-products approved by organic farming regulations little is known about their effects on the greenhouse gas balance of the soil, in particular on N2O emissions. In t

  20. Pineapple by-product and canola oil as partial fat replacers in low-fat beef burger: Effects on oxidative stability, cholesterol content and fatty acid profile.

    Science.gov (United States)

    Selani, Miriam M; Shirado, Giovanna A N; Margiotta, Gregório B; Rasera, Mariana L; Marabesi, Amanda C; Piedade, Sonia M S; Contreras-Castillo, Carmen J; Canniatti-Brazaca, Solange G

    2016-05-01

    The effect of freeze-dried pineapple by-product and canola oil as fat replacers on the oxidative stability, cholesterol content and fatty acid profile of low-fat beef burgers was evaluated. Five treatments were performed: conventional (CN, 20% fat) and four low-fat formulations (10% fat): control (CT), pineapple by-product (PA), canola oil (CO), and pineapple by-product and canola oil (PC). Low-fat cooked burgers showed a mean cholesterol content reduction of 9.15% compared to the CN. Canola oil addition improved the fatty acid profile of the burgers, with increase in the polyunsaturated/saturated fatty acids ratio and decrease in the n-6/n-3 ratio, in the atherogenic and thrombogenic indexes. The oxidative stability of the burgers was affected by the vegetable oil addition. However, at the end of the storage time (120 days), malonaldehyde values of CO and PC were lower than the threshold for the consumer's acceptance. Canola oil, in combination with pineapple by-product, can be considered promising fat replacers in the development of healthier burgers.

  1. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

    Science.gov (United States)

    Walavalkar, M.; Sharma, A.; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, P. D.; Bajaj, P. N.

    2013-03-01

    In view of the importance of the oxidation pathways of alkenes in the troposphere, and the significance of Cl atom as an oxidant in marine boundary layer (MBL) and polluted industrial atmosphere, the reactions of four 1-alkenes (C6-C9) with Cl atoms are investigated. The rate coefficients at 298 K are measured to be (4.0 ± 0.5), (4.4 ± 0.7), (5.5 ± 0.9) and (5.9 ± 1.7) × 10-10 cm3 molecule-1 s-1 for 1-hexene, 1-heptene, 1-octene and 1-nonene, respectively. The quoted errors include the experimental 2σ, along with the error in the reference rate coefficients. From the systematic increase in the rate coefficients with the number of carbon atoms, an approximate value for the average rate coefficient for hydrogen abstraction per CH2 group in alkenes is estimated to be (4.9 ± 0.3) × 10-11 cm3 molecule-1 s-1. Based on these rate coefficients, the contribution of Cl atom reactions towards the degradation of these molecules is found to be comparable to that of OH radical reactions, under MBL conditions. The products identified in gas phase indicate that Cl atom addition occurs mainly at the terminal carbon, leading to the formation of 1-chloro-2-ketones and 1-chloro-2-ols. The major gas phase products from the alkenyl radicals (formed by H atom abstraction) are different positional isomers of long chain enols and enones. A preference for dissociation leading to an allyl radical, resulting in aldehydes, lower by three carbon atoms, is indicated. The observed relative yields suggest that in general, the increased contribution of the reactions of Cl atoms towards degradation of 1-alkenes in NOx free air does not result in an increase in the generation of small aldehydes (carbon number < 4), including chloroethanal, as compared to that in the reaction of 1-butene.

  2. Stabilization of coacervate systems by products of abiogenic oxidation of low-molecular-weight compounds using the energy of. gamma. radiation

    Energy Technology Data Exchange (ETDEWEB)

    Evreinova, T.N.; Kuzin, A.M.; Kryukova, L.M.; Kameneva, T.G.; Khrust, Yu.R.

    1976-01-01

    The purpose of the study was to determine the possibility of stabilization of protein-carbohydrate and protein-nucleic acid systems by products of the abiogenic oxidation of pyrocatechol, pyrogallol, and o-dianisidine using the energy of gamma radiation. The protein-nucleic acid system was produced by mixing the following reagents: histone, DNA, acetate buffer, and a solution of oxidized compounds. The protein-carbohydrate system was produced by mixing the following reagents: histone, gum arabic, acetate buffer, and a solution of oxidized compounds. Results indicated that the stabilization of coacervate systems occurs when stabilizing low-molecular-weight compounds of the type of quinones and the imino form of o-dianisidine are included in them. These compounds may be formed under the action of physical factors without the participation of enzymes. (HLW)

  3. Missing SO2 oxidant in the coastal atmosphere? – Evidence from high resolution measurements of OH and atmospheric sulfur compounds

    Directory of Open Access Journals (Sweden)

    H. Berresheim

    2014-01-01

    Full Text Available Diurnal and seasonal variations of gaseous sulfuric acid (H2SO4 and methane sulfonic acid (MSA were measured in N.E. Atlantic air at the Mace Head atmospheric research station during the years 2010 and 2011. The measurements utilized selected ion/chemical ionization mass spectrometry (SI/CIMS with a detection limit for both compounds of 4.3 × 10 4 cm−3 at 5 min signal integration. The H2SO4 and MSA gas-phase concentrations were analysed in conjunction with the condensational sink for both compounds derived from 3 nm–10 μm (diameter aerosol size distributions. Accommodation coefficients of 1.0 for H2SO4 and 0.12 for MSA were assumed leading to estimated atmospheric lifetimes of the order of 7 min and 25 min, respectively. With the SI/CIMS instrument in OH measurement mode alternating between OH signal and background (non-OH signal evidence was obtained for the presence of one or more unknown oxidants of SO2 in addition to OH. Depending on the nature of the oxidant(s their ambient concentration may be enhanced in the CIMS inlet system by additional production. The apparent unknown SO2 oxidant was additionally confirmed by direct measurements of SO2 in conjunction with calculated H2SO4 concentrations. The calculated concentrations were consistently lower than the measured concentrations by a factor 4.8 ± 3.4 when considering the oxidation of SO2 by OH as the only source of H2SO4. Both the OH and the background signal were also observed to increase significantly during daytime aerosol nucleation events, independent of the ozone photolysis frequency, J(O1D, and were followed by peaks in both H2SO4 and MSA concentrations. This suggests a strong relation between the unknown oxidant(s, OH chemistry, and the atmospheric photo-oxidation of biogenic iodine compounds. As to the identity of the oxidant(s, we have been able to exclude ClO, BrO, IO, and OIO as possible candidates based on ab initio calculations. Stabilized Criegee intermediates (s

  4. Advances of study on atmospheric methane oxidation (consumption) in forest soil

    Institute of Scientific and Technical Information of China (English)

    WANG Chen-rui; SHI Yi; YANG Xiao-ming; WU Jie; YUE Jin

    2003-01-01

    Next to CO2, methane (CH4) is the second important contributor to global warming in the atmosphere and global atmospheric CH4 budget depends on both CH4 sources and sinks. Unsaturated soil is known as a unique sink for atmospheric CH4 in terrestrial ecosystem. Many comparison studies proved that forest soil had the biggest capacity of oxidizing atmospheric CH4 in various unsaturated soils. However, up to now, there is not an overall review in the aspect of atmospheric CH4 oxidation (consumption) in forest soil. This paper analyzed advances of studies on the mechanism of atmospheric CH4 oxidation, and related natural factors (Soil physical and chemical characters, temperature and moisture, ambient main greenhouse gases concentrations, tree species, and forest fire) and anthropogenic factors (forest clear-cutting and thinning, fertilization, exogenous aluminum salts and atmospheric deposition, adding biocides, and switch of forest land use) in forest soils. It was believed that CH4 consumption rate by forest soil was limited by diffusion and sensitive to changes in water status and temperature of soil. CH4 oxidation was also particularly sensitive to soil C/N, Ambient CO2, CH4 and N2O concentrations, tree species and forest fire. In most cases, anthropogenic disturbances will decrease atmospheric CH4 oxidation, thus resulting in the elevating of atmospheric CH4. Finally, the author pointed out that our knowledge of atmospheric CH4 oxidation (consumption) in forest soil was insufficient. In order to evaluate the contribution of forest soils to atmospheric CH4 oxidation and the role of forest played in the process of global environmental change, and to forecast the trends of global warming exactly, more researchers need to studies further on CH4 oxidation in various forest soils of different areas.

  5. Development of atmospheric pressure CVD processes for highquality transparent conductive oxides

    NARCIS (Netherlands)

    Graaf, A. de; Deelen, J. van; Poodt, P.W.G.; Mol, A.M.B. van; Spee, C.I.M.A.; Grob, F.; Kuypers, A.

    2010-01-01

    For the past decade TNO has been involved in the research and development of atmospheric pressure CVD (APCVD) and plasma enhanced CVD (PECVD) processes for deposition of transparent conductive oxides (TCO), such as tin oxide and zinc oxide. It is shown that by combining precursor development, fundam

  6. The Autistic Phenotype Exhibits a Remarkably Localized Modification of Brain Protein by Products of Free Radical-Induced Lipid Oxidation

    Directory of Open Access Journals (Sweden)

    Teresa A. Evans

    2008-01-01

    Full Text Available Oxidative damage has been documented in the peripheral tissues of autism patients. In this study, we sought evidence of oxidative injury in autistic brain. Carboxyethyl pyrrole (CEP and iso[4]levuglandin (iso[4]LGE2-protein adducts, that are uniquely generated through peroxidation of docosahexaenoate and arachidonate-containing lipids respectively, and heme oxygenase-1 were detected immunocytochemically in cortical brain tissues and by ELISA in blood plasma. Significant immunoreactivity toward all three of these markers of oxidative damage in the white matter and often extending well into the grey matter of axons was found in every case of autism examined. This striking threadlike pattern appears to be a hallmark of the autistic brain as it was not seen in any control brain, young or aged, used as controls for the oxidative assays. Western blot and immunoprecipitation analysis confirmed neurofilament heavy chain to be a major target of CEP-modification. In contrast, in plasma from 27 autism spectrum disorder patients and 11 age-matched healthy controls we found similar levels of plasma CEP (124.5 ± 57.9 versus 110.4 ± 30.3 pmol/mL, iso[4]LGE2 protein adducts (16.7 ± 5.8 versus 13.4 ± 3.4 nmol/mL, anti-CEP (1.2 ± 0.7 versus 1.2 ± 0.3 and anti-iso[4]LGE2 autoantibody titre (1.3 ± 1.6 versus 1.0 ± 0.9, and no differences between the ratio of NO2Tyr/Tyr (7.81 E-06 ± 3.29 E-06 versus 7.87 E-06 ± 1.62 E-06. These findings provide the first direct evidence of increased oxidative stress in the autistic brain. It seems likely that oxidative injury of proteins in the brain would be associated with neurological abnormalities and provide a cellular basis at the root of autism spectrum disorders.

  7. Nitric oxide and nitrous oxide emission from Hungarian forest soils; link with atmospheric N-deposition

    Directory of Open Access Journals (Sweden)

    L. Horváth

    2005-06-01

    Full Text Available Studies of forest nitrogen (N budgets generally measure inputs to the atmosphere in wet and dry precipitation and outputs via hydrologic export. Although denitrification has been shown to be important in many wetland ecosystems, emission of nitrogen oxides from forest soils is an important, and often overlooked, component of an ecosystem nitrogen budget. During one year (2002-2003, emissions of nitric oxide (NO and nitrous oxide (N2O were measured from Sessile oak and Norway spruce forest soils in northeast Hungary. Accumulation in small static chambers followed by gas chromatography-mass spectrometry detection was used for the estimation of N2O emission flux. Because there are rapid chemical reactions of NO and ozone, small dynamic chambers were used for in situ NO flux measurements. Average soil emissions of NO were 1.2 and 2.1 µgNm-2h-1, and for N2O were 15 and 20 µgNm-2h-1, for spruce and oak soils, respectively. The previously determined nitrogen balance between the atmosphere and the forest ecosystem was re-calculated using these soil emission figures. The total (dry + wet atmospheric N-deposition to the soil was 1.42 and 1.59gNm-2yr-1 for spruce and oak, respectively, while the soil emissions are 0.14 and 0.20 gNm-2yr-1. Thus, about 10-13% of N compounds deposited to the soil, mostly as NH3/NH4+ and HNO3/NO3-, are transformed in the soil and emitted back to the atmosphere, mostly as a greenhouse gas (N2O.

  8. Avocado by-products as inhibitors of color deterioration and lipid and protein oxidation in raw porcine patties subjected to chilled storage.

    Science.gov (United States)

    Rodríguez-Carpena, J G; Morcuende, D; Estévez, M

    2011-10-01

    Processing of avocados generates an important amount of by-products such as peels and seeds that are rich in bioactive substances with proven radical suppressing activities. The objective of this study was to evaluate the effectiveness of peel and seed extracts from two avocado varieties-'Hass' and 'Fuerte'-as inhibitors of lipid and protein oxidation and color deterioration of raw porcine patties during chilled storage (4 °C/15 days). Avocado extracts significantly (pHass' extracts. Patties treated with avocado extracts had significantly lower amounts of TBA-RS than control ones throughout the storage. 'Hass' avocado extracts significantly inhibited the formation of protein carbonyls in chilled patties at day 15. The present results highlight the potential usage of extracts from avocado by-products as ingredients for the production of muscle foods with enhanced quality traits.

  9. Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon

    Science.gov (United States)

    Daines, Stuart J.; Mills, Benjamin J. W.; Lenton, Timothy M.

    2017-02-01

    It is unclear why atmospheric oxygen remained trapped at low levels for more than 1.5 billion years following the Paleoproterozoic Great Oxidation Event. Here, we use models for erosion, weathering and biogeochemical cycling to show that this can be explained by the tectonic recycling of previously accumulated sedimentary organic carbon, combined with the oxygen sensitivity of oxidative weathering. Our results indicate a strong negative feedback regime when atmospheric oxygen concentration is of order pO2~0.1 PAL (present atmospheric level), but that stability is lost at pO2biological productivity and resultant organic carbon burial drove the Great Oxidation Event.

  10. Decolourisation of Acid Orange 7 recalcitrant auto-oxidation coloured by-products using an acclimatised mixed bacterial culture.

    Science.gov (United States)

    Bay, Hui Han; Lim, Chi Kim; Kee, Thuan Chien; Ware, Ismail; Chan, Giek Far; Shahir, Shafinaz; Ibrahim, Zaharah

    2014-03-01

    This study focuses on the biodegradation of recalcitrant, coloured compounds resulting from auto-oxidation of Acid Orange 7 (AO7) in a sequential facultative anaerobic-aerobic treatment system. A novel mixed bacterial culture, BAC-ZS, consisting of Brevibacillus panacihumi strain ZB1, Lysinibacillus fusiformis strain ZB2, and Enterococcus faecalis strain ZL bacteria were isolated from environmental samples. The acclimatisation of the mixed culture was carried out in an AO7 decolourised solution. The acclimatised mixed culture showed 98 % decolourisation within 2 h of facultative anaerobic treatment using yeast extract and glucose as co-substrate. Subsequent aerobic post treatment caused auto-oxidation reaction forming dark coloured compounds that reduced the percentage decolourisation to 73 %. Interestingly, further agitations of the mixed culture in the solution over a period of 48 h significantly decolourise the coloured compounds and increased the decolourisation percentage to 90 %. Analyses of the degradation compounds using UV-visible spectrophotometer, Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) showed complete degradation of recalcitrant AO7 by the novel BAC-ZS. Phytotoxicity tests using Cucumis sativus confirmed the dye solution after post aerobic treatment were less toxic compared to the parent dye. The quantitative real-time PCR revealed that E. faecalis strain ZL was the dominant strain in the acclimatised mix culture.

  11. Physicochemical nature of iron oxidation in a damp atmospheric condition

    Institute of Scientific and Technical Information of China (English)

    Tongyan PAN; Yunpinq XI

    2011-01-01

    The surface oxidation patterns of iron or low-carbon steels are critical to their life when serving in typical damp environments.An accurate determination of the oxidation pattern entails tracking the iron atoms oxidized at the iron/steel-moisture interface.Using a quantum chemistry-based force field that is capable of simulating chemical reactions,this paper studies the process of iron oxidation under a typical moist condition. The oxidation of iron surface was found to be highly thermodynamic and dependent on the availability of reactants.A triplex structure was formed at the end of a three-stage oxidation process to reduce the overall oxidation speed.The results from this study shed light on the atomistic mechanism of iron oxidation; therefore can be used to guide the protection of general ferrous-based iron/steel structures.

  12. Ozone oxidation of antidepressants in wastewater –Treatment evaluation and characterization of new by-products by LC-QToFMS

    Directory of Open Access Journals (Sweden)

    Lajeunesse André

    2013-01-01

    Full Text Available Abstract Background The fate of 14 antidepressants along with their respective N-desmethyl metabolites and the anticonvulsive drug carbamazepine was examined in a primary sewage treatment plant (STP and following advanced treatments with ozone (O3. The concentrations of each pharmaceutical compound were determined in raw sewage, effluent and sewage sludge samples by LC-MS/MS analysis. The occurrence of antidepressant by-products formed in treated effluent after ozonation was also investigated. Results Current primary treatments using physical and chemical processes removed little of the compounds (mean removal efficiency: 19%. Experimental sorption coefficients (Kd of each studied compounds were also calculated. Sorption of venlafaxine, desmethylvenlafaxine, and carbamazepine on sludge was assumed to be negligible (log Kd ≤ 2, but higher sorption behavior can be expected for sertraline (log Kd ≥ 4. Ozonation treatment with O3 (5 mg/L led to a satisfactory mean removal efficiency of 88% of the compounds. Screening of the final ozone-treated effluent samples by high resolution-mass spectrometry (LC-QqToFMS did confirm the presence of related N-oxide by-products. Conclusion Effluent ozonation led to higher mean removal efficiencies than current primary treatment, and therefore represented a promising strategy for the elimination of antidepressants in urban wastewaters. However, the use of O3 produced by-products with unknown toxicity.

  13. Nitrogen atmosphere and natural antioxidants effect on muesli oxidation during long-time storage

    Directory of Open Access Journals (Sweden)

    Dorota Klensporf-Pawlik

    2009-03-01

    Full Text Available The effects of natural antioxidants from raspberry and black currant seeds and modified atmosphere packaging on muesli oxidative stability measured by monitoring volatile lipid oxidation products were evaluated. The effectiveness toward lipid oxidation was investigated during 10 months storage at ambient temperature. Both ethanolic extracts as well as nitrogen atmosphere influenced lipid oxidation rate in muesli measured by volatile compounds content. The most abundant lipid derived volatile compounds was hexanal. After storage, its concentration changed from 802 µg/kg to 9.8 mg/kg in muesli stored in air atmosphere, whereas in muesli stored in nitrogen atmosphere with raspberry seed extract addition it raised to 3.1 mg/kg. Although, both natural antioxidants rich in phenolic compounds, were effective towards lipid oxidation, the strongest inhibiting effect had modified atmosphere packaging. The addition of ethanolic extracts did not fortify its positive effect. Total concentration of volatile compounds in muesli after 10 months of storage was 19.6 mg/kg when stored in air and 13.7 and 11.8 mg/kg when stored with raspberry and black currant seeds extract addition respectively, while 9.8 mg/kg when stored in nitrogen atmosphere without antioxidants, and 9.7 and 9.9 mg/kg when stored with antioxidants mentioned above.

  14. Oxidation Products of Biogenic Emissions Contribute to Nucleation of Atmospheric Particles

    CERN Document Server

    Riccobono, Francesco; Baltensperger, Urs; Worsnop, Douglas R; Curtius, Joachim; Carslaw, Kenneth S; Wimmer, Daniela; Wex, Heike; Weingartner, Ernest; Wagner, Paul E; Vrtala, Aron; Viisanen, Yrjö; Vaattovaara, Petri; Tsagkogeorgas, Georgios; Tomé, Antonio; Stratmann, Frank; Stozhkov, Yuri; Spracklen, Dominick V; Sipilä, Mikko; Praplan, Arnaud P; Petäjä, Tuukka; Onnela, Antti; Nieminen, Tuomo; Mathot, Serge; Makhmutov, Vladimir; Lehtipalo, Katrianne; Laaksonen, Ari; Kvashin, Alexander N.; Kürten, Andreas; Kupc, Agnieszka; Keskinen, Helmi; Kajos, Maija; Junninen, Heikki; Hansel, Armin; Franchin, Alessandro; Flagan, Richard C; Ehrhart, Sebastian; Duplissy, Jonathan; Dunne, Eimear M; Downard, Andrew; David, André; Breitenlechner, Martin; Bianchi, Federico; Amorim, Antonio; Almeida, João; Rondo, Linda; Ortega, Ismael K; Dommen, Josef; Scott, Catherine E; Vrtala, Aron; Santos, Filipe D; Schallhart, Simon; Seinfeld, John H; Sipila, Mikko; Donahue, Neil M; Kirkby, Jasper; Kulmala, Markku

    2014-01-01

    Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations.

  15. Oxidation Behaviour of Si3N4 Materials in Air and Nitrogen Atmosphere

    Institute of Scientific and Technical Information of China (English)

    ZHANGQitu; LINGZhida

    1999-01-01

    Si3N4 powder and hot-pressed Si3N4 ceramics added with Al2O3 are used for investigate their oxidation behvior in air and nitrogen atmosphere(with oxygen partial pressure PO2=1-10Pa),The oxidation products of Si3N4 are examined by chemical analysi,X-ray diffraction (XRD) and XPS method,Also, thermodynamic calculation is made to analyze oxidation behavior of Si3N4.The results show that only passive oxidation will occur when Si3N4 is oxidized in air at high temperature,whereas in N2 at high temperature,the active oxidation is dominant in spite of the existence of a little passive oxidation.

  16. Oxidation Control of Atmospheric Plasma Sprayed FeAl Intermetallic Coatings Using Dry-Ice Blasting

    Science.gov (United States)

    Song, Bo; Dong, Shujuan; Coddet, Pierre; Hansz, Bernard; Grosdidier, Thierry; Liao, Hanlin; Coddet, Christian

    2013-03-01

    The performance of atmospheric plasma sprayed FeAl coatings has been remarkably limited because of oxidation and phase transformation during the high-temperature process of preparation. In the present work, FeAl intermetallic coatings were prepared by atmospheric plasma spraying combined with dry-ice blasting. The microstructure, oxidation, porosity, and surface roughness of FeAl intermetallic coatings were investigated. The results show that a denser FeAl coating with a lower content of oxide and lower degree of phase transformation can be achieved because of the cryogenic, the cleaning, and the mechanical effects of dry-ice blasting. The surface roughness value decreased, and the adhesive strength of FeAl coating increased after the application of dry-ice blasting during the atmospheric plasma spraying process. Moreover, the microhardness of the FeAl coating increased by 72%, due to the lower porosity and higher dislocation density.

  17. High Temperature Corrosion of Fe-C-S Cast Irons in Oxidizing and Sulfidizing Atmospheres

    Institute of Scientific and Technical Information of China (English)

    Thuan-Dinh NGUYEN; Dong-Bok LEE

    2008-01-01

    The corrosion behavior of spheroidal graphite and flake graphite cast irons was studied in oxidizing and sulfidizing atmospheres between 600 and 800℃ for 50 h. The corrosion rate in the sulfidizing atmosphere was faster than that in air above 700℃, due to the formation of the Feo.975S sulfide. The corrosion rate of the spheroidal graphite cast iron was similar to that of the flake graphite cast iron.

  18. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol.

    Science.gov (United States)

    Kroll, Jesse H; Donahue, Neil M; Jimenez, Jose L; Kessler, Sean H; Canagaratna, Manjula R; Wilson, Kevin R; Altieri, Katye E; Mazzoleni, Lynn R; Wozniak, Andrew S; Bluhm, Hendrik; Mysak, Erin R; Smith, Jared D; Kolb, Charles E; Worsnop, Douglas R

    2011-02-01

    A detailed understanding of the sources, transformations and fates of organic species in the environment is crucial because of the central roles that they play in human health, biogeochemical cycles and the Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here, we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state, a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of the average carbon oxidation state, using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number.

  19. Isoprene oxidation products are a significant atmospheric aerosol component

    Directory of Open Access Journals (Sweden)

    S. N. Matsunaga

    2005-11-01

    Full Text Available Glycolaldehyde, hydroxyacetone, and methylglyoxal, which are known isoprene oxidation products, were collected during two field experiments using an annular denuder sampling system and compared to a model calculation. The compounds in gas and aerosol phases were determined during both experiments. Global variation and distribution of the aerosol mass contribution of the compounds were predicted using the measurements, the box model results, and gas-phase concentrations and humidity simulated by a global 3-D model. Here we report the estimates of a global annual contribution of 35 (10–120 Tg of aerosol organic matter from isoprene.

  20. NEW CATHODE MATERIALS FOR INERT AND OXIDIZING ATMOSPHERE PLASMA APPLICATION

    OpenAIRE

    1990-01-01

    This study has been carried out to develop new cathode materials for two types of thermionic cathode. First is concerning to the tungsten electrodes for the plasma furnace and welding torches. The second one is the electrodes for air plasma cutting torch. Tungsten electrodes activated with a single and combined additives of rare earth metal oxides, such as La2O3, Y2O3 and CeO2, are produced and pared with pure and thoriated tungsten electrode conventionally used, from the point of view of ele...

  1. Branching between fragmentation and functionalization pathways in the oxidation of atmospheric organics

    Science.gov (United States)

    Kroll, J. H.; Smith, J. D.; Wilson, K. R.; Worsnop, D. R.; Ahmed, M.; Leone, S. R.

    2008-12-01

    Oxidation reactions that affect the volatility of organics are of central importance to the chemistry of the troposphere, as they lead to the formation of secondary organic aerosol, and can change the properties or loadings of existing particulate matter via oxidative processing ("aging"). Atmospheric oxidation can decrease the vapor pressure of an organic compound by adding oxygen-containing functional groups (increasing its polarity), or increase vapor pressure by breaking carbon-carbon bonds (decreasing its molecular weight). Despite being a fundamental determinant of the changes to volatilities of atmospheric organics, the functionalization/fragmentation branching ratio is not well-constrained for large atmospheric organics, especially for highly oxidized ones. Here we present laboratory measurements of this branching ratio for the heterogeneous oxidation of particulate organics. Particles of pure squalane (a branched C30 alkane) are sent into a flow reactor and are rapidly oxidized by exposure to high levels of OH; particle size and composition are measured as a function of OH exposure using a scanning mobility particle sizer (SMPS) and high-resolution time-of-flight aerosol mass spectrometer (AMS). Oxidation reactions are found to decrease particle mass, indicating volatilization (from carbon-carbon bond breaking) and also to increase the oxygen/carbon (O/C) ratio of the particulate organics, indicating the addition of functional groups. The relative rates of these two processes allows for the determination of the branching ratio between fragmentation and functionalization. Functionalization is found to dominate the oxidation of the pure hydrocarbon, but the importance of fragmentation increases as the organics become increasingly oxidized. Fragmentation pathways appear to dominate for organics with O/C ratios above ~30%.

  2. Soot Surface Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix I

    Science.gov (United States)

    Xu, F.; El-Leathy, A. M.; Kim, C. H.; Faeth, G. M.; Yuan, Z.-G. (Technical Monitor); Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2003-01-01

    Soot surface oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round fuel jets burning in coflowing dry air considering acetylene-nitrogen, ethylene, propyiene-nitrogen, propane and acetylene-benzene-nitrogen in the fuel stream. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of major stable gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2, C2H6, C3H6, C3H8, and C6H6) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by deconvoluted Li/LiOH atomic absorption and flow velocities by laser velocimetry. For present test conditions, it was found that soot surface oxidation rates were not affected by fuel type, that direct rates of soot surface oxidation by O2 estimated from Nagle and Strickland-Constable (1962) were small compared to observed soot surface oxidation rates because soot surface oxidation was completed near the flame sheet where O2 concentrations were less than 3% by volume, and that soot surface oxidation rates were described by the OH soot surface oxidation mechanism with a collision efficiency of 0.14 and an uncertainty (95% confidence) of +/- 0.04 when allowing for direct soot surface oxidation by O2, which is in reasonably good agreement with earlier observations of soot surface oxidation rates in both premixed and diffusion flames at atmospheric pressure.

  3. Conventional methanotrophs are responsible for atmospheric methane oxidation in paddy soils

    Science.gov (United States)

    Cai, Yuanfeng; Zheng, Yan; Bodelier, Paul L. E.; Conrad, Ralf; Jia, Zhongjun

    2016-06-01

    Soils serve as the biological sink of the potent greenhouse gas methane with exceptionally low concentrations of ~1.84 p.p.m.v. in the atmosphere. The as-yet-uncultivated methane-consuming bacteria have long been proposed to be responsible for this `high-affinity' methane oxidation (HAMO). Here we show an emerging HAMO activity arising from conventional methanotrophs in paddy soil. HAMO activity was quickly induced during the low-affinity oxidation of high-concentration methane. Activity was lost gradually over 2 weeks, but could be repeatedly regained by flush-feeding the soil with elevated methane. The induction of HAMO activity occurred only after the rapid growth of methanotrophic populations, and a metatranscriptome-wide association study suggests that the concurrent high- and low-affinity methane oxidation was catalysed by known methanotrophs rather than by the proposed novel atmospheric methane oxidizers. These results provide evidence of atmospheric methane uptake in periodically drained ecosystems that are typically considered to be a source of atmospheric methane.

  4. Low-temperature sintering process for UO2 pellets in partially-oxidative atmosphere

    Institute of Scientific and Technical Information of China (English)

    YANG Xiao-dong; GAO Jia-cheng; WANG Yong; CHANG Xin

    2008-01-01

    Low-temperature sintering(LTS) experiments of UO2 pellets and their results were reported. Moreover, a routine process of LTS for UO2 pellets was primarily established. Being sintered at 1 400 ℃ for 3 h in a partially-oxidative atmosphere, the relative density of the pellet can be up to around 94%. Pellets with such a high density are of benefit for following-up reduction-sintering processes. Orthogonal test indicates that the importance of factors affecting the density decreases in the sequence of partial-oxidative sintering temperature and time, reduction-sintering time and temperature, and sintering atmosphere. It is found that it is helpful to introducing a small amount of water vapor into the sintering atmosphere during the latter stage. It is believed that it is the key factor to raise the O/U ratio of original powder in order to improve the properties of the low-temperature sintered pellets.

  5. Fast low-temperature plasma reduction of monolayer graphene oxide at atmospheric pressure

    Science.gov (United States)

    Bodik, Michal; Zahoranova, Anna; Micusik, Matej; Bugarova, Nikola; Spitalsky, Zdenko; Omastova, Maria; Majkova, Eva; Jergel, Matej; Siffalovic, Peter

    2017-04-01

    We report on an ultrafast plasma-based graphene oxide reduction method superior to conventional vacuum thermal annealing and/or chemical reduction. The method is based on the effect of non-equilibrium atmospheric-pressure plasma generated by the diffuse coplanar surface barrier discharge in proximity of the graphene oxide layer. As the reduction time is in the order of seconds, the presented method is applicable to the large-scale production of reduced graphene oxide layers. The short reduction times are achieved by the high-volume power density of plasma, which is of the order of 100 W cm‑3. Monolayers of graphene oxide on silicon substrate were prepared by a modified Langmuir–Schaefer method and the efficient and rapid reduction by methane and/or hydrogen plasma was demonstrated. The best results were obtained for the graphene oxide reduction in hydrogen plasma, as verified by x-ray photoelectron spectroscopy and Raman spectroscopy.

  6. Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Massachusetts Institute of Technology; Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.; Kessler, Sean H.; Canagaratna, Manjula R.; Wilson, Kevin R.; Altieri, Katye E.; Mazzoleni, Lynn R.; Wozniak, Andrew S.; Bluhm, Hendrik; Mysak, Erin R.; Smith, Jared D.; Kolb, Charles E.; Worsnop, Douglas R.

    2010-11-05

    A detailed understanding of the sources, transformations, and fates of organic species in the environment is crucial because of the central roles that organics play in human health, biogeochemical cycles, and Earth's climate. However, such an understanding is hindered by the immense chemical complexity of environmental mixtures of organics; for example, atmospheric organic aerosol consists of at least thousands of individual compounds, all of which likely evolve chemically over their atmospheric lifetimes. Here we demonstrate the utility of describing organic aerosol (and other complex organic mixtures) in terms of average carbon oxidation state (OSC), a quantity that always increases with oxidation, and is readily measured using state-of-the-art analytical techniques. Field and laboratory measurements of OSC , using several such techniques, constrain the chemical properties of the organics and demonstrate that the formation and evolution of organic aerosol involves simultaneous changes to both carbon oxidation state and carbon number (nC).

  7. Atmospheric oxidation mechanism of phenol initiated by OH radical.

    Science.gov (United States)

    Xu, Cui; Wang, Liming

    2013-03-21

    The gas-phase oxidation mechanism of phenol initiated by OH radical was investigated using DFT and ab initio calculations. The initiation of the reaction is dominated by OH addition to ortho-position, forming P2, which subsequently combines with O2 at the ipso-position to form P2-1-OO adduct. A concerted HO2 elimination process from P2-1-OO was found to be much faster than the common ring closure to bicyclic intermediates. The HO2 elimination process from P2-1-OO forms 2-hydroxy-3,5-cyclohexadienone (HCH) as the main product and is also responsible for the experimental fact that the rate constants for reaction between P2 and O2 are about 2 orders of magnitude higher than those between other aromatic-OH adducts and O2. It was speculated that HCH would isomerize to catechol, which is thermodynamically more stable than HCH and was the experimentally observed main product, possibly through heterogeneous processes. Reaction of P2 with NO2 proceeded by addition to form P2-n-NO2 (n = 1, 3, 5), followed by HONO elimination from P2-1/3-NO2 to form catechol. The barriers for HONO elimination and catechol formation are below the separate reactants P2 and NO2, being consistent with the experimental observation of catechol in the absence of O2, while H2O elimination from P2-1/3-NO2 to form 2-nitrophenol (2NP) is hindered by high barriers. The most likely pathway for 2NP is the reaction of phenoxy radical and NO2.

  8. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    Directory of Open Access Journals (Sweden)

    Matthias Augustin

    2015-01-01

    Full Text Available Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx+ oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species.

  9. Lifespan and oxidative stress show a non-linear response to atmospheric oxygen in Drosophila.

    Science.gov (United States)

    Rascón, Brenda; Harrison, Jon F

    2010-10-15

    Oxygen provides the substrate for most ATP production, but also serves as a source of reactive oxygen species (ROS), which can induce cumulative macromolecular oxidative damage and cause aging. Pure oxygen atmospheres (100 kPa) are known to strongly reduce invertebrate lifespan and induce aging-related physiological changes. However, the nature of the relationship between atmospheric oxygen, oxidative stress, and lifespan across a range of oxygen levels is poorly known. Developmental responses are likely to play a strong role, as prior research has shown strong effects of rearing oxygen level on growth, size and respiratory system morphology. In this study, we examined (1) the effect of oxygen on adult longevity and (2) the effect of the oxygen concentration experienced by larvae on adult lifespan by rearing Drosophila melanogaster in three oxygen atmospheres throughout larval development (10, 21 and 40 kPa), then measuring the lifespan of adults in five oxygen tensions (2, 10, 21, 40, 100 kPa). We also assessed the rate of protein carbonyl production for flies kept at 2, 10, 21, 40 and 100 kPa as adults (all larvae reared in normoxia). The rearing of juveniles in varying oxygen treatments affected lifespan in a complex manner, and the effect of different oxygen tensions on adult lifespan was non-linear, with reduced longevity and heightened oxidative stress at extreme high and low atmospheric oxygen levels. Moderate hypoxia (10 kPa) extended maximum, but not mean lifespan.

  10. Mechanistic studies on the OH-initiated atmospheric oxidation of selected aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nehr, Sascha

    2012-07-01

    Benzene, toluene, the xylenes, and the trimethylbenzenes are among the most abundant aromatic trace constituents of the atmosphere mainly originating from anthropogenic sources. The OH-initiated atmospheric photo-oxidation of aromatic hydrocarbons is the predominant removal process resulting in the formation of O{sub 3} and secondary organic aerosol. Therefore, aromatics are important trace constituents regarding air pollution in urban environments. Our understanding of aromatic photo-oxidation processes is far from being complete. This work presents novel approaches for the investigation of OH-initiated atmospheric degradation mechanisms of aromatic hydrocarbons. Firstly, pulsed kinetic studies were performed to investigate the prompt HO{sub 2} formation from OH+ aromatic hydrocarbon reactions under ambient conditions. For these studies, the existing OH reactivity instrument, based on the flash photolysis/laser-induced fluorescence (FP/LIF) technique, was extended to the detection of HO{sub 2} radicals. The experimental design allows for the determination of HO{sub 2} formation yields and kinetics. Results of the pulsed kinetic experiments complement previous product studies and help to reduce uncertainties regarding the primary oxidation steps. Secondly, experiments with aromatic hydrocarbons were performed under atmospheric conditions in the outdoor atmosphere simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction chamber) located at Forschungszentrum Juelich. The experiments were aimed at the evaluation of up-to-date aromatic degradation schemes of the Master Chemical Mechanism (MCMv3.2). The unique combination of analytical instruments operated at SAPHIR allows for a detailed investigation of HO{sub x} and NO{sub x} budgets and for the determination of primary phenolic oxidation product yields. MCMv3.2 deficiencies were identified and most likely originate from shortcomings in the mechanistic representation of ring

  11. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    CERN Document Server

    Schobesberger, Siegfried; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molec...

  12. Oxidative stability during storage of fish oil from filleting by-products of rainbow trout (Oncorhynchus mykiss) is largely independent of the processing and production temperature

    DEFF Research Database (Denmark)

    Honold, Philipp; Nouard, Marie-Louise; Jacobsen, Charlotte

    2016-01-01

    Rainbow trout (Oncorhynchus mykiss) is the main fish species produced in Danish fresh water farming. Large amounts of fileting by-products like heads, bones, tails (HBT), and intestines are produced when rainbow trout is processed to smoked rainbow trout filets. The filleting by-products can...

  13. Automated sequence analysis of atmospheric oxidation pathways: SEQUENCE version 1.0

    Directory of Open Access Journals (Sweden)

    T. M. Butler

    2009-10-01

    Full Text Available An algorithm for the sequential analysis of the atmospheric oxidation of chemical species using output from a photochemical model is presented. Starting at a "root species", the algorithm traverses all possible reaction sequences which consume this species, and lead, via intermediate products, to final products. The algorithm keeps track of the effects of all of these reactions on their respective reactants and products. Upon completion, the algorithm has built a detailed picture of the effects of the oxidation of the root species on its chemical surroundings. The output of the algorithm can be used to determine product yields, radical recycling fractions, and ozone production potentials of arbitrary chemical species.

  14. Enhanced oxidative weathering in glaciated mountain catchments: A stabilising feedback on atmospheric carbon dioxide?

    Science.gov (United States)

    Horan, K.; Hilton, R. G.; Burton, K. W.; Selby, D. S.; Ottley, C. J.

    2015-12-01

    Mountain belts act as sources of carbon dioxide (CO2) to the atmosphere if physical erosion and exhumation expose rock-derived organic carbon ('petrogenic' organic carbon, OCpetro) to chemical weathering. Estimates suggest 15x1021g of carbon is stored in rocks globally as OCpetro, ~25,000 times the amount of carbon in the pre-industrial atmosphere. Alongside volcanic and metamorphic degassing, OCpetro weathering is thought to be the main source of CO2 to the atmosphere over geological timescales. Erosion in mountain river catchments has been shown to enhance oxidative weathering and CO2 release. However, we still lack studies which quantify this process. In addition, it is not clear how glaciation may impact OCpetro oxidation. In analogy with silicate weathering, large amounts of fine sediment in glacial catchments may enhance oxidative weathering. Here we quantify oxidative weathering in nine catchments draining OCpetro bearing rocks in the western Southern Alps, New Zealand. Using rhenium (Re) as a tracer of oxidative weathering, we develop techniques to precisely measure Re concentration at sub-ppt levels in river waters. Using [Re]water/[Re]rock as a weathering tracer, we estimate that the weathering efficiency in glacial catchments is >4 times that of non-glacial catchments. Combining this with the OCpetro content of rocks and dissolved Re flux, we estimate the CO2 release by OCpetro oxidation. The analysis suggests that non-glacial catchments in the western Southern Alps release similar amounts of CO2 as catchments in Taiwan where erosion rates are comparable. In this mountain belt, the CO2 release does not negate CO2 drawdown by silicate weathering and by riverine transfer of organic matter. Based on our results, we propose that mountain glaciation may greatly enhance OCpetro oxidation rates. Depending on the global fluxes involved, this provides a feedback to damp low atmospheric CO2 levels and global cooling. During glacial periods (low CO2, low global

  15. Performance Testing of a Photocatalytic Oxidation Module for Spacecraft Cabin Atmosphere Revitalization

    Science.gov (United States)

    Perry, Jay L.; Abney, Morgan B.; Frederick, Kenneth R.; Scott, Joseph P.; Kaiser, Mark; Seminara, Gary; Bershitsky, Alex

    2011-01-01

    Photocatalytic oxidation (PCO) is a candidate process technology for use in high volumetric flow rate trace contaminant control applications in sealed environments. The targeted application for PCO as applied to crewed spacecraft life support system architectures is summarized. Technical challenges characteristic of PCO are considered. Performance testing of a breadboard PCO reactor design for mineralizing polar organic compounds in a spacecraft cabin atmosphere is described. Test results are analyzed and compared to results reported in the literature for comparable PCO reactor designs.

  16. Kinetic and photochemical data for atmospheric chemistry reactions of the nitrogen oxides

    Science.gov (United States)

    Hampson, R. F., Jr.

    1980-01-01

    Data sheets for thermal and photochemical reactions of importance in the atmospheric chemistry of the nitrogen oxides are presented. For each reaction the available experimental data are summarized and critically evaluated, and a preferred value of the rate coefficient is given. The selection of the preferred value is discussed and an estimate of its accuracy is given. For the photochemical process, the data are summarized, and preferred for the photoabsorption cross section and primary quantum yields are given.

  17. Reagent use efficiency with removal of nitrogen from pig slurry via struvite: A study on magnesium oxide and related by-products.

    Science.gov (United States)

    Romero-Güiza, M S; Tait, S; Astals, S; Del Valle-Zermeño, R; Martínez, M; Mata-Alvarez, J; Chimenos, J M

    2015-11-01

    Controlled struvite formation has been attracting increasing attention as a near mature technology to recover nutrients from wastewater. However, struvite feasibility is generally limited by the high cost of chemical reagents. With the aim to understand and control reagent use efficiency, experiments and equilibrium model simulations examined inorganic nitrogen (TAN) removal from pig manure via struvite with added magnesium and phosphate reagents. Four industrial magnesium oxide (MgO), a commercial product and three by-products from magnesite calcination, were tested with phosphate added as a highly soluble potassium salt. TAN removal extents with the MgOs ranged from 47 to 72%, with the highest grade MgO providing the greatest extent of TAN removal. However, model analysis showed that all the MgO reagents were poorly soluble (only about 40% of added magnesium actually dissolved). The model results suggested that this poor dissolution was due to kinetic limitations, not solubility constraints. A further set of additional reagents (termed stabilization agents) were prepared by pre-treating the MgO reagents with phosphoric acid, and were tested separately as a source of both magnesium and phosphate. Results showed that acid pre-treatment of moderate to highly reactive MgOs (soft to medium-burnt) primarily formed bobierrite as the stabilizing agent, whereas the pre-treatment of very low reactivity MgOs (dead-burnt) mostly formed newberyite. The newberyite stabilizing agents achieved very high TAN removal extents of about 80%, which is significant, considering that these were formed from dead-burnt/low-grade MgOs. However, the bobierrite stabilizing agents achieved a substantially lower TAN removal extent than their medium-to-high reactivity precursor MgOs. Again, model analysis showed that the bobierrite stabilizing agents were poorly soluble, due to kinetic limitations, not solubility constraints. In contrast, the model suggested that the newberyite stabilizing

  18. Instability of oxidation front during laser heating of metals in oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Alimov, D.T.; Bunkin, V.F.; Edvabnyj, I.V.; Kirichenko, N.A.; Luk' yanchuk, B.S.; Khabibullaev, P.K. (AN SSSR, Moscow. Fizicheskij Inst.)

    1982-09-01

    Consideration is given to the features of a heterogeneous reaction - oxidation of metals by laser heating in the air. It is shown that even at uniform distribution of irradiation along the metal surface there can be local instabilities leading to nonuniformities of the oxide layer thickness. The development of localized (axially symmetric) perturbations is investigated. The role of surface and thermal diffusion in the development of instabilities is analysed in detail. In particular, it is shown that diffusion processes can lead to stabilization of instabilities of spatial scale considerably differing from the characteristic length of reagent diffusion up to the moment of a reaction.

  19. Atmospheric oxygen regulation at low Proterozoic levels by incomplete oxidative weathering of sedimentary organic carbon

    Science.gov (United States)

    Daines, Stuart J.; Mills, Benjamin J. W.; Lenton, Timothy M.

    2017-01-01

    It is unclear why atmospheric oxygen remained trapped at low levels for more than 1.5 billion years following the Paleoproterozoic Great Oxidation Event. Here, we use models for erosion, weathering and biogeochemical cycling to show that this can be explained by the tectonic recycling of previously accumulated sedimentary organic carbon, combined with the oxygen sensitivity of oxidative weathering. Our results indicate a strong negative feedback regime when atmospheric oxygen concentration is of order pO2∼0.1 PAL (present atmospheric level), but that stability is lost at pO2<0.01 PAL. Within these limits, the carbonate carbon isotope (δ13C) record becomes insensitive to changes in organic carbon burial rate, due to counterbalancing changes in the weathering of isotopically light organic carbon. This can explain the lack of secular trend in the Precambrian δ13C record, and reopens the possibility that increased biological productivity and resultant organic carbon burial drove the Great Oxidation Event. PMID:28148950

  20. Monitoring atmospheric nitrous oxide background concentrations at Zhongshan Station, east Antarctica.

    Science.gov (United States)

    Ye, Wenjuan; Bian, Lingen; Wang, Can; Zhu, Renbin; Zheng, Xiangdong; Ding, Minghu

    2016-09-01

    At present, continuous observation data for atmospheric nitrous oxide (N2O) concentrations are still lacking, especially in east Antarctica. In this paper, nitrous oxide background concentrations were measured at Zhongshan Station (69°22'25″S, 76°22'14″E), east Antarctica during the period of 2008-2012, and their interannual and seasonal characteristics were analyzed and discussed. The mean N2O concentration was 321.9nL/L with the range of 320.5-324.8nL/L during the five years, and it has been increasing at a rate of 0.29% year(-1). Atmospheric N2O concentrations showed a strong seasonal fluctuation during these five years. The concentrations appeared to follow a downtrend from spring to autumn, and then increased in winter. Generally the highest concentrations occurred in spring. This trend was very similar to that observed at other global observation sites. The overall N2O concentration at the selected global sites showed an increasing annual trend, and the mean N2O concentration in the Northern Hemisphere was slightly higher than that in the Southern Hemisphere. Our result could be representative of atmospheric N2O background levels at the global scale. This study provided valuable data for atmospheric N2O concentrations in east Antarctica, which is important to study on the relationships between N2O emissions and climate change.

  1. Soot Oxidation in Laminar Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix D

    Science.gov (United States)

    Xu, F.; El-Leathy, A. M.; Faeth, G. M.

    2000-01-01

    Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, proplyene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, 02, CO, CO2, CH4, C2H2, C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable, because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.

  2. Soot Oxidation in Hydrocarbon/Air Diffusion Flames at Atmospheric Pressure. Appendix K

    Science.gov (United States)

    Xu, F.; El-Leathy, A. M.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2001-01-01

    Soot oxidation was studied experimentally in laminar hydrocarbon/air diffusion flames at atmospheric pressure. Measurements were carried out along the axes of round jets burning in coflowing air considering acetylene, ethylene, propylene and propane as fuels. Measurements were limited to the initial stages of soot oxidation (carbon consumption less than 70%) where soot oxidation mainly occurs at the surface of primary soot particles. The following properties were measured as a function of distance above the burner exit: soot concentrations by deconvoluted laser extinction, soot temperatures by deconvoluted multiline emission, soot structure by thermophoretic sampling and analysis using Transmission Electron Microscopy (TEM), concentrations of stable major gas species (N2, H2O, H2, O2, CO, CO2, CH4, C2H2,C2H4, C2H6, C3H6, and C3H8) by sampling and gas chromatography, concentrations of some radical species (H, OH, O) by the deconvoluted Li/LiOH atomic absorption technique and flow velocities by laser velocimetry. It was found that soot surface oxidation rates are not particularly affected by fuel type for laminar diffusion flames and are described reasonably well by the OH surface oxidation mechanism with a collision efficiency of 0.10, (standard deviation of 0.07) with no significant effect of fuel type in this behavior; these findings are in good agreement with the classical laminar premixed flame measurements of Neoh et al. Finally, direct rates of surface oxidation by O2 were small compared to OH oxidation for present conditions, based on estimated O2 oxidation rates due to Nagle and Strickland-Constable (1962), because soot oxidation was completed near the flame sheet where O2 concentrations were less than 1.2% by volume.

  3. Five pesticides decreased oxidation of atmospheric methane in a forest soil

    DEFF Research Database (Denmark)

    Priemé, Anders; Ekelund, Flemming

    2001-01-01

    We found that five tested pesticides (the insecticide Dimethoat 40 EC, the herbicide Tolkan, and the fungicides Tilt 250 EC, Tilt Top, and Corbel) decreased the oxidation of atmospheric methane in slurries from a Danish forest soil. Dimethoat 40 EC was the most toxic with an EC50 value (i.......e. the concentration which caused a 50% inhibition of the methane oxidation) of 10 mg active ingredient (AI) l-1, followed by Tilt 250 EC (EC50=56 mg AI l-1). EC50 of Tilt Top was 350 AI mg l-1, the value of Tolkan was 410 mg AI l-1, while Corbel had a value of 1600 mg AI l-1. Dimethoat 40 EC and Tolkan inhibited...... the oxidation of atmospheric methane at concentrations expected in natural soil after application of the pesticides. Pesticides, therefore, may be partly responsible for the lowered methane oxidation rates in arable soils compared to forest soils....

  4. Laboratory investigations of the hydroxyl radical-initiated oxidation of atmospheric volatile organic compounds

    Science.gov (United States)

    Vimal, Deepali

    The hydroxyl radical (OH) is one of the most important oxidants in the atmosphere, because reaction with OH is the dominant atmospheric fate of most trace atmospheric species. OH is intimately involved in a complex non-linear photochemical pathway involving anthropogenic and biogenic emissions of volatile organic compounds (VOCs) and nitrogen oxides that are emitted from vehicular exhaust and industrial emissions. This chemistry generates secondary tropospheric ozone which is an important greenhouse gas as well as a component of photochemical smog. In addition, this chemistry leads to the formation of secondary organic aerosols in the atmosphere which have implications for public health and climate change. The focus of this dissertation is to improve our understanding of this complex chemistry by investigating the rate-limiting elementary reactions which are part of the OH-initiated oxidation of important VOCs. Experimental (discharge flow technique coupled with resonance fluorescence and laser induced fluorescence) and theoretical studies (Density Functional Theory computations) of the kinetics of three atmospheric VOCs, acetic acid, 1,3-butadiene and methyl ethyl ketone are discussed. The acetic acid and OH reaction has been thought to undergo a hydrogen-bonded complex mediated pathway instead of a direct one leading to faster rate constants at lower temperature. Our results for the experimental investigation between 263-373 K and pressures of 2-5 Torr for the gas phase reaction of acetic acid with OH confirm the complex mediated reaction mechanism and indicate that acetic acid can play an important role especially in the oxidative chemistry of upper troposphere. The 1,3-butadiene and OH reaction is thought to undergo electrophilicaddition by OH which could display a complex pressure dependence similar to isoprene and 232-butenol as noted earlier in this laboratory. However, our results for the kinetics of the reaction between 273-423 K and a pressure range of 1

  5. Waiting ages for atmospheric oxygen: A titration hourglass and the oxidation of the solid Earth. (Invited)

    Science.gov (United States)

    Catling, D. C.; Claire, M.; Zahnle, K. J.

    2013-12-01

    Atmospheric O2 increased from less than 1 ppm to 0.2-2% at 2.45-2.22 Ga in the Great Oxidation Event (GOE). A minority opinion is that the GOE happened close to the time when oxygenic photosynthesis originated but evidence from the concentration of redox-sensitive elements in shales and their isotopes, as well as the setting and morphology of stromatolites supports the consensus view that oxygenic photosynthesis had originated by 2.8-2.7 Ga. Models show that O2 can be consumed rapidly by reductants in the Archean so that the air can remain anoxic even after photosynthesis began pumping out O2. Why did the world ultimately shift away from this balance? What conditions were needed to oxygenate the atmosphere in addition to oxygenic photosynthesis? A general principle is that a shift to an oxic environment from a reducing one requires net export of reductant. In planetary science, for example, the oxidation of the surfaces and atmospheres of other planets or satellites is universally attributed to the escape of hydrogen to space. Hydrogen escape explains the redness of Mars, several characteristics of the atmosphere of Venus, and the presence of tenuous O2 atmospheres on Ganymede, Europa, Rhea and Dione. For the Earth's rise of oxygen, many ideas focus on a decline in mantle or seafloor reductant fluxes (driven by internal geologic evolution) to the point where these fluxes were surpassed by biogenic oxygen fluxes. But for such a shift (without a role for hydrogen escape), the surface still has to export net reductant to the mantle. Such net export depends on the ratio of subducted ferric iron versus reduced carbon during the Archean, which remains poorly constrained. Over a decade ago, we proposed that rapid escape of hydrogen to space from the pre-GOE atmosphere would have gradually oxidized the Earth's surface and crust, accompanied by falling levels of atmospheric CH4 [1]. The idea is that Earth underwent a redox titration. A point would be reached where O2 became

  6. Analysis of Residual Performance of UD-CMC in Oxidation Atmosphere Based on a Notch-like Oxidation Model

    Science.gov (United States)

    Sun, Zhigang; Shao, Hongyan; Chen, Xihui; Song, Yingdong

    2016-10-01

    Experimental observation indicates unidirectional ceramic matrix composites (UD-CMC) will react with oxygen under high-temperature atmosphere inhomogeneous. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. Stress concentration near by the fiber notch causes a decline of the mechanic performance of UD-CMC. In this paper, the change rule of fiber notch depth is fitted by circular function. Based on this formula the residual strength and modulus of UD-CMC under 400-900 °C atmosphere are derived. The mechanical performance of unidirectional C/SiC composite is simulated by finite element method. The stress distribution of fiber, matrix and interface are obtained. The residual properties of unidirectional C/SiC composite are predicted by theoretical method and finite element method. And the predicting results are compared with the experiment data. The predicting results show a good accordance with experiment data, which means the notch-like oxidation model can analyze the mechanic performance of UD-CMC efficiently.

  7. Oxidation of elemental mercury in the atmosphere; Constraints imposed by global scale modelling

    Energy Technology Data Exchange (ETDEWEB)

    Bergan, Torbjoern; Rodhe, Henning [Stockholm Univ. (Sweden). Dept. of Meteorology

    2000-05-01

    Based on the global mercury model published by Bergan et al. (1999), we present here further results from simulations where the central theme has been to evaluate the role of ozone and the hydroxyl radical as possible gas phase oxidants for the oxidation of elemental mercury in the atmosphere. The magnitude of natural and man-made mercury emissions are taken from recent literature estimates and the flux from land areas is assumed to vary by season. We consider only two mercury reservoirs, elemental mercury, Hg{sup 0}, and the more soluble divalent form, Hgll. Wet and dry deposition of Hgll is explicitly treated. Applying monthly mean fields of ozone for the oxidation of gas phase Hg{sup 0} and using the reaction rate by Hall (1995) yields a global transformation of Hg{sup 0} to Hgll which is too slow to keep the simulated concentration of Hg{sup 0} near observed values. This shows that there are additional important removal processes for Hg{sup 0} or that the reaction rate proposed by Hall (1995) is too slow. A simulation in which the oxidation rate was artificially increased, so that the global turn-over time of Hg{sup 0} was one year and the simulated average concentration of Hg{sup 0} was realistic, produced latitudinal and seasonal variations in Hg{sup 0} that did not support the hypothesis that gas phase reaction with O{sub 3} is the major oxidation process for Hg{sup 0}. Recent studies indicate that OH may be an important gas phase oxidant for Hg{sup 0}. Using OH as the oxidant and applying the preliminary oxidation rate by Sommar et al. (1999) gave an unrealistically large removal of Hg{sup 0} from the atmosphere. From calculations using a slower reaction rate, corresponding to a turn-over time of Hg{sup 0} of one year, we calculated concentrations of both Hg{sup 0} in surface air and Hgll in precipitation which correspond, both in magnitude and temporal variation, to seasonal observations in Europe and North America. This result supports the suggestion that

  8. Heterogeneous Oxidation of Atmospheric Organic Aerosol: Kinetics of Changes to the Amount and Oxidation State of Particle-Phase Organic Carbon.

    Science.gov (United States)

    Kroll, Jesse H; Lim, Christopher Y; Kessler, Sean H; Wilson, Kevin R

    2015-11-01

    Atmospheric oxidation reactions are known to affect the chemical composition of organic aerosol (OA) particles over timescales of several days, but the details of such oxidative aging reactions are poorly understood. In this study we examine the rates and products of a key class of aging reaction, the heterogeneous oxidation of particle-phase organic species by the gas-phase hydroxyl radical (OH). We compile and reanalyze a number of previous studies from our laboratories involving the oxidation of single-component organic particles. All kinetic and product data are described on a common basis, enabling a straightforward comparison among different chemical systems and experimental conditions. Oxidation chemistry is described in terms of changes to key ensemble properties of the OA, rather than to its detailed molecular composition, focusing on two quantities in particular, the amount and the oxidation state of the particle-phase carbon. Heterogeneous oxidation increases the oxidation state of particulate carbon, with the rate of increase determined by the detailed chemical mechanism. At the same time, the amount of particle-phase carbon decreases with oxidation, due to fragmentation (C-C scission) reactions that form small, volatile products that escape to the gas phase. In contrast to the oxidation state increase, the rate of carbon loss is nearly uniform among most systems studied. Extrapolation of these results to atmospheric conditions indicates that heterogeneous oxidation can have a substantial effect on the amount and composition of atmospheric OA over timescales of several days, a prediction that is broadly in line with available measurements of OA evolution over such long timescales. In particular, 3-13% of particle-phase carbon is lost to the gas phase after one week of heterogeneous oxidation. Our results indicate that oxidative aging represents an important sink for particulate organic carbon, and more generally that fragmentation reactions play a major

  9. Photooxidation of carbonyl sulfide in the presence of the typical oxides in atmospheric aerosol

    Institute of Scientific and Technical Information of China (English)

    WU; Hongbo; WANG; Xiao; CHEN; Jianmin

    2005-01-01

    Photooxidation of carbonyl sulfide (COS) under UV irradiation and the role of the oxides such as SiO2, Al2O3 and Fe2O3 were investigated by in situ FTIR in a long optical path cell. The major products were identified as SO2 and CO2 by means of IR spectra and GC-MS. SO2 was partially oxidized into SO42- on the surface of the oxides and interior wall of the reactor, which was determined by XPS. The photooxidation is pseudo first order with respect to COS, and the apparent rate constant is approximately 9.30×10-4·s-1. SiO2 and Al2O3 promote the photooxida- tion of COS significantly, but Fe2O3 has no obvious influence on the reaction. The reaction rates in the presence of the oxides or not, rank as: UV + SiO2 > UV + Al2O3 > UV, UV + Fe2O3. The potentiality of the oxides for promoting the photooxidation of COS implicates that the aerosol particles may contribute to the photooxidation of COS in the atmosphere.

  10. Synthesis of nitrous oxide by lightning in the early anoxic Earth's atmosphere

    Science.gov (United States)

    Navarro, K. F.; Navarro-Gonzalez, R.; McKay, C. P.

    2013-12-01

    Carbon dioxide (CO2) was the main atmospheric component of the early Earth's atmosphere and exerted a key role in climate by maintaining a hydrosphere during a primitive faint Sun [1]; however, CO2 was eventually removed from the atmosphere by rock weathering and sequestered in the Earth's crust and mantle [1]. Nitric oxide (NO) was fixed by lightning discharges at a rate of 1×1016 molecules J-1 in CO2 (50-80%) rich atmospheres [2]. As the levels of atmospheric CO2 dropped to 20%, the production rate of NO by lightning rapidly decreased to 2×1014 molecules J-1 and then slowly diminished to 1×1014 molecules J-1 at CO2 levels of about 2.5% [2]. In order to maintain the existence of liquid water in the early Earth, it is required to warm up the planet with other greenhouse gases such as methane (CH4) [3]. Here we report an experimental study of the effects of lightning discharges on the nitrogen fixation rate during the evolution of the Earth's early atmosphere from 10 to 0.8 percent of carbon dioxide with methane concentrations from 0 to 1,000 ppm in molecular nitrogen. Lightning was simulated in the laboratory by a plasma generated with a pulsed Nd-YAG laser [2]. Our results show that the production of NO by lightning is independent of the presence of methane but drops from 3×1014 molecules J-1 in 10% CO2 to 5×1013 molecules J-1 in 1% CO2. Surprisingly, nitrous oxide (N2O) is also produced at a rate of 4×1013 molecules J-1 independent of the levels of CH4 and CO2. N2O is produced by lightning in the contemporaneous oxygenated Earth's atmosphere at a comparable rate of (0.4-1.5)×1013 molecules J-1 [4, 5], but was not detected in nitrogen-carbon dioxide mixtures in the absence of oxygen [6]. The only previously reported abiotic synthesis of N2O was by corona discharges in rich CO2 atmospheres (20-80%) with a production rate of 8×1012 molecules J-1 [6]; however at lower CO2 (atmosphere was the main source of N2O in nitrogen dominated atmospheres. N2O is not

  11. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces

    OpenAIRE

    Chapleski, Robert C.; Zhang, Yafen; Troya, Diego; Morris, John R.

    2015-01-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, research...

  12. The Influence of Atmosphere on the Oxidation of Ground Walnut During Storage at 20 °C

    Directory of Open Access Journals (Sweden)

    Rajko Vidrih

    2012-01-01

    Full Text Available The aim of this study is to determine the impact of atmosphere on the oxidation of ground walnut during storage at 20 °C. Seven varieties of walnut (Juglans regia L. were ground and stored under O2 or N2 atmospheres in hermetically sealed vials for 10 months at room temperature. Antioxidative potential, total phenolic content, fatty acid composition, and oxidative degradation products were determined after 10 months of storage. Cultivar, atmosphere and cultivar×atmosphere interactions significantly influenced the antioxidative potential. Cultivar and atmosphere significantly influenced the content of total polyphenols, with more polyphenols found in walnut stored in the N2 atmosphere. The mass fraction of unsaturated linolenic acid tended to decrease during storage under the O2 atmosphere; statistically significant differences were only found between individual varieties. The O2 atmosphere also resulted in an increase in the synthesis of oxidative degradation products. Among the degradation products, hexanal was the most abundant volatile compound, followed by 1-octen-3-ol, octanal, as well as the mixture of 2-octenal and 1-octen-3-ol. In general, higher concentrations of these degradation products were found in walnut stored under the O2 atmosphere, although these differences were statistically significant only between individual varieties for some compounds.

  13. Glass-ceramic sealant for solid oxide fuel cells application: Characterization and performance in dual atmosphere

    Science.gov (United States)

    Sabato, A. G.; Cempura, G.; Montinaro, D.; Chrysanthou, A.; Salvo, M.; Bernardo, E.; Secco, M.; Smeacetto, F.

    2016-10-01

    A glass-ceramic composition was designed and tested for use as a sealant in solid oxide fuel cell (SOFC) planar stack design. The crystallization behaviour was investigated by calculating the Avrami parameter (n) and the activation energy for crystallization (Ec) was obtained. The calculated values for n and Ec were 3 and 413.5 kJ/mol respectively. The results of thermal analyses indicate that this composition shows no overlap between the sintering and crystallization stages and thus an almost pore-free sealant can be deposited and sintered at 850 °C in air for 30 min. A gas tightness test has been carried out at 800 °C for 1100 h in dual atmosphere (Ar-H2 and air) without recording any leakage. Morphological and crystalline phase analyses were conducted prior and following tests in dual atmospheres in order to assess the compatibility of the proposed sealant with the metallic interconnect.

  14. Atmospheric nitrogen oxides (NO and NO2) at Dome C, East Antarctica, during the OPALE campaign

    Science.gov (United States)

    Frey, M. M.; Roscoe, H. K.; Kukui, A.; Savarino, J.; France, J. L.; King, M. D.; Legrand, M.; Preunkert, S.

    2015-07-01

    Mixing ratios of the atmospheric nitrogen oxides NO and NO2 were measured as part of the OPALE (Oxidant Production in Antarctic Lands & Export) campaign at Dome C, East Antarctica (75.1° S, 123.3° E, 3233 m), during December 2011 to January 2012. Profiles of NOx mixing ratios of the lower 100 m of the atmosphere confirm that, in contrast to the South Pole, air chemistry at Dome C is strongly influenced by large diurnal cycles in solar irradiance and a sudden collapse of the atmospheric boundary layer in the early evening. Depth profiles of mixing ratios in firn air suggest that the upper snowpack at Dome C holds a significant reservoir of photolytically produced NO2 and is a sink of gas-phase ozone (O3). First-time observations of bromine oxide (BrO) at Dome C show that mixing ratios of BrO near the ground are low, certainly less than 5 pptv, with higher levels in the free troposphere. Assuming steady state, observed mixing ratios of BrO and RO2 radicals are too low to explain the large NO2 : NO ratios found in ambient air, possibly indicating the existence of an unknown process contributing to the atmospheric chemistry of reactive nitrogen above the Antarctic Plateau. During 2011-2012, NOx mixing ratios and flux were larger than in 2009-2010, consistent with also larger surface O3 mixing ratios resulting from increased net O3 production. Large NOx mixing ratios at Dome C arise from a combination of continuous sunlight, shallow mixing height and significant NOx emissions by surface snow (FNOx). During 23 December 2011-12 January 2012, median FNOx was twice that during the same period in 2009-2010 due to significantly larger atmospheric turbulence and a slightly stronger snowpack source. A tripling of FNOx in December 2011 was largely due to changes in snowpack source strength caused primarily by changes in NO3- concentrations in the snow skin layer, and only to a secondary order by decrease of total column O3 and associated increase in NO3- photolysis rates. A

  15. Self-sustained carbon monoxide oxidation oscillations on size-selected platinum nanoparticles at atmospheric pressure

    DEFF Research Database (Denmark)

    Jensen, Robert; Andersen, Thomas; Nierhoff, Anders Ulrik Fregerslev

    2013-01-01

    High-quality mass spectrometry data of the oscillatory behavior of CO oxidation on SiO2 supported Pt-nanoparticles at atmospheric pressure have been acquired as a function of pressure, coverage, gas composition and nanoparticle size. The oscillations are self-sustained for several days at constant......, temperature, pressure and CO/O2 ratio. The frequency of the oscillations is very well defined and increases over time. The oscillation frequency is furthermore strongly temperature dependent with increasing temperature resulting in increasing frequency. A plausible mechanism for the oscillations is proposed...

  16. Atmospheric-pressure glow plasma synthesis of plasmonic and photoluminescent zinc oxide nanocrystals

    Science.gov (United States)

    Bilik, N.; Greenberg, B. L.; Yang, J.; Aydil, E. S.; Kortshagen, U. R.

    2016-06-01

    In this paper, we present a large-volume (non-micro) atmospheric pressure glow plasma capable of rapid, large-scale zinc oxide nanocrystal synthesis and deposition (up to 400 μg/min), whereas in the majority of the literature, nanoparticles are synthesized using micro-scale or filamentary plasmas. The reactor is an RF dielectric barrier discharge with a non-uniform gap spacing. This design encourages pre-ionization during the plasma breakdown, making the discharge uniform over a large volume. The produced zinc oxide nanocrystals typically have diameters ranging from 4 to 15 nm and exhibit photoluminescence at ≈550 nm and localized surface plasmon resonance at ≈1900 cm-1 due to oxygen vacancies. The particle size can be tuned to a degree by varying the gas temperature and the precursor mixing ratio.

  17. Heterogeneous chemistry and reaction dynamics of the atmospheric oxidants, O3, NO3, and OH, on organic surfaces.

    Science.gov (United States)

    Chapleski, Robert C; Zhang, Yafen; Troya, Diego; Morris, John R

    2016-07-01

    Heterogeneous chemistry of the most important atmospheric oxidants, O3, NO3, and OH, plays a central role in regulating atmospheric gas concentrations, processing aerosols, and aging materials. Recent experimental and computational studies have begun to reveal the detailed reaction mechanisms and kinetics for gas-phase O3, NO3, and OH when they impinge on organic surfaces. Through new research approaches that merge the fields of traditional surface science with atmospheric chemistry, researchers are developing an understanding for how surface structure and functionality affect interfacial chemistry with this class of highly oxidizing pollutants. Together with future research initiatives, these studies will provide a more complete description of atmospheric chemistry and help others more accurately predict the properties of aerosols, the environmental impact of interfacial oxidation, and the concentrations of tropospheric gases.

  18. Atmospheric Oxidation of Squalene: Molecular Study Using COBRA Modeling and High-Resolution Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Fooshee, David R.; Aiona, Paige K.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey; Baldi, Pierre

    2015-10-22

    Squalene is a major component of skin and plant surface lipids, and is known to be present at high concentrations in indoor dust. Its high reactivity toward ozone makes it an important ozone sink and a natural protectant against atmospheric oxidizing agents. While the volatile products of squalene ozonolysis are known, the condensed-phase products have not been characterized. We present an analysis of condensed-phase products resulting from an extensive oxidation of squalene by ozone probed by electrospray ionization (ESI) high-resolution mass spectrometry (HR-MS). A complex distribution of nearly 1,300 peaks assignable to molecular formulas is observed in direct infusion positive ion mode ESI mass spectra. The distribution of peaks in the mass spectra suggests that there are extensive cross-coupling reactions between hydroxy-carbonyl products of squalene ozonolysis. To get additional insights into the mechanism, we apply a Computational Brewing Application (COBRA) to simulate the oxidation of squalene in the presence of ozone, and compare predicted results with those observed by the HR-MS experiments. The system predicts over one billion molecular structures between 0-1450 Da, which correspond to about 27,000 distinct elemental formulas. Over 83% of the squalene oxidation products inferred from the mass spectrometry data are matched by the simulation. Simulation indicates a prevalence of peroxy groups, with hydroxyl and ether groups being the second-most important O-containing functional groups formed during squalene oxidation. These highly oxidized products of squalene ozonolysis may accumulate on indoor dust and surfaces, and contribute to their redox capacity.

  19. CO oxidation over ruthenium: identification of the catalytically active phases at near-atmospheric pressures

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Feng; Goodman, Wayne D.

    2012-05-21

    CO oxidation was carried out over Ru(0001) and RuO2(110) thin film grown on Ru(0001) at various O2/CO ratios near atmospheric pressures. Reaction kinetics, coupled with in situ polarization modulation infrared reflection absorption spectroscopy (PM-IRAS) and post-reaction Auger electron spectroscopy (AES) measurements were used to identify the catalytically relevant phases at different reaction conditions. Under stoichiometric and reducing conditions at all reaction temperatures, as well as net-oxidizing reaction conditions below {approx}475 K, a reduced metallic phase with chemisorbed oxygen is the thermodynamically stable and catalytically active phase. On this surface CO oxidation occurs at surface defect sites, for example step edges. Only at net-oxidizing reaction conditions and above {approx}475 K is the RuO2 thin film grown on metallic Ru stable and active. However, RuO2 is not active itself without the existence of the metal substrate, suggesting the importance of a strong metal-substrate interaction (SMSI).

  20. Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown

    2009-03-01

    Full Text Available We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS, a proton transfer reaction mass spectrometer (PTR-MS, and a thermal desorption aerosol GC-MS (TAG – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO, a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  1. Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown

    2008-11-01

    Full Text Available We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS, a proton transfer reaction mass spectrometer (PTR-MS, and a thermal desorption aerosol GC-MS (TAG – and found to be abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO, a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  2. Carbon isotope excursions and the oxidant budget of the Ediacaran atmosphere and ocean

    Science.gov (United States)

    Bristow, Thomas F.; Kennedy, Martin J.

    2008-11-01

    A possible global drop in marine carbon isotope values to aslow as -12 Peedee belemnite (PDB), recorded in the EdiacaranShuram Formation of Oman, has been attributed to the non-steady-stateoxidation of oceanic dissolved organic carbon (DOC) resultingfrom the rise in atmospheric oxygen to near modern values atthe end of the Precambrian. Geologic constraints indicate thatthe excursion lasted between 25 and 50 m.y., requiring a DOCpool thousands of times to 10,000 times the modern inventoryto conform with carbon isotope mass balance calculations fora -12 excursion. At the consequent rates of DOC oxidation,oceanic sulfate and oxygen in the atmosphere and oceans areexhausted on a time scale of 800 k.y. Oxidant depletion isincompatible with independent geochemical and biological indicatorsthat show oceanic sulfate and oxygen levels were maintainedor increased during the Shuram excursion. Furthermore, a DOC-drivenexcursion does not explain strong covariation between the carbonand oxygen isotope record. These indicators show that negativeisotope excursions recorded in the Shuram and other Ediacaransections are unlikely to represent a global ocean signal.

  3. Fast time resolution oxidized mercury measurements during the Reno Atmospheric Mercury Intercomparison Experiment (RAMIX).

    Science.gov (United States)

    Ambrose, Jesse L; Lyman, Seth N; Huang, Jiaoyan; Gustin, Mae S; Jaffe, Daniel A

    2013-07-02

    The Reno Atmospheric Mercury Intercomparison Experiment (RAMIX) was carried out from 22 August to 16 September, 2011 in Reno, NV to evaluate the performance of new and existing methods to measure atmospheric mercury (Hg). Measurements were made using a common sampling manifold to which controlled concentrations of Hg species, including gaseous elemental mercury (GEM) and HgBr2 (a surrogate gaseous oxidized mercury (GOM) compound), and potential interferents were added. We present an analysis of Hg measurements made using the University of Washington's Detector for Oxidized Hg Species (DOHGS), focusing on tests of GEM and HgBr2 spike recovery, the potential for interference from ozone (O3) and water vapor (WV), and temporal variability of ambient reactive mercury (RM). The mean GEM and HgBr2 spike recoveries measured with the DOHGS were 95% and 66%, respectively. The DOHGS responded linearly to HgBr2. We found no evidence that elevated O3 interfered in the DOHGS RM measurements. A reduction in RM collection and retention efficiencies at very high ambient WV mixing ratios is possible. Comparisons between the DOHGS and participating Hg instruments demonstrate good agreement for GEM and large discrepancies for RM. The results suggest that existing GOM measurements are biased low.

  4. Atmospheric nitrous oxide observations above the oceanic surface during CHINARE-18

    Institute of Scientific and Technical Information of China (English)

    ZHU Renbin; SUN Liguang; LIU Xiaodong

    2003-01-01

    The gas samples in the marine boundary layer were collected from the track for research ship Xuelong during the 18th Chinese Antarctic Research Expedition (CHINARE-18) and nitrous oxide measurements were made by HP5890ECD-GC in the laboratory. The results represent the shipboard N2O data set obtained within the lower troposphere with the average concentration of (313.5±2.6)nL*L-1 from 31°N to 69°S. The results showed a latitudinally weighted, mean interhemispheric difference of 0.61 nL*L-1. The latitudinal distribution of atmospheric N2O concentration was analyzed from northern midlatitudes to Southern Ocean around the Antarctic continent and it was showed that N2O concentration in the current confluences was higher than that in other oceanic areas. This indicated that strong N2O emissions occurred there. The longitudinal distribution of N2O concentrations in the Southern Ocean also showed similar situation. According to the interhemispheric difference of atmospheric N2O concentrations and the two-box model, we estimated that 2/5 of the global flux of N2O into the atmosphere is derived from the sources in the southern hemisphere.

  5. Process-Scale Modeling of Atmosphere-Snowpack Exchange of Nitrogen Oxides

    Science.gov (United States)

    Murray, K. A.; Doskey, P. V.; Ganzeveld, L.

    2013-12-01

    Snowpack over glacial ice is a reservoir for reactive nitrogen gases. Previous studies indicate nitrogen oxides (NOx) are generated in snowpack interstitial air through photolysis of nitrate (NO3-). Gradients in NOx mixing ratios between snowpack interstitial air and the overlying atmosphere regulate exchange of NOx with snowpack, which affects the Arctic ozone budget and climate. To better understand the dynamics of cryosphere-atmosphere exchange of NOx in the Arctic, we collected 2 years of meteorological and chemical data in and above the snowpack at Summit, Greenland. The comprehensive dataset indicates NOx emissions are episodic, with NOx enhancements in snowpack in early spring during high wind speed events (10-20 mph), which elevate NOx levels to ~500 pptv at depths of 2.5 m. Analysis of the observations will be based upon application of a 1-D process-scale model of atmosphere-snowpack exchange of NOx. The model will include representations of the snowpack chemistry in gas and aqueous phases, mass transfer of chemical species between phases, and physical transport by diffusion and wind pumping. The model will calculate the chemical and physical tendencies in three dimensions: depth, time, and intensity. Analysis of the tendencies will allow us to perform model sensitivity tests of pertinent snowpack physical and chemical processes. The end-goal of the project is to simplify the major tendencies into a parameterized model add-on for use in global models to determine the importance of properly representing snowpack in global model simulations.

  6. Electrochemical capacitance of iron oxide nanotube (Fe-NT): effect of annealing atmospheres

    Science.gov (United States)

    Sarma, Biplab; Jurovitzki, Abraham L.; Ray, Rupashree S.; Smith, York R.; Mohanty, Swomitra K.; Misra, Mano

    2015-07-01

    The effect of annealing atmosphere on the supercapacitance behavior of iron oxide nanotube (Fe-NT) electrodes has been explored and reported here. Iron oxide nanotubes were synthesized on a pure iron substrate through an electrochemical anodization process in an ethylene glycol solution containing 3% H2O and 0.5 wt.% NH4F. Subsequently, the annealing of the nanotubes was carried out at 500 °C for 2 h in various gas atmospheres such as air, oxygen (O2), nitrogen (N2), and argon (Ar). The morphology and crystal phases evolved after the annealing processes were examined via field emission scanning electron microscopy, x-ray diffraction, Raman spectroscopy, and x-ray photoelectron spectroscopy. The electrochemical capacitance properties of the annealed Fe-NT electrodes were evaluated by conducting cyclic voltammetry (CV), galvanostatic charge-discharge, and electrochemical impedance spectroscopy tests in the Li2SO4 electrolyte. Based on these experiments, it was found that the capacitance of the Fe-NT electrodes annealed in air and O2 atmospheres shows mixed behavior comprising both the electric double layer and pseudocapacitance. However, annealing in N2 and Ar environments resulted in well-defined redox peaks in the CV profiles of the Fe-NT electrodes, which are therefore attributed to the relatively higher pseudonature of the capacitance in these electrodes. Based on the galvanostatic charge-discharge studies, the specific capacitance achieved in the Fe-NT electrode after annealing in Ar was about 300 mF cm-2, which was about twice the value obtained for N2-annealed Fe-NTs and three times higher than those annealed in air and O2. The experiments also demonstrated excellent cycle stability for the Fe-NT electrodes with 83%-85% capacitance retention, even after many charge-discharge cycles, irrespective of the gas atmospheres used during annealing. The increase in the specific capacitance was discussed in terms of increased oxygen vacancies as a result of the

  7. Methyl hydroperoxide (CH3OOH in urban, suburban and rural atmosphere: ambient concentration, budget, and contribution to the atmospheric oxidizing capacity

    Directory of Open Access Journals (Sweden)

    Y. Zhao

    2012-05-01

    Full Text Available Methyl hydroperoxide (MHP, one of the most important organic peroxides in the atmosphere, contributes to the tropospheric oxidizing capacity either directly as an oxidant or indirectly as a free radical precursor. In this study we report measurements of MHP from seven field campaigns at urban, suburban and rural sites in China in winter 2007 and summer 2006/2007/2008. MHP was usually present in the order of several hundreds of pptv level, but the average mixing ratios have shown a wide range depending on the season and measuring site. Primary sources and sinks of MHP are investigated to understand the impact of meteorological and chemical parameters on the atmospheric MHP budget. The MHP/(MHP+H2O2 ratio is also presented here to examine different sensitivities of MHP and H2O2 to certain atmospheric processes. The diurnal cycle of MHP/(MHP+H2O2, which is out of phase with the diurnal cycle of both H2O2 and MHP, could imply that MHP production is more sensitive to the ambient NO concentration, while H2O2 is more strongly influenced by the wet deposition and the subsequent aqueous chemistry. It is interesting to note that our observation at urban Beijing site in winter 2007 provides evidence for the occasional transport of MHP-containing air masses from the marine boundary layer to the continent. Highly constrained box model is performed to study the influence of MHP on the free radical cycle. The simulation shows that MHP has a significant impact on the CH3O2 racial budget in the atmosphere. Furthermore, the contribution of MHP as an atmospheric oxidant to the overall tropospheric oxidizing capacity is also assessed based on the "Counter Species" concept.

  8. Photolysis and OH-Initiated oxidation of glycolaldehyde under atmospheric conditions.

    Science.gov (United States)

    Magneron, I; Mellouki, A; Le Bras, G; Moortgat, G K; Horowitz, A; Wirtz, K

    2005-05-26

    The photolysis and OH-initiated oxidation of glycolaldehyde (HOCH(2)CHO), which are relevant atmospheric processes, have been investigated under different conditions using complementary methods in three different laboratories. The UV absorption cross sections of glycolaldehyde determined in two of the laboratories are in excellent agreement. The photolysis of glycolaldehyde in air has been investigated in a quartz cell with sunlamps and in the EUPHORE chamber irradiated by sunlight. The mean photolysis rate measured under solar radiation was (1.1 +/- 0.3) x 10(-5) s(-1) corresponding to a mean effective photolysis quantum yield of (1.3 +/- 0.3). The major products detected were HCHO and CO, whereas CH(3)OH was also observed with an initial yield around 10%. Evidence for OH production was found in both experiments using either OH scavenger or OH tracer species. Photolysis of glycolaldehyde was used as the OH source to measure the reaction rate constants of OH with a series of dienes by the relative method and to identify and quantify the oxidation products of the OH-initiated oxidation of 2-propanol. The different experiments suggest that OH is produced by the primary channel: HOCH(2)CHO + hnu --> OH + CH(2)CHO (1). The rate constant of the OH reaction with glycolaldehyde has been measured at 298 K using the relative method: k(glyc) = (1.2 +/- 0.3) x 10(-11) cm(3) molecule(-1) s(-1). The product study of the OH-initiated oxidation of glycolaldehyde in air has been performed using both a FEP bag and the EUPHORE chamber. HCHO was observed to be the major product with a primary yield of around 65%. Glyoxal (CHOCHO) was also observed in EUPHORE with a primary yield of (22 +/- 6)%. This yield corresponds to the branching ratio ( approximately 20%) of the H-atom abstraction channel from the CH(2) group in the OH + HOCH(2)CHO reaction, the major channel ( approximately 80%) being the H-atom abstraction from the carbonyl group. The data obtained in this work, especially the

  9. Atmospheric nitrous oxide observations above the oceanic surface during the first Chinese Arctic Research Expedition

    Institute of Scientific and Technical Information of China (English)

    朱仁斌; 孙立广; 谢周清; 赵俊琳

    2003-01-01

    339 gas samples above oceanic surface were collected on the cruise of "Xuelong" expeditionary ship and nitrous oxide concentrations were analyzed in the laboratory. Results showed that Atmospheric average N20 concentration was 309 ± 3.8nL/L above the surface of northern Pacific and Arctic ocean. N2O concentrations were significantly different on the northbound and southbound track in the range of the same latitude, 308.0 ± 3.5 nL/L from Shanghai harbor to the Arctic and 311.9 ± 2.5 nL/L from the Arctic to Shanghai harbor. N2O concentration had a greater changing magnitude on the mid- and high-latitude oceanic surface of northern Pacific Ocean than in the other latitudinal ranges. The correlation between the concentrations of the compositions in the aerosol samples and atmospheric N2O showed that continental sources had a great contribution on atmospheric N2 O concentration above the oceanic surface. Atmospheric N2O concentration significantly increased when the expeditionary ship approached Shanghai harbor. The average N2O concentrations were 315.1 ±2.5 nL/L, 307.2 ±1.4 nL/L and 306.2 ±0.7 nL/L, respectively, at Shanghai harbor, at ice stations and at floating ices. The distribution of N2O concentrations was related with air pressure and temperature above the mid- and high-latitude Pacific Ocean.

  10. Product characteristics from the torrefaction of oil palm fiber pellets in inert and oxidative atmospheres.

    Science.gov (United States)

    Chen, Wei-Hsin; Zhuang, Yi-Qing; Liu, Shih-Hsien; Juang, Tarng-Tzuen; Tsai, Chi-Ming

    2016-01-01

    The aim of this work was to study the characteristics of solid and liquid products from the torrefaction of oil palm fiber pellets (OPFP) in inert and oxidative environments. The torrefaction temperature and O2 concentration in the carrier gas were in the ranges of 275-350°C and 0-10 vol%, respectively, while the torrefaction duration was 30 min. The oxidative torrefaction of OPFP at 275°C drastically intensified the HHV of the biomass when compared to the non-oxidative torrefaction. OPFP torrefied at 300°C is recommended to upgrade the biomass, irrespective of the atmosphere. The HHV of condensed liquid was between 10.1 and 13.2 MJ kg(-)(1), and was promoted to 23.2-28.7 MJ kg(-)(1) following dewatering. This accounts for 92-139% improvement in the calorific value of the liquid. This reveals that the recovery of condensed liquid with dewatering is able to enhance the energy efficiency of a torrefaction system.

  11. Investigation of MACR oxidation by OH in the atmosphere simulation chamber SAPHIR at low NO concentrations.

    Science.gov (United States)

    Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Brauers, Theo; Dorn, Hans-Peter; Häseler, Rolf; Hofzumahaus, Andreas; Holland, Frank; Li, Xin; Lu, Keding; Lutz, Anna; Kaminski, Martin; Nehr, Sascha; Rohrer, Franz; Tillmann, Ralf; Wegener, Robert; Wahner, Andreas

    2013-04-01

    During recent field campaigns, hydroxyl radical (OH) concentrations were up to a factor of ten larger than predicted by current chemical models for conditions of high OH reactivity and low nitrogen monoxide (NO) concentrations. These discrepancies were observed in forests, where isoprene oxidation turnover rates were large. Methacrolein (MACR) is one of the major first generation products of isoprene oxidation, so that MACR was also an important reactant for OH. Here, we present a detailed investigation of the MACR oxidation mechanism including a full set of accurate and precise radical measurements in the atmosphere simulation chamber SAPHIR in Juelich, Germany. The conditions during the chamber experiments were comparable to those during field campaigns with respect to radical and trace gas concentrations. In particular, OH reactivity was as high as 15 per second and NO mixing ratios were as low as 200pptv. Results of the experiments were compared to model predictions using the Master Chemical Mechanism, in order to identify so far unknown reaction pathways, which potentially recycle OH radicals without reactions with NO.

  12. OH regeneration from methacrolein oxidation investigated in the atmosphere simulation chamber SAPHIR

    Science.gov (United States)

    Fuchs, H.; Acir, I.-H.; Bohn, B.; Brauers, T.; Dorn, H.-P.; Häseler, R.; Hofzumahaus, A.; Holland, F.; Kaminski, M.; Li, X.; Lu, K.; Lutz, A.; Nehr, S.; Rohrer, F.; Tillmann, R.; Wegener, R.; Wahner, A.

    2014-08-01

    Hydroxyl radicals (OH) are the most important reagent for the oxidation of trace gases in the atmosphere. OH concentrations measured during recent field campaigns in isoprene-rich environments were unexpectedly large. A number of studies showed that unimolecular reactions of organic peroxy radicals (RO2) formed in the initial reaction step of isoprene with OH play an important role for the OH budget in the atmosphere at low mixing ratios of nitrogen monoxide (NO) of less than 100 pptv. It has also been suggested that similar reactions potentially play an important role for RO2 from other compounds. Here, we investigate the oxidation of methacrolein (MACR), one major oxidation product of isoprene, by OH in experiments in the simulation chamber SAPHIR under controlled atmospheric conditions. The experiments show that measured OH concentrations are approximately 50% larger than calculated by the Master Chemical Mechanism (MCM) for conditions of the experiments (NO mixing ratio of 90 pptv). The analysis of the OH budget reveals an OH source that is not accounted for in MCM, which is correlated with the production rate of RO2 radicals from MACR. In order to balance the measured OH destruction rate, 0.77 OH radicals (1σ error: ± 0.31) need to be additionally reformed from each reaction of OH with MACR. The strong correlation of the missing OH source with the production of RO2 radicals is consistent with the concept of OH formation from unimolecular isomerization and decomposition reactions of RO2. The comparison of observations with model calculations gives a lower limit of 0.03 s-1 for the reaction rate constant if the OH source is attributed to an isomerization reaction of MACR-1-OH-2-OO and MACR-2-OH-2-OO formed in the MACR + OH reaction as suggested in the literature (Crounse et al., 2012). This fast isomerization reaction would be a competitor to the reaction of this RO2 species with a minimum of 150 pptv NO. The isomerization reaction would be the dominant

  13. Silica-based composite and mixed-oxide nanoparticles from atmospheric pressure flame synthesis

    Science.gov (United States)

    Akurati, Kranthi K.; Dittmann, Rainer; Vital, Andri; Klotz, Ulrich; Hug, Paul; Graule, Thomas; Winterer, Markus

    2006-08-01

    Binary TiO2/SiO2 and SnO2/SiO2 nanoparticles have been synthesized by feeding evaporated precursor mixtures into an atmospheric pressure diffusion flame. Particles with controlled Si:Ti and Si:Sn ratios were produced at various flow rates of oxygen and the resulting powders were characterized by BET (Brunauer-Emmett-Teller) surface area analysis, XRD, TEM and Raman spectroscopy. In the Si-O-Ti system, mixed oxide composite particles exhibiting anatase segregation formed when the Si:Ti ratio exceeded 9.8:1, while at lower concentrations only mixed oxide single phase particles were found. Arrangement of the species and phases within the particles correspond to an intermediate equilibrium state at elevated temperature. This can be explained by rapid quenching of the particles in the flame and is in accordance with liquid phase solubility data of Ti in SiO2. In contrast, only composite particles formed in the Sn-O-Si system, with SnO2 nanoparticles predominantly found adhering to the surface of SiO2 substrate nanoparticles. Differences in the arrangement of phases and constituents within the particles were observed at constant precursor mixture concentration and the size of the resultant segregated phase was influenced by varying the flow rate of the oxidant. The above effect is due to the variation of the residence time and quenching rate experienced by the binary oxide nanoparticles when varying the oxygen flow rate and shows the flexibility of diffusion flame aerosol reactors.

  14. Response of Atmospheric-Methane Oxidation to Methane-Flux Manipulation in a Laboratory Soil-Column Experiment

    Science.gov (United States)

    Schroth, M. H.; Mignola, I.; Henneberger, R.

    2015-12-01

    Upland soils are an important sink for atmospheric methane (CH4). Uptake of atmospheric CH4 in soils is generally diffusion limited, and is mediated by aerobic CH4 oxidizing bacteria (MOB) that possess a high-affinity form of a key enzyme, allowing CH4 consumption at near-atmospheric concentrations (≤ 1.9 µL/L). As cultivation attempts for these high-affinity MOB have shown little success, there remains much speculation regarding their functioning in different environments. For example, it is frequently assumed that they are highly sensitive to physical disturbance, but their response in activity and abundance to changes in substrate availability remains largely unknown. We present results of a laboratory column experiment conducted to investigate the response in activity and abundance of high-affinity MOB to an increase in CH4 flux. Intact soil cores, collected at a field site where atmospheric CH4 oxidation activity is frequently quantified, were transferred into two 1-m-long, 12-cm-dia. columns. The columns were operated at constant temperature in the dark, their headspace being continuously flushed with air. Diffusive gas-transport conditions were maintained in the reference column, whereas CH4 flux was increased in several steps in the treatment column by inducing advective gas flow using a diaphragm pump. Soil-gas samples periodically collected from ports installed along the length of the columns were analyzed for CH4 content. Together with measurements of soil-water content, atmospheric CH4 oxidation was quantified using the soil-profile method. First results indicate that atmospheric CH4 oxidation activity comparable with the field was maintained in the reference column throughout the experiment. Moreover, high-affinity MOB quickly adjusted to an increase in CH4 flux in the treatment column, efficiently consuming CH4. Quantification of MOB abundance is currently ongoing. Our data provide new insights into controls on atmospheric CH4 oxidation in soils.

  15. Sensitivity of Oxygen Isotopes of Sulfate in Ice Cores to Past Changes in Atmospheric Oxidant Concentrations

    Science.gov (United States)

    Sofen, E. D.; Alexander, B.; Kunasek, S. A.; Mickley, L.; Murray, L. T.; Kaplan, J. O.

    2009-12-01

    The oxygen isotopic composition (Δ17O) of sulfate from ice cores allows for a quantitative assessment of the past oxidative capacity of the atmosphere, which has implications for the lifetime of pollutants (e.g. CO) and greenhouse gases (e.g. CH4), and changes in the sulfur budget on various timescales. Using Δ17O of sulfate measurements from the WAIS-Divide, Antarctica and Site-A, Greenland ice cores as constraints, we use the GEOS-Chem global three-dimensional chemical transport model to study changes in the concentrations of OH, O3, and H2O2 and their impact on sulfate Δ17O between the preindustrial and present-day. The Greenland ice core sulfate oxygen isotope observations are insensitive to changes in oxidant concentrations on the preindustrial-industrial timescale due to the rising importance of metal catalyzed S(IV) oxidation in mid- to high-northern latitudes resulting from anthropogenic metal emissions. The small change in Antarctic ice core sulfate Δ17O observations on this timescale is consistent with simultaneous increases in boundary layer O3 (32%) and H2O2 (49%) concentrations in the Southern Hemisphere, which have opposing effects on the sulfate O-isotope anomaly. Sulfate Δ17O is insensitive to the relatively small (-12%) decrease in Southern Hemisphere OH concentrations on this timescale due to the dominance of in-cloud versus gas-phase formation of sulfate in the mid-to-high southern latitudes. We find that the fraction of sulfate formed globally through gas-phase oxidation has not changed substantially between preindustrial and present times, however the total amount of sulfate formed in the gas-phase has nearly quadrupled due to rising anthropogenic emissions of sulfur dioxide. Measurements over a glacial-interglacial cycle from the Vostok core indicate dramatic changes in the Δ17O of sulfate on this timescale, which provide a strong constraint for glacial-era atmospheric chemistry modeling efforts. We will present preliminary results of

  16. On-line coating of glass with tin oxide by atmospheric pressure chemical vapor deposition.

    Energy Technology Data Exchange (ETDEWEB)

    Allendorf, Mark D.; Sopko, J.F. (PPF Industries, Pittsburgh, PA); Houf, William G.; Chae, Yong Kee; McDaniel, Anthony H.; Li, M. (PPF Industries, Pittsburgh, PA); McCamy, J.W. (PPF Industries, Pittsburgh, PA)

    2006-11-01

    Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accurate data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are

  17. THE EFFECT OF OLIVE BY PRODUCTS AND THEIR EXTRACTS ON ANTIOXIDATIVE STATUS OF LAYING HENS AND OXIDATIVE STABILITY OF EGGS ENRICHED WITH N-3 FATTY ACIDS

    Directory of Open Access Journals (Sweden)

    Vida Rezar

    2015-09-01

    Full Text Available The aim of the study was to assess the effects olive leaves, pulp and their extract supplementation on performance, antioxidant status and oxidative stability of eggs. Oxidative stress was induced by the addition of 6% linseed oil in the feed. 94 individually caged laying hens, 40 weeks old, were included in the study. Animals were divided into 6 groups. The feed of each group was composed of a basic feed, supplemented with: group Cont - no supplement, Vit E - 150 IU of α-tocopherol acetate /kg, Olive L - 1% of olive leaves, Olive Ex - extract from olive leaves, the Pulp group - 1% of dried and ground pulp and Pulp Ex - extract from pulp. Based on the results we found out that supplementation of vitamin E, olive leaves, pulp and their extracts had no effect on the performance of hens and showed neither a lymphocyte DNA damage preventive activity nor influence malondialdehyde (MDA concentration in plasma. The results suggest that α-tocopherol acetate and olive leaves supplementation had significant effect on the MDA content of the stored eggs. Supplements, except vitamin E had neither influence on antioxidant activity (ACL in eggs nor on n-3 PUFA in fresh and 40 days stored eggs.

  18. Atmospheric methane and nitrous oxide of the Late Pleistocene from Antarctic ice cores.

    Science.gov (United States)

    Spahni, Renato; Chappellaz, Jérôme; Stocker, Thomas F; Loulergue, Laetitia; Hausammann, Gregor; Kawamura, Kenji; Flückiger, Jacqueline; Schwander, Jakob; Raynaud, Dominique; Masson-Delmotte, Valérie; Jouzel, Jean

    2005-11-25

    The European Project for Ice Coring in Antarctica Dome C ice core enables us to extend existing records of atmospheric methane (CH4) and nitrous oxide (N2O) back to 650,000 years before the present. A combined record of CH4 measured along the Dome C and the Vostok ice cores demonstrates, within the resolution of our measurements, that preindustrial concentrations over Antarctica have not exceeded 773 +/- 15 ppbv (parts per billion by volume) during the past 650,000 years. Before 420,000 years ago, when interglacials were cooler, maximum CH4 concentrations were only about 600 ppbv, similar to lower Holocene values. In contrast, the N2O record shows maximum concentrations of 278 +/- 7 ppbv, slightly higher than early Holocene values.

  19. The optical constants of several atmospheric aerosol species - Ammonium sulfate, aluminum oxide, and sodium chloride

    Science.gov (United States)

    Toon, O. B.; Pollack, J. B.; Khare, B. N.

    1976-01-01

    An investigation is conducted of problems which are related to a use of measured optical constants in the simulation of the optical constants of real atmospheric aerosols. The techniques of measuring optical constants are discussed, taking into account transmission measurements through homogeneous and inhomogeneous materials, the immersion of a material in a liquid of a known refractive index, the consideration of the minimum deviation angle of prism measurement, the interference of multiply reflected light, reflectivity measurements, and aspects of mathematical analysis. Graphs show the real and the imaginary part of the refractive index as a function of wavelength for aluminum oxide, NaCl, and ammonium sulfate. Tables are provided for the dispersion parameters and the optical constants.

  20. Coarsening of Pd nanoparticles in an oxidizing atmosphere studied by in situ TEM

    DEFF Research Database (Denmark)

    Simonsen, Søren Bredmose; Chorkendorff, Ib; Dahl, Søren;

    2016-01-01

    The coarsening of supported palladium nanoparticles in an oxidizing atmosphere was studied in situ by means of transmission electron microscopy (TEM). Specifically, the Pd nanoparticles were dispersed on a planar and amorphous Al2O3 support and were observed during the exposure to 10 mbar technical...... air at 650 °C. Time-resolved TEM image series reveal that the Pd nanoparticles were immobile and that a few percent of the nanoparticles grew or shrank, indicating a coarsening process mediated by the Ostwald ripening mechanism. The TEM image contrast suggests that the largest nanoparticles tended...... to wet the Al2O3 support to a higher degree than the smaller nanoparticles and that the distribution of projected particle sizes consequently broadens by the appearance of an asymmetric tail toward the larger particle sizes. A comparison with computer simulations based on a simple mean-field model...

  1. Translation Effects in Fluorine Doped Tin Oxide Thin Film Properties by Atmospheric Pressure Chemical Vapour Deposition

    Directory of Open Access Journals (Sweden)

    Mohammad Afzaal

    2016-10-01

    Full Text Available In this work, the impact of translation rates in fluorine doped tin oxide (FTO thin films using atmospheric pressure chemical vapour deposition (APCVD were studied. We demonstrated that by adjusting the translation speeds of the susceptor, the growth rates of the FTO films varied and hence many of the film properties were modified. X-ray powder diffraction showed an increased preferred orientation along the (200 plane at higher translation rates, although with no actual change in the particle sizes. A reduction in dopant level resulted in decreased particle sizes and a much greater degree of (200 preferred orientation. For low dopant concentration levels, atomic force microscope (AFM studies showed a reduction in roughness (and lower optical haze with increased translation rate and decreased growth rates. Electrical measurements concluded that the resistivity, carrier concentration, and mobility of films were dependent on the level of fluorine dopant, the translation rate and hence the growth rates of the deposited films.

  2. Methyl hydroperoxide (CH3OOH in urban, suburban and rural atmosphere: ambient concentration, budget, and contribution to the atmospheric oxidizing capacity

    Directory of Open Access Journals (Sweden)

    Y. Zhao

    2012-10-01

    Full Text Available Methyl hydroperoxide (MHP, one of the most important organic peroxides in the atmosphere, contributes to the tropospheric oxidizing capacity either directly as an oxidant or indirectly as a free radical precursor. In this study we report measurements of MHP from seven field campaigns at urban, suburban and rural sites in China in winter 2007 and summer 2006/2007/2008. MHP was usually present in the order of several hundreds of pptv level, but the average mixing ratios have shown a wide range depending on the season and measuring site. Primary sources and sinks of MHP are investigated to understand the impact of meteorological and chemical parameters on the atmospheric MHP budget. The MHP/(MHP+H2O2 ratio is also presented here to examine different sensitivities of MHP and H2O2 to certain atmospheric processes. The diurnal cycle of MHP/(MHP+H2O2, which is out of phase with that of both H2O2 and MHP, could imply that MHP production is more sensitive to the ambient NO concentration, while H2O2 is more strongly influenced by the wet deposition and the subsequent aqueous chemistry. It is interesting to note that our observation at urban Beijing site in winter 2007 provides evidence for the occasional transport of MHP-containing air masses from the marine boundary layer to the continent. Furthermore, the contribution of MHP as an atmospheric oxidant to the oxidizing capacity of an air parcel is assessed based on the "Counter Species" concept.

  3. Mechanical characterisation of tungsten–1 wt.% yttrium oxide as a function of temperature and atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Palacios, T.; Jiménez, A. [Materials Science Department, Technical University of Madrid, E.T.S. de Ingenieros de Caminos, Canales y Puertos, C/Profesor Aranguren s/n, 28040 Madrid (Spain); Muñóz, A.; Monge, M.A.; Ballesteros, C. [Departamento de Física, Universidad Carlos III de Madrid, Leganés (Spain); Pastor, J.Y. [Materials Science Department, Technical University of Madrid, E.T.S. de Ingenieros de Caminos, Canales y Puertos, C/Profesor Aranguren s/n, 28040 Madrid (Spain)

    2014-11-15

    This study evaluates the mechanical behaviour of an Y{sub 2}O{sub 3}-dispersed tungsten (W) alloy and compares it to a pure W reference material. Both materials were processed via mechanical alloying (MA) and subsequent hot isostatic pressing (HIP). We performed non-standard three-point bending (TPB) tests in both an oxidising atmosphere and vacuum across a temperature range from 77 K, obtained via immersion in liquid nitrogen, to 1473 K to determine the mechanical strength, yield strength and fracture toughness. This research aims to evaluate how the mechanical behaviour of the alloy is affected by oxides formed within the material at high temperatures, primarily from 873 K, when the materials undergo a massive thermal degradation. The results indicate that the alloy is brittle to a high temperature (1473 K) under both atmospheres and that the mechanical properties degrade significantly above 873 K. We also used Vickers microhardness tests and the dynamic modulus by impulse excitation technique (IET) to determine the elastic modulus at room temperature. Moreover, we performed nanoindentation tests to determine the effect of size on the hardness and elastic modulus; however, no significant differences were found. Additionally, we calculated the relative density of the samples to assess the porosity of the alloy. Finally, we analysed the microstructure and fracture surfaces of the tested materials via field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In this way, the relationship between the macroscopic mechanical properties and micromechanisms of failure could be determined based on the temperature and oxides formed.

  4. Mechanical characterisation of tungsten-1 wt.% yttrium oxide as a function of temperature and atmosphere

    Science.gov (United States)

    Palacios, T.; Jiménez, A.; Muñóz, A.; Monge, M. A.; Ballesteros, C.; Pastor, J. Y.

    2014-11-01

    This study evaluates the mechanical behaviour of an Y2O3-dispersed tungsten (W) alloy and compares it to a pure W reference material. Both materials were processed via mechanical alloying (MA) and subsequent hot isostatic pressing (HIP). We performed non-standard three-point bending (TPB) tests in both an oxidising atmosphere and vacuum across a temperature range from 77 K, obtained via immersion in liquid nitrogen, to 1473 K to determine the mechanical strength, yield strength and fracture toughness. This research aims to evaluate how the mechanical behaviour of the alloy is affected by oxides formed within the material at high temperatures, primarily from 873 K, when the materials undergo a massive thermal degradation. The results indicate that the alloy is brittle to a high temperature (1473 K) under both atmospheres and that the mechanical properties degrade significantly above 873 K. We also used Vickers microhardness tests and the dynamic modulus by impulse excitation technique (IET) to determine the elastic modulus at room temperature. Moreover, we performed nanoindentation tests to determine the effect of size on the hardness and elastic modulus; however, no significant differences were found. Additionally, we calculated the relative density of the samples to assess the porosity of the alloy. Finally, we analysed the microstructure and fracture surfaces of the tested materials via field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In this way, the relationship between the macroscopic mechanical properties and micromechanisms of failure could be determined based on the temperature and oxides formed.

  5. Kinetic assessment and modeling of an ozonation step for full-scale municipal wastewater treatment: micropollutant oxidation, by-product formation and disinfection.

    Science.gov (United States)

    Zimmermann, Saskia G; Wittenwiler, Mathias; Hollender, Juliane; Krauss, Martin; Ort, Christoph; Siegrist, Hansruedi; von Gunten, Urs

    2011-01-01

    The kinetics of oxidation and disinfection processes during ozonation in a full-scale reactor treating secondary wastewater effluent were investigated for seven ozone doses ranging from 0.21 to 1.24 g O(3) g(-1) dissolved organic carbon (DOC). Substances reacting fast with ozone, such as diclofenac or carbamazepine (k(P, O3) > 10(4) M(-1) s(-1)), were eliminated within the gas bubble column, except for the lowest ozone dose of 0.21 g O(3) g(-1) DOC. For this low dose, this could be attributed to short-circuiting within the reactor. Substances with lower ozone reactivity (k(P, O3) scale measurements. Monte Carlo simulations showed that the observed differences were higher than model uncertainties. The overestimation of micropollutant oxidation was attributed to a protection of micropollutants from ozone attack by the interaction with aquatic colloids. Laboratory-scale batch experiments using wastewater from the same full-scale treatment plant could predict the oxidation of slowly-reacting micropollutants on the full-scale level within a factor of 1.5. The Rct value, the experimentally determined ratio of the concentrations of hydroxyl radicals and ozone, was identified as a major contribution to this difference. An increase in the formation of bromate, a potential human carcinogen, was observed with increasing ozone doses. The final concentration for the highest ozone dose of 1.24 g O(3) g(-1) DOC was 7.5 μg L(-1), which is below the drinking water standard of 10 μg L(-1). N-Nitrosodimethylamine (NDMA) formation of up to 15 ng L(-1) was observed in the first compartment of the reactor, followed by a slight elimination during sand filtration. Assimilable organic carbon (AOC) increased up to 740 μg AOC L(-1), with no clear trend when correlated to the ozone dose, and decreased by up to 50% during post-sand filtration. The disinfection capacity of the ozone reactor was assessed to be 1-4.5 log units in terms of total cell counts (TCC) and 0.5 to 2.5 log units for

  6. Oxidation of atmospheric methane in Northern European soils, comparison with other ecosystems, and uncertainties in the global terrestrial sink

    DEFF Research Database (Denmark)

    Smith, K.A.; Dobbie, K.E.; Ball, B.C.

    2000-01-01

    . Soil bulk density, water content and gas diffusivity had major impacts on oxidation rates. Trends were similar to those derived from other published work. Increasing acidity reduced oxidation, partially but not wholly explained by poor diffusion through litter layers which did not themselves contribute...... to the oxidation. The effect of temperature was small, attributed to substrate limitation and low atmospheric concentration. Analysis of all available data for CH4 oxidation rates in situ showed similar log-normal distributions to those obtained for our results, with generally little difference between different...... sink, and examines the effect of land-use change and other factors on the oxidation rate. Only soils with a very high water table were sources of CH4; all others were sinks. Oxidation rates varied from 1 to nearly 200 µg CH4 m-2 h-1; annual rates for sites measured for =1 y were 0.1-9.1 kg CH4 ha-1 y-1...

  7. Oxidative stress and anxiety-like symptoms related to withdrawal of passive cigarette smoke in mice: beneficial effects of pecan nut shells extract, a by-product of the nut industry.

    Science.gov (United States)

    Reckziegel, P; Boufleur, N; Barcelos, R C S; Benvegnú, D M; Pase, C S; Muller, L G; Teixeira, A M; Zanella, R; Prado, A C P; Fett, R; Block, J M; Burger, M E

    2011-09-01

    The present study evaluated the role of pecan nut (Carya illinoensis) shells aqueous extract (AE) against oxidative damage induced by cigarette smoke exposure (CSE) and behavioral parameters of smoking withdrawal. Mice were passively exposed to cigarette smoke for 3 weeks (6, 10, and 14 cigarettes/day) and orally treated with AE (25 g/L). CSE induced lipid peroxidation in brain and red blood cells (RBC), increased catalase (CAT) activity in RBC, and decreased plasma ascorbic acid levels. AE prevented oxidative damage and increased antioxidant defenses of mice exposed to cigarette smoke. In addition, AE reduced the locomotor activity and anxiety symptoms induced by smoking withdrawal, and these behavioral parameters showed a positive correlation with RBC lipid peroxidation. Our results showed the beneficial effects of this by-product of the pecan industry, indicating its usefulness in smoking cessation.

  8. Oxygen dynamics in the aftermath of the Great Oxidation of Earth’s atmosphere

    Science.gov (United States)

    Canfield, Donald E.; Ngombi-Pemba, Lauriss; Hammarlund, Emma U.; Bengtson, Stefan; Chaussidon, Marc; Gauthier-Lafaye, François; Meunier, Alain; Riboulleau, Armelle; Rollion-Bard, Claire; Rouxel, Olivier; Asael, Dan; Pierson-Wickmann, Anne-Catherine; El Albani, Abderrazak

    2013-01-01

    The oxygen content of Earth’s atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth’s oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth’s oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest–lived positive δ13C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years. PMID:24082125

  9. Oxygen dynamics in the aftermath of the Great Oxidation of Earth's atmosphere.

    Science.gov (United States)

    Canfield, Donald E; Ngombi-Pemba, Lauriss; Hammarlund, Emma U; Bengtson, Stefan; Chaussidon, Marc; Gauthier-Lafaye, François; Meunier, Alain; Riboulleau, Armelle; Rollion-Bard, Claire; Rouxel, Olivier; Asael, Dan; Pierson-Wickmann, Anne-Catherine; El Albani, Abderrazak

    2013-10-15

    The oxygen content of Earth's atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth's oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth's oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest-lived positive δ(13)C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years.

  10. The impact of Southwest Airline's contribution to atmospheric Carbon Dioxide and Nitrous Oxide totals

    Science.gov (United States)

    Wilkerson, Cody L.

    Over the last century, aviation has grown to become an economical juggernaut. The industry creates innovation, connects people, and maintains a safety goal unlike any other field. However, as the world becomes more populated with technology and individuals, a general curiosity as to how human activity effects the planet is becoming of greater interest. This study presents what one domestic airline in the United States, Southwest Airlines, contributes to the atmospheric make-up of the planet. Utilizing various sources of quantifiable data, an outcome was reached that shows the amount of Carbon Dioxide and Nitrous Oxide produced by Southwest Airlines from 2002 to 2013. This topic was chosen due to the fact that there are no real quantifiable values of emission statistics from airlines available to the public. Further investigation allowed for Southwest Airlines to be compared to the overall Carbon Dioxide and Nitrous Oxide contributions of the United States for the year 2011. The results showed that with the absence of any set standard on emissions, it is vital that one should be established. The data showed that the current ICAO standard emission values showed a higher level of emissions than when Southwest Airline's fleet was analyzed using their actual fleet mix.

  11. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2008-07-01

    Full Text Available We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1 and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM. Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(OOONO2. Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2, methyl peroxide (CH3OOH, methanol (CH3OH, formaldehyde (HCHO, peroxy acetyl nitrate (PAN, and formic and acetic acids (HCOOH and CH3C(OOH, being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK, methacrolein (MACR, hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO, propene (CH2=CHCH3 and glyoxal (CHOCHO with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by more

  12. Atmospheric observations and emissions estimates of methane and nitrous oxide from regional to global scale

    Science.gov (United States)

    Kort, Eric Adam

    2011-12-01

    Methane (CH4) and Nitrous Oxide (N2O) are the two most significant anthropogenic, long-lived, non-CO2 greenhouse gases, together perturbing the earth's energy balance by an amount comparable to that of CO2. This dissertation will focus on the use of atmospheric observations to quantify emissions of CH4 and N2O. First top-down emissions constraints on the regional scale, covering large areas of the U.S and southern Canada, are derived from airborne observations made in Spring of 2003. Using a receptor-oriented Lagrangian particle dispersion model provides robust validation of bottom-up emission estimates from EDGAR 32FT2000 and GEIA inventories. It is found that EDGAR CH4 emission rates are slightly low by a factor of 1.08 +/- 0.15 (2 sigma), while both EDGAR and GEIA N2O emissions are significantly too low, by factors of 2.62 +/- 0.50 and 3.05 +/- 0.61 respectively. This analysis is then extended over a full calendar year in 2004 with observations from NOAA's tall tower and aircraft profile network. EDGAR 32FT2000 CH 4 emissions are found to be consistent with observations, though the newer EDGAR v4.0 reduces CH4 emissions by 30%, and this reduction is not consistent with this study. Scaling factors found for N2O in May/June of 2003 (2.62 & 3.05) are found to hold for February-May of 2004, suggesting inventories are significantly too low in primary growing season coincident with significant fertilizer inputs. A new instrument for airborne observation of CO2, CH 4, N2O, and CO is introduced, and its operation and in-field performance are highlighted (demonstrated 1-sec precisions of 20 ppb, 0.5 ppb, 0.09 ppb, and 0.15 ppb respectively). Finally, global N2O observations collected with this sensor on the HIPPO (Hlaper Pole to Pole Observations) campaign are assessed. Comparison with a global model and subsequent inversion indicates strong, episodic inputs of nitrous oxide from tropical regions are necessary to bring observations and model in agreement. Findings

  13. Iohexol degradation in wastewater and urine by UV-based Advanced Oxidation Processes (AOPs): Process modeling and by-products identification.

    Science.gov (United States)

    Giannakis, Stefanos; Jovic, Milica; Gasilova, Natalia; Pastor Gelabert, Miquel; Schindelholz, Simon; Furbringer, Jean-Marie; Girault, Hubert; Pulgarin, César

    2016-07-11

    In this work, an Iodinated Contrast Medium (ICM), Iohexol, was subjected to treatment by 3 Advanced Oxidation Processes (AOPs) (UV, UV/H2O2, UV/H2O2/Fe(2+)). Water, wastewater and urine were spiked with Iohexol, in order to investigate the treatment efficiency of AOPs. A tri-level approach has been deployed to assess the UV-based AOPs efficacy. The treatment was heavily influenced by the UV transmittance and the organics content of the matrix, as dilution and acidification improved the degradation but iron/H2O2 increase only moderately. Furthermore, optimization of the treatment conditions, as well as modeling of the degradation was performed, by step-wise constructed quadratic or product models, and determination of the optimal operational regions was achieved through desirability functions. Finally, global chemical parameters (COD, TOC and UV-Vis absorbance) were followed in parallel with specific analyses to elucidate the degradation process of Iohexol by UV-based AOPs. Through HPLC/MS analysis the degradation pathway and the effects the operational parameters were monitored, thus attributing the pathways the respective modifications. The addition of iron in the UV/H2O2 process inflicted additional pathways beneficial for both Iohexol and organics removal from the matrix.

  14. Effect of oxygen level on the oxidative stability of two different retail pork products stored using modified atmosphere packaging (MAP)

    DEFF Research Database (Denmark)

    Spanos, Dimitrios; Ann Tørngren, Mari; Christensen, Mette;

    2016-01-01

    The characteristics and the oxidative stability of pork steaks and of pork mince were investigated during 2, 5 and 7 days of refrigerated storage using oxygen (O2) levels of 0%, 20%, 50% and 80% in modified atmosphere packaging (MAP). Steaks stored during 7 days were not affected by an increase...

  15. Influence of the atmospheric species water, oxygen, nitrogen and carbon dioxide on the degradation of aluminum doped zinc oxide layers

    NARCIS (Netherlands)

    Theelen, M.; Dasgupta, S.; Vroon, Z.; Kniknie, B.; Barreau, N.; Berkum, J. van; Zeman, M.

    2014-01-01

    Aluminum doped zinc oxide (ZnO:Al) layers were exposed to the atmospheric gases carbon dioxide (CO2), oxygen (O2), nitrogen (N 2) and air as well as liquid H2O purged with these gases, in order to investigate the chemical degradation behavior of these layers. The samples were analyzed by electrical,

  16. Catalytic Oxidation of Benzophenone Hydrazone with Alumina-supported KMnO{sub 4} under Oxygen Atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Kang Hyeok; Ko, Kwang Youn [Ajou University, Suwon (Korea, Republic of)

    2006-02-15

    KMnO{sub 4}/alumina reagent, which is cheap and environmentally safe, can serve as a catalytic oxidant under O{sub 2} atmosphere for the oxidation of benzophenone hydrazone. To the best of our knowledge, the present works are the first example where KMnO{sub 4}/alumina reagent acts as a catalytic oxidant under O{sub 2} atmosphere. Diphenyldiazomethane (Ph{sub 2}CN{sub 2}) is widely used for the protection of carboxylic acids by conversion to their diphenylmethyl (dpm) esters since dpm group can be easily deprotected by mild acidic condition or hydrogenolysis, especially in the field of b-lactams and peptides. Diphenyldiazomethane has been prepared by the oxidation of benzophenone hydrazone with reagents such as active manganese dioxide, mercuric oxide, peracetic acid, iodosobenzene diacetate or OXONE. However, some methods suffer from a disadvantage such as toxic nature of reagent, strong oxidative conditions or incompatibility with certain functional groups. For example, OXONE may not be employed for the in situ protection of carboxylic acid containing sulfide group due to the possibility of the concomitant oxidation of sulfide group.

  17. Atmospheric plasma generates oxygen atoms as oxidizing species in aqueous solutions

    Science.gov (United States)

    Mokhtar Hefny, Mohamed; Pattyn, Cedric; Lukes, Petr; Benedikt, Jan

    2016-10-01

    A remote microscale atmospheric pressure plasma jet (µAPPJ) with He, He/H2O, He/O2, and He/O2/H2O gas mixtures was used to study the transport of reactive species from the gas phase into the liquid and the following aqueous phase chemistry. The effects induced by the µAPPJ in water were quantitatively studied using phenol as a chemical probe and by measuring H2O2 concentration and pH values. These results were combined with the analysis of the absolute densities of the reactive species and the modeling of convective/diffusion transport and recombination reactions in the effluent of the plasma jet. Additionally, modified plasma jets were used to show that the role of emitted photons in aqueous chemistry is negligible for these plasma sources. The fastest phenol degradation was measured for the He/O2 plasma, followed by He/H2O, He/O2/H2O, and He plasmas. The modeled quantitative flux of O atoms into the liquid in the He/O2 plasma case was highly comparable with the phenol degradation rate and showed a very high transfer efficiency of reactive species from the plasma into the liquid, where more than half of the O atoms leaving the jet nozzle entered the liquid. The results indicate that the high oxidative effect of He/O2 plasma was primarily due to solvated O atoms, whereas OH radicals dominated the oxidative effects induced in water by plasmas with other gas mixtures. These findings help to understand, in a quantitative way, the complex interaction of cold atmospheric plasmas with aqueous solutions and will allow a better understanding of the interaction of these plasmas with water or buffered solutions containing biological macromolecules, microorganisms, or even eukaryotic cells. Additionally, the µAPPJ He/O2 plasma source seems to be an ideal tool for the generation of O atoms in aqueous solutions for any future studies of their reactivity.

  18. Oxidative capacity of the Mexico City atmosphere - Part 2: A ROx radical cycling perspective

    Science.gov (United States)

    Sheehy, P. M.; Volkamer, R.; Molina, L. T.; Molina, M. J.

    2010-07-01

    A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study oxidative capacity (our ability to predict OH radicals) and ROx (ROx=OH+HO2+RO2+RO) radical cycling in a polluted (i.e., very high NOx=NO+NO2) atmosphere. Model simulations were performed using the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds (VOC)), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx (=OH+HO2) concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. We conclude that the most likely scenario to reconcile model predictions with observations is the existence of a currently unidentified additional source for RO2 radicals, in combination with an additional sink for HO2 radicals that does not form OH. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length. We present a first attempt to calculate chain length rigorously i.e., we define two parameters that account for atmospheric complexity, and are based on (1) radical initiation, n(OH), and (2) radical termination, ω. We find very high values of n(OH) in the early morning are incompatible with our current understanding of ROx termination routes. We also observe missing reactivity in the rate of ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. We argue that this uncertainty is partly accounted for in lumped chemical codes that are optimized to predict

  19. Oxidative capacity of the Mexico City atmosphere – Part 2: A ROx radical cycling perspective

    Directory of Open Access Journals (Sweden)

    M. J. Molina

    2010-07-01

    Full Text Available A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003 is presented to study oxidative capacity (our ability to predict OH radicals and ROx (ROx=OH+HO2+RO2+RO radical cycling in a polluted (i.e., very high NOx=NO+NO2 atmosphere. Model simulations were performed using the Master Chemical Mechanism (MCMv3.1 constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc., radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds (VOC, meteorological parameters (temperature, pressure, water vapor concentration, dilution, and photolysis frequencies. Modeled HOx (=OH+HO2 concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. We conclude that the most likely scenario to reconcile model predictions with observations is the existence of a currently unidentified additional source for RO2 radicals, in combination with an additional sink for HO2 radicals that does not form OH. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length. We present a first attempt to calculate chain length rigorously i.e., we define two parameters that account for atmospheric complexity, and are based on (1 radical initiation, n(OH, and (2 radical termination, ω. We find very high values of n(OH in the early morning are incompatible with our current understanding of ROx termination routes. We also observe missing reactivity in the rate of ozone production (P(O3. For example, the integral amount of ozone produced could be under-predicted by a factor of two. We argue that this uncertainty is partly accounted for in lumped chemical codes that are optimized to

  20. Mainz Isoprene Mechanism 2 (MIM2: an isoprene oxidation mechanism for regional and global atmospheric modelling

    Directory of Open Access Journals (Sweden)

    D. Taraborrelli

    2009-04-01

    Full Text Available We present an oxidation mechanism of intermediate size for isoprene (2-methyl-1,3-butadiene suitable for simulations in regional and global atmospheric chemistry models, which we call MIM2. It is a reduction of the corresponding detailed mechanism in the Master Chemical Mechanism (MCM v3.1 and intended as the second version of the well-established Mainz Isoprene Mechanism (MIM. Our aim is to improve the representation of tropospheric chemistry in regional and global models under all NOx regimes. We evaluate MIM2 and re-evaluate MIM through comparisons with MCM v3.1. We find that MIM and MIM2 compute similar O3, OH and isoprene mixing ratios. Unlike MIM, MIM2 produces small relative biases for NOx and organic nitrogen-containing species due to a good representation of the alkyl and peroxy acyl nitrates (RONO2 and RC(OOONO2. Moreover, MIM2 computes only small relative biases with respect to hydrogen peroxide (H2O2, methyl peroxide (CH3OOH, methanol (CH3OH, formaldehyde (HCHO, peroxy acetyl nitrate (PAN, and formic and acetic acids (HCOOH and CH3C(OOH, being always below ≈6% in all NOx scenarios studied. Most of the isoprene oxidation products are represented explicitly, including methyl vinyl ketone (MVK, methacrolein (MACR, hydroxyacetone and methyl glyoxal. MIM2 is mass-conserving with respect to carbon, including CO2 as well. Therefore, it is suitable for studies assessing carbon monoxide (CO from biogenic sources, as well as for studies focused on the carbon cycle. Compared to MIM, MIM2 considers new species like acetaldehyde (CH3CHO, propene (CH2=CHCH3 and glyoxal (CHOCHO with global chemical production rates for the year 2005 of 7.3, 9.5 and 33.8 Tg/yr, respectively. Our new mechanism is expected to substantially improve the results of atmospheric chemistry models by

  1. Modeling the possible role of iodine oxides in atmospheric new particle formation

    Directory of Open Access Journals (Sweden)

    S. Pechtl

    2006-01-01

    Full Text Available We studied the possible role of iodine oxides in atmospheric new particle formation with the one-dimensional marine boundary layer model MISTRA, which includes chemistry in the gas and aerosol phase as well as aerosol microphysics. The chemical reaction set focuses on halogen (Cl-Br-I chemistry. We included a two-step nucleation parameterization, where in the first step, the 'real' nucleation process is parameterized, i.e., the formation of cluster-sized nuclei via homogeneous condensation of gases. We considered both ternary sulfuric acid-ammonia-water nucleation and homomolecular homogeneous OIO nucleation. For the latter, we derived a parameterization based on combined laboratory-model studies. The second step of the nucleation parameterization treats the 'apparent' nucleation rate, i.e., the growth of clusters into the model's lowest size bin by condensable vapors such as OIO. We compared different scenarios for a clean marine versus a polluted continental background atmosphere. In every scenario, we assumed the air to move, independent of its origin, first over a coastal region (where it is exposed to surface fluxes of different reactive iodine precursors and later over the open ocean. According to these sensitivity studies, in the clean marine background atmosphere OIO can be responsible for both homogeneous nuclei formation and the subsequent growth of the clusters to detectable sizes. In contrast to this, in the continental case with its higher levels of pollutants, gas phase OIO mixing ratios, and hence related nucleation rates, are significantly lower. Compared to ternary H2SO4-NH3-H2O nucleation, homogeneous OIO nucleation can be neglected for new particle formation in this case, but OIO can contribute to early particle growth, i.e., to apparent nucleation rates. In general, we found OIO to be more important for the growth of newly formed particles than for the formation of new nuclei. According to our studies, observations of

  2. Fighting global warming by greenhouse gas removal: destroying atmospheric nitrous oxide thanks to synergies between two breakthrough technologies.

    Science.gov (United States)

    Ming, Tingzhen; de Richter, Renaud; Shen, Sheng; Caillol, Sylvain

    2016-04-01

    Even if humans stop discharging CO2 into the atmosphere, the average global temperature will still increase during this century. A lot of research has been devoted to prevent and reduce the amount of carbon dioxide (CO2) emissions in the atmosphere, in order to mitigate the effects of climate change. Carbon capture and sequestration (CCS) is one of the technologies that might help to limit emissions. In complement, direct CO2 removal from the atmosphere has been proposed after the emissions have occurred. But, the removal of all the excess anthropogenic atmospheric CO2 will not be enough, due to the fact that CO2 outgases from the ocean as its solubility is dependent of its atmospheric partial pressure. Bringing back the Earth average surface temperature to pre-industrial levels would require the removal of all previously emitted CO2. Thus, the atmospheric removal of other greenhouse gases is necessary. This article proposes a combination of disrupting techniques to transform nitrous oxide (N2O), the third most important greenhouse gas (GHG) in terms of current radiative forcing, which is harmful for the ozone layer and possesses quite high global warming potential. Although several scientific publications cite "greenhouse gas removal," to our knowledge, it is the first time innovative solutions are proposed to effectively remove N2O or other GHGs from the atmosphere other than CO2.

  3. Fog composition at Baengnyeong Island in the Eastern Yellow Sea: detecting markers of aqueous atmospheric oxidations

    Directory of Open Access Journals (Sweden)

    A. J. Boris

    2015-09-01

    Full Text Available Samples of fog water were collected at Baengnyeong Island (BYI in the Yellow Sea during the summer of 2014. The most abundant chemical species in the fog water were NH4+ (mean of 2220 μM, NO3− (1260 μM, SO4−2 (730 μM, and Na+ (551 μM, with substantial contributions from other ions consistent with marine and biomass burning influence on some dates. The pH of the samples ranged between 3.48 and 5.00, with a mean of 3.94, intermediate within pH values of fog/cloud water reported previously in Southeast Asia. Back trajectories (72 h showed that high relative humidity (> 80 % was encountered upwind of the sampling site by all but one of the sampled air masses, and that the fog composition at BYI can be impacted by several different source regions, including the Sea of Japan, Northeastern China, and the East China Sea. Sulfur in the collected fog was highly oxidized: low S(IV concentrations were measured (mean of 2.36 μM in contrast to SO4−2 and in contrast to fog/cloud S(IV concentrations from pollutant source regions; organosulfate species were also observed and were most likely formed through aging of mainly biogenic volatile organic compounds. Low molecular mass organic acids were major contributors to total organic carbon (TOC; 36–69 %, comprising a fraction of TOC at the upper end of that seen in fogs and clouds in other polluted environments. Large contributions were observed from not only acetic and formic acids, but also oxalic, succinic, maleic, and other organic acids that can be produced in aqueous atmospheric organic processing (AAOP reactions. These samples of East Asian fog water containing highly oxidized components represent fog downwind of pollutant sources and can provide new insight into the fate of regional emissions. In particular, these samples demonstrate the result of extensive photochemical aging during multiday transport, including oxidation within wet aerosols and fogs.

  4. Torrefaction of agricultural by-products (abstract)

    Science.gov (United States)

    Torrefaction of biomass involves heating at 200°C-300°C under inert atmosphere to remove volatiles and produce materials with higher energy values and low moisture. Agricultural by-products, such as apple, grape, olive, and tomato pomaces as well as almond and walnut shells, were torrefied at differ...

  5. Effect of atmospheric oxidative plasma treatments on polypropylenic fibers surface: Characterization and reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Nisticò, Roberto, E-mail: roberto.nistico@unito.it [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Magnacca, Giuliana [University of Torino, Department of Chemistry and NIS Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Faga, Maria Giulia; Gautier, Giovanna [CNR-IMAMOTER, Strada delle Cacce 73, 10135 Torino (Italy); D’Angelo, Domenico; Ciancio, Emanuele [Clean-NT Lab, Environment Park S.p.A., Via Livorno 60, 10144 Torino (Italy); Lamberti, Roberta; Martorana, Selanna [Herniamesh S.r.l., Via F.lli Meliga 1/C, 10034 Chivasso (Italy)

    2013-08-15

    Atmospheric pressure plasma-dielectric barrier discharge (APP-DBD, open chamber configuration) was used to functionalize polypropylene (PP) fibers surface in order to generate oxidized-reactive groups such as hydroperoxides, alcohols and carbonyl species (i.e. ketones and others). Such a species increased the surface polarity, without causing material degradation. Three different types of plasma mixture (He, He/O{sub 2}, He/O{sub 2}/H{sub 2}O) under three different values of applied power (750, 1050, 1400 W) were investigated. The formed plasma species (O{sub 2}{sup +}, O single atom and OH radical) and their distribution were monitored via optical emission spectrometry (OES) measurements, and the plasma effects on PP surface species formation were followed by X-ray photoemission spectroscopy (XPS). Results allowed to better understand the reaction pathways between plasma phase and PP fibers. In fact, two reaction mechanisms were proposed, the first one concerning the plasma phase reactions and the second one involving material surface modifications.

  6. Fabrication and electrochemical performance of solid oxide fuel cell components by atmospheric and suspension plasma spray

    Institute of Scientific and Technical Information of China (English)

    XIA Wei-sheng; YANG Yun-zhen; ZHANG Hai-ou; WANG Gui-lan

    2009-01-01

    The theory of functionally graded material (FGM) was applied in the fabrication process of PEN (Positive- Electrolyte-Negative),the core component of solid oxide fuel cell (SOFC).To enhance its electrochemical performance,the functionally graded PEN of planar SOFC was prepared by atmospheric plasma spray (APS).The cross-sectional SEM micrograph and element energy spectrum of the resultant PEN were analyzed.Its interface resistance was also compared with that without the graded layers to investigate the electrochemical performance enhanced by the functionally graded layers.Moreover,a new process,suspension plasma spray (SPS) was applied to preparing the SOFC electrolyte.Higher densification of the coating by SPS,1.61%,is observed,which is helpful to effectively improve its electrical conductivity.The grain size of the electrolyte coating fabricated by SPS is also smaller than that by APS,which is more favourable to obtain the dense electrolyte coatings.To sum up,all mentioned above can prove that the hybrid process of APS and SPS could be a better approach to fabricate the PEN of SOFC stacks,in which APS is for porous electrodes and SPS for dense electrolyte.

  7. Subcooled flow boiling heat transfer of dilute alumina, zinc oxide, and diamond nanofluids at atmospheric pressure

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Joong; McKrell, Tom [Nuclear Science and Engineering Department, Massachusetts Institute of Technology (United States); Buongiorno, Jacopo, E-mail: jacopo@mit.ed [Nuclear Science and Engineering Department, Massachusetts Institute of Technology (United States); Hu Linwen [Nuclear Reactor Laboratory, Massachusetts Institute of Technology (United States)

    2010-05-15

    A nanofluid is a colloidal suspension of nano-scale particles in water, or other base fluids. Previous pool boiling studies have shown that nanofluids can improve the critical heat flux (CHF) by as much as 200%. In a previous paper, we reported on subcooled flow boiling CHF experiments with low concentrations of alumina, zinc oxide, and diamond nanoparticles in water (<=0.1% by volume) at atmospheric pressure, which revealed a substantial CHF enhancement (approx40-50%) at the highest mass flux (G = 2500 kg/m{sup 2} s) and concentration (0.1 vol.%) for all nanoparticle materials (). In this paper, we focus on the flow boiling heat transfer coefficient data collected in the same tests. It was found that for comparable test conditions the values of the nanofluid and water heat transfer coefficient are similar (within +-20%). The heat transfer coefficient increased with mass flux and heat flux for water and nanofluids alike, as expected in flow boiling. A confocal microscopy-based examination of the test section revealed that nanoparticle deposition on the boiling surface occurred during nanofluid boiling. Such deposition changes the number of micro-cavities on the surface, but also changes the surface wettability. A simple model was used to estimate the ensuing nucleation site density changes, but no definitive correlation between the nucleation site density and the heat transfer coefficient data could be found.

  8. Optimizing the electrical excitation of an atmospheric pressure plasma advanced oxidation process.

    Science.gov (United States)

    Olszewski, P; Li, J F; Liu, D X; Walsh, J L

    2014-08-30

    The impact of pulse-modulated generation of atmospheric pressure plasma on the efficiency of organic dye degradation has been investigated. Aqueous samples of methyl orange were exposed to low temperature air plasma and the degradation efficiency was determined by absorbance spectroscopy. The plasma was driven at a constant frequency of 35kHz with a duty cycle of 25%, 50%, 75% and 100%. Relative concentrations of dissolved nitrogen oxides, pH, conductivity and the time evolution of gas phase ozone were measured to identify key parameters responsible for the changes observed in degradation efficiency. The results indicate that pulse modulation significantly improved dye degradation efficiency, with a plasma pulsed at 25% duty showing a two-fold enhancement. Additionally, pulse modulation led to a reduction in the amount of nitrate contamination added to the solution by the plasma. The results clearly demonstrate that optimization of the electrical excitation of the plasma can enhance both degradation efficiency and the final water quality.

  9. Investigation of isoprene oxidation in the atmosphere simulation chamber SAPHIR at low NO concentrations

    Science.gov (United States)

    Fuchs, H.; Rohrer, F.; Hofzumahaus, A.; Bohn, B.; Brauers, T.; Dorn, H.; Häseler, R.; Holland, F.; Li, X.; Lu, K.; Nehr, S.; Tillmann, R.; Wahner, A.

    2012-12-01

    During recent field campaigns, hydroxyl radical (OH) concentrations that were measured by laser-induced fluorescence spectroscopy (LIF) were up to a factor of ten larger than predicted by current chemical models for conditions of high OH reactivity and low nitrogen monoxide (NO) concentrations. These discrepancies were observed in the Pearl-River-Delta, China, which is an urban-influenced rural area, in rainforests, and forested areas in North America and Europe. Isoprene contributed significantly to the total OH reactivity in these field studies, so that potential explanations for the missing OH focused on new reaction pathways in the isoprene degradation mechanism. These pathways regenerate OH without oxidation of NO and thus without ozone production. In summer 2011, a series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Juelich, Germany, in order to investigate the photochemical degradation of isoprene at low NO concentrations (NOSAPHIR by established chemical models like the Master Chemical Mechanism (MCM). Moreover, OH concentration measurements of two independent instruments (LIF and DOAS) agreed during all chamber experiments. Here, we present the results of the experiments and compare measurements with model predictions using the MCM. Furthermore, the validity of newly proposed reaction pathways in the isoprene degradation is evaluated by comparison with observations.

  10. Multi-scale Model of Residual Strength of 2D Plain Weave C/SiC Composites in Oxidation Atmosphere

    Science.gov (United States)

    Chen, Xihui; Sun, Zhigang; Sun, Jianfen; Song, Yingdong

    2016-06-01

    Multi-scale models play an important role in capturing the nonlinear response of woven carbon fiber reinforced ceramic matrix composites. In plain weave carbon fiber/silicon carbon (C/SiC) composites, the carbon fibers and interphases will be oxidized at elevated temperature and the strength of the composite will be degraded when oxygen enters micro-cracks formed in the as-produced parts due to the mismatch in thermal properties between constituents. As a result of the oxidation on fiber surface, fiber shows a notch-like morphology. In this paper, the change rule of fiber notch depth is fitted by circular function. And a multi-scale model based upon the change rule of fiber notch depth is developed to simulate the residual strength and post-oxidation stress-strain curves of the composite. The multi-scale model is able to accurately predict the residual strength and post-oxidation stress-strain curves of the composite. Besides, the simulated residual strength and post-oxidation stress-strain curves of 2D plain weave C/SiC composites in oxidation atmosphere show good agreements with experimental results. Furthermore, the oxidation time and temperature of the composite are investigated to show their influences upon the residual strength and post-oxidation stress-strain curves of plain weave C/SiC composites.

  11. Enhanced Removal of Biogenic Hydrocarbons in Power Plant Plumes Constrains the Dependence of Atmospheric Hydroxyl Concentrations on Nitrogen Oxides

    Science.gov (United States)

    De Gouw, J. A.; Trainer, M.; Parrish, D. D.; Brown, S. S.; Edwards, P.; Gilman, J.; Graus, M.; Hanisco, T. F.; Kaiser, J.; Keutsch, F. N.; Kim, S. W.; Lerner, B. M.; Neuman, J. A.; Pollack, I. B.; Roberts, J. M.; Ryerson, T. B.; Veres, P. R.; Warneke, C.; Wolfe, G.

    2015-12-01

    Hydroxyl (OH) radicals in the atmosphere provide one of the main chemical mechanisms for the removal of trace gases. OH plays a central role in determining the atmospheric lifetime and radiative forcing of greenhouse gases like methane. OH also plays a major role in the oxidation of organic trace gases, which can lead to formation of secondary pollutants such as ozone and PM2.5. Due to its very short atmospheric lifetime of seconds or less, OH concentrations are extremely variable in space and time, which makes measurements and their interpretation very challenging. Several recent measurements have yielded higher than expected OH concentrations. To explain these would require the existence of unidentified, radical recycling processes, but issues with the measurements themselves are also still being discussed. During the NOAA airborne SENEX study in the Southeast U.S., the biogenic hydrocarbons isoprene and monoterpenes were consistently found to have lower mixing ratios in air masses with enhanced nitrogen oxides from power plants. We attribute this to faster oxidation rates of biogenic hydrocarbons due to increased concentrations of OH in the power plant plumes. Measurements at different downwind distances from the Scherer and Harllee Branch coal-fired power plants near Atlanta are used to constrain the dependence of OH on nitrogen oxides. It is found that OH concentrations were highest at nitrogen dioxide concentrations of 1-2 ppbv and decreased at higher and at lower concentrations. These findings agree with the expected dependence of OH on nitrogen oxide concentrations, but do not appear to be consistent with the reports in the literature that have shown high OH concentrations in regions of the atmosphere with high biogenic emissions and low NOx concentrations that would require unidentified radical recycling processes to be explained.

  12. High-temperature and high-speed oxidation of 4H-SiC by atmospheric pressure thermal plasma jet

    Science.gov (United States)

    Hanafusa, Hiroaki; Ishimaru, Ryosuke; Higashi, Seiichiro

    2017-04-01

    The application of atmospheric pressure thermal plasma jet (TPJ) annealing to the high-temperature and high-speed thermal oxidation of Si-face of 4H-SiC wafer is reported. A high SiO2 film growth rate of 288 nm min‑1 was obtained at an oxidation temperature of 1640 °C without intentional dry O2 gas feeding. Ambient analysis suggested that ozone generated from oxygen in the ambient air by the plasma irradiation was supplied to the SiC surface. It is implied that a mono-oxygen decomposed from ozone was diffused into the oxide growth interface. As a result, high-speed oxidation occurred by combination of high-temperature TPJ annealing and ozone feeding.

  13. Numerically controlled atmospheric-pressure plasma sacrificial oxidation using electrode arrays for improving silicon-on-insulator layer uniformity

    Science.gov (United States)

    Takei, Hiroyasu; Yoshinaga, Keinosuke; Matsuyama, Satoshi; Yamauchi, Kazuto; Sano, Yasuhisa

    2015-01-01

    Silicon-on-insulator (SOI) wafers are important semiconductor substrates in high-performance devices. In accordance with device miniaturization requirements, ultrathin and highly uniform top silicon layers (SOI layers) are required. A novel method involving numerically controlled (NC) atmospheric-pressure plasma sacrificial oxidation using an electrode array system was developed for the effective fabrication of an ultrathin SOI layer with extremely high uniformity. Spatial resolution and oxidation properties are the key factors controlling ultraprecision machining. The controllability of plasma oxidation and the oxidation properties of the resulting experimental electrode array system were examined. The results demonstrated that the method improved the thickness uniformity of the SOI layer over one-sixth of the area of an 8-in. wafer area.

  14. Corrosion of Iron and Four Commercial Steels in a Cl-Containing Oxidizing Atmosphere at 500~600℃

    Institute of Scientific and Technical Information of China (English)

    Ke ZHANG; Yah NIU; Chaoliu ZENG; Weitao WU

    2004-01-01

    The corrosion behaviors of Fe and four commercial steels with different Cr contents were investigated in an oxidizing atmosphere containing HCI at 500~600℃, which simulated the environment to which materials are usually exposed in waste incineration. All the test materials underwent an accelerated corrosion in this atmosphere and small amounts of chlorine could be detected at the metal/scale interface. The corrosion mechanism is discussed on the basis of thermodynamic considerations for the reactions between metals and mixed O-CI gases.

  15. The magnetic and oxidation behavior of bare and silica-coated iron oxide nanoparticles synthesized by reverse co-precipitation of ferrous ion (Fe2+) in ambient atmosphere

    Science.gov (United States)

    Mahmed, N.; Heczko, O.; Lancok, A.; Hannula, S.-P.

    2014-03-01

    The synthesis of iron oxide nanoparticles, i.e., magnetite was attempted by using only ferrous ion (Fe2+) as a magnetite precursor, under an ambient atmosphere. The room temperature reverse co-precipitation method was used, by applying two synthesis protocols. The freshly prepared iron oxide was also immediately coated with Stöber silica (SiO2) layer, forming the coreshell structure. The phase, stoichiometry, crystallite and the particle size of the synthesized powders were determined by using X-ray diffraction (XRD) and transmission electron microscope (TEM), while the magnetic and oxidation behaviors were studied by using the vibrating sample magnetometer (VSM) and Mössbauer spectroscopy. Based on the results, the bare iron oxide nanoparticles are in the stoichiometry between the magnetite and the maghemite stoichiometry, i.e., oxidation occurs. This oxidation is depending on the synthesis protocols used. With the silica coating, the oxidation can be prevented, as suggested by the fits of Mössbauer spectra and low temperature magnetic measurement.

  16. Standard method for continuous measurement of nitric oxide, nitrogen dioxide, and ozone in the atmosphere. [Calorimetrically using Griess Reagent

    Energy Technology Data Exchange (ETDEWEB)

    1975-01-01

    Nitrogen dioxide is absorbed from the atmosphere in a modified Griess reagent which contains 0.5 percent sulfanilic acid and 50 ppM of N-(1-naphthyl)-ethylene diamine hydrochloride in 5 percent acetic acid that produces a red dye. The red dye is measured continuously in a recording colorimeter by comparison with a blank of unreacted reagent. Nitric oxide from the atmosphere passes through the absorber practically unaffected and is oxidized to nitrogen dioxide by bubbling through a dilute permanganate solution prior to determination with modified Griess reagent in a separate cell. Optionally, ozone in the air sample may be determined in a third absorber-colorimeter cell unit by adding about 0.5 to 1.0 ppM of pure nitric oxide to another sample of air and noting the increase in nitrogen dioxide level due to the rapid oxidation of nitric oxide to nitrogen dioxide by ozone. The overall accuracy of the results of the method is +-10 percent. (BLM)

  17. Potential atmospheric production of small volatile organic compounds from soot oxidation

    Science.gov (United States)

    Horn, A.; Carpenter, L.; Daly, H.; Jones, C.

    2003-04-01

    In the polluted troposphere, VOCs are involved in a range of interlinked chemical and photochemical cycles with a direct bearing on the production of ozone. The rates of emission, production and reaction of VOC are therefore an important component of atmospheric models. Recent urban measurements using 2D-GC methods show that there are a large number of unidentified and unattributed VOC components. Any new sources of such material with high photochemical ozone creation potentials may therefore be significant. Hydrocarbon, fossil fuel and biomass burning produces particulate carbonaceous aerosols (soot) in addition to gas phase products. Soot in the atmosphere is known to undergo oxidation becoming hydrophilic in aged urban plumes and the process is also known to produce water soluble organic compounds. In our experiments, soot samples are prepared by combustion of appropriate liquid hydrocarbons and reacted with ozone in a glass reaction vessel. Analysis of the surface and gas-phase during the course of this reaction confirms kinetic measurements showing irreversible uptake of O_3 on soot and further identify that the reaction has oxidised the surface. Transmission electron micrographs of the fresh and ozonised soot reveal small, coagulated particles: fresh soot particle size ranges from 50--90 nm which reduces to 40--50 nm after ozonolysis. Separation of the soluble components of fresh and ozonised soot samples analysed by GC/MS reveal the presence of polyaromatic and unsaturated components in unreacted soot and partially oxidised components post-ozonolysis. ATR-IR spectra of soot extracts and ozonised soot confirm that surface features due to the creation of oxidised surface products grow in with exposure time. These include carbonyl, ester and alcohol functional groups. Direct sampling of the gas-phase during the ozone reaction allows some gaseous products to be identified as small organic acids, ketones and alcohols. Overall, the reaction of ozone with soot

  18. Transport and deposition of nitrogen oxides and ozone in the atmospheric surface layer

    Science.gov (United States)

    Li, Yongxian

    Tropospheric ozone is an important photochemical air pollutant, which increases respiratory-related diseases, decreases crop yields, and causes other environmental problems. This research has focused on the measurement of soil biogenic emissions of nitric oxide (NO), one of the precursors for ozone formation, from intensively managed soils in the Southeast US, and examined the transport and deposition of NOx (NO + NO2) and ozone in the atmospheric surface layer, and the effects of NO emissions and its chemical reactions on ozone flux and deposition to the earth's surface. Emissions of nitric oxide were measured from an intensively managed agricultural soil, in the lower coastal plain of North Carolina (near Plymouth, NC), using a dynamic chamber technique. Measurements of soil NO emissions in several crop canopies were conducted at four different sites in North Carolina during late spring and summer of 1994-1996. The turbulent fluxes of NO2 and O3 at 5 m and 10 m above the ground were measured using the eddy-correlation technique near Plymouth, NC during late spring of 1995 and summer of 1996, concurrent with measurements of soil NO emissions using the dynamic chamber system. Soil NO emission from within the corn field was high averaging approximately 35 ng N/m2/s during the measurement period of 1995. In another study, vertical measurements of ozone were made on a 610 m tall tower located 15 km Southeast of Raleigh, NC during the summers of 1993-1997, as part of an effort by the State of North Carolina to develop a State Implementation Plan (SIP) for ozone control in the Raleigh Metropolitan Statistical Area. A strong correlation was observed between the nighttime and early morning ozone concentrations in the residual layer (CR) above the NBL and the maximum ground level concentration (C o max) the following afternoon. Based on this correlation, an empirical regression equation (Co max = 27.67*exp(0.016 CR)) was developed for predicting maximum ground level ozone

  19. The atmospheric oxidation mechanism of 1,2,4-trimethylbenzene initiated by OH radicals.

    Science.gov (United States)

    Li, Yun; Wang, Liming

    2014-09-07

    The atmospheric oxidation mechanism of 1,2,4-trimethylbenzene (1,2,4-TMB) initiated by OH radicals is investigated using quantum chemistry calculations at M06-2X and ROCBS-QB3 levels. The calculations show that the initiation of the reaction is dominated by OH addition to C1, C3 and C5 to form 1,2,4-TMB-OH adducts R1, R3, and R5 with branching ratios of 0.22, 0.19, and 0.38, respectively, using ROCBS-QB3 energies. In the troposphere, the adducts react with O2 by irreversible H-abstraction to form phenolic compounds and by reversible addition to TMB-OH-O2 peroxy radicals, which will cyclize to bicyclic radicals, similar to those in benzene, toluene, and xylenes. The bicyclic radicals can further recombine with O2 to generate bicyclic peroxy and alkoxyl radicals. The bicyclic alkoxyl radicals would break the ring directly to form 1,2-dicarbonyl products and unsaturated 1,4-dicarbonyl co-products, or undergo another cyclization to form an epoxy group, followed by the ring-breakage to form 1,2-dicarbonyl products and epoxy-1,4-dicarbonyl co-products. The predicted yields of products agree reasonably with the previous experimental measurements, while considerable discrepancies also exist for the yields of nitrates, biacetyl, 4-oxo-2-pentenal, and butenedial, etc. Our mechanism also predicts a new type of epoxy-1,4-dicarbonyl compounds with a total yield of ∼0.32. The epoxy-1,4-dicarbonyl compounds have not been suggested or reported in previous studies.

  20. 3-D laser confocal microscopy study of the oxidation of NdFeB magnets in atmospheric conditions

    Energy Technology Data Exchange (ETDEWEB)

    Meakin, J.P., E-mail: jxm764@bham.ac.uk; Speight, J.D.; Sheridan, R.S.; Bradshaw, A.; Harris, I.R.; Williams, A.J.; Walton, A.

    2016-08-15

    Highlights: • Room temperature atmospheric oxidation behaviour of sintered NdFeB. • 3D laser confocal microscopy measurement of oxide phase growth. • Significant height increase of oxide phase only observed at triple points. • Raman spectroscopy identified oxide phase to be Nd{sub 2}O{sub 3}. • Diffusion coefficient determined to be 4 × 10{sup −13} cm{sup 2}/s. - Abstract: Neodymium iron boron (NdFeB) magnets are used in a number of important applications, such as generators in gearless wind turbines, motors in electric vehicles and electronic goods (e.g.— computer hard disk drives, HDD). Hydrogen can be used as a processing gas to separate and recycle scrap sintered Nd-Fe-B magnets from end-of-life products to form a powder suitable for recycling. However, the magnets are likely to have been exposed to atmospheric conditions prior to processing, and any oxidation could lead to activation problems for the hydrogen decrepitation reaction. Many previous studies on the oxidation of NdFeB magnets have been performed at elevated temperatures; however, few studies have been formed under atmospheric conditions. In this paper a combination of 3-D laser confocal microscopy and Raman spectroscopy have been used to assess the composition, morphology and rate of oxidation/corrosion on scrap sintered NdFeB magnets. Confocal microscopy has been employed to measure the growth of surface reaction products at room temperature, immediately after exposure to air. The results showed that there was a significant height increase at the triple junctions of the Nd-rich grain boundaries. Using Raman spectroscopy, the product was shown to consist of Nd{sub 2}O{sub 3} and formed only on the Nd-rich triple junctions. The diffusion coefficient of the triple junction reaction product growth at 20 °C was determined to be approximately 4 × 10{sup −13} cm{sup 2}/sec. This value is several orders of magnitude larger than values derived from the diffusion controlled oxide growth

  1. Oxidation and nitration of tyrosine by ozone and nitrogen dioxide: reaction mechanisms and biological and atmospheric implications.

    Science.gov (United States)

    Sandhiya, L; Kolandaivel, P; Senthilkumar, K

    2014-04-01

    The nitration of tyrosine by atmospheric oxidants, O3 and NO2, is an important cause for the spread of allergenic diseases. In the present study, the mechanism and pathways for the reaction of tyrosine with the atmospheric oxidants O3 and NO2 are studied using DFT-M06-2X, B3LYP, and B3LYP-D methods with the 6-311+G(d,p) basis set. The energy barrier for the initial oxidation reactions is also calculated at the CCSD(T)/6-31+G(d,p) level of theory. The reaction is studied in gas, aqueous, and lipid media. The initial oxidation of tyrosine by O3 proceeds by H atom abstraction and addition reactions and leads to the formation of six different intermediates. The subsequent nitration reaction is studied for all the intermediates, and the results show that the nitration affects both the side chain and the aromatic ring of tyrosine. The rate constant of the favorable oxidation and nitration reaction is calculated using variational transition state theory over the temperature range of 278-350 K. The spectral properties of the oxidation and nitration products are calculated at the TD-M06-2X/6-311+G(d,p) level of theory. The fate of the tyrosine radical intermediate is studied by its reaction with glutathione antioxidant. This study provides an enhanced understanding of the oxidation and nitration of tyrosine by O3 and NO2 in the context of improving the air quality and reducing the allergic diseases.

  2. Influences of hydrogen-enriched atmosphere under coke oven gas injection on reduction swelling behaviors of oxidized pellet

    Institute of Scientific and Technical Information of China (English)

    龙红明; 王宏涛; 狄瞻霞; 春铁军; 柳政根

    2016-01-01

    It is of great importance to elucidate reduction swelling behaviors and reaction mechanism of oxidized pellet in hydrogen-enriched atmosphere under coke oven gas injection. In this work, the effects of hydrogen concentration in N2−CO−H2 atmosphere with unchanged CO content on reduction swelling behaviors of oxidized pellet at 1173 K were studied, to clarify the mechanism of hydrogen-enriched reduction and exclude the influences of CO. Then, the reduction swelling behaviors of oxidized pellet at 1173 K in actual atmosphere under coke oven gas (COG) injection, got from the simulation results of multi-fluid blast furnace model, were investigated. The results show that with the concentration of hydrogen increasing in N2−CO−H2 gas from 2% to 18%, the reduction swelling index of pellet decreases from 10.12% to 5.57% while the reduction ratio of pellet increases obviously from 39.85% to 69.58%. In addition, with COG injection rate increasing from 0 to 152.34 m3/t, the reduction swelling index of pellet decreases slightly from 10.71% to 9.54% while the reduction ratio of pellet is increased from 31.57% to 36.39%. The microstructures of pellet are transformed from the platy structure to the flocculent structure.

  3. A perovskite oxide with high conductivities in both air and reducing atmosphere for use as electrode for solid oxide fuel cells.

    Science.gov (United States)

    Lan, Rong; Cowin, Peter I; Sengodan, Sivaprakash; Tao, Shanwen

    2016-08-22

    Electrode materials which exhibit high conductivities in both oxidising and reducing atmospheres are in high demand for solid oxide fuel cells (SOFCs) and solid oxide electrolytic cells (SOECs). In this paper, we investigated Cu-doped SrFe0.9Nb0.1O3-δ finding that the primitive perovskite oxide SrFe0.8Cu0.1Nb0.1O3-δ (SFCN) exhibits a conductivity of 63 Scm(-1)and 60 Scm(-1) at 415 °C in air and 5%H2/Ar respectively. It is believed that the high conductivity in 5%H2/Ar is related to the exsolved Fe (or FeCu alloy) on exposure to a reducing atmosphere. To the best of our knowledge, the conductivity of SrFe0.8Cu0.1Nb0.1O3-δ in a reducing atmosphere is the highest of all reported oxides which also exhibit a high conductivity in air. Fuel cell performance using SrFe0.8Cu0.1Nb0.1O3-δ as the anode, (Y2O3)0.08(ZrO2)0.92 as the electrolyte and La0.8Sr0.2FeO3-δ as the cathode achieved a power density of 423 mWcm(-2) at 700 °C indicating that SFCN is a promising anode for SOFCs.

  4. A perovskite oxide with high conductivities in both air and reducing atmosphere for use as electrode for solid oxide fuel cells

    Science.gov (United States)

    Lan, Rong; Cowin, Peter I.; Sengodan, Sivaprakash; Tao, Shanwen

    2016-08-01

    Electrode materials which exhibit high conductivities in both oxidising and reducing atmospheres are in high demand for solid oxide fuel cells (SOFCs) and solid oxide electrolytic cells (SOECs). In this paper, we investigated Cu-doped SrFe0.9Nb0.1O3‑δ finding that the primitive perovskite oxide SrFe0.8Cu0.1Nb0.1O3‑δ (SFCN) exhibits a conductivity of 63 Scm‑1and 60 Scm‑1 at 415 °C in air and 5%H2/Ar respectively. It is believed that the high conductivity in 5%H2/Ar is related to the exsolved Fe (or FeCu alloy) on exposure to a reducing atmosphere. To the best of our knowledge, the conductivity of SrFe0.8Cu0.1Nb0.1O3‑δ in a reducing atmosphere is the highest of all reported oxides which also exhibit a high conductivity in air. Fuel cell performance using SrFe0.8Cu0.1Nb0.1O3‑δ as the anode, (Y2O3)0.08(ZrO2)0.92 as the electrolyte and La0.8Sr0.2FeO3‑δ as the cathode achieved a power density of 423 mWcm‑2 at 700 °C indicating that SFCN is a promising anode for SOFCs.

  5. Selective oxidation of glycerol by using a hydrotalcite-supported platinum catalyst under atmospheric oxygen pressure in water.

    Science.gov (United States)

    Tsuji, Akihiro; Rao, Kasanneni Tirumala Venkateswara; Nishimura, Shun; Takagaki, Atsushi; Ebitani, Kohki

    2011-04-18

    A hydrotalcite-supported platinum (Pt/HT) catalyst was found to be a highly active and selective heterogeneous catalyst for glycerol oxidation in pure water under atmospheric oxygen pressure in a high glycerol/metal molar ratio up to 3125. High selectivity toward glyceric acid (78 %) was obtained even at room temperature under air atmosphere. The Pt/HT catalyst selectively oxidized the primary hydroxyl group of 1,2-propandiol to give the corresponding carboxylic acid (lactic acid) as well as glycerol. The activity of the catalyst was greatly influenced by the Mg/Al ratio of hydrotalcite. Glycerol conversion increased with increasing the Mg/Al ratio of hydrotalcite (from trace to 56 %). X-ray absorption fine structure (XAFS) measurements indicated that the catalytic oxidation activity was proportional to the metallic platinum concentration, and more than 35 % of metallic platinum was necessary for this reaction. TEM measurements and titration analysis by using benzoic acid suggested that the solid basicity of hydrotalcite plays important roles in the precise control of platinum size and metal concentration as well as the initial promotion of alcohol oxidation.

  6. Oxidation of the Martian surface - Constraints due to chemical processes in the atmosphere

    Science.gov (United States)

    Mcelroy, M. B.; Kong, T. Y.

    1976-01-01

    Dissociation of water in the Martian atmosphere may supply oxygen to the surface and may result in the formation of minerals such as goethite, as proposed by Huguenin. The supply rate is limited by chemical processes in the atmosphere which regulate the abundance of O2. The net surface sink for atmospheric oxygen can be as large as 33 million atoms per sq cm per sec which compares to the escape rate of 60 million atoms per sq cm per sec.

  7. A comparison of the Ge-Sb-Te and Si-Sb-Te film oxidization at atmosphere

    Science.gov (United States)

    Ren, Wanchun; Liu, Bo; Song, Zhitang; Jing, Xuezhen; Xiang, Yanghui; Xiao, Haibo; Wang, Zongtao; Zhang, Beichao; Xu, Jia; Wu, Guanping; Qi, Ruijuan; Fan, Chunyan; Duan, Shuqing; Yu, Qinqin; Feng, Songlin

    New phase change materials development has become one of the most critical modules in the fabrication of low power consumption and good data retention phase change memory (PCM). Among various candidates of new phase change materials, SiSbTe (SST) is one of the most promising materials due to its benefits of low RESET current, high crystallization temperature, good adhesion and small volume shrinkage during phase change from amorphous to crystalline state. However, the oxidization of SST film was found when exposing to the atmosphere. By analyzing the depth profile of chemical states, we found oxygen more easily penetrated into the SST film and bonded with Si and Sb compared to GeSbTe (GST) film. The oxidization mechanism between SST and GST was briefly discussed. We achieved 80% improvement of oxidization issue by nitrogen and argon surface treatment. We proposed a manufacturing solution of SST for PCM.

  8. Exploring Atmospheric Aqueous Chemistry (and Secondary Organic Aerosol Formation) through OH Radical Oxidation Experiments, Droplet Evaporation and Chemical Modeling

    Science.gov (United States)

    Turpin, B. J.; Kirkland, J. R.; Lim, Y. B.; Ortiz-Montalvo, D. L.; Sullivan, A.; Häkkinen, S.; Schwier, A. N.; Tan, Y.; McNeill, V. F.; Collett, J. L.; Skog, K.; Keutsch, F. N.; Sareen, N.; Carlton, A. G.; Decesari, S.; Facchini, C.

    2013-12-01

    Gas phase photochemistry fragments and oxidizes organic emissions, making water-soluble organics ubiquitous in the atmosphere. My group and others have found that several water-soluble compounds react further in the aqueous phase forming low volatility products under atmospherically-relevant conditions (i.e., in clouds, fogs and wet aerosols). Thus, secondary organic aerosol can form as a result of gas followed by aqueous chemistry (aqSOA). We have used aqueous OH radical oxidation experiments coupled with product analysis and chemical modeling to validate and refine the aqueous chemistry of glyoxal, methylglyoxal, glycolaldehyde, and acetic acid. The resulting chemical model has provided insights into the differences between oxidation chemistry in clouds and in wet aerosols. Further, we conducted droplet evaporation experiments to characterize the volatility of the products. Most recently, we have conducted aqueous OH radical oxidation experiments with ambient mixtures of water-soluble gases to identify additional atmospherically-important precursors and products. Specifically, we scrubbed water-soluble gases from the ambient air in the Po Valley, Italy using four mist chambers in parallel, operating at 25-30 L min-1. Aqueous OH radical oxidation experiments and control experiments were conducted with these mixtures (total organic carbon ≈ 100 μM-C). OH radicals (3.5E-2 μM [OH] s-1) were generated by photolyzing H2O2. Precursors and products were characterized using electrospray ionization mass spectrometry (ESI-MS), ion chromatography (IC), IC-ESI-MS, and ultra high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Chemical modeling suggests that organic acids (e.g., oxalate, pyruvate, glycolate) are major products of OH radical oxidation at cloud-relevant concentrations, whereas organic radical - radical reactions result in the formation of oligomers in wet aerosols. Products of cloud chemistry and droplet evaporation have

  9. Kinetics, Mechanism and Product Yields in the Atmospheric Oxidation of Dimethylsulfide

    Science.gov (United States)

    2016-06-14

    Rosenstiel School of Marine and Atmospheric Science University of Miami 4600 Rickenbacker Causeway Miami, Florida 33149-1098 ahynes...decomposition and reaction, b) direct confirmation of production, and quantitative product yields of potential reaction products and intermediates...School of Marine and Atmospheric Science ,4600 Rickenbacker Causeway,Miami,FL,33149 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING

  10. Climatic, tectonic, and biological factors affecting the oxidation state of the atmosphere and oceans: Implications for Phanerozoic O2 evolution

    Science.gov (United States)

    Ozaki, K.; Tajika, E.

    2015-12-01

    The Earth's atmosphere and oceans have seen fundamental changes in its oxidation state in response to the climatic, tectonic and geochemical variations. Over the past decade, several geochemical proxies have led to significant progress in understanding the paleredox states of ancient oceans. However, a quantitative interpretation of these data for atmospheric O2 levels remain unclear because the relationship between atmospheric O2 levels (pO2) and oceanic redox state depends on several environmental factors, such as terrestrial weathering rate, sea-level stands, and sinking rate of particulate organic matter (POM) in the water column and so on. It is widely thought that the redox-dependent P cycling also plays a crucial role in regulating pO2 because it acts as a negative feedback on a geological timescale. It is important that strength of this feedback for a given pO2 is also modulated by environmental factors, affecting not only O2 levels at steady state but also its susceptibility to environmental changes. In this study, a quantitative role of environmental factors in the oxidation state of Earth's surface environment is evaluated with an oceanic biogeochemical cycle model (CANOPS) coupled with global C cycle model, which enables us to understand the ancient CO2 and O2 evolution. Our results demonstrate that atmospheric O2 level at steady state is affected by CO2 input flux from Earth's interior via changes in biogeochemical cycles, but its response is modulated by several internal factors such as shelf area and POM sinking rate. We also found that early Paleozoic atmospheric O2 levels before the advent of land plant would be determined so that oceans may locate at the "edge of anoxia (EoA)" where the redox-dependency of marine P cycle plays a crucial role in regulating O2 cycle, and that POM sinking rate has a great impact on the EoA. Our findings provide insights into the O2 cycle over the Phanerozoic in response to the climatic and tectonic variations and

  11. Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?

    Science.gov (United States)

    Jagoutz, Oliver

    2014-05-01

    A fundamental shift in the nature of granitoids occurs at approximately the Archean-Proterozoic boundary. Archean crust is dominated Na-rich tonalite-trondhjemite-granodiorites (TTGs), whereas post-Archean granitoids are characterized by K-rich granodiorite-granite (GG). Due to the HREE depletion commonly found in TTGs indicating the presence of residual garnet, many researchers have proposed that the difference in Na/K is related to the deeper melting depth of the TTG parental liquids. Here I present a compilation of the relevant experimental data, documenting that no correlation exists between the Na/K of derivative felsic liquids and the pressure of partial melting/fractional crystallization. Instead, the Na/K ratio of the felsic liquid best correlates with the Na/K ratio of the source. This implies that in Archean time the source material of TTG rocks must have been Na/K enriched relative to the modern. Modern granitoids are dominantly formed in a supra subduction zone environment, where a feedback loop exists between subducted materials (oceanic crust and sediments) and arc magmatism. Sea-floor weathering and the Na/K of the altered oceanic crust strongly depends on f(O2) conditions during alteration, which likely changed with earth history. During alteration under oxidized condition K2O is fixated due to the formation of celadonite (K-Mica), wheres during anoxic condition saponite (Na-Smectite) is the stable alteration mineral. I propose that the rise of oxygen at 2600-2400 Ma triggered associated changes in f(O2) seafloor alteration conditions. The change in the dominant seafloor alteration mineral from reduced to oxidized causes a change in the nature of the arc magma source and provides a possible explanation for the observed transition from TTGrocks in the Archean to the GG-granitoids in post-Archean times.

  12. 3-D laser confocal microscopy study of the oxidation of NdFeB magnets in atmospheric conditions

    Science.gov (United States)

    Meakin, J. P.; Speight, J. D.; Sheridan, R. S.; Bradshaw, A.; Harris, I. R.; Williams, A. J.; Walton, A.

    2016-08-01

    Neodymium iron boron (NdFeB) magnets are used in a number of important applications, such as generators in gearless wind turbines, motors in electric vehicles and electronic goods (e.g.- computer hard disk drives, HDD). Hydrogen can be used as a processing gas to separate and recycle scrap sintered Nd-Fe-B magnets from end-of-life products to form a powder suitable for recycling. However, the magnets are likely to have been exposed to atmospheric conditions prior to processing, and any oxidation could lead to activation problems for the hydrogen decrepitation reaction. Many previous studies on the oxidation of NdFeB magnets have been performed at elevated temperatures; however, few studies have been formed under atmospheric conditions. In this paper a combination of 3-D laser confocal microscopy and Raman spectroscopy have been used to assess the composition, morphology and rate of oxidation/corrosion on scrap sintered NdFeB magnets. Confocal microscopy has been employed to measure the growth of surface reaction products at room temperature, immediately after exposure to air. The results showed that there was a significant height increase at the triple junctions of the Nd-rich grain boundaries. Using Raman spectroscopy, the product was shown to consist of Nd2O3 and formed only on the Nd-rich triple junctions. The diffusion coefficient of the triple junction reaction product growth at 20 °C was determined to be approximately 4 × 10-13 cm2/sec. This value is several orders of magnitude larger than values derived from the diffusion controlled oxide growth observations at elevated temperatures in the literature. This indicates that the growth of the room temperature oxidation products are likely defect enhanced processes at the NdFeB triple junctions.

  13. A study on oxidation treatment of uranium metal chip under controlling atmosphere for safe storage

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Chang Kyu; Ji, Chul Goo; Bae, Sang Oh; Woo, Yoon Myeoung; Kim, Jong Goo; Ha, Yeong Keong [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2011-08-15

    The U metal chips generated in developing nuclear fuel and a gamma radioisotope shield have been stored under immersion of water in KAERI. When the water of the storing vessels vaporizes or drains due to unexpected leaking, the U metal chips are able to open to air. A new oxidation treatment process was raised for a long time safe storage with concepts of drying under vacuum, evaporating the containing water and organic material with elevating temperature, and oxidizing the uranium metal chips at an appropriate high temperature under conditions of controlling the feeding rate of oxygen gas. In order to optimize the oxidation process the uranium metal chips were completely dried at higher temperature than 300 .deg. C and tested for oxidation at various temperatures, which are 300 .deg. C, 400 .deg. C, and 500 .deg. C. When the oxidation temperature was 400 .deg. C, the oxidized sample for 7 hours showed a temperature rise of 60 .deg. C in the self-ignition test. But the oxidized sample for 14 hours revealed a slight temperature rise of 7 .deg. C representing a stable behavior in the self-ignition test. When the temperature was 500 .deg. C, the shorter oxidation for 7 hours appeared to be enough because the self-ignition test represented no temperature rise. By using several chemical analyses such as carbon content determination, X-ray deflection (XRD), Infrared spectra (IR) and Thermal gravimetric analysis (TGA) on the oxidation treated samples, the results of self-ignition test of new oxidation treatment process for U metal chip were interpreted and supported

  14. SCR atmosphere induced reduction of oxidized mercury over CuO-CeO2/TiO2 catalyst.

    Science.gov (United States)

    Li, Hailong; Wu, Shaokang; Wu, Chang-Yu; Wang, Jun; Li, Liqing; Shih, Kaimin

    2015-06-16

    CuO-CeO2/TiO2 (CuCeTi) catalyst synthesized by a sol-gel method was employed to investigate mercury conversion under a selective catalytic reduction (SCR) atmosphere (NO, NH3 plus O2). Neither NO nor NH3 individually exhibited an inhibitive effect on elemental mercury (Hg(0)) conversion in the presence of O2. However, Hg(0) conversion over the CuCeTi catalyst was greatly inhibited under SCR atmosphere. Systematic experiments were designed to investigate the inconsistency and explore the in-depth mechanisms. The results show that the copresence of NO and NH3 induced reduction of oxidized mercury (Hg(2+), HgO in this study), which offset the effect of catalytic Hg(0) oxidation, and hence resulted in deactivation of Hg(0) conversion. High NO and NH3 concentrations with a NO/NH3 ratio of 1.0 facilitated Hg(2+) reduction and therefore lowered Hg(0) conversion. Hg(2+) reduction over the CuCeTi catalyst was proposed to follow two possible mechanisms: (1) direct reaction, in which NO and NH3 react directly with HgO to form N2 and Hg(0); (2) indirect reaction, in which the SCR reaction consumed active surface oxygen on the CuCeTi catalyst, and reduced species on the CuCeTi catalyst surface such as Cu2O and Ce2O3 robbed oxygen from adjacent HgO. Different from the conventionally considered mechanisms, that is, competitive adsorption responsible for deactivation of Hg(0) conversion, this study reveals that oxidized mercury can transform into Hg(0) under SCR atmosphere. Such knowledge is of fundamental importance in developing efficient and economical mercury control technologies for coal-fired power plants.

  15. Soil carbon content and relative abundance of high affinity H2-oxidizing bacteria predict atmospheric H2 soil uptake activity better than soil microbial community composition

    NARCIS (Netherlands)

    Khdhiri, Mondher; Hesse, Laura; Popa, Maria Elena; Quiza, Liliana; Lalonde, Isabelle; Meredith, Laura K.; Röckmann, Thomas; Constant, Philippe

    2015-01-01

    Soil-atmosphere exchange of H2 is controlled by gas diffusion and the microbial production and oxidation activities in soil. Among these parameters, the H2 oxidation activity catalyzed by soil microorganisms harboring high affinity hydrogenase is the most difficult variable to parameterize because i

  16. Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process.

    Science.gov (United States)

    Guo, Yufang; Liao, Xiaobin; Fu, Mingli; Huang, Haibao; Ye, Daiqi

    2015-02-01

    Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.

  17. Corrosion behavior of NiCr alloys in HCl-containing oxidation atmosphere at 700-800 ℃

    Institute of Scientific and Technical Information of China (English)

    张轲; 牛焱; 潘太军; 吴维(山文)

    2004-01-01

    Corrosion behaviors of pure Ni and three NiCr alloys were investigated in an HCl-containing oxidizing atmosphere at 700 ℃ and 800 ℃. All materials suffer from accelerated corrosion at both temperatures. NiCr alloys show an initial mass loss due to the formation of volatile CrCl3 and CrO2Cl2. Some chlorides are detected at the scale/substrate interface and many voids are also found there. NiCr alloys with higher chromium content have better corrosion resistance. However, Ni50Cr is inferior to Ni25Cr due to its two-phase structure, which makes it easy for chlorine to diffuse along grain boundary and to occur inner oxidation. The relevant corrosion mechanism was also discussed.

  18. Effect of flue gas composition on deposit induced high temperature corrosion under laboratory conditions mimicking biomass firing. Part I: Exposures in oxidizing and chlorinating atmospheres

    DEFF Research Database (Denmark)

    Okoro, Sunday Chukwudi; Kiamehr, Saeed; Montgomery, Melanie;

    2016-01-01

    bothoxidizing and oxidizing-chlorinating atmospheres, and the resulting corrosionproducts were comprehensively studied with scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD)techniques. The results show that deposit-free samples suffer grain boundaryattack...... only in an oxidizing-chlorinating atmosphere, otherwise corrosionresults in formation of a duplex oxide. Corrosion attack on deposit-coatedsamples was higher than on deposit-free samples irrespective of the gaseousatmosphere. Specifically, severe volatilization of alloying elements occurred ondeposit...

  19. Nitric oxide-assisted atmospheric pressure corona discharge ionization for the analysis of automobile hydrocarbon emission species.

    Science.gov (United States)

    Dearth, M A; Komiski, T J

    1994-12-01

    Nitric oxide reagent gas has been found to improve the sensitivity and robustness of the atmospheric pressure corona discharge ionization (APCDI) process. Sensitivity has been increased by a factor of 20-100, depending on the compound, over APCDI without nitric oxide. The robustness (defined as the sensitivity to matrix interferences) of APCDI in the presence of water has been improved by a factor of 3 over normal APCDI. These improvements are due in part to a modification of the commercial inlet system and ionization chamber that allows the chamber and sample gases to be heated to 100 and 350°C, respectively. Nitric oxide was chosen as the reagent gas because of the variety and selectivity of its interaction with hydrocarbons with differing functional groups. Product ions of nitric oxide ionization and their subsequent tandem mass spectra are presented and discussed for selected alkanes; alkenes, alkylbenzenes, alcohols; aldehydes, and an ether. A tandem mass spectrometry (unique parent ion-daughter ion transition) method was developed to quantify compounds of specific interest in vehicle emissions. The absolute sensitivity for these compounds, under ideal conditions, was determined and ranges from 0.006 ppb for xylene (most sensitive) to 80 ppb for C8 (or larger) normal alkanes. Routine sensitivity for real-world samples was in the single parts per billion range for aromatic and olefinic species. Potential applications include the real-time, on-line monitoring of selected hydrocarbons in automobile exhaust.

  20. Synergy of CuO and CeO2 combination for mercury oxidation under low-temperature selective catalytic reduction atmosphere

    KAUST Repository

    Li, Hailong

    2016-07-19

    Synergy for low temperature Hg0 oxidation under selective catalytic reduction (SCR) atmosphere was achieved when copper oxides and cerium oxides were combined in a CuO-CeO2/TiO2 (CuCeTi) catalyst. Hg0 oxidation efficiency as high as 99.0% was observed on the CuCeTi catalyst at 200 °C, even the gas hourly space velocity was extremely high. To analyze the synergistic effect, comparisons of catalyst performance in the presence of different SCR reaction gases were systematically conducted over CuO/TiO2 (CuTi), CeO2/TiO2 (CeTi) and CuCeTi catalysts prepared by sol-gel method. The interactions between copper oxides and cerium oxides in CuCeTi catalyst yielded more surface chemisorbed oxygen, and facilitated the conversion of gas-phase O2 to surface oxygen, which are favorable for Hg0 oxidation. Copper oxides in the combination interacted with NO forming more chemisorbed oxygen for Hg0 oxidation in the absence of gas-phase O2. Cerium oxides in the combination promoted Hg0 oxidation through enhancing the transformations of NO to NO2. In the absence of NO, NH3 exhibited no inhibitive effect on Hg0 oxidation, because enough Lewis acid sites due to the combination of copper oxides and cerium oxides scavenged the competitive adsorption between NH3 and Hg0. In the presence of NO, although NH3 lowered Hg0 oxidation rate through inducing reduction of oxidized mercury, complete recovery of Hg0 oxidation activity over the CuCeTi catalyst was quickly achieved after cutting off NH3. This study revealed the synergistic effect of the combination of copper oxides and cerium oxides on Hg0 oxidation, and explored the involved mechanisms. Such knowledge would help obtaining maximum Hg0 oxidation co-benefit from SCR units in coal-fired power plants.

  1. Biomass torrefaction characteristics in inert and oxidative atmospheres at various superficial velocities.

    Science.gov (United States)

    Chen, Wei-Hsin; Lu, Ke-Miao; Liu, Shih-Hsien; Tsai, Chi-Ming; Lee, Wen-Jhy; Lin, Ta-Chang

    2013-10-01

    The reaction characteristics of four biomass materials (i.e. oil palm fiber, coconut fiber, eucalyptus, and Cryptomeria japonica) with non-oxidative and oxidative torrefaction at various superficial velocities are investigated where nitrogen and air are used as carrier gases. Three torrefaction temperatures of 250, 300, and 350 °C are considered. At a given temperature, the solid yield of biomass is not affected by N2 superficial velocity, revealing that the thermal degradation is controlled by heat and mass transfer in biomass. Increasing air superficial velocity decreases the solid yield, especially in oil palm fiber and coconut fiber, implying that the torrefaction reaction of biomass is dominated by surface oxidation. There exists an upper limit of air superficial velocity in the decrement of solid yield, suggesting that beyond this limit the thermal degradation of biomass is no longer governed by surface oxidation, but rather is controlled by internal mass transport.

  2. Total atmospheric deposition of oxidized nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet and dry deposition of oxidized nitrogen in the Pacific...

  3. Total atmospheric deposition of oxidized and reduced nitrogen in the United States Pacific Northwest for 2002

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — This spatial data set was created by the U.S. Geological Survey (USGS) to represent the amount of wet and dry deposition of oxidized and reduced nitrogen in the...

  4. Effect of oxygen on the electrical conductivity of some metal oxides in inert and reducing atmospheres at high temperature

    Energy Technology Data Exchange (ETDEWEB)

    Jones, T.A.; Firth, J.G.; Mann, B.

    1985-12-01

    An investigation has been carried out on the electrical behaviour at 900/sup 0/C of some ceramic oxides as a function of oxygen pressure. Measurements have been made in an inert (N/sub 2/) atmosphere and in an inert atmosphere containing reducing gases (CO, H/sub 2/ and CH/sub 4/). The oxides for which data are presented are Cr/sub 2/O/sub 3/, Nb/sub 2/O/sub 5/, CeO/sub 2/, ThO/sub 2/ and Ga/sub 2/O/sub 3/. The factors affecting the electrical conductivities of these materials are briefly reviewed. The conductivities of Cr/sub 2/O/sub 3/, Nb/sub 2/O/sub 5/ and CeO/sub 2/ showed a switch-like behaviour at the stoichiometric mixture of oxygen and reducing gas. Ga/sub 2/O/sub 3/ and ThO/sub 2/ do not exhibit this type of behaviour, the conductivities changing monotonically with increasing oxygen pressure. The possible reasons for this difference in behaviour are discussed. Data are also presented showing the behaviour of a sensor based on Ga/sub 2/O/sub 3/ in a vehicle exhaust. This shows its potential as a means of monitoring exhaust emissions with a view to controlling the air/fuel ratios at around the stoichiometric mixture.

  5. Nanostructured europium oxide thin films deposited by pulsed laser ablation of a metallic target in a He buffer atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Luna, H.; Franceschini, D. F.; Prioli, R.; Guimaraes, R. B.; Sanchez, C. M.; Canal, G. P.; Barbosa, M. D. L.; Galvao, R. M. O. [Instituto de Fisica, Universidade Federal do Rio de Janeiro, Cx. Postal 68528, Rio de Janeiro, RJ 21941-972 (Brazil); Instituto de Fisica, Universidade Federal Fluminense, Niteroi, RJ 24210-346 (Brazil); Departamento de Fisica, Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, 22453-970, Rio de Janeiro, RJ (Brazil); Instituto de Fisica, Universidade Federal Fluminense, Niteroi, RJ 24210-346 (Brazil); Centro Brasileiro de Pesquisas Fisicas, Laboratorio de Plasmas Aplicados, Rua Xavier Sigaud 150, 22290-180, Rio de Janeiro, RJ (Brazil); Instituto de Fisica, Departamento de Fisica Nuclear, Universidade de Sao Paulo, Caixa Postal 66328, 05315-970, Sao Paulo, SP (Brazil); Centro Brasileiro de Pesquisas Fisicas, Laboratorio de Plasmas Aplicados, Rua Xavier Sigaud 150, 22290-180, Rio de Janeiro, RJ (Brazil)

    2010-09-15

    Nanostrucured europium oxide and hydroxide films were obtained by pulsed Nd:YAG (532 nm) laser ablation of a europium metallic target, in the presence of a 1 mbar helium buffer atmosphere. Both the produced film and the ambient plasma were characterized. The plasma was monitored by an electrostatic probe, for plume expansion in vacuum or in the presence of the buffer atmosphere. The time evolution of the ion saturation current was obtained for several probe to substrate distances. The results show the splitting of the plume into two velocity groups, being the lower velocity profile associated with metal cluster formation within the plume. The films were obtained in the presence of helium atmosphere, for several target-to-substrate distances. They were analyzed by Rutherford backscattering spectrometry, x-ray diffraction, and atomic force microscopy, for as-deposited and 600 deg. C treated-in-air samples. The results show that the as-deposited samples are amorphous and have chemical composition compatible with europium hydroxide. The thermally treated samples show x-ray diffraction peaks of Eu{sub 2}O{sub 3}, with chemical composition showing excess oxygen. Film nanostructuring was shown to be strongly correlated with cluster formation, as shown by velocity splitting in probe current versus time plots.

  6. Sensitivity of measured steam oxidation kinetics to atmospheric control and impurities

    Science.gov (United States)

    Sooby Wood, E.; Terrani, K. A.; Nelson, A. T.

    2016-08-01

    The most direct means of improving the ability of water cooled reactors to withstand excessive cladding oxidation during a loss of coolant accident is to either modify or replace zirconium cladding. It is important to understand what level of agreement is to be expected as a function of systematic differences in steam oxidation testing techniques and instrumentation among testing facilities. The present study was designed to assess the sensitivities of some of the current and proposed reactor cladding materials. Steam oxidation sensitivity of Zircaloy-2, FeCrAl and Mo to O2 impurities in steam were examined. It was shown that the effect of O2 impurities is negligible for the two former materials while significant in the case of Mo.

  7. Waste/By-Product Hydrogen

    Science.gov (United States)

    2011-01-13

    By‐ product Hydrogen Fuel Flexibility Biogas : generated from organic waste �Wastewater treatment plants can provide multiple MW of renewable... Waste /By product Hydrogen Waste H2 sources include: � Waste bio‐mass: biogas to high temp fuel cells to produce H2 – there are over two dozen sites...13 Waste /By product Hydrogen ‐ Biogas

  8. Analysis of High Frequency Site-Specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

    Science.gov (United States)

    McClellan, M. J.; Harris, E. J.; Olszewski, W.; Ono, S.; Prinn, R. G.

    2014-12-01

    Atmospheric nitrous oxide (N2O) significantly impacts Earth's climate due to its dual role as an inert potent greenhouse gas in the troposphere and as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. However, there remain significant uncertainties in the global budget of this gas. The marked spatial divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on climate. Source and sink processes of N2O lead to varying concentrations of N2O isotopologues (14N14N16O, 14N15N16O, 15N14N16O, and 14N14N18O being measured) due to preferential isotopic production and elimination in different environments. Estimation of source and sink fluxes can be improved by combining isotopically resolved N2O observations with simulations using a chemical transport model with reanalysis meteorology and treatments of isotopic signatures of specific surface sources and stratospheric intrusions. We present the first few months of site-specific nitrogen and oxygen isotopic composition data from the Stheno-TILDAS instrument (Harris et al, 2013) at Mace Head, Ireland and compare these to results from MOZART-4 (Model for Ozone and Related Chemical Tracers, version 4) chemical transport model runs including N2O isotopic fractionation processes and reanalysis meterological fields (NCEP/NCAR, MERRA, and GEOS-5). This study forms the basis for future inverse modeling experiments that will improve the accuracy of isotopically differentiated N2O emission and loss estimates. Ref: Harris, E., D. Nelson, W. Olszewski, M. Zahniser, K. Potter, B. McManus, A. Whitehill, R. Prinn, and S. Ono, Development of a spectroscopic technique for continuous online monitoring of oxygen and site-specific nitrogen isotopic composition of atmospheric nitrous oxide, Analytical Chemistry, 2013; DOI: 10.1021/ac403606u.

  9. Regional Air Quality Model Application of the Aqueous-Phase Photo Reduction of Atmospheric Oxidized Mercury by Dicarboxylic Acids

    Directory of Open Access Journals (Sweden)

    Jesse O. Bash

    2013-12-01

    Full Text Available In most ecosystems, atmospheric deposition is the primary input of mercury. The total wet deposition of mercury in atmospheric chemistry models is sensitive to parameterization of the aqueous-phase reduction of divalent oxidized mercury (Hg2+. However, most atmospheric chemistry models use a parameterization of the aqueous-phase reduction of Hg2+ that has been shown to be unlikely under normal ambient conditions or use a non mechanistic value derived to optimize wet deposition results. Recent laboratory experiments have shown that Hg2+ can be photochemically reduced to elemental mercury (Hg in the aqueous-phase by dissolved organic matter and a mechanism and the rate for Hg2+ photochemical reduction by dicarboxylic acids (DCA has been proposed. For the first time in a regional scale model, the DCA mechanism has been applied. The HO2-Hg2+ reduction mechanism, the proposed DCA reduction mechanism, and no aqueous-phase reduction (NAR of Hg2+ are evaluated against weekly wet deposition totals, concentrations and precipitation observations from the Mercury Deposition Network (MDN using the Community Multiscale Air Quality (CMAQ model version 4.7.1. Regional scale simulations of mercury wet deposition using a DCA reduction mechanism evaluated well against observations, and reduced the bias in model evaluation by at least 13% over the other schemes evaluated, although summertime deposition estimates were still biased by −31.4% against observations. The use of the DCA reduction mechanism physically links Hg2+ reduction to plausible atmospheric processes relevant under typical ambient conditions.

  10. Surface passivation and protection of Pt loaded multicrystalline pn+ silicon photocathodes by atmospheric plasma oxidation for improved solar water splitting

    Science.gov (United States)

    Fan, Ronglei; Tang, Chengshuang; Xin, Yu; Su, Xiaodong; Wang, Xiaodong; Shen, Mingrong

    2016-12-01

    In the traditional methods such as atomic layer deposition and sputtering, a thin metal oxide layer was usually deposited before the loading of catalysts to protect Si photoelectrodes from oxidation during solar water splitting, and this often results in the transfer of photogenerated carriers from Si to electrolyte more or less inhibited. We here use an atmospheric plasma oxidation method to improve this. A SiO2 protective layer, also an effective passivation layer of Si to increase the life time of carriers, is fabricated on Pt loaded multicrystalline pn+-Si photocathodes. Compared with the un-protected one, the energy conversion efficiency of the plasma-treated Pt/pn+-Si photocathode increases from 6.2% to 8.9% under 100 mW/cm2 Xe lamp, and its stability improves from less than 1-22 h under continuous H2 production. This research provides a conceptual strategy to ensure the direct contact among the Si/Pt/electrolyte and protect and passivate the other part of Si simultaneously.

  11. Non-thermal atmospheric pressure HF plasma source: generation of nitric oxide and ozone for bio-medical applications

    Science.gov (United States)

    Kühn, S.; Bibinov, N.; Gesche, R.; Awakowicz, P.

    2010-01-01

    A new miniature high-frequency (HF) plasma source intended for bio-medical applications is studied using nitrogen/oxygen mixture at atmospheric pressure. This plasma source can be used as an element of a plasma source array for applications in dermatology and surgery. Nitric oxide and ozone which are produced in this plasma source are well-known agents for proliferation of the cells, inhalation therapy for newborn infants, disinfection of wounds and blood ozonation. Using optical emission spectroscopy, microphotography and numerical simulation, the gas temperature in the active plasma region and plasma parameters (electron density and electron distribution function) are determined for varied nitrogen/oxygen flows. The influence of the gas flows on the plasma conditions is studied. Ozone and nitric oxide concentrations in the effluent of the plasma source are measured using absorption spectroscopy and electro-chemical NO-detector at variable gas flows. Correlations between plasma parameters and concentrations of the particles in the effluent of the plasma source are discussed. By varying the gas flows, the HF plasma source can be optimized for nitric oxide or ozone production. Maximum concentrations of 2750 ppm and 400 ppm of NO and O3, correspondingly, are generated.

  12. A sub-atmospheric chemical vapor deposition process for deposition of oxide liner in high aspect ratio through silicon vias.

    Science.gov (United States)

    Lisker, Marco; Marschmeyer, Steffen; Kaynak, Mehmet; Tekin, Ibrahim

    2011-09-01

    The formation of a Through Silicon Via (TSV) includes a deep Si trench etching and the formation of an insulating layer along the high-aspect-ratio trench and the filling of a conductive material into the via hole. The isolation of the filling conductor from the silicon substrate becomes more important for higher frequencies due to the high coupling of the signal to the silicon. The importance of the oxide thickness on the via wall isolation can be verified using electromagnetic field simulators. To satisfy the needs on the Silicon dioxide deposition, a sub-atmospheric chemical vapor deposition (SA-CVD) process has been developed to deposit an isolation oxide to the walls of deep silicon trenches. The technique provides excellent step coverage of the 100 microm depth silicon trenches with the high aspect ratio of 20 and more. The developed technique allows covering the deep silicon trenches by oxide and makes the high isolation of TSVs from silicon substrate feasible which is the key factor for the performance of TSVs for mm-wave 3D packaging.

  13. Preparation of Aluminium Oxynitride by Carbothermal Reduction of Aluminium Oxide in a Flowing N2 Atmosphere

    Institute of Scientific and Technical Information of China (English)

    LIYa-wei; YUANRun-zhang; 等

    1996-01-01

    Carbothermal reduction of alumina into aluminium oxynitride(AlON) spinel in a flowing nitrogen atmosphere was studied.The effects of Al2O3/C ratio temperature,soaking time,heating rate molding pressure of samples,and nitrogen flow rate on reactions were investigated.Then the stability of AlON was elucidated and AlON wa confirmed as an intermediate compound in reduction of alumina.

  14. Testing hypotheses on global emissions of nitrous oxide using atmospheric models

    NARCIS (Netherlands)

    Bouwman, A.F.; Taylor, J.A.; Kroeze, C.

    2000-01-01

    The nitrous oxide (N2O) budget has been the least well constrained of the global trace gas budgets. For biogenic sources the uncertainty is caused by their extreme spatial and temporal heterogeneity. For the anthropogenic sources political, economic and cultural factors are major uncertainties assoc

  15. Nitrous oxide in the Schelde estuary: production by nitrification and emission to the atmosphere

    NARCIS (Netherlands)

    De Wilde, H.; De Bie, M.J.M.

    2000-01-01

    Concentrations of nitrous oxide (N2O), oxygen, nitrate, and ammonium, as well as nitrification activity were determined along the salinity gradient of the Schelde Estuary, Northwest Europe, in October 1993, March 1994, and July 1996, The entire estuary was always supersaturated with N2O. Concentrati

  16. The catalytic removal of ammonia and nitrogen oxides from spacecabin atmospheres

    Science.gov (United States)

    Gully, A. J.; Graham, R. R.; Halligan, J. E.; Bentsen, P. C.

    1973-01-01

    Investigations were made on methods for the removal of ammonia and to a lesser extent nitrogen oxides in low concentrations from air. The catalytic oxidation of ammonia was studied over a temperature range of 250 F to 600 F and a concentration range 20 ppm to 500 ppm. Of the catalysts studied, 0.5 percent ruthenium supported on alumina was found to be superior. This material is active at temperatures as low as 250 F and was found to produce much less nitrous oxide than the other two active catalysts, platinum on alumina and Hopcalite. A quantitative design model was developed which will permit the performance of an oxidizer to be calculated. The ruthenium was found to be relatively insensitive to low concentrations of water and to oxygen concentration between 21 percent and 100 percent. Hydrogen sulfide was found to be a poison when injected in relatively large quantities. The adsorption of ammonia by copper sulfate treated silica gel was investigated at temperatures of 72 F and 100 F. A quantitative model was developed for predicting adsorption bed behavior.

  17. Influence of Inert and Oxidizing Atmospheres on the Physical and Optical Properties of Luminescent Carbon Dots Prepared through Pyrolysis of a Model Molecule.

    Science.gov (United States)

    Machado, Cláudia Emanuele; Tartuci, Letícia Gazola; de Fátima Gorgulho, Honória; de Oliveira, Luiz Fernando Cappa; Bettini, Jefferson; Pereira dos Santos, Daniela; Ferrari, Jefferson Luis; Schiavon, Marco Antônio

    2016-03-18

    This work used L-tartaric acid as a model molecule to evaluate how the use of inert and oxidizing atmospheres during pyrolysis affected the physical and optical properties of the resulting carbon dots (CDs). Pyrolysis revealed to be a simple procedure that afforded CDs in a single step, dismissed the addition of organic solvents, and involved only one extraction stage that employed water. By X-ray diffraction a dependency between the structure of the CDs and the atmosphere (oxidizing or inert) used during the pyrolysis was found. Potentiometric titration demonstrated that the CDs were largely soluble in water; it also aided characterization of the various groups that contained sp(3) -hybridized carbon atoms on the surface of the dots. Raman spectroscopy suggested that different amounts of sp(2)- and sp(3)-hybridized carbon atoms emerged on the CDs depending on the pyrolysis atmosphere. In conclusion, the pyrolysis atmosphere influenced the physical properties, such as the composition and the final structure.

  18. Atmospheric oxidation of sulphur dioxide in water droplets in presence of ammonia

    Energy Technology Data Exchange (ETDEWEB)

    McKay, H.A.C.

    1971-01-01

    The kinetics of the conversion of ammonia and sulphur dioxide to ammonium sulphate in water droplets in the atmosphere in the absence of metal ion catalysts has been reconsidered. It is concluded that the reaction is an order of magnitude faster than earlier work suggested, and that lowering the temperature increases the rate by a large factor. In a cloud or a thick mist appreciable amounts of ammonium sulphate may be formed in a few minutes; nevertheless a substantial proportion of unreacted ammonia may sometimes persist for hours, even though excess sulphur dioxide is present and the initial reaction is fast.

  19. Induced apoptosis in melanocytes cancer cell and oxidation in biomolecules through deuterium oxide generated from atmospheric pressure non-thermal plasma jet

    Science.gov (United States)

    Kumar, Naresh; Attri, Pankaj; Yadav, Dharmendra Kumar; Choi, Jinsung; Choi, Eun Ha; Uhm, Han Sup

    2014-12-01

    Recently, atmospheric-pressure non-thermal plasma-jets (APPJ) are being for the cancer treatment. However, APPJ still has drawbacks such as efficiency and rise in temperature after treatment. So, in this work, a synergetic agent D2O vapour is attached to APPJ which not only increase the efficiency of plasma source against cancer treatment, but also controlled the temperature during the treatment. OD generated by the combination of D2O + N2 plasma helped in enhancing the efficiency of APPJ. We observed OD induced apoptosis on melanocytes G361 cancer cells through DNA damage signalling cascade. Additionally, we observed that plasma induces ROS, which activated MAPK p38 and inhibits p42/p44 MAPK, leading to cancer cell death. We have also studied DNA oxidation by extracting DNA from treated cancer cell and then analysed the effects of OD/OH/D2O2/H2O2 on protein modification and oxidation. Additionally, we attempted molecular docking approaches to check the action of D2O2 on the apoptosis related genes. Further, we confirmed the formation of OD/OH simultaneously in the solution using optical emission spectroscopy. Moreover, the simultaneous generation of D2O2/H2O2 was detected by the use of confocal Raman spectroscopy and density measurements.

  20. Induced apoptosis in melanocytes cancer cell and oxidation in biomolecules through deuterium oxide generated from atmospheric pressure non-thermal plasma jet.

    Science.gov (United States)

    Kumar, Naresh; Attri, Pankaj; Yadav, Dharmendra Kumar; Choi, Jinsung; Choi, Eun Ha; Uhm, Han Sup

    2014-12-23

    Recently, atmospheric-pressure non-thermal plasma-jets (APPJ) are being for the cancer treatment. However, APPJ still has drawbacks such as efficiency and rise in temperature after treatment. So, in this work, a synergetic agent D2O vapour is attached to APPJ which not only increase the efficiency of plasma source against cancer treatment, but also controlled the temperature during the treatment. OD generated by the combination of D2O + N2 plasma helped in enhancing the efficiency of APPJ. We observed OD induced apoptosis on melanocytes G361 cancer cells through DNA damage signalling cascade. Additionally, we observed that plasma induces ROS, which activated MAPK p38 and inhibits p42/p44 MAPK, leading to cancer cell death. We have also studied DNA oxidation by extracting DNA from treated cancer cell and then analysed the effects of OD/OH/D2O2/H2O2 on protein modification and oxidation. Additionally, we attempted molecular docking approaches to check the action of D2O2 on the apoptosis related genes. Further, we confirmed the formation of OD/OH simultaneously in the solution using optical emission spectroscopy. Moreover, the simultaneous generation of D2O2/H2O2 was detected by the use of confocal Raman spectroscopy and density measurements.

  1. Advanced Gasification By-Product Utilization

    Energy Technology Data Exchange (ETDEWEB)

    Rodney Andrews; Aurora Rubel; Jack Groppo; Brock Marrs; Ari Geertsema; Frank Huggins; M. Mercedes Maroto-Valer; Brandie M. Markley; Zhe Lu; Harold Schobert

    2006-08-31

    With the passing of legislation designed to permanently cap and reduce mercury emissions from coal-fired utilities, it is more important than ever to develop and improve upon methods of controlling mercury emissions. One promising technique is carbon sorbent injection into the flue gas of the coal-fired power plant. Currently, this technology is very expensive as costly commercially activated carbons are used as sorbents. There is also a significant lack of understanding of the interaction between mercury vapor and the carbon sorbent, which adds to the difficulty of predicting the amount of sorbent needed for specific plant configurations. Due to its inherent porosity and adsorption properties as well as on-site availability, carbons derived from gasifiers are potential mercury sorbent candidates. Furthermore, because of the increasing restricted use of landfilling, the coal industry is very interested in finding uses for these materials as an alternative to the current disposal practice. The results of laboratory investigations and supporting technical assessments conducted under DOE Subcontract No. DE-FG26-03NT41795 are reported. This contract was with the University of Kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Research and The Pennsylvania State University Energy Institute. The worked described was part of a project entitled ''Advanced Gasification By-Product Utilization''. This work involved the development of technologies for the separation and characterization of coal gasification slags from operating gasification units, activation of these materials to increase mercury and nitrogen oxide capture efficiency, assessment of these materials as sorbents for mercury and nitrogen oxides, assessment of the potential for leaching of Hg captured by the carbons, analysis of the slags for cement applications, and characterization of these materials for use as polymer fillers. The

  2. Advanced Gasification By-Product Utilization

    Energy Technology Data Exchange (ETDEWEB)

    Rodney Andrews; Aurora Rubel; Jack Groppo; Brock Marrs; Ari Geertsema; Frank Huggins; M. Mercedes Maroto-Valer; Brandie M. Markley; Zhe Lu; Harold Schobert

    2006-08-31

    With the passing of legislation designed to permanently cap and reduce mercury emissions from coal-fired utilities, it is more important than ever to develop and improve upon methods of controlling mercury emissions. One promising technique is carbon sorbent injection into the flue gas of the coal-fired power plant. Currently, this technology is very expensive as costly commercially activated carbons are used as sorbents. There is also a significant lack of understanding of the interaction between mercury vapor and the carbon sorbent, which adds to the difficulty of predicting the amount of sorbent needed for specific plant configurations. Due to its inherent porosity and adsorption properties as well as on-site availability, carbons derived from gasifiers are potential mercury sorbent candidates. Furthermore, because of the increasing restricted use of landfilling, the coal industry is very interested in finding uses for these materials as an alternative to the current disposal practice. The results of laboratory investigations and supporting technical assessments conducted under DOE Subcontract No. DE-FG26-03NT41795 are reported. This contract was with the University of Kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Research and The Pennsylvania State University Energy Institute. The worked described was part of a project entitled ''Advanced Gasification By-Product Utilization''. This work involved the development of technologies for the separation and characterization of coal gasification slags from operating gasification units, activation of these materials to increase mercury and nitrogen oxide capture efficiency, assessment of these materials as sorbents for mercury and nitrogen oxides, assessment of the potential for leaching of Hg captured by the carbons, analysis of the slags for cement applications, and characterization of these materials for use as polymer fillers. The

  3. Technical Note: Synthesis of isoprene atmospheric oxidation products: isomeric epoxydiols and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran

    Directory of Open Access Journals (Sweden)

    A. Gold

    2012-09-01

    Full Text Available Isoprene epoxydiol (IEPOX isomers are key gas-phase intermediates of isoprene atmospheric oxidation. Secondary organic aerosols derived from such intermediates have important impacts on air quality and health. We report here convergent and unambiguous pathways developed for the synthesis of isomeric IEPOX species and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran in good yield. The availability of such compounds is necessary to expedite research on isoprene atmospheric oxidation mechanisms and subsequent aerosol formation as well as the toxicological properties of the aerosols.

  4. Technical Note: Synthesis of isoprene atmospheric oxidation products: isomeric epoxydiols and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran

    Directory of Open Access Journals (Sweden)

    A. Gold

    2012-06-01

    Full Text Available Isoprene epoxydiol (IEPOX isomers are key gas-phase intermediates of isoprene atmospheric oxidation. Secondary organic aerosols derived from such intermediates have important impacts on air quality and health. We report here convergent and unambiguous pathways developed for the synthesis of isomeric IEPOX species and the rearrangement products cis- and trans-3-methyl-3,4-dihydroxytetrahydrofuran in good yield. The availability of such compounds is necessary to expedite research on isoprene atmospheric oxidation mechanisms and subsequent aerosol formation as well as the toxicological properties of the aerosols.

  5. Controlling the nitric and nitrous oxide production of an atmospheric pressure plasma jet

    Science.gov (United States)

    Douat, Claire; Hubner, Simon; Engeln, Richard; Benedikt, Jan

    2016-09-01

    Atmospheric pressure plasma jets are non-thermal plasmas and have the ability to create reactive species. These features make it a very attractive tool for biomedical applications. In this work, we studied NO and N2O production, which are two species having biomedical properties. NO plays a role in the vascularization and in ulcer treatment, while N2O is used as anesthetic and analgesic gas. In this study, the plasma source is similar to the COST Reference Microplasma Jet (µ-APPJ). Helium is used as feed gas with small admixtures of molecular nitrogen and oxygen of below 1%. The absolute densities of NO and N2O were measured in the effluent of an atmospheric pressure RF plasma jet by means of ex-situ quantum-cascade laser absorption spectroscopy via a multi-pass cell in Herriot configuration. We will show that the species' production is dependent on several parameters such as power, flow and oxygen and nitrogen admixture. The NO and N2O densities are strongly dependent on the N2-O2 ratio. Changing this ratio allows for choosing between a NO-rich or a N2O-rich regime.

  6. Laboratory Studies of Processing of Carbonaceous Aerosols by Atmospheric Oxidants/Hygroscopicity and CCN Activity of Secondary & Processed Primary Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Ziemann, P.J.; Arey, J.; Atkinson, R.; Kreidenweis, S.M.; Petters, M.D.

    2012-06-13

    The atmosphere is composed of a complex mixture of gases and suspended microscopic aerosol particles. The ability of these particles to take up water (hygroscopicity) and to act as nuclei for cloud droplet formation significantly impacts aerosol light scattering and absorption, and cloud formation, thereby influencing air quality, visibility, and climate in important ways. A substantial, yet poorly characterized component of the atmospheric aerosol is organic matter. Its major sources are direct emissions from combustion processes, which are referred to as primary organic aerosol (POA), or in situ processes in which volatile organic compounds (VOCs) are oxidized in the atmosphere to low volatility reaction products that subsequent condense to form particles that are referred to as secondary organic aerosol (SOA). POA and VOCs are emitted to the atmosphere from both anthropogenic and natural (biogenic) sources. The overall goal of this experimental research project was to conduct laboratory studies under simulated atmospheric conditions to investigate the effects of the chemical composition of organic aerosol particles on their hygroscopicity and cloud condensation nucleation (CCN) activity, in order to develop quantitative relationships that could be used to more accurately incorporate aerosol-cloud interactions into regional and global atmospheric models. More specifically, the project aimed to determine the products, mechanisms, and rates of chemical reactions involved in the processing of organic aerosol particles by atmospheric oxidants and to investigate the relationships between the chemical composition of organic particles (as represented by molecule sizes and the specific functional groups that are present) and the hygroscopicity and CCN activity of oxidized POA and SOA formed from the oxidation of the major classes of anthropogenic and biogenic VOCs that are emitted to the atmosphere, as well as model hydrocarbons. The general approach for this project was

  7. The relative importance of chlorine and bromine radicals in the oxidation of atmospheric mercury at Barrow, Alaska

    Science.gov (United States)

    Stephens, Chelsea R.; Shepson, Paul B.; Steffen, Alexandra; Bottenheim, Jan W.; Liao, Jin; Huey, L. Greg; Apel, Eric; Weinheimer, Andy; Hall, Samuel R.; Cantrell, Christopher; Sive, Barkley C.; Knapp, D. J.; Montzka, D. D.; Hornbrook, Rebecca S.

    2012-07-01

    Mercury is a toxic environmental contaminant originating from both natural and anthropogenic sources. Gaseous elemental mercury (GEM) is relatively long lived in the midlatitudes and can be transported long distances in the atmosphere. In the Polar Regions, mercury can have a much shorter lifetime and is known to experience episodic depletions following polar sunrise in concert with ozone depletion events. A series of photochemically initiated reactions involving halogen radicals is believed to be the primary pathway responsible for converting elemental mercury to oxidized forms of reactive gaseous mercury (RGM) that are subsequently deposited to snow and ice surfaces. Using field measurements from the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) 2009 field campaign of GEM, RGM, ozone, and a large suite of both inorganic halogen and volatile organic compounds, we calculated steady state Br and Cl atom concentrations and investigated the contribution of Br, BrO, Cl, ClO, O3, and OH to the observed decay of GEM for five cases of apparent first-order decay. The results of this study indicate that Br and BrO are the dominant oxidizers for Arctic mercury depletion events, with Br having the greatest overall contribution to GEM decay. Ozone is likely the primary factor controlling the relative contribution of Br and BrO, as BrO is a product of the reaction of Br with ozone, and reaction with O3 can be the largest Br atom sink. Cl was not found to be significant in any of the studied events; however, this result is highly dependent on the rate constant, for which there is a large range in the literature. Modeled 48 h back trajectories of the mercury depletion events studied here indicate significant time spent over sea ice-covered regions, where the concentration of halogen radicals is likely higher than those estimated using local-scale chemical mole fractions.

  8. Ruthenium nanoparticles for oxygen reduction and/or hydrogen oxidation, prepared by pyrolysis in a reducing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Altamirano-Gutierrez, A.; Villagran-Naredo, J.L.A.; Jimenez-Sandoval, O. [Inst. Politecnico Nacional (Mexico). Centro de Investigacion y de Estudios Avanzados; Hernandez-Castellanos, R. [Centro de Investigacion y Desarrollo Technologic en Electroquimica (Mexico)

    2006-07-01

    An investigation of the synthesis, structural and electrochemical characterization of ruthenium-based materials prepared by pyrolysis was presented. Ru{sub 3}(CO){sub 12} materials were pyrolized in a hydrogen atmosphere at 80, 140, 360 and 460 degrees C. The materials were then characterized using Fourier Transform Infrared (FTIR) spectroscopy; X-ray diffraction (XRD) and scanning electron microscopy (SEM). Oxygen reduction reactions (ORR) and hydrogen oxidation reactions (HOR) were evaluated through the use of rotating disk electrode measurements in a 0.5 M hydrogen peroxide (H{sub 2}SO{sub 4}) electrolyte at room temperature. Results of the investigation indicated that the Ru{sub 3}(CO){sub 12} precursor was completely decarbonylated in H{sub 2} at 140 degrees C. Carbonyl group bands were observed when the materials were prepared at 80 degrees C due to the formation of an inactive Ru cluster resulting from a structural rearrangement of the cluster. Polarization curves indicated that the materials prepared at 140 degrees C were able to perform the ORR and HOR in an acid medium similar to the medium present in proton exchange (PE) fuel cells. The electrokinetic parameters indicated that the exchange current densities were of the same order as platinum (Pt) current densities, and that the ORR occurred via 4 electrons due to the direct formation of water. Tafel slope values for the HOR suggested that the mechanism of the reaction was related to Herovsky/Volmer types. It was concluded that the use of a reductive atmosphere in the preparation process of ruthenium-based materials prevents the formation of undesirable ruthenium oxides. The nano-sized materials prepared during the experiment did not exhibit loss of their catalytic properties after being exposed to air for several weeks. 4 refs., 2 figs.

  9. Oxidation of siloxanes during biogas combustion and nanotoxicity of Si-based particles released to the atmosphere.

    Science.gov (United States)

    Tansel, Berrin; Surita, Sharon C

    2014-01-01

    Siloxanes have been detected in the biogas produced at municipal solid waste landfills and wastewater treatment plants. When oxidized, siloxanes are converted to silicon oxides. The objectives of this study were to evaluate the transformation of siloxanes and potential nanotoxicity of Si-based particles released to the atmosphere from the gas engines which utilize biogas. Data available from nanotoxicity studies were used to assess the potential health risks associated with the inhalation exposure to Si-based nanoparticles. Silicon dioxide formed from siloxanes can range from 5 nm to about 100 nm in diameter depending on the combustion temperature and particle clustering characteristics. In general, silicon dioxide particles formed during from combustion process are typically 40-70 nm in diameter and can be described as fibrous dusts and as carcinogenic, mutagenic, astmagenic or reproductive toxic (CMAR) nanoparticles. Nanoparticles deposit in the upper respiratory system, conducting airways, and the alveoli. Size ranges between 5 and 50 nm show effective deposition in the alveoli where toxic effects are higher. In this study the quantities for the SiO₂ formed and release during combustion of biogas were estimated based on biogas utilization characteristics (gas compositions, temperature). The exposure to Si-based particles and potential effects in humans were analyzed in relation to their particle size, release rates and availability in the atmosphere. The analyses showed that about 54.5 and 73 kg/yr of SiO₂ can be released during combustion of biogas containing D4 and D5 at 14.1 mg/m(3) (1 ppm) and 15.1 mg/m(3) (1ppm), respectively, per MW energy yield.

  10. Nitric oxide densities and their diurnal asymmetry in the upper middle atmosphere as revealed by ionospheric measurements

    Science.gov (United States)

    Laštovička, J.

    2001-01-01

    The nitric oxide (NO) density is of principal importance for the lower ionosphere as it is the source of the main ionized component. The mesospheric NO density climatology based on HALOE//UARS measurements (Siskind et al., Advances in Space Research 21 (1998) 1353-1362) and a comparison of the HALOE NO density data with some ionospheric data (Friedrich et al., Journal of Atmospheric and Solar-Terrestrial Physics 60 (1998) 1445-1457) revealed, among others, a large ``puzzling'' diurnal asymmetry of the NO density. In this paper, the existence of a diurnal asymmetry of the NO density is confirmed by independent data and is extended from the sunrise//sunset HALOE data to the entire daytime. We analyzed multi-frequency radio wave absorption measurements in the lower ionosphere over Central Europe, partly together with solar Lyman-/α and X-ray fluxes, in order to estimate the NO density. The results show that our ``ionospheric'' NO densities are comparable to, or somewhat higher than, the climatological NO densities of Siskind et al. (1998). They also show that the diurnal asymmetry in summer is a stable and regular feature of the lower ionosphere throughout the daytime, and that there is a substantial diurnal asymmetry in the NO density in the upper middle atmosphere that coincides with that revealed by the HALOE data and which is responsible for the asymmetry in the lower ionosphere.

  11. Spatial and Temporal Variability in Atmospheric-Methane-Oxidizing Bacterial Community Structure and Activity in an Alpine Glacier Forefield

    Science.gov (United States)

    Chiri, E.; Nauer, P. A.; Rainer, E. M.; Zeyer, J. A.; Schroth, M. H.

    2015-12-01

    High-affinity methane-oxidizing bacteria (MOB) play a crucial role in regulating the sink strength for atmospheric methane (CH4) in upland soils. Community structure and activity of MOB have been extensively studied in developed soils. However, little is known about their ecosystem service in young, developing soils. Examples of developing soils are found in Alpine glacier forefields, which progressively expand due to glacial retreat. Glacier forefields exhibit diverse geomorphological landforms, which may differ in biogeochemical properties. Also, glacier forefields are subject to seasonal variability in environmental parameters such as soil temperature and water content, which may affect MOB community structure and activity. We recently showed that glacier-forefield soils are a sink for atmospheric CH4, but a comprehensive understanding of crucial factors affecting MOB community structure and activity is still missing. In this study we assessed soil-atmosphere CH4 flux and MOB community structure in three different glacier-forefield landforms (sandhills, floodplains, terraces) throughout a snow-free sampling season. Specifically, we quantified CH4 flux using the soil-gas-profile method and static flux chambers. The MOB community structure was assessed using next-generation sequencing technology (Illumina-MiSeqTM) targeting the functional gene pmoA. We observed substantial differences in CH4 flux between soils of different landforms, with largest fluxes observed in well-drained sandhills (up to -2.2 mg CH4 m-2 d-1) and considerably smaller fluxes in other landforms. Methane flux showed a prominent seasonal variability, which was attenuated in older forefield soils. High-diversity MOB communities and a remarkable number of landform-specific operational taxonomic units were found in sandhills, whereas a lower diversity was observed in other landforms. Our phylogenetic analysis suggests the presence of a potentially new group of MOB inhabiting glacier-forefield soils.

  12. Oxygen dynamics in the aftermath of the Great Oxidation of Earth’s atmosphere

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene; Ngombi-Pemba, Lauriss; Hammarlund, Emma

    2013-01-01

    -oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest–lived positive δ13C excursion in Earth history, generating a huge......The oxygen content of Earth’s atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth’s oxygenation as a series of steps...... followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth’s oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well...

  13. Thermal decomposition of wood in oxidizing atmosphere: A kinetic study from non-isothermal TG experiments

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, T.; Rodriguez-Maroto, F.G.; Rodriguez, J.J. (Univ. of Malaga (Spain))

    1991-11-22

    The kinetics of thermal decomposition of four wood species in oxygen-bearing atmospheres of 5, 10 and 20% molar O{sub 2} concentrations have been studied from temperature-programmed experiments carried out at 5, 10 and 20 K min{sup {minus}1} heating rate. Devolatilization as well as combustion of the reamining solid have been considered to analyze the weight loss curves. The homogeneous volume reaction (VR) model has been used to describe devolatilization, whereas for solid combustion the grain model has been also checked. A two-stage approach has been used to fit the conversion-time curves and to derive the corresponding apparent kinetic parameters. The VR/VR (pyrolysis/combustion) combination provided a better description of the experimental {alpha}-t curves than the VR/grain combination. Holm oak and cork oak showed very close reactivities, whereas some differences were observed for aleppo pine and eucalyptus. 6 figs. 8 tabs., 20 refs.

  14. Protective effect of atmospheric pressure plasma on oxidative stress-induced neuronal injuries: an in vitro study

    Science.gov (United States)

    Yan, Xu; Qiao, Yajun; Ouyang, Jiting; Jia, Mei; Li, Jiaxin; Yuan, Fang

    2017-03-01

    Atmospheric pressure plasma jet (APPJ) can produce biological active species for biomedical applications. This work proves direct evidence of the protective effects of APPJ against oxidative stress. SH-SY5Y cells, a commonly used cell model for the study of neurotoxicity and neuroprotection, were treated with APPJ for different durations. Then, cells were exposed to 200 µM H2O2 for 24 h and cell viability was measured using a CCK-8 kit. Changes in cell apoptosis were further confirmed by calcein-AM fluorescence imaging and flow cytometry. Extracellular NO production was detected using the Griess method. The results showed that APPJ protected SH-SY5Y from H2O2-induced apoptosis in a time-dependent manner. Moreover, extracellular NO production was significantly increased with the APPJ treatment. The results show in vitro that APPJ treatment could protect SH-SY5Y cells from oxidative stress by reducing cell apoptosis, which might be related to the reactive nitrogen species induced by the APPJ treatment. Our results indicate that the APPJ may have therapeutic potential as a novel ‘NO donor drug’ in neuroprotection and in the treatment of neurodegenerative diseases.

  15. Conductivity of SrTiO3 based oxides in the reducing atmosphere at high temperature

    DEFF Research Database (Denmark)

    Hashimoto, Shin-Ichi; Poulsen, Finn Willy; Mogensen, Mogens Bjerg

    2007-01-01

    The conductivities of several donor-doped SrTiO3 based oxides, which were prepared in air, were studied in a reducing atmosphere at high temperature. The conductivities of all specimens increased slowly with time at 1000 degrees C in 9% H-2/N-2, even after 100 h. Nb-doped SrTiO3 showed relatively...... fast reduction and high conductivity compared with the other SrTiO3 based oxides. The conductivity of Nb-doped SrTiO3 was ca. 50 S cm(-1) at 500 degrees C after reduction at 1200 degrees C. After strong reduction, the conductivity of Nb-doped SrTiO3 was almost independent of the oxygen partial pressure...... at 500-800 degrees C, while that of La-doped SrTiO3 dropped immediately on exposure to air. The conduction behavior of Nb-doped SrTiO3 was explained by reduction of Ti4+ and/or Nb5+ and the relatively slow oxygen diffusibility. (c) 2006 Elsevier B.V. All rights reserved....

  16. Rapid atmospheric pressure plasma jet processed reduced graphene oxide counter electrodes for dye-sensitized solar cells.

    Science.gov (United States)

    Liu, Hsiao-Wei; Liang, Sheng-Ping; Wu, Ting-Jui; Chang, Haoming; Kao, Peng-Kai; Hsu, Cheng-Che; Chen, Jian-Zhang; Chou, Pi-Tai; Cheng, I-Chun

    2014-09-10

    In this work, we present the use of reduced graphene oxide (rGO) as the counter electrode materials in dye-sensitized solar cells (DSSCs). rGO was first deposited on a fluorine-doped tin oxide glass substrate by screen-printing, followed by post-treatment to remove excessive organic additives. We investigated the effect of atmospheric pressure plasma jet (APPJ) treatment on the DSSC performance. A power conversion efficiency of 5.19% was reached when DSSCs with an rGO counter electrode were treated by APPJs in the ambient air for a few seconds. For comparison, it requires a conventional calcination process at 400 °C for 15 min to obtain comparable efficiency. Scanning electron micrographs show that the APPJ treatment modifies the rGO structure, which may reduce its conductivity in part but simultaneously greatly enhances its catalytic activity. Combined with the rapid removal of organic additives by the highly reactive APPJ, DSSCs with APPJ-treated rGO counter electrode show comparable efficiencies to furnace-calcined rGO counter electrodes with greatly reduced process time. This ultrashort process time renders an estimated energy consumption per unit area of 1.1 kJ/cm(2), which is only one-third of that consumed in a conventional furnace calcination process. This new methodology thus saves energy, cost, and time, which is greatly beneficial to future mass production.

  17. Impact of Atmospheric Microparticles on the Development of Oxidative Stress in Healthy City/Industrial Seaport Residents

    Directory of Open Access Journals (Sweden)

    Kirill Golokhvast

    2015-01-01

    Full Text Available Atmospheric microsized particles producing reactive oxygen species can pose a serious health risk for city residents. We studied the responses of organisms to microparticles in 255 healthy volunteers living in areas with different levels of microparticle air pollution. We analyzed the distribution of microparticles in snow samples by size and content. ELISA and flow cytometry methods were employed to determine the parameters of the thiol-disulfide metabolism, peroxidation and antioxidant, genotoxicity, and energy state of the leukocytes. We found that, in the park areas, microparticles with a size of 800 μm or more were predominant (96%, while in the industrial areas, they tended to be less than 50 μm (93%, including size 200–300 nm (7%. In the industrial areas, we determined the oxidative modification of proteins (21% compared to the park areas, p≤0.05 and DNA (12%, p≤0.05, as well as changes in leukocytes’ energy potential (53%, p≤0.05. An increase in total antioxidant activity (82%, p≤0.01 and thiol-disulfide system response (thioredoxin increasing by 33%, p≤0.01; glutathione, 30%, p≤0.01 with stable reductases levels maintains a balance of peroxidation-antioxidant processes, protecting cellular and subcellular structures from significant oxidative damage.

  18. Gas chromatographic vapor pressure determination of atmospherically relevant oxidation products of β-caryophyllene and α-pinene

    Science.gov (United States)

    Hartonen, Kari; Parshintsev, Jevgeni; Vilja, Vesa-Pekka; Tiala, Heidi; Knuuti, Sinivuokko; Lai, Ching Kwan; Riekkola, Marja-Liisa

    2013-12-01

    Vapor pressures (subcooled liquid, pliquid) of atmospherically relevant oxidation products of β-caryophyllene (β-caryophyllene aldehyde 0.18 ± 0.03 Pa and β-nocaryophyllene aldehyde 0.17 ± 0.03 Pa), and α-pinene (pinonaldehyde 16.8 ± 0.20 Pa, cis-pinic acid 0.12 ± 0.06 Pa, and cis-pinonic acid 0.99 ± 0.19 Pa) at 298 K were obtained by gas chromatography with flame ionization detection (FID) and mass spectrometric (MS) detection. The effects of stationary phase polarity and column film thickness on the vapor pressure values were investigated. Increase in stationary phase polarity provided smaller values, while increase in film thickness gave slightly higher values. Values for vapor pressure were at least two orders of magnitude lower when obtained by a method utilizing vaporization enthalpy (determined by gas chromatography-mass spectrometry) than by retention index method. Finally, the results were compared with values calculated by group contribution theory. For the β-caryophyllene oxidation products, the values measured by gas chromatography were slightly lower than those obtained by theoretical calculations. The opposite trend was observed for the α-pinene oxidation products. The methods based on gas chromatography are concluded to be highly useful for the determination of vapor pressures of semi-volatile compounds. Except for the most polar pinic and pinonic acids, differences between vapor pressure values obtained by GC-FID and GC-MS were small. Since GC-MS provides structural information simultaneously, the use of GC-MS is recommended.

  19. Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

    Directory of Open Access Journals (Sweden)

    K. Kristensen

    2012-08-01

    Full Text Available Formation of carboxylic acids and dimer esters from α-pinene oxidation were investigated in a smog chamber and in ambient aerosol samples collected during the Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX. Chamber experiments of α-pinene ozonolysis in dry air and at low NOx concentrations demonstrated formation of two dimer esters, pinyl-diaterpenyl (MW 358 and pinonyl-pinyl dimer ester (MW 368, under both low and high temperature conditions. Concentration levels of the pinyl-diaterpenyl dimer ester were lower than the assumed first-generation oxidation products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA and diaterpenylic acid acetate (DTAA. Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural precursors. However, the sampling time resolution precluded conclusive evidence regarding formation from gas- or particle-phase processes. CCN activities of the particles formed in the smog chamber displayed a modest variation during the course of experiments with κ values in the range 0.06–0.09 (derived at a supersaturation of 0.19%.

    The pinyl-diaterpenyl dimer ester was also observed in ambient aerosol samples collected above a ponderosa pine forest in the Sierra Nevada Mountains of California during two seasonally distinct field campaigns in September 2007 and July 2009. The pinonyl-pinyl ester was observed for the first time in ambient air during the 2009 campaign, and although present at much lower concentrations, it was correlated with the abundance of the pinyl-diaterpenyl ester suggesting similarities in their formation. The maximum concentration of the pinyl-diaterpenyl ester was almost 10 times higher during the warmer 2009 campaign relative to 2007, while the concentration of cis-pinic acid was approximately the same during both

  20. Were ancient granitoid compositions influenced by contemporaneous atmospheric and hydrosphere oxidation states?

    Science.gov (United States)

    Jagoutz, O. E.

    2013-12-01

    A fundamental shift in the nature of granitoids occurs at approximately the Archean-Proterozoic boundary. Archean crust is dominated Na-rich tonalite-trondhjemite-granodiorites (TTGs), whereas post-Archean granitoids are characterized by K-rich granodiorite-granite (GG). Due to the HREE depletion commonly found in TTGs indicating the presence of residual garnet, many researchers have proposed that the difference in Na/K is related to the deeper melting depth of the TTG parental liquids. Here I present a compilation of the relevant experimental data, documenting that no correlation exists between the Na/K of derivative felsic liquids and the pressure of partial melting/fractional crystallization. Instead, the Na/K ratio of the felsic liquid best correlates with the Na/K ratio of the source. This implies that in Archean time the source material of TTG rocks must have been Na/K enriched relative to the modern. Modern granitoids are dominantly formed in a supra subduction zone environment, where a feedback loop exists between subducted materials (oceanic crust and sediments) and arc magmatism. Sea-floor weathering and the Na/K of the altered oceanic crust strongly depends on f(O2) conditions during alteration, which likely changed with earth history. During alteration under oxidized condition K2O is fixated due to the formation of celadonite (K-Mica), wheres during anoxic condition saponite (Na-Smectite) is the stable alteration mineral. I propose that the rise of oxygen at 2600-2400 Ma triggered associated changes in f(O2) seafloor alteration conditions. The change in the dominant seafloor alteration mineral from reduced to oxidized causes a change in the nature of the arc magma source and provides a possible explanation for the observed transition from TTGrocks in the Archean to the GG-granitoids in post-Archean times.

  1. ADVANCED GASIFICATION BY-PRODUCT UTILIZATION

    Energy Technology Data Exchange (ETDEWEB)

    Rodney Andrews; Aurora Rubel; Jack Groppo; Ari Geertsema; M. Mercedes Maroto-Valer; Zhe Lu; Harold Schobert

    2005-04-01

    The results of laboratory investigations and supporting technical assessments conducted under DOE Subcontract No. DE-FG26-03NT41795 are reported for the period September 1, 2003 to August 31, 2004. This contract is with the University of Kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Research and The Pennsylvania State University Energy Institute. The worked described was part of a project entitled ''Advanced Gasification By-Product Utilization''. This work involves the development of technologies for the separation and characterization of coal gasification slags from operating gasification units, activation of these materials to increase mercury and nitrogen oxide capture efficiency, assessment of these materials as sorbents for mercury and nitrogen oxides, and characterization of these materials for use as polymer fillers.

  2. Atmospheric oxidation of N-PAC and nitro substituted N-PAC in water droplets

    DEFF Research Database (Denmark)

    Feilberg, A.; Holcman, J.; Nielsen, T.

    1999-01-01

    A pulse radiolysis technique was used to study the formation of OH-adducts of quinoline (Q) and 5-nitroquinoline (5NQ) and the subsequent reactions of the OH-adducts with O-2 in both acidic and alkaline aqueous solution. The rate constants in alkaline solution were: k(Q+OH) = (9.0+/-1.0)lozenge 10.......4+/-0.1)lozenge 10(9) dm(3)mol(-1)s(-1), k(Q-OH+O-2) = (1.8+/-0.1)lozenge 10(7) dm(3)mol(-1)s(-1), k(5NQ-OH+O-2) = (8.7+/-0.6)lozenge 10(5) dm(3)mol(-1)s(-1). Absorption spectra of the OH-adducts were also measured. The results suggest that the lifetime of quinoline and 5-nitroquinoline with respect to reaction...... with OH in water droplets in the atmosphere is less than 1 hour. It is estimated that the degradation of Q is accelerated in the presence of aqueous droplets with comparable contributions from aqueous and gas phase chemistry at neutral pH. Under acidic conditions the aqueous phase degradation is predicted...

  3. Electrical and optical properties of thin indium tin oxide films produced by pulsed laser ablation in oxygen or rare gas atmospheres

    DEFF Research Database (Denmark)

    Thestrup, B.; Schou, Jørgen; Nordskov, A.

    1999-01-01

    Films of indium tin oxide (ITO) have been produced in different background gases by pulsed laser deposition (PLD). The Films deposited in rare gas atmospheres on room temperature substrates were metallic, electrically conductive, but had poor transmission of visible light. For substrate...

  4. The influence of atmospheric species on the degradation of aluminum doped zinc oxide and Cu(In,Ga)Se2 solar cells

    NARCIS (Netherlands)

    Theelen, M.J.; Foster, C.; Dasgupta, S.; Vroon, Z.A.E.P.; Barreau, N.; Zeman, M.

    2014-01-01

    Aluminum doped zinc oxide (ZnO:Al) layers were exposed to the atmospheric gases carbondioxide (CO2), oxygen (O2), nitrogen (N2) and air as well as liquid H2O purged with these gases, in order to investigate the chemical degradation behavior of these layers. The samples were analyzed by electrical, c

  5. Self-sealing of unsealed aluminium anodic oxide films in very different atmospheres

    Directory of Open Access Journals (Sweden)

    González, J. A.

    2003-12-01

    Full Text Available It is widely believed that the corrosion resistance behaviour of bare aluminium in natural environments is superior to that of unsealed anodised aluminium. However, results obtained in the exposure of unsealed anodised aluminium specimens with three different film thicknesses, in 9 atmospheres of Ibero-America with salinity levels between 3.9 and 517 mg.m-2.d-1 chloride, clearly shows the reverse to be true. After a sufficient time, which is shorter the higher the precipitation rate and the environmental relative humidity, a self-sealing process takes place, leading to coatings that surpass the quality standards demanded in industrial practice. Anodic films, sealed and unsealed, are protective coatings whose quality improves with ageing in most natural environments.

    Está muy difundida la idea de que el comportamiento del aluminio es superior al del aluminio anodizado y sin sellar, desde el punto de vista de la resistencia a la corrosión, en los ambientes naturales. Sin embargo, los resultados obtenidos en la exposición de anodizados sin sellar, de tres espesores diferentes, a 9 atmósferas de Iberoamérica, con salinidades comprendidas entre 3,9 y 517 mg.m-2.d-1 de cloruros, muestran, sin lugar a dudas, lo contrario. Con tiempo suficiente, tanto más rápidamente cuanto mayor sean las precipitaciones y la humedad relativa ambiental, tiene lugar un proceso de autosellado que conduce a recubrimientos que superan las normas de calidad exigidas en la práctica industrial. Los anodizados, sellados y sin sellar, son recubrimientos protectores que mejoran su calidad, en la mayoría de los ambientes naturales, con el envejecimiento.

  6. Modelling of gaseous dimethylamine in the global atmosphere: impacts of oxidation and aerosol uptake

    Directory of Open Access Journals (Sweden)

    F. Yu

    2014-07-01

    Full Text Available Recent laboratory studies indicate that while a dimethylamine concentration ([DMA] of several pptv can substantially enhance nucleation rates, such an enhancement drops significantly as [DMA] decreases below a few pptv. Here we study global distributions of amines with a chemistry transport model. DMA's lifetime is quite short (1–2 h in some regions due to aerosol uptake and oxidation. Aerosol uptake is important over regions of high anthropogenic emissions, while the decrease of the uptake coefficient (γ from 0.03 to 0.001 in these regions increases the modeled amine concentrations by a factor of ~5. Further decrease of γ from 0.001 to 0 has a small (<10% effect on the predicted amine concentrations. With the estimated global emission flux, from the reference, our simulations indicate that [DMA] in the surface layer is generally less than 1 pptv over major continents and below 0.1 pptv over oceans, decreasing quickly with altitude. Total concentrations of methylamines are about one order of magnitude higher than that of DMA. A comparison of simulated and observed [DMA] shows that the values of the simulated [DMA] are close to the measured values for the various urban sites but are substantially lower (by 1–2 orders of magnitude than those measured at the rural, coastal, and marine sites.

  7. Influence of packaging atmosphere on the formation of cholesterol oxides in [gamma]-irradiated egg powder

    Energy Technology Data Exchange (ETDEWEB)

    Lebovics, V.K.; Gaal, O. (National Inst. of Food Hygiene and Nutrition, Budapest (Hungary)); Farkas, J.; Somogyi, L. (University of Horticulture and Food Industry, Budapest (Hungary))

    1993-09-01

    In the present work the influence of aerobic and anoxic conditions have been comparatively investigated to study the chemical changes of cholesterol in [gamma]-irradiated egg powder. The irradiation treatment was carried out with powdered egg packed under air and also under vacuum in polyethylene (PE) bags and in laminated, oxygen impermeable three-layer (polyester-aluminium-polyethylene) foil to dosage levels 2 and 4 kGy at room temperature. The cholesterol oxidation is demonstrated by thin-layer chromatograms. In the egg powder wrapped in Pe bags the predominant cholesterol derivatives -7-hydroxycholesterol isomers ([alpha] and [beta]) - accumulated in significant amounts (increasing with dose) while vacuum-packaging in laminated foil considerably suppressed the quantity of these products and prevented the formation of cholesterol 5[alpha], 6[alpha]-epoxide as well as 7-ketocholesterol. Little or no change was observed in non-irradiated (control) vacuum-packed egg powder stored at approximately 22[sup o]C for up to 5 months. Peroxide values showed changes parallel to the formation of COPs. (author).

  8. Rapid detection of lipid oxidation in beef muscle packed under modified atmosphere by measuring volatile organic compounds using SIFT-MS.

    Science.gov (United States)

    Olivares, Alicia; Dryahina, Kseniya; Spaněl, Patrik; Flores, Mónica

    2012-12-01

    The objective of this work was to evaluate the use of a direct analysis technique (SIFT-MS) to measure the lipid oxidation process in beef meat packed under high oxygen atmosphere and compare it to conventional techniques such as gas chromatography-mass spectrometry analysis and TBARS values. Meat samples from two suppliers were selected and packaged under the same atmosphere conditions. The fatty acid content, the physicochemical (TBARS and volatile compounds) and sensory parameters were measured. The samples from supplier 2 had a highest content of PUFA and n6 fatty acids that was related with a highest oxidation during storage. SIFT-MS and SPME-GC-MS detected a significant increase for most of the volatiles compounds analyzed during storage especially, in aldehyde compounds. High correlation coefficients between TBARS values and linear aldehydes (C3-C7) measured by both techniques were obtained and this indicates that SIFT-MS can be used to monitor lipid oxidation changes.

  9. Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Yuan; Zhang, Chenxi; Yang, Wenbo; Hu, Jingtian [Environment Research Institute, Shandong University, Jinan 250100 (China); Sun, Xiaomin, E-mail: sxmwch@sdu.edu.cn [Environment Research Institute, Shandong University, Jinan 250100 (China); State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy Of Science, Lanzhou 730000 (China)

    2012-03-01

    Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311 + G(3df,2p)//MPWB1K/6-31 + G(d,p) level. The study shows that H abstraction reaction from the CH{sub 3} group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH{sub 3}O){sub 2}POOH (P1), CCl{sub 3}CHOHPOOH(OCH{sub 3}) (P2), CH{sub 3}OPO{sub 2} (P3), CCl{sub 3}COPO(OCH{sub 3}){sub 2} (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800 K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study. - Highlights: Black-Right-Pointing-Pointer The H-abstracted reaction and OH addition reaction are favorable channels. Black-Right-Pointing-Pointer The Arrhenius formulas of rate constants with the temperature are fitted. Black-Right-Pointing-Pointer The rate constants of TCF relative to OH radical is 4.95 Multiplication-Sign 10{sup -15} cm{sup 3} molecule{sup -1} s{sup -1}.

  10. Snowpack-atmosphere gas exchanges of carbon dioxide, ozone, and nitrogen oxides at a hardwood forest site in northern Michigan

    Directory of Open Access Journals (Sweden)

    Brian Seok

    2015-03-01

    Full Text Available Abstract Snowpack-atmosphere gas exchanges of CO2, O3, and NOx (NO + NO2 were investigated at the University of Michigan Biological Station (UMBS, a mid-latitude, low elevation hardwood forest site, during the 2007–2008 winter season. An automated trace gas sampling system was used to determine trace gas concentrations in the snowpack at multiple depths continuously throughout the snow-covered period from two adjacent plots. One natural plot and one with the soil covered by a Tedlar sheet were setup for investigating whether the primary source of measured trace gases was biogenic (i.e., from the soil or non-biogenic (i.e., from the snowpack. The results were compared with the “White on Green” study conducted at the Niwot Ridge (NWT Long Term Ecological Research site in Colorado. The average winter CO2 flux ± s.e. from the soil at UMBS was 0.54 ± 0.037 µmol m-2 s-1 using the gradient diffusion method and 0.71 ± 0.012 µmol m-2 s-1 using the eddy covariance method, and in a similar range as found for NWT. Observed snowpack-O3 exchange was also similar to NWT. However, nitrogen oxides (NOx fluxes from snow at UMBS were 10 times smaller than those at NWT, and fluxes were bi-directional with the direction of the flux dependent on NOx concentrations in ambient air. The compensation point for the change in the direction of NOx flux was estimated to be 0.92 nmol mol-1. NOx in snow also showed diurnal dependency on incident radiation. These NOx dynamics in the snow at UMBS were notably different compared to NWT, and primarily determined by snow-atmosphere interactions rather than by soil NOx emissions.

  11. A Comparison of Process-Scale Modeling and Measurements of Atmosphere-Snowpack Exchange of Nitrogen Oxides at Summit, Greenland

    Science.gov (United States)

    Murray, K. A.; Helmig, D.; Kramer, L. J.; Doskey, P. V.; Van Dam, B. A.; Seok, B.; Ganzeveld, L.

    2015-12-01

    Snowpack over glacial ice is a reservoir for reactive nitrogen gases. Previous studies indicate nitrogen oxides (NOx) are generated in snowpack interstitial air through photolysis of nitrate (NO3-). Gradients in NOx mixing ratios between snowpack interstitial air and the overlying atmosphere regulate NOx surface exchange, which affects the Arctic ozone budget and climate. To better understand the dynamics of cryosphere-atmosphere exchange of NOx in the Arctic, we use a 1-D process-scale model to evaluate measurements of NOxin and above the snowpack during March-May 2009 at Summit, Greenland. The model is based upon the processes previously presented in the snowpack chemistry and physics model, MISTRA-SNOW, which represents snow grains as spheres with surfaces uniformly coated by an aqueous phase. Modeled profiles of NO, NO2, and O3 up to ~ 2 meters deep into the snowpack for March-May 2009 have been compared to measured profiles and will be presented. During the March-May time period at Summit, low irradiances are observed during March, diurnal irradiance profiles are observed during April, and the sun never sets in May. The model results suggest a key chemical pathway for the formation of NO2 during "nighttime" that was previously unexplained. In addition, modeled 24-hour NOx fluxes are compared to measured NOx fluxes from a MET tower at Summit. Modeled fluxes of NOx in April 2009 are the same order of magnitude as the measurements; however, modeled fluxes of NOx deviate up to one order of magnitude from measurements in May 2009. A detailed analysis of the modeled/measured flux comparison will be presented.

  12. Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

    Directory of Open Access Journals (Sweden)

    M. J. Molina

    2007-04-01

    Full Text Available A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA. During spring of 2003 (MCMA-2003 field campaign an extensive set of measurements was collected to quantify time resolved ROx (sum of OH, HO2, RO2 radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1 was constrained by measurements of (1 concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO, formaldehyde (HCHO, ozone (O3, glyoxal (CHOCHO, and other oxygenated volatile organic compounds (OVOCs; (2 respective photolysis-frequencies (J-values; (3 concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated and oxidants, i.e., OH- and NO3 radicals, O3; and (4 NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals. Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: HCHO and O3 photolysis, each about 20%; O3/alkene reactions and HONO photolysis, each about 15%; unmeasured sources about 30%. While the direct contribution of O3/alkene reactions appears to be moderately small, source-apportionment of ambient HCHO and HONO identifies O3/alkene reactions as being largely responsible for jump-starting photochemistry about one hour after sunrise. The peak radical production is found to be higher than in any other urban influenced environment studied to date; further, differences exist in the timing of radical production. Our measurements and analysis comprise a

  13. Measurement and Modeling of Site-specific Nitrogen and Oxygen Isotopic Composition of Atmospheric Nitrous Oxide at Mace Head, Ireland

    Science.gov (United States)

    McClellan, M. J.; Saikawa, E.; Prinn, R. G.; Ono, S.

    2015-12-01

    Global mixing ratios of atmospheric nitrous oxide (N2O), a potent greenhouse gas, have increased nearly linearly from the beginning of the modern industrial period to today, with the current global average in excess of 325 ppb. This increase can be largely attributed to anthropogenic activity above the level of N2O emissions from natural biotic sources. The effect of N2O on Earth's climate is twofold: in the troposphere, N2O is radiatively active and chemically inert, while it serves as a reactive source of ozone-destroying nitrogen oxides in the stratosphere. The marked altitudinal divide in its reactivity means that all stages in the N2O life cycle—emission, transport, and destruction—must be examined to understand the overall effect of N2O on Earth's climate. However, the understanding of the total impact of N2O is incomplete, as there remain significant uncertainties in the global budget of this gas. Due to unique isotopic substitutions (15N and 18O) made by different N2O sources and stratospheric chemical reactions, the measurement of N2O isotopic ratios in ambient air can help identify the distribution and magnitude of distinct source types. We present the first year of site-specific nitrogen and oxygen isotopic composition data from the MIT Stheno-tunable infrared direct absorption spectroscopy (TILDAS) instrument at Mace Head, Ireland. Aided by the Stheno preconcentration system, Stheno-TILDAS can achieve measurement precisions of 0.10‰ or greater for all isotopic ratios (δ15N and δ18O) in ambient N2O. We further compare these data to the results from Model for Ozone and Related Tracers version 4 (MOZART-4) simulations, including N2O isotopic fractionation processes and MERRA/GEOS-5 reanalysis meteorological fields. These results will form the basis of future Bayesian inverse modeling simulations that will constrain global N2O source, circulation, and sink dynamics better.

  14. Dissociation against oxidation kinetics for the conversion of VOCs in non-thermal plasmas of atmospheric gases

    Science.gov (United States)

    Pasquiers, Stéphane; Blin-Simiand, Nicole; Magne, Lionel

    2016-08-01

    The kinetics of four volatile organic compounds (VOCs) (propene, propane, acetaldehyde, acetone) were studied in plasmas of atmospheric gases using a photo-triggered discharge (homogeneous plasma) or a dielectric barrier discharge (filamentary plasma). It was shown for the homogeneous plasma that quenchings of nitrogen metastable states, A3Ʃ+u and the group of singlets a' 1Ʃ-u, a 1Πg and w 1∆u, are important processes for the decomposition of such molecules. Recent measurements of the H2 concentration produced in the N2/C3H6 mixture emphasize that the hydrogen molecule can be an exit route for propene dissociation. It is also found that H2 and CO molecules are efficiently produced following the dissociation of CH3COCH3 and the subsequent chemical reactivity induced by radicals coming from acetone. Addition of oxygen to a N2/VOC mixture can change drastically the kinetics. However, the quenching processes of N2 metastables by the VOC are always present and compete with oxidation reactions for the conversion of the pollutant. At low temperature, oxidations by O or by OH are not always sufficiently effective to induce an increase of the molecule decomposition when oxygen is added to the mixture. In particular, the presence of O2 has a detrimental effect on the acetone removal. Also, as evidenced for acetaldehyde and propane, some kinetic analogies appear between filamentary and homogeneous plasmas. Contribution to the topical issue "6th Central European Symposium on Plasma Chemistry (CESPC-6)", edited by Nicolas Gherardi, Ester Marotta and Cristina Paradisi

  15. Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

    Directory of Open Access Journals (Sweden)

    Z. Peng

    2015-09-01

    Full Text Available Oxidation flow reactors (OFRs using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D, O(3P, and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH and external OH reactivity (OHRext, as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D, O(3P, and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under "pathological OFR conditions" of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab

  16. Seasonal variability of atmospheric nitrogen oxides and non-methane hydrocarbons at the GEOSummit station, Greenland

    Directory of Open Access Journals (Sweden)

    L. J. Kramer

    2014-05-01

    Full Text Available Measurements of atmospheric NOx (NOx = NO + NO2, peroxyacetyl nitrate (PAN, NOy and non-methane hydrocarbons (NMHC were taken at the GEOSummit Station, Greenland (72.34° N, 38.29° W, 3212 m.a.s.l from July 2008 to July 2010. The data set represents the first year-round concurrent record of these compounds sampled at a high latitude Arctic site in the free troposphere. Here, the study focused on the seasonal variability of these important ozone (O3 precursors in the Arctic free troposphere and the impact from transported anthropogenic and biomass burning emissions. Our analysis shows that PAN is the dominant NOy species in all seasons at Summit, varying from 49% to 78%, however, we find that odd NOy species (odd NOy = NOy − PAN-NOx contribute a large amount to the total NOy speciation with monthly means of up to 95 pmol mol−1 in the winter and ∼40 pmol mol−1 in the summer, and that the level of odd NOy species at Summit during summer is greater than that of NOx. We hypothesize that the source of this odd NOy is most likely alkyl nitrates from transported pollution, and photochemically produced species such as HNO3 and HONO. FLEXPART retroplume analysis and tracers for anthropogenic and biomass burning emissions, were used to identify periods when the site was impacted by polluted air masses. Europe contributed the largest source of anthropogenic emissions during the winter and spring months, with up to 82% of the simulated anthropogenic black carbon originating from this region between December 2009 and March 2010, whereas, North America was the primary source of biomass burning emissions. Polluted air masses were typically aged, with median transport times to the site from the source region of 11 days for anthropogenic events in winter, and 14 days for BB plumes. Overall we find that the transport of polluted air masses to the high altitude Arctic typically resulted in high variability in levels of O3 and O3 precursors. During winter

  17. Oxidative capacity of the Mexico City atmosphere - Part 1: A radical source perspective

    Science.gov (United States)

    Volkamer, R.; Sheehy, P.; Molina, L. T.; Molina, M. J.

    2010-07-01

    A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes - if any - a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm-3 s-1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of

  18. Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

    Directory of Open Access Journals (Sweden)

    R. Volkamer

    2010-07-01

    Full Text Available A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA. During spring of 2003 (MCMA-2003 field campaign an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2 radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1 was constrained by measurements of (1 concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO, formaldehyde (HCHO, ozone (O3, glyoxal (CHOCHO, and other oxygenated volatile organic compounds (OVOCs; (2 respective photolysis-frequencies (J-values; (3 concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated and oxidants, i.e., OH- and NO3 radicals, O3; and (4 NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals.

    Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes – if any – a very small contribution (~2%. The peak radical production of ~7.5 107 molec cm−3 s−1 is

  19. High temperature cyclic oxidation of AISI 310 steel in atmospheres with variable oxidation content; Oxidacion ciclica de un acero refractario AISI 310 a alta temperatura en atmosferas con centenidos de oxigeno variables

    Energy Technology Data Exchange (ETDEWEB)

    Higuera-Hidalgo, V.; Belzunce-Varela, F. J.; Riba-Lopez, J.

    2005-07-01

    High temperature oxidation test of an AISI 310 stainless steel was performed in two different environments: in an standard atmosphere (21% oxygen) at 704, 800, 884 and 1,000 degree centigree and in the typical environment of a gas turbine and vapor generator of a combined-cycle electric generation unit (10%oxygen) at 800 and 1,000 degree centigree. The oxidation kinetics was determined by means of the measurements of the weight gain per unit surface of the specimen and also determining the thickness of the oxide layer. Comparable results have been obtained using both methodologies and the effect of the oxygen content along with the other experimental differences were determined observing the oxidation kinetics in both environments. The cyclic oxidation of AISI 310 deteriorates at temperatures higher than 1,000 degree centigree. (Author) 9 refs.

  20. Experimental and modeling study of the oxidation of acetaldehyde in an atmospheric-pressure pulsed corona discharge

    Science.gov (United States)

    Klett, C.; Touchard, S.; Vega-Gonzalez, A.; Redolfi, M.; Bonnin, X.; Hassouni, K.; Duten, X.

    2012-08-01

    This paper reports the results obtained for the degradation of acetaldehyde by an atmospheric plasma corona discharge working in a pulsed regime. It was shown that a few hundred ppm of acetaldehyde diluted in a pure N2 gas flow can be removed up to 80% by a discharge fed with an electric power lower than 1 W. Under the same conditions, adding up to 5% of O2 allowed the removal of up to 95% of the initial acetaldehyde. The main identified end products were CO2, CO and methanol. A quasi-homogeneous zero-dimensional chemical model was developed to investigate the respective efficiency of the discharge and post-discharge periods in the global removal of the pollutant. The identified main pathways of acetaldehyde degradation were quenching of N2 metastable states during plasma pulses and oxidation by O and OH radicals during the post-discharge. This latter contribution increased with input power because of ozone accumulation in the gas mixture acting as an additional oxygen reservoir.

  1. Evaporation rates and vapor pressures of individual aerosol species formed in the atmospheric oxidation of alpha- and beta-pinene.

    Science.gov (United States)

    Bilde, M; Pandis, S N

    2001-08-15

    The semivolatile oxidation products (trans-norpinic acid, pinic acid, cis-pinonic acid, etc.) of the biogenic monoterpenes (alpha-pinene, beta-pinene, etc.) contribute to the atmospheric burden of particulate matter. Using the tandem differential mobility analysis (TDMA) technique evaporation rates of glutaric acid, trans-norpinic acid, and pinic acid particles were measured in a laminar flow reactor. The vapor pressure of glutaric acid was found to be log(p0 glutaric/Pa) = - 3,510 K/T + 8.647 over the temperature range 290-300 K in good agreement with the values previously reported by Tao and McMurry (1989). The measured vapor pressure of trans-norpinic acid over the temperature range 290-312 K is log(p0 norpinic/Pa) = - 2,196.9 K/T + 3.522, and the vapor pressure of pinic acid is log(p0 pinic/ Pa) = - 5,691.7 K/T + 14.73 over the temperature range 290-323 K. The uncertainty on the reported vapor pressures is estimated to be approximately +/- 50%. The vapor pressure of cis-pinonic acid is estimated to be of the order of 7 x 10(-5) Pa at 296 K.

  2. Photocatalytic Decomposition of Methyl Red Dye by Using Nanosized Zinc Oxide Deposited on Glass Beads in Various pH and Various Atmosphere

    Directory of Open Access Journals (Sweden)

    H. R. Ebrahimi

    2013-01-01

    Full Text Available Photocatalytic decomposition of methyl red (MR as a pollutant in wastewater samples is investigated in this study. This photodegradation was investigated in water in neutral, alkaline, and acidic media under external UV light irradiation by zinc oxide nanosized catalysts on granule glass. The effect of four atmosphere types including air, nitrogen, oxygen, and argon was investigated. Finally, it was found that photodecomposition using nanosized ZnO layered on glass is a new alternative route for efficient wastewater treatment. The results showed that the titled dye is degraded by various rate under different atmosphere and pH.

  3. The magnetic and oxidation behavior of bare and silica-coated iron oxide nanoparticles synthesized by reverse co-precipitation of ferrous ion (Fe{sup 2+}) in ambient atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Mahmed, N., E-mail: norsuria.mahmed@aalto.fi [Aalto University School of Chemical Technology, Department of Materials Science and Engineering, P.O. Box 16200, FI-00076 Aalto (Finland); School of Materials Engineering, Kompleks Pusat Pengajian UniMAP, Taman Muhibbah, Universiti Malaysia Perlis, 02600 Jejawi, Perlis (Malaysia); Heczko, O., E-mail: heczko@fzu.cz [Institute of Physics, Academy of Sciences, Czech Republic Na Slovance 2, CZ-182 21 Praha 8 (Czech Republic); Lancok, A., E-mail: Lancok@seznam.cz [Institute of Physics, Academy of Sciences, Czech Republic Na Slovance 2, CZ-182 21 Praha 8 (Czech Republic); Hannula, S-P., E-mail: simo-pekka.hannula@aalto.fi [Aalto University School of Chemical Technology, Department of Materials Science and Engineering, P.O. Box 16200, FI-00076 Aalto (Finland)

    2014-03-15

    The synthesis of iron oxide nanoparticles, i.e., magnetite was attempted by using only ferrous ion (Fe{sup 2+}) as a magnetite precursor, under an ambient atmosphere. The room temperature reverse co-precipitation method was used, by applying two synthesis protocols. The freshly prepared iron oxide was also immediately coated with Stöber silica (SiO{sub 2}) layer, forming the coreshell structure. The phase, stoichiometry, crystallite and the particle size of the synthesized powders were determined by using X-ray diffraction (XRD) and transmission electron microscope (TEM), while the magnetic and oxidation behaviors were studied by using the vibrating sample magnetometer (VSM) and Mössbauer spectroscopy. Based on the results, the bare iron oxide nanoparticles are in the stoichiometry between the magnetite and the maghemite stoichiometry, i.e., oxidation occurs. This oxidation is depending on the synthesis protocols used. With the silica coating, the oxidation can be prevented, as suggested by the fits of Mössbauer spectra and low temperature magnetic measurement. - Highlights: • Synthesis of magnetite was attempted by using ferrous ion (Fe{sup 2+}) in air. • The synthesized particle has a stoichiometry in between magnetite and maghemite. • Silica shell partly prevented the oxidation as suggested by magnetic and Mössbauer study.

  4. Non-OH chemistry in oxidation flow reactors for the study of atmospheric chemistry systematically examined by modeling

    Science.gov (United States)

    Peng, Zhe; Day, Douglas A.; Ortega, Amber M.; Palm, Brett B.; Hu, Weiwei; Stark, Harald; Li, Rui; Tsigaridis, Kostas; Brune, William H.; Jimenez, Jose L.

    2016-04-01

    Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to water vapor mixing ratio (H2O) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportionally to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to volatile organic compound (VOC) consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. We define "riskier OFR conditions" as those with either low H2O ( 200 s-1 in OFR254). We strongly suggest avoiding such conditions as the importance of non-OH reactants can be substantial for the most sensitive species, although OH may still dominate under some riskier conditions, depending on the species present. Photolysis at non-tropospheric wavelengths (185 and 254 nm) may play a significant (> 20 %) role in the degradation of some aromatics, as well as some oxidation intermediates, under riskier reactor conditions, if the quantum yields are high. Under riskier conditions, some biogenics can have substantial destructions by O3, similarly to the troposphere. Working under low O2 (volume mixing

  5. Methane and nitrous oxide measurements onboard the UK Atmospheric Research Aircraft using quantum cascade laser spectrometry (QCL)

    Science.gov (United States)

    Muller, J. B.; O'Shea, S.; Dorsey, J.; Bauguitte, S.; Cain, M.; Allen, G.; Percival, C. J.; Gallagher, M. W.

    2012-12-01

    A Aerodyne Research© Mini-Quantum Cascade Laser (QCL) spectrometer was installed on the UK Facility of Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft and employed during summer 2012. Methane (CH4) and nitrous oxide (N2O) concentrations were measured within the Arctic Circle as part of the MAMM project (Methane and other greenhouse gases in the Arctic - Measurements, process studies and Modelling) as well as around the UK as part of the ClearfLo project (Clean Air for London). A range of missions were flown, including deep vertical profiles up to the stratosphere, providing concentration profiles of CH4 and N2O, as well as low altitude level runs exploring near surface diffuse emission sources such as the wetlands in Arctic Lapland and point emissions sources such as gas platforms off the UK coast. Significant pollution plumes were observed both in the Arctic and around the UK with elevated CH4 concentrations, as well as enhanced CO, O3 and aerosol levels. The NAME Lagrangian particle dispersion model will be used to investigate the origins of these CH4 plumes to identify the locations of the emissions sources. The first set of flights using QCL on the FAAM research aircraft have been successful and regular in-flight calibrations (high/low span) and target concentrations were used to determine instrument accuracy and precision. Additional data quality control checks could be made by comparison with an onboard Los Gatos Fast Greenhouse Gas Analyser (FGGA) for CO2 and CH4 and provide the basis for further instrument development and implementation for future Arctic MAMM flights during spring and summer 2013.

  6. Atmospheric oxidation and antioxidants

    CERN Document Server

    Meurant, Gerard

    1993-01-01

    Volume I reviews current understanding of autoxidation, largely on the basis of the reactions of oxygen with characterised chemicals. From this flows the modern mechanism of antioxidant actions and their application in stabilisation technology.

  7. Fluctuations in late Neoproterozoic atmospheric oxidation — Cr isotope chemostratigraphy and iron speciation of the late Ediacaran lower Arroyo del Soldado Group (Uruguay)

    DEFF Research Database (Denmark)

    Frei, Robert; Gaucher, Claudio; Stolper, Daniel

    2013-01-01

    Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations...... in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (d53Cr up to + 5.......0‰) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (FeHR) to total iron (Fetot...

  8. Data on the identification and characterization of by-products from N-Cbz-3-aminopropanal and t-BuOOH/H2O2 chemical reaction in chloroperoxidase-catalyzed oxidations

    Directory of Open Access Journals (Sweden)

    Gerard Masdeu

    2016-09-01

    Full Text Available This data article is related to the subject of a publication in Process Biochemistry, entitled “Chloroperoxidase-catalyzed amino alcohol oxidation: Substrate specificity and novel strategy for the synthesis of N-Cbz-3-aminopropanal” (Masdeu et al., 2016 [1]. Here, the products of the chemical reaction involving the amino aldehyde (N-Cbz-3-aminopropanal and peroxides (tert-butyl hydroperoxide and H2O2 are characterized by NMR. 1H and 13C NMR full characterization of the products was obtained based on 2D NMR, 1D selective NOESY and diffusion spectroscopy (DOSY experiments.

  9. A tris(triazolate) ligand for a highly active and magnetically recoverable palladium catalyst of selective alcohol oxidation using air at atmospheric pressure.

    Science.gov (United States)

    Wang, Dong; Deraedt, Christophe; Salmon, Lionel; Labrugère, Christine; Etienne, Laetitia; Ruiz, Jaime; Astruc, Didier

    2015-04-20

    High efficiency and selectivity, easy magnetic recovery and recycling, and use of air as the oxidant at atmospheric pressure are major objectives for oxidation catalysis in terms of sustainable and green processes. A tris(triazolyl) ligand, so far only used in copper-catalyzed alkyne azide cycloadditions, was found to be extremely efficient in SiO2 /γ-Fe2 O3 -immobilized palladium complexes. It was characterized by inductively coupled plasma (ICP) analysis, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectra (XPS) and found to fulfill the combined conditions for the selective oxidation of alcohols to aldehydes and ketones.

  10. Nanofitas de óxido de estanho: controle do estado de oxidação pela atmosfera de síntese Tin oxide nanobelts: oxidation state control by the synthesis atmosphere

    Directory of Open Access Journals (Sweden)

    M. O. Orlandi

    2004-03-01

    Full Text Available Nanofitas de óxido de estanho com diferentes estados de oxidação foram produzidas pelo método de redução carbotérmica a 1260 ºC. As nanoestruturas foram caracterizadas por difração de raios X, microscopia eletrônica de varredura e espectroscopia por dispersão de energia de raios X. O controle do estado de oxidação das nanoestruturas foi feito pela variação da atmosfera de síntese dentro do forno. Em atmosferas sem oxigênio os materiais obtidos foram nanofitas de SnO e de SnO2, enquanto em atmosferas com oxigênio (aproximadamente 10% obteve-se apenas o crescimento de nanofitas de SnO2.Tin oxide nanobelts in different states of oxidation were produced by carbothermal reduction at 1260 ºC. The nanostructures were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy. The state of oxidation of the nanostructures was controlled by the synthesis atmosphere inside the furnace. The materials obtained in atmospheres without oxygen were SnO and SnO2 nanobelts, while atmospheres with oxygen (about 10% only allowed for the growth of SnO2 nanobelts.

  11. Nitrous oxide in the Changjiang (Yangtze River Estuary and its adjacent marine area: Riverine input, sediment release and atmospheric fluxes

    Directory of Open Access Journals (Sweden)

    G.-L. Zhang

    2010-11-01

    Full Text Available Dissolved nitrous oxide (N2O was measured in the waters of the Changjiang (Yangtze River Estuary and its adjacent marine area during five surveys covering the period of 2002–2006. Dissolved N2O concentrations ranged from 6.04 to 21.3 nM, and indicate great temporal and spatial variations. Distribution of N2O in the Changjiang Estuary was influenced by multiple factors and the key factor varied between cruises. Dissolved riverine N2O was observed monthly at station Xuliujing of the Changjiang, and ranged from 12.4 to 33.3 nM with an average of 19.4 ± 7.3 nM. N2O concentrations in the river waters showed obvious seasonal variations with higher values occurring in both summer and winter. Annual input of N2O from the Changjiang to the estuary was estimated to be 15.0 × 106 mol/yr. N2O emission rates from the sediments of the Changjiang Estuary in spring ranged from −1.88 to 2.02 μmol m−2 d−1, which suggests that sediment can act as either a source or a sink of N2O in the Changjiang Estuary. Average annual sea-to-air N2O fluxes from the studied area were estimated to be 7.7 ± 5.5, 15.1 ± 10.8 and 17.0 ± 12.6 μmol m−2d−1 using LM86, W92 and RC01 relationships, respectively. Hence the Changjiang Estuary and its adjacent marine area are a net source of atmospheric N2O.

  12. 植物副产物浸出分离氧化型锰银矿的研究%Study on leaching separation of oxidized manganese-silver ore with plant by-product

    Institute of Scientific and Technical Information of China (English)

    余丽秀; 孙亚光; 张然; 宋广毅

    2012-01-01

    介绍了利用植物副产物(秸秆、粮食加工副产壳类等)作为还原剂还原浸出氧化型锰银精矿中的锰、浸锰渣氰化浸银的锰银分离工艺.玉米秸秆还原浸锰条件:秸秆粉在95℃预降解糖化0.5 h、降解糖化液与精矿的体积质量比为3 mL/g、硫酸与锰的物质的量比为1.4、秸秆与精矿的质量比为0.275、95℃浸出5h,在此条件下锰的浸出率约92%.浸锰渣氰化浸银条件:每吨浸锰渣氰化钠用量为3 kg、常温浸银3h,在此条件下银的浸出率达到92.20%.研究的锰银分离工艺具有较好的综合效果.%The manganese-silver separation process,which uses plant by-product (straw and husk by-produced from grain processing etc.) as reducing agent for reduction leaching manganese in manganese-silver concentrate and for silver leaching from residue of manganese-leaching with cyanide was introduced.The conditions of corn straw reduction leaching manganese were as follows: straw powder pre-degradation and saccharification at 95℃ for 0.5 h, volume-mass ratio of degradation saccharifi-cation liquid to manganese-silver concentrate was 3 mL/g,amount of substance ratio-of-sulfuric acid to manganese was 1.4, mass ratio of straw to ore powder was 0.275, and leaching temperature and time were 95℃. and 5 h, respectively .The manganese leaching rate was about 92% under those conditions.Ag leaching rate of 92.20% could be achieved under the conditions when the dosage of NaCN was 3 kg per ton of the residue of manganese-leaching and the leaching temperature and time were room temperature and 3 h, respectively .The separation technology of manganese and silver had a very good comprehensive effect.

  13. Atmospheric-Pressure DBD Cold Plasma for Preparation of High Active Au/P25 Catalysts for Low-Temperature CO Oxidation

    Institute of Scientific and Technical Information of China (English)

    DI Lanbo; ZHAN Zhibin; ZHANG Xiuling; QI Bin; XU Weijie

    2016-01-01

    Cold plasma generated by dielectric barrier discharge (DBD) at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts (Au/P25-P) with the assistance of the deposition-precipitation procedure.The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated.CO oxidation was performed to investigate the catalytic activity of thc Au/P25 catalysts.The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process,and Au/P25-P (4 min) exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies.In order to form more oxygen vacancies active species,Au/P25-P was calcined to obtain Au/P25-PC catalysts.Interestingly,Au/P25-PC exhibited the highest activity for CO oxidation among the Au/P25 samples.The results of transmission electron microscopy (TEM) indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC.Atmospheric-pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts.

  14. Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source.

    Science.gov (United States)

    Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

    2016-12-19

    A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H](+) was observed in the case of individual alkanes (C5-C19) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. Graphical Abstract ᅟ.

  15. Atmospheric chemistry of 3-pentanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX.

    Science.gov (United States)

    Hurley, M D; Wallington, T J; Bjarrum, M; Javadi, M S; Nielsen, O J

    2008-09-04

    Smog chamber/FTIR techniques were used to study the atmospheric chemistry of 3-pentanol and determine rate constants of k(Cl+3-pentanol) = (2.03 +/- 0.23) x 10 (-10) and k(OH+3-pentanol) = (1.32 +/- 0.15) x 10 (-11) cm (3) molecule (-1) s (-1) in 700 Torr of N 2/O 2 diluent at 296 +/- 2 K. The primary products of the Cl atom initiated oxidation of 3-pentanol in the absence of NO were (with molar yields) 3-pentanone (26 +/- 2%), propionaldehyde (12 +/- 2%), acetaldehyde (13 +/- 2%) and formaldehyde (2 +/- 1%). The primary products of the Cl atom initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (51 +/- 4%), propionaldehyde (39 +/- 2%), acetaldehyde (44 +/- 4%) and formaldehyde (4 +/- 1%). The primary products of the OH radical initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (58 +/- 3%), propionaldehyde (28 +/- 2%), and acetaldehyde (37 +/- 2%). In all cases the product yields were independent of oxygen concentration over the partial pressure range 10-700 Torr. The reactions of Cl atoms and OH radicals with 3-pentanol proceed 26 +/- 2 and 58 +/- 3%, respectively, via attack on the 3-position to give an alpha-hydroxyalkyl radical, which reacts with O 2 to give 3-pentanone. The results are discussed with respect to the literature data and atmospheric chemistry of 3-pentanol.

  16. Atmospheric reactivity of vinyl acetate: kinetic and mechanistic study of its gas-phase oxidation by OH, O3, and NO3.

    Science.gov (United States)

    Picquet-Varrault, B; Scarfogliero, M; Doussin, J-F

    2010-06-15

    Vinyl acetate is widely used in industry. It has been classified as a high-production volume (HPV) chemical in the United States. To evaluate its impact on the environment and air quality, its atmospheric reactivity toward the three main tropospheric oxidants (OH, NO(3), and O(3)) has been investigated. Kinetic and mechanistic experiments have been conducted at room temperature and atmospheric pressure using an indoor Pyrex simulation chamber coupled to Fourier transform infrared (FTIR) and UV-visible spectrometers. Rate constants for the reactions of vinyl acetate with OH, NO(3), and O(3) were equal to (2.3 +/- 0.3) x 10(-11), (7.3 +/- 1.8) x 10(-15), and (3.0 +/- 0.4) x 10(-18) cm(3) molecule(-1) s(-1), respectively. From these data, tropospheric lifetimes of vinyl acetate have been estimated as follows: tau(OH) = 6 h, tau(NO(3)) = 6 days, and tau(O(3)) = 5 days. This demonstrates that reaction with OH radicals is the main tropospheric loss process of this compound. From the mechanistic experiments, main oxidation products have been identified and quantified and oxidation schemes have been proposed for each studied reaction.

  17. Advanced Gasification By-Product Utilization

    Energy Technology Data Exchange (ETDEWEB)

    Rodney Andrews; Aurora Rubel; Jack Groppo; Ari Geertsema; Frank Huggins; M. Mercedes Maroto-Valer; Brandie M. Markley; Harold Schobert

    2006-02-01

    With the recent passing of new legislation designed to permanently cap and reduce mercury emissions from coal-fired utilities, it is more important than ever to develop and improve upon methods of controlling mercury emissions. One promising technique is carbon sorbent injection into the flue gas of the coal-fired power plant. Currently, this technology is very expensive as costly commercially activated carbons are used as sorbents. There is also a significant lack of understanding of the interaction between mercury vapor and the carbon sorbent, which adds to the difficulty of predicting the amount of sorbent needed for specific plant configurations. Due to its inherent porosity and adsorption properties as well as on-site availability, carbons derived from gasifiers are potential mercury sorbent candidates. Furthermore, because of the increasing restricted use of landfilling, the coal industry is very interested in finding uses for these materials as an alternative to the current disposal practice. The results of laboratory investigations and supporting technical assessments conducted under DOE Subcontract No. DE-FG26-03NT41795 are reported for the period September 1, 2004 to August 31, 2005. This contract is with the University of Kentucky Research Foundation, which supports work with the University of Kentucky Center for Applied Energy Research and The Pennsylvania State University Energy Institute. The worked described was part of a project entitled ''Advanced Gasification By-Product Utilization''. This work involves the development of technologies for the separation and characterization of coal gasification slags from operating gasification units, activation of these materials to increase mercury and nitrogen oxide capture efficiency, assessment of these materials as sorbents for mercury and nitrogen oxides, and characterization of these materials for use as polymer fillers.

  18. Mixed-valence iron minerals on Venus: Fe(2+)-Fe(3+) oxides and oxy-silicates formed by surface-atmosphere interactions

    Science.gov (United States)

    Burns, Roger G.; Straub, Darcy W.

    1992-01-01

    Inferences from these investigations are that Fe(3+)-bearing minerals such as hematite magnesioferrite, acmite, and epidote are thermodynamically unstable, and that magnetite is the predominant mixed-valence iron oxide mineral on venus. Recently, the Fe(2+)-Fe(3+) silicate mineral laihunite was proposed to be a reaction product of olivine with the venusian atmosphere. This possibility is discussed further here. We suggest that other mixed-valence Fe(2+)-Fe(3+)-Oz-OH(-) silicates could also result from surface-atmosphere interactions on Venus. Topics discussed include the following: (1) conversion of hematite to magnetite; (2) stability of laihunite; (3) the possible existence of oxy-amphiboles and oxy-micas on Venus; and (4) other mixed-valence Fe(2+)-Fe(3+) silicates likely to exist on Venus.

  19. Timing and characterization of the change in the redox state of uranium in Precambrian surface environments: A proxy for the oxidation state of the atmosphere

    Science.gov (United States)

    Pollack, Gerald D.

    The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere and oceans during sedimentary processes. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading, but the whole rock Pb isotope composition may be used to determine a sample's apparent time-integrated Th/U ratio (kappaa) and the timing associated with the onset of the U-Th-Pb geochemistry. Rare earth element (REE) concentrations were determined by isotope dilution mass spectrometry to evaluate the influence of multiple provenance components and potential mobility of Th, U, and Pb during post-depositional processes on the Th/U ratio. The Pb isotope compositions and REE concentrations were determined for six Paleoproterozoic sedimentary sequences, which were the focus of previous studies involving the timing of the rise of atmospheric oxygen. The Mount McRae Shale, Huronian Supergroup, and Zaonezhskaya Formation have been interpreted as experiencing post-depositional alteration (perhaps associated with orogenic events) due to Pb-Pb ages that are younger than the likely depositional age and observed fractionation of REE in chondrite normalized REE patterns and interelement REE ratios (e.g. La/Nd, La/Yb, Eu/Eu*). Similar geochemical proxies have been interpreted as sedimentary geochemical features of the Timeball Hill Formation, Hotazel Formation, and Sengoma Argillite Formation. This study of Paleoproterozoic sedimentary units constrains the onset of U-Th decoupling, most likely due to the onset of oxidative weathering conditions, began by 2.32 Ga, the latest. Index words. Pb isotopes, Rare earth elements, Th/U ratios, Time-integrated, Atmospheric evolution, Oxygen content of the atmosphere, U-Th decoupling

  20. Poisoning of noble metal catalysts by arsenic and silicon compounds in an oxidizing atmosphere. Die Vergiftung von Edelmetall-Katalysatoren durch Arsen- und Siliziumverbindungen unter oxidierenden Verbindungen

    Energy Technology Data Exchange (ETDEWEB)

    Kaizik, A.

    1984-01-12

    The dissertation deals with the poisoning of noble metal catalysts by arsenic and silicon compounds in an oxidizing atmosphere. The problem was studied in the field of catalytic exhaust and waste air post-combustion, but the findings can be applied to other catalytic processes in which arsenic and silicon compounds may occur as catalyst poisons. The following issues were investigated: 1. Kinetics of arsenic and silicon poisoning of platinum-containing carrier catalysts; 2. Regeneration of poisoned catalysts; 3. mathematical modelling of the poisoning processes.

  1. High throughput measurement of high temperature strength of ceramics in controlled atmosphere and its use on solid oxide fuel cell anode supports

    DEFF Research Database (Denmark)

    Frandsen, Henrik Lund; Curran, Declan; Rasmussen, Steffen;

    2014-01-01

    In the development of structural and functional ceramics for high temperature electrochemical conversion devices such as solid oxide fuel cells, their mechanical properties must be tested at operational conditions, i.e. at high temperature and controlled atmospheres. Furthermore, characterization...... of the strength of ceramic components requires testing of a high number of samples due to stochastic failures. Successive heating and testing a single sample is very time consuming and consequently this hinders thorough studies with sufficient samples at operational conditions. This work presents a methodology...

  2. Mechanistic studies of NO{sub x} reduction reactions under oxidative atmosphere on alumina supported 0.2wt% platinum catalyst treated under microwave. Part 2

    Energy Technology Data Exchange (ETDEWEB)

    Ringler, Sandrine; Girard, Paule; Maire, Gilbert; Garin, Francois [Laboratoire d`Etudes de la Reactivite Catalytique, des Surfaces et Interfaces (LERCSI), UMR 7515 du CNRS - ECPM, Universite Louis Pasteur - Institut Le Bel 4, rue Blaise Pascal 67, 070 Strasbourg Cedex (France); Hilaire, Stephanie; Roussy, Georges [Laboratoire de Spectroscopie et des Techniques Micro-Ondes LSTM, Universite de Nancy I, BP 239 54506, Vandoeuvre-les-Nancy Cedex (France)

    1999-03-08

    Reduction of nitrogen oxides under oxidative atmosphere is a very extensively studied reaction, but it is still very difficult to understand and to follow the various pathways of the reaction. Two alumina supported 0.2wt% platinum catalysts, reduced by hydrogen in an oven heated either by microwave irradiations or by Joule effect, with different metal dispersion of 60% and 90%, respectively, were studied. By the use of labelled compounds we were able to show the presence of an exchange reaction between 15N16O and 15N18O which occurred on both catalysts. It means that [15N16O18O] is the intermediate species. Such product, 15N18O, is less formed on the microwave catalyst `MW` than on the classical one `CT`. Experiments were performed at 22 and 550Torr, between 150C and 250C. Near atmospheric pressure, `MW` catalyst gives higher initial rates for 15N{sub 2} formation than the `CT` catalysts. At low temperature, the nitrogen selectivity is higher on `MW` catalyst than on the other catalyst. From the apparent activation energy values, one may deduce that several mechanisms are responsible for the 15N{sub 2} formation depending on the reaction temperature and the catalyst used. On the 0.2% Pt/Al{sub 2}O{sub 3} `CT` catalyst, an additive process between propene and 15NO takes place at low temperature giving nitroso and oxime intermediate species. At high temperature, a partial oxidation of propene occurs, giving a ketone, before the 15NO reduction to 15N{sub 2}. With this catalyst only two sites with different activity are involved. On the 0.2% Pt/Al{sub 2}O{sub 3} `MW` catalyst the reactants are seated on three sites with different activity. This particularity reinforce the proposals concerning the `MW` catalyst which may exhibit particular shapes for the aggregates having different crystallographic orientations. What is surprising, for this `MW` catalyst, is the fact that we already observed a specific reactivity under reductive atmosphere in reforming reactions and now

  3. Oxidative capacity and radical chemistry in the polluted atmosphere of Hong Kong and Pearl River Delta region: analysis of a severe photochemical smog episode

    Science.gov (United States)

    Xue, Likun; Gu, Rongrong; Wang, Tao; Wang, Xinfeng; Saunders, Sandra; Blake, Donald; Louie, Peter K. K.; Luk, Connie W. Y.; Simpson, Isobel; Xu, Zheng; Wang, Zhe; Gao, Yuan; Lee, Shuncheng; Mellouki, Abdelwahid; Wang, Wenxing

    2016-08-01

    We analyze a photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD) region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2) is constrained by an intensive set of field observations to elucidate the budgets of ROx (ROx = OH+HO2+RO2) and NO3 radicals. Highly abundant radical precursors (i.e. O3, HONO and carbonyls), nitrogen oxides (NOx) and volatile organic compounds (VOCs) facilitate strong production and efficient recycling of ROx radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs), followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde) is the dominant primary source of ROx with average daytime contributions of 34-47 %. HONO photolysis is the largest contributor to OH and the second-most significant source (19-22 %) of ROx. Other considerable ROx sources include O3 photolysis (11-20 %), formaldehyde photolysis (10-16 %), and ozonolysis reactions of unsaturated VOCs (3.9-6.2 %). In one case when solar irradiation was attenuated, possibly by the high aerosol loadings, NO3 became an important oxidant and the NO3-initiated VOC oxidation presented another significant ROx source (6.2 %) even during daytime. This study suggests the possible impacts of daytime NO3 chemistry in the polluted atmospheres under conditions with the co-existence of abundant O3, NO2, VOCs and aerosols, and also provides new insights into the radical chemistry that essentially drives the formation of photochemical smog in the high-NOx environment of Hong Kong and the PRD region.

  4. Anthropogenic emissions of oxidized sulfur and nitrogen into the atmosphere of the former Soviet Union in 1985 and 1990

    Energy Technology Data Exchange (ETDEWEB)

    Ryaboshapko, A.G.; Brukhanov, P.A.; Gromov, S.A.; Proshina, Yu.V; Afinogenova, O.G. [Institute of Global Climate and Ecology, Moscow (Russian Federation)

    1996-09-01

    Anthropogenic emissions of oxidized sulfur and nitrogen over the former Soviet Union for 1985 and 1990 were calculated on the basis of a combination of `bottom-up` and `top-down` approaches. Sulfur dioxide emissions from combustion of hard coal, brown coal, oil products, natural gas, shale oil, peat, wood as well as from metallurgy, sulfuric acid production, and cement production were estimated. Nitrogen oxides emissions were considered separately for large power plants, small power plants, industrial boilers, residential combustion units, and for transport. The sulfur and nitrogen emissions were spatially distributed over the former Soviet Union with 1 x 1 degree resolution. Data on 721 point sources of sulfur dioxide emissions and on the 242 largest power stations as nitrogen oxides sources were used. The area sources of both sulfur dioxide and nitrogen oxides were distributed according to the population density separately for about 150 administrative units of the former Soviet Union. 63 refs., 19 tabs.

  5. Surface water and atmospheric carbon dioxide and nitrous oxide observations by shipboard automated gas chromatography: Results from expeditions between 1977 and 1990

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, R.F.; Van Woy, F.A.; Salameh, P.K. (Scripps Institution of Oceanography, La Jolla, CA (United States)); Sepanski, R.J. (Tennessee Univ., Knoxville, TN (United States). Energy, Environment and Resources Center)

    1992-12-01

    This document presents the results of surface water and atmospheric carbon dioxide (CO[sub 2]) and nitrous oxide (N[sub 2]O) measurements carried out by shipboard gas chromatography over the period 1977--1990. These data include results from 11 different oceanic surveys for a total of 41 expedition legs. Collectively, they represent a globally distributed sampling that includes locations in the Atlantic, Pacific, Indian, and Southern Oceans, as well as the Mediterranean and Red Seas. The measurements were made by an automated high-precision shipboard gas chromatographic system developed during the late 1970s and used extensively over the intervening years. This instrument measures CO[sub 2] by flame ionization after quantitative reaction to methane in a stream of hydrogen. Nitrous oxide is measured by a separate electron capture detector. The chromatographic system measures 196 dry-gas samples a day, divided equally among the atmosphere, gas equilibrated with surface water, a low-range gas standard, and a high-range gas standard.

  6. Atmospheric Photochemistry

    Science.gov (United States)

    Massey, Harrie; Potter, A. E.

    1961-01-01

    The upper atmosphere offers a vast photochemical laboratory free from solid surfaces, so all reactions take place in the gaseous phase. At 30 km altitude the pressure has fallen to about one-hundredth of that at ground level, and we shall, rather arbitrarily, regard the upper atmosphere as beginning at that height. By a little less than 100 km the pressure has fallen to 10(exp -3) mm Hg and is decreasing by a power of ten for every 15 km increase in altitude. Essentially we are concerned then with the photochemistry of a nitrogen-oxygen mixture under low-pressure conditions in which photo-ionization, as well as photodissociation, plays an important part. Account must also be taken of the presence of rare constituents, such as water vapour and its decomposition products, including particularly hydroxyl, oxides of carbon, methane and, strangely enough, sodium, lithium and calcium. Many curious and unfamiliar reactions occur in the upper atmosphere. Some of them are luminescent, causing the atmosphere to emit a dim light called the airglow. Others, between gaseous ions and neutral molecules, are almost a complete mystery at this time. Similar interesting phenomena must occur in other planetary atmospheres, and they might be predicted if sufficient chemical information were available.

  7. Solvent-free aerobic oxidation of ethylbenzene over supported Ni catalysts using molecular oxygen at atmospheric pressure

    Institute of Scientific and Technical Information of China (English)

    G.Raju; P. Shiva Reddy; J.Ashok; B.Mahipal Reddy; A.Venugopal

    2008-01-01

    We investigated the aerobic oxidation of ethylbenzene in the absence of solvent or any additive carded out over Ni on difierent types of supports namely SiO2,hydroxyapatite,SBA-15,and USY Zeolites.The oxidation of ethylbenzene activities was measured in a round bottom flask immersed in oil bath at known reaction temperature.The physicochemical characteristics of the catalysts were examined by BET surface area.XRD.FT-IR and the oxidation activities were correlated with the acidities of the catalysts obtained bv TPD of NH3.It was observed that both hydroxyapatite and USY(13%Na2O)supported Ni catalysts displayed higher ethylbenzene conversion and 80%selectivity towards acetophenone.

  8. Atmospheric-Pressure DBD Cold Plasma for Preparation of High Active Au/P25 Catalysts for Low-Temperature CO Oxidation

    Science.gov (United States)

    Di, Lanbo; Zhan, Zhibin; Zhang, Xiuling; Qi, Bin; Xu, Weijie

    2016-05-01

    Cold plasma generated by dielectric barrier discharge (DBD) at atmospheric pressure was adopted for preparation of commercial TiO2 Degussa P25 supported Au catalysts (Au/P25-P) with the assistance of the deposition-precipitation procedure. The influences of the plasma reduction time and calcination on the performance of the Au/P25-P catalysts were investigated. CO oxidation was performed to investigate the catalytic activity of the Au/P25 catalysts. The results show that DBD cold plasma for the fabrication of Au/P25-P catalysts is a fast process, and Au/P25-P (4 min) exhibited the highest CO oxidation activity due to the complete reduction of Au compounds and less consumption of oxygen vacancies. In order to form more oxygen vacancies active species, Au/P25-P was calcined to obtain Au/P25-PC catalysts. Interestingly, Au/P25-PC exhibited the highest activity for CO oxidation among the Au/P25 samples. The results of transmission electron microscopy (TEM) indicated that the smaller size and high distribution of Au nanoparticles are the mean reasons for a high performance of Au/P25-PC. Atmospheric-pressure DBD cold plasma was proved to be of great efficiency in preparing high performance supported Au catalysts. supported by National Natural Science Foundation of China (Nos. 11505019, 21173028), the Science and Technology Research Project of Liaoning Provincial Education Department (No. L2013464), the Scientific Research Foundation for the Doctor of Liaoning Province (No. 20131004), and the Dalian Jinzhou New District Science and Technology Plan Project (No. KJCX-ZTPY-2014-0001)

  9. Flame spray synthesis under a non-oxidizing atmosphere: Preparation of metallic bismuth nanoparticles and nanocrystalline bulk bismuth metal

    Energy Technology Data Exchange (ETDEWEB)

    Grass, Robert N.; Stark, Wendelin J. [Institute for Chemical and Bioengineering, ETH Zuerich (Switzerland)], E-mail: wendelin.stark@chem.ethz.ch

    2006-10-15

    Metallic bismuth nanoparticles of over 98% purity were prepared by a modified flame spray synthesis method in an inert atmosphere by oxygen-deficient combustion of a bismuth-carboxylate based precursor. The samples were characterized by X-ray diffraction, thermal analysis and scanning electron microscopy confirming the formation of pure, crystalline metallic bismuth nanoparticles. Compression of the as-prepared powder resulted in highly dense, nanocrystalline pills with strong electrical conductivity and bright metallic gloss.

  10. Influence of temperature and atmosphere on the strength and elastic modulus of solid oxide fuel cell anode supports

    DEFF Research Database (Denmark)

    Ni, De Wei; Charlas, Benoit; Kwok, Kawai;

    2016-01-01

    Solid Oxide Fuel Cells are subjected to significant stresses during production and operation. The various stress-generating conditions impose strength requirements on the cell components, and thus the mechanical properties of the critical load bearing materials at relevant operational conditions ...

  11. Damage of polyesters by the atmospheric free radical oxidant NO3 (•): a product study involving model systems.

    Science.gov (United States)

    Goeschen, Catrin; Wille, Uta

    2013-01-01

    Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO3 (•) in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed 'hot spots' in polyesters that are particularly vulnerable to attack by NO3 (•) and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions.

  12. Damage of polyesters by the atmospheric free radical oxidant NO3•: a product study involving model systems

    Directory of Open Access Journals (Sweden)

    Catrin Goeschen

    2013-09-01

    Full Text Available Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO3• in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed ‘hot spots’ in polyesters that are particularly vulnerable to attack by NO3• and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions.

  13. Effect of high-oxygen atmosphere packaging on oxidative stability and sensory quality of two chicken muscles during chill storage

    DEFF Research Database (Denmark)

    Jongberg, Sisse; Wen, Jinzhu; Tørngren, Mari Ann;

    2014-01-01

    of secondary lipid oxidation products. However, while breast stored in MAP-O clearly scored lower in tenderness and higher in rancidity compared to breast in non-oxygen storage, the effect of MAP-O for the sensory quality of thigh was negligible. These results show that thigh is more suitable for storage...

  14. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2005-01-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature have been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and, where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  15. Development of a detailed chemical mechanism (MCMv3.1 for the atmospheric oxidation of aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    C. Bloss

    2004-09-01

    Full Text Available The Master Chemical Mechanism has been updated from MCMv3 to MCMv3.1 in order to take into account recent improvements in the understanding of aromatic photo-oxidation. Newly available kinetic and product data from the literature has been incorporated into the mechanism. In particular, the degradation mechanisms for hydroxyarenes have been revised following the observation of high yields of ring-retained products, and product studies of aromatic oxidation under relatively low NOx conditions have provided new information on the branching ratios to first generation products. Experiments have been carried out at the European Photoreactor (EUPHORE to investigate key subsets of the toluene system. These results have been used to test our understanding of toluene oxidation, and where possible, refine the degradation mechanisms. The evaluation of MCMv3 and MCMv3.1 using data on benzene, toluene, p-xylene and 1,3,5-trimethylbenzene photosmog systems is described in a companion paper, and significant model shortcomings are identified. Ideas for additional modifications to the mechanisms, and for future experiments to further our knowledge of the details of aromatic photo-oxidation are discussed.

  16. Investigation of the influence of inert and oxidizing atmospheres on the efficiency of decomposition of waste printed circuit boards (WPCBs)

    Science.gov (United States)

    Kumari, Anjan; Jha, Manis Kumar; Singh, Rajendra Prasad; Ranganathan, S.

    2016-08-01

    Thermo-gravimetry was used for studying the influence of the furnace atmosphere during the pyrolysis waste circuit boards (WPCBs). Pyrolysis in argon atmosphere resulted in a continuous decrease of mass of the sample. Rapid mass loss occurred at about 573 K. Heating the WPCBs in air and oxygen atmospheres resulted in an increase in the mass of the sample in the early stages until rapid mass loss occurred at about 573 K. When pyrolysis of larger sample mass (about 5 g each) was carried out in tubular furnace, about 20.43 % mass loss was observed during the pyrolysis of WPCBs in a flowing stream of argon at 548 K during a period of 4 min. On the other hand, a maximum of about 2.26 % mass loss was recorded when the WPCBs were heated at about 600 K for the same time interval in the still air. The mass transfer during the pyrolysis of WPCBs in flowing stream of inert gas was also modeled. It is found that controlling the flow rate of inert gas and the geometry of the equipment can enhance the rate of mass loss significantly.

  17. Atmospheric fate of OH initiated oxidation of terpenes. Reaction mechanism of alpha-pinene degradation and secondary organic aerosol formation.

    Science.gov (United States)

    Librando, Vito; Tringali, Giuseppe

    2005-05-01

    This paper studies the reaction products of alpha-pinene, beta-pinene, sabinene, 3-carene and limonene with OH radicals and of alpha-pinene with ozone using FT-IR spectroscopy for measuring gas phase products and HPLC-MS-MS to measure products in the aerosol phase. These techniques were used to investigate the secondary organic aerosol (SOA) formation from the terpenes. The gas phase reaction products were all quantified using reference compounds. At low terpene concentrations (0.9-2.1 ppm), the molar yields of gas phase reaction products were: HCHO 16-92%, HCOOH 10-54% (OH source: H2O2, 6-25 ppm); HCHO 127-148%, HCOOH 4-6% (OH source: CH3ONO, 5-8 ppm). At high terpene concentrations (4.1-13.2 ppm) the results were: HCHO 9-27%, HCOOH 15-23%, CH3(CO)CH3 0-14%, CH3COOH 0-5%, nopinone 24% (only from beta-pinene oxidation), limona ketone 61% (only from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source H2O2, 23-30 ppm); HCHO 76-183%, HCOOH 12-15%, CH3(CO)CH3 0-12%, nopinone 17% (from beta-pinene oxidation), limona ketone 48% (from limonene oxidation), pinonaldehyde was identified during alpha-pinene degradation (OH source CH3ONO, 14-16 ppm). Pinic acid, pinonic acid, limonic acid, limoninic acid, 3-caric acid, 3-caronic acid and sabinic acid were identified in the aerosol phase. On the basis of these results, we propose a formation mechanism for pinonic and pinic acid in the aerosol phase explaining how degradation products could influence SOA formation and growth in the troposphere.

  18. Influence of thermal treatment in N{sub 2} atmosphere on chemical, microstructural and optical properties of indium tin oxide and nitrogen doped indium tin oxide rf-sputtered thin films

    Energy Technology Data Exchange (ETDEWEB)

    Stroescu, H.; Anastasescu, M.; Preda, S.; Nicolescu, M.; Stoica, M. [Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania); Stefan, N. [National Institute for Lasers, Plasma and Radiation Physics, Atomistilor 409, RO-77125, Bucharest-Magurele (Romania); Kampylafka, V.; Aperathitis, E. [FORTH-IESL, Crete (Greece); Modreanu, M. [Tyndall National Institute, University College Cork, Cork (Ireland); Zaharescu, M. [Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania); Gartner, M., E-mail: mgartner@icf.ro [Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy, Spl. Independentei 202, 060021 Bucharest (Romania)

    2013-08-31

    We report the influence of the normal thermal treatment (TT) and of rapid thermal annealing (RTA) on the microstructural, optical and electrical properties of indium tin oxide (ITO) and nitrogen doped indium tin oxide (ITO:N) thin films. The TT was carried out for 1 h at 400 °C and the RTA for 1 min up to 400 °C, both in N{sub 2} atmosphere. The ITO and ITO:N films were deposited by reactive sputtering in Argon, and respectively Nitrogen plasma, on Si with (100) and (111) orientation. The present study brings data about the microstructural and optical properties of ITO thin films with thicknesses around 300–400 nm. Atomic Force Microscopy analysis showed the formation of continuous and homogeneous films, fully covered by quasi-spherical shaped particles, with higher roughness values on Si(100) as compared to Si(111). Spectroscopic ellipsometry allowed the determination of film thickness, optical band gap as well as of the dispersion curves of n and k optical constants. X-ray diffraction analysis revealed the presence of diffraction peaks corresponding to the same nominal bulk composition of ITO, but with different intensities and preferential orientation depending on the substrate, atmosphere of deposition and type of thermal treatment. - Highlights: ► Stability of the films can be monitored by experimental ellipsometric spectra. ► The refractive index of indium tin oxide film on 0.3–30 μm range is reported. ► Si(100) substrate induces rougher film surfaces than Si(111). ► Rapid thermal annealing and normal thermal treatment lead to stable conductive film. ► The samples have a higher preferential orientation after rapid thermal annealing.

  19. Degradation of polyethylene induced by plasma in oxidizing atmospheres; Degradacion de polietileno inducido por plasma en atmosferas oxidantes

    Energy Technology Data Exchange (ETDEWEB)

    Colin, E.; Olayo, M.G.; Cruz, G.J. [Facultad de Quimica, UAEM, Av. Tollocan y Colon, 50000 Toluca (Mexico)

    2002-07-01

    The garbage of polyethylene is not easily degradable in normal environmental conditions . The indiscriminate use of this polymer and the enormous quantity of garbage which is generated carries a damage to the environment due to its long life as waste. The objective of this work is to study the conditions in which can be carried out the degradation of polyethylene. A form of accelerating the degradation is exposing it to plasma with reactive atmospheres. In this work a study of surface modification of polyethylene by plasmas with discharges of direct current of oxygen and nitrogen is presented. (Author)

  20. Atmospheric Chemistry of cis-CF3CH=CHF: Kinetics of reactions with OH radicals and O3 and products of OH radical initiated oxidation

    DEFF Research Database (Denmark)

    Nilsson, Elna Johanna Kristina; Nielsen, Ole John; Johnson, Matthew Stanley

    2009-01-01

    Long path length FTIR-smog chamber techniques were used to measure k(OH + cis-CF3CH@CHF) = (1.20 ± 0.14) 1012 and k(O3 + cis-CF3CH@CHF) = (1.65 ± 0.16) 1021 cm3 molecule 1 s1 in 700 Torr of N2/O2 diluent at 296 K. The OH initiated oxidation of cis-CF3CH@CHF gives CF3CHO and HCOF in molar yields...... which are indistinguishable from 100%. The atmospheric lifetime of cis-CF3CH@CHF is determined by its reaction with OH and is approximately 10 days. cis-CF3CH@CHF has an integrated IR absorption cross section (600–2000 cm1) of (1.71 ± 0.09) 1016 cm molecule1 and a global warming potential...

  1. Microbial ecology of á-Proteobacteria ammonia-oxidizers along a concentration gradient of dry atmospheric nitrogen deposition in the San Bernadino Mountain Range.

    Science.gov (United States)

    Jordan, F. L.; Fenn, M. E.; Stein, L. Y.

    2002-12-01

    The fate of atmospherically-deposited nitrogen from industrial pollution is of major concern in the montane ecosystems bordering the South Coast California Air Basin. Nitrogen deposition rates in the more exposed regions of the San Bernardino Mountains (SBM) are among the highest in North America often exceeding 40 kg ha-1 year-1 in throughfall deposition of nitrate and ammonium (Fenn and Poth, 1999). Forest ecosystems with elevated N deposition generally exhibit elevated accumulation of soil nitrate, leaching and runoff, elevated emissions of nitrogenous gases, increased nitrification, and decreased litter decomposition rates. The role of nitrifying microbial populations, especially those taxonomically associated with the beta-Proteobacteria ammonia-oxidizers (AOB), will provide insight into nitrogen-cycling in these extremely N-saturated environments. Using 16S ribosomal DNA-based molecular techniques (16S rDNA clone library construction and Restriction Fragment Length Polymorphism), we are comparing AOB community diversity at 3 different locations along a natural atmospheric N-deposition concentration gradient in the SBM: from high at Camp Paviaka (CP), medium at Strawberry Peak (SP) to low at Dogwood (DW). As observed for wet N-deposition systems on the east coast, we hypothesized a negative correlation between AOB community diversity, abundance and function with nitrogen loading in the dry N deposition system of SBM. Nitrification potentials determined for the 3 sites along the N-deposition gradient were in the order of CP less than SP less than DW. Preliminary results indicate no correlation between diversity of AOB and increased nitrogen loading. Shannon-Weiner diversity indices calculated for ammonia-oxidizer RFLP group units were 2.22, 2.66 and 1.80 for CP, SP and DW, respectively.

  2. UV absorption cross sections of nitrous oxide (N2O and carbon tetrachloride (CCl4 between 210 and 350 K and the atmospheric implications

    Directory of Open Access Journals (Sweden)

    C. H. Jackman

    2010-07-01

    Full Text Available Absorption cross sections of nitrous oxide (N2O and carbon tetrachloride (CCl4 are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm at temperatures in the range 210–350 K. In addition, UV absorption spectra of CCl4 are reported between 200–235 nm as a function of temperature (225–350 K. The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5–7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in atmospheric model calculations is presented.

  3. UV absorption cross sections of nitrous oxide (N2O and carbon tetrachloride (CCl4 between 210 and 350 K and the atmospheric implications

    Directory of Open Access Journals (Sweden)

    C. H. Jackman

    2010-04-01

    Full Text Available Absorption cross sections of nitrous oxide (N2O and carbon tetrachloride (CCl4 are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm at temperatures in the range 210–350 K. In addition, UV absorption spectra of CCl4 are reported between 200–235 nm as a function of temperature (225–350 K. The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5–7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in atmospheric model calculations is presented.

  4. Section i: Thermodynamic Properties of Hydrocarbon Radicals, Peroxy Hydrocarbon and Peroxy Chlorohydrocarbon Molecules and Radicals. Section II. Kinetics and Reaction Mechanisms For: (1) Chloroform Pyrolysis and Oxidation; (2) Benzene and Toluene Oxidation Under Atmospheric Conditions.

    Science.gov (United States)

    Lay, Tsan-Horng

    1995-01-01

    Alkyl radicals are important active intermediates in gas phase photochemistry and combustion reaction systems. With the exception of a limited number of the most elementary radicals, accurate thermodynamic properties of alkyl radicals are either not available or only rough estimations exist. An H atom Bond Increment approach is developed and a data base is derived, for accurately estimating thermodynamic properties (Delta H_{f }^circ298, S ^circ298 and Cp(T)) for generic classes of hydrocarbon radical species. Reactions of alkyl radicals with molecular oxygen are one of the major reaction paths for these radicals in atmospheric photochemistry, oxidation of hydrocarbon liquids and combustion process. Alkyl hydroperoxides are subsequently formed through the alkyl peroxy radicals reactions with varied chemical species present in the reaction system. Thermodynamic properties of the alkyl hydroperoxides and related radicals are therefore frequently required in gas phase modeling and kinetic studies on these systems. The thermodynamic properties of alkyl hydroperoxides, alkyl peroxy radicals and hydroperoxyl-1-ethyl radicals including the species with fluorine and chlorine substituents on the alpha-carbon are evaluated using molecular orbital calculations. Chloroform is used as a model chlorocarbon system with high Cl/H ratio to investigate thermal decomposition processes of chlorocarbons in oxidative and pyrolytic reaction environments. A detailed reaction mechanism is developed to describe the important features of products and reagent loss and is shown to predict the experimental data well. Reaction pathways and rate constants are developed for CCl _3, CCl_2 and rm C_2Cl_3 radical addition to O_2 and combination with O, OH HO_2 and ClO. The reversible addition reaction of OH radical with benzene to form the hydroxyl-2,4-cyclohexadienyl (benzene -OH) adduct and the subsequent reactions of this benzene -OH adduct with O_2 are important initial steps for the

  5. Atmospheric pressure plasma jet treatment evokes transient oxidative stress in HaCaT keratinocytes and influences cell physiology.

    Science.gov (United States)

    Wende, Kristian; Straßenburg, Susanne; Haertel, Beate; Harms, Manuela; Holtz, Sarah; Barton, Annemarie; Masur, Kai; von Woedtke, Thomas; Lindequist, Ulrike

    2014-04-01

    Modern non-thermal atmospheric pressure plasma sources enable controllable interaction with biological systems. Their future applications - e.g. wound management - are based on their unique mixture of reactive components sparking both stimulatory as well as inhibitory processes. To gain detailed understanding of plasma-cell interaction and with respect to risk awareness, key mechanisms need to be identified. This study focuses on the impact of an argon non-thermal atmospheric pressure plasma jet (kINPen 09) on human HaCaT keratinocytes. With increasing duration, cell viability decreased. In accordance, cells accumulated in G2/M phase within the following 24 h. DNA single-strand breaks were detected immediately after treatment and receded in the aftermath, returning to control levels after 24 h. No directly plasma-related DNA double-strand breaks were detected over the same time. Concurrently, DNA synthesis decreased. Coincident with treatment time, an increase in intracellular 2',7'-dichlorodihydrofluorescein diacetate (H(2)DCFDA) conversion increased reactive oxygen species (ROS) levels. The radical scavenging activity of culture medium crucially influenced these effects. Thus, ROS changed DNA integrity, and the effectiveness of cellular defence mechanisms characterises the interaction of non-thermal plasma and eukaryotic cells. Effects were time-dependent, indicating an active response of the eukaryotic cells. Hence, a stimulation of eukaryotic cells using short-term non-thermal plasma treatment seems possible, eg in the context of chronic wound care. Long-term plasma treatments stopped in cell proliferation and apoptosis, which might be relevant in controlling neoplastic conditions.

  6. Tensile Strength and Oxide Analysis of Carbon Steel in Concrete Exposed in Atmospheric Environment for 53 Years

    Institute of Scientific and Technical Information of China (English)

    FENG Xingguo; LU Xiangyu; ZUO Yu; CHEN Da; SU Xiaodong

    2015-01-01

    The tensile strength of a corroded rebar in a 53-year-old concrete structure was studied. The microstructure of the metallic substrate, the fracture surface, and the corrosion product layers were investigated. Metallographic observation results showed that the carbon steel was constituted of ferrite and some pearlite. The tensile test results indicated that the corroded rebar presented low strength and elongation. In addition, the fracture surface of the rebar in the tensile test displayed dimple fracture behavior. The Raman spectroscopy results indicated that corrosion products at the general corrosion zone were obviously different from those at the localized corrosion zone. The rust layer at the general corrosion zone was composed of goethite (α-FeOOH), magnetite (Fe3O4), and hematite (α-Fe2O3), while that of the pitting zone was made of feroxyhyte (δ-FeOOH), goethite (α-FeOOH), and hematite (α-Fe2O3). However, the general tendencies that the corrosion products were constituted of a mix of oxides and hydroxides, the oxides mainly existed in the internal part and the hydroxides more presented in the external layer were observed.

  7. Effects of atmospheric-pressure non-thermal bio-compatible plasma and plasma activated nitric oxide water on cervical cancer cells

    Science.gov (United States)

    Li, Ying; Ho Kang, Min; Sup Uhm, Han; Joon Lee, Geon; Ha Choi, Eun; Han, Ihn

    2017-01-01

    Atmospheric-pressure non-thermal bio-compatible plasma is a partially ionized gas with electrically charged particles. Previous studies demonstrated that dielectric barrier discharge (DBD) plasma could induce apoptosis of various cancer cells, in particular demonstrating the selective cytotoxicity of cancer cells over normal cells. Therefore, DBD plasma can be considered as a potential cancer treatment method for clinical applications. We previously developed a microwave jet plasma system, producing nitric oxide called nitric oxide-plasma activated water (NO-PAW). In this study, we explored the effects of NO-PAW on a cervical cancer cell line, in comparison with DBD plasma. The cytotoxicity results showed that the treatment of HeLa cell with DBD for 4 minutes and 7 μM concentration of NO-PAW could reach almost IC60. For the apoptosis assay, 4 minutes treatment of DBD could induce 7% apoptotic effect, whereas 7 μM NO-PAW could induce 18% apoptotic effect. In addition, we assumed that both DBD plasma and NO-PAW could induce HeLa cell apoptosis by facilitating an accumulation of intracellular reactive oxygen and nitrogen species (RONS). Although further detail on the molecular signal pathway is still needed, DBD and NO-PAW could become promising applications for effective and safe clinical trials for cancer therapy. PMID:28361987

  8. Degradation of cationic red GTL by catalytic wet air oxidation over Mo-Zn-Al-O catalyst under room temperature and atmospheric pressure.

    Science.gov (United States)

    Xu, Yin; Li, Xiaoyi; Cheng, Xiang; Sun, Dezhi; Wang, Xueye

    2012-03-06

    To overcome the drawback of catalytic wet air oxidation (CWAO) with high temperature and high pressure, the catalytic activity of Mo-Zn-Al-O catalyst for degradation of cationic red GTL under room temperature and atmospheric pressure was investigated. Mo-Zn-Al-O catalyst was prepared by coprecipitation and impregnation. XRD, TG-DTG, and XPS were used to characterize the resulting sample. Central composition design using response surface methodology was employed to optimize correlation of factors on the decolorization of cationic red GTL. The results show that the optimal conditions of pH value, initial concentration of dye and catalyst dosage were found to be 4.0, 85 mg/L and 2.72 g/L, respectively, for maximum decolorization of 80.1% and TOC removal of 50.9%. Furthermore, the reaction on the Mo-Zn-Al-O catalyst and degradation mechanism of cationic red GTL was studied by Electron spin resonance (ESR) and GC-MS technique. The possible reaction mechanism was that the Mo-Zn-Al-O catalyst can efficiently react with adsorbed oxygen/H(2)O to produce ·OH and (1)O(2) and finally induce the degradation of cationic red GTL. GC-MS analysis of the degradation products indicates that cationic red GTL was initiated by the cleavage of -N ═ N- and the intermediates were further oxidized by ·OH or (1)O(2).

  9. Effects of atmospheric-pressure non-thermal bio-compatible plasma and plasma activated nitric oxide water on cervical cancer cells.

    Science.gov (United States)

    Li, Ying; Ho Kang, Min; Sup Uhm, Han; Joon Lee, Geon; Ha Choi, Eun; Han, Ihn

    2017-03-31

    Atmospheric-pressure non-thermal bio-compatible plasma is a partially ionized gas with electrically charged particles. Previous studies demonstrated that dielectric barrier discharge (DBD) plasma could induce apoptosis of various cancer cells, in particular demonstrating the selective cytotoxicity of cancer cells over normal cells. Therefore, DBD plasma can be considered as a potential cancer treatment method for clinical applications. We previously developed a microwave jet plasma system, producing nitric oxide called nitric oxide-plasma activated water (NO-PAW). In this study, we explored the effects of NO-PAW on a cervical cancer cell line, in comparison with DBD plasma. The cytotoxicity results showed that the treatment of HeLa cell with DBD for 4 minutes and 7 μM concentration of NO-PAW could reach almost IC60. For the apoptosis assay, 4 minutes treatment of DBD could induce 7% apoptotic effect, whereas 7 μM NO-PAW could induce 18% apoptotic effect. In addition, we assumed that both DBD plasma and NO-PAW could induce HeLa cell apoptosis by facilitating an accumulation of intracellular reactive oxygen and nitrogen species (RONS). Although further detail on the molecular signal pathway is still needed, DBD and NO-PAW could become promising applications for effective and safe clinical trials for cancer therapy.

  10. Strong metal-support interaction in novel core-shell Au-CeO2 nanostructures induced by different pretreatment atmospheres and its influence on CO oxidation.

    Science.gov (United States)

    Wang, Zhihua; Fu, Huifen; Tian, Ziwei; Han, Dongmei; Gu, Fubo

    2016-03-21

    Yolk-shell Au/CeO2 (Y-Au/CeO2) and encapsulated Au/CeO2 (E-Au/CeO2) nanocatalysts were prepared by using silica templates. A strong metal-support interaction (SMSI) in the Au/CeO2 nanostructures induced by different pretreatment atmospheres and its influence on CO oxidation were studied. E-Au/CeO2 pretreated in O2 had the best performance, followed by Y-Au/CeO2 pretreated in O2, Y-Au/CeO2 pretreated in H2, and E-Au/CeO2 pretreated in H2. The reasons for the different activities were discussed. There were two kinds of strong metal-support interactions (SMSI) between Au and CeO2 termed as R-SMSI (pretreated in reductive atmosphere) and O-SMSI (pretreated in oxidation atmosphere). Because of the smaller size of the Au and the larger contact area, both the R-SMSI and O-SMSI of E-Au/CeO2 were larger than those of Y-Au/CeO2. The O-SMSI was accompanied by the formation of cationic Au species that were beneficial to the enhancing of activity. As expected, the activity of E-Au/CeO2 pretreated in O2 with a Au size less than 5 nm was higher than that of Y-Au/CeO2 pretreated in O2 with 25 nm Au. However, it is surprisingly found that the activity of Y-Au/CeO2 pretreated in H2 with 25 nm Au was higher than that of E-Au/CeO2 pretreated in H2 with a Au size less than 5 nm. R-SMSI resulted in the formation of a AuCe alloy that had a negative effect on the activity. Compared with E-Au/CeO2 pretreated in H2, Y-Au/CeO2 pretreated in H2 exhibited a smaller relative content of the AuCe alloy, leading to a better activity of Y-Au/CeO2 pretreated in H2.

  11. OH Oxidation of α-Pinene in the Atmosphere Simulation Chamber SAPHIR: Investigation of the Role of Pinonaldehyde Photolysis as an HO2 Source

    Science.gov (United States)

    Kaminski, M.; Acir, I. H.; Bohn, B.; Dorn, H. P.; Fuchs, H.; Häseler, R.; Hofzumahaus, A.; Li, X.; Rohrer, F.; Tillmann, R.; Wegener, R.; Kiendler-Scharr, A.; Wahner, A.

    2015-12-01

    About one third of the land surface is covered by forests, emitting approximately 75% of the total biogenic volatile organic compounds (BVOCs). The main atmospheric sink of these BVOCs during daytime is the oxidation by the hydroxyl radical (OH). Over the last decades field campaigns investigating the radical chemistry in forested regions showed that atmospheric chemistry models are often not able to describe the measured OH concentration well. At low NO concentrations and an OH reactivity dominated by BVOCs the OH was underestimated. This discrepancy could only partly be explained by the discovery of new OH regeneration pathways in the isoprene oxidation mechanism. Field campaigns in the U.S.A and Finland (Kim 2013 ACP, Hens 2014 ACP) demonstrated that in monoterpene (e.g. α-pinene) dominated environments model calculations also underpredict the observed HO2 and OH concentrations significantly even if the OH budget was closed by the measured OH production and destruction terms. These observations suggest the existence of an unaccounted source of HO2. One potential HO2 source in forests is the photolysis of monoterpene degradation products such as aldehydes. In the present study the photochemical degradation mechanism of α-pinene was investigated in the Jülich atmosphere simulation chamber SAPHIR. The focus of this study was in particular on the investigation of the role of pinonaldehyde, a main first generation product of α-pinene, as a possible HO2 source. For that purpose the pinonaldehyde yields of the reaction α-pinene + OH were determined at ambient monoterpene concentrations (<5 ppb) under low NOx as well as high NOx conditions. The pinonaldehyde yield under high NOx conditions (30.5 %) is in agreement with literature values of Wisthaler (2001 AE) and Aschmann (2002 JGR), under low NOx conditions the yield (10.8 %) is approximately a factor of three lower than the value published by Eddingsaas (2012 ACP). In a second set of experiments the photolysis

  12. Inductively coupled plasma torch efficiency at atmospheric pressure for organo-chlorine liquid waste removal: chloroform destruction in oxidative conditions.

    Science.gov (United States)

    Kamgang-Youbi, Georges; Poizot, Karine; Lemont, Florent

    2013-01-15

    The performance of a plasma reactor for the degradation of chlorinated hydrocarbon waste is reported. Chloroform was used as a target for a recently patented destruction process based using an inductive plasma torch. Liquid waste was directly injected axially into the argon plasma with a supplied power of ~4kW in the presence of oxygen as oxidant and carrier gas. Decomposition was performed at CHCl(3) feed rates up to 400 g h(-1) with different oxygen/waste molar ratios, chloroform destruction was obtained with at least 99% efficiency and the energy efficiency reached 100 g kWh(-1). The conversion end products were identified and assayed by online FTIR spectroscopy (CO(2), HCl and H(2)O) and redox titration (Cl(2)). Considering phosgene as representative of toxic compounds, only very small quantities of toxics were released (mineral salts, hence, only CO(2) and H(2)O have been found in the final off-gases composition.

  13. NATURAL ANTIOXIDANT INGREDIENT FROM BY-PRODUCTS OF FRUITS

    Directory of Open Access Journals (Sweden)

    G. S. El-Baroty

    2014-01-01

    used safely in the edible oil industry and cosmetics to delay its oxidation. It can be applied in other food industries as a natural antioxidant instead of synthetic antioxidants. Further study should be carried out to identify the predominant phenolics responsible for the antioxidant activity of by product extracts.

  14. Inductively coupled plasma torch efficiency at atmospheric pressure for organo-chlorine liquid waste removal: Chloroform destruction in oxidative conditions

    Energy Technology Data Exchange (ETDEWEB)

    Kamgang-Youbi, Georges, E-mail: kamyougeo@yahoo.fr [French Atomic Commission-CEA, Marcoule-DTCD/SCDV/LPIC, BP 17171, 30207 Bagnols-Sur-Cèze Cedex (France); Department of Inorganic Chemistry, The University of Yaounde I, P.O Box, 812 Yaounde (Cameroon); Poizot, Karine; Lemont, Florent [French Atomic Commission-CEA, Marcoule-DTCD/SCDV/LPIC, BP 17171, 30207 Bagnols-Sur-Cèze Cedex (France)

    2013-01-15

    Highlights: ► Inductively plasma torch is used for the decomposition of organochlorine molecule. ► We examine the impact of liquid water substitution by oxygen gas as oxidant. ► Complete and safe decomposition is achieved with the presence of oxygen. ► The energy efficiency and capabilities of process are better with O{sub 2} than H{sub 2}O. -- Abstract: The performance of a plasma reactor for the degradation of chlorinated hydrocarbon waste is reported. Chloroform was used as a target for a recently patented destruction process based using an inductive plasma torch. Liquid waste was directly injected axially into the argon plasma with a supplied power of ∼4 kW in the presence of oxygen as oxidant and carrier gas. Decomposition was performed at CHCl{sub 3} feed rates up to 400 g h{sup −1} with different oxygen/waste molar ratios, chloroform destruction was obtained with at least 99% efficiency and the energy efficiency reached 100 g kWh{sup −1}. The conversion end products were identified and assayed by online FTIR spectroscopy (CO{sub 2}, HCl and H{sub 2}O) and redox titration (Cl{sub 2}). Considering phosgene as representative of toxic compounds, only very small quantities of toxics were released (<1 g h{sup −1}) even with high waste feed rates. The experimental results were very close to the equilibrium composition predicted by thermodynamic calculations. At the bottom of the reactor, the chlorinated acids were successfully trapped in a scrubber and transformed into mineral salts, hence, only CO{sub 2} and H{sub 2}O have been found in the final off-gases composition.

  15. Preparation of nitrogen doped silicon oxides thin films by plasma polymerization of 3-aminopropyltriethoxylsilane using atmospheric pressure plasma jet

    Science.gov (United States)

    Lin, Yu-Chun; Wang, Meng-Jiy

    2016-01-01

    Surface modification techniques have been applied in various applications including self-cleaning surface, antibacterial filter, and biomaterials. In this study we employed the atmospheric pressure plasma jet (APPJ) deposition, a dry process for surface modification, to deposit 3-aminopropyltriethoxylsilane (APTES) on stainless steel (SS) on the purposes of simultaneously incorporating SiOx and nitrogen containing functionalities for the modulation of biofunctionality. The APPJ deposition allowed to form a thin layer of APTES with linear growth rate by controlling the deposition time. In addition, the surface chemical and physical properties, such as surface chemical composition, wettability, film thickness, and interactions with mammalian cells were evaluated by using different analytical methods. The results showed that the surface wettability was improved significantly due to the APTES deposition along with the increase of the incorporated nitrogen content. Moreover, the viability of L-929 fibroblasts was clearly promoted on the APTES deposited SS, which is most probably due to the thicker deposited films and higher density of nitrogen-containing functional groups. The outcomes of this research showed great potential to apply on metallic substrates in real time for biomedical related applications.

  16. Computational study on the mechanisms and rate constants of the OH-initiated oxidation of ethyl vinyl ether in atmosphere.

    Science.gov (United States)

    Han, Dandan; Cao, Haijie; Li, Jing; Li, Mingyue; He, Maoxia; Hu, Jingtian

    2014-09-01

    The hydroxylation reactions of ethyl vinyl ether (EVE) in the present of O2 and NO are analyzed by using MPWB1K/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of theory. According to the calculated thermodynamic data, the detailed reaction mechanisms of EVE and OH are proposed. All of the ten possible reaction pathways are discussed. The major products of the title reaction are ethyl formate and formaldehyde, which is in accordance with experimental detection. The rate constants of the primary reactions over the temperature of 250-400K and the pressure range of 100-2000Torr are computed by employing MESMER program. At 298K and 760Torr, OH-addition channels are predominate and the total rate constant is ktot=4.53×10(-11)cm(3)molecule(-1)s(-1). The Arrhenius equation is obtained as ktot=6.27×10(-12)exp(611.5/T), according to the rate constants given at different temperatures. Finally, the atmospheric half life of EVE with respect to OH is estimated to be 2.13h.

  17. Research in Physical Chemistry and Chemical Education: Part A--Water Mediated Chemistry of Oxidized Atmospheric Compounds Part B--The Development of Surveying Tools to Determine How Effective Laboratory Experiments Contribute to Student Conceptual Understanding

    Science.gov (United States)

    Maron, Marta Katarzyna

    2011-01-01

    This dissertation is a combination of two research areas, experimental physical chemistry, Chapters I to V, and chemical education, Chapters VI to VII. Chapters I to V describe research on the water-mediated chemistry of oxidized atmospheric molecules and the impact that water has on the spectra of these environmental systems. The role of water…

  18. Kinetics of and atmospheric effects on gallium removal from a CeO{sub 2} based mixed oxide surrogate

    Energy Technology Data Exchange (ETDEWEB)

    Park, Y.S.; Taylor, T.N.; Atencio, A.; Butt, D.P.

    1998-12-31

    This paper describes preliminary experimental results on the kinetics of Ga removal from Ga{sub 2}O{sub 3}-doped CeO{sub 2{minus}x}, a surrogate for weapons grade PuO{sub 2{minus}x}. Ga is removed from the surrogate feedstock material using thermal techniques. An Ar-6% H{sub 2} gas was used in order to reduce the oxide to gaseous Ga{sub 2}O. Experiments were done in the temperature range of 600--1,200 C as a function of time, gas flow rate, and sample geometry. Samples were analyzed through measurements of weight change, scanning electron microscopy/energy dispersive spectroscopy, x-ray photoelectron spectroscopy, proton induced x-ray emission, and direct current plasma analysis. Gallium levels were reduced by as much as 98% (130 ppm Ga residue) of that in the starting material. Studies to date have shown CeO{sub 2{minus}x} is a very good surrogate for PuO{sub 2{minus}x}.

  19. Cements containing by-product gypsum

    Energy Technology Data Exchange (ETDEWEB)

    Bensted, J. [University of Greenwich, London (United Kingdom). School of Biological and Chemical Sciences

    1995-12-31

    Chemical by-product gypsum can readily replace natural gypsum in Portland cements and in blended cements like Portland pfa cement and Portland blast furnace cement without technical detriment in many instances. Indeed, sometimes the technical performance of the cement can be enhanced. The hydration chemistry is often changed, in that where there is at least some retardation of setting, more AFT phase (ettringite) is formed during early hydration at the expense of calcium silicate hydrates. By-product gypsum can also replace natural gypsum in speciality products like calcium aluminate cement-Portland cement mixes for producing quick setting cements and in calcium sulphoaluminate-type expansive cements. However, by-products gypsum have proved to be less successful for utilization in API Classes of oilwell cements, because of the greater difficulty in obtaining batch-to-batch consistency in properties like thickening time and slurry rheology. 11 refs., 3 figs., 5 tabs.

  20. Effects on surface atmospheric photo-oxidants over Greece during the total solar eclipse event of 29 March 2006

    Directory of Open Access Journals (Sweden)

    P. Zanis

    2007-08-01

    Full Text Available This study investigates the effects of the total solar eclipse of 29 March 2006 on surface air-quality levels over Greece based on observations at a number of sites in conjunction with chemical box modelling and 3-D air-quality modelling. Emphasis is given on surface ozone and other photooxidants at four Greek sites Kastelorizo, Finokalia (Crete, Pallini (Athens and Thessaloniki, which are located at gradually increasing distances from the path of the eclipse totality and are characterized by different air pollution levels. The eclipse offered the opportunity to test our understanding of air pollution build-up and the response of the gas-phase chemistry of photo-oxidants during a photolytical perturbation using both a photochemical box model and a regional air-quality offline model based on the modeling system WRF/CAMx. At the relatively unpolluted sites of Kastelorizo and Finokalia no clear impact of the solar eclipse on surface O3, NO2 and NO concentrations can be deduced from the observations and model simulations as the calculated changes in net ozone production rates between eclipse and non eclipse conditions are rather small compared to the ozone variability and hence the solar eclipse effects on ozone can be easily masked by transport. At the polluted sites of Thessaloniki and Pallini, the solar eclipse effects on O3, NO2 and NO concentrations are clearly revealed from both the measurements and 3-D air-quality modeling with the net effect being a decrease in O3 and NO and an increase in NO2 as NO2 formed from the reaction of O3 with NO while at the same time NO2 is not efficiently photolysed. It is evident from the 3-D air quality modeling over Greece that the maximum effects of the eclipse on O3, NO2 and NO are reflected at the large urban agglomerations of Athens, and Thessaloniki where the maximum of the emissions

  1. Effects on surface atmospheric photo-oxidants over Greece during the total solar eclipse event of 29 March 2006

    Directory of Open Access Journals (Sweden)

    P. Zanis

    2007-12-01

    Full Text Available This study investigates the effects of the total solar eclipse of 29 March 2006 on surface air-quality levels over Greece based on observations at a number of sites in conjunction with chemical box modelling and 3-D air-quality modelling. Emphasis is given on surface ozone and other photooxidants at four Greek sites Kastelorizo, Finokalia (Crete, Pallini (Athens and Thessaloniki, which are located at gradually increasing distances from the path of the eclipse totality and are characterized by different air pollution levels. The eclipse offered the opportunity to test our understanding of air pollution build-up and the response of the gas-phase chemistry of photo-oxidants during a photolytical perturbation using both a photochemical box model and a regional air-quality offline model based on the modeling system WRF/CAMx. At the relatively unpolluted sites of Kastelorizo and Finokalia no clear signal of the solar eclipse on surface O3, NO2 and NO concentrations can be deduced from the observations while there is no correlation of observed O3, NO2 and NO with observed global radiation. The box and regional model simulations for the two relatively unpolluted sites indicate that the calculated changes in net ozone production rates between eclipse and non eclipse conditions are rather small compared to the observed short-term ozone variability. Furthermore the simulated ozone lifetime is in the range of a few days at these sites and hence the solar eclipse effects on ozone can be easily masked by local and regional transport. At the polluted sites of Thessaloniki and Pallini, the solar eclipse effects on O3, NO2 and NO concentrations are revealed from both the measurements and modeling with the net effect being a decrease in O3 and NO and an increase in NO2 as NO2 formed from the reaction of O3 with NO while at the same time NO2 is

  2. Oxidation of SO2 by stabilized Criegee intermediate (sCI radicals as a crucial source for atmospheric sulfuric acid concentrations

    Directory of Open Access Journals (Sweden)

    M. Boy

    2013-04-01

    Full Text Available The effect of increased reaction rates of stabilized Criegee intermediates (sCIs with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012 increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO with SO2 according to the values recommended by Welz et al. (2012 increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

  3. Anaerobic digestion of slaughterhouse by-products

    DEFF Research Database (Denmark)

    Hejnfelt, Anette; Angelidaki, Irini

    2009-01-01

    giving the best results. High concentrations of long-chain fatty acids and ammonia in the by-products were found to inhibit the biogas process at concentrations higher than 5 g lipids dm(-3) and 7 gN dm(-3) respectively. Pretreatment (pasteurization: 70 degrees C, sterilization: 133 degrees C, and alkali...

  4. SO2 oxidation products other than H2SO4 as a trigger of new particle formation – Part 2: Comparison of ambient and laboratory measurements, and atmospheric implications

    Directory of Open Access Journals (Sweden)

    B. Umann

    2008-05-01

    Full Text Available Atmospheric new particle formation is generally thought to occur due to homogeneous or ion-induced nucleation of sulphuric acid. We compare ambient nucleation rates with laboratory data from nucleation experiments involving either sulphuric acid or oxidized SO2. Atmospheric nucleation occurs at H2SO4 concentrations 2–4 orders of magnitude lower than binary or ternary H2SO4 nucleation. In contrast, the atmospheric nucleation rates and H2SO4 concentrations are very well replicated in the SO2 oxidation experiments. We explain these features by the formation of free HSO5 radicals in pace with H2SO4 during the SO2 oxidation. We suggest that at temperatures above ~250 K these radicals produce nuclei of new aerosols much more efficiently than H2SO4. These nuclei are activated to further growth by H2SO4 and possibly other trace species. However, at lower temperatures the atmospheric relative acidity is high enough for the H2SO4–H2O nucleation to dominate.

  5. Capture of atmospheric CO2 into (BiO)2CO3/graphene or graphene oxide nanocomposites with enhanced photocatalytic performance

    Science.gov (United States)

    Zhang, Wendong; Dong, Fan; Zhang, Wei

    2015-12-01

    Self-assembly of (BiO)2CO3 nanoflakes on graphene (Ge) and graphene oxide (GO) nanosheets, as an effective strategy to improve the photocatalytic performance of two-dimensional (2D) nanostructured materials, were realized by a one-pot efficient capture of atmospheric CO2 at room temperature. The as-synthesized samples were characterized by XRD, SEM, TEM, XPS, UV-vis DRS, Time-resolved ns-level PL and BET-BJH measurement. The photocatalytic activity of the obtained samples was evaluated by the removal of NO at the indoor air level under simulated solar-light irradiation. Compared with pure (BiO)2CO3, (BiO)2CO3/Ge and (BiO)2CO3/GO nanocomposites exhibited enhanced photocatalytic activity due to their large surface areas and pore volume, and efficient charge separation and transfer. The present work could provide a simple method to construct 2D nanocomposites by efficient utilization of CO2 in green synthetic strategy.

  6. Development, testing, and deployment of an air sampling manifold for spiking elemental and oxidized mercury during the Reno Atmospheric Mercury Intercomparison Experiment (RAMIX).

    Science.gov (United States)

    Finley, B D; Jaffe, D A; Call, K; Lyman, S; Gustin, M Sexauer; Peterson, C; Miller, M; Lyman, T

    2013-07-02

    The Reno Atmospheric Mercury Intercomparison Experiment (RAMIX) was in Reno, NV from August 22, 2011 to September 16, 2011. The goals of the experiment were to compare existing and new methods for measurements of ambient elemental and oxidized Hg, and to test these with quantitative spikes of Hg(0), HgBr2, O3 and water vapor. In this paper we describe the design, testing, and deployment of a high flow manifold system designed to deliver ambient air and spiked compounds to multiple instruments simultaneously. The manifold was constructed of 1" OD PFA tubing and heated to 115 °C for the entire active zone. Manifold flow was controlled at ∼200 LPM using a blower and a velocity sensor in a feedback control system. Permeation tubes in controlled ovens were used to deliver Hg(0) and HgBr2. Ozone was generated from a small UV lamp in a flow of high purity O2. Water vapor was generated by pumping a flow of purified N2 through heated, high purity water. The spiking delivery for Hg(0), HgBr2, O3, and water vapor after dilution in the manifold ranged up to 20 ng m(-3), 0.64 ng m(-3), 100 ppbv, and 20 g kg(-1), respectively. During laboratory tests the average transmission efficiencies for Hg(0), HgBr2, and O3 were found to be 92%, 76%, and 93%, respectively.

  7. Torsion-rotation-vibration effects in the ground and first excited states of methacrolein, a major atmospheric oxidation product of isoprene

    Energy Technology Data Exchange (ETDEWEB)

    Zakharenko, O.; Motiyenko, R. A.; Aviles Moreno, J.-R.; Huet, T. R., E-mail: Therese.Huet@univ-lille1.fr [Laboratoire de Physique des Lasers, Atomes et Molécules, UMR8523 CNRS – Université Lille 1, Bâtiment P5, F- 59655 Villeneuve d’Ascq Cedex (France); Jabri, A. [Laboratoire Inter-universitaire des Systèmes Atmosphériques, CNRS - Universités Paris Est Créteil et Paris Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil Cedex (France); Institute for Physical Chemistry, RWTH Aachen University, Aachen (Germany); Kleiner, I. [Laboratoire Inter-universitaire des Systèmes Atmosphériques, CNRS - Universités Paris Est Créteil et Paris Diderot, 61 Avenue du Général de Gaulle, 94010 Créteil Cedex (France)

    2016-01-14

    Methacrolein is a major oxidation product of isoprene emitted in the troposphere. New spectroscopy information is provided with the aim to allow unambiguous identification of this complex molecule, characterized by a large amplitude motion associated with the methyl top. State-of-the-art millimeter-wave spectroscopy experiments coupled to quantum chemical calculations have been performed. For the most stable s-trans conformer of atmospheric interest, the torsional and rotational structures have been characterized for the ground state, the first excited methyl torsional state (ν{sub 27}), and the first excited skeletal torsional state (ν{sub 26}). The inverse sequence of A and E tunneling sub-states as well as anomalous A-E splittings observed for the rotational lines of v{sub 26} = 1 state clearly indicates a coupling between methyl torsion and skeletal torsion. A comprehensive set of molecular parameters has been obtained. The far infrared spectrum of Durig et al. [Spectrochim. Acta, Part A 42, 89–103 (1986)] was reproduced, and a Fermi interaction between ν{sub 25} and 2ν{sub 27} was evidenced.

  8. Atmospheric-Pressure Plasma Jet Processed Pt-Decorated Reduced Graphene Oxides for Counter-Electrodes of Dye-Sensitized Solar Cells

    Directory of Open Access Journals (Sweden)

    Ting-Hao Wan

    2016-10-01

    Full Text Available Ultrafast atmospheric-pressure plasma jet (APPJ processed Pt-decorated reduced graphene oxides (rGOs were used as counter-electrodes in dye-sensitized solar cells (DSSCs. Pastes containing rGO, ethyl cellulose, terpineol, and chloroplatinic acid were screen-printed and sintered by nitrogen dc-pulse APPJs. Pt nanodots were uniformly distributed on the rGO flakes. When using Pt-decorated rGOs as the counter electrodes of DSSCs, the efficiency of the DSSC first increased and then decreased as the APPJ processing time increased. Nitrogen APPJs can effectively remove organic binders and can reduce chloroplatinic acid to Pt, thereby improving the efficiency of DSSCs. However, over-calcination by APPJ can damage the graphenes and degrade the DSSCs. The addition of Pt mainly improves the fill factor, which thereby increases the efficiency of DSSCs. The optimized APPJ processing time was merely 9 s owing to the vigorous interaction among the rGOs, chloroplatinic acid and nitrogen APPJs.

  9. Torrefaction of agricultural by-products: Effects of temperature and time on energy yields

    Science.gov (United States)

    Agricultural by-products, such as apple, grape, olive, and tomato pomaces as well as almond and walnut shells, were torrefied at different temperatures and times. Torrefaction of biomass involves heating in an inert atmosphere to remove volatile components for improved grindability and increased ene...

  10. Effect of oxidizing and reducing atmospheres on Ba(Ti0.90Zr0.10O3:2V ceramics as characterized by piezoresponse force microscopy

    Directory of Open Access Journals (Sweden)

    Francisco Moura

    2011-09-01

    Full Text Available The effect of annealing atmospheres (At amb, N2 and O2 on the electrical properties of Ba(Ti0.90Zr0.10O3:2V (BZT10:2V ceramics obtained by the mixed oxide method was investigated. X-ray photoelectron spectroscopy (XPS analysis indicates that oxygen vacancies present near Zr and Ti ions reduce ferroelectric properties, especially in samples treated in an ambient atmosphere (At amb. BZT10:2V ceramics sintered in a nitrogen atmosphere showed better dielectric behaviour at room temperature with a dielectric permittivity measured at a frequency of 10 kHz equal to 16800 with dielectric loss of 0.023. Piezoelectric force microscopy (PFM images reveal improvement in the piezoelectric coefficient by sintering the sample under nitrogen atmosphere. Thus, BZT10:2V ceramics sintered under a nitrogen atmosphere can be useful for practical applications which include nonvolatile digital memories, spintronics and data-storage media.

  11. Nitrous Oxide Flux

    Data.gov (United States)

    U.S. Geological Survey, Department of the Interior — Nitrous Oxide (N20) flux is the net rate of nitrous oxide exchange between an ecosystem and the atmosphere. Data of this variable were generated by the USGS...

  12. Formation of C7F15COOH (PFOA) and other perfluorocarboxylic acids during the atmospheric oxidation of 8:2 fluorotelomer alcohol

    DEFF Research Database (Denmark)

    Wallington, T. J.; Hurley, M. D.; Xia, J.;

    2006-01-01

    Calculations using a three-dimensional global atmospheric chemistry model (IMPACT) indicate that n-C8F17CH2CH2-OH (widely used in industrial and consumer products) degrades in the atmosphere to give perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs). PFOA is persistent, bio...

  13. DISINFECTION BY-PRODUCT FORMATION AND CONTROL BY OZONATION AND BIOTREATMENT

    Science.gov (United States)

    There is increasing interest in using ozone in water treatment because it is a strong disinfectant and is able to oxidize the precursors of some disinfection by-products (DBPs). However, ozonation itself produces DBPs, like aldehydes and ketones, and increases the concentration ...

  14. Effects of by-products from wet-oxidation explosion on the growth and fermentation of Saccharomyces cerevisiae%湿氧化爆破副产物对酿酒酵母的生长和发酵过程的影响

    Institute of Scientific and Technical Information of China (English)

    李小娟; 黄瑞; 张超; 李志军; 赵儒铭; 龚大春

    2013-01-01

    研究了湿氧化爆破副产物甲酸、乙酸、糠醛对酿酒酵母生长、发酵过程、糖酵解和能量代谢以及细胞膜完整性的影响.通过研究发现,酿酒酵母对于甲酸、乙酸、糠醛的最大耐受浓度分别为1.8,6.0,2.0g/L.抑制剂对酿酒酵母乙醇发酵毒性依次为甲酸>乙酸>糠醛.在1×IC80时,乙酸对酿酒酵母糖酵解和能量代谢影响最小,在2×IC80和3×IC80时,糠醛对酿酒酵母糖酵解和能量代谢影响最小,而甲酸不论在任何浓度对酿酒酵母糖酵解和能量代谢都会产生很大的影响.与乙醇相比,甲酸、乙酸、糠醛对细胞膜完整性无显著的影响,从1 ×IC80~3×IC80分别造成的镁离子百分比为11%~20%,5%~12%,4.5%~8.4%,对照物乙醇则为55%.%Effects of by-products from wet-oxidation explosion,such as formic acid,acetic acid,furfural on growth,fermentation,glycolysis,energy metabolism and cytomembrane integrality of Saccharomyces cerevisiae were studied.The results showed that the maximum tolerated concentration of S.cerevisiae was 1.8 g/L formic acid,6.0 g/L acetic acid,2.0 g/L furfural,respectively.The inhibition strengths of the inhibitors to ethanol fermentation were in the order of formic acid>acetic acid>furfural.When the concentration of inhibitors is 1 ×IC80,acetic acid has the minimum impacts on glycolysis and energy metabolism.When the concentration of inhibitors is 2×IC80,furfural has minimum impacts on glycolysis and energy metabolism.However,formic acid can inhibit strongly the glycolysis and energy metabolism of Saccharomyces cerevisiae with any concentration.When compared with ethanol,the impact of inhibitors on cytomembrane integrality of Saccharomyces cerevisiae was not very significant.When the concentration of inhibitors vary from 1 ×IC80to 3×IC80,the results is 11%~20%,5%~12% and 4.5%~8.4%,respectively.However,the result of ethanol that lead to the leak of magnesium ion is 55%.

  15. Preparation of Gold-Silver Alloy Nanoparticles Supported on NiCo2O4 Spinel Oxides for the Treatment of CO in Atmosphere.

    Science.gov (United States)

    Chinh, Vu Duc; Trung, Nguyen Quoc

    2015-06-01

    Heterometallics are an important class of catalysts. Alloy nanoparticles have higher activities than monometallic counterparts in catalysis because of the synergistic effects between the two metals. The Ni-Co composition, which is a typical alloy chemical composition, has a remarkable effect on catalytic activity. Ni-Co mixed oxides were characterized by thermal effect, X-ray diffraction, energy dispersive X-ray spectroscopy, Scanning Electron Microscope and BET specific surface area techniques. X-ray diffraction show that the formation of small spinel oxides nanoparticles. Very small amounts of gold-silver alloy nanoparticles deposited on such mixed oxides improve the catalytical activity for CO oxidation.

  16. Temperature Dependence of Carbon Kinetic Isotope Effect for the Oxidation Reaction of Ethane by Hydroxyl Radicals Under Atmospherically Relevant Conditions: Experimental and Theoretical Studies

    OpenAIRE

    Piansawan, Tammarat

    2016-01-01

           Ethane is the second most abundant hydrocarbon in the atmosphere, after methane, impacting on air quality, human health and climate. A quantification of its effects requires accurate knowledge of sources, processes along transport, and sinks. Carbon stable isotopic ratio investigations, complementarily to concentration measurements, were demonstrated to give more insight in source apportionment and atmospheric processing of organic compounds.        Yet, apportionment of atmospher...

  17. High temperature corrosion of 9Cr-1Mo ferritic steel P91 modified, in oxidizing-carburizing atmospheres; Corrosion a temperatura alta del acero ferritico 9Cr-1Mo modificado P91, en atmosferas simuladas oxidantes-carburantes

    Energy Technology Data Exchange (ETDEWEB)

    Pena-Ballesteros, D. Y.; Vazquez-Quintero, C.; Laverde-Catano, D.; Serna, G.

    2012-11-01

    High temperature corrosion in processing units of the chemical, petrochemical, and thermoelectric carbochemical is of high interest, due to the costs generated by sudden failures caused by deterioration in the mechanical properties of metals, being the carburization of the metallic matrix the most important corrosion mechanism resulting in loss of ductility and creep resistance. In this research a 9Cr-1Mo modified steel P91 was exposed to simulated atmospheres oxidant-fuel gas mixtures simultaneous in equilibrium of CO, CO{sub 2}, CH{sub 4}, H{sub 2}O and H{sub 2}, similar to those produced in the refining industry, at temperatures between 550 and 750 degree centigrade. The microstructural evolution of the metal matrix was analyzed, also the growth, evolution and behavior of oxide layers and carburized, establishing the mechanism of deterioration of the material and the extent of damage for times exceeding 700 h of exposure. (Author) 21 refs.

  18. Staging atmospheres

    DEFF Research Database (Denmark)

    Bille, Mikkel; Bjerregaard, Peter; Sørensen, Tim Flohr

    2015-01-01

    The article introduces the special issue on staging atmospheres by surveying the philosophical, political and anthropological literature on atmosphere, and explores the relationship between atmosphere, material culture, subjectivity and affect. Atmosphere seems to occupy one of the classic...... localities of tensions between matter and the immaterial, the practical and the ideal, and subject and object. In the colloquial language there can, moreover, often seem to be something authentic or genuine about atmosphere, juxtaposing it to staging, which is implied to be something simulated or artificial....... This introduction seeks to outline how a number of scholars have addressed the relationship between staged atmospheres and experience, and thus highlight both the philosophical, social and political aspects of atmospheres...

  19. Research in physical chemistry and chemical education: Part A: Water Mediated Chemistry of Oxidized Atmospheric Compounds Part B: The Development of Surveying Tools to Determine How Effective Laboratory Experiments Contribute to Student Conceptual Understanding

    Science.gov (United States)

    Maron, Marta Katarzyna

    This dissertation is a combination of two research areas, experimental physical chemistry, Chapters I to V, and chemical education, Chapters VI to VII. Chapters I to V describe research on the water-mediated chemistry of oxidized atmospheric molecules and the impact that water has on the spectra of these environmental systems. The role of water in the Earth's atmosphere has been of considerable interest due to its ability to impact chemistry and climate. Oxidized atmospheric molecules in the presence of water have the ability to form hydrogen bonded water complexes. The spectroscopic investigation of nitric acid-water complexes, outlined in Chapter III, was undertaken to characterize intermolecular hydrogen bonds in a water-restricted environment at ambient temperatures. Additionally, this characterization of nitric acid-water complexes allowed for the comparison of calculated overtone OH-stretching vibrational band frequencies, intensities, and anharmonicities of intermolecular hydrogen-bonded water complexes with experimental observations. Oxidized organic molecules, such as aldehydes and ketones, in addition to forming hydrogen-bonded water complexes can undergo a hydration reaction of the carbonyl group and form germinal diols in the presence of water. This chemistry has been studied extensively in bulk aqueous media, however little is known about this process in the gas-phase at low water concentrations. The focus of the studies outlined in Chapters IV and V is motivated by the ability of pyruvic acid and formaldehyde to form germinal diols and water complexes in water-restricted environment. This water-mediated chemistry changes the physical and chemical properties of these organic molecules, therefore, impacting the partitioning between gas and particle phase, as well as the chemistry and photochemistry of oxidized organic molecules in the Earth's atmosphere. The results presented in this dissertation may help resolve the significant discrepancy between

  20. Synergistic Effects of Stress-Rupture and Cyclic Loading on Strain Response of Fiber-Reinforced Ceramic-Matrix Composites at Elevated Temperature in Oxidizing Atmosphere

    Directory of Open Access Journals (Sweden)

    Longbiao Li

    2017-02-01

    Full Text Available In this paper, the synergistic effects of stress rupture and cyclic loading on the strain response of fiber-reinforced ceramic-matrix composites (CMCs at elevated temperature in air have been investigated. The stress-strain relationships considering interface wear and interface oxidation in the interface debonded region under stress rupture and cyclic loading have been developed to establish the relationship between the peak strain, the interface debonded length, the interface oxidation length and the interface slip lengths. The effects of the stress rupture time, stress levels, matrix crack spacing, fiber volume fraction and oxidation temperature on the peak strain and the interface slip lengths have been investigated. The experimental fatigue hysteresis loops, interface slip lengths, peak strain and interface oxidation length of cross-ply SiC/MAS (magnesium alumino-silicate, MAS composite under cyclic fatigue and stress rupture at 566 and 1093 °C in air have been predicted.

  1. Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

    DEFF Research Database (Denmark)

    Hurley, MD; Ball, JC; Wallington, TJ;

    2004-01-01

    Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, an...

  2. Energy, atmospheric chemistry, and global climate

    Science.gov (United States)

    Levine, Joel S.

    1991-01-01

    Global atmospheric changes due to ozone destruction and the greenhouse effect are discussed. The work of the Intergovernmental Panel on Climate Change is reviewed, including its judgements regarding global warming and its recommendations for improving predictive capability. The chemistry of ozone destruction and the global atmospheric budget of nitrous oxide are reviewed, and the global sources of nitrous oxide are described.

  3. Disinfection by-product formation during seawater desalination: A review.

    Science.gov (United States)

    Kim, Daekyun; Amy, Gary L; Karanfil, Tanju

    2015-09-15

    Due to increased freshwater demand across the globe, seawater desalination has become the technology of choice in augmenting water supplies in many parts of the world. The use of chemical disinfection is necessary in desalination plants for pre-treatment to control both biofouling as well as the post-disinfection of desalinated water. Although chlorine is the most commonly used disinfectant in desalination plants, its reaction with organic matter produces various disinfection by-products (DBPs) (e.g., trihalomethanes [THMs], haloacetic acids [HAAs], and haloacetonitriles [HANs]), and some DBPs are regulated in many countries due to their potential risks to public health. To reduce the formation of chlorinated DBPs, alternative oxidants (disinfectants) such as chloramines, chlorine dioxide, and ozone can be considered, but they also produce other types of DBPs. In addition, due to high levels of bromide and iodide concentrations in seawater, highly cytotoxic and genotoxic DBP species (i.e., brominated and iodinated DBPs) may form in distribution systems, especially when desalinated water is blended with other source waters having higher levels of organic matter. This article reviews the knowledge accumulated in the last few decades on DBP formation during seawater desalination, and summarizes in detail, the occurrence of DBPs in various thermal and membrane plants involving different desalination processes. The review also identifies the current challenges and future research needs for controlling DBP formation in seawater desalination plants and to reduce the potential toxicity of desalinated water.

  4. Aqueous chlorination of mefenamic acid: kinetics, transformation by-products and ecotoxicity assessment.

    Science.gov (United States)

    Adira Wan Khalit, Wan Nor; Tay, Kheng Soo

    2016-05-18

    Mefenamic acid (Mfe) is one of the most frequently detected nonsteroidal anti-inflammatory drugs in the environment. This study investigated the kinetics and the transformation by-products of Mfe during aqueous chlorination. The potential ecotoxicity of the transformation by-products was also evaluated. In the kinetic study, the second-order rate constant (kapp) for the reaction between Mfe and free available chlorine (FAC) was determined at 25 ± 0.1 °C. The result indicated that the degradation of Mfe by FAC is highly pH-dependent. When the pH was increased from 6 to 8, it was found that the kapp for the reaction between Mfe and FAC was decreased from 16.44 to 4.4 M(-1) s(-1). Characterization of the transformation by-products formed during the chlorination of Mfe was carried out using liquid chromatography-quadrupole time-of-flight accurate mass spectrometry. Four major transformation by-products were identified. These transformation by-products were mainly formed through hydroxylation, chlorination and oxidation reactions. Ecotoxicity assessment revealed that transformation by-products, particularly monohydroxylated Mfe which is more toxic than Mfe, can be formed during aqueous chlorination.

  5. Exoplanet Atmospheres

    CERN Document Server

    Seager, S

    2010-01-01

    At the dawn of the first discovery of exoplanets orbiting sun-like stars in the mid-1990s, few believed that observations of exoplanet atmospheres would ever be possible. After the 2002 Hubble Space Telescope detection of a transiting exoplanet atmosphere, many skeptics discounted it as a one-object, one-method success. Nevertheless, the field is now firmly established, with over two dozen exoplanet atmospheres observed today. Hot Jupiters are the type of exoplanet currently most amenable to study. Highlights include: detection of molecular spectral features; observation of day-night temperature gradients; and constraints on vertical atmospheric structure. Atmospheres of giant planets far from their host stars are also being studied with direct imaging. The ultimate exoplanet goal is to answer the enigmatic and ancient question, "Are we alone?" via detection of atmospheric biosignatures. Two exciting prospects are the immediate focus on transiting super Earths orbiting in the habitable zone of M-dwarfs, and u...

  6. A Theory of Atmospheric Oxygen

    OpenAIRE

    2015-01-01

    There is no direct geologic record of the level of free oxygen in the atmosphere over Earth history. Indirect proxy records have led to a canonical view of atmospheric pO2, according to which the atmosphere has passed through three stages. During the first of these periods, corresponding roughly to the Archean eon, pO2 was less than 0.001% present atmospheric levels (PAL). Oxygen levels rose abruptly around 2.4 billion years ago, a transition referred to as the “Great Oxidation Event” (GOE...

  7. Atmospheric Neutrinos

    OpenAIRE

    Takaaki Kajita

    1994-01-01

    Atmospheric neutrinos are produced as decay products in hadronic showers resulting from collisions of cosmic rays with nuclei in the atmosphere. Electron-neutrinos and muon-neutrinos are produced mainly by the decay chain of charged pions to muons to electrons. Atmospheric neutrino experiments observed zenith angle and energy-dependent deficit of muon-neutrino events. It was found that neutrino oscillations between muon-neutrinos and tau-neutrinos explain these data well. This paper discusses...

  8. Articulating Atmospheres

    DEFF Research Database (Denmark)

    Kinch, Sofie

    2011-01-01

    This paper presents an architectural approach to designing computational interfaces by articulating the notion of atmosphere in the field of interaction design. It draws upon the concept of kinesthetic interaction and a philosophical notion on atmosphere emphasizing the importance of bodily...... experience in space, presented as middle ground experience. In the field of HCI, middle ground experiences complete the unarticulated spectrum between designing for foreground of attention or background awareness. When “Articulating Atmospheres through Middle Ground Experiences in Interaction Design...

  9. Efficiencies of metal separation and recovery in ash-melting of municipal solid waste under non-oxidative atmospheres with different reducing abilities.

    Science.gov (United States)

    Okada, Takashi; Tomikawa, Hiroki

    2016-01-15

    Ash-melting of municipal solid waste produces molten metal that contains Fe and Cu, and melting furnace fly ash (MFA) that contains Pb and Zn. To recover the metal from the fly ash, Pb and Zn are extracted from the ash by water or enriched in the ash by washing out salts; this separation depends on their leachability. In this study, we investigated the effects of the reducing ability of the atmosphere on the efficiencies of metal separation during melting and metal recovery in water treatment. Different feedstocks (incineration residues) were melted under N2 or CO + N2 atmospheres. In some of the feedstock materials, volatilization of metallic Cu into MFA was promoted under the atmosphere with greater reducing ability (CO + N2). This increased volatilization inhibited the metal separation in the ash-melting process. Moreover, the higher reducing ability inhibited the formation of water-soluble lead chlorides and decreased the efficiency of metal recovery from the MFA because of the water leaching of the lead compounds. The reducing ability of the atmosphere is difficult to control uniformly in actual ash-melting plants, and we investigated appropriate melting conditions under which the effect of the reducing ability was minimized to promote metal separation and recovery. This minimization was achieved by melting incineration fly ash without additives with Cl gas treatment at 1400 °C.

  10. Atmospheric Neutrinos

    Directory of Open Access Journals (Sweden)

    Takaaki Kajita

    2012-01-01

    Full Text Available Atmospheric neutrinos are produced as decay products in hadronic showers resulting from collisions of cosmic rays with nuclei in the atmosphere. Electron-neutrinos and muon-neutrinos are produced mainly by the decay chain of charged pions to muons to electrons. Atmospheric neutrino experiments observed zenith angle and energy-dependent deficit of muon-neutrino events. It was found that neutrino oscillations between muon-neutrinos and tau-neutrinos explain these data well. This paper discusses atmospheric neutrino experiments and the neutrino oscillation studies with these neutrinos.

  11. Atmospheric electricity

    CERN Document Server

    Chalmers, J Alan

    1957-01-01

    Atmospheric Electricity brings together numerous studies on various aspects of atmospheric electricity. This book is composed of 13 chapters that cover the main problems in the field, including the maintenance of the negative charge on the earth and the origin of the charges in thunderstorms. After a brief overview of the historical developments of atmospheric electricity, this book goes on dealing with the general principles, results, methods, and the MKS system of the field. The succeeding chapters are devoted to some aspects of electricity in the atmosphere, such as the occurrence and d

  12. How and why electrostatic charge of combustible nanoparticles can radically change the mechanism and rate of their oxidation in humid atmosphere

    CERN Document Server

    Meshcheryakov, Oleg

    2010-01-01

    Electrostatically charged aerosol nanoparticles strongly attract surrounding polar gas molecules due to a charge-dipole interaction. In humid air, the substantial electrostatic attraction and acceleration of surrounding water vapour molecules towards charged combustible nanoparticles cause intense electrostatic hydration and preferential oxidation of these nanoparticles by accelerated water vapor molecules rather than non-polar oxygen molecules. In particular, electrostatic acceleration, acquired by surrounding water vapour molecules at a distance of their mean free path from the minimally charged iron metal nanoparticle can increase an oxidative activity of these polar molecules with respect to the nanoparticle by a factor of one million. Intense electrostatic hydration of charged metal nanoparticles converts the nanoparticle's oxide based shells into the hydroxide based electrolyte shells, transforming these nanoparticles into metal/air core-shell nanobatteries, periodically short-circuited by intra-particl...

  13. Surface enrichment of Pt in stable Pt-Ir nano-alloy particles on MgAl 2 O 4 spinel in oxidizing atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wei-Zhen; Nie, Lei; Cheng, Yingwen; Kovarik, Libor; Liu, Jun; Wang, Yong

    2017-04-01

    With the capability of MgAl2O4 spinel {111} nano-facets in stabilizing small Rh, Ir and Pt particles, bimetallic Ir-Pt catalysts on the same support were investigated, aiming at further lowering the catalyst cost by substituting expensive Pt with cheaper Ir in the bulk. Small Pt-Ir nano-alloy particles (< 2nm) were successfully stabilized on the spinel {111} nano-facets as expected. Interestingly, methanol oxidative dehydrogenation (ODH) rate on the surface Pt atoms increases with oxidizing aging but decreases upon reducing treatment, where Ir is almost inactive under the same reaction conditions. Up to three times enhancement in Pt exposure was achieved when the sample was oxidized at 800 °C in air for 1 week and subsequently reduced by H2 for 2 h, demonstrating successful surface enrichment of Pt on Pt-Ir nano-alloy particles. A dynamic stabilization mechanism involving wetting\

  14. Dynamic Response of CoSb2O6 Trirutile-Type Oxides in a CO2 Atmosphere at Low-Temperatures

    Science.gov (United States)

    Guillén-Bonilla, Alex; Rodríguez-Betancourtt, Verónica-María; Flores-Martínez, Martín; Blanco-Alonso, Oscar; Reyes-Gómez, Juan; Gildo-Ortiz, Lorenzo; Guillén-Bonilla, Héctor

    2014-01-01

    Experimental work on the synthesis of the CoSb2O6 oxide and its CO2 sensing properties is presented here. The oxide was synthesized by a microwave-assisted colloidal method in presence of ethylenediamine after calcination at 600 °C. This CoSb2O6 oxide crystallized in a tetragonal structure with cell parameters a = 4.6495 and c = 9.2763 Å, and space group P42/mnm. To prove its physical, chemical and sensing properties, the oxide was subjected to a series of tests: Raman spectroscopy, Scanning Electron Microscopy (SEM) and impedance (Z) measurements. Microstructures, like columns, bars and hollow hemispheres, were observed. For the CO2 sensing test, a thick film of CoSb2O6 was used, measuring the impedance variations on the presence of air/CO2 flows (0.100 sccm/0.100 sccm) using AC (alternating current) signals in the frequency-range 0.1–100 kHz and low relative temperatures (250 and 300 °C). The CO2 sensing results were quite good. PMID:25162232

  15. Yields of aerosol precursor substances by the oxidation of DMS as a function of atmospheric conditions (temperature and NOx). Final report; Ausbeuten von Aerosolvorlaeufersubstanzen bei der DMS-Oxidation als Funktion von atmosphaerischen Bedingungen (Temperatur und NO{sub x}). Abschlussbericht

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, I.; Albu, M.; Arsene, C.; Butkovskaya, N.I.; Patroescu, I.V.

    2002-04-28

    In-depth analyses have been made of the products and aerosol formation from the OH-radical initiated oxidation of dimethyl sulphide (CH3SCH3: DMS) as a function of temperature, O2 partial pressure and initial NO concentration in large photoreactors. The investigations have provided new insights into the oxidation mechanisms of both DMS and DMSO, e.g., it has been shown that interactions of the DMS-OH adduct with O2 form DMSO in the absence of NO and dimethyl sulphone (CH3SO2CH3: DMSO2) in its presence. The data support an SO2 yield of around 70% from OH + DMS in the remote marine atmosphere. Investigations on the OH-radical initiated oxidation of dimethyl sulphoxide (CH3SOCH3: DMSO) have shown for the first time that methane sulphinic acid (CH3S(O)OH: MSIA) is the major product. Within the experimental conditions employed in the experiments only a modest dependence of the aerosol yield on temperature and initial NO concentration was observed. The experiments support that sulphuric acid formed from OH + SO2 is the major component of the aerosol with only minor contributions from MSA and MSIA. The mechanistic information is being incorporated into a DMS atmospheric chemistry modeule for CTMs (http://www.dmi.dk/f+u/luft/eng/elcid/elcid.html) and also in a simplified form for a global climate model (http://ask.ii.uib.no/.climate/elcid/). (orig.)

  16. Atmospheric materiality

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2016-01-01

    experience and, consequently, to the conceptual and methodological shifts in the production of space, and hence in the way we think about materiality. In this context, architectural space is understood as a contingent construction – a space of engagement that appears to us as a result of continuous...... characteristics of atmosphere as a spatial phenomenon, the aim of this text is to illustrate these associations and draw out design protocols, focusing on ways in which atmosphere can be conditioned architecturally. In other words, the objective is to trace the conceptual contours of ‘atmospheric materiality’....

  17. Atmospheric Dispositifs

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2015-01-01

    , the conceptual foundations and protocols for the production of atmosphere in architecture might be found beneath the surface of contemporary debates. In this context, the notion of atmospheric dispositif – illustrated through an oeuvre of the German architect Werner Ruhnau and its theoretical and historical...... as a spatial phenomenon, exploring a multiplicity of conditions that constitute their resonant origins – i.e. the production sites from and within they have emerged. The intention is also to argue that despite the fact that atmosphere as an aesthetic category has crystallised over the last few decades...... contextualisation – provides a platform for revealing productive entanglements between heterogeneous elements, disciplines and processes. It also allows rendering atmosphere as a site of co-production open to contingencies and affective interplay on multiples levels: at the moment of its conceptualisation...

  18. Atmospheric composition

    Science.gov (United States)

    Daniels, G. E.

    1973-01-01

    The earth's atmosphere is made up of a number of gases in different relative amounts. Near sea level and up to about 90 km, the amount of these atmospheric gases in clean, relatively dry air is practically constant. Four of these gases, nitrogen, oxygen, argon, and carbon dioxide, make up 99.99 percent by volume of the atmosphere. Two gases, ozone and water vapor, change in relative amounts, but the total amount of these two is very small compared to the amount of the other gases. The atmospheric composition shown in a table can be considered valid up to 90 km geometric altitude. Above 90 km, mainly because of molecular dissociation and diffusive separation, the composition changes.

  19. The synthesis of tungsten trioxide gel by dissolution of tungsten in hydrogen peroxide and its transformations during the heat treatment in oxidation and reduction atmospheres

    Directory of Open Access Journals (Sweden)

    Georgijević Radovan

    2011-01-01

    Full Text Available The structure and the thermal behavior of WO3 samples in air and in reduction atmosphere were studied. The sample I was prepared by the dissolution of fine metallic tungsten powder in hydrogen peroxide followed by solvent evaporation in the air at 60°C. Sample II was obtained by draining a part of the sample I at 60°C and then heating it up to 430°C. By the means of X-ray diffractometry, scanning electron microscopy and thermal analysis it was evidenced that the sample I was the amorphous hydrated gel, with the WO3•1.5H2O composition, while the second one was the anhidrous monoclinic WO3 with the mean particle size of 100 nm. Additionally, using the thermogravimetric and the differential thermal analysis simultaneously in the reduction atmosphere, both samples types were examined. After reduction the distribution of the metal particles number in respect to the diameters of the anhidrous sample was examined using the electron microscopy.

  20. Biogeochemical aspects of atmospheric methane

    OpenAIRE

    Cicerone, RJ; Oremland, RS

    1988-01-01

    Methane is the most abundant organic chemical in Earth's atmosphere, and its concentration is increasing with time, as a variety of independent measurements have shown. Photochemical reactions oxidize methane in the atmosphere; through these reactions, methane exerts strong influence over the chemistry of the troposphere and the stratosphere and many species including ozone, hydroxyl radicals, and carbon monoxide. Also, through its infrared absorption spectrum, methane is an important greenho...

  1. Effect of chlorine dioxide on cyanobacterial cell integrity, toxin degradation and disinfection by-product formation.

    Science.gov (United States)

    Zhou, Shiqing; Shao, Yisheng; Gao, Naiyun; Li, Lei; Deng, Jing; Zhu, Mingqiu; Zhu, Shumin

    2014-06-01

    Bench scale tests were conducted to study the effect of chlorine dioxide (ClO2) oxidation on cell integrity, toxin degradation and disinfection by-product formation of Microcystis aeruginosa. The simulated cyanobacterial suspension was prepared at a concentration of 1.0×10(6)cells/mL and the cell integrity was measured with flow cytometry. Results indicated that ClO2 can inhibit the photosynthetic capacity of M. aeruginosa cells and almost no integral cells were left after oxidation at a ClO2 dose of 1.0mg/L. The total toxin was degraded more rapidly with the ClO2 dosage increasing from 0.1mg/L to 1.0mg/L. Moreover, the damage on cell structure after oxidation resulted in released intracellular organic matter, which contributed to the formation of trihalomethanes (THMs) and haloacetic acids (HAAs) as disinfection by-products. Therefore, the use of ClO2 as an oxidant for treating algal-rich water should be carefully considered.

  2. Digestion kinetics of carbohydrate fractions of citrus by-products.

    Science.gov (United States)

    Lashkari, Saman; Taghizadeh, Akbar

    2015-01-01

    The present experiment was carried out to determine the digestion kinetics of carbohydrate fractions of citrus by-products. Grapefruit pulp (GP), lemon pulp (LE), lime pulp (LI) and orange pulp (OP) were the test feed. Digestion kinetic of whole citrus by-products and neutral detergent fiber (NDF) fraction and acid detergent fiber (ADF) fractions of citrus by-products were measured using the in vitro gas production technique. Fermentation kinetics of the neutral detergent soluble carbohydrates (NDSC) fraction and hemicelluloses were calculated using a curve subtraction. The fermentation rate of whole was the highest for the LE (p fractions. There was no significant difference among potential gas production (A) volumes of whole test feeds (p fractions of citrus by-products have high potential for degradability. It could also be concluded that carbohydrate fractions of citrus by-products have remarkable difference in digestion kinetics and digestive behavior.

  3. Isotope modeling of nitric acid formation in the atmosphere using ISO-RACM: testing the importance of NO oxidation, heterogeneous reactions, and trace gas chemistry

    Directory of Open Access Journals (Sweden)

    G. Michalski

    2010-03-01

    Full Text Available Here we present ISO-RACM, an isotope mass balance model that utilizes the Regional Atmospheric Chemistry Mechanism to predict Δ17O values in atmospheric nitrate. A large number of simulations were carried out that varied atmospheric parameters that are important in altering the magnitude and range of Δ17O values generated in photochemically produce nitrate. These parameters included temperature, relative humidity, actinic flux, aerosol surface area and chemical speciation, and three different N2O5 uptake parameterizations. Trace gas mixing ratios were also varied including CH4, CO, NOx, O3, volatile organic compounds and biogenic organic compounds. The model predicts that there are seasonal, latitudinal and diurnal variations in Δ17O values due to changes in actinic flux with lower values corresponding to higher actinic fluxes. There was also a minor positive correlation between higher Δ17O values and increased temperature. There were distinct differences in Δ17O depending on which N2O5 parameterization was used, mostly the result of changing relative humidity being a factor in two of the parameterization schemes. Changing CO and CH4 mixing ratios had negligible impact on Δ17O values but significant variation in magnitude and range were predicted with NOx, O3, and organic loading. High NOx and O3 generated high Δ17O with a narrow (10 ‰ range, while high organics led to low Δ17O values and a wider range of possible values. Implications for using Δ17O to evaluate NOx-NOy chemistry and aerosol formation processes are discussed, as is needed future research.

  4. Microwave assisted catalytic wet air oxidation of H-acid in aqueous solution under the atmospheric pressure using activated carbon as catalyst.

    Science.gov (United States)

    Zhang, Yaobin; Quan, Xie; Chen, Shuo; Zhao, Yazhi; Yang, Fenglin

    2006-09-01

    Catalytic wet air oxidation (CWAO) is a promising method for the treatment of heavily contaminated wastewater. However, its application is restricted due to severe operation conditions (high pressure and high temperature). A microwave (MW) assisted oxidation method was investigated aiming to treat heavily contaminated wastewater under milder conditions. H-acid (1-amino-8-naphthol-3, 6-disulfonic acid) was selected as target compound to evaluate the performance of this novel process. The removal of H-acid and TOC (total organic carbon) for H-acid solution of 3000 mg/L reached as high as 92.6% in 20 min and 84.2% in 60 min, respectively under optimal conditions. The existence of activated carbon and oxygen proved to be critical for effective treatment. The activated carbon acted not only as a catalyst for H-acid decomposition, but also as a special material for the absorption of MW energy. Air was supplied to the reactor as an oxygen source at constant flows. The amino group in H-acid was converted ultimately into nitrate, and sulfonic group into sulfate. This observation gave an evidence of H-acid mineralization although other organic intermediates were unable to be determined. The value of BOD(5)/COD (ratio of 5d biochemical oxygen demand to chemical oxygen demand) increased from 0.008 to 0.467 indicating a significant improvement of biodegradability for the solution, which is beneficial for the further biological treatment of the wastewater.

  5. Equilibration of plain carbon and alloy steels with endothermic carburizing atmospheres: Part II. Oxidation of plain carbon and Armco steels during carburizing at 1000 °C and 1038 °C

    Science.gov (United States)

    Hwang, Jong-Il; Jhee, Tae-Gu; Kim, Young-Kyu; Hwang, Tae-Young

    2010-10-01

    Carbon contents by the weight gain of AISI type 1010 steel foils equilibrated with CO-CO2 mixtures at 1000 °C were 0.03 wt.% to 0.07 wt.% higher than those by chemical analysis at carbon potentials of 0.2 wt.%C to 0.7 wt.%C. The lower the carbon potential, the bigger the difference became. This difference of 0.05 wt.% to 0.08 wt.% was also measured when the same materials were equilibrated with CO-CO2 mixtures at 1038 °C at carbon potentials below 0.4 wt.%C. Oxygen analyses of these equilibrated steel foils confirmed that those differences of 0.03 wt.% to 0.07 wt.% and 0.05 wt.% to 0.08 wt.% were mainly due to the selective oxidation of manganese. When Armco steels and type 1010 steels were equilibrated simultaneously with endothermic-base carburizing atmospheres at 1038 °C, oxidation was negligible and the carbon contents of the both steels were identical at carbon potentials of 0.2 wt.%C to 1.4 wt.%C.

  6. Atmospheric thermodynamics

    CERN Document Server

    Iribarne, J V

    1973-01-01

    The thermodynamics of the atmosphere is the subject of several chapters in most textbooks on dynamic meteorology, but there is no work in English to give the subject a specific and more extensive treatment. In writing the present textbook, we have tried to fill this rather remarkable gap in the literature related to atmospheric sciences. Our aim has been to provide students of meteorology with a book that can playa role similar to the textbooks on chemical thermodynamics for the chemists. This implies a previous knowledge of general thermodynamics, such as students acquire in general physics courses; therefore, although the basic principles are reviewed (in the first four chapters), they are only briefly discussed, and emphasis is laid on those topics that will be useful in later chapters, through their application to atmospheric problems. No attempt has been made to introduce the thermodynamics of irreversible processes; on the other hand, consideration of heterogeneous and open homogeneous systems permits a...

  7. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implication for PM2.5

    Science.gov (United States)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-06-01

    -phase photooxidation products have also been examined. The contribution of SOA products from 13BD oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, d-threitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m-3. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.

  8. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

    Science.gov (United States)

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-12-01

    examined. The contribution of SOA products from 13BD oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, d-threitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m-3. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.

  9. A Review of Antioxidant Peptides Derived from Meat Muscle and By-Products

    Science.gov (United States)

    Liu, Rui; Xing, Lujuan; Fu, Qingquan; Zhou, Guang-hong; Zhang, Wan-gang

    2016-01-01

    Antioxidant peptides are gradually being accepted as food ingredients, supplemented in functional food and nutraceuticals, to positively regulate oxidative stress in the human body against lipid and protein oxidation. Meat muscle and meat by-products are rich sources of proteins and can be regarded as good materials for the production of bioactive peptides by use of enzymatic hydrolysis or direct solvent extraction. In recent years, there has been a growing number of studies conducted to characterize antioxidant peptides or hydrolysates derived from meat muscle and by-products as well as processed meat products, including dry-cured hams. Antioxidant peptides obtained from animal sources could exert not only nutritional value but also bioavailability to benefit human health. This paper reviews the antioxidant peptides or protein hydrolysates identified in muscle protein and by-products. We focus on the procedure for the generation of peptides with antioxidant capacity including the acquisition of crude peptides, the assessment of antioxidant activity, and the purification and identification of the active fraction. It remains critical to perform validation experiments with a cell model, animal model or clinical trial to eliminate safety concerns before final application in the food system. In addition, some of the common characteristics on structure-activity relationship are also reviewed based on the identified antioxidant peptides. PMID:27657142

  10. A Review of Antioxidant Peptides Derived from Meat Muscle and By-Products

    Directory of Open Access Journals (Sweden)

    Rui Liu

    2016-09-01

    Full Text Available Antioxidant peptides are gradually being accepted as food ingredients, supplemented in functional food and nutraceuticals, to positively regulate oxidative stress in the human body against lipid and protein oxidation. Meat muscle and meat by-products are rich sources of proteins and can be regarded as good materials for the production of bioactive peptides by use of enzymatic hydrolysis or direct solvent extraction. In recent years, there has been a growing number of studies conducted to characterize antioxidant peptides or hydrolysates derived from meat muscle and by-products as well as processed meat products, including dry-cured hams. Antioxidant peptides obtained from animal sources could exert not only nutritional value but also bioavailability to benefit human health. This paper reviews the antioxidant peptides or protein hydrolysates identified in muscle protein and by-products. We focus on the procedure for the generation of peptides with antioxidant capacity including the acquisition of crude peptides, the assessment of antioxidant activity, and the purification and identification of the active fraction. It remains critical to perform validation experiments with a cell model, animal model or clinical trial to eliminate safety concerns before final application in the food system. In addition, some of the common characteristics on structure-activity relationship are also reviewed based on the identified antioxidant peptides.

  11. Atmospheric escape, redox evolution, and planetary habitability

    Science.gov (United States)

    Catling, D. C.; Zahnle, K. J.

    2011-12-01

    Through the greenhouse effect, the presence and composition of an atmosphere is critical for defining a (conventional) circumstellar habitable zone in terms of planetary surface temperatures suitable for liquid water. Lack of knowledge of planetary atmospheres is likely to frustrate attempts to say with any certainty whether detected terrestrial-sized exoplanets may or may not be habitable. Perhaps an underappreciated role in such considerations is the evolutionary effect of atmospheric escape for determining atmospheric composition or whether an atmosphere exists in the first place. Whether atmospheres exist at all on planets is demonstrably connected to the effect of integrated atmospheric escape. When we observe our own Solar System and transiting exoplanets, the existence of an atmosphere is clearly delineated by a relative vulnerability to thermal escape and impact erosion. The prevalence of thermal escape as a key evolutionary determinant for the presence of planetary atmosphere is shown by a relationship between the relative solar (or stellar) heating and the escape velocity. Those bodies with too much stellar heating and too smaller escape velocity end up devoid of atmospheres. Impact erosion is evident in the relationship between impact velocity and escape velocity. Escape due to impacts is particularly important for understanding the large differences in the atmospheres of giant planet moons, such as Ganymede versus Titan. It is also significant for Mars-sized planets. The oxidation state of atmospheres is important for some theories of the origin of life (where an early reducing atmosphere is helpful for organic synthesis) and the evolution of advanced life (where free molecular oxygen is the best source of high energy metabolism). Surfaces on some relatively small planets and moons are observed to have evolved to an oxidized state, which theory and observation can explain through atmospheric escape. There are several examples in the Solar System where a

  12. Atmospheric and aerosol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    McNeill, V. Faye [Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; Ariya, Parisa A. (ed.) [McGill Univ. Montreal, QC (Canada). Dept. of Chemistry; McGill Univ. Montreal, QC (Canada). Dept. of Atmospheric and Oceanic Sciences

    2014-09-01

    This series presents critical reviews of the present position and future trends in modern chemical research. Short and concise reports on chemistry, each written by the world renowned experts. Still valid and useful after 5 or 10 years. More information as well as the electronic version of the whole content available at: springerlink.com. Christian George, Barbara D'Anna, Hartmut Herrmann, Christian Weller, Veronica Vaida, D. J. Donaldson, Thorsten Bartels-Rausch, Markus Ammann Emerging Areas in Atmospheric Photochemistry. Lisa Whalley, Daniel Stone, Dwayne Heard New Insights into the Tropospheric Oxidation of Isoprene: Combining Field Measurements, Laboratory Studies, Chemical Modelling and Quantum Theory. Neil M. Donahue, Allen L. Robinson, Erica R. Trump, Ilona Riipinen, Jesse H. Kroll Volatility and Aging of Atmospheric Organic Aerosol. P. A. Ariya, G. Kos, R. Mortazavi, E. D. Hudson, V. Kanthasamy, N. Eltouny, J. Sun, C. Wilde Bio-Organic Materials in the Atmosphere and Snow: Measurement and Characterization V. Faye McNeill, Neha Sareen, Allison N. Schwier Surface-Active Organics in Atmospheric Aerosols.

  13. IDENTIFICATION OF NEW DISINFECTION BY-PRODUCTS IN DRINKING WATER

    Science.gov (United States)

    Due to concern over the potential adverse health effects of trihalomethanes (THMs) and other chlorinated by-products in chlorinated drinking water, alternative disinfectants are being explored. Ozone, chlorine dioxide, and chloramine are popular alternatives, as they produce low...

  14. Formation and Occurrence of Disinfection By-Products

    Science.gov (United States)

    Disinfection by-products (DBPs) are formed when disinfectants such as chlorine, ozone, chlorine dioxide, or chloramines react with naturally occurring organic matter, anthropogenic contaminants, bromide, and iodide during the production of drinking water. There is concern about D...

  15. Atmospheric Refraction

    CERN Document Server

    Nauenberg, Michael

    2016-01-01

    Calculations of atmospheric refraction are generally based on a simplified model of atmospheric density in the troposphere which assumes that the temperature decreases at a constant lapse rate from sea level up to a height equal to eleven km, and that afterwards it remains constant. In this model, the temperature divided by the lapse rate determines the length scale in the calculations for altitudes less than this height. But daily balloon measurements across the U.S.A. reveal that in some cases the air temperature actually increases from sea level up to a height of about one km, and only after reaching a plateau, it decreases at an approximately constant lapse rate. Moreover, in three examples considered here, the temperature does not remain constant at eleven km , but continues to decreases to a minimum at about sixteen kilometers , and then increases at higher altitudes at a lower rate. Calculations of atmospheric refraction based on this atmospheric data is compared with the results of simplified models.

  16. SOA formation from the atmospheric oxidation of 2-methyl-3-buten-2-ol and its implications for PM2.5

    Directory of Open Access Journals (Sweden)

    W. A. Lonneman

    2012-02-01

    Full Text Available The formation of secondary organic aerosol (SOA generated by irradiating 2-methyl-3-buten-2-ol (MBO in the presence and/or absence of NOx, H2O2, and/or SO2 was examined. Experiments were conducted in smog chambers operated in either dynamic or static mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The structural characterization of gas and particulate products was investigated using BSTFA, BSTFA + PFBHA, and DNPH derivatization techniques followed by GC-MS and liquid chromatography analysis. This analysis showed the occurrence of more than 68 oxygenated organic compounds in the gas and particle phases, 28 of which were tentatively identified. The major components observed include 2,3-dihydroxyisopentanol (DHIP, 2-hydroxy-2-oxoisopentanol, 2,3-dihydroxy-3-methylbutanal, 2,3-dihydroxy-2-methylsuccinic acid, 2-hydroxy-2-methylpropanedioic acid, acetone, glyoxal, methylglyoxal, glycolaldehyde, and formaldehyde. Most of these oxygenated compounds were detected for the first time in this study. While measurements of the gas-phase photooxidation products have been made, the focus of this work has been an examination of the particle phase. SOA from some experiments was analyzed for the organic mass to organic carbon ratio (OM/OC, the effective enthalpy of vaporization (ΔHvapeff, and the aerosol yield. Additionally, aerosol size, volume, and number concentrations were measured by a Scanning Mobility Particle Sizer coupled to a Condensation Particle Counter system. The OM/OC ratio was 2.1 in the MBO/H2O2 system. The ΔHvapeff was 41 kJ mol−1, a value similar to that of isoprene SOA. The laboratory SOA yield measured in this study was 0.7% in MBO/H2O2 for an aerosol mass of 33 μg m−3. Secondary organic aerosol was found to be negligible under conditions with oxides of nitrogen (NOx present. Time profiles and proposed reaction schemes are provided for selected compounds. The contribution

  17. ANALYSIS OF BY-PRODUCTS MARKET IN RUSSIA

    Directory of Open Access Journals (Sweden)

    Keniyz N. V.

    2015-01-01

    Full Text Available Changing style of life, its rhythm and tendencies dictate their own conditions. The deficit of time makes us economize it on all, including the time for cooking. Among the main trends of the domestic meat market - switching consumers from frozen meat products to fresh cooled products. In connection with it the amount of consumers of meat semi-finished products grows. In the work there was considered the results of research of the Russian market of by-products. The market of frozen meat by-products is actively developed in large cities, where it has its own production. The participants of the market state that consumers have started to buy more frozen by-products by weight and the analysis of meat by-products assortment in retailing trade for 2014 testifies it. Trying to fasten their positions, operators of the market not only develop the production powers but work out new products and the analysis of dynamics of production volumes of meat by-products and shares of federal districts – producers of meat by-products testify it. The main players in this segment see the future market for complex, receipt, combined products and ready dishes that will lead to change of structure of meat semi-finished products sales

  18. Microstructure evolution and oxidation states of Co in perovskite-type oxide Ba1.0Co0.7Fe0.2Nb0.1O3-δannealed in CO2 atmosphere

    Institute of Scientific and Technical Information of China (English)

    Chengzhang Wu; He Wang; Xingxing Zhang; Yuwen Zhang; Weizhong Ding; Chenghua Sun

    2014-01-01

    Ba1.0Co0.7Fe0.2Nb0.1O3-δ (BCFN) oxide with perovskite cubic structure was synthesized by solid state reaction method. CO2 corrosion of BCFN membrane was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance infrared Fourier-transformed spectroscopy (DRIFT) and X-ray absorption fine structure spectroscopy (XAFS). Cobalt (Co) K-edge absorption spectra of BCFN annealed in CO2 reveal that the oxidation states of Co in all the samples were larger than+3 and they decreased with the increase of calcination time. At 800◦C, 1%CO2 introduced into He could speed up the reduction of Co cations in comparison with pure He. In addition, sulfate ions in the bulk of BCFN membrane preferred to migrate to the surface under CO2 calcination and form monoclinic Ba(CO3)0.9(SO4)0.1 besides orthorhombic witherite. Moreover, SEM results indicate that the nucleation and growth of carbonates grains started at the grain boundary of the membrane.

  19. Atmospheric oxidation of vinyl and allyl acetate: product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NO(x).

    Science.gov (United States)

    Blanco, María B; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A

    2012-08-21

    The products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NO(x) using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NO(x) and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NO(x). For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NO(x) and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NO(x). The present results indicate that in the absence of NO(x) the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH(2)(OH)CO(•) radicals and in the case of allyl acetate reaction of the radical with O(2) to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH(3)C(O)OCH(2)C(O)CH(2)OH). In contrast, in the presence of NO(x) the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed.

  20. Drinking Water Disinfection by In-line Electrolysis: Product and Inorganic By-Product Formation

    Science.gov (United States)

    Bergmann, M. E. Henry

    This section covers peculiarities of so-called in-line electrolysis when drinking water is electrolysed to produce disinfection species killing microorganisms. Mainly mixed oxide electrodes (MIO) based on IrO2 and/or RuO2 coatings and boron-doped diamond electrodes were used in the studies. Artificial and real drinking water systems were electrolysed in continuous and discontinuous operating mode, varying water composition, current density and electrode materials. Results show, besides the ability of producing active chlorine, risks of inorganic disinfection by-products (DBPs) such as chlorate, perchlorate, nitrite, ammonium, chloramines, hydrogen peroxide and others. DBPs are responsible for analysis errors using DPD method for active chlorine measurements. Geometry may influence by-product yield. As a conclusion, the necessity of developing test routines for practical cell applications must be underlined.

  1. Highly oxidized superconductors

    Science.gov (United States)

    Morris, Donald E.

    1994-01-01

    Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed.

  2. Oxidization of squalene, a human skin lipid: a new and reliable marker of environmental pollution studies.

    Science.gov (United States)

    Pham, D-M; Boussouira, B; Moyal, D; Nguyen, Q L

    2015-08-01

    A review of the oxidization of squalene, a specific human compound produced by the sebaceous gland, is proposed. Such chemical transformation induces important consequences at various levels. Squalene by-products, mostly under peroxidized forms, lead to comedogenesis, contribute to the development of inflammatory acne and possibly modify the skin relief (wrinkling). Experimental conditions of oxidation and/or photo-oxidation mechanisms are exposed, suggesting that they could possibly be bio-markers of atmospheric pollution upon skin. Ozone, long UVA rays, cigarette smoke… are shown powerful oxidizing agents of squalene. Some in vitro, ex vivo and in vivo testings are proposed as examples, aiming at studying ingredients or products capable of boosting or counteracting such chemical changes that, globally, bring adverse effects to various cutaneous compartments.

  3. SOA formation from the atmospheric oxidation of 2-methyl-3-buten-2-ol and its implications for PM2.5

    Directory of Open Access Journals (Sweden)

    W. A. Lonneman

    2011-08-01

    Full Text Available The formation of secondary organic aerosol (SOA generated by irradiating 2-methyl-3-buten-2-ol (MBO in the presence and/or absence of NOx, H2O2, and/or SO2 was examined. Experiments were conducted in smog chambers operated either in dynamic or steady-state mode. A filter/denuder sampling system was used for simultaneously collecting gas and particle phase products. The structural characterization of gas and particulate products was investigated using BSTFA, BSTFA + PFBHA, and DNPH derivatization techniques followed by GC-MS and liquid chromatography analysis. This analysis showed the occurrence of more than 68 oxygenated organic compounds in the gas and particle phase, 28 of which were identified. The major components observed include 2,3-dihydroxyisopentanol (DHIP, 2-hydroxy-2-oxoisopentanol, 2,3-dihydroxy-3-methylbutanal, 2,3-dihydroxy-2-methylsuccinic acid, 2-hydroxy-2-methylpropanedioic acid, acetone, glyoxal, methylglyoxal, glycolaldehyde, and formaldehyde. Most of these oxygenated compounds were detected for the first time in this study. While measurements of the gas phase photooxidation products have been made, the focus of this work has been an examination of the particle phase. SOA from some experiments was analyzed for the organic mass to organic carbon ratio (OM/OC, the effective enthalpy of vaporization (ΔHvapeff, and the aerosol yield. Additionally, aerosol size, volume, and number concentrations were measured by a Scanning Mobility Particle Sizer coupled to a Condensation Particle Counter system. The OM/OC was found to be 2.1 in MBO/H2O2 system. The ΔHvapeff was 41 kJ mol−1, a value similar to that of isoprene SOA. The laboratory SOA yield measured in this study was found to be 0.7 % in MBO/H2O2 for an aerosol mass of 33 μg m−3. Time profiles and proposed reaction schemes are provided for selected compounds. The contribution of SOA products from MBO oxidation to ambient PM2.5 was investigated by analyzing a series of ambient

  4. Atmospheric Neutrinos

    CERN Document Server

    Gaisser, Thomas K

    2016-01-01

    In view of the observation by IceCube of high-energy astrophysical neutrinos, it is important to quantify the uncertainty in the background of atmospheric neutrinos. There are two sources of uncertainty, the imperfect knowledge of the spectrum and composition of the primary cosmic rays that produce the neutrinos and the limited understanding of hadron production, including charm, at high energy. This paper is an overview of both aspects.

  5. Atmospheric Chemistry and Air Pollution

    Directory of Open Access Journals (Sweden)

    Jeffrey S. Gaffney

    2003-01-01

    Full Text Available Atmospheric chemistry is an important discipline for understanding air pollution and its impacts. This mini-review gives a brief history of air pollution and presents an overview of some of the basic photochemistry involved in the production of ozone and other oxidants in the atmosphere. Urban air quality issues are reviewed with a specific focus on ozone and other oxidants, primary and secondary aerosols, alternative fuels, and the potential for chlorine releases to amplify oxidant chemistry in industrial areas. Regional air pollution issues such as acid rain, long-range transport of aerosols and visibility loss, and the connections of aerosols to ozone and peroxyacetyl nitrate chemistry are examined. Finally, the potential impacts of air pollutants on the global-scale radiative balances of gases and aerosols are discussed briefly.

  6. Atmospheric emission of nitrogen oxide from kraft recovery boilers in Sweden; Kartlaeggning av NO{sub x}-utslaepp fraan sodapannor i Sverige

    Energy Technology Data Exchange (ETDEWEB)

    Kjoerk, Anders; Herstad Swaerd, Solvie [S.E.P. Scandinavian Energy Project AB, Goeteborg (Sweden)

    2000-05-01

    Recovery boiler NO{sub x} emissions are low compared with those from power boilers. However tighter environmental requirements to decrease the acidic emissions implies that all sources have to be addressed. There are an ongoing evaluation and development of NO{sub x} control technologies in the pulp industry. Basically air staging, selective catalytic reduction, SCR, and selective noncatalytic reduction, SNCR, have been discussed. Other NO{sub x} control options may be available as a result of ongoing research and development. As a background in the work to reduce the acid rain it has been considered necessary to have a good picture of the NO{sub x} emission from recovery boilers, and the Thermal Engineering Research Institute in Sweden have therefore sponsored this study. The intention is to give a good general view and try to explain the reasons for the large differences between boilers. Data from the 30 kraft recovery boilers which were in operation in Sweden during 1999 have been collected. Both NO{sub x} levels and specific conditions which could have an influence on the level have been included. The evaluation show a clear correlation between the nitrogen content in the liquor and the NO{sub x} level. It seams also that a long retention time in the furnace give an opportunity to reduce the amount of nitrogen oxide. For most boilers in Sweden the NO{sub x} levels are reported in mg/MJ and comparison could be done between different types of boilers. However for recovery boilers there could be a large uncertainty in the calculation which gives the amount (mg) of NO{sub x}, the definition of the heat input to be used (MJ) is either not clear. As a base for the study the measured concentration in ppm is used instead. The reported values are in the range of 30 - 100 ppm, however the majority of the boilers operate in a more narrow range 60-80 ppm. Air staging and other combustion methods could not reasonably reduce the NO{sub x} emission with more than 20% in the

  7. 常压下Pt-Bi双金属催化剂上甘油选择性氧化%Glycerol Oxidation with Oxygen over Bimetallic Pt-Bi Catalysts under Atmospheric Pressure

    Institute of Scientific and Technical Information of China (English)

    梁丹; 崔世玉; 高静; 王军华; 陈平; 侯昭胤

    2011-01-01

    制备了一系列活性碳(AC)负载的Pt-Bi双金属催化剂,考察了催化剂中Bi含量对其催化甘油选择性氧化反应性能的影响.结果表明,适量Bi的添加可以改善催化剂中Pt的氧化还原性能,从而有利于催化剂活性的提高和二羟基丙酮(DIHA)产物的生成.当Bi的含量为5%时,该催化剂的活性最高,甘油转化率和DIHA选择性分别达到91.5%和49.0%.表征结果显示,Pt-Bi颗粒的平均粒径为3.8 nm,且高度分散在催化剂表面,这是该催化剂具有较高活性的主要原因.%A series of bimetallic Pt-Bi catalysts with a constant platinum content of 5.0 wt% and a varied bismuth content (3.0-7.0 wt%)supported on active carbon were prepared and used for glycerol oxidation with oxygen under atmospheric pressure.The bimetallic Pt-Bi/C was efficient for the selective oxidation of glycerol to dihydroxyacetone (DIHA) and the selectivity for DIHA reached 49.0% at a 91.5%conversion of glycerol over the 5%Pt-5%Bi/C catalyst.X-ray diffraction and transmission electron microscopy analysis revealed that the specially configured Pt-Bi nanoparticles in 5%Pt-5%Bi/C were highly dispersed (3.8 nm) over the active carbon support,which is proposed to contribute to the improved performance.

  8. Total Sulfur Deposition (wet+dry) from the Atmosphere

    Data.gov (United States)

    U.S. Environmental Protection Agency — Sulfur Dioxide (SO2) is emitted primarily as a by-product of coal combustion from power plants. Sulfur Dioxide reacts in the atmosphere to form other chemical such...

  9. Identification and Mitigation of Generated Solid By-Products during Advanced Electrode Materials Processing.

    Science.gov (United States)

    Tsai, Candace S J; Dysart, Arthur D; Beltz, Jay H; Pol, Vilas G

    2016-03-01

    A scalable, solid-state elevated-temperature process was developed to produce high-capacity carbonaceous electrode materials for energy storage devices via decomposition of a starch-based precursor in an inert atmosphere. In a separate study, it is shown that the fabricated carbonaceous architectures are useful as an excellent electrode material for lithium-ion, sodium-ion, and lithium-sulfur batteries. This article focuses on the study and analysis of the formed nanometer-sized by-products during the lab-scale synthesis of the carbon material. The material production process was studied in operando (that is, during the entire duration of heat treatment). The unknown downstream particles in the process exhaust were collected and characterized via aerosol and liquid suspensions, and they were quantified using direct-reading instruments for number and mass concentrations. The airborne emissions were collected using the Tsai diffusion sampler (TDS) for characterization and further analysis. Released by-product aerosols collected in a deionized (DI) water trap were analyzed, and the aerosols emitted from the post-water-suspension were collected and characterized. After long-term sampling, individual particles in the nanometer size range were observed in the exhaust aerosol with layer-structured aggregates formed on the sampling substrate. Upon the characterization of the released aerosol by-products, methods were identified to mitigate possible human and environmental exposures upon industrial implementation.

  10. Processes regulating nitric oxide emissions from soils

    DEFF Research Database (Denmark)

    Pilegaard, Kim

    2013-01-01

    Nitric oxide (NO) is a reactive gas that plays an important role in atmospheric chemistry by influencing the production and destruction of ozone and thereby the oxidizing capacity of the atmosphere. NO also contributes by its oxidation products to the formation of acid rain. The major sources...

  11. Alarming atmospheres

    DEFF Research Database (Denmark)

    Højlund, Marie; Kinch, Sofie

    2014-01-01

    . As a response to this situation, our design artefact, the interactive furniture Kidkit, invites children to become accustomed to the alarming sounds sampled from the ward while they are waiting in the waiting room. Our design acknowledges how atmospheres emerge as temporal negotiations between the rhythms......, a familiar relationship with the alarming sounds in the ward, enabling her to focus later more on the visit with the relative. The article discusses the proposed design strategy behind this solution and the potentiality for its use in hospital environments in general....

  12. Evolution of the atmosphere.

    Science.gov (United States)

    Nunn, J F

    1998-01-01

    Planetary atmospheres depend fundamentally upon their geochemical inventory, temperature and the ability of their gravitational field to retain gases. In the case of Earth and other inner planets, early outgassing released mainly carbon dioxide and water vapour. The secondary veneer of comets and meteorites added further volatiles. Photodissociation caused secondary changes, including the production of traces of oxygen from water. Earth's gravity cannot retain light gases, including hydrogen. but retains oxygen. Water vapour generally does not pass the cold trap at the stratopause. In the archaean, early evolution of life, probably in hydrothermal vents, and the subsequent development of photosynthesis in surface waters, produced oxygen, at 3500 Ma or even earlier, becoming a significant component of the atmosphere from about 2000 Ma. Thereafter banded iron formations became rare, and iron was deposited in oxidized red beds. Atmospheric levels of carbon dioxide and oxygen have varied during the Phanerozoic: major changes may have caused extinctions. particularly the Permian/Triassic. The declining greenhouse effect due to the long-term decrease in carbon dioxide has largely offset increasing solar luminosity, and changes in carbon dioxide levels relate strongly to cycles of glaciation.

  13. Atmospheric Chemistry in a Changing World

    Science.gov (United States)

    Brune, William H.

    The world is changing,and the atmosphere's composition is changing with it. Human activity is responsible for much of this. Global population growth and migration to urban centers, extensive biomass burning, the spread of fertilizer-intensive agribusiness, globalization of business and industry, rising standards of living in the developing world, and increased energy use fuels atmospheric change. If current practices continue, atmospheric increases are likely for the greenhouse gases carbon dioxide, methane, nitrous oxide; and for the chemically active gases nitric oxide, sulfur dioxide,and ammonia. Increases in global tropospheric ozone and aerosols are a distinct possibility.

  14. Maximizing Utilization of Energy from Crop By-products

    Directory of Open Access Journals (Sweden)

    Budi Haryanto

    2014-03-01

    Full Text Available The availability of crop by-products is huge during harvesting times as related to the vast agricultural land area; however, their utilization is still limited due to lack of knowledge and handling problem. Seasonal effect is obvious especially during wet season when high rainfall hinders proper management of crop by-products. Crop by-products are energy rich feedstuffs in the form of chemical substance such as cellulose and hemicellulose. The utilization of cellulose and hemicellulose as sources of energy can be maximized by the application of technologies to increase the digestibility. Cellulose is polymer of glucose while hemicellulose is polymer of xylose which both can be converted to volatile fatty acids by rumen microbial enzyme activities and subsequently used by the host animal as source of energy. In addition, cellulose and hemicellulose can also be used as substrates for bioethanol production leaving behind residual matter with higher concentration of protein which is also appropriate for ruminant feeds. The fat content of crop by-products such as those in rice bran and corn germ can be extracted for oil production that can be used for human consumption with concomitant production of high nutritive value of residues for ruminant feeds. The oil extraction technologies are available; however the high cost of ethanol and oil production should obtain high attention to make the technologies more applicable at farmers’ level.

  15. Genotoxicity of Disinfection By-products: Comparison to Carcinogenicity

    Science.gov (United States)

    Disinfection by-products (DBPs) can be formed when water is disinfected by various agents such as chlorine, ozone, or chloramines. Among the >600 DBPs identified in drinking water, 11 are regulated by the U.S. Environmental Protection Agency, and another ~70 DBPs that occur at s...

  16. Bioassay-guided fractionation of a hepatoprotective and antioxidant extract of pea by-product.

    Science.gov (United States)

    Seida, Ahmed A; El Tanbouly, Nebal D; Islam, Wafaa T; Eid, Hanaa H; El Maraghy, Shohda A; El Senousy, Amira S

    2015-01-01

    The hepatoprotective and antioxidant activities of the hydroalcoholic extract (PE) of pea (Pisum sativum L.) by-product were evaluated, using CCl4-induced oxidative stress and hepatic damage in rats. These activities were assessed via measuring alanine aminotransferase (ALT), aspartate aminotransferase (AST), total protein and albumin, malondialdehyde (MDA), reduced glutathione (GSH), protein thiols (PSH), nitrite/nitrate levels, glutathione-peroxidase (GSH-Px), glutathione-S-transferase (GST) activities, as well as, histopathological evaluation. PE revealed significant hepatoprotective and antioxidant activities mostly found in n-butanol fraction. Chromatographic fractionation of this active fraction led to the isolation of five flavonoid glycosides namely, quercetin-3-O-sophorotrioside (1), quercetin-3-O-rutinoside (2), quercetin-3-O-(6″″-O-E sinapoyl)-sophorotrioside (3), quercetin-3-O-(6″″-O-E feruloyl)-sophorotrioside (4) and quercetin-3-O-β-D-glucopyranoside (5). The isolated compounds were quantified in PE, using a validated HPLC method and the nutritional composition of pea by-product was also investigated. Our results suggest that pea by-product contained biologically active constituents which can be utilised to obtain high value added products for nutraceutical use.

  17. Land application uses for dry FGD by-products

    Energy Technology Data Exchange (ETDEWEB)

    Bigham, J.; Dick, W.; Forster, L.; Hitzhusen, F.; McCoy, E.; Stehouwer, R.; Traina, S.; Wolfe, W. (Ohio State Univ., Columbus, OH (United States)); Haefner, R. (Geological Survey, Columbus, OH (United States). Water Resources Div.)

    1993-04-01

    The 1990 amendments to the Clean Air Act have spurred the development of flue gas desulfurization (FGD) processes, several of which produce a dry, solid by-product material consisting of excess sorbent, reaction products containing sulfates and sulfites, and coal fly ash. Presently FGD by-product materials are treated as solid wastes and must be landfilled. However, landfill sites are becoming more scarce and tipping fees are constantly increasing. It is, therefore, highly desirable to find beneficial reuses for these materials provided the environmental impacts are minimal and socially acceptable. Phase 1 results of a 4 and 1/2 year study to demonstrate large volume beneficial uses of FGD by-products are reported. The purpose of the Phase 1 portion of the project was to characterize the chemical, physical, mineralogical and engineering properties of the FGD by-product materials obtained from various FGD technologies being developed in the state of Ohio. Phase 1 also involved the collection of baseline economic data related to the beneficial reuse of these FGD materials. A total of 58 samples were collected and analyzed. In summary Phase 1 results revealed that FGD by-product materials are essentially coal fly ash materials diluted with unreacted sorbent and reaction products. High volume beneficial reuses will depend on the economics of their substituting for existing materials for various types of applications (e.g. as an agricultural liming material, soil borrow for highway embankment construction, and reclamation of active and abandoned surface coal mines). Environmental constraints to the beneficial reuse of dry FGD byproduct materials, based on laboratory and leachate studies, seem to be less than for coal fly ash.

  18. By-product materials in cement clinker manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Gadayev, A. [ICS and E, Aurora, CO (United States); Kodess, B. [VNIIMS Gosstandart of Russia, Moscow (Russian Federation)

    1999-02-01

    The use of Cl- and SO{sub 3}-containing by-products from chemical industries for manufacturing Portland cement clinker using a wet process was examined. The chemical and mineralogical compositions of the by-products and raw materials were determined. Homogeneous raw mixes containing different concentrations of by-products (5--30%) were prepared and the influence of the by-products on all steps of burning the mixes in a kiln to form a cement clinker was investigated. It was shown that introducing Cl- and SO{sub 3}-containing by-products to the raw mixes significantly changes all the cement clinker producing stages and changes the chemical and mineralogical compositions at all intermediate stages and in the finished products, forming new minerals containing Cl and SO{sub 3} [CaO{sub x} (SiO{sub 2}){sub y} CaCl{sub 2}] or [CaO{sub x} (SiO{sub 2}){sub y} CaSO{sub 4}] and increasing the amount of well-known intermediate minerals. The presence of the chlorides and sulfates in the cement clinker burning processes removes alkali from the raw mixes, turning them to volatile forms, accelerating the raw mineral decomposition processes and accelerating the formation processes of cement minerals (C{sub 2}S, C{sub 12}A{sub 7}, C{sub 4}AF) and formation of chloride and sulfate cycles in the kiln, forming clinker liquids and decreasing the formation and growth of the main cement minerals (C{sub 3}A, C{sub 3}S). The cement clinker contains some quantity of minerals with Cl or SO{sub 3}. Their presence in the final product decreases cement quality by reducing the amount of active CaO (C) and reducing the active CaO/SiO{sub 2} ratio.

  19. Atmospheric influence of Earth's earliest sulfur cycle

    Science.gov (United States)

    Farquhar; Bao; Thiemens

    2000-08-01

    Mass-independent isotopic signatures for delta(33)S, delta(34)S, and delta(36)S from sulfide and sulfate in Precambrian rocks indicate that a change occurred in the sulfur cycle between 2090 and 2450 million years ago (Ma). Before 2450 Ma, the cycle was influenced by gas-phase atmospheric reactions. These atmospheric reactions also played a role in determining the oxidation state of sulfur, implying that atmospheric oxygen partial pressures were low and that the roles of oxidative weathering and of microbial oxidation and reduction of sulfur were minimal. Atmospheric fractionation processes should be considered in the use of sulfur isotopes to study the onset and consequences of microbial fractionation processes in Earth's early history.

  20. Disinfection by-products in ballast water treatment: an evaluation of regulatory data.

    Science.gov (United States)

    Werschkun, Barbara; Sommer, Yasmin; Banerji, Sangeeta

    2012-10-15

    To reduce the global spread of invasive aquatic species, international regulations will soon require reductions of the number of organisms in ballast water discharged by ships. For this purpose, ballast water treatment systems were developed and approved by an international procedure. These systems rely on established water treatment principles which, to different degrees, have been proven to generate disinfection by-products with hazardous properties but have only scarcely been investigated in marine environments. Our study evaluates the publicly available documentation about approved ballast water treatment systems with regard to by-product formation. The most commonly employed methods are chlorination, ozonation, and ultraviolet (UV) irradiation. Chlorination systems generate trihalomethanes, halogenated acetic acids, and bromate in substantially larger quantities than reported for other areas of application. Levels are highest in brackish water, and brominated species predominate, in particular bromoform and dibromoacetic acid. Ozonation, which is less frequently utilized, produces bromoform in lower concentrations but forms higher levels of bromate, both of which were effectively reduced by active carbon treatment. In systems based on UV radiation, medium pressure lamps are employed as well as UV-induced advanced oxidation. For all UV systems, by-product formation is reported only occasionally. The most notable observations were small increases in nitrite, hydrogen peroxide, halogenated methanes and acetic acids. The assessment of by-product formation during ballast water treatment is limited by the lacking completeness and quality of available information. This concerns the extent and statistical characterisation of chemical analysis as well as the documentation of the test water parameters.

  1. Solar photocatalytic oxidation of recalcitrant natural metabolic by-products of amoxicillin biodegradation.

    Science.gov (United States)

    Pereira, João H O S; Reis, Ana C; Homem, Vera; Silva, José A; Alves, Arminda; Borges, Maria T; Boaventura, Rui A R; Vilar, Vítor J P; Nunes, Olga C

    2014-11-15

    The contamination of the aquatic environment by non-metabolized and metabolized antibiotic residues has brought the necessity of alternative treatment steps to current water decontamination technologies. This work assessed the feasibility of using a multistage treatment system for amoxicillin (AMX) spiked solutions combining: i) a biological treatment process using an enriched culture to metabolize AMX, with ii) a solar photocatalytic system to achieve the removal of the metabolized transformation products (TPs) identified via LC-MS, recalcitrant to further biological degradation. Firstly, a mixed culture (MC) was obtained through the enrichment of an activated sludge sample collected in an urban wastewater treatment plant (WWTP). Secondly, different aqueous matrices spiked with AMX were treated with the MC and the metabolic transformation products were identified. Thirdly, the efficiency of two solar assisted photocatalytic processes (TiO2/UV or Fe(3+)/Oxalate/H2O2/UV-Vis) was assessed in the degradation of the obtained TPs using a lab-scale prototype photoreactor equipped with a compound parabolic collector (CPC). Highest AMX specific biodegradation rates were obtained in buffer and urban wastewater (WW) media (0.10 ± 0.01 and 0.13 ± 0.07 g(AMX) g(biomass)(-1) h(-1), respectively). The resulting TPs, which no longer presented antibacterial activity, were identified as amoxicilloic acid (m/z = 384). The performance of the Fe(3+)/Oxalate/H2O2/UV-Vis system in the removal of the TPs from WW medium was superior to the TiO2/UV process (TPs no longer detected after 40 min (QUV = 2.6 kJ L(-1)), against incomplete TPs removal after 240 min (QUV = 14.9 kJ L(-1)), respectively).

  2. Energy applications of olive-oil industry by-products: 1. The exhaust foot cake

    Energy Technology Data Exchange (ETDEWEB)

    Masghouni, M. [Ecole Nationale des Ingenieurs de Tunis, Belvedere (Tunisia). Laboratoire de synthese et d' analyse des materiaux; Hassairi, M. [Ecole Nationale des Ingenieurs de Tunis, Belvedere (Tunisia). Laboratoire de thermique industrielle

    2000-07-01

    The energy characteristics of the exhaust foot cake (EFC) from the olive-oil extraction industry are described in this paper. This biomass has proved to be an interesting energy source. The use of this solid-waste as a combustible in brick manufacture is economically profitable: 1100 tons of EFC yearly substitute 420 EOT of No. 2 heavy fuel containing 4% of sulphur. The use of this solid-waste as an energy source is environment friendly, as it reduces the nuisance of solid-waste and gas emissions to the atmosphere, particularly sulphur oxides. (author)

  3. Atmospheric Gas-Phase Reactions of Fluorinated Compounds and Alkenes

    DEFF Research Database (Denmark)

    Østerstrøm, Freja From

    3)2CHOCH3, (CF3)2CHOCHO, CF3C(0)OCH3, Z- and E-CF 3CH=CHCF3. These studies include determining the kinetics of the reactions of the compounds with atmospheric oxidants, the products of the reactions, and assessing the atmospheric impact of the compounds by estimating their atmospheric lifetime...

  4. Utilization of biodiesel by-products for mosquito control.

    Science.gov (United States)

    Pant, Megha; Sharma, Satyawati; Dubey, Saurabh; Naik, Satya Narayan; Patanjali, Phool Kumar

    2016-03-01

    The current paper has elaborated the efficient utilization of non-edible oil seed cakes (NEOC), by-products of the bio-diesel extraction process to develop a herbal and novel mosquitocidal composition against the Aedes aegypti larvae. The composition consisted of botanical active ingredients, inerts, burning agents and preservatives; where the botanical active ingredients were karanja (Pongamia glabra) cake powder and jatropha (Jatropha curcas) cake powder, products left after the extraction of oil from karanja and jatropha seed. The percentage mortality value recorded for the combination with concentration, karanja cake powder (20%) and jatropha cake powder (20%), 1:1 was 96%. The coil formulations developed from these biodiesel by-products are of low cost, environmentally friendly and are less toxic than the synthetic active ingredients.

  5. The origins of religion: evolved adaptation or by-product?

    Science.gov (United States)

    Pyysiäinen, Ilkka; Hauser, Marc

    2010-03-01

    Considerable debate has surrounded the question of the origins and evolution of religion. One proposal views religion as an adaptation for cooperation, whereas an alternative proposal views religion as a by-product of evolved, non-religious, cognitive functions. We critically evaluate each approach, explore the link between religion and morality in particular, and argue that recent empirical work in moral psychology provides stronger support for the by-product approach. Specifically, despite differences in religious background, individuals show no difference in the pattern of their moral judgments for unfamiliar moral scenarios. These findings suggest that religion evolved from pre-existing cognitive functions, but that it may then have been subject to selection, creating an adaptively designed system for solving the problem of cooperation.

  6. By-product information can stabilize the reliability of communication.

    Science.gov (United States)

    Schaefer, H Martin; Ruxton, G D

    2012-12-01

    Although communication underpins many biological processes, its function and basic definition remain contentious. In particular, researchers have debated whether information should be an integral part of a definition of communication and how it remains reliable. So far the handicap principle, assuming signal costs to stabilize reliable communication, has been the predominant paradigm in the study of animal communication. The role of by-product information produced by mechanisms other than the communicative interaction has been neglected in the debate on signal reliability. We argue that by-product information is common and that it provides the starting point for ritualization as the process of the evolution of communication. Second, by-product information remains unchanged during ritualization and enforces reliable communication by restricting the options for manipulation and cheating. Third, this perspective changes the focus of research on communication from studying signal costs to studying the costs of cheating. It can thus explain the reliability of signalling in many communication systems that do not rely on handicaps. We emphasize that communication can often be informative but that the evolution of communication does not cause the evolution of information because by-product information often predates and stimulates the evolution of communication. Communication is thus a consequence but not a cause of reliability. Communication is the interplay of inadvertent, informative traits and evolved traits that increase the stimulation and perception of perceivers. Viewing communication as a complex of inadvertent and derived traits facilitates understanding of the selective pressures shaping communication and those shaping information and its reliability. This viewpoint further contributes to resolving the current controversy on the role of information in communication.

  7. New insights into meat by-product utilization.

    Science.gov (United States)

    Toldrá, Fidel; Mora, Leticia; Reig, Milagro

    2016-10-01

    Meat industry generates large volumes of by-products like blood, bones, meat trimmings, skin, fatty tissues, horns, hoofs, feet, skull and viscera among others that are costly to be treated and disposed ecologically. These costs can be balanced through innovation to generate added value products that increase its profitability. Rendering results in feed ingredients for livestock, poultry and aquaculture as well as for pet foods. Energy valorization can be obtained through the thermochemical processing of meat and bone meal or the use of waste animal fats for the production of biodiesel. More recently, new applications have been reported like the production of polyhydroxyalkanoates as alternative to plastics produced from petroleum. Other interesting valorization strategies are based on the hydrolysis of by-products to obtain added value products like bioactive peptides with relevant physiological effects as antihypertensive, antioxidant, antidiabetic, antimicrobial, etc. with promising applications in the food, pharmaceutical and cosmetics industry. This paper reports and discusses the latest developments and trends in the use and valorisation of meat industry by-products.

  8. Fingerprinting the reactive toxicity pathways of 50 drinking water disinfection by-products.

    Science.gov (United States)

    Stalter, Daniel; O'Malley, Elissa; von Gunten, Urs; Escher, Beate I

    2016-03-15

    A set of nine in vitro cellular bioassays indicative of different stages of the cellular toxicity pathway was applied to 50 disinfection by-products (DBPs) to obtain a better understanding of the commonalities and differences in the molecular mechanisms of reactive toxicity of DBPs. An Eschericia coli test battery revealed reactivity towards proteins/peptides for 64% of the compounds. 98% activated the NRf2-mediated oxidative stress response and 68% induced an adaptive stress response to genotoxic effects as indicated by the activation of the tumor suppressor protein p53. All DBPs reactive towards DNA in the E. coli assay and activating p53 also induced oxidative stress, confirming earlier studies that the latter could trigger DBP's carcinogenicity. The energy of the lowest unoccupied molecular orbital ELUMO as reactivity descriptor was linearly correlated with oxidative stress induction for trihalomethanes (r(2)=0.98) and haloacetamides (r(2)=0.58), indicating that potency of these DBPs is connected to electrophilicity. However, the descriptive power was poor for haloacetic acids (HAAs) and haloacetonitriles (r(2) (0.80, indicating that HAAs' potency is connected to both, electrophilicity and speciation. Based on the activation of oxidative stress response and the soft electrophilic character of most tested DBPs we hypothesize that indirect genotoxicity-e.g., through oxidative stress induction and/or enzyme inhibition-is more plausible than direct DNA damage for most investigated DBPs. The results provide not only a mechanistic understanding of the cellular effects of DBPs but the effect concentrations may also serve to evaluate mixture effects of DBPs in water samples.

  9. Total Nitrogen Deposition (wet+dry) from the Atmosphere

    Data.gov (United States)

    U.S. Environmental Protection Agency — Oxides of Nitrogen are emitted primarily as by-products of combustion. Sources include power plants, industrial boilers, and automobiles. In addition, agricultural...

  10. Atmospheric chemistry in volcanic plumes.

    Science.gov (United States)

    von Glasow, Roland

    2010-04-13

    Recent field observations have shown that the atmospheric plumes of quiescently degassing volcanoes are chemically very active, pointing to the role of chemical cycles involving halogen species and heterogeneous reactions on aerosol particles that have previously been unexplored for this type of volcanic plumes. Key features of these measurements can be reproduced by numerical models such as the one employed in this study. The model shows sustained high levels of reactive bromine in the plume, leading to extensive ozone destruction, that, depending on plume dispersal, can be maintained for several days. The very high concentrations of sulfur dioxide in the volcanic plume reduces the lifetime of the OH radical drastically, so that it is virtually absent in the volcanic plume. This would imply an increased lifetime of methane in volcanic plumes, unless reactive chlorine chemistry in the plume is strong enough to offset the lack of OH chemistry. A further effect of bromine chemistry in addition to ozone destruction shown by the model studies presented here, is the oxidation of mercury. This relates to mercury that has been coemitted with bromine from the volcano but also to background atmospheric mercury. The rapid oxidation of mercury implies a drastically reduced atmospheric lifetime of mercury so that the contribution of volcanic mercury to the atmospheric background might be less than previously thought. However, the implications, especially health and environmental effects due to deposition, might be substantial and warrant further studies, especially field measurements to test this hypothesis.

  11. Controlled decomposition and oxidation: A treatment method for gaseous process effluents

    Science.gov (United States)

    Mckinley, Roger J. B., Sr.

    1990-01-01

    The safe disposal of effluent gases produced by the electronics industry deserves special attention. Due to the hazardous nature of many of the materials used, it is essential to control and treat the reactants and reactant by-products as they are exhausted from the process tool and prior to their release into the manufacturing facility's exhaust system and the atmosphere. Controlled decomposition and oxidation (CDO) is one method of treating effluent gases from thin film deposition processes. CDO equipment applications, field experience, and results of the use of CDO equipment and technological advances gained from the field experiences are discussed.

  12. Utilization of Biodiesel By-Products for Biogas Production

    Directory of Open Access Journals (Sweden)

    Nina Kolesárová

    2011-01-01

    Full Text Available This contribution reviews the possibility of using the by-products from biodiesel production as substrates for anaerobic digestion and production of biogas. The process of biodiesel production is predominantly carried out by catalyzed transesterification. Besides desired methylesters, this reaction provides also few other products, including crude glycerol, oil-pressed cakes, and washing water. Crude glycerol or g-phase is heavier separate liquid phase, composed mainly by glycerol. A couple of studies have demonstrated the possibility of biogas production, using g-phase as a single substrate, and it has also shown a great potential as a cosubstrate by anaerobic treatment of different types of organic waste or energy crops. Oil cakes or oil meals are solid residues obtained after oil extraction from the seeds. Another possible by-product is the washing water from raw biodiesel purification, which is an oily and soapy liquid. All of these materials have been suggested as feasible substrates for anaerobic degradation, although some issues and inhibitory factors have to be considered.

  13. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

    Science.gov (United States)

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-07-20

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation.

  14. Reducing the formation of disinfection by-products by pre-ozonation.

    Science.gov (United States)

    Chang, Cheng-Nan; Ma, Ying-Shih; Zing, Fang-Fong

    2002-01-01

    The objective of this study is to apply the pre-ozonation process to reduce the formation of disinfection by-products (DBPs). The raw water sample, collected from the Te-Chi Reservoir in central Taiwan, has been polluted by fertilizer. Three types of resins were used to isolate the natural organic matter into seven types of organic fractions. The pre-ozonation was used to oxidize each organic fraction to study the reduction of DBPs of each fraction. Experimental results indicated that the pre-ozonation could reduce the concentration of dissolved organic carbon resulting in the reduction of DBP formation. With the pre-ozonation, 9-54% of DOC and more than 40% of DBPs were reduced. With the analysis of UV adsorption and Fourier transform infrared spectrometer (FTIR), the reduction of A254 and unsaturated functional groups such as aromatic ring and C=C bond containing in the water sample is the major reaction mechanism.

  15. Atmospheric Electrodeless Microwave Plasma-torch for Gas Decomposition

    Science.gov (United States)

    Kim, J. H.; Hong, Y. C.; Uhm, H. S.

    2001-10-01

    Increasing environmental awareness and regulation have motivated research into new method to remediate toxins from atmospheric pressure gas streams. Plasma remediation was identified as a promising technology treating contaminated gas streams and air. Plasma remediation of toxic gas streams from mobile emitting sources (i. e., Nox, Sox, soot emission from diesel truck engines) and cleaning processes (i.e., global warming gases) require inexpensive, compact, and reliable systems which efficiently and selectively convert the toxic gas to benign or more treatable products. Environmental clean-up and energy efficiency enhancement utilize plasma generated from air at the atmospheric pressure. Electrodes of the arc plasma torches oxidize very quickly due to the oxygen molecules in air. That is why the conventional thermal plasma torch can not be used in environmental applications. In order to solve this difficult problem, we developed a thermal plasma source operating without electrodes. One of electrodeless torches is the microwave plasma which can produce plasmas in large quantities. We can generate plasma at the atmospheric pressure by making use of magnetrons in microwave-ovens. Most of the magnetrons are operated at the frequency of 2.45GHz. Typical magnetron power of home-microwave oven is about 1kW. Electromagnetic waves from magnetron propagate through a waveguide. Plasma is generated under resonant condition, by initiation of an auxiliary ignition system. The plasma is stabilized by vortex stabilization. The eventual application of this research is in air pollution control. Perfluorocarbon Compounds(PFCs), , , and any other global warming gases from etching and cleaning processes have very long lifetime and high global warming potential. We will conduct an experiment to eliminate global warming gases. FT-IR and QMS will be used to analyze and identify by-products after plasma treatment.

  16. Aqueous photodegradation of 4-tert-butylphenol: By-products, degradation pathway and theoretical calculation assessment

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Yanlin [State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Shi, Jin; Chen, Hongche [Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China); Zhao, Jianfu [State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Dong, Wenbo, E-mail: wbdong@fudan.edu.cn [Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China)

    2016-10-01

    4-tert-butylphenol (4-t-BP), an endocrine disrupting chemical, is widely distributed in natural bodies of water but is difficult to biodegrade. In this study, we focused on the transformation of 4-t-BP in photo-initiated degradation processes. The steady-state photolysis and laser flash photolysis (LFP) experiments were conducted in order to elucidate its degradation mechanism. Identification of products was performed using the GC–MS, LC-MS and theoretical calculation techniques. The oxidation pathway of 4-t-BP by hydroxyl radical (HO·) was also studied and H{sub 2}O{sub 2} was added to produce HO·. 4-tert-butylcatechol and 4-tert-butylphenol dimer were produced in 4-t-BP direct photolysis. 4-tert-butylcatechol and hydroquinone were produced by the oxidation of HO·. But the formation mechanism of 4-tert-butylcatechol in the two processes was different. The benzene ring was fractured in 4-t-BP oxidation process and 29% of TOC was degraded after 16 h irradiation. - Highlights: • Photodegradation of 4-t-BP, an endocrine disrupting chemical, has been investigated. • 3 stable byproducts were identified from photolysis and oxidation processes. • 5 transient by-products were concluded from LFP experiments. • The theoretical calculation was performed to confirm the byproducts. • 4-t-BP was degraded with increasing efficiency: 254 nm < H{sub 2}O{sub 2}/313 nm < H{sub 2}O{sub 2}/254 nm.

  17. The alkaline comet assay used in evaluation of genotoxic damage of drinking water disinfection by-products (bromoform and chloroform

    Directory of Open Access Journals (Sweden)

    Messaouda Khallef

    2015-06-01

    Full Text Available The alkaline comet assay (pH 12.3 is a useful method for monitoring genotoxic effects of environmental pollutants in the root nuclei of Allium cepa and various plants; it allows the detection of single- and double-strand breaks, incomplete excision-repair sites and cross-links. It has been introduced to detect even small changes in DNA structure. It is a technically simple, highly sensitive, fast and economic test which detects in vitro and in vivo genotoxicity (DNA integrity and packing mode in any cell types examined, and requires just a few cells for its execution (Liman et al., 2011; Yıldız et al., 2009. Chloroform and bromoform are the most important trihalomethanes found in drinking water. Different concentrations of bromoform (25, 50, 75and 100µg/ml and chloroform (25, 50, 100 and 200 µg/ml were introduced to onion tuber roots. Distilled water was used as a negative control and methyl methansulfonate (MMS-10 µg/ml as positive control. All obtained data were subjected to statistical analyses by using SPSS 15.0 for Windows software. For comparison purposes, Duncan multiple range tests using one-way analysis of variance (ANOVA were employed and p<0.05 was accepted as the test of significance. Comet assay results showed that DNA damage was significant at p <0.05 for the different concentrations of chloroform and bromoform compared to the negative control which has a damage rate equal to 3.5 ± 0.7 and the positive control which has damage rate equal to 13.5 ± 2.12. The exposure of root tip cells to these disinfection by-products increases DNA damage. All concentrations examined in this study of bromoform and chloroform cause significant harm, which could be due to DNA damage induced by oxidative stress. The measurement of DNA damage in the nuclei of higher plant tissues is a new area of study with SCGE. This assay could be incorporated into in situ monitoring of atmosphere, water and soil: the comet assay allows a fast detection without

  18. Solar photocatalytic treatment of landfill leachate using a solid mineral by-product as a catalyst.

    Science.gov (United States)

    Poblete, Rodrigo; Prieto-Rodríguez, Lucia; Oller, Isabel; Maldonado, Manuel I; Malato, Sixto; Otal, Emilia; Vilches, Luis F; Fernández-Pereira, Constantino

    2012-08-01

    The treatment of municipal solid waste landfill leachate in a pilot plant made up of solar compound parabolic collectors, using a solid industrial titanium by-product (WTiO(2)) containing TiO(2) and Fe(III) as a photocatalyst, was investigated. In the study evidence was found showing that the degradation performed with WTiO(2) was mainly due to the Fe provided by this by-product, instead of TiO(2). However, although TiO(2) had very little effect by itself, a synergistic effect was observed between Fe and TiO(2). The application of WTiO(2), which produced coupled photo-Fenton and heterogeneous catalysis reactions, achieved a surprisingly high depuration level (86% of COD removal), higher than that reached by photo-Fenton using commercial FeSO(4) (43%) in the same conditions. After the oxidation process the biodegradability and toxicity of the landfill leachate were studied. The results showed that the leachate biodegradability was substantially increased, at least in the first stages of the process, and again that WTiO(2) was more efficient than FeSO(4) in terms of increasing biodegradability.

  19. Atmospheric Hydrogen Scavenging: from Enzymes to Ecosystems

    OpenAIRE

    2014-01-01

    We have known for 40 years that soils can consume the trace amounts of molecular hydrogen (H2) found in the Earth's atmosphere. This process is predicted to be the most significant term in the global hydrogen cycle. However, the organisms and enzymes responsible for this process were only recently identified. Pure culture experiments demonstrated that several species of Actinobacteria, including streptomycetes and mycobacteria, can couple the oxidation of atmospheric H2 to the reduction of am...

  20. Atmosphere: Power, Critique, Politics

    DEFF Research Database (Denmark)

    Albertsen, Niels

    2016-01-01

    This paper hans three interrelated parts. First, atmosphere is approached through the concept of power. Atmospheres 'grip' us directly or mediate power indirectly by manipulating moods and evoking emotions. How does atmosphere relate to different conceptions of power? Second, atmospheric powers m...... be critiqued. Which conception of critique can be involved? Third, critiquing atmospheric powers can generate political conflict. How does atmospheric disputes relate to conceptions of politics and the political?...

  1. Non-equilibrium,Atmospheric-pressure Plasma Jet for Depositing Silicon Oxide Films%大气压非平衡等离子体沉积氧化硅薄膜

    Institute of Scientific and Technical Information of China (English)

    林江; 张溪文; 韩高荣

    2012-01-01

    本文搭建了一套大气压等离子体薄膜沉积系统,其装置采用喷枪方式,结合运动机构控制喷枪按特定轨迹移动镀膜。四乙氧基硅烷(TEOS)作为硅的先驱体,氮气为先驱体载气和等离子体放电气体,基底温度50℃~300℃,进行了大气压等离子体化学气相沉积氧化硅薄膜的研究。运用红外光谱(FTIR)、光学椭偏仪,扫描电镜(SEM)和纳米压痕仪对沉积的薄膜进行了表征。研究表明,薄膜中富含Si—O—Si键且有少量S—OH键;较高基底温度有利于在硅基底上得到一层平整致密的薄膜;基底温度300℃时薄膜硬度达到4.8GPa,略低于采用PECVD方法沉积的氧化硅薄膜。%A non-equilibrium atmospheric-pressure plasma jet was developed.A kinetic controlling system was integrated to control the movement of plasma jet,which was used to deposit silicon oxide films.TEOS was used as the precursor.N2 gas was used to generate plasma and carry precursor.Substrate temperature was varied from 50℃ to 300℃.As-deposited films were characterized by ellipsometrry,Fourier transform infrared(FTIR) spectroscopy,scanning electron microscopy(SEM) and nano-indentometry.FTIR spectra indicate that there are a majority of Si-O-Si bonds and a minority of Si-OH bonds in the as-deposited films.Higher substrate temperature is contributive to depositing flat and compact films.Under substrate temperature 300℃,film hardness is up to 4.8GPa,which is slightly less than that of films deposited by plasma enhanced chemical vapor deposition(PECVD).

  2. Chlorine dioxine DBPs (disinfection by-products in drinking water

    Directory of Open Access Journals (Sweden)

    C. Lasagna

    2013-01-01

    Full Text Available Since the 1970s it has been well known that, though water for human consumption is generally disinfected before being distributed along the network, the use of chemicals results in the formation of many different Disinfection By-Products (DBPs. In the case of chlorine dioxide, the most important and represented DBPs are chlorite and chlorate: after an introduction concerning the current Italian regulation on this subject, in the experimental part the results of a 7-year minitoring campaign, concerning water of different origin collected from taps in various Italian regions, are shown. The analytical technique used for the determination of chlorite and chlorate was Ion Chromatography. The result obtained are finally discussed.

  3. Detection of regulated disinfection by-products in cheeses.

    Science.gov (United States)

    Cardador, Maria Jose; Gallego, Mercedes; Cabezas, Lourdes; Fernández-Salguero, Jose

    2016-08-01

    Cheese can contain regulated disinfection by-products (DBPs), mainly through contact with brine solutions prepared in disinfected water or sanitisers used to clean all contact surfaces, such as processing equipment and tanks. This study has focused on the possible presence of up to 10 trihalomethanes (THMs) and 13 haloacetic acids (HAAs) in a wide range of European cheeses. The study shows that 2 THMs, (in particular trichloromethane) and 3 HAAs (in particular dichloroacetic acid) can be found at μg/kg levels in the 56 cheeses analysed. Of the two types of DBPs, HAAs were generally present at higher concentrations, due to their hydrophilic and non-volatile nature. Despite their different nature (THMs are lipophilic), both of them have an affinity for fatty cheeses, increasing their concentrations as the percentage of water decreased because the DBPs were concentrated in the aqueous phase of the cheeses.

  4. Valorisation of by Products from Bleached Eucalyptus Kraft Pulp Mill

    Science.gov (United States)

    Silva, M. C.; Lopes, O. R.; Colodette, J. L.; Porto, A. O.; Rieumont, J.; Chaussy, D.; Belgacem, M. N.; Silva, G. G.

    2008-08-01

    Three industrial wastes arising from bleached hardwood kraft pulps, namely: unbleached screen rejects (USR), effluent treatment (ETW), and eucalyptus bark (EB) were analyzed with the aim of their possible valorization as an alternative source of cellulose. Their morphological properties were determined using MorFi apparatus. For this study the sample bleached kraft pulp, BKP, was analyzed as a reference. Lignin and carbohydrate contents were also quantified. These by-products were studied as such (i.e. without careful purification) because we intended to find rational and low-cost way of valorization. In fact any additional operation will induce an over cost. The results obtained indicate that these industrial wastes can be potential raw material in fibre-based applications (paper, composites…), since they contain a high proportion of cellulose with preserved fibrillar morphology. Some of these materials have low lignin and inorganic residue contents.

  5. Effect of Celebrity Endorsement in Advertising Activities by Product Type

    Directory of Open Access Journals (Sweden)

    Karasiewicz Grzegorz

    2014-12-01

    Full Text Available This article seeks to answer two related questions: are celebrity endorsements more likely to be result in a higher evaluation of the product being advertised than use of an anonymous individual (e.g. a typical consumer; and, if present, do these positive effects vary by product category? To answer these two questions research was conducted on a 237 student sample employing a quasi-experiment consisting of four groups (two product categories and two types of endorsers using data collected through an online survey. The results indicate that celebrity endorsements do have a positive impact on the evaluation of durable goods, but do not affect the evaluation of frequently purchased products. This finding largely confirms the assumptions of the match-up model, the meaning transfer model, and the ELM model.

  6. Wheat germ: not only a by-product.

    Science.gov (United States)

    Brandolini, Andrea; Hidalgo, Alyssa

    2012-03-01

    The wheat germ (embryonic axis and scutellum) represents about 2.5-3.8% of total seed weight and is an important by-product of the flour milling industry. The germ contains about 10-15% lipids, 26-35% proteins, 17% sugars, 1.5-4.5% fibre and 4% minerals, as well as significant quantities of bioactive compounds such as tocopherols [300-740 mg/kg dry matter (DM)], phytosterols (24-50 mg/kg), policosanols (10 mg/kg), carotenoids (4-38 mg/kg), thiamin (15-23 mg/kg) and riboflavin (6-10 mg/kg). Oil recovery is achieved by mechanical pressing or solvent extraction, which retrieve about 50% or 90% lipids, respectively; innovative approaches, such as supercritical carbon dioxide extraction, are also proposed. The oil is rich in triglycerides (57% of total lipids), mainly linoleic (18:2), palmitic (16:0) and oleic (18:1) acids, but relevant amounts of sterols, mono- and diglycerides, phospho- and glycolipids are present. The lypophilic antioxidants tocopherols and carotenoids are also abundant. The main by-product of oil extraction is defatted germ meal, which has high protein content (30-32%), is rich in albumin (34.5% of total protein) and globulin (15.6%), and thus presents a well-balanced amino acid profile. Its principal mineral constituents are potassium, magnesium, calcium, zinc and manganese, in decreasing order. Total flavonoid content is about 0.35 g rutin equivalent/100 g DM. The wheat germ is therefore a unique source of concentrated nutrients, highly valued as food supplement. While the oil is widely appreciated for its pharmaceutical and nutritional value, the defatted germ meal is a promising source of high-quality vegetable proteins. Better nutrient separation from the kernel and improved fractioning techniques could also provide high-purity molecules with positive health benefits.

  7. Antioxidant activity, cytotoxic activity and metabolic profiling of juices obtained from saffron (Crocus sativus L.) floral by-products.

    Science.gov (United States)

    Tuberoso, Carlo I G; Rosa, Antonella; Montoro, Paola; Fenu, Maurizio Antonio; Pizza, Cosimo

    2016-05-15

    Juices obtained from cold-pressed saffron (Crocus sativus L.) floral by-products were evaluated as a potential source of compounds with antioxidant and cytotoxic activities. Floral by-products were split in two batches for extraction 24 and 48h after flower harvesting, respectively. The in vitro anti-oxidant activity of these extracts was tested using the FRAP and DPPH assays, and two biological models of lipid oxidation (activity in preventing cholesterol degradation and protection against Cu(2+)-mediated degradation of the liposomal unsaturated fatty acids). The cytotoxic activity was evaluated using the MTT assay. The results show that extracts obtained 48h post-harvest contained higher levels of total polar phenols and had the highest antioxidant activity in all of the performed assays. The LC-DAD and LC-ESI-(HR)MS(n) metabolic profiles showed high levels of kaempferol derivatives and anthocyanins. This study suggests that juices from saffron floral by-products could potentially be used to develop new products for the food and health industry.

  8. Sampling from stochastic reservoir models constrained by production data

    Energy Technology Data Exchange (ETDEWEB)

    Hegstad, Bjoern Kaare

    1997-12-31

    When a petroleum reservoir is evaluated, it is important to forecast future production of oil and gas and to assess forecast uncertainty. This is done by defining a stochastic model for the reservoir characteristics, generating realizations from this model and applying a fluid flow simulator to the realizations. The reservoir characteristics define the geometry of the reservoir, initial saturation, petrophysical properties etc. This thesis discusses how to generate realizations constrained by production data, that is to say, the realizations should reproduce the observed production history of the petroleum reservoir within the uncertainty of these data. The topics discussed are: (1) Theoretical framework, (2) History matching, forecasting and forecasting uncertainty, (3) A three-dimensional test case, (4) Modelling transmissibility multipliers by Markov random fields, (5) Up scaling, (6) The link between model parameters, well observations and production history in a simple test case, (7) Sampling the posterior using optimization in a hierarchical model, (8) A comparison of Rejection Sampling and Metropolis-Hastings algorithm, (9) Stochastic simulation and conditioning by annealing in reservoir description, and (10) Uncertainty assessment in history matching and forecasting. 139 refs., 85 figs., 1 tab.

  9. Synthesis of zeolite phases from combustion by-products

    Energy Technology Data Exchange (ETDEWEB)

    Pimraksa, K.; Chindaprasirt, P.; Setthaya, N. [Chiang Mai University, Chiang Mai (Thailand). Dept. of Industrial Chemistry

    2010-12-15

    Synthesis of zeolites from combustion by-products, including fly ash, bottom ash and rice husk ash, was studied. A molar ratio of SiO{sub 2}/Al2O{sub 3} of 1.5 was used for the syntheses. Refluxing and hydrothermal methods were also used for synthesis for comparison. The reaction temperatures of refluxing and hydrothermal methods were 100{sup o}C and 130{sup o}C, respectively. Sodalite, phillipsite-K, and zeolite P1 with analcime were obtained when fly ash, bottom ash and rice husk ash were used as starting materials, respectively. With rice husk ash as a starting material, zeolite P1 was produced. This result had advantages over previous studies as there was no prior activation required for the synthesis. The concentrations and types of alkaline used in the synthesis also determined the zeolite type. The different zeolites obtained from three systems were measured for specific surface area and pore size by using BET and Hg-porosimetry, respectively. Ammonium exchange capacities of the synthesised powders containing zeolites, sodalite, zeolite P1 and phillipsite-K were 38.5, 65.0 and 154.7 meq 100 g{sup 1}, respectively.

  10. Synthesis of zeolite phases from combustion by-products.

    Science.gov (United States)

    Pimraksa, Kedsarin; Chindaprasirt, Prinya; Setthaya, Naruemon

    2010-12-01

    Synthesis of zeolites from combustion by-products, including fly ash, bottom ash and rice husk ash, was studied. A molar ratio of SiO2/Al2O3 of 1.5 was used for the syntheses. Refluxing and hydrothermal methods were also used for synthesis for comparison. The reaction temperatures of refluxing and hydrothermal methods were 100 degrees C and 130 degrees C, respectively. Sodalite, phillipsite-K, and zeolite P1 with analcime were obtained when fly ash, bottom ash and rice husk ash were used as starting materials, respectively. With rice husk ash as a starting material, zeolite P1 was produced. This result had advantages over previous studies as there was no prior activation required for the synthesis. The concentrations and types of alkaline used in the synthesis also determined the zeolite type. The different zeolites obtained from three systems were measured for specific surface area and pore size by using BET and Hg-porosimetry, respectively. Ammonium exchange capacities of the synthesised powders containing zeolites, sodalite, zeolite P1 and phillipsite-K were 38.5, 65.0 and 154.7 meq 100 g(-1), respectively.

  11. Health impact of disinfection by-products in swimming pools

    Directory of Open Access Journals (Sweden)

    Cristina M. Villanueva

    2012-12-01

    Full Text Available This article is focused on the epidemiological evidence on the health impacts related to disinfection by-products (DBPs in swimming pools, which is a chemical hazard generated as an undesired consequence to reduce the microbial pathogens. Specific DBPs are carcinogenic, fetotoxic and/or irritant to the airways according to experimental studies. Epidemiological evidence shows that swimming in pools during pregnancy is not associated with an increased risk of reproductive outcomes. An epidemiological study suggested an increased risk of bladder cancer with swimming pool attendance, although evidence is inconclusive. A higher prevalence of respiratory symptoms including asthma is found among swimming pool workers and elite swimmers, although the causality of this association is unclear. The body of evidence in children indicates that asthma is not increased by swimming pool attendance. Overall, the available knowledge suggests that the health benefits of swimming outweigh the potential health risks of chemical contamination. However, the positive effects of swimming should be enhanced by minimising potential risks.

  12. UTILIZATION OF LOW NOx COAL COMBUSTION BY-PRODUCTS

    Energy Technology Data Exchange (ETDEWEB)

    J.Y. Hwang; X. Huang; M.G. McKimpson; R.E. Tieder; A.M. Hein; J.M. Gillis; D.C. Popko; K.L. Paxton; Z. Li; X. Liu; X. Song; R.I. Kramer

    1998-12-01

    Low NO{sub x} combustion practices are critical for reducing NO{sub x} emissions from power plants. These low NO{sub x} combustion practices, however, generate high residual carbon contents in the fly ash produced. These high carbon contents threaten utilization of this combustion by-product. This research has successfully developed a separation technology to render fly ash into useful, quality-controlled materials. This technology offers great flexibility and has been shown to be applicable to all of the fly ashes tested (more than 10). The separated materials can be utilized in traditional fly ash applications, such as cement and concrete, as well as in nontraditional applications such as plastic fillers, metal matrix composites, refractories, and carbon adsorbents. Technologies to use beneficiated fly ash in these applications are being successfully developed. In the future, we will continue to refine the separation and utilization technologies to expand the utilization of fly ash. The disposal of more than 31 million tons of fly ash per year is an important environmental issue. With continued development, it will be possible to increase economic, energy and environmental benefits by re-directing more of this fly ash into useful materials.

  13. Minimization of the formation of disinfection by-products.

    Science.gov (United States)

    Badawy, Mohamed I; Gad-Allah, Tarek A; Ali, Mohamed E M; Yoon, Yeoman

    2012-09-01

    The drinking water industry is required to minimize DBPs levels while ensuring adequate disinfection. In this study, efficient and appropriate treatment scheme for the reduction of disinfection by-product (DBPs) formation in drinking water containing natural organic matter has been established. This was carried out by the investigation of different treatment schemes consisting of enhanced coagulation, sedimentation, disinfection by using chlorine dioxide/ozone, filtration by sand filter, or granular activated carbon (GAC). Bench scale treatment schemes were applied on actual samples from different selected sites to identify the best conditions for the treatment of water. Samples were collected from effluent of each step in the treatment train in order to analyze pH, UV absorbance at 254 nm (UVA(254)), specific UV absorbance at 254 nm (SUVA(254)), dissolved organic carbon (DOC), haloacetic acids (HAAs) and trihalomethanes (THMs). The obtained results indicated that using pre-ozonation/enhanced coagulation/activated carbon filtration treatment train appears to be the most effective method for reducing DBPs precursors in drinking water treatment.

  14. Photochemical processing of aqueous atmospheric brown carbon

    Directory of Open Access Journals (Sweden)

    R. Zhao

    2015-01-01

    Full Text Available Atmospheric Brown Carbon (BrC is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS or methylglyoxal (MGAS are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate atmospheric relevance of this work, we also performed direct photolysis experiments on water soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

  15. Photochemical processing of aqueous atmospheric brown carbon

    Directory of Open Access Journals (Sweden)

    R. Zhao

    2015-06-01

    Full Text Available Atmospheric brown carbon (BrC is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report on a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS or methylglyoxal (MGAS are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water-soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate the atmospheric relevance of this work, we also performed direct photolysis experiments on water-soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in the optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

  16. Photochemical processing of aqueous atmospheric brown carbon

    Science.gov (United States)

    Zhao, R.; Lee, A. K. Y.; Huang, L.; Li, X.; Yang, F.; Abbatt, J. P. D.

    2015-06-01

    Atmospheric brown carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report on a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS) or methylglyoxal (MGAS) are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water-soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate the atmospheric relevance of this work, we also performed direct photolysis experiments on water-soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in the optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

  17. DEVELOPMENT OF ACTIVATED CARBONS FROM COAL COMBUSTION BY-PRODUCTS

    Energy Technology Data Exchange (ETDEWEB)

    Harold H. Schobert; M. Mercedes Maroto-Valer; Zhe Lu

    2003-09-30

    The increasing role of coal as a source of energy in the 21st century will demand environmental and cost-effective strategies for the use of coal combustion by-products (CCBPs), mainly unburned carbon in fly ash. Unburned carbon is nowadays regarded as a waste product and its fate is mainly disposal, due to the present lack of efficient routes for its utilization. However, unburned carbon is a potential precursor for the production of adsorbent carbons, since it has gone through a devolatilization process while in the combustor, and therefore, only requires to be activated. Accordingly, the principal objective of this work was to characterize and utilize the unburned carbon in fly ash for the production of activated carbons. The unburned carbon samples were collected from different combustion systems, including pulverized utility boilers, a utility cyclone, a stoker, and a fluidized bed combustor. LOI (loss-on-ignition), proximate, ultimate, and petrographic analyses were conducted, and the surface areas of the samples were characterized by N2 adsorption isotherms at 77K. The LOIs of the unburned carbon samples varied between 21.79-84.52%. The proximate analyses showed that all the samples had very low moisture contents (0.17 to 3.39 wt %), while the volatile matter contents varied between 0.45 to 24.82 wt%. The elemental analyses show that all the unburned carbon samples consist mainly of carbon with very little hydrogen, nitrogen, sulfur and oxygen In addition, the potential use of unburned carbon as precursor for activated carbon (AC) was investigated. Activated carbons with specific surface area up to 1075m{sup 2}/g were produced from the unburned carbon. The porosity of the resultant activated carbons was related to the properties of the unburned carbon feedstock and the activation conditions used. It was found that not all the unburned carbon samples are equally suited for activation, and furthermore, their potential as activated carbons precursors could be

  18. Atmospheric oxygenation three billion years ago.

    Science.gov (United States)

    Crowe, Sean A; Døssing, Lasse N; Beukes, Nicolas J; Bau, Michael; Kruger, Stephanus J; Frei, Robert; Canfield, Donald E

    2013-09-26

    It is widely assumed that atmospheric oxygen concentrations remained persistently low (less than 10(-5) times present levels) for about the first 2 billion years of Earth's history. The first long-term oxygenation of the atmosphere is thought to have taken place around 2.3 billion years ago, during the Great Oxidation Event. Geochemical indications of transient atmospheric oxygenation, however, date back to 2.6-2.7 billion years ago. Here we examine the distribution of chromium isotopes and redox-sensitive metals in the approximately 3-billion-year-old Nsuze palaeosol and in the near-contemporaneous Ijzermyn iron formation from the Pongola Supergroup, South Africa. We find extensive mobilization of redox-sensitive elements through oxidative weathering. Furthermore, using our data we compute a best minimum estimate for atmospheric oxygen concentrations at that time of 3 × 10(-4) times present levels. Overall, our findings suggest that there were appreciable levels of atmospheric oxygen about 3 billion years ago, more than 600 million years before the Great Oxidation Event and some 300-400 million years earlier than previous indications for Earth surface oxygenation.

  19. Atmospheric degradation mechanism of organic sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Benter, T.; Arsene, C.

    2002-02-01

    In the present work a detailed product study has been performed on the OH radical initiated oxidation of dimethyl sulphide and dimethyl sulphoxide, under different conditions of temperature, partial pressure of oxygen and NO{sub x} concentration, in order to better define the degradation mechanism of the above compounds under conditions which prevail in the atmosphere. (orig.)

  20. BUILDING MATERIALS MADE FROM FLUE GAS DESULFURIZATION BY-PRODUCTS

    Energy Technology Data Exchange (ETDEWEB)

    Michael W. Grutzeck; Maria DiCola; Paul Brenner

    2006-03-30

    Flue gas desulphurization (FGD) materials are produced in abundant quantities by coal burning utilities. Due to environmental restrains, flue gases must be ''cleaned'' prior to release to the atmosphere. They are two general methods to ''scrub'' flue gas: wet and dry. The choice of scrubbing material is often defined by the type of coal being burned, i.e. its composition. Scrubbing is traditionally carried out using a slurry of calcium containing material (slaked lime or calcium carbonate) that is made to contact exiting flue gas as either a spay injected into the gas or in a bubble tower. The calcium combined with the SO{sub 2} in the gas to form insoluble precipitates. Some plants have been using dry injection of these same materials or their own Class C fly ash to scrub. In either case the end product contains primarily hannebachite (CaSO{sub 3} {center_dot} 1/2H{sub 2}O) with smaller amounts of gypsum (CaSO{sub 4} {center_dot} 2H{sub 2}O). These materials have little commercial use. Experiments were carried out that were meant to explore the feasibility of using blends of hannebachite and fly ash mixed with concentrated sodium hydroxide to make masonry products. The results suggest that some of these mixtures could be used in place of conventional Portland cement based products such as retaining wall bricks and pavers.

  1. Atmospheric composition change: Ecosystems-Atmosphere interactions

    NARCIS (Netherlands)

    Fowler, D.; Pilegaard, K.; Sutton, M.A.; Ambus, P.; Raivonen, M.; Duyzer, J.; Simpson, D.; Fagerli, H.; Fuzzi, S.; Schjoerring, J.K.; Granier, C.; Neftel, A.; Isaksen, I.S.A.; Laj, P.; Maione, M.; Monks, P.S.; Burkhardt, J.; Daemmgen, U.; Neirynck, J.; Personne, E.; Wichink Kruit, R.J.; Butterbach-Bahl, K.; Flechard, C.; Tuovinen, J.P.; Coyle, M.; Gerosa, G.; Loubet, B.; Altimir, N.; Gruenhage, L.; Ammann, C.; Cieslik, S.; Paoletti, E.; Mikkelsen, T.N.; Ro-Poulsen, H.; Cellier, P.; Cape, J.N.; Horvath, L.; Loreto, F.; Niinemets, U.; Palmer, P.I.; Rinne, J.; Misztal, P.; Nemitz, E.; Nilsson, D.; Pryor, S.; Gallagher, M.W.; Vesala, T.; Skiba, U.; Brueggemann, N.; Zechmeister-Boltenstern, S.; Williams, J.; O'Dowd, C.; Facchini, M.C.; Leeuw, de G.; Flossman, A.; Chaumerliac, N.; Erisman, J.W.

    2009-01-01

    Ecosystems and the atmosphere: This review describes the state of understanding the processes involved in the exchange of trace gases and aerosols between the earth's surface and the atmosphere. The gases covered include NO, NO2, HONO, HNO3, NH3, SO2, DMS, Biogenic VOC, O-3, CH4, N2O and particles i

  2. Enrichment of functional properties of ice cream with pomegranate by-products.

    Science.gov (United States)

    Çam, Mustafa; Erdoğan, Fatma; Aslan, Duygu; Dinç, Merve

    2013-10-01

    Pomegranate peel rich in phenolics, and pomegranate seed which contain a conjugated fatty acid namely punicic acid in lipid fraction remain as by-products after processing the fruit into juice. Ice cream is poor in polyunsaturated fatty acids and phenolics, therefore, this study was conducted to improve the functional properties of ice cream by incorporating pomegranate peel phenolics and pomegranate seed oil. Incorporation of the peel phenolics into ice cream at the levels of 0.1% and 0.4% (w/w) resulted in significant changes in the pH, total acidity, and color of the samples. The most prominent outcomes of phenolic incorporation were sharp improvements in antioxidant and antidiabetic activities as well as the phenolic content of ice creams. Replacement of pomegranate seed oil by milk fat at the levels of 2.0% and 4.0% (w/w) increased the conjugated fatty acid content. However, perception of oxidized flavor increased with the additional seed oil. When one considers the functional and nutritional improvements in the enrichment of the ice cream together with overall acceptability results of the sensory analysis, then it follows from this study that ice creams enriched with pomegranate peel phenolics up to 0.4% (w/w) and pomegranate seed oil up to 2.0% (w/w) could be introduced to markets as functional ice cream. Enrichment of ice creams with pomegranate by-products might provide consumers health benefits with striking functional properties of punicalagins in pomegranate peel, and punicic acid in pomegranate seed oil.

  3. Coal slurry solids/coal fluidized bed combustion by-product mixtures as plant growth media

    Science.gov (United States)

    Darmody, R.G.; Green, W.P.; Dreher, G.B.

    1998-01-01

    Fine-textured, pyritic waste produced by coal cleaning is stored in slurry settling ponds that eventually require reclamation. Conventionally, reclamation involves covering the dewatered coal slurry solids (CSS) with 1.3 m of soil to allow plant growth and prevent acid generation by pyrite oxidation. This study was conducted to determine the feasiblity of a less costly reclamation approach that would eliminate the soil cover and allow direct seeding of plants into amended CSS materials. Potential acidity of the CSS would be neutralized by additions of fluidized-bed combustion by-product (FBCB), an alkaline by-product of coal combustion. The experiment involved two sources of CSS and FBCB materials from Illinois. Birdsfoot trefoil (Lotus corniculatus L.), tall fescue (Festuca arundinacea Schreb.), and sweet clover (Melilotus officinalis (L.) Lam.) were seeded in the greenhouse into pots containing mixtures of the materials. CSS-1 had a high CaCO3:FeS2 ratio and needed no FBCB added to compensate for its potential acidity. CSS-2 was mixed with the FBCB materials to neutralize potential acidity (labeled Mix A and B). Initial pH was 5.6, 8.8, and 9.2 for the CSS-1, Mix A, and Mix B materials, respectively. At the end of the 70-day experiment, pH was 5.9 for all mixtures. Tall fescue and sweet clover grew well in all the treatments, but birdsfoot trefoil had poor emergence and survival. Elevated tissue levels of B, Cd, and Se were found in some plants. Salinity, low moisture holding capacity, and potentially phytotoxic B may limit the efficacy of this reclamation method.

  4. The global atmospheric budget of ethanol revisited

    Directory of Open Access Journals (Sweden)

    W. V. Kirstine

    2012-01-01

    Full Text Available Ethanol is an important biogenic volatile organic compound, which is increasingly used as a fuel for motor vehicles; therefore, an improved understanding of its atmospheric cycle is important. In this paper we use three sets of observational data, measured emissions of ethanol from living plants, measured concentrations of ethanol in the atmosphere and measured hydroxyl concentrations in the atmosphere (by methyl chloroform titration, to make two independent estimates related to the rate of cycling of ethanol through the atmosphere. In the first estimate, simple calculations give the emission rate of ethanol from living plants as 26 (range, 10–38 Tg yr−1. This contributes significantly to the total global ethanol source of 42 (range, 25–56 Tg yr−1. In the second estimate, the total losses of ethanol from the global atmosphere are 70 (range, 50–90 Tg yr−1, with about three-quarters of the ethanol removed by reaction with hydroxyl radicals in the gaseous and aqueous phases of the atmosphere, and the remainder lost through wet and dry deposition to land. These values of both the source of ethanol from living plants and the removal of atmospheric ethanol via oxidation by hydroxyl radicals (derived entirely from observations are significantly larger than those in recent literature. We suggest that a revision of the estimate of global ethanol emissions from plants to the atmosphere to a value comparable with this analysis is warranted.

  5. Methane oxidation needs less stressed plants.

    Science.gov (United States)

    Zhou, Xiaoqi; Smaill, Simeon J; Clinton, Peter W

    2013-12-01

    Methane oxidation rates in soil are liable to be reduced by plant stress responses to climate change. Stressed plants exude ethylene into soil, which inhibits methane oxidation when present in the soil atmosphere. Here we discuss opportunities to use 1-aminocyclopropane-1-carboxylate deaminase to manage methane oxidation by regulating plant stress responses.

  6. Identification of ozonation by-products of 4- and 5-methyl-1H-benzotriazole during the treatment of surface water to drinking water.

    Science.gov (United States)

    Müller, Alexander; Weiss, Stefan C; Beisswenger, Judith; Leukhardt, H Georg; Schulz, Wolfgang; Seitz, Wolfram; Ruck, Wolfgang K L; Weber, Walter H

    2012-03-01

    During the treatment of surface water to drinking water, ozonation is often used for disinfection and to remove organic trace substances, whereby oxidation by-products can be formed. Here we use the example of tolyltriazole to describe an approach for identifying relevant oxidation by-products in the laboratory and subsequently detecting them in an industrial-scale process. The identification process involves ozonation experiments with pure substances at laboratory level (concentration range mg L(-1)). The reaction solutions from different ozone contact times were analyzed by high performance liquid chromatography - quadrupole time-of-flight mass spectrometry (HPLC-QTOF-MS) in full scan mode. Various approaches were used to detect the oxidation by-products: (i) target searches of postulated oxidation by-products, (ii) comparisons of chromatograms (e.g., UV/VIS) of the different samples, and (iii) color-coded abundance time courses (kinetic) of all detected compounds were illustrated in a kind of a heat map. MS/MS, H/D exchange, and derivatization experiments were used for structure elucidation for the detected by-product. Due to the low contaminant concentrations (ng L(-1)-range) of contaminants in the untreated water, the conversion of results from laboratory experiments to an industrial-scale required the use of HPLC-MS/MS with sample enrichment (e.g., solid phase extraction.) In cases where reference substances were not available or oxidation by-products without clear structures were detected, reaction solutions from laboratory experiments were used to optimize the analytical method to detect ng L(-1) in the samples of the industrial processes. We exemplarily demonstrated the effectiveness of the methodology with the industrial chemicals 4- and 5-methyl-1H-benzotriazole (4- and 5-MBT) as an example. Moreover, not only did we identify several oxidation by-products in the laboratory experiments tentatively, but also detected three of the eleven reaction

  7. Growth of ∼5 cm2V−1s−1 mobility, p-type Copper(I oxide (Cu2O films by fast atmospheric atomic layer deposition (AALD at 225°C and below

    Directory of Open Access Journals (Sweden)

    D. Muñoz-Rojas

    2012-12-01

    Full Text Available Phase pure, dense Cu2O thin films were grown on glass and polymer substrates at 225°C by rapid atmospheric atomic layer deposition (AALD. Carrier mobilities of 5 cm2V−1s−1 and carrier concentrations of ∼1016 cm−3 were achieved in films of thickness 50 - 120 nm, over a >10 cm2 area. Growth rates were ∼1 nm·min−1 which is two orders of magnitude faster than conventional ALD.. The high mobilities achieved using the atmospheric, low temperature method represent a significant advance for flextronics and flexible solar cells which require growth on plastic substrates.

  8. The kinetics of chemical processes affecting acidity in the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Pienaar, J.J.; Helas, G. [Potchefstroom University of Christian Higher Education, Potchefstroom (South Africa). Atmospheric Chemistry Research Group

    1996-03-01

    The dominant chemical reactions affecting atmospheric pollution chemistry and in particular, those leading to the formation of acid rain are outlined. The factors controlling the oxidation rate of atmospheric pollutants as well as the rate laws describing these processes are discussed in the light of our latest results and the current literature.

  9. Mirador - Atmospheric Composition

    Data.gov (United States)

    National Aeronautics and Space Administration — Earth Science data access made simple. Atmospheric Composition is focused on the composition of Earth's atmosphere in relation to climate prediction, solar effects,...

  10. Planetary Atmospheric Electricity

    CERN Document Server

    Leblanc, F; Yair, Y; Harrison, R. G; Lebreton, J. P; Blanc, M

    2008-01-01

    This volume presents our contemporary understanding of atmospheric electricity at Earth and in other solar system atmospheres. It is written by experts in terrestrial atmospheric electricity and planetary scientists. Many of the key issues related to planetary atmospheric electricity are discussed. The physics presented in this book includes ionisation processes in planetary atmospheres, charge generation and separation, and a discussion of electromagnetic signatures of atmospheric discharges. The measurement of thunderstorms and lightning, including its effects and hazards, is highlighted by articles on ground and space based instrumentation, and new missions.Theory and modelling of planetary atmospheric electricity complete this review of the research that is undertaken in this exciting field of space science. This book is an essential research tool for space scientists and geoscientists interested in electrical effects in atmospheres and planetary systems. Graduate students and researchers who are new to t...

  11. Our shared atmosphere

    Science.gov (United States)

    Our atmosphere is a precious and fascinating resource, providing air to breath, shielding us from harmful ultraviolet radiation (UV), and maintaining a comfortable climate. Since the industrial revolution, people have significantly altered the composition of the atmosphere throu...

  12. Bioanalytical and chemical evaluation of disinfection by-products in swimming pool water.

    Science.gov (United States)

    Yeh, Ruby Y L; Farré, Maria José; Stalter, Daniel; Tang, Janet Y M; Molendijk, Jeffrey; Escher, Beate I

    2014-08-01

    Pool water disinfection is vital to prevent microbial pathogens. However, potentially hazardous disinfection by-products (DBP) are formed from the reaction between disinfectants and organic/inorganic precursors. The aim of this study was to evaluate the presence of DBPs in various swimming pool types in Brisbane, Australia, including outdoor, indoor and baby pools, and the dynamics after a complete water renewal. Chemical analysis of 36 regulated and commonly found DBPs and total adsorbable organic halogens as well as in vitro bioassays targeting cytotoxicity, oxidative stress and genotoxicity were used to evaluate swimming pool water quality. Dichloroacetic acid and trichloroacetic acid dominated in the pool water samples with higher levels (up to 2600 μg/L) than the health guideline values set by the Australian Drinking Water Guidelines (100 μg/L). Chlorinated DBPs occurred at higher concentrations compared to tap water, while brominated DBPs decreased gradually with increasing pool water age. Biological effects were expressed as chloroacetic acid equivalent concentrations and compared to predicted effects from chemical analysis and biological characterisation of haloacetic acids. The quantified haloacetic acids explained 35-118% of the absorbable organic halogens but less than 4% of the observed non-specific toxicity (cytotoxicity), and less than 1% of the observed oxidative stress response and genotoxicity. While the DBP concentrations in Australian pools found in this study are not likely to cause any adverse health effect, they are higher than in other countries and could be reduced by better hygiene of pool users, such as thorough showering prior to entering the pool and avoiding urination during swimming.

  13. Atmospheric and accelerator neutrinos

    Energy Technology Data Exchange (ETDEWEB)

    Suzuki, Yoichiro [Kamioka Observatory, Institute for Cosmic Ray Research, University of Tokyo Higashi-Mozumi, Kamioka, Hida-City, Gifu 506-1205 (Japan)

    2006-05-15

    Results from the atmospheric neutrino measurements are presented. Evidence for the {nu}{sub {tau}} appearance in the atmospheric neutrino events was shown by statistical methods. The long baseline oscillation experiment using man-made neutrinos has confirmed the atmospheric neutrino oscillation. The future accelerator experiments are briefly discussed.

  14. Atmospheric refraction : a history

    NARCIS (Netherlands)

    Lehn, WH; van der Werf, S

    2005-01-01

    We trace the history of atmospheric refraction from the ancient Greeks up to the time of Kepler. The concept that the atmosphere could refract light entered Western science in the second century B.C. Ptolemy, 300 years later, produced the first clearly defined atmospheric model, containing air of un

  15. Atmospheric Composition Change: Climate-Chemistry Interactions

    Science.gov (United States)

    Isaksen, I.S.A.; Granier, C.; Myhre, G.; Bernsten, T. K.; Dalsoren, S. B.; Gauss, S.; Klimont, Z.; Benestad, R.; Bousquet, P.; Collins, W.; Cox, T.; Eyring, V.; Fowler, D.; Fuzzi, S.; Jockel, P.; Laj, P.; Lohmann, U.; Maione, M.; Monks, T.; Prevot, A. S. H.; Raes, F.; Richter, A.; Rognerud, B.; Schulz, M.; Shindell, D.; Stevenson, D. S.; Storelvmo, T.; Wang, W.-C.; vanWeele, M.; Wild, M.; Wuebbles, D.

    2011-01-01

    Chemically active climate compounds are either primary compounds such as methane (CH4), removed by oxidation in the atmosphere, or secondary compounds such as ozone (O3), sulfate and organic aerosols, formed and removed in the atmosphere. Man-induced climate-chemistry interaction is a two-way process: Emissions of pollutants change the atmospheric composition contributing to climate change through the aforementioned climate components, and climate change, through changes in temperature, dynamics, the hydrological cycle, atmospheric stability, and biosphere-atmosphere interactions, affects the atmospheric composition and oxidation processes in the troposphere. Here we present progress in our understanding of processes of importance for climate-chemistry interactions, and their contributions to changes in atmospheric composition and climate forcing. A key factor is the oxidation potential involving compounds such as O3 and the hydroxyl radical (OH). Reported studies represent both current and future changes. Reported results include new estimates of radiative forcing based on extensive model studies of chemically active climate compounds such as O3, and of particles inducing both direct and indirect effects. Through EU projects such as ACCENT, QUANTIFY, and the AEROCOM project, extensive studies on regional and sector-wise differences in the impact on atmospheric distribution are performed. Studies have shown that land-based emissions have a different effect on climate than ship and aircraft emissions, and different measures are needed to reduce the climate impact. Several areas where climate change can affect the tropospheric oxidation process and the chemical composition are identified. This can take place through enhanced stratospheric-tropospheric exchange of ozone, more frequent periods with stable conditions favouring pollution build up over industrial areas, enhanced temperature-induced biogenic emissions, methane releases from permafrost thawing, and enhanced

  16. Catalysts development to base of Cu and Ni supported in ZrO{sub 2} for the H{sub 2} generation by the methanol reformed in oxidizing atmosphere;Desarrollo de catalizadores a base de Cu y Ni soportados en ZrO{sub 2} para la generacion de H{sub 2} mediante el reformado de metanol en atmosfera oxidante

    Energy Technology Data Exchange (ETDEWEB)

    Lopez C, P.; Gutierrez, A.; Gutierrez W, C.; Mendoza A, D.; Martinez, G.; Perez H, R., E-mail: raul.perez@inin.gob.m [ININ, Departamento de Tecnologia de Materiales, Carretera Mexico-Toluca s/n, Ocoyoacac 52750, Estado de Mexico (Mexico)

    2009-07-01

    The search of new alternating sources of energy is at the present time one of the primordial objectives to world level because of the global heating caused by the high emissions of CO{sub 2} at the atmosphere. In this sense the employment of H{sub 2} through the fuel cells offers a more viable alternative for the use of the energy coming from the connection H-H that can be appointed for use of mobile, industrial and homemade applications. However, to generate H{sub 2} in enough quantities is a great challenge at technological level for the necessity of to count with highly selective and efficient catalysts to low reaction temperatures as well as a source that comes from renewable resources. Under this context the methanol reformed in oxidizing atmosphere offers great ecological as energetics and industrial advantages; inside this investigation plane, the Cu seems to be one of the suitable candidates for this reaction due to its high capacity to generate H{sub 2}, besides the great potential of improvement in its physical-chemical properties when being worked in nano metric size and /or associated with other materials. On the other hand, it is known that the Ni addition improvement the catalytic properties because of a better material dispersion, what offers big possibilities of being applied in the H{sub 2} generation in situ by means of the methanol reformed reaction in oxidizing atmosphere; and that the conformation of bimetallic particles Cu/Ni presented high selectivity and catalytic activity for the reaction in question. (Author)

  17. Evolution of Oxidative Continental Weathering

    Science.gov (United States)

    Konhauser, Kurt; Lalonde, Stefan

    2014-05-01

    The Great Oxidation Event (GOE) is currently viewed as a protracted process during which atmospheric oxygen levels increased above 10-5 times the present atmospheric level. This value is based on the loss of sulphur isotope mass independent fractionation (S-MIF) from the rock record, beginning at 2.45 Ga and disappearing by 2.32 Ga. However, a number of recent papers have pushed back the timing for oxidative continental weathering, and by extension, the onset of atmospheric oxygenation several hundreds of million years earlier despite the presence of S-MIF (e.g., Crowe et al., 2013). This apparent discrepancy can, in part, be resolved by the suggestion that recycling of older sedimentary sulphur bearing S-MIF might have led to this signal's persistence in the rock record for some time after atmospheric oxygenation (Reinhard et al., 2013). Here we suggest another possibility, that the earliest oxidative weathering reactions occurred in environments at profound redox disequilibrium with the atmosphere, such as biological soil crusts, riverbed and estuarine sediments, and lacustrine microbial mats. We calculate that the rate of O2 production via oxygenic photosynthesis in these terrestrial microbial ecosystems provides largely sufficient oxidizing potential to mobilise sulphate and a number of redox-sensitive trace metals from land to the oceans while the atmosphere itself remained anoxic with its attendant S-MIF signature. These findings reconcile geochemical signatures in the rock record for the earliest oxidative continental weathering with the history of atmospheric sulphur chemistry, and demonstrate the plausible antiquity of a terrestrial biosphere populated by cyanobacteria. Crowe, S.A., Dossing, L.N., Beukes, N.J., Bau, M., Kruger, S.J., Frei, R. & Canfield, D.E. Atmospheric oxygenation three billion years ago. Nature 501, 535-539 (2013). Reinhard, C.T., Planavsky, N.J. & Lyons, T.W. Long-term sedimentary recycling of rare sulphur isotope anomalies. Nature 497

  18. Atmospheric Habitable Zones in Y Dwarf Atmospheres

    Science.gov (United States)

    Yates, Jack S.; Palmer, Paul I.; Biller, Beth; Cockell, Charles S.

    2017-02-01

    We use a simple organism lifecycle model to explore the viability of an atmospheric habitable zone (AHZ), with temperatures that could support Earth-centric life, which sits above an environment that does not support life. To illustrate our model, we use a cool Y dwarf atmosphere, such as WISE J085510.83–0714442.5, whose 4.5–5.2 μm spectrum shows absorption features consistent with water vapor and clouds. We allow organisms to adapt to their atmospheric environment (described by temperature, convection, and gravity) by adopting different growth strategies that maximize their chance of survival and proliferation. We assume a constant upward vertical velocity through the AHZ. We found that the organism growth strategy is most sensitive to the magnitude of the atmospheric convection. Stronger convection supports the evolution of more massive organisms. For a purely radiative environment, we find that evolved organisms have a mass that is an order of magnitude smaller than terrestrial microbes, thereby defining a dynamical constraint on the dimensions of life that an AHZ can support. Based on a previously defined statistical approach, we infer that there are of the order of 109 cool Y brown dwarfs in the Milky Way, and likely a few tens of these objects are within 10 pc from Earth. Our work also has implications for exploring life in the atmospheres of temperate gas giants. Consideration of the habitable volumes in planetary atmospheres significantly increases the volume of habitable space in the galaxy.

  19. The epidemiology and possible mechanisms of disinfection by-products in drinking water.

    Science.gov (United States)

    Nieuwenhuijsen, Mark J; Grellier, James; Smith, Rachel; Iszatt, Nina; Bennett, James; Best, Nicky; Toledano, Mireille

    2009-10-13

    This paper summarizes the epidemiological evidence for adverse health effects associated with disinfection by-products (DBPs) in drinking water and describes the potential mechanism of action. There appears to be good epidemiological evidence for a relationship between exposure to DBPs, as measured by trihalomethanes (THMs), in drinking water and bladder cancer, but the evidence for other cancers including colorectal cancer is inconclusive and inconsistent. There appears to be some evidence for an association between exposure to DBPs, specifically THMs, and little for gestational age/intrauterine growth retardation and, to a lesser extent, pre-term delivery, but evidence for relationships with other outcomes such as low birth weight, stillbirth, congenital anomalies and semen quality is inconclusive and inconsistent. Major limitations in exposure assessment, small sample sizes and potential biases may account for the inconclusive and inconsistent results in epidemiological studies. Moreover, most studies have focused on total THMs as the exposure metric, whereas other DBPs appear to be more toxic than the THMs, albeit generally occurring at lower levels in the water. The mechanisms through which DBPs may cause adverse health effects including cancer and adverse reproductive effects have not been well investigated. Several mechanisms have been suggested, including genotoxicity, oxidative stress, disruption of folate metabolism, disruption of the synthesis and/or secretion of placental syncytiotrophoblast-derived chorionic gonadotropin and lowering of testosterone levels, but further work is required in this area.

  20. In situ detection of lipid peroxidation by-products in chronic liver diseases.

    Science.gov (United States)

    Paradis, V; Kollinger, M; Fabre, M; Holstege, A; Poynard, T; Bedossa, P

    1997-07-01

    Lipid peroxidation is an autocatalytic mechanism leading to oxidative destruction of cellular membranes. The deleterious consequences of this mechanism are related in part to the formation of reactive aldehydic products that bind to intra- or extracellular molecules to form adducts. Specific antibodies directed against malondialdehyde (MDA) and 4-hydroxynonenal (HNE) adducts, major aldehydic metabolites of lipid peroxidation, allowed us to investigate in situ, with an immunohistochemical procedure, the occurrence of lipid peroxidation in a panel of different chronic liver diseases. Intracellular HNE and MDA adducts were detected respectively in 24 of 39 cases (62%) and in 12 of 34 cases investigated (35%). They were localized mainly in the cytoplasm of hepatocytes, with the strongest staining observed in hemochromatosis, Wilson's disease, and in areas of acute alcoholic hepatitis in cases of alcoholic liver diseases. A peculiar pattern of immunostaining was observed in primary biliary cirrhosis where biliary cells of destroyed but also intact bile ducts strongly expressed HNE adducts. The liver extracellular matrix also displayed MDA adducts (30 of 34 cases, 88%) and HNE adducts (23 of 39 cases, 59%). While HNE adducts were specifically localized on large bundles of collagen fibers, MDA adducts were detected in a thin reticular network and in sinusoidal cells around portal tracts or fibrous septa. In conclusion, lipid peroxidation by-products are detectable in chronic liver diseases. Immunohistochemical results suggest that this mechanism is implicated very early in the pathogenesis of some of these diseases.

  1. Bioanalytical and chemical assessment of the disinfection by-product formation potential: role of organic matter.

    Science.gov (United States)

    Farré, Maria José; Day, Sophie; Neale, Peta A; Stalter, Daniel; Tang, Janet Y M; Escher, Beate I

    2013-09-15

    Disinfection by-products (DBP) formed from natural organic matter and disinfectants like chlorine and chloramine may cause adverse health effects. Here, we evaluate how the quantity and quality of natural organic matter and other precursors influence the formation of DBPs during chlorination and chloramination using a comprehensive approach including chemical analysis of regulated and emerging DBPs, total organic halogen quantification, organic matter characterisation and bioanalytical tools. In vitro bioassays allow us to assess the hazard potential of DBPs early in the chain of cellular events, when the DBPs react with their molecular target(s) and activate stress response and defence mechanisms. Given the reactive properties of known DBPs, a suite of bioassays targeting reactive modes of toxic action including genotoxicity and sensitive early warning endpoints such as protein damage and oxidative stress were evaluated in addition to cytotoxicity. Coagulated surface water was collected from three different drinking water treatment plants, along with reverse osmosis permeate from a desalination plant, and DBP formation potential was assessed after chlorination and chloramination. While effects were low or below the limit of detection before disinfection, the observed effects and DBP levels increased after disinfection and were generally higher after chlorination than after chloramination, indicating that chlorination forms higher concentrations of DBPs or more potent DBPs in the studied waters. Bacterial cytotoxicity, assessed using the bioluminescence inhibition assay, and induction of the oxidative stress response were the most sensitive endpoints, followed by genotoxicity. Source waters with higher dissolved organic carbon levels induced increased DBP formation and caused greater effects in the endpoints related to DNA damage repair, glutathione conjugation/protein damage and the Nrf2 oxidative stress response pathway after disinfection. Fractionation studies

  2. Alternative pathway for atmospheric particles growth.

    Science.gov (United States)

    Monge, Maria Eugenia; Rosenørn, Thomas; Favez, Olivier; Müller, Markus; Adler, Gabriela; Abo Riziq, Ali; Rudich, Yinon; Herrmann, Hartmut; George, Christian; D'Anna, Barbara

    2012-05-01

    Credible climate change predictions require reliable fundamental scientific knowledge of the underlying processes. Despite extensive observational data accumulated to date, atmospheric aerosols still pose key uncertainties in the understanding of Earth's radiative balance due to direct interaction with radiation and because they modify clouds' properties. Specifically, major gaps exist in the understanding of the physicochemical pathways that lead to aerosol growth in the atmosphere and to changes in their properties while in the atmosphere. Traditionally, the driving forces for particle growth are attributed to condensation of low vapor pressure species following atmospheric oxidation of volatile compounds by gaseous oxidants. The current study presents experimental evidence of an unaccounted-for new photoinduced pathway for particle growth. We show that heterogeneous reactions activated by light can lead to fast uptake of noncondensable Volatile Organic Compounds (VOCs) at the surface of particles when only traces of a photosensitizer are present in the seed aerosol. Under such conditions, size and mass increase; changes in the chemical composition of the aerosol are also observed upon exposure to volatile organic compounds such as terpenes and near-UV irradiation. Experimentally determined growth rate values match field observations, suggesting that this photochemical process can provide a new, unaccounted-for pathway for atmospheric particle growth and should be considered by models.

  3. Evolution of Earth-like Extrasolar Planetary Atmospheres: Assessing the Atmospheres and Biospheres of Early Earth Analog Planets with a Coupled Atmosphere Biogeochemical Model

    Science.gov (United States)

    Gebauer, S.; Grenfell, J. L.; Stock, J. W.; Lehmann, R.; Godolt, M.; von Paris, P.; Rauer, H.

    2017-01-01

    Understanding the evolution of Earth and potentially habitable Earth-like worlds is essential to fathom our origin in the Universe. The search for Earth-like planets in the habitable zone and investigation of their atmospheres with climate and photochemical models is a central focus in exoplanetary science. Taking the evolution of Earth as a reference for Earth-like planets, a central scientific goal is to understand what the interactions were between atmosphere, geology, and biology on early Earth. The Great Oxidation Event in Earth's history was certainly caused by their interplay, but the origin and controlling processes of this occurrence are not well understood, the study of which will require interdisciplinary, coupled models. In this work, we present results from our newly developed Coupled Atmosphere Biogeochemistry model in which atmospheric O2 concentrations are fixed to values inferred by geological evidence. Applying a unique tool (Pathway Analysis Program), ours is the first quantitative analysis of catalytic cycles that governed O2 in early Earth's atmosphere near the Great Oxidation Event. Complicated oxidation pathways play a key role in destroying O2, whereas in the upper atmosphere, most O2 is formed abiotically via CO2 photolysis. The O2 bistability found by Goldblatt et al. (2006) is not observed in our calculations likely due to our detailed CH4 oxidation scheme. We calculate increased CH4 with increasing O2 during the Great Oxidation Event. For a given atmospheric surface flux, different atmospheric states are possible; however, the net primary productivity of the biosphere that produces O2 is unique. Mixing, CH4 fluxes, ocean solubility, and mantle/crust properties strongly affect net primary productivity and surface O2 fluxes. Regarding exoplanets, different "states" of O2 could exist for similar biomass output. Strong geological activity could lead to false negatives for life (since our analysis suggests that reducing gases remove O2 that

  4. [Photosynthesis and oxygenation of the earth's atmosphere].

    Science.gov (United States)

    Kuznetsov, A P; Vinogradov, M E; Lappo, S S

    2002-01-01

    Based on the contemporary data concerning photosynthesis as a global biogeochemical mechanism of solar energy utilization and organic matter and oxygen production, the formation of photosynthesis in the Proterozoic is considered, as well as its role in transformation of the pre-Proterozoic oceanic hydrosphere and the Earth's atmosphere from a reduced to an oxidized state. Photosynthesis is considered the longest stage of organic world evolution. The problem of production of "excessive" oxygen is considered, which entered and is entering the atmosphere through the oceanic hydrosphere and determines the process of its organization.

  5. Chemistry of Planetary Atmospheres: Insights and Prospects

    Science.gov (United States)

    Yung, Yuk

    2015-11-01

    Using observations from the Mariners, Pioneers, Vikings, Voyagers, Pioneer Venus, Galileo, Venus Express, Curiosity, Cassini, New Horizons, and numerous observatories both in orbit of Earth and on the ground, I will give a survey of the major chemical processes that control the composition of planetary atmospheres. For the first time since the beginning of the space age, we understand the chemistry of planetary atmospheres ranging from the primitive atmospheres of the giant planets to the highly evolved atmospheres of terrestrial planets and small bodies. Our understanding can be distilled into three important ideas: (1) The stability of planetary atmospheres against escape of their constituents to space, (2) the role of equilibrium chemistry in determining the partitioning of chemical species, and (3) the role of disequilibrium chemistry, which produces drastic departures from equilibrium chemistry. To these three ideas we must also add a fourth: the role of biochemistry at Earth's surface, which makes its atmospheric chemistry unique in the cosmochemical environment. Only in the Earth's atmosphere do strong reducing and oxidizing species coexist to such a degree. For example, nitrogen species in the Earth's atmosphere span eight oxidation states from ammonia to nitric acid. Much of the Earth's atmospheric chemistry consists of reactions initiated by the degradation of biologically produced molecules. Life uses solar energy to drive chemical reactions that would otherwise not occur; it represents a kind of photochemistry that is special to Earth, at least within the Solar System. It remains to be seen how many worlds like Earth there are beyond the Solar System, especially as we are now exploring the exoplanets using Kepler, TESS, HST, Spitzer, soon to be launched missions such as JWST and WFIRST, and ground-based telescopes. The atmospheres of the Solar System provide a benchmark for studying exoplanets, which in turn serve to test and extend our current

  6. Fluctuations in Precambrian atmospheric oxygenation recorded by chromium isotopes

    Science.gov (United States)

    Frei, Robert; Gaucher, Claudio; Poulton, Simon W.; Canfield, Don E.

    2009-09-01

    Geochemical data suggest that oxygenation of the Earth's atmosphere occurred in two broad steps. The first rise in atmospheric oxygen is thought to have occurred between ~2.45 and 2.2Gyr ago, leading to a significant increase in atmospheric oxygen concentrations and concomitant oxygenation of the shallow surface ocean. The second increase in atmospheric oxygen appears to have taken place in distinct stages during the late Neoproterozoic era (~800-542Myr ago), ultimately leading to oxygenation of the deep ocean ~580Myr ago, but details of the evolution of atmospheric oxygenation remain uncertain. Here we use chromium (Cr) stable isotopes from banded iron formations (BIFs) to track the presence of Cr(VI) in Precambrian oceans, providing a time-resolved picture of the oxygenation history of the Earth's atmosphere-hydrosphere system. The geochemical behaviour of Cr is highly sensitive to the redox state of the surface environment because oxidative weathering processes produce the oxidized hexavalent [Cr(VI)] form. Oxidation of reduced trivalent [Cr(III)] chromium on land is accompanied by an isotopic fractionation, leading to enrichment of the mobile hexavalent form in the heavier isotope. Our fractionated Cr isotope data indicate the accumulation of Cr(VI) in ocean surface waters ~2.8 to 2.6Gyr ago and a likely transient elevation in atmospheric and surface ocean oxygenation before the first great rise of oxygen 2.45-2.2Gyr ago (the Great Oxidation Event). In ~1.88-Gyr-old BIFs we find that Cr isotopes are not fractionated, indicating a decline in atmospheric oxygen. Our findings suggest that the Great Oxidation Event did not lead to a unidirectional stepwise increase in atmospheric oxygen. In the late Neoproterozoic, we observe strong positive fractionations in Cr isotopes (δ53Cr up to +4.9‰), providing independent support for increased surface oxygenation at that time, which may have stimulated rapid evolution of macroscopic multicellular life.

  7. Atmospheric Habitable Zones in Y Dwarf Atmospheres

    CERN Document Server

    Yates, Jack S; Biller, Beth; Cockell, Charles S

    2016-01-01

    We use a simple organism lifecycle model to explore the viability of an atmospheric habitable zone (AHZ), with temperatures that could support Earth-centric life, which sits above an environment that does not support life. We illustrate this idea using the object WISE J085510.83-0714442.5, which is a cool, free-floating brown dwarf. We allow organisms to adapt to their atmospheric environment (described by temperature, convection, and gravity) by adopting different growth strategies that maximize their chance of survival and proliferation. We assume a constant upward vertical velocity through the AHZ. We found that the organism growth strategy is most sensitive to the magnitude of the atmospheric convection. Stronger convection supports the evolution of more massive organisms. For a purely radiative environment we find that evolved organisms have a mass that is an order of magnitude smaller than terrestrial microbes, thereby defining a dynamical constraint on the dimensions of life that an AHZ can support. Ba...

  8. Measurement of the Atmospheric $\

    CERN Document Server

    Aartsen, M G; Abdou, Y; Ackermann, M; Adams, J; Aguilar, J A; Ahlers, M; Altmann, D; Andeen, K; Auffenberg, J; Bai, X; Baker, M; Barwick, S W; Baum, V; Bay, R; Beattie, K; Beatty, J J; Bechet, S; Tjus, J Becker; Becker, K -H; Bell, M; Benabderrahmane, M L; BenZvi, S; Berdermann, J; Berghaus, P; Berley, D; Bernardini, E; Bertrand, D; Besson, D Z; Bindig, D; Bissok, M; Blaufuss, E; Blumenthal, J; Boersma, D J; Bohaichuk, S; Bohm, C; Bose1, D; Boser, S; Botner, O; Brayeur, L; Brown, A M; Bruijn, R; Brunner, J; Buitink, S; Carson, M; Casey, J; Casier, M; Chirkin, D; Christy, B; Clark, K; Clevermann, F; Cohen, S; Cowen, D F; Silva, A H Cruz; Danninger, M; Daughhetee, J; Davis, J C; De Clercq, C; De Ridder, S; Descamps, F; Desiati, P; de Vries-Uiterweerd, G; DeYoung, T; Diaz-Velez, J C; Dreyer, J; Dumm, J P; Dunkman, M; Eagan, R; Eberhardt, B; Eisch, J; Ellsworth, R W; Engdegard, O; Euler, S; Evenson, P A; Fadiran, O; Fazely, A R; Fedynitch, A; Feintzeig, J; Feusels, T; Filimonov, K; Finley, C; Fischer-Wasels, T; Flis, S; Franckowiak, A; Franke, R; Frantzen, K; Fuchs, T; Gaisser, T K; Gallagher, J; Gerhardt, L; Gladstone, L; Glusenkamp, T; Goldschmidt, A; Golup, G; Goodman, J A; Gora, D; Grant, D; Gross, A; Grullon, S; Gurtner, M; Ha, C; Ismail, A Haj; Hallgren, A; Halzen, F; Hanson, K; Heereman, D; Heimann, P; Heinen, D; Helbing, K; Hellauer, R; Hickford, S; Hill, G C; Hoffman, K D; Hoffmann, R; Homeier, A; Hoshina, K; Huelsnitz, W; Hulth, P O; Hultqvist, K; Hussain, S; Ishihara, A; Jacobi, E; Jacobsen, J; Japaridze, G S; Jlelati, O; Kappes, A; Karg, T; Karle, A; Kiryluk, J; Kislat, F; Klas, J; Klein, S R; Kohne, J -H; Kohnen, G; Kolanoski, H; Kopke, L; Kopper, C; Kopper, S; Koskinen, D J; Kowalski, M; Krasberg, M; Kroll, G; Kunnen, J; Kurahashi, N; Kuwabara, T; Labare, M; Landsman, H; Larson, M J; Lauer, R; Lesiak-Bzdak, M; Lunemann, J; Madsen, J; Maruyama, R; Mase, K; Matis, H S; McNally, F; Meagher, K; Merck, M; Meszaros, P; Meures, T; Miarecki, S; Middell, E; Milke, N; Miller, J; Mohrmann, L; Montaruli, T; Morse, R; Nahnhauer, R; Naumann, U; Nowicki, S C; Nygren, D R; Obertacke, A; Odrowski, S; Olivas, A; Olivo, M; O'Murchadha, A; Panknin, S; Paul, L; Pepper, J A; Heros, C Perez de los; Pieloth, D; Pirk, N; Posselt, J; Price, P B; Przybylski, G T; Radel, L; Rawlins, K; Redl, P; Resconi, E; Rhode, W; Ribordy, M; Richman, M; Riedel, B; Rodrigues, J P; Rott, C; Ruhe, T; Ruzybayev, B; Ryckbosch, D; Saba, S M; Salameh, T; Sander, H -G; Santander, M; Sarkar, S; Schatto, K; Scheel, M; Scheriau, F; Schmidt, T; Schmitz, M; Schoenen, S; Schoneberg, S; Schonherr, L; Schonwald, A; Schukraft, A; Schulte, L; Schulz, O; Seckel, D; Seo, S H; Sestayo, Y; Seunarine, S; Sheremata, C; Smith, M W E; Soiron, M; Soldin, D; Spiczak, G M; Spiering, C; Stamatikos, M; Stanev, T; Stasik, A; Stezelberger, T; Stokstad, R G; Stoss, A; Strahler, E A; Strom, R; Sullivan, G W; Taavola, H; Taboada, I; Tamburro, A; Ter-Antonyan, S; Tilav, S; Toale, P A; Toscano, S; Usner, M; van der Drift, D; van Eijndhoven, N; Van Overloop, A; van Santen, J; Vehring, M; Voge1, M; Vraeghe, M; Walck, C; Waldenmaier, T; Wallraff, M; Walter, M; Wasserman, R; Weaver, Ch; Wendt, C; Westerhoff, S; Whitehorn, N; Wiebe, K; Wiebusch, C H; Williams, D R; Wissing, H; Wolf, M; Wood, T R; Woschnagg, K; Xu, C; Xu, D L; Xu, X W; Yanez, J P; Yodh, G; Yoshida, S; Zarzhitsky, P; Ziemann, J; Zierke, S; Zilles, A; Zoll, M

    2012-01-01

    We report the first observation in a high energy neutrino telescope of cascades induced by atmospheric electron neutrinos and by neutral current interactions of atmospheric neutrinos of all flavors. Using data recorded during the first year of operation of IceCube's DeepCore low energy extension, a sample of 1029 events is observed in 281 days of data. The number of observed cascades is $N_{\\rm cascade} = 496 \\pm 66 (stat.) \\pm 88(syst.)$ and the rest of the sample consists of residual backgrounds due to atmospheric muons and charged current interactions of atmospheric muon neutrinos. The flux of the atmospheric electron neutrinos is determined in the energy range between approximately 80 GeV and 6 TeV and is consistent with models of atmospheric neutrinos.

  9. Atmospheric Circulation of Exoplanets

    CERN Document Server

    Showman, Adam P; Menou, Kristen

    2009-01-01

    We survey the basic principles of atmospheric dynamics relevant to explaining existing and future observations of exoplanets, both gas giant and terrestrial. Given the paucity of data on exoplanet atmospheres, our approach is to emphasize fundamental principles and insights gained from Solar-System studies that are likely to be generalizable to exoplanets. We begin by presenting the hierarchy of basic equations used in atmospheric dynamics, including the Navier-Stokes, primitive, shallow-water, and two-dimensional nondivergent models. We then survey key concepts in atmospheric dynamics, including the importance of planetary rotation, the concept of balance, and scaling arguments to show how turbulent interactions generally produce large-scale east-west banding on rotating planets. We next turn to issues specific to giant planets, including their expected interior and atmospheric thermal structures, the implications for their wind patterns, and mechanisms to pump their east-west jets. Hot Jupiter atmospheric d...

  10. Atmospheric chemistry of CH3O(CF2CF2O)(n)CH3 (n=1-3): Kinetics and mechanism of oxidation initiated by Cl atoms and OH radicals, IR spectra, and global warmin potentials

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Hurley, MD; Wallington, TJ

    2004-01-01

    Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH3O(CF2CF2O)(n)CH3 (n = 1-3) in 720 +/- 20 Torr of air at 296 +/- 3 K. Relative rate techniques were used to measure k(Cl + CH3O(CF2CF2O)(n)CH3) (3.7 +/- 10.7) x 10(-13) and k(OH +...

  11. Atmospheric Measurements Laboratory (AML)

    Data.gov (United States)

    Federal Laboratory Consortium — The Atmospheric Measurements Laboratory (AML) is one of the nation's leading research facilities for understanding aerosols, clouds, and their interactions. The AML...

  12. The early atmosphere: a new picture.

    Science.gov (United States)

    Levine, J S

    1986-01-01

    Over the last several years, many of the fundamental ideas concerning the composition and chemical evolution of the Earth's early atmosphere have changed. While many aspects of this subject are clouded--either uncertain or unknown, a new picture is emerging. We are just beginning to understand how astronomical, geochemical, and atmospheric processes each contributed to the development of the gaseous envelope around the third planet from the sun some 4.6 billion years ago and how that envelope chemically evolved over the history of our planet. Simple compounds in that gaseous envelope, energized by atmospheric lightning and/or solar ultraviolet radiation, formed molecules of increasing complexity that eventually evolved into the first living systems on our planet. This process is called "chemical evolution" and immediately preceded biological evolution; once life developed and evolved, it began to alter the chemical composition of the atmosphere that provided the very essence of its creation. Photosynthetic organisms which have the ability to biochemically transform carbon dioxide and water to carbohydrates, which they use for food, produce large amounts of molecular oxygen (O2) as a by-product of the reaction. Atmospheric oxygen photochemically formed ozone, which absorbs ultraviolet radiation from the sun and shields the Earth's surface from this biologically lethal radiation. Once atmospheric ozone levels increased sufficiently, life could leave the safety of the oceans and go ashore for the first time. Throughout the history of our planet, there has been strong interaction between life and the atmosphere. Understanding our cosmic roots is particularly relevant as we embark on a search for life outside the Earth. At this very moment, several radio telescopes around the world are searching for extraterrestrial intelligence (SETI).

  13. Worldwide trend of atmospheric mercury since 1995

    Directory of Open Access Journals (Sweden)

    F. Slemr

    2011-01-01

    Full Text Available Concern about the adverse effects of mercury on human health and ecosystems has led to tightening emission controls since the mid 1980s. But the resulting mercury emissions reductions in many parts of the world are believed to be offset or even surpassed by the increasing emissions in rapidly industrializing countries. Consequently, concentrations of atmospheric mercury are expected to remain roughly constant. Here we show that the worldwide atmospheric mercury concentration have decreased by about 20 to 38% since 1996 as indicated by long term monitoring at stations in the Southern and Northern Hemispheres combined with intermittent measurements of latitudinal distribution over the Atlantic Ocean. The total reduction of the atmospheric mercury burden of this magnitude within 14 yrs is unprecedented among most of atmospheric trace gases and is at odds with the current mercury emission inventories with nearly constant emissions over the period. It suggests a major shift in the biogeochemical cycle of mercury including oceans and soil reservoirs. Decreasing reemissions from the legacy of historical mercury emissions are the most likely explanation for this decline since the hypothesis of an accelerated oxidation rate of elemental mercury in the atmosphere is not supported by the observed trends of other trace gases. Consequently, models of the atmospheric mercury cycle have to include soil and ocean mercury pools and their dynamics to be able to make projections of future trends.

  14. Formation of Disinfection By-products (DBPs) and Strategies to Reduce Their Concentration in the Water Treatment Plant in Përlepnica – Gjilan, Kosovo

    OpenAIRE

    , A. Azizi; , K. Berisha; , S. Jusufi

    2011-01-01

    Chlorine is the most widely used disinfection agent in drinking water industry in the world. Chlorine is a strong oxidant, and has the ability to kill or inactivate most pathogenic micro organisms commonly found in water. As such, chlorine used for disinfection of drinking water reacts with natural organic matter (NOM) contained in raw water, and forms the so called disinfection by-products (DBPs), of which trihalomethanes (THMs) and halo acetic acids (HAAs) are the two main groups of DBPs. I...

  15. Adsorption of Atmospheric Gases on Pu Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Nelson, A J; Holliday, K S; Stanford, J A; Grant, W K; Erler, R G; Allen, P G; McLean, W; Roussel, P

    2012-03-29

    Surface adsorption represents a competition between collision and scattering processes that depend on surface energy, surface structure and temperature. The surface reactivity of the actinides can add additional complexity due to radiological dissociation of the gas and electronic structure. Here we elucidate the chemical bonding of gas molecules adsorbed on Pu metal and oxide surfaces. Atmospheric gas reactions were studied at 190 and 300 K using x-ray photoelectron spectroscopy. Evolution of the Pu 4f and O 1s core-level states were studied as a function of gas dose rates to generate a set of Langmuir isotherms. Results show that the initial gas dose forms Pu{sub 2}O{sub 3} on the Pu metal surface followed by the formation of PuO{sub 2} resulting in a layered oxide structure. This work represents the first steps in determining the activation energy for adsorption of various atmospheric gases on Pu.

  16. Chlorinated and nitrogenous disinfection by-product formation from ozonation and post-chlorination of natural organic matter surrogates.

    Science.gov (United States)

    Bond, Tom; Templeton, Michael R; Rifai, Omar; Ali, Hussain; Graham, Nigel J D

    2014-09-01

    Ozonation before chlorination is associated with enhanced formation of chloropicrin, a halonitromethane disinfection by-product (DBP), during drinking water treatment. In order to elucidate reasons for this, five natural organic matter (NOM) surrogates were treated using both chlorination and ozonation-chlorination under controlled laboratory conditions. Selected surrogates comprised two phenolic compounds, two free amino acids and one dipeptide; these were resorcinol, 3-aminophenol, L-aspartic acid, β-alanine and ala-ala, respectively. Quantified DBPs included chloropicrin, chloroform, dichloroacetonitrile and trichloroacetonitrile. Relative to chlorination alone, increases in the formation of chloropicrin from ozonation-chlorination varied from 138% for 3-aminophenol to 3740% for ala-ala for the four amine surrogates. This indicates that ozone is more effective than chlorine in mediating a rate-limiting oxidation step in chloropicrin formation, most plausibly involving conversion of an amine group to a nitro group. While both hydrophilic and hydrophobic surrogates acted as chloropicrin precursors, ala-ala was the most reactive precursor following ozonation-chlorination. Since peptides are far commoner in drinking water sources than free amino acids, further research into chemical oxidation of these species by ozone and chlorine is recommended. In contrast, oxidation with ozone prior to chlorination reduced chloroform formation moderately for the two phenolic compounds.

  17. The Atmospheric Fate of Organic Nitrogen Compounds

    Science.gov (United States)

    Borduas, Nadine

    Organic nitrogen compounds are present in our atmosphere from biogenic and anthropogenic sources and have impacts on air quality and climate. Due to recent advances in instrumentation, these compounds are being detected in the gas and particle phases, raising questions as to their source, processing and sinks in the environment. With their recently identified role as contributors to aerosol formation and growth, their novel large scale use as solvents in carbon capture and storage (CCS) technology and their emissions from cigarette smoke, it is now important to address the gaps in our understanding of the fate of organic nitrogen. Experimentally and theoretically, I studied the chemical atmospheric fate of specific organic nitrogen compounds in the amine, amide and isocyanate families, yielding information that can be used in chemical transport models to assess the fate of this emerging class of atmospheric molecules. I performed kinetic laboratory studies in a smog chamber to measure the room temperature rate coefficient for reaction with the hydroxyl radical of monoethanolamine, nicotine, and five different amides. I employed online-mass spectrometry techniques to quantify the oxidation products. I found that amines react quickly with OH radicals with lifetimes of a few hours under sunlit conditions, producing amides as oxidation products. My studies on amides revealed that they have much longer lifetimes in the atmosphere, ranging from a few hours to a week. Photo-oxidation of amides produces isocyanates and I investigated these mechanisms in detail using ab initio calculations. Furthermore, I experimentally measured isocyanic acid's Henry's Law constant as well as its hydrolysis rate constants to better understand its sinks in the atmosphere. Finally, I re-examined the structure-activity relationship (SAR) of organic nitrogen molecules for improved model parameterizations.

  18. Dielectric Barrier Discharge Air Plasma at Atmospheric Pressure Induced Oxidative Stress in Saccharomyces cerevisiae%大气压介质阻挡放电空气等离子体引起酿酒酵母氧化应激的研究

    Institute of Scientific and Technical Information of China (English)

    陈慧黠; 修志龙; 白凤武

    2013-01-01

    在产生等离子体的过程中会同时产生大量的自由基和准分子.作者研究了经大气压介质阻挡放电(dielectric barrier discharge,DBD)空气等离子体处理后酿酒酵母(Saccharomyce cerevisiae)细胞的氧化应激,发现酿酒酵母细胞在DBD空气等离子体处理后,胞内总抗氧化能力和谷胱甘肽还原酶活力都不同程度被激活,丙二醛含量也随处理时间的延长不断增加,胞内活性氧(reactive oxygen species,ROS)含量明显增加,细胞周期也出现严重的G1期阻滞,说明等离子体产生的大量自由基可引发酵母细胞的氧化应激.%Atmospheric pressure dielectric barrier discharge (DBD) air plasma is a source of reactive species,such as OH*,H*,O*,H2O2,O3,etc.The oxidative stress in Saccharomyces cerevisiae which was exposed to DBD air plasma at atmospheric pressure was studied.It was showed that the intracellular total antioxidant capability (T-AOC) and activity of glutathione reductase (GR) were activated,malondialdehyde (MDA) content increased in a treatment time-dependent manner,intracellular reactive oxygen species (ROS) content increased,and cell cycle arrested in G1 phase significantly.It was proved that oxidative stress was induced in S.cerevisiae when the cells were exposed to DBD air plasma.

  19. Effect of industrial by-products containing electron acceptors on mitigating methane emission during rice cultivation.

    Science.gov (United States)

    Ali, Muhammad Aslam; Lee, Chang Hoon; Kim, Sang Yoon; Kim, Pil Joo

    2009-10-01

    Three industrial by-products (fly ash, phosphogypsum and blast furnace slag), were evaluated for their potential re-use as soil amendments to reduce methane (CH(4)) emission resulting from rice cultivation. In laboratory incubations, CH(4) production rates from anoxic soil slurries were significantly reduced at amendment levels of 0.5%, 1%, 2% and 5% (wt wt(-1)), while observed CO(2) production rates were enhanced. The level of suppression in methane production was the highest for phosphogypsum, followed by blast slag and then fly ash. In the greenhouse experiment, CH(4) emission rates from the rice planted potted soils significantly decreased with the increasing levels (2-20 Mg ha(-1)) of the selected amendments applied, while rice yield simultaneously increased compared to the control treatment. At 10 Mg ha(-1) application level of the amendments, total seasonal CH(4) emissions were reduced by 20%, 27% and 25%, while rice grain yields were increased by 17%, 15% and 23% over the control with fly ash, phosphogypsum, and blast slag amendments, respectively. The suppression of CH(4) production rates as well as total seasonal CH(4) flux could be due to the increased concentrations of active iron, free iron, manganese oxides, and sulfate in the amended soil, which acted as electron acceptors and controlled methanogens' activity by limiting substrates availability. Among the amendments, blast furnace slag and fly ash contributed mainly to improve the soil nutrients balance and increased the soil pH level towards neutral point, but soil acidity was developed with phosphogypsum application. Conclusively, blast slag among the selected amendments would be a suitable soil amendment for reducing CH(4) emissions as well as sustaining rice productivity.

  20. Designing Dynamic Atmospheres

    DEFF Research Database (Denmark)

    Højlund, Marie; Kinch, Sofie

    2012-01-01

    This paper addresses the notion of atmospheres from a designerly perspective, and discusses temporal challenges facing interaction designers when acknowledging the dynamic character of it. As atmospheres are created in the relation between body, space, and time, a pragmatic approach seems useful...

  1. Proterozoic atmospheric oxygen

    DEFF Research Database (Denmark)

    Canfield, Donald Eugene

    2014-01-01

    This article is concerned with the evolution of atmospheric oxygen concentrations through the Proterozoic Eon. In particular, this article will seek to place the history of atmospheric oxygenation through the Proterozoic Eon in the context of the evolving physical environment including the histor...

  2. Clouds in Planetary Atmospheres

    Science.gov (United States)

    West, R.; Murdin, P.

    2000-11-01

    What are clouds? The answer to that question is both obvious and subtle. In the terrestrial atmosphere clouds are familiar as vast collections of small water drops or ice crystals suspended in the air. In the atmospheres of Venus, Mars, Jupiter, Saturn, Saturn's moon Titan, Uranus, Neptune, and possibly Pluto, they are composed of several other substances including sulfuric acid, ammonia, hydroge...

  3. Atmospheric Capture On Mars (and Processing)

    Science.gov (United States)

    Muscatello, Tony

    2017-01-01

    The ultimate destination of NASA's human exploration program is Mars. In Situ Resource Utilization (ISRU) is a key technology required to enable such missions, as first proposed by Prof. Robert Ash in 1976. This presentation will review progress in the systems required to produce rocket propellant, oxygen, and other consumables on Mars using the carbon dioxide atmosphere and other potential resources. For many years, NASA, commercial companies, and academia have been developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Other gases will be required to be separated from Martian atmospheric gases to provide pure CO2 for processing elements. Significant progress has been demonstrated in CO2 collection via adsorption by molecular sieves, freezing, and direct compression. Early stage work in adsorption in Ionic Liquids followed by electrolysis to oxygen is also underway. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and could be captured as well. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from unreacted carbon oxides (CO2-CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, and (3) carbon oxides from oxygen from a trash/waste processing reaction.

  4. Atmospheric composition change: Ecosystems–Atmosphere interactions

    DEFF Research Database (Denmark)

    Fowler, D.; Pilegaard, Kim; Sutton, M.A.

    2009-01-01

    and techniques in micrometeorology. For some of the compounds there have been paradigm shifts in approach and application of both techniques and assessment. These include flux measurements over marine surfaces and urban areas using micrometeorological methods and the up-scaling of flux measurements using...... in the size range 1 nm–10 μm including organic and inorganic chemical species. The main focus of the review is on the exchange between terrestrial ecosystems, both managed and natural and the atmosphere, although some new developments in ocean–atmosphere exchange are included. The material presented is biased...... towards the last decade, but includes earlier work, where more recent developments are limited or absent. New methodologies and instrumentation have enabled, if not driven technical advances in measurement. These developments have advanced the process understanding and upscaling of fluxes, especially...

  5. Photosynthesis in Hydrogen-Dominated Atmospheres

    Directory of Open Access Journals (Sweden)

    William Bains

    2014-11-01

    Full Text Available The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life.

  6. Photosynthesis in Hydrogen-Dominated Atmospheres

    Science.gov (United States)

    Bains, William; Seager, Sara; Zsom, Andras

    2014-01-01

    The diversity of extrasolar planets discovered in the last decade shows that we should not be constrained to look for life in environments similar to early or present-day Earth. Super-Earth exoplanets are being discovered with increasing frequency, and some will be able to retain a stable, hydrogen-dominated atmosphere. We explore the possibilities for photosynthesis on a rocky planet with a thin H2-dominated atmosphere. If a rocky, H2-dominated planet harbors life, then that life is likely to convert atmospheric carbon into methane. Outgassing may also build an atmosphere in which methane is the principal carbon species. We describe the possible chemical routes for photosynthesis starting from methane and show that less energy and lower energy photons could drive CH4-based photosynthesis as compared with CO2-based photosynthesis. We find that a by-product biosignature gas is likely to be H2, which is not distinct from the hydrogen already present in the environment. Ammonia is a potential biosignature gas of hydrogenic photosynthesis that is unlikely to be generated abiologically. We suggest that the evolution of methane-based photosynthesis is at least as likely as the evolution of anoxygenic photosynthesis on Earth and may support the evolution of complex life. PMID:25411926

  7. Photochemistry in Terrestrial Exoplanet Atmospheres. I. Photochemistry Model and Benchmark Cases

    Science.gov (United States)

    Hu, Renyu; Seager, Sara; Bains, William

    2012-12-01

    We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission, and thermal escape of O, H, C, N, and S bearing species, as well as formation and deposition of elemental sulfur and sulfuric acid aerosols. We validate the model by computing the atmospheric composition of current Earth and Mars and find agreement with observations of major trace gases in Earth's and Mars' atmospheres. We simulate several plausible atmospheric scenarios of terrestrial exoplanets and choose three benchmark cases for atmospheres from reducing to oxidizing. The most interesting finding is that atomic hydrogen is always a more abundant reactive radical than the hydroxyl radical in anoxic atmospheres. Whether atomic hydrogen is the most important removal path for a molecule of interest also depends on the relevant reaction rates. We also find that volcanic carbon compounds (i.e., CH4 and CO2) are chemically long-lived and tend to be well mixed in both reducing and oxidizing atmospheres, and their dry deposition velocities to the surface control the atmospheric oxidation states. Furthermore, we revisit whether photochemically produced oxygen can cause false positives for detecting oxygenic photosynthesis, and find that in 1 bar CO2-rich atmospheres oxygen and ozone may build up to levels that have conventionally been accepted as signatures of life, if there is no surface emission of reducing gases. The atmospheric scenarios presented in this paper can serve as the benchmark atmospheres for

  8. Glacial atmospheric phosphorus deposition

    Science.gov (United States)

    Kjær, Helle Astrid; Dallmayr, Remi; Gabrieli, Jacopo; Goto-Azuma, Kumiko; Hirabayashi, Motohiro; Svensson, Anders; Vallelonga, Paul

    2016-04-01

    Phosphorus in the atmosphere is poorly studied and thus not much is known about atmospheric phosphorus and phosphate transport and deposition changes over time, though it is well known that phosphorus can be a source of long-range nutrient transport, e.g. Saharan dust transported to the tropical forests of Brazil. In glacial times it has been speculated that transport of phosphorus from exposed shelves would increase the ocean productivity by wash out. However whether the exposed shelf would also increase the atmospheric load to more remote places has not been investigated. Polar ice cores offer a unique opportunity to study the atmospheric transport of aerosols on various timescales, from glacial-interglacial periods to recent anthropogenic influences. We have for the first time determined the atmospheric transport of phosphorus to the Arctic by means of ice core analysis. Both total and dissolved reactive phosphorus were measured to investigate current and past atmospheric transport of phosphorus to the Arctic. Results show that glacial cold stadials had increased atmospheric total phosphorus mass loads of 70 times higher than in the past century, while DRP was only increased by a factor of 14. In the recent period we find evidence of a phosphorus increase over the past 50 yrs in ice cores close to human occupation likely correlated to forest fires. References: Kjær, Helle Astrid, et al. "Continuous flow analysis method for determination of dissolved reactive phosphorus in ice cores." Environmental science & technology 47.21 (2013): 12325-12332. Kjær, Helle Astrid, et al. "Greenland ice cores constrain glacial atmospheric fluxes of phosphorus." Journal of Geophysical Research: Atmospheres120.20 (2015).

  9. Neutralization/prevention of acid rock drainage using mixtures of alkaline by-products and sulfidic mine wastes.

    Science.gov (United States)

    Alakangas, Lena; Andersson, Elin; Mueller, Seth

    2013-11-01

    Backfilling of open pit with sulfidic waste rock followed by inundation is a common method for reducing sulfide oxidation after mine closure. This approach can be complemented by mixing the waste rock with alkaline materials from pulp and steel mills to increase the system's neutralization potential. Leachates from 1 m3 tanks containing sulfide-rich (ca.30 wt %) waste rock formed under dry and water saturated conditions under laboratory conditions were characterized and compared to those formed from mixtures. The waste rock leachate produced an acidic leachate (pH9). The decrease of elemental concentration in the leachate was most pronounced for Pb and Zn, while Al and S were relatively high. Overall, the results obtained were promising and suggest that alkaline by-products could be useful additives for minimizing ARD formation.

  10. Evaluation of potential antigenotoxic, cytotoxic and proapoptotic effects of the olive oil by-product "alperujo", hydroxytyrosol, tyrosol and verbascoside.

    Science.gov (United States)

    Anter, Jaouad; Tasset, Inmaculada; Demyda-Peyrás, Sebastián; Ranchal, Isidora; Moreno-Millán, Miguel; Romero-Jimenez, Magdalena; Muntané, Jordi; Luque de Castro, María Dolores; Muñoz-Serrano, Andrés; Alonso-Moraga, Ángeles

    2014-09-15

    Olive oil is an integral ingredient of the "Mediterranean diet". The olive oil industry generates large quantities of a by-product called "alperujo" (AL) during the two-phase centrifugation system developed in the early nineties. AL could be a potent exploitable source of natural phenolic antioxidants. Our results showed that AL and its distinctive phenols hydroxytyrosol, tyrosol and verbascoside were not genotoxic in the Somatic Mutation and Recombination Test (SMART) of Drosophila melanogaster and exerted antigenotoxic activity against DNA oxidative damage generated by hydrogen peroxide (H2O2). Alperujo and hydroxytyrosol also exhibited notable antiproliferative and caspase 3-dependent proapoptotic effects toward the human tumoral cell line HL60. AL can provide a cheap and efficient source of chemopreventive phenolic compounds with strong antioxidant properties, becoming a promising and potent therapeutic drug in the future.

  11. High surface area, electrically conductive nanocarbon-supported metal oxide

    Energy Technology Data Exchange (ETDEWEB)

    Worsley, Marcus A.; Han, Thomas Yong-Jin; Kuntz, Joshua D.; Cervantes, Octavio; Gash, Alexander E.; Baumann, Theodore F.; Satcher, Jr., Joe H.

    2015-07-14

    A metal oxide-carbon composite includes a carbon aerogel with an oxide overcoat. The metal oxide-carbon composite is made by providing a carbon aerogel, immersing the carbon aerogel in a metal oxide sol under a vacuum, raising the carbon aerogel with the metal oxide sol to atmospheric pressure, curing the carbon aerogel with the metal oxide sol at room temperature, and drying the carbon aerogel with the metal oxide sol to produce the metal oxide-carbon composite. The step of providing a carbon aerogel can provide an activated carbon aerogel or provide a carbon aerogel with carbon nanotubes that make the carbon aerogel mechanically robust.

  12. Atmosphere beyond Poetics

    DEFF Research Database (Denmark)

    Wieczorek, Izabela

    2014-01-01

    . In doing so, analysing the Crystal Palace – recognised as the epitome of controlled immersive experience as well as of atmospheric engineering (Sloterdijk 2008 (2005) – in parallel with other examples and theoretical explorations, will provide a canvas for discerning the means of creation of atmosphere...... Physical Presence in Space.” Oase #91, Building Atmosphere, 21-33 Sloterdijk, Peter. (2005) 2008. “The Crystal Palace.” Translated by Michael Darroch. Public 37: Public?, 12-15. Originally published in Peter Sloterdijk. Im Weltinnenraum des Kapitals: Für eine philoso-phische Theorie der Globalisierung, 265...

  13. 40 CFR 63.302 - Standards for by-product coke oven batteries.

    Science.gov (United States)

    2010-07-01

    ... batteries. 63.302 Section 63.302 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... National Emission Standards for Coke Oven Batteries § 63.302 Standards for by-product coke oven batteries... oven emissions from each affected existing by-product coke oven battery that exceed any of...

  14. Nutritional diversity of agricultural and agro-industrial by-products for ruminant feeding

    Directory of Open Access Journals (Sweden)

    J.A.G. Azevêdo

    2012-10-01

    Full Text Available Fifty-seven by-products were collected from regions throughout Brazil. Chemical composition, in vitro neutral detergent fiber digestibility (IVNDFD, and total digestible nutrients (TDN were determined with the objective of grouping by-products with similar nutritional characteristics. The by-products belonging to group one (G1 presented the highest content of neutral detergent fiber exclusive of ash and nitrogenous compounds [aNDFom(n] and lowest energy content, with 42.5% and 38.8% of IVNDFD and TDN, respectively. A new cluster analysis was carried in order to better characterize G2 by-products, six subgroups (SGs were established (SG1 to SG6. SG1 by-products had the highest and the lowest values for lignin and TDN, respectively. SG2 by-products had the highest aNDFom(n value, with TDN and IVNDFD values greater than 600 and 700g/kg, respectively, and crude protein (CP value below 200g/kg in dry matter (DM. Among all the subgroups, SG3 had the highest TDN (772g/kg and IVNDFD (934g/kg values and the lowest lignin (23g/kg in DM value. The ether extract was what most influenced the hierarchical establishment of residual grouping in SG4. SG5 by-products had the highest concentration of non-fibrous carbohydrate. Different from the other subgroups, SG6 by-products had the highest value of available CP.

  15. Preserving high-protein fish by-products through silages and fermentates

    Science.gov (United States)

    n Alaska, over three million metric tons of fish by-products are generated each year. However, due to the remote locations and seasonal nature of salmon fisheries, by-products are generally not fully utilized unless a fish meal plant is located nearby. Acidification is a common method for inhibiting...

  16. Hazard Analysis and identification of Critical Control Points of collagen extraction from cod by-products

    NARCIS (Netherlands)

    Aalberts, C.H.J.

    2004-01-01

    The aim of the European research project “UTILISATION AND STABILISATION OF BY-PRODUCTS FROM COD SPECIES” (QLK1-CT-2000-01017 QLRT-2001-02829) is to investigate whether collagen from fish by-products could serve as an important raw material in high quality food. Since Atlantic cod is a major commodit

  17. In situ ruminal crude protein degradability of by-products from cereals, oilseeds and animal origin

    NARCIS (Netherlands)

    Habib, G.; Khan, N.A.; Ali, M.; Bezabih, M.

    2013-01-01

    The aim of this study was to establish a database on in situ ruminal crude protein (CP) degradability characteristics of by-products from cereal grains, oilseeds and animal origin commonly fed to ruminants in Pakistan and South Asian Countries. The oilseed by-products were soybean meal, sunflower me

  18. Wheat milling by-products and their impact on bread making.

    Science.gov (United States)

    Hemdane, Sami; Leys, Sofie; Jacobs, Pieter J; Dornez, Emmie; Delcour, Jan A; Courtin, Christophe M

    2015-11-15

    This study investigates the relationship between the properties of dietary fiber (DF) rich wheat milling by-products and their impact on bread making. From coarse bran over coarse and fine weatings to low grade flour, the content of starch and lipids increased, while that of DF and ash decreased. Enzyme activity levels differed strongly and were not related to other by-product properties. Average particle size of the by-products was positively correlated with DF and ash contents and their hydration properties. When meals from flour and by-products were composed on the same overall starch level to compensate for differences in endosperm contamination in the by-products, bread specific volume was more strongly depressed with fine weatings and low grade flour than with coarse bran and weatings. This suggests that the properties of the former were intrinsically more detrimental to bread making than those of the latter.

  19. Mango (Mangifera indica L.) by-products and their valuable components: a review.

    Science.gov (United States)

    Jahurul, M H A; Zaidul, I S M; Ghafoor, Kashif; Al-Juhaimi, Fahad Y; Nyam, Kar-Lin; Norulaini, N A N; Sahena, F; Mohd Omar, A K

    2015-09-15

    The large amount of waste produced by the food industries causes serious environmental problems and also results in economic losses if not utilized effectively. Different research reports have revealed that food industry by-products can be good sources of potentially valuable bioactive compounds. As such, the mango juice industry uses only the edible portions of the mangoes, and a considerable amount of peels and seeds are discarded as industrial waste. These mango by-products come from the tropical or subtropical fruit processing industries. Mango by-products, especially seeds and peels, are considered to be cheap sources of valuable food and nutraceutical ingredients. The main uses of natural food ingredients derived from mango by-products are presented and discussed, and the mainstream sectors of application for these by-products, such as in the food, pharmaceutical, nutraceutical and cosmetic industries, are highlighted.

  20. Atmospheric oxygenation caused by a change in volcanic degassing pressure.

    Science.gov (United States)

    Gaillard, Fabrice; Scaillet, Bruno; Arndt, Nicholas T

    2011-10-12

    The Precambrian history of our planet is marked by two major events: a pulse of continental crust formation at the end of the Archaean eon and a weak oxygenation of the atmosphere (the Great Oxidation Event) that followed, at 2.45 billion years ago. This oxygenation has been linked to the emergence of oxygenic cyanobacteria and to changes in the compositions of volcanic gases, but not to the composition of erupting lavas--geochemical constraints indicate that the oxidation state of basalts and their mantle sources has remained constant since 3.5 billion years ago. Here we propose that a decrease in the average pressure of volcanic degassing changed the oxidation state of sulphur in volcanic gases, initiating the modern biogeochemical sulphur cycle and triggering atmospheric oxygenation. Using thermodynamic calculations simulating gas-melt equilibria in erupting magmas, we suggest that mostly submarine Archaean volcanoes produced gases with SO(2)/H(2)S atmosphere.

  1. Selective oxidation of isobutane on V–Mo–O mixed oxide catalysts

    Directory of Open Access Journals (Sweden)

    GHEORGHITA MITRAN

    2008-01-01

    Full Text Available Four V–Mo–O mixed metal oxides were prepared, characterized and tested for the selective oxidation of isobutane in the temperature range 350–550 °C, at atmospheric pressure. Isobutane was mainly oxidized to iso-butene and carbon oxides. The systems with low vanadium contents showed low activities but high isobutene selectivities, while the systems with high vanadium contents showed high activities with high carbon oxides selectivities. The effects of temperature, contact time and the molar ratio iso-butane to oxygen on the conversion of isobutane and the selectivity of the oxidation were studied.

  2. Carbon neutron star atmospheres

    CERN Document Server

    Suleimanov, V F; Pavlov, G G; Werner, K

    2013-01-01

    The accuracy of measuring the basic parameters of neutron stars is limited in particular by uncertainties in chemical composition of their atmospheres. For example, atmospheres of thermally - emitting neutron stars in supernova remnants might have exotic chemical compositions, and for one of them, the neutron star in CasA, a pure carbon atmosphere has recently been suggested by Ho & Heinke (2009). To test such a composition for other similar sources, a publicly available detailed grid of carbon model atmosphere spectra is needed. We have computed such a grid using the standard LTE approximation and assuming that the magnetic field does not exceed 10^8 G. The opacities and pressure ionization effects are calculated using the Opacity Project approach. We describe the properties of our models and investigate the impact of the adopted assumptions and approximations on the emergent spectra.

  3. The invention of atmosphere.

    Science.gov (United States)

    Martin, Craig

    2015-08-01

    The word "atmosphere" was a neologism Willebrord Snellius created for his Latin translation of Simon Stevin's cosmographical writings. Astronomers and mathematical practitioners, such as Snellius and Christoph Scheiner, applying the techniques of Ibn Mu'ādh and Witelo, were the first to use the term in their calculations of the height of vapors that cause twilight. Their understandings of the atmosphere diverged from Aristotelian divisions of the aerial region. From the early years of the seventeenth century, the term was often associated with atomism or corpuscular matter theory. The concept of the atmosphere changed dramatically with the advent of pneumatic experiments in the middle of the seventeenth century. Pierre Gassendi, Walter Charleton, and Robert Boyle transformed the atmosphere of the mathematicians giving it the characteristics of weight, specific gravity, and fluidity, while disputes about its extent and border remained unresolved.

  4. Atmospheric muons: experimental aspects

    OpenAIRE

    Cecchini, S.; Spurio, M.

    2012-01-01

    We present a review of atmospheric muon flux and energy spectrum measurements over almost six decades of muon momentum. Sea-level and underground/water/ice experiments are considered. Possible sources of systematic errors in the measurements are examinated. The characteristics of underground/water muons (muons in bundle, lateral distribution, energy spectrum) are discussed. The connection between the atmospheric muon and neutrino measurements are also reported.

  5. Atmospheric muons: experimental aspects

    Directory of Open Access Journals (Sweden)

    S. Cecchini

    2012-11-01

    Full Text Available We present a review of atmospheric muon flux and energy spectrum measurements over almost six decades of muon momentum. Sea level and underground/water/ice experiments are considered. Possible sources of systematic errors in the measurements are examined. The characteristics of underground/water muons (muons in bundle, lateral distribution, energy spectrum are discussed. The connection between the atmospheric muon and neutrino measurements are also reported.

  6. Global atmospheric changes.

    OpenAIRE

    Piver, W T

    1991-01-01

    Increasing concentrations of CO2 and other greenhouse gases in the atmosphere can be directly related to global warming. In terms of human health, because a major cause of increasing atmospheric concentrations of CO2 is the increased combustion of fossil fuels, global warming also may result in increases in air pollutants, acid deposition, and exposure to ultraviolet (UV) radiation. To understand better the impacts of global warming phenomena on human health, this review emphasizes the proces...

  7. Integrated Disinfection By-Products Mixtures Research: Concentration by Reverse Osmosis Membrane Techniques of Disinfection By-Products from Water Disinfected by Chlorination and Ozonation/Postchlorination

    Science.gov (United States)

    To conduct the health-effect studies described in subsequent articles in this series, concentrated aqueous mixtures of disinfection by-products were required for the two water treatment trains described in the preceding article (Miltner et al., 2008). To accomplish this, the fini...

  8. Biochars made from agro-industrial by-products remove chlorine and lower water toxicity

    Science.gov (United States)

    Tzachristas, Andreas; Xirou, Maria; Manariotis, Ioannis D.; Dailianis, Stefanos; Karapanagioti, Hrissi K.

    2016-04-01

    Chlorination is the most common disinfection process for water and treated wastewater. For the industrial use of water in food production, chlorine can add undesired taste and odor to the final product. For this reason, dechlorination is desired for food industries that use municipal tap water. For treated wastewater discharge or reuse, chlorine can be toxic to the receiving aqueous systems and to the irrigated plants. In both the above cases, dechlorination is also required. Traditionally activated carbon has been used as the ideal material for the removal of chlorine. The main mechanisms that describe the interaction between activated carbon and HOCl or OCl- are described by the following equations (AWWA, 1990): HOCl + C* → C*O + H+ + Cl- (1), OCl- + C* → C*O + Cl- (2) Where C* and C*O represent the activated carbon surface and a surface oxide, respectively. The present study proposes the use of agro-industrial by-products for the production of biochars that will be used for dechlorination of tap-water used for food-industry production. Different raw materials such as malt spent rootlets, coffee residue, olive and grape seeds, etc. are used for the production of biochar. Various temperatures and air-to-solid ratios are tested for optimizing biochar production. Batch tests as well as a column test are employed to study the dechlorination efficiency and kinetics of the different raw and biochar materials as well as those of commercial activated carbons. As chlorine concentration increases the removal also increases linearily. After 1 and 24 hours of contact the chlorine relative removal efficiencies for the biochar made from olive seeds are 50 and 77 ± 4%, respectively. It seems that the removal kinetics are faster during the first hour; then, removal continues but with a slower rate. Most of the biochars tested (with 3 mg of solid in 20 mL of chlorine solution at initial concentration Co=1.5 mg/L) demonstrated removal efficiencies with an average of 9.4 ± 0

  9. Quantification of bioactive compounds in pulps and by-products of tropical fruits from Brazil.

    Science.gov (United States)

    Ribeiro da Silva, Larissa Morais; Teixeira de Figueiredo, Evania Altina; Silva Ricardo, Nagila Maria Pontes; Pinto Vieira, Icaro Gusmao; Wilane de Figueiredo, Raimundo; Brasil, Isabella Montenegro; Gomes, Carmen L

    2014-01-15

    This study aimed to quantify the levels of resveratrol, coumarin, and other bioactives in pulps and by-products of twelve tropical fruits from Brazil obtained during pulp production process. Pineapple, acerola, monbin, cashew apple, guava, soursop, papaya, mango, passion fruit, surinam cherry, sapodilla, and tamarind pulps were evaluated as well as their by-products (peel, pulp's leftovers, and seed). Total phenolic, anthocyanins, yellow flavonoids, β-carotene and lycopene levels were also determined. Resveratrol was identified in guava and surinam cherry by-products and coumarin in passion fruit, guava and surinam cherry by-products and mango pulp. These fruit pulp and by-products could be considered a new natural source of both compounds. Overall, fruit by-products presented higher (P<0.05) bioactive content than their respective fruit pulps. This study provides novel information about tropical fruits and their by-products bioactive composition, which is essential for the understanding of their nutraceutical potential and future application in the food industry.

  10. Magnesium Oxide

    Science.gov (United States)

    Magnesium is an element your body needs to function normally. Magnesium oxide may be used for different reasons. Some ... to relieve heartburn, sour stomach, or acid indigestion. Magnesium oxide also may be used as a laxative ...

  11. Ultrasound-assisted activation of zero-valent magnesium for nitrate denitrification: identification of reaction by-products and pathways.

    Science.gov (United States)

    Ileri, Burcu; Ayyildiz, Onder; Apaydin, Omer

    2015-07-15

    Zero-valent magnesium (Mg(0)) was activated by ultrasound (US) in an aim to promote its potential use in water treatment without pH control. In this context, nitrate reduction was studied at batch conditions using various doses of magnesium powder and ultrasound power. While neither ultrasound nor zero-valent magnesium alone was effective for reducing nitrate in water, their combination removed up to 90% of 50 mg/L NO3-N within 60 min. The rate of nitrate reduction by US/Mg(0) enhanced with increasing ultrasonic power and magnesium dose. Nitrogen gas (N2) and nitrite (NO2(-)) were detected as the major reduction by-products, while magnesium hydroxide Mg(OH)2 and hydroxide ions (OH(-)) were identified as the main oxidation products. The results from SEM-EDS measurements revealed that the surface oxide level decreased significantly when the samples of Mg(0) particles were exposed to ultrasonic treatment. The surface passivation of magnesium particles was successfully minimized by mechanical forces of ultrasound, which in turn paved the way to sustain the catalyst activity toward nitrate reduction.