WorldWideScience

Sample records for model photochemical oxidant

  1. European scale modeling of sulfur, oxidized nitrogen and photochemical oxidants. Model development and evaluation for the 1994 growing season

    Energy Technology Data Exchange (ETDEWEB)

    Langner, J.; Bergstroem, R. [Swedish Meteorological and Hydrological Inst., Norrkoeping (Sweden); Pleijel, K. [Swedish Environmental Research Inst., Goeteborg (Sweden)

    1998-09-01

    A chemical mechanism, including the relevant reactions leading to the production of ozone and other photochemical oxidants, has been implemented in the MATCH regional tracer transport/chemistry/deposition model. The aim has been to develop a model platform that can be used as a basis for a range of regional scale studies involving atmospheric chemistry, including assessment of the importance of different sources of pollutants to the levels of photochemical oxidants and air pollutant forecasting. Meteorological input data to the model were taken from archived output from the operational version of HIRLAM at SMHI. Evaluation of model calculations over Europe for a six month period in 1994 for a range of chemical components show good results considering known sources of error and uncertainties in input data and model formulation. With limited further work the system is sufficiently good to be applied for scenario studies and for regional scale air pollutant forecasts 42 refs, 24 figs, 17 tabs

  2. Modelling photochemical oxidant formation, transport, deposition and exposure of terrestrial ecosystems.

    Science.gov (United States)

    Fowler, D; Cape, J N; Coyle, M; Smith, R I; Hjellbrekke, A G; Simpson, D; Derwent, R G; Johnson, C E

    1999-01-01

    The chemical processes responsible for production of photochemical oxidants within the troposphere have been the subject of laboratory and field study throughout the last three decades. During the same period, models to simulate the atmospheric chemistry, transport and deposition of ozone (O(3)) from individual urban sources and from regions have been developed. The models differ greatly in the complexity of chemical schemes, in the underlying meteorology and in spatial and temporal resolution. Input information from land use, spatial and temporally disaggregated emission inventories and meteorology have all improved considerably in recent years and are not fully implemented in current models. The development of control strategies in both North America and Europe to close the gaps between current exceedances of environmental limits, guide values, critical levels or loads and full compliance with these limits provides the focus for policy makers and the support agencies for the research. The models represent the only method of testing a range of control options in advance of implementation. This paper describes currently applied models of photochemical oxidant production and transport at global and regional scales and their ability to simulate individual episodes as well as photochemical oxidant climatology. The success of current models in quantifying the exposure of terrestrial surfaces and the population to potentially damaging O(3) concentrations (and dose) is examined. The analysis shows the degree to which the underlying processes and their application within the models limit the quality of the model products.

  3. Modeling Perchloroethylene Degradation Under Ultrasonic Irradiation and Photochemical Oxidation in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Mahmood Alimohammadi

    2012-12-01

    Full Text Available Sonolysis and photochemical degradation of different compounds such as chlorinated aliphatic hydrocarbons are among the recent advanced oxidation processes.Perchloroethylene is one of these compounds that has been mainly used as a solvent and degreaser. In this work, elimination of perchloroethylene in aqueous solution by ultrasonic irradiation, andphotochemical oxidation by ultra violet ray and hydrogen peroxide were investigated. Three different initial concentrations of perchloroethylene at different pH values, detention periods , and concentrations of hydrogen peroxide were investigated. Headspace gas chromatography with FID detector was used for analyses of perchloroethylene.This research was performed in 9 months from April through December 2011.Results showed that perchloroethylene could be effectively and rapidly degraded by ultrasonic irradiation, photochemical oxidation by ultra violet ray, hydrogen peroxide and acombination of these methods. Kinetics of perchloroethylene was strongly influenced by time, initial concentration and pH value. Degradation of Perchloroethylene increased withdecrease in the initial concentration of perchloroethylene from 0.3 to 10 mg/L at all initial pH. The results showed an optimum degradation condition achieved at pH = 5 but did notaffect significantly the perchloroethylene destruction in the various pH values. Kinetic modeling applied for the obtained results showed that the degradation of perchloroethyleneby ultrasound and photo-oxidation followed first order and second order model. The percentage of removal in the hybrids reactor was higher than each of the reactors alone, the reason being the role of hydroxyl radical induced by ultrasound and photochemical reaction.

  4. Photochemical modelling of photo-oxidant levels over the Swiss plateau and emission reduction scenarios

    International Nuclear Information System (INIS)

    Rosselet, C.M.; Kerr, J.A.

    1993-05-01

    During summertime high pressure conditions, high photo-oxidant (O 3 , H 2 O 2 , PAN and others) levels are frequently observed in the planetary boundary layer in central Europe. It is well known that close to the earth's surface ozone is formed by complex reactions involving VOC, NO x , and sunlight. Substantial reductions of both precursors are needed to reduce photo-oxidant levels. In this context the reductions of the abundance of the precursors and the variation of their ratios is of great importance. Here we report model calculations from the Harwell Photochemical Trajectory Model of the levels of O 3 , H 2 O 2 and PAN along a trajectory over the Swiss Plateau from Lake Constance to Lake Geneva. These calculations are in satisfactory agreement with measurements made during the intensive observation period of the research program POLLUMET (Pollution and Meteorology in Switzerland). Sensitivity calculations of emission reduction scenarios indicate that on the Swiss Plateau the ozone production may be mainly NO x -limited; under conditions where the CO levels are closer to the upper limit within the range (120-600 ppbv). The calculated peak ozone level reduction caused by an exclusive NO x -emission reduction is about three times larger than that caused by an exclusive VOC reduction. The combined reduction of all precursor compounds is the most efficient strategy, although it is only marginally more efficient than the NO x -reduction scenario alone. (author) figs., tabs., 75 refs

  5. HANDBOOK ON ADVANCED PHOTOCHEMICAL OXIDATION ...

    Science.gov (United States)

    This handbook summarizes commercial-scale system performance and cost data for advanced photochemical oxidation (APO) treatment of contaminated water, air, and solids. Similar information from pilot- and bench-scale evaluations of APO processes is also included to supplement the commercial-scale data. Performance and cost data is summarized for various APO processes, including vacuum ultraviolet (VUV) photolysis, ultraviolet (UV)/oxidation, photo-Fenton, and dye- or semiconductor-sensitized APO processes. This handbook is intended to assist engineering practitioners in evaluating the applicability of APO processes and in selecting one or more such processes for site-specific evaluation.APO has been shown to be effective in treating contaminated water and air. Regarding contaminated water treatment, UV/oxidation has been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest. Regarding contaminated air treatment, the sensitized APO processes have been evaluated for the most contaminants, while VUV photolysis has been evaluated for the fewest.APO processes for treating contaminated solids generally involve treatment of contaminated slurry or leachate generated using an extraction process such as soil washing. APO has been shown to be effective in treating contaminated solids, primarily at the bench-scale level. Information

  6. The photochemical role of tropospheric nitrogen oxides

    Science.gov (United States)

    Chameides, W. L.

    1978-01-01

    The role of nitrogen oxides in the tropospheric photochemical system is re-evaluated in the light of recent measurements of the rate constants for two key reactions. A model for nitrogen oxides is discussed which yields surface NO(x) (NO+NO2) levels approaching 1 ppb in NO(x) source regions but less than 0.1 ppb outside source regions. Applying the new rate coefficients implies increased radical concentrations and a more intense O3 and CO photochemistry. Even for densities of 0.1 ppb or less, NO(x) still leads to significant local O3 production and conversion of HO2 to OH. Unrealistic O3 profiles are obtained with the new rate coefficients for surface NO(x) densities of about 1 ppb, while reasonable agreement with observation is obtained with lower NO(x) densities. Feedback processes between CO, NO(x), OH, and CH4 are also discussed.

  7. Photochemical oxidants: state of the science.

    Science.gov (United States)

    Kley, D; Kleinmann, M; Sanderman, H; Krupa, S

    1999-01-01

    Atmospheric photochemical processes resulting in the production of tropospheric ozone (O(3)) and other oxidants are described. The spatial and temporal variabilities in the occurrence of surface level oxidants and their relationships to air pollution meteorology are discussed. Models of photooxidant formation are reviewed in the context of control strategies and comparisons are provided of the air concentrations of O(3) at select geographic locations around the world. This overall oxidant (O(3)) climatology is coupled to human health and ecological effects. The discussion of the effects includes both acute and chronic responses, mechanisms of action, human epidemiological and plant population studies and briefly, efforts to establish cause-effect relationships through numerical modeling. A short synopsis is provided of the interactive effects of O(3) with other abiotic and biotic factors. The overall emphasis of the paper is on identifying the current uncertainties and gaps in our understanding of the state of the science and some suggestions as to how they may be addressed.

  8. Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy phenols from biomass burning

    Science.gov (United States)

    Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

    2014-03-01

    We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O : C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O : C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to depend on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O : C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

  9. Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy-phenols from biomass burning

    Science.gov (United States)

    Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

    2013-10-01

    We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy-phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O:C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O:C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to be dependent on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O:C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

  10. Photochemical oxidation: A solution for the mixed waste dilemma

    Energy Technology Data Exchange (ETDEWEB)

    Prellberg, J.W.; Thornton, L.M.; Cheuvront, D.A. [Vulcan Peroxidation Systems, Inc., Tucson, AZ (United States)] [and others

    1995-12-31

    Numerous technologies are available to remove organic contamination from water or wastewater. A variety of techniques also exist that are used to neutralize radioactive waste. However, few technologies can satisfactorily address the treatment of mixed organic/radioactive waste without creating unacceptable secondary waste products or resulting in extremely high treatment costs. An innovative solution to the mixed waste problem is on-site photochemical oxidation. Liquid-phase photochemical oxidation has a long- standing history of successful application to the destruction of organic compounds. By using photochemical oxidation, the organic contaminants are destroyed on-site leaving the water, with radionuclides, that can be reused or disposed of as appropriate. This technology offers advantages that include zero air emissions, no solid or liquid waste formation, and relatively low treatment cost. Discussion of the photochemical process will be described, and several case histories from recent design testing, including cost analyses for the resulting full-scale installations, will be presented as examples.

  11. Partial Photochemical Oxidation Was a Dominant Fate of Deepwater Horizon Surface Oil.

    Science.gov (United States)

    Ward, Collin P; Sharpless, Charles M; Valentine, David L; French-McCay, Deborah P; Aeppli, Christoph; White, Helen K; Rodgers, Ryan P; Gosselin, Kelsey M; Nelson, Robert K; Reddy, Christopher M

    2018-02-20

    Following the Deepwater Horizon (DWH) blowout in 2010, oil floated on the Gulf of Mexico for over 100 days. In the aftermath of the blowout, substantial accumulation of partially oxidized surface oil was reported, but the pathways that formed these oxidized residues are poorly constrained. Here we provide five quantitative lines of evidence demonstrating that oxidation by sunlight largely accounts for the partially oxidized surface oil. First, residence time on the sunlit sea surface, where photochemical reactions occur, was the strongest predictor of partial oxidation. Second, two-thirds of the partial oxidation from 2010 to 2016 occurred in less than 10 days on the sunlit sea surface, prior to coastal deposition. Third, multiple diagnostic biodegradation indices, including octadecane to phytane, suggest that partial oxidation of oil on the sunlit sea surface was largely driven by an abiotic process. Fourth, in the laboratory, the dominant photochemical oxidation pathway of DWH oil was partial oxidation to oxygenated residues rather than complete oxidation to CO 2 . Fifth, estimates of partial photo-oxidation calculated with photochemical rate modeling overlap with observed oxidation. We suggest that photo-oxidation of surface oil has fundamental implications for the response approach, damage assessment, and ecosystem restoration in the aftermath of an oil spill, and that oil fate models for the DWH spill should be modified to accurately reflect the role of sunlight.

  12. Photochemical Phenomenology Model for the New Millennium

    Science.gov (United States)

    Bishop, James; Evans, J. Scott

    2001-01-01

    The "Photochemical Phenomenology Model for the New Millennium" project tackles the issue of reengineering and extension of validated physics-based modeling capabilities ("legacy" computer codes) to application-oriented software for use in science and science-support activities. While the design and architecture layouts are in terms of general particle distributions involved in scattering, impact, and reactive interactions, initial Photochemical Phenomenology Modeling Tool (PPMT) implementations are aimed at construction and evaluation of photochemical transport models with rapid execution for use in remote sensing data analysis activities in distributed systems. Current focus is on the Composite Infrared Spectrometer (CIRS) data acquired during the CASSINI flyby of Jupiter. Overall, the project has stayed on the development track outlined in the Year 1 annual report and most Year 2 goals have been met. The issues that have required the most attention are: implementation of the core photochemistry algorithms; implementation of a functional Java Graphical User Interface; completion of a functional CORBA Component Model framework; and assessment of performance issues. Specific accomplishments and the difficulties encountered are summarized in this report. Work to be carried out in the next year center on: completion of testing of the initial operational implementation; its application to analysis of the CASSINI/CIRS Jovian flyby data; extension of the PPMT to incorporate additional phenomenology algorithms; and delivery of a mature operational implementation.

  13. Assessing photochemical ozone formation in the Pearl River Delta with a photochemical trajectory model

    Science.gov (United States)

    Cheng, H. R.; Guo, H.; Saunders, S. M.; Lam, S. H. M.; Jiang, F.; Wang, X. M.; Simpson, I. J.; Blake, D. R.; Louie, P. K. K.; Wang, T. J.

    2010-11-01

    A photochemical trajectory model (PTM), coupled with the Master Chemical Mechanism (MCM) describing the degradation of 139 volatile organic compounds (VOCs) in the troposphere, was developed and used for the first time to simulate the formation of photochemical pollutants at Wangqingsha (WQS), Guangzhou during photochemical pollution episodes between 12 and 17 November, 2007. The simulated diurnal variations and mixing ratios of ozone were in good agreement with observed data ( R2 = 0.80, P toluene, etc. A further investigation of the relative contribution of the main emission source categories to ozone formation suggested that mobile sources were the largest contributor to regional O 3 formation (40%), followed by biogenic sources (29%), VOC product-related sources (23%), industry (6%), biomass burning (1%), and power plants (1%). The findings obtained in this study would advance our knowledge of air quality in the PRD region, and provide useful information to local government on effective control of photochemical smog in the region.

  14. Modelling approach for photochemical pollution studies

    International Nuclear Information System (INIS)

    Silibello, C.; Catenacci, G.; Calori, G.; Crapanzano, G.; Pirovano, G.

    1996-01-01

    The comprehension of the relationships between primary pollutants emissions and secondary pollutants concentration and deposition is necessary to design policies and strategies for the maintenance of a healthy environment. The use of mathematical models is a powerful tool to assess the effect of the emissions and of physical and chemical transformations of pollutants on air quality. A photochemical model, Calgrid, developed by CARB (California Air Resources Board), has been used to test the effect of different meteorological and air quality, scenarios on the ozone concentration levels. This way we can evaluate the influence of these conditions to determine the most important chemical species and reactions in atmosphere. The ozone levels are strongly related to the reactive hydrocarbons concentrations and to the solar radiation flux

  15. Global emissions and models of photochemically active compounds

    International Nuclear Information System (INIS)

    Penner, J.E.; Atherton, C.S.; Graedel, T.E.

    1993-01-01

    Anthropogenic emissions from industrial activity, fossil fuel combustion, and biomass burning are now known to be large enough (relative to natural sources) to perturb the chemistry of vast regions of the troposphere. A goal of the IGAC Global Emissions Inventory Activity (GEIA) is to provide authoritative and reliable emissions inventories on a 1 degree x 1 degree grid. When combined with atmospheric photochemical models, these high quality emissions inventories may be used to predict the concentrations of major photochemical products. Comparison of model results with measurements of pertinent species allows us to understand whether there are major shortcomings in our understanding of tropospheric photochemistry, the budgets and transport of trace species, and their effects in the atmosphere. Through this activity, we are building the capability to make confident predictions of the future consequences of anthropogenic emissions. This paper compares IGAC recommended emissions inventories for reactive nitrogen and sulfur dioxide to those that have been in use previously. We also present results from the three-dimensional LLNL atmospheric chemistry model that show how emissions of anthropogenic nitrogen oxides might potentially affect tropospheric ozone and OH concentrations and how emissions of anthropogenic sulfur increase sulfate aerosol loadings

  16. Global emissions and models of photochemically active compounds

    Energy Technology Data Exchange (ETDEWEB)

    Penner, J.E.; Atherton, C.S. [Lawrence Livermore National Lab., CA (United States); Graedel, T.E. [AT and T Bell Labs., Murray Hill, NJ (United States)

    1993-05-20

    Anthropogenic emissions from industrial activity, fossil fuel combustion, and biomass burning are now known to be large enough (relative to natural sources) to perturb the chemistry of vast regions of the troposphere. A goal of the IGAC Global Emissions Inventory Activity (GEIA) is to provide authoritative and reliable emissions inventories on a 1{degree} {times} 1{degree} grid. When combined with atmospheric photochemical models, these high quality emissions inventories may be used to predict the concentrations of major photochemical products. Comparison of model results with measurements of pertinent species allows us to understand whether there are major shortcomings in our understanding of tropospheric photochemistry, the budgets and transport of trace species, and their effects in the atmosphere. Through this activity, we are building the capability to make confident predictions of the future consequences of anthropogenic emissions. This paper compares IGAC recommended emissions inventories for reactive nitrogen and sulfur dioxide to those that have been in use previously. We also present results from the three-dimensional LLNL atmospheric chemistry model that show how emissions of anthropogenic nitrogen oxides might potentially affect tropospheric ozone and OH concentrations and how emissions of anthropogenic sulfur increase sulfate aerosol loadings.

  17. Photochemical Phenomenology Model for the New Millenium

    Science.gov (United States)

    Bishop, James; Evans, J. Scott

    2000-01-01

    This project tackles the problem of conversion of validated a priori physics-based modeling capabilities, specifically those relevant to the analysis and interpretation of planetary atmosphere observations, to application-oriented software for use in science and science-support activities. The software package under development, named the Photochemical Phenomenology Modeling Tool (PPMT), has particular focus on the atmospheric remote sensing data to be acquired by the CIRS instrument during the CASSINI Jupiter flyby and orbital tour of the Saturnian system. Overall, the project has followed the development outline given in the original proposal, and the Year 1 design and architecture goals have been met. Specific accomplishments and the difficulties encountered are summarized in this report. Most of the effort has gone into complete definition of the PPMT interfaces within the context of today's IT arena: adoption and adherence to the CORBA Component Model (CCM) has yielded a solid architecture basis, and CORBA-related issues (services, specification options, development plans, etc.) have been largely resolved. Implementation goals have been redirected somewhat so as to be more relevant to the upcoming CASSINI flyby of Jupiter, with focus now being more on data analysis and remote sensing retrieval applications.

  18. Sunlight-induced photochemical decay of oxidants in natural waters: implications in ballast water treatment.

    Science.gov (United States)

    Cooper, William J; Jones, Adam C; Whitehead, Robert F; Zika, Rod G

    2007-05-15

    The transport and discharge of ship ballast water has been recognized as a major vector for the introduction of invasive species. Chemical oxidants, long used in drinking water and wastewater treatment, are alternative treatment methods for the control of invasive species currently being tested for use on ships. One concern when a ballasted vessel arrives in port is the adverse effects of residual oxidant in the treated water. The most common oxidants include chlorine (HOCl/OCl-), bromine (HOBr/OBr-), ozone (03), hydrogen peroxide (H2O2), chlorine dioxide (ClO2), and monochloramine (NH2Cl). The present study was undertaken to evaluate the sunlight-mediated photochemical decomposition of these oxidants. Sunlight photodecomposition was measured at various pH using either distilled water or oligotrophic Gulf Stream water for specific oxidants. For selected oxidants, quantum yields at specific wavelengths were obtained. An environmental photochemical model, GCSOLAR, also provided predictions of the fate (sunlight photolysis half-lives) of HOCI/OCl-, HOBr/OBr-, ClO2, and NH2Cl for two different seasons at latitude 40 degrees and in water with two different concentrations of chromophoric dissolved organic matter. These data are useful in assessing the environmental fate of ballast water treatment oxidants if they were to be discharged in port.

  19. Anoxic photochemical oxidation of siderite generates molecular hydrogen and iron oxides

    Science.gov (United States)

    Kim, J. Dongun; Yee, Nathan; Nanda, Vikas; Falkowski, Paul G.

    2013-01-01

    Photochemical reactions of minerals are underappreciated processes that can make or break chemical bonds. We report the photooxidation of siderite (FeCO3) by UV radiation to produce hydrogen gas and iron oxides via a two-photon reaction. The calculated quantum yield for the reaction suggests photooxidation of siderite would have been a significant source of molecular hydrogen for the first half of Earth’s history. Further, experimental results indicate this abiotic, photochemical process may have led to the formation of iron oxides under anoxic conditions. The reaction would have continued through the Archean to at least the early phases of the Great Oxidation Event, and provided a mechanism for oxidizing the atmosphere through the loss of hydrogen to space, while simultaneously providing a key reductant for microbial metabolism. We propose that the photochemistry of Earth-abundant minerals with wide band gaps would have potentially played a critical role in shaping the biogeochemical evolution of early Earth. PMID:23733945

  20. Kinetic analyses and mathematical modeling of primary photochemical and photoelectrochemical processes in plant photosystems

    NARCIS (Netherlands)

    Vredenberg, W.J.

    2011-01-01

    In this paper the model and simulation of primary photochemical and photo-electrochemical reactions in dark-adapted intact plant leaves is presented. A descriptive algorithm has been derived from analyses of variable chlorophyll a fluorescence and P700 oxidation kinetics upon excitation with

  1. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (First External Review Draft, Feb 2011)

    Science.gov (United States)

    EPA announced that the First External Review Draft of the Integrated Science Assessment for Ozone and Related Photochemical Oxidants has been made available for independent peer review and public review. This draft document represents a concise synthesis and evaluation of ...

  2. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Second External Review Draft, Sep 2011)

    Science.gov (United States)

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Second External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant scienc...

  3. Integrated Science Assessment (ISA) of Ozone and Related Photochemical Oxidants (Third External Review Draft, Jun 2012)

    Science.gov (United States)

    EPA has released the Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review Draft) for independent peer review and public review. This draft document represents a concise synthesis and evaluation of the most policy-relevant science...

  4. Detection of Chlorine in a Non-aqueous Solution via Anodic Oxidation and a Photochemical Reaction.

    Science.gov (United States)

    Nakagawa, Shogo; Nishimura, Hajime; Kodera, Fumihiro

    2018-01-01

    In this study, we developed a new chlorine gas detection method using anodic oxidation and a photochemical reaction. Chlorine gas was temporarily solvated with an aprotic polar solvent having an extensive potential range in the positive direction, and the solvated chlorine molecule was detected by an anodic oxidation reaction. In addition, when combined with ultraviolet light irradiation, we could detect high sensitivity using the photochemical reaction.

  5. 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.

  6. Decoupling photochemical Fe(II) oxidation from shallow-water BIF deposition

    DEFF Research Database (Denmark)

    Konhauser, Kurt O.; Amskold, Larry; Lalonde, Stefan V.

    2007-01-01

    -type systems, then we are driven to conclude that oxide-facies BIF are the product of a rapid, non-photochemical oxidative process, the most likely candidates being direct or indirect biological oxidation, and that a significant fraction of BIF could have initially been deposited as ferrous minerals. ?? 2007...... the chemistry of ambient Precambrian seawater mixing with Fe(II)-rich hydrothermal fluids with, and without, UV irradiation. We find that if Fe(II) was effused from relatively shallow seamount-type vent systems directly into an anoxic photic zone, the photochemical contribution to solid-phase precipitation...... Elsevier B.V. All rights reserved....

  7. Modeling of photochemical pollution in Athens, Greece. Application of the RAMS-CALGRID modeling system

    Science.gov (United States)

    Pilinis, Christodoulos; Kassomenos, Pavlos; Kallos, George

    The causes of the poor air quality in Athens, Greece during the severe episode of 25-26 May 1990 has been studied, using a prognostic model (RAMS) and a three-dimensional Eulerian air quality model (CALGRID). The modeling effort indicates that the main urban area of Athens exhibited high concentrations of nitrogen oxides, the main sources of which are automobiles, while the NNE suburban area exhibited high ozone concentrations, the product of photochemical activity of the primary pollutants that were transported by the sea-breeze. The application of the models also demonstrated the need for an accurate emission inventory for improved predictions of the pollutant concentrations. It was also found that a 50% reduction of the nitrogen oxide emissions will increase the ozone levels in the downtown area substantially.

  8. Photochemical Grafting and Patterning of Organic Monolayers on Indium Tin Oxide Substrates

    NARCIS (Netherlands)

    Li, Y.; Zuilhof, H.

    2012-01-01

    Covalently attached organic layers on indium tin oxide (ITO) surfaces were prepared by the photochemical grafting with 1-alkenes. The surface modification was monitored with static water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) measurements.

  9. Technical development of UV-C- and VUV-photochemically induced oxidative degradation processes.

    Science.gov (United States)

    Braun, A M; Pintori, I G; Popp, H P; Wakahata, Y; Wörner, M

    2004-01-01

    Technical development work is presented, where the VUV photochemically induced oxidative degradation is used: (i) for analytic purposes, and (ii) for small to medium scale (lamp/reactor combination may be used for functionalization purposes prior to e.g. GC or HPLC analyses. In the second case, mass transfer limitations between the non-irradiated bulk volume and the irradiated volume are overcome by the electrochemical generation of molecular oxygen within or close to the irradiated volume and by the design of the photochemical part of the reactor.

  10. Computer Modelling of Photochemical Smog Formation

    Science.gov (United States)

    Huebert, Barry J.

    1974-01-01

    Discusses a computer program that has been used in environmental chemistry courses as an example of modelling as a vehicle for teaching chemical dynamics, and as a demonstration of some of the factors which affect the production of smog. (Author/GS)

  11. Photochemical reactions of various model protocell systems

    Science.gov (United States)

    Folsome, C. E.

    1986-01-01

    Models for the emergence of cellular life on the primitive Earth, and for physical environments of that era have been studied that embody these assumptions: (1) pregenetic cellular forms were phase-bounded systems primarily photosynthetic in nature, and (2) the early Earth environment was anoxic (lacking appreciable amounts of free hydrogen). It was found that organic structures can also be formed under anoxic conditions (N2, CO3=, H2O) by protracted longwavelength UV radiation. Apparently these structures form initially as organic layers upon CaCO3 crystalloids. The question remains as to whether the UV photosynthetic ability of such phase bounded structures is a curiosity, or a general property of phase bounded systems which is of direct interest to the emergence of cellular life. The question of the requirement and sailient features of a phase boundary for UV photosynthetic abilities was addressed by searching for similar general physical properties which might be manifest in a variety of other simple protocell-like structures. Since it has been shown that laboratory protocell models can effect the UV photosynthesis of low molecular weight compounds, this reaction is being used as an assay to survey other types of structures for similar UV photosynthetic reactions. Various kinds of structures surveyed are: (1) proteinoids; (2) liposomes; (3) reconstituted cell membrane spheroids; (4) coacervates; and (5) model protocells formed under anoxic conditions.

  12. Measurement of pollutant species in automotive exhaust: application of a 3D Eulerian model about the photochemical oxidant formation in the troposphere

    International Nuclear Information System (INIS)

    Caplain, I.

    2005-05-01

    Automotive pollution has become a more and more worrying problem. Pollution regulations are more severe today but even if some pollutants have to fulfill strict emission standards, other compounds like volatile organic compounds (VOCs) and carbonyl compounds, are less controlled but remain toxic for human beings in a direct way (primary pollution) or in an indirect way (secondary pollution). This work deals with the experimental measurements of exhaust pollution, the inventory of pollutant emissions from transports, and the modeling of air quality. The experimental measurements are performed in the framework of the European project Artemis (assessment and reliability of transport emission models and inventory systems) under the coordination of INRETS, on a set of 30 gasoline and diesel vehicles of recent technology. These vehicles are submitted to various road tests in order to improve the emissions database for private vehicles. The main pollutants measured are the light VOCs (C2 to C6), the heavy VOCs (C7 to C15) and the carbonyl compounds. About a hundred of compounds are thus measured. The emissions factor of each pollutant has been determined for each vehicle and has been used for the elaboration of an emission map of the Nord-Pas-de-Calais region. These pollutant data have been used as input data for a physicochemical simulation model of troposphere (UAM: urban air-shed model). A previous study about the introduction of the detailed molecular speciation of VOCs and the use of the CBIV mechanism did not lead to concluding results about the speciation impact on ozone formation. The introduction of a new mechanism would allow to take into account the overall compounds and to see their eventual contribution to the ozone formation. This would require a modification of the model and in particular the addition of a flexible chemical mechanism (FCM) interface for the introduction of a new chemical mechanism (SAPRC 99 instead of CBIV) in the model. The overall input

  13. Study of the photochemical oxidation of mercury: application to the separation of mercury isotopes

    International Nuclear Information System (INIS)

    Morand, J.P.

    Investigation of the mechanism of the isotopic photo-oxidation of mercury has enabled the existence of an unstable excited complex (HgO 2 *) to be demonstrated. In the presence of butadiene, this complex gives stable mercuric oxide. Butadiene does not act purely as an interceptor for oxidizing species. By theoretical investigation of the complex HgO 2 *, its electronic structure ( 3 PI) could be determined and its energy of formation (4.6 eV) predicted. The phenomenon of photodecomposition of mercuric oxide was demonstrated and its importance evaluated. The results obtained made it possible to develop an apparatus for the photochemical separation of the isotopes of mercury, whose efficiency is acceptable despite the low quantum yield. Since the method for the photochemical separation of the isotopes has only been studied for mercury, an identical study for other elements, and particularly for elements of the same group as mercury (zinc, cadmium), could lead in the future to new aspects in the study of photochemical mechanisms

  14. The reactions of O(ID) and OH with CH3OH, oxidation of the HCO radial, and the photochemical oxidation of formaldehyde. [photochemical reactions in stratosphere

    Science.gov (United States)

    Osif, T. L.

    1976-01-01

    An experimental, laboratory study of the various photochemical reactions that can occur in the mesosphere and stratosphere is presented. N2O was photolyzed at 2139 A in the presence of CH3OH and CO. The O(id) produced in the photolysis reacted with CH3OH to produce OH radicals, and thus the reactions of both O(id) and OH were able to be studied. Also considered was the oxidation of the HCO radical. Mixtures of Cl2, O2, H2CO, and sometimes N2 or He were irradiated at 3660 A at several temperatures to photodecompose the Cl2. The photochemical oxidation of formaldehyde was studied as follows: formaldehyde in the presence of N2 and/or O2 (usually dry air) was photolyzed with a medium pressure Hg lamp used in conjunction with various filters which transmit different relative amounts of Hg lines from 2894 A to 3660 A. Results are presented and discussed, along with a description of experimental procedures and apparatus, and chemical reaction kinetics.

  15. Eulerian modeling of photochemical pollutants over the Swiss Plateau and control strategy analysis

    Science.gov (United States)

    Kuebler, J.; Giovannoni, J.-M.; Russell, A. G.

    A three-dimensional Eulerian photochemical model was applied to the Swiss Plateau for the 28-30 July 1993 period to follow the evolution of ozone and other photochemical oxidants. The results of the three-day base case simulation showed good to excellent agreement across the region not only for ozone, nitrogen oxide, nitrogen dioxide and carbon monoxide, but also for other pollutants such as peroxyacetyl nitrate and hydrogen peroxide. The effect of the boundary and initial conditions were found to be negligible. The next step was to determine quantitatively the effects of differing levels of ROG and NO x controls on O 3 and other photo-oxidant levels. Twelve calculations combining different precursor emission levels were performed in order to simulate the effects of controls on ozone peaks, as well as exposure to the various pollutants. The results suggest that reducing NO x emissions, on a percentage basis, is more effective for lowering both ozone peaks and exposure than is reducing ROG. PAN responds in a similar fashion to ozone. Given the model performance, and the fewer limitations involved in using three-dimensional Eulerian models than other methods, this is a powerful tool for conducting further control strategy evaluations.

  16. Oxidative Capacity Predicted Using Photochemical Age Approximation from SAMBBA Airborne Observations in the Amazon Rainforest

    Science.gov (United States)

    dos Santos, F. C.; Longo, K.; Guenther, A. B.; Freitas, S. R.; Moreira, D. S.; Flávio, L.; Braz, R.; Oram, D.; Lee, J. D.; Bauguitte, S.

    2016-12-01

    Emitted by vegetation, isoprene (2-methyl-1,3-butadiene) is the most abundant non-methane hydrocarbons, with an annual global emission calculated ranging from 440 to 660Tg carbon, depending on the driving variables like temperature, solar radiation, leaf area index and plant functional type. It is estimated, for example, that the natural compounds like isoprene and terpenes present in the troposphere are about 90% and 50%, respectively, removed from the atmosphere by oxidation performed by hydroxyl radical (OH). Furthermore, the oxidation products of isoprene may contribute to secondary organic aerosol (SOA) formation, affecting the climate and altering the properties and lifetimes of clouds. Considering the importance of these emissions and the hydroxyl radical reaction in the atmosphere, the SAMBBA (South American Biomass Burning Analysis) experiment, which occurred during the dry season (September 2012) in the Amazon Rainforest, provided information about the chemical composition of the atmosphere through airborne observations. Although primarily focused on biomass burning flights, the SAMBBA project carried out other flights providing indirect oxidative capacity data in different environments: natural emission dominated flights and biomass-burning flights with fresh plumes and aged plumes. In this study, we evaluate the oxidative capacity of the Amazon rainforest in different environments, both for the unpolluted and biomass-burning disturbed atmosphere using the ratio [MVK + MACR]/[Isoprene]. Beyond that, we propose an improvement on the formulation of indirect OH density calculation, using the photochemical aging [O3]/[CO] as a parameter. During the day (11am-8pm - local time), the [OH] values for natural emission flights (8.1 x 106 molecules/cm3) and biomass-burning (9.4 x 106 molecules/cm3) are comparable with GABRIEL-2015 field campaign along Guyanas tropical rainforest and suggest that biomass-burning increase the oxidative capacity around 18% in average

  17. Investigation of Phenol Removal in Aqueous Solutions Using Advanced Photochemical Oxidation (APO

    Directory of Open Access Journals (Sweden)

    Naser Jamshidi

    2010-01-01

    Full Text Available Most organic compounds are resistant to conven­tional chemical and biological treatments. For this reason, other methods are being studied as alter­natives to the biological and classical physico-chemical pro­cesses. In this study, advanced photochemical oxidation (APO processes (UV, UV/H2O2, UV/H2O2/Fe(II, andUV/H2O2/Fe(III were investigated in lab-scale experiments for the degradation of phenol in an aqueous solution. A medium-pressure 300 watt (UV-C mercury ultraviolet lamp was used as the radiation source and H2O2 30% as the oxidant. Phenol (initial concentration= 0.5 mmol/L was selected as the model due to its high use and application. Some important parameters such as pH, H2O2 input concentration, iron catalyst concentration, the type of iron salt, and duration of UV radiation were studied based on the standard methods. The results showed that the Photo-Fenton process was the most effective treatment under acidic conditions producing a higher rate of phenol degradation over a very short radiation time. The process accelerated the oxidation rate by 4-5 times the rate of the UV/H2O2 process. The optimum conditions were obtained at a pH value of 3, with a molar ratio of 11.61 for H2O2/Phenol and molar ratios of 0.083 and 0.067for Iron/H2O2 in the UV/H2O2/Fe (II and the UV/H2O2/Fe (III systems, respectively.

  18. On the in-vivo photochemical rate parameters for PDT reactive oxygen species modeling

    Science.gov (United States)

    Kim, Michele M.; Ghogare, Ashwini A.; Greer, Alexander; Zhu, Timothy C.

    2017-01-01

    Photosensitizer photochemical parameters are crucial data in accurate dosimetry for photodynamic therapy (PDT) based on photochemical modeling. Progress has been made in the last few decades in determining the photochemical properties of commonly used photosensitizers (PS), but mostly in solution or in-vitro. Recent developments allow for the estimation of some of these photochemical parameters in-vivo. This review will cover the currently available in-vivo photochemical properties of photosensitizers as well as the techniques for measuring those parameters. Furthermore, photochemical parameters that are independent of environmental factors or are universal for different photosensitizers will be examined. Most photosensitizers discussed in this review are of the type II (singlet oxygen) photooxidation category, although type I photosensitizers that involve other reactive oxygen species (ROS) will be discussed as well. The compilation of these parameters will be essential for ROS modeling of PDT. PMID:28166056

  19. Intercontinental transport of aerosols and photochemical oxidants from Asia and its consequences

    International Nuclear Information System (INIS)

    Wuebbles, Donald J.; Lei, Hang; Lin, Jintai

    2007-01-01

    The intercontinental transport of aerosols and photochemical oxidants from Asia is a crucial issue for air quality concerns in countries downwind of the significant emissions and concentrations of pollutants occurring in this important region of the world. Since the lifetimes of some important pollutants are long enough to be transported over long distance in the troposphere, regional control strategies for air pollution in downwind countries might be ineffective without considering the effects of long-range transport of pollutants from Asia. Field campaigns provide strong evidence for the intercontinental transport of Asian pollutants. They, together with ground-based observations and model simulations, show that the air quality over parts of North America is being affected by the pollutants transported from Asia. This paper examines the current understanding of the intercontinental transport of gases and aerosols from Asia and resulting effects on air quality, and on the regional and global climate system. - Air quality over parts of North America is being affected by pollutants transported from Asia

  20. Photochemical changes and oxidative damage in the aquatic macrophyte Cymodocea nodosa exposed to paraquat-induced oxidative stress.

    Science.gov (United States)

    Moustakas, Michael; Malea, Paraskevi; Zafeirakoglou, Aristi; Sperdouli, Ilektra

    2016-01-01

    The non-selective herbicide paraquat (Pq) is being extensively used for broad-spectrum weed control. Through water runoff and due to its high water solubility it contaminates aquatic environments. Thus, the present study was carried out to investigate the photochemical changes and oxidative damage in the aquatic macrophyte Cymodocea nodosa to short- (2h) and long-term (24h) exposure to 2, 20, 200 and 1000μM paraquat (Pq) toxicity by using chlorophyll fluorescence imaging and H2O2 real-time imaging. The effective quantum yield of PSII (ΦPSII) show a tendency to increase at 2μM Pq after 2h exposure, and increased significantly at 20 and 200μM Pq. Τhe maximum oxidative effect on C. nodosa leaves was observed 2h after exposure to 200μM Pq concentration when the highest increases of ΦPSII due to high electron transport rate (ETR) resulted in a significant increase of H2O2 production due to the lowest non-photochemical quenching (NPQ) that was not efficient to serve as a protective mechanism, resulting in photooxidation. Prolonged exposure (24h) to 200μM Pq resulted in a decreased ΦPSII not due to an increase of the photoprotective mechanism NPQ, but due to high quantum yield of non-regulated energy loss in PSII (ΦNO), resulting to the lowest fraction of open PSII reaction centers (qp). This decreased ΦPSII has resulted to less Pq radicals to be formed, with a consequence of a small increase of H2O2 production compared to control C. nodosa leaves, but substantial lower than that of 2h exposure to 200μM Pq. Exposure of C. nodosa leaves to 1000μM Pq toxicity had lower effects on the efficiency of photochemical reactions of photosynthesis under both short- (2h) and long-term (24h) exposure than 200μM Pq. This was evident by an almost unchanged ΦPSII and qp, that remained unchanged even at a longer exposure time (48h), compared to control C. nodosa leaves. Thus, the response of C. nodosa leaves to Pq toxicity fits the "Threshold for Tolerance Model", with a

  1. Technical development of UV-C- and VUV-photochemically induced oxidative degradation processes

    Energy Technology Data Exchange (ETDEWEB)

    Braun, A.M.; Gassiot Pintori, I.; Wakahata, Y.; Woerner, M. [Lehrstuhl fuer Umweltmesstechnik, Univ. Karlsruhe, Karlsruhe (Germany); Popp, H.P. [Lehrstuhl fuer Umweltmesstechnik, Univ. Karlsruhe, Karlsruhe (Germany)]|[Lichttechnisches Inst., Univ. Karlsruhe, Karlsruhe (Germany)

    2003-07-01

    Technical development work is presented, where the VUV photochemically induced oxidative degradation is used (i) for analytic purposes and (ii) for small to medium scale (< 10 m{sup 2}/d) waste water treatment processes or ultra pure water production. In the first case, small xe-excimer radiation sources with an integrated reaction space designed for optimal conditions, as far as incident photon flux density, turbulence and concentration of dissolved molecular oxygen are concerned, have been built and tested. Under conditions of exhaustive oxidation and/or mineralization of pollutants in a continuous regime, they may be used for sample pre-treatment modules prior TOC, TOX and electrochemical trace metal analysis. Under conditions of partial oxidation or mineralization, the same lamp/reactor combination may be used for functionalization purposes prior to e.g. GC or HPLC analyses. In the second case, mass transfer limitations between the non-irradiated bulk volume and the irradiated volume are overcome by the electrochemical generation of molecular oxygen within or close to the irradiated volume and by the design of the photochemical part of the reactor. (orig.)

  2. Model estimates of enhanced photochemical production of ozone resulting from convective transport of precursors

    Science.gov (United States)

    Pickering, Kenneth E.; Thompson, Anne M.; Dickerson, Russell R.

    1989-01-01

    Vertical profiles of net photochemical ozone production rates and total tropospheric column production rates were estimated using two models, a simple photochemical box model and a time-dependent one-dimensional transport/kinetics model. Photochemical production of ozone is found to dominate over destruction throughout the vertical extent of the troposphere over the central United States during typical summertime convective conditions. The column net production can be enhanced by the transport of the ozone precursors NO and NMHC from the boundary layer to the free troposphere by convective activity.

  3. Photo-chemical transport modelling of tropospheric ozone: A review

    Science.gov (United States)

    Sharma, Sumit; Sharma, Prateek; Khare, Mukesh

    2017-06-01

    Ground level ozone (GLO), a secondary pollutant having adverse impact on human health, ecology, and agricultural productivity, apart from being a major contributor to global warming, has been a subject matter of several studies. In order to identify appropriate strategies to control GLO levels, accurate assessment and prediction is essential, for which elaborate simulation and modelling is required. Several studies have been undertaken in the past to simulate GLO levels at different scales and for various applications. It is important to evaluate these studies, widely spread over in literature. This paper aims to critically review various studies that have been undertaken, especially in the past 15 years (2000-15) to model GLO. The review has been done of the studies that range over different spatial scales - urban to regional and continental to global. It also includes a review of performance evaluation and sensitivity analysis of photo-chemical transport models in order to assess the extent of application of these models and their predictive capability. The review indicates following major findings: (a) models tend to over-estimate the night-time GLO concentrations due to limited titration of GLO with NO within the model; (b) dominance of contribution from far-off regional sources to average ozone concentration in the urban region and higher contribution of local sources during days of high ozone episodes; requiring strategies for controlling precursor emissions at both regional and local scales; (c) greater influence of NOx over VOC in export of ozone from urban regions due to shifting of urban plumes from VOC-sensitive regime to NOx-sensitive as they move out from city centres to neighbouring rural regions; (d) models with finer resolution inputs perform better to a certain extent, however, further improvement in resolutions (beyond 10 km) did not show improvement always; (e) future projections show an increase in GLO concentrations mainly due to rise in

  4. Review of photochemical reaction constants of organic micropollutants required for UV advanced oxidation processes in water.

    Science.gov (United States)

    Wols, B A; Hofman-Caris, C H M

    2012-06-01

    Emerging organic contaminants (pharmaceutical compounds, personal care products, pesticides, hormones, surfactants, fire retardants, fuel additives etc.) are increasingly found in water sources and therefore need to be controlled by water treatment technology. UV advanced oxidation technologies are often used as an effective barrier against organic contaminants. The combined operation of direct photolysis and reaction with hydroxyl radicals ensures good results for a wide range of contaminants. In this review, an overview is provided of the photochemical reaction parameters (quantum yield, molar absorption, OH radical reaction rate constant) of more than 100 organic micropollutants. These parameters allow for a prediction of organic contaminant removal by UV advanced oxidation systems. An example of contaminant degradation is elaborated for a simplified UV/H(2)O(2) system. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Diagnostic Evaluation of Ozone Production and Horizontal Transport in a Regional Photochemical Air Quality Modeling System

    Science.gov (United States)

    A diagnostic model evaluation effort has been performed to focus on photochemical ozone formation and the horizontal transport process since they strongly impact the temporal evolution and spatial distribution of ozone (O3) within the lower troposphere. Results from th...

  6. Photochemical oxidation of As(III) by vacuum-UV lamp irradiation.

    Science.gov (United States)

    Yoon, Sung-Hwan; Lee, Jai H; Oh, Sangeun; Yang, Jae E

    2008-07-01

    In this study, vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights has been investigated as a new oxidation method for As(III). Laboratory scale experiments were conducted with a batch reactor and a commercial VUV lamp. Under the experimental conditions of this study, the employed VUV lamp showed a higher performance for As(III) oxidation compared to other photochemical oxidation methods (UV-C/H(2)O(2), UV-A/Fe(III)/H(2)O(2), and UV-A/TiO2). The VUV lamp oxidized 100 microM As(III) almost completely in 10 min, and the reaction occurred mainly due to OH radicals which were produced by photo-splitting of water (H(2)O+hv (lambda=185 nm)-->OH.+H.). There was a little possibility that photo-generated H(2)O(2) acted as a minor oxidant of As(III) at alkaline pHs. The effects of Fe(III), H(2)O(2), and humic acid (HA) on the As(III) oxidation by VUV lamp irradiation were investigated. While Fe(III) and H(2)O(2) increased the As(III) oxidation efficiency, HA did not cause a significant effect. The employed VUV lamp was effective for oxidizing As(III) not only in a Milli-Q water but also in a real natural water, without significant decrease in the oxidation efficiency. Since the formed As(V) should be removed from water, activated alumina (AA) was added as an adsorbent during the As(III) oxidation by VUV lamp irradiation. The combined use of VUV lamp irradiation and AA was much more effective for the removal of total arsenic (As(tot)=As(III)+As(V)) than the single use of AA. The As(tot) removal seemed to occur as a result of the pre-oxidation of As(III) and the subsequent adsorption of As(V) on AA. Alternatively, the combination of VUV lamp irradiation and coagulation/precipitation with FeCl(3) was also an effective removal strategy for As(tot). This study shows that vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights is a powerful and environmentally friendly method for As(III) oxidation which does not require additional oxidants or

  7. Photochemical decoration of silver nanoparticles on graphene oxide nanosheets and their optical characterization

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Nguyen Thi; Chi, Do Thi; Dinh, Ngo Xuan; Hung, Nguyen Duy; Lan, Hoang [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Tuan, Pham Anh [Vietnam Metrology Institute, 08 Hoang Quoc Viet Road, Cau Giay District, Hanoi (Viet Nam); Thang, Le Hong [School of Materials Science and Engineering, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Trung, Nguyen Ngoc [School of Engineering Physics, Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Hoa, Nguyen Quang [Department of Physics, Hanoi University of Science, 334 Nguyen Trai, Thanh Xuan, Hanoi (Viet Nam); Huy, Tran Quang [Laboratory for Ultrastructure and Bionanotechnology (LUBN), National Institute of Hygiene and Epidemiology (NIHE), No. 1 Yecxanh Street, Hai Ba Trung District, Hanoi (Viet Nam); Quy, Nguyen Van [International Training Institute for Materials Science (ITIMS), Hanoi University of Science and Technology (HUST), 01 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Duong, Thanh-Tung [Department of Materials Engineering, Chungnam National University, Daeduk Science Town, 305-764 Daejeon (Korea, Republic of); Phan, Vu Ngoc [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam); Le, Anh-Tuan, E-mail: tuan.leanh1@hust.edu.vn [Department of Nanoscience and Nanotechnology, Advanced Institute for Science and Technology (AIST), Hanoi University of Science and Technology (HUST), No. 1 Dai Co Viet Street, Hai Ba Trung District, Hanoi (Viet Nam)

    2014-12-05

    Highlights: • A photochemical method for effective decoration of the Ag-NPs on GO nanosheets is presented. • The average size of the Ag-NPs on the GO nanosheets obtained ∼6–7 nm with uniform size distribution. • Surface interaction of Ag-NPs with GO nanosheets leads to surface plasmon-enhanced luminescence. - Abstract: Nanohybrid materials based on silver nanoparticles (Ag-NPs) and graphene oxide (GO) are attracting considerable research interest because of their potential many applications including surface-enhanced Raman scattering, catalysis, sensors, biomedicine and antimicrobials. In this study, we established a simple and effective method of preparing a finely dispersed Ag-GO aqueous solution using modified Hummer and photochemical technique. The Ag-NPs formation on GO nanosheets was analyzed by X-ray diffraction, transmission electron microscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. The average size of Ag-NPs on the GO nanosheets was approximately 6–7 nm with nearly uniform size distribution. The Ag-GO nanohybrid also exhibits an adsorption band at 435 nm because of the presence of Ag-NPs on the GO nanosheets. Photoluminescence emission of the Ag-GO nanohybrid was found at 400 and 530 nm, which can be attributed to the interaction between the luminescence of exploited GO nanosheets and localized surface plasmon resonance from metallic Ag-NPs. The observed excellent optical properties of the as-prepared Ag-GO nanohybrid showed a significant potential for optoelectronics applications.

  8. Homogeneous photochemical water oxidation by biuret-modified Fe-TAML: evidence of Fe(V)(O) intermediate.

    Science.gov (United States)

    Panda, Chakadola; Debgupta, Joyashish; Díaz Díaz, David; Singh, Kundan K; Sen Gupta, Sayam; Dhar, Basab B

    2014-09-03

    Water splitting, leading to hydrogen and oxygen in a process that mimics natural photosynthesis, is extremely important for devising a sustainable solar energy conversion system. Development of earth-abundant, transition metal-based catalysts that mimic the oxygen-evolving complex of photosystem II, which is involved in oxidation of water to O2 during natural photosynthesis, represents a major challenge. Further, understanding the exact mechanism, including elucidation of the role of active metal-oxo intermediates during water oxidation (WO), is critical to the development of more efficient catalysts. Herein, we report Fe(III) complexes of biuret-modified tetra-amidomacrocyclic ligands (Fe-TAML; 1a and 1b) that catalyze fast, homogeneous, photochemical WO to give O2, with moderate efficiency (maximum TON = 220, TOF = 0.76 s(-1)). Previous studies on photochemical WO using iron complexes resulted in demetalation of the iron complexes with concomitant formation of iron oxide nanoparticles (NPs) that were responsible for WO. Herein, we show for the first time that a high valent Fe(V)(O) intermediate species is photochemically generated as the active intermediate for the oxidation of water to O2. To the best of our knowledge, this represents the first example of a molecular iron complex catalyzing photochemical WO through a Fe(V)(O) intermediate.

  9. Protein Footprinting by Carbenes on a Fast Photochemical Oxidation of Proteins (FPOP) Platform

    Science.gov (United States)

    Zhang, Bojie; Rempel, Don L.; Gross, Michael L.

    2016-03-01

    Protein footprinting combined with mass spectrometry provides a method to study protein structures and interactions. To improve further current protein footprinting methods, we adapted the fast photochemical oxidation of proteins (FPOP) platform to utilize carbenes as the footprinting reagent. A Nd-YAG laser provides 355 nm laser for carbene generation in situ from photoleucine as the carbene precursor in a flow system with calmodulin as the test protein. Reversed-phase liquid chromatography coupled with mass spectrometry is appropriate to analyze the modifications produced in this footprinting. By comparing the modification extent of apo and holo calmodulin on the peptide level, we can resolve different structural domains of the protein. Carbene footprinting in a flow system is promising.

  10. Dosimetry Determines the Initial OH Radical Concentration in Fast Photochemical Oxidation of Proteins (FPOP)

    Science.gov (United States)

    Niu, Ben; Zhang, Hao; Giblin, Daryl; Rempel, Don L.; Gross, Michael L.

    2015-05-01

    Fast photochemical oxidation of proteins (FPOP) employs laser photolysis of hydrogen peroxide to give OH radicals that label amino acid side-chains of proteins on the microsecond time scale. A method for quantitation of hydroxyl radicals after laser photolysis is of importance to FPOP because it establishes a means to adjust the yield of •OH, offers the opportunity of tunable modifications, and provides a basis for kinetic measurements. The initial concentration of OH radicals has yet to be measured experimentally. We report here an approach using isotope dilution gas chromatography/mass spectrometry (GC/MS) to determine quantitatively the initial •OH concentration (we found ~0.95 mM from 15 mM H2O2) from laser photolysis and to investigate the quenching efficiencies for various •OH scavengers.

  11. Potential oxidative stress in the bodies of electric arc welding operators: effect of photochemical smog.

    Science.gov (United States)

    Zhu, You-Gen; Zhou, Jun-Fu; Shan, Wei-Ying; Zhou, Pei-Su; Tong, Gui-Zhong

    2004-12-01

    To investigate whether photochemical smog emitted during the process of electric arc welding might cause oxidative stress and potential oxidative damage in the bodies of welding operators. Seventy electric arc welding operators (WOs) and 70 healthy volunteers (HVs) were enrolled in a randomized controlled study design, in which the levels of vitamin C (VC) and vitamin E (VE) in plasma as well as the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX), and the level of lipoperoxide (LPO) in erythrocytes were determined by spectrophotometry. Compared with the average values of the above experimental parameters in the HVs group, the average values of VC and VE in plasma as well as those of SOD, CAT and GPX in erythrocytes in the WOs group were significantly decreased (P smog the values of VC, VE, SOD, and GPX, except for CAT, in the WOs were decreased gradually (P smog in the bodies of WOs, thereby causing potential oxidative and lipoperoxidative damages in their bodies.

  12. Degradation of benzalkonium chloride coupling photochemical advanced oxidation technologies with biological processes

    International Nuclear Information System (INIS)

    Meichtry, J; Lamponi, A; Gautier, E; Acosta, T; Fiol, P; Curutchet, G; Candal, R; Litter, M

    2005-01-01

    The combination of Advanced Oxidation Technologies (AOTs) and biological processes can be visualized as a very successful technological option for treatment of effluents, because it combines high oxidizing technologies with a conventional, low-cost and well-established treatment technology.Photochemical AOTs, like UV-C with or without H 2 O 2 , photo-Fenton (PF, UV/H 2 O 2 /Fe(II-III)) and UV/TiO 2 heterogeneous photo catalysis involve the generation and use of powerful oxidizing species, mainly the hydroxyl radical.In almost all AOTs, it is possible to use sunlight. Benzalkonium chloride (dodecyldimetylbencylammonium chloride, BKC) is a widely used surfactant, which has many industrial applications.Due to its antibacterial effect, it cannot be eliminated from effluents by a biological treatment, and the complexity of its chemical structure makes necessary the use of drastic oxidizing treatments to achieve complete mineralization and to avoid the formation of byproducts even more toxic than the initial compound.In this study, different alternatives for BKC treatment using photochemical AOTs followed by bio catalytic techniques are presented.Three AOTs were tested: a) UV-C (254 nm, germicide lamp) with and without H 2 O 2 , b) PF (366 nm), c) UV/TiO 2 (254 and 366 nm). PF at a 15:1:1 H 2 O 2 total/BKC 0 /Fe 0 molar ratio at 55 degree C was the most efficient treatment in order to decrease the tensioactivity and the total organic carbon of the solution . The biocatalysis was studied in a reactor fitted with a biofilm of microorganisms coming from a sludge-water treatment plant. To evaluate the maximal BKC concentration that could be allowed to ingress to the biological reactor after the AOT treatment, the toxicity of solutions of different BKC concentrations was analyzed. The study of the relevant parameters of both processes and their combination allowed to establish the preliminary conditions for optimizing the pollutant degradation

  13. Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

    Science.gov (United States)

    Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

    2013-03-06

    Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.

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

    Directory of Open Access Journals (Sweden)

    L. Xue

    2016-08-01

    Full Text Available 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.

  15. QSARs for phenols and phenolates: oxidation potential as a predictor of reaction rate constants with photochemically produced oxidants.

    Science.gov (United States)

    Arnold, William A; Oueis, Yan; O'Connor, Meghan; Rinaman, Johanna E; Taggart, Miranda G; McCarthy, Rachel E; Foster, Kimberley A; Latch, Douglas E

    2017-03-22

    Quantitative structure-activity relationships (QSARs) for prediction of the reaction rate constants of phenols and phenolates with three photochemically produced oxidants, singlet oxygen, carbonate radical, and triplet excited state sensitizers/organic matter, are developed. The predictive variable is the one-electron oxidation potential (E 1 ), which is calculated for each species using density functional theory. The reaction rate constants are obtained from the literature, and for singlet oxygen, are augmented with new experimental data. Calculated E 1 values have a mean unsigned error compared to literature values of 0.04-0.06 V. For singlet oxygen, a single linear QSAR that includes both phenols and phenolates is developed that predicts experimental rate constants, on average, to within a factor of three. Predictions for only 6 out of 87 compounds are off by more than a factor of 10. A more limited data set for carbonate radical reactions with phenols and phenolates also gives a single linear QSAR with prediction of rate constant being accurate to within a factor of three. The data for the reactions of phenols with triplet state sensitizers demonstrate that two sensitizers, 2-acetonaphthone and methylene blue, most closely predict the reactivity trend of triplet excited state organic matter with phenols. Using sensitizers with stronger reduction potentials could lead to overestimation of rate constants and thus underestimation of phenolic pollutant persistence.

  16. Photochemical modeling of glyoxal at a rural site: observations and analysis from BEARPEX 2007

    Directory of Open Access Journals (Sweden)

    A. J. Huisman

    2011-09-01

    Full Text Available We present roughly one month of high time-resolution, direct, in situ measurements of gas-phase glyoxal acquired during the BEARPEX 2007 field campaign. The research site, located on a ponderosa pine plantation in the Sierra Nevada mountains, is strongly influenced by biogenic volatile organic compounds (BVOCs; thus this data adds to the few existing measurements of glyoxal in BVOC-dominated areas. The short lifetime of glyoxal of ~1 h, the fact that glyoxal mixing ratios are much higher during high temperature periods, and the results of a photochemical model demonstrate that glyoxal is strongly influenced by BVOC precursors during high temperature periods.

    A zero-dimensional box model using near-explicit chemistry from the Leeds Master Chemical Mechanism v3.1 was used to investigate the processes controlling glyoxal chemistry during BEARPEX 2007. The model showed that MBO is the most important glyoxal precursor (~67 %, followed by isoprene (~26 % and methylchavicol (~6 %, a precursor previously not commonly considered for glyoxal production. The model calculated a noon lifetime for glyoxal of ~0.9 h, making glyoxal well suited as a local tracer of VOC oxidation in a forested rural environment; however, the modeled glyoxal mixing ratios over-predicted measured glyoxal by a factor 2 to 5. Loss of glyoxal to aerosol was not found to be significant, likely as a result of the very dry conditions, and could not explain the over-prediction. Although several parameters, such as an approximation for advection, were found to improve the model measurement discrepancy, reduction in OH was by far the most effective. Reducing model OH concentrations to half the measured values decreased the glyoxal over-prediction from a factor of 2.4 to 1.1, as well as the overprediction of HO2 from a factor of 1.64 to 1.14. Our analysis has shown that glyoxal is particularly sensitive to OH concentration compared to other BVOC oxidation products. This

  17. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling. Evaluation No. 12

    Science.gov (United States)

    DeMore, W. B.; Sander, S. P.; Golden, D. M.; Hampson, R. F.; Kurylo, M. J.; Howard, C. J.; Ravishankara, A. R.; Kolb, C. E.; Molina, M. J.

    1997-01-01

    This is the twelfth in a series of evaluated sets of rate constants and photochemical cross sections compiled by the NASA Panel for Data Evaluation. The primary application of the data is in the modeling of stratospheric processes, with special emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena.

  18. Ozonolysis and Subsequent Photolysis of unsaturated organic molecules: Model Systems for Photochemical Aging of Organic Aerosol Particles

    Science.gov (United States)

    Park, J.; Gomez, A. L.; Walser, M. L.; Lin, A.; Nizkorodov, S. A.

    2005-12-01

    Chemical and photochemical aging of organic species adsorbed on aerosol particle surfaces is believed to have a significant effect on cloud condensation properties of atmospheric aerosols. Ozone initiated oxidation reactions of thin films of undecylenic acid and alkene-terminated self assembled monolayers (SAMs) on SiO2 surface were investigated using a combination of spectroscopic and mass spectrometric techniques. Photolysis of the oxidized film in the tropospheric actinic region (λ>290 nm) readily produces formaldehyde and formic acid as gas-phase products. Photodissociation action spectra of the oxidized film suggest that organic peroxides are responsible for the enhanced photochemical activity. The presence of peroxides in the oxidized sample was confirmed by mass-spectrometric analysis and by an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is also observed. The reaction mechanism and its implications for photochemical aging of atmospheric aerosol particles will be discussed.

  19. Implications of imprecision in kinetic rate data for photochemical model calculations

    Energy Technology Data Exchange (ETDEWEB)

    Stewart, R.W.; Thompson, A.M. [National Aeronautics and Space Administration, Greenbelt, MD (United States). Goddard Space Flight Center

    1997-12-31

    Evaluation of uncertainties in photochemical model calculations is of great importance to scientists performing assessment modeling. A major source of uncertainty is the measurement imprecision inherent in photochemical reaction rate data that modelers rely on. A rigorous method of evaluating the impact of data imprecision on computational uncertainty is the study of error propagation using Monte Carlo techniques. There are two problems with the current implementation of the Monte Carlo method. First, there is no satisfactory way of accounting for the variation of imprecision with temperature in 1, 2, or 3D models; second, due to its computational expense, it is impractical in 3D model studies. These difficulties are discussed. (author) 4 refs.

  20. Linking photochemical transformation of an Antarctica Fulvic Acid to diminished bioavailability and oxidation of organic electron shuttles

    Science.gov (United States)

    Fimmen, R. L.; Guerard, J. J.; Miller, P. L.; Cory, R. M.; Chin, Y.; Foreman, C. M.; McKnight, D. M.

    2007-12-01

    Photolysis of fulvic acid isolated from Pony Lake, Antarctica, a hypereutrophic coastal pond located on Ross Island, was evaluated for transformation kinetics and photo-bleaching mechanisms by spectroscopy, as well as changes in bioavailability. The fulvic acid fraction of Pony Lake was isolated by sorption to non-ionic XAD-8 resin, and represents the fraction of the dissolved organic matter considered to be the most photo-reactive fraction. Spectroscopic and electrochemical analysis during Pony Lake fulvic acid photolysis reveals three fundamental alterations to the natural organic matter isolate: decreased molar absorptivity, decreased fluorescence, and a loss of reduced organic functional groups (potential electron shuttles). Surprisingly we observed no carbon loss to mineralization. Evaluation of the light absorbance decay kinetics in the presence/absence of oxygen indicate that approximately 70% of photo-bleaching occurs via direct pathways and 30% is due to reaction with photochemically generated reactive oxygen species (ROS). Of the ROS mediated pathways approximately 70% of the reactivity is attributable to hydroxyl-radical oxidation. Molecular level changes in fulvic acid showed a loss of electron-rich (reduced) components during photolysis, specifically redox active N/S functional groups. Reduced forms of organic nitrogen (amines) decrease in concentration, while sulfur moieties (thiols) are essentially eliminated during photolysis. Furthermore, as the suite of reduced fulvic acid components are photochemically oxidized, we observe a concomitant production of hydrogen peroxide, presumably due to the photo-reduction of dissolved oxygen coupled to organic matter oxidation. Decay kinetics of fluorescent components identified in the fulvic acid isolate were evaluated using parallel factor component analysis (PARAFAC) of excitation-emission matrices (EEMs), and further illustrate a loss of overall fluorescence and a decrease in the redox-active (electron

  1. A box model study on photochemical interactions between VOCs and reactive halogen species in the marine boundary layer

    Directory of Open Access Journals (Sweden)

    K. Toyota

    2004-01-01

    Full Text Available A new chemical scheme is developed for the multiphase photochemical box model SEAMAC (size-SEgregated Aerosol model for Marine Air Chemistry to investigate photochemical interactions between volatile organic compounds (VOCs and reactive halogen species in the marine boundary layer (MBL. Based primarily on critically evaluated kinetic and photochemical rate parameters as well as a protocol for chemical mechanism development, the new scheme has achieved a near-explicit description of oxidative degradation of up to C3-hydrocarbons (CH4, C2H6, C3H8, C2H4, C3H6, and C2H2 initiated by reactions with OH radicals, Cl- and Br-atoms, and O3. Rate constants and product yields for reactions involving halogen species are taken from the literature where available, but the majority of them need to be estimated. In particular, addition reactions of halogen atoms with alkenes will result in forming halogenated organic intermediates, whose photochemical loss rates are carefully evaluated in the present work. Model calculations with the new chemical scheme reveal that the oceanic emissions of acetaldehyde (CH3CHO and alkenes (especially C3H6 are important factors for regulating reactive halogen chemistry in the MBL by promoting the conversion of Br atoms into HBr or more stable brominated intermediates in the organic form. The latter include brominated hydroperoxides, bromoacetaldehyde, and bromoacetone, which sequester bromine from a reactive inorganic pool. The total mixing ratio of brominated organic species thus produced is likely to reach 10-20% or more of that of inorganic gaseous bromine species over wide regions over the ocean. The reaction between Br atoms and C2H2 is shown to be unimportant for determining the degree of bromine activation in the remote MBL. These results imply that reactive halogen chemistry can mediate a link between the oceanic emissions of VOCs and the behaviors of compounds that are sensitive to halogen chemistry such as dimethyl

  2. Mercury in Arctic snow: Quantifying the kinetics of photochemical oxidation and reduction

    International Nuclear Information System (INIS)

    Mann, E.A.; Mallory, M.L.; Ziegler, S.E.; Tordon, R.; O'Driscoll, N.J.

    2015-01-01

    Controlled experiments were performed with frozen and melted Arctic snow to quantify relationships between mercury photoreaction kinetics, ultra violet (UV) radiation intensity, and snow ion concentrations. Frozen (− 10 °C) and melted (4 °C) snow samples from three Arctic sites were exposed to UV (280–400 nm) radiation (1.26–5.78 W · m −2 ), and a parabolic relationship was found between reduction rate constants in frozen and melted snow with increasing UV intensity. Total photoreduced mercury in frozen and melted snow increased linearly with greater UV intensity. Snow with the highest concentrations of chloride and iron had larger photoreduction and photooxidation rate constants, while also having the lowest Hg(0) production. Our results indicate that the amount of mercury photoreduction (loss from snow) is the highest at high UV radiation intensities, while the fastest rates of mercury photoreduction occurred at both low and high intensities. This suggests that, assuming all else is equal, earlier Arctic snow melt periods (when UV intensities are less intense) may result in less mercury loss to the atmosphere by photoreduction and flux, since less Hg(0) is photoproduced at lower UV intensities, thereby resulting in potentially greater mercury transport to aquatic systems with snowmelt. - Highlights: • Mercury photochemical kinetics were studied in frozen and melted Arctic snow. • UV-induced photoreduction and photooxidation rate constants were quantified. • Chloride ion, iron, and DOC influence mercury photoreactions in snow. • Frozen and melted snow have different mercury photoreduction characteristics. • Kinetic information provided can be used to model mercury fate in the Arctic

  3. Studies on Photochemical Reactions of Air Pollutants. IX. Formation of o-Nitrophenol and p-Nitrophenol by Reaction of Benzene Oxide with NO2 in Air

    OpenAIRE

    野島, 一宏; 大谷, 武司; 菅野, 三郎; 広部, 雅昭

    1982-01-01

    When benzene oxide was brought into contact with nitrogen dioxide in air, o-nitro-phenol and p-nitrophenol were formed together with fog. Benzene oxide seems to be an intermediate in the photochemical reaction of benzene with nitrogen dioxide in air.

  4. Oxidative decomposition of atrazine in water in the presence of hydrogen peroxide using an innovative microwave photochemical reactor.

    Science.gov (United States)

    Chen, Huilun; Bramanti, Emilia; Longo, Iginio; Onor, Massimo; Ferrari, Carlo

    2011-02-28

    The simultaneous application of microwave (MW) power and UV light leads to improved results in photochemical processes. This study investigates the oxidative decomposition of atrazine in water using an innovative MW and UV photochemical reactor, which activates a chemical reaction with MW and UV radiation using an immersed source without the need for a MW oven. We investigated the influence of reaction parameters such as initial H(2)O(2) concentrations, reaction temperatures and applied MW power and identified the optimal conditions for the oxidative decomposition of atrazine. Atrazine was completely degraded by MW/UV/H(2)O(2) in a very short time (i.e. t(1/2) = 1.1 min for 20.8 mg/L in optimal conditions). From the kinetic study, the disappearance rate of atrazine can be expressed as dX/dt = k(PH)[M](0)(b-X)(1-X), where b ≡ [H(2)O(2)](0)/[M](0)+k(OH)[·OH]/k(PH)[M](0), and X is the atrazine conversion, which correlates well with the experimental data. The kinetic analysis also showed that an indirect reaction of atrazine with an OH radical is dominant at low concentrations of H(2)O(2) and a direct reaction of atrazine with H(2)O(2) is dominant when the concentration of H(2)O(2) is more than 200 mg/L. Copyright © 2010 Elsevier B.V. All rights reserved.

  5. Photochemical Air Quality Model Evaluation and Rog Reactivity Analysis

    Science.gov (United States)

    McNair, Laurie A.

    1995-11-01

    This thesis is concerned with the model performance evaluation and the analysis of control strategies. First, the model was applied to Los Angeles and a suite of statistical and graphical analyses found that the model could predict ozone within a GNE of 31%. It was also found that the variability of the observations was similar to predictions (GNE of 27%) and that these variations may need to be taken into account when evaluating models. The model was also applied to Mexico City and model results indicated that the vertical diffusivity may not be represented well. An alternate algorithm showed the model predictions for ozone were within a GNE of 36% and that the spatial variability of the observations was similar to those found for Los Angeles. Next, the model was applied to an episode in Los Angeles when liquid water was present in order to determine the effect of modeling aqueous phase chemistry. It was found to have no affect on gas phase species, but to be important for acid deposition. The thesis then focused on using the differences in the ozone forming potential (or reactivity) to determine control strategies. First, the reactivity of 10 ROG classes commonly present in automobile exhaust were found. Next, these reactivities were used to calculate reactivity adjustment factors to determine the allowable emissions for an alternatively fueled vehicle. A test was then performed to see if the reactivity adjusted emissions for three AFVs led to similar ozone formation. It was found that M85 led to 10% more ozone formation than a conventionally fueled vehicle during very stagnant meteorologies. Next, the exemption of acetone from ROG regulations was explored to estimate how the exemption of a less reactive ROG could affect the use of more reactive compounds which performed the same function. It was found that acetone was about as reactive as ethane, although this varied due to ROG/NO_{rm x} conditions. Thus, California would have to decide if they wished to

  6. Advanced oxidation treatment and photochemical fate of selected antidepressant pharmaceuticals in solutions of Suwannee River humic acid

    International Nuclear Information System (INIS)

    Santoke, Hanoz; Song, Weihua; Cooper, William J.; Peake, Barrie M.

    2012-01-01

    Highlights: ► We elucidate the photochemical degradation of three antidepressant pharmaceuticals. ► Hydroxyl radical is the most significant contributor to the degradation. ► Excited state dissolved organic matter also plays a significant role for duloxetine. ► Tentative reaction byproducts are identified. - Abstract: Antidepressant pharmaceuticals have recently been detected at low concentrations in wastewater and surface water. This work reports studies of the direct and indirect photochemical fate and treatment by advanced oxidation of three antidepressant compounds (duloxetine, venlafaxine and bupropion) in solutions of humic acid in order to elucidate their behavior in the natural environment prior to reaching a water treatment facility and potentially entering a potable water supply. Humic acid solution was prepared by adding to distilled water a known amount of organic matter as a photosensitizer. All three antidepressants react very rapidly with hydroxyl radicals (·OH) and hydrated electrons (e − aq ) with rate constants of ∼10 8 to 10 10 M −1 s −1 , but significantly slower with singlet oxygen ( 1 ΔO 2 ) (∼10 3 to 10 5 M −1 s −1 ). The steady-state concentrations of ·OH and 1 ΔO 2 , in a sample of humic acid solution were measured and used with the second order rate constants to show that the hydroxyl radical was an order of magnitude more effective than the singlet oxygen in the solar-induced photochemical degradation of the antidepressants. Excited state dissolved organic matter also accounted for a substantial portion of degradation of duloxetine, decreasing its half-life by 27% under solar irradiation. Several reaction pathways and by-products arising from the photodegradation were identified using gamma-irradiation followed by LC–MS analysis.

  7. Advanced oxidation treatment and photochemical fate of selected antidepressant pharmaceuticals in solutions of Suwannee River humic acid

    Energy Technology Data Exchange (ETDEWEB)

    Santoke, Hanoz, E-mail: hsantoke@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song, Weihua, E-mail: wsong@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Department of Environmental Science and Engineering, Fudan University, Shanghai, 200433 (China); Cooper, William J., E-mail: wcooper@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Peake, Barrie M., E-mail: bpeake@chemistry.otago.ac.nz [Chemistry Department, University of Otago, P.O. Box 56, Dunedin 9054 (New Zealand)

    2012-05-30

    Highlights: Black-Right-Pointing-Pointer We elucidate the photochemical degradation of three antidepressant pharmaceuticals. Black-Right-Pointing-Pointer Hydroxyl radical is the most significant contributor to the degradation. Black-Right-Pointing-Pointer Excited state dissolved organic matter also plays a significant role for duloxetine. Black-Right-Pointing-Pointer Tentative reaction byproducts are identified. - Abstract: Antidepressant pharmaceuticals have recently been detected at low concentrations in wastewater and surface water. This work reports studies of the direct and indirect photochemical fate and treatment by advanced oxidation of three antidepressant compounds (duloxetine, venlafaxine and bupropion) in solutions of humic acid in order to elucidate their behavior in the natural environment prior to reaching a water treatment facility and potentially entering a potable water supply. Humic acid solution was prepared by adding to distilled water a known amount of organic matter as a photosensitizer. All three antidepressants react very rapidly with hydroxyl radicals ({center_dot}OH) and hydrated electrons (e{sup -}{sub aq}) with rate constants of {approx}10{sup 8} to 10{sup 10} M{sup -1} s{sup -1}, but significantly slower with singlet oxygen ({sup 1}{Delta}O{sub 2}) ({approx}10{sup 3} to 10{sup 5} M{sup -1} s{sup -1}). The steady-state concentrations of {center_dot}OH and {sup 1}{Delta}O{sub 2}, in a sample of humic acid solution were measured and used with the second order rate constants to show that the hydroxyl radical was an order of magnitude more effective than the singlet oxygen in the solar-induced photochemical degradation of the antidepressants. Excited state dissolved organic matter also accounted for a substantial portion of degradation of duloxetine, decreasing its half-life by 27% under solar irradiation. Several reaction pathways and by-products arising from the photodegradation were identified using gamma-irradiation followed by LC

  8. Compilation and evaluation of a Paso del Norte emission inventory for use in photochemical dispersion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Haste, T.L.; Kumar, N.; Chinkin, L.R.; Roberts, P.T.; Saeger, M.; Mulligan, S.; Yarbrough, J.

    1999-07-01

    Emission inventories are routinely used for planning purposes and as input to comprehensive photochemical air quality models. Photochemical model performance and the development of an effective control strategy are predicated on the accuracy of an underlying emission inventory. The purpose of this study was to compile an ozone precursor emission inventory for the El Paso/Ciudad Juarez/Southern Dona Ana region; generate a spatially and temporally resolved, speciated emission inventory; and evaluate the accuracy and representativeness of the inventory. Existing point, area, and mobile source emissions data were obtained from local government agencies. Emissions were spatially and temporally allocated to a gridded domain using region-specific demographic and land cover information. The inventory was processed using the US Environmental Protection Agency (EPA) recommended Urban Airshed Model Emissions Preprocessor System 2.0 (UAM-EPS 2.0) which generates emissions files that can be directly used as input to the Urban Airshed Model. An evaluation of the emission inventory was then performed by comparing inventory non-methane hydrocarbon (NMHC)/NO{sub x} and CO/NO{sub x} ratios to ambient ratios using air quality data collected during the 1996 Paso del Norte Ozone Study. Detailed NMHC species comparisons were also made in order to investigate the relative composition of individual hydrocarbon species in the emission inventory and in the ambient data. This initial emission inventory is expected to undergo substantial revisions during the upcoming photochemical modeling phase of the effort to better understand and improve the air quality of the El Paso/Ciudad Juarez/Southern Dona Ana region.

  9. Photochemical Oxidative Cyclisation of Stilbenes and Stilbenoids—The Mallory-Reaction

    Directory of Open Access Journals (Sweden)

    Kåre B. Jørgensen

    2010-06-01

    Full Text Available After Mallory described in 1964 the use of iodine as catalyst for the photochemical cyclisation of stilbenes, this reaction has proven its effectiveness in the synthesis of phenanthrenes, other PAHs and phenacenes with a surprisingly large selection of substituents. The “early age” of the reaction was reviewed by Mallory in 1984in a huge chapter in the Organic Reactions series, but the development has continued. Alternative conditions accommodate more sensitive substituents, and isomers can be favoured by sacrificial substituents. Herein the further developments and applications of this reaction after 1984 are discussed and summarized.

  10. Modeling of photochemical air pollution in the Barcelona area with highly disaggregated anthropogenic and biogenic emissions

    International Nuclear Information System (INIS)

    Toll, I.; Baldasano, J.M.

    2000-01-01

    The city of Barcelona and its surrounding area, located in the western Mediterranean basin, can reach high levels of O 3 in spring and summertime. To study the origin of this photochemical pollution, a numerical modeling approach was adopted and the episode that took place between 3 and 5 August 1990 was chosen. The main meteorological mesoscale flows were reproduced with the meteorological non-hydrostatic mesoscale model MEMO for 5 August 1990, when weak pressure synoptic conditions took place. The emissions inventory was calculated with the EIM-LEM model, giving highly disaggregated anthropogenic and biogenic emissions in the zone studied, an 80 x 80 km 2 area around the city of Barcelona. Major sources of VOC were road traffic (51%) and vegetation (34%), while NO x were mostly emitted by road traffic (88%). However, emissions from some industrial stacks can be locally important and higher than those from road traffic. Photochemical simulation with the MARS model revealed that the combination of mesoscale wind flows and the above-mentioned local emissions is crucial in the production and transport of O 3 in the area. On the other hand, the geostrophic wind also played an important role in advecting the air masses away from the places O 3 had been generated. The model simulations were also evaluated by comparing meteorological measurements from nine surface stations and concentration measurements from five surface stations, and the results proved to be fairly satisfactory. (author)

  11. Multi-objective optimization of oxidative desulfurization in a sono-photochemical airlift reactor.

    Science.gov (United States)

    Behin, Jamshid; Farhadian, Negin

    2017-09-01

    Response surface methodology (RSM) was employed to optimize ultrasound/ultraviolet-assisted oxidative desulfurization in an airlift reactor. Ultrasonic waves were incorporated in a novel-geometry reactor to investigate the synergistic effects of sono-chemistry and enhanced gas-liquid mass transfer. Non-hydrotreated kerosene containing sulfur and aromatic compounds was chosen as a case study. Experimental runs were conducted based on a face-centered central composite design and analyzed using RSM. The effects of two categorical factors, i.e., ultrasound and ultraviolet irradiation and two numerical factors, i.e., superficial gas velocity and oxidation time were investigated on two responses, i.e., desulfurization and de-aromatization yields. Two-factor interaction (2FI) polynomial model was developed for the responses and the desirability function associate with overlay graphs was applied to find optimum conditions. The results showed enhancement in desulfurization ability corresponds to more reduction in aromatic content of kerosene in each combination. Based on desirability approach and certain criteria considered for desulfurization/de-aromatization, the optimal desulfurization and de-aromatization yields of 91.7% and 48% were obtained in US/UV/O 3 /H 2 O 2 combination, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. A programmable soft chemo-mechanical actuator exploiting a catalyzed photochemical water-oxidation reaction.

    Science.gov (United States)

    Yuan, P; McCracken, J M; Gross, D E; Braun, P V; Moore, J S; Nuzzo, R G

    2017-10-18

    We describe a composite hydrogel containing an embedding coupled chemistry for light-sensitized catalytic reactions that enables chemo-mechanical actuation of poly(acrylic acid)-based gels. In these materials, a photosensitizer and catalyst-ruthenium trisbipyridine and iridium dioxide nanoparticles, respectively-are incorporated into the hydrogel where together, with visible light irradiation, they undergo a catalytic water-oxidation reaction that lowers the pH and induces a dissipative/chemically-driven strain change in the gel. To demonstrate the capacity for 3D chemo-mechanical actuation, a layer of non-pH responsive poly(2-hydroxyethyl methacrylate) is added to the photo-active composite gel to create a model bimorph actuator. Triggering and terminating the water-oxidation reaction leads to a programmatic expansion and contraction of the active layer, which induces different modes of biomimetic curling motions in the bimorph actuator in light and dark environments. The efficiency of this system is fundamentally limited by the system-level design, which provides no capacity to sustain a local pH gradient against diffusive mixing. Even so, if the initial pH of the background solution is reestablished either actively or passively between each reaction cycle, it is possible to realize multiple cycles of reversible actuation. We describe a thermodynamic analysis of this system which identifies specific features mediating efficiency losses and conceptual requirements for mesoscopic design rules for optimization of this system and for advancing soft actuation systems in general.

  13. Photochemical oxidation processes for the elimination of phenyl-urea herbicides in waters

    Energy Technology Data Exchange (ETDEWEB)

    Benitez, F. Javier [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)]. E-mail: javben@unex.es; Real, Francisco J. [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain); Acero, Juan L. [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain); Garcia, Carolina [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)

    2006-11-16

    Four phenyl-urea herbicides (linuron, chlorotoluron, diuron, and isoproturon) were individually photooxidized by monochromatic UV radiation in ultra-pure aqueous solutions. The influence of pH and temperature on the photodegradation process was established, and the first-order rate constants and quantum yields were evaluated. The sequence of photodecomposition rates was: linuron > chlorotoluron > diuron > isoproturon. The simultaneous photooxidation of mixtures of the selected herbicides in several types of waters was then performed by means of UV radiation alone, and by UV radiation combined with hydrogen peroxide. The types of waters used were: ultra-pure water, a commercial mineral water, a groundwater, and a lake water. The influence of the independent variables in these processes - the presence or absence of tert-butyl alcohol, types of herbicide and waters, and concentration of hydrogen peroxide - were established and discussed. A kinetic study was performed using a competitive kinetic model that allowed various rate constants to be evaluated for each herbicide. This kinetic model allows one to predict the elimination of these phenyl-urea herbicides in contaminated waters by the oxidation systems used (UV alone and combined UV/H{sub 2}O{sub 2}). The herbicide concentrations predicted by this model agree well with the experimental results that were obtained.

  14. Photochemical oxidation processes for the elimination of phenyl-urea herbicides in waters

    International Nuclear Information System (INIS)

    Benitez, F. Javier; Real, Francisco J.; Acero, Juan L.; Garcia, Carolina

    2006-01-01

    Four phenyl-urea herbicides (linuron, chlorotoluron, diuron, and isoproturon) were individually photooxidized by monochromatic UV radiation in ultra-pure aqueous solutions. The influence of pH and temperature on the photodegradation process was established, and the first-order rate constants and quantum yields were evaluated. The sequence of photodecomposition rates was: linuron > chlorotoluron > diuron > isoproturon. The simultaneous photooxidation of mixtures of the selected herbicides in several types of waters was then performed by means of UV radiation alone, and by UV radiation combined with hydrogen peroxide. The types of waters used were: ultra-pure water, a commercial mineral water, a groundwater, and a lake water. The influence of the independent variables in these processes - the presence or absence of tert-butyl alcohol, types of herbicide and waters, and concentration of hydrogen peroxide - were established and discussed. A kinetic study was performed using a competitive kinetic model that allowed various rate constants to be evaluated for each herbicide. This kinetic model allows one to predict the elimination of these phenyl-urea herbicides in contaminated waters by the oxidation systems used (UV alone and combined UV/H 2 O 2 ). The herbicide concentrations predicted by this model agree well with the experimental results that were obtained

  15. CALGRID Photochemical Modeling of Air Quality Impacts of Alternative Transportation Fuel Use in Los Angeles

    Energy Technology Data Exchange (ETDEWEB)

    Moore, G. E.; Londergan, R. J.; Fernau, M. E.

    1998-11-19

    The National Renewable Energy Laboratory has been conducting a comprehensive program to quantify and assess the air quality impacts of the emissions of ozone precursors, air toxins, and greenhouse gases from alternative fuel vehicles. This program includes both an emissions estimation component and a photochemical modeling component to study three fuels: reformulated gasoline, compressed natural gas, and 85% methanol (M85). This report describes the use of the CALGRID model in the Los Angeles modeling domain using the State-Wide Air Pollution Research Center (SAPRC90) chemical mechanism and an early version of the SAPRC93 mechanism. A variety of conclusions can be drawn from the results of this study, including results from chemical mechanism testing; development of meteorological inputs; model evaluation and comparison; and the analyses of the impacts of the emissions scenarios. The report summarizes the study's major findings in these areas.

  16. Atmospheric photochemical reactivity and ozone production at two sites in Hong Kong: Application of a Master Chemical Mechanism-photochemical box model

    Science.gov (United States)

    Ling, Z. H.; Guo, H.; Lam, S. H. M.; Saunders, S. M.; Wang, T.

    2014-09-01

    A photochemical box model incorporating the Master Chemical Mechanism (v3.2), constrained with a full suite of measurements, was developed to investigate the photochemical reactivity of volatile organic compounds at a semirural site (Mount Tai Mo Shan (TMS)) and an urban site (Tsuen Wan (TW)) in Hong Kong. The levels of ozone (O3) and its precursors, and the magnitudes of the reactivity of O3 precursors, revealed significant differences in the photochemistry at the two sites. Simulated peak hydroperoxyl radical (HO2) mixing ratios were similar at TW and TMS (p = 0.05), while the simulated hydroxyl radical (OH) mixing ratios were much higher at TW (p TMS, but at TW, both HCHO and O3 photolyses were found to be major contributors. By contrast, radical-radical reactions governed HOx radical losses at TMS, while at TW, the OH + NO2 reaction was found to dominate in the morning and the radical-radical reactions at noon. Overall, the conversion of NO to NO2 by HO2 dictated the O3 production at the two sites, while O3 destruction was dominated by the OH + NO2 reaction at TW, and at TMS, O3 photolysis and the O3 + HO2 reaction were the major mechanisms. The longer OH chain length at TMS indicated that more O3 was produced for each radical that was generated at this site.

  17. Overview: oxidant and particle photochemical processes above a south-east Asian tropical rainforest (the OP3 project: introduction, rationale, location characteristics and tools

    Directory of Open Access Journals (Sweden)

    C. N. Hewitt

    2010-01-01

    Full Text Available In April–July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3 project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (~100 pptv/pptv, current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm−3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.

  18. Photochemical generation and 1H NMR detection of alkyl allene oxides in solution

    International Nuclear Information System (INIS)

    Breen, L.E.; Schepp, N.P.; Tan, C.-H.E.

    2005-01-01

    Irradiation of substituted 5-alkyl-4,5-epoxyvalerophenones leads to the formation of alkyl allene oxides that, in some cases, are sufficiently long-lived to be detected at room temperature by 1 H NMR spectroscopy. Absolute lifetime measurements show that the size of the alkyl group has a significant influence on the reactivity of the allene oxide, with tert-butyl allene oxide having a lifetime of 24 h in CD 3 CN at room temperature that is considerably longer than the 1.5 h lifetime of the ethyl allene oxide. The allene oxides react rapidly with water to give α-hydroxyketones. The mechanism involves nucleophilic attack to the epoxide carbon to give an enol, which can also be detected as an intermediate by 1 H NMR spectroscopy. (author)

  19. Photophysical and photochemical effects of UV and VUV photo-oxidation and photolysis on PET and PEN

    Science.gov (United States)

    Morgan, Andrew

    Polyethylene Terephthalate (PET) is a widely used polymer in the bottling, packaging, and clothing industry. In recent years an increasing global demand for PET has taken place due to the Solar Disinfection (SODIS) process. SODIS is a method of sterilizing fresh water into drinkable water. The PET bottles are used in the process to contain the water during solar irradiation due to its highly transparent optical property. Alongside PET, polyethylene 2,6-napthalate (PEN) is used in bottling and flexible electronic applications. The surface of PEN would need to be modified to control the hydrophilicity and the interaction it exudes as a substrate. The UV light absorption properties of PET and PEN are of great importance for many applications, and thus needs to be studied along with its photochemical resistance. The optical and chemical nature of PET was studied as it was treated by UV photo-oxidation, photo-ozonation, and photolysis under atmospheric pressure. Another investigation was also used to study PEN and PET as they are treated by vacuum UV (VUV) photo-oxidation, VUV photolysis, and remote oxygen reactions. The extent of the photoreactions' effect into the depth of the polymers is examined as treatment conditions are changed. The different experimental methods established the rate of several competing photoreactions on PET and PEN during irradiance, and their effect on the optical quality of the polymers.

  20. UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors

    Directory of Open Access Journals (Sweden)

    Changsong Chen

    2018-01-01

    Full Text Available The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO for ultraviolet (UV photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm−2, on/off current ratio of 3.01 × 104, and responsivity of 1.83 A·W−1 when a UV irradiation of 3.26 mW·cm−2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite.

  1. UV-Assisted Photochemical Synthesis of Reduced Graphene Oxide/ZnO Nanowires Composite for Photoresponse Enhancement in UV Photodetectors.

    Science.gov (United States)

    Chen, Changsong; Zhou, Peng; Wang, Na; Ma, Yang; San, Haisheng

    2018-01-05

    The weak photon absorption and high recombination rate of electron-hole pairs in disordered zinc oxide nanowires (ZNWs) limit its application in UV photodetection. This limitation can be overcome by introducing graphene sheets to the ZNWs. Herein we report a high-performance photodetector based on one-dimensional (1D) wide band-gap semiconductor disordered ZNWs composited with reduced graphene oxide (RGO) for ultraviolet (UV) photoresponse enhancement. The RGO/ZNWs composites have been successfully synthetized through UV-assisted photochemical reduction of GO in ZNWs suspension. The material characterizations in morphology, Raman scattering, and Ultraviolet-visible light absorption verified the formation of graphene sheets attached in ZNWs network and the enhancement of UV absorption due to the introduction of graphene. In comparison with photodetectors based on pure ZNWs, the photodetectors based on RGO/ZNWs composite exhibit enhanced photoresponse with photocurrent density of 5.87 mA·cm -2 , on/off current ratio of 3.01 × 10⁴, and responsivity of 1.83 A·W -1 when a UV irradiation of 3.26 mW·cm -2 and 1.0 V bias were used. Theory analysis is also presented to get insight into the inherent mechanisms of separation and transportation of photo-excited carriers in RGO/ZNWs composite.

  2. Photochemical smog modeling for assessment of potential impacts of different management strategies on air quality of the Bangkok Metropolitan Region, Thailand.

    Science.gov (United States)

    Oanh, Nguyen Thi Kim; Zhang, Baoning

    2004-10-01

    A photochemical smog model system, the Variable-Grid Urban Airshed Model/Systems Applications International Mesoscale Model (UAM-V/SAIMM), was used to investigate photochemical pollution in the Bangkok Metropolitan Region (BMR). The model system was first applied to simulate a historical photochemical smog episode of two days (January 13-14, 1997) using the 1997 anthropogenic emission database available at the Pollution Control Department and an estimated biogenic emission. The output 1-hr ozone (O3) for BMR, however, did not meet the U.S. Environmental Protection Agency suggested performance criteria. The simulated minimum and maximum O3 values in the domain were much higher than the observations. Multiple model runs with different precursor emission reduction scenarios showed that the best model performance with the simulated 1-hr O3 meeting all the criteria was obtained when the volatile organic compound (VOC) and oxides of nitrogen (NOx) emission from mobile source reduced by 50% and carbon monoxide by 20% from the original database. Various combinations of anthropogenic and biogenic emissions in Bangkok and surrounding provinces were simulated to assess the contribution of different sources to O3 pollution in the city. O3 formation in Bangkok was found to be more VOC-sensitive than NOx-sensitive. To attain the Thailand ambient air quality standard for 1-hr O3 of 100 ppb, VOC emission in BMR should be reduced by 50-60%. Management strategies considered in the scenario study consist of Stage I, Stage II vapor control, replacement of two-stroke by four-stroke motorcycles, 100% compressed natural gas bus, 100% natural gas-fired power plants, and replacement of methyltertiarybutylether by ethanol as an additive for gasoline.

  3. Photochemical internalization in bladder cancer - development of an orthotopic in vivo model.

    Science.gov (United States)

    Gederaas, Odrun A; Johnsson, Anders; Berg, Kristian; Manandhar, Rojlina; Shrestha, Chetana; Skåre, Daniel; Ekroll, Ingvild Kinn; Høgset, Anders; Hjelde, Astrid

    2017-11-08

    The possibility of using photochemical internalization (PCI) to enhance the effects of the cytotoxic drug bleomycin is investigated, together with photophysical determination and outlines of a possible treatment for intravesical therapy of bladder cancer. In vitro experiments indicated that the employment of PCI technology using the novel photosensitizer TPCS 2a ® can enhance the cytotoxic effect of bleomycin in bladder cancer cells. Furthermore, experiments in an orthotopic in vivo bladder cancer model show an effective reduction in both the necrotic area and the bladder weight after TPCS 2a based photodynamic therapy (PDT). The tumor selectivity and PDT effects may be sufficient to destroy tumors without damaging the detrusor muscle layer. Our results present a possible new treatment strategy for non-muscle invasive bladder cancer, with the intravesical instillation of the photosensitizer and bleomycin followed by illumination through an optic fiber by using a catheter.

  4. Lombardia region photochemical characterization by means of modelling simulation; Caratterizzazione fotochimica dell'area lombarda

    Energy Technology Data Exchange (ETDEWEB)

    Gabusi, V.; Finzi, G. [Brescia Univ., Brescia (Italy). Dipt. di Elettronica per l' Automazione

    2001-08-01

    The following study is part of a project aimed to develop a comprehensive modelling system designed to analyse and select possible air quality strategies in metropolitan areas by means of emission abatement measure impact simulation. In this work, a system prototype is proposed, adopting selected software codices, which have been implemented and tested in a Northern Italy domain including the whole of Regione Lombardia, often affected by severe photochemical pollution episodes. The assessment of the relation between ozone, NO{sub x} and VOC is especially important as a starting point for environmental policy. So the modelling system has been applied for the evaluation and comparison of some different emission control strategies, in order to point out the photochemical regime of the domain. [Italian] Uno studio nel quadro di un progetto di ricerca finalizzato allo sviluppo di modelli per l'analisi e la scelta di strategie di risanamento della qualita' dell'aria in ambito metropolitano, attraverso la simulazione dell'impatto del contenimento delle emissioni. Il sistema modellistico e' stato implementato e testato su und dominio dell'Italia settentrionale, comprendente l'intera regione Lombardia, dove si verificano spesso episodi critici di inquinamento fotochimico. La valutazione della relazione fra l'ozono, gli NO{sub x} e i VOC, e' il punto di partenza nelle strategie di risanamento. Pertanto il sistema modellistico e' stato impiegato per la valutazione e il confronto di diverse strategie di controllo delle emissioni al fine di caratterizzare dal punto di vista fotochimico il dominio di indagine.

  5. Photochemical smog and plants

    Energy Technology Data Exchange (ETDEWEB)

    Sawada, T.

    1974-07-01

    Surveys of plant damage due to photochemical smog are summarized. The components of smog which appear to be responsible for plant damage include ozone and peroxyacyl nitrates. Their phytotoxic effects are much greater than those due to sulfur oxides. Damage surveys since 1970 reveal the following symptoms appearing on herbaceous plants (morning glory, cocks comb, dahlia, knotweed, petunia, chickweed, Welsh onion, spinach, Chinese cabbage, chard, taro): yellowish-white leaf discoloration, white and brown spots on matured leaves, and silvering of the lower surfaces of young leaves. Symptoms which appear on arboraceous plants such as zelkova, poplar, ginkgo, planetree, rose mallow, magnolia, pine tree, and rhododendron include early yellowing and reddening, white or brown spots, and untimely leaf-fall. The above plants are now utilized as indicator plants of photochemical smog. Surveys covering a broad area of Tokyo and three other prefectures indicate that plant damage due to photochemical smog extends to relatively unpolluted areas.

  6. Photochemical oxidation of antibiotic gemifloxacin in aqueous solutions – A comparative study

    Directory of Open Access Journals (Sweden)

    G. Shankaraiah

    2017-12-01

    Full Text Available The amount of organic micro pollutants like antibiotics detected in effluents, lakes, rivers, hospital wastewater, sewage water and ground water. These antibiotics are affecting aquatic organisms. Common wastewater treatment plants are not built to remove these substances. Thus there is a need for new technologies. The present study focuses on the application of a promising technology, that is the use of advanced oxidation processes (AOPs, which works based on the intermediacy of hydroxyl and other radicals to oxidized non-biodegradable compounds. Hence, in the present study treatment of certain gemifloxacin commonly used in day-to-day life has been carried out. The combination of UV, UV/H2O2, Fenton, and UV/Fenton systems has been studied. Gemifloxacin concentration degradation, Chemical Oxygen Demand (COD and Total Organic Carbon (TOC are monitored. Among all the processes studied photo-Fenton process has been found to be the maximum removal of gemifloxacin (97%. Keywords: Antibiotics, Pharmaceuticals, Oxidation technologies, Non-biodegradable, Gemifloxacin

  7. Photoprotection through ultrafast charge recombination in photochemical reaction centres under oxidizing conditions.

    Science.gov (United States)

    Ma, Fei; Swainsbury, David J K; Jones, Michael R; van Grondelle, Rienk

    2017-09-26

    Engineering natural photosynthesis to address predicted shortfalls in food and energy supply requires a detailed understanding of its molecular basis and the intrinsic photoprotective mechanisms that operate under fluctuating environmental conditions. Long-lived triplet or singlet excited electronic states have the potential to cause photodamage, particularly in the presence of oxygen, and so a variety of mechanisms exist to prevent formation of such states or safely dissipate their energy. Here, we report a dramatic difference in spectral evolution in fully reduced and partially oxidized Rhodobacter sphaeroides reaction centres (RCs) following excitation of the monomeric bacteriochlorophyll (BChl) cofactors at 805 nm. Three types of preparation were studied, including RCs purified as protein/lipid nanodiscs using the copolymer styrene maleic acid. In fully reduced RCs such excitation produces membrane-spanning charge separation. In preparations of partially oxidized RCs the spectroscopic signature of this charge separation is replaced by that of an energy dissipation process, including in the majority sub-population of reduced RCs. This process, which appears to take place on both cofactor branches, involves formation of a BChl + /bacteriopheophytin - radical pair that dissipates energy via recombination to a vibrationally hot ground state. The possible physiological role of this dissipative process under mildly oxidizing conditions is considered.This article is part of the themed issue 'Enhancing photosynthesis in crop plants: targets for improvement'. © 2017 The Author(s).

  8. Effects of inorganic seeds on secondary organic aerosol formation from photochemical oxidation of acetone in a chamber

    Science.gov (United States)

    Ge, Shuangshuang; Xu, Yongfu; Jia, Long

    2017-12-01

    Photochemical oxidations of acetone were studied under different inorganic seed (NaCl, (NH4)2SO4 and NaNO3) conditions in a self-made chamber. The results show that no secondary organic aerosol (SOA) can be formed in the experiments either in the absence of artificially added seed particles or in the presence of solid status of the added particles. Liquid water content is the key factor for the formation of SOA in the experiments with seeds. The amount of SOA was only about 4-7 μg m-3 in the experiments with the initial acetone of ∼15 ppm under different seed conditions. The analysis of SOA compositions by Exactive-Orbitrap mass spectrometer equipped with electro-spray interface (ESI-MS) shows that chlorine-containing and sulfur-containing compounds were detected in SOA formed from the experiments with NaCl and (NH4)2SO4 seeds, respectively, which were not identified in SOA from those with NaNO3. The compositions of SOA were mainly esters, organonitrates, hydroperoxides, etc. It is concluded that inorganic seed particles participated into the formation of SOA. Acetone SOA was mainly formed in the aqueous phase in which dissolved SOA precursors underwent further oxidation reactions, esterification reactions and/or radical-radical reactions. Our experiments further demonstrate that low-molecular-weight VOCs, such as acetone, can form SOA under certain conditions in the atmosphere, although their contributions to SOA may not be large.

  9. Study of Efficiency of Photochemical Oxidation Process with UV/Peroxidisulfate for Removal of Alizarin Red S from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Fariba Hafezi

    2016-12-01

    Full Text Available Introduction and purpose: Treatment of dye wastewater produced by textile industries is a major challenge for the environment. About 15% of the total produced dyes in the world are released in sewages during dyeing activities. Alizarin red S (ARS, a synthetic dye produced from Alizarin sulfonate is the most widely used dye in the textile industry. The aim of this study was to remove ARS dye from aqueous solutions through advanced photochemical oxidation process using UV/peroxidedisulfate. Methods: In this study, the effect of pH, concentration of persulfate, dye concentration, and UV radiation on removal of ARS were studied in laboratory scale using a reactor containing UV-C lamp (6 watts by batch method. ARS concentration was determined by UV/Visible spectrophotometer. Results: The results showed that removal efficiency increased by increasing the disulfate concentration, ultraviolet radiation intensity, and reaction time and decreased by increasing dye concentration and pH. The optimum condition was obtained at pH=7, peroxidisulfate concentration of 0.02 Mmol/L, and 50 mg/L dye concentration. Also, the ARS removal by UV/peroxidisulfate process follows a first-order kinetic. Conclusion: Due to the high removal efficiency of this process in removing ARS (96.5%, use of this process can be a good choice in the treatment of dye and industrial wastewater. 

  10. Proton transfer in phenothiazine photochemical oxidation: Laser flash photolysis and fluorescence studies

    International Nuclear Information System (INIS)

    Gao Yuhe; Chen Jiafu; Zhuang Xiujuan; Wang Jinting; Pan Yang; Zhang Limin; Yu Shuqin

    2007-01-01

    Phenothiazine (PTH) cation and neutral radical have been characterized by nanosecond laser flash photolysis in basic and acid acetonitrile. In the presence of water or small amounts of base, the radical cation (PTH +· ) was not detected and the neutral radical (PT · ) was the only observed radical in photoionization process. Triplet PTH ( 3 PTH*) was quenched by diethyl fumarate in acetonitrile at a rapid rate (k q T =6.1x10 9 M -1 s -1 ), and then, it was observed a specific absorption around 410 nm that is assigned to PT · formed via photoinduced electron/proton transfer. However, no PT · was detected on 3 PTH*quenching by cinnamonitrile (China). On the basis of the results, the fast proton transfer in the oxidation process is mainly dependent on the basic groups, such as the carbonyl group in electron acceptors. The quenching rate constants (k q T ) of 3 PTH* by various electron acceptors have been determined at 470 nm as well as fluorescence quenching rate constants k q S obtained by Stern-Volmer equation. All k q T and k q S values approach the diffusion limit. The driving force dependence of bimolecular quenching rate constants was evaluated in light of Rehm-Weller analysis. In addition, disharmonic k q values by CN in endergonic region might be the contribution of charge transfer

  11. Photochemical Oxidation of Thioketones by Singlet Molecular Oxygen Revisited: Insights into Photoproducts, Kinetics, and Reaction Mechanism.

    Science.gov (United States)

    Sánchez-Arroyo, Antonio J; Pardo, Zulay D; Moreno-Jiménez, Florencio; Herrera, Antonio; Martín, Nazario; García-Fresnadillo, David

    2015-11-06

    Photosensitized oxidation of trimethyl[2.2.1]bicycloheptane thioketones by (1)O2 can yield more photoproducts than exclusively ketones and sulfines. Moreover, the ketone/sulfine ratio can be reversed when protic conditions and high thioketone concentrations are used, conversely to earlier results reporting ketones as the main photoproducts. A new mechanistic proposal for sulfine formation is suggested following intermolecular oxygen transfer from a peroxythiocarbonyl intermediate to a second thioketone molecule. Reaction quantum yields (10(-5)-10(-2)) depend on the reaction conditions and time. Sulfine production reaches a maximum at short irradiation times, whereas decomposition to the corresponding ketone is observed at long reaction times. When the thioketone substrate has a hydrogen atom at the α position a peroxyvinylsulfenic acid intermediate can be formed by proton transfer. Reaction of this intermediate with another thioketone molecule can yield more sulfine and its tautomeric vinylsulfenic acid, which dimerizes in situ to the thiosulfinate. The hydroperoxyl group of the peroxyvinylsulfenic acid can also rearrange to the α position, and by reaction with the starting thioketone, α-hydroxy thioketone and additional sulfine can be formed, while dehydration yields the α-oxo thioketone. In situ [2 + 2] and [4 + 2] self-cycloaddition of the α-oxo thioketone yields significant amounts of the corresponding adducts at prolonged irradiation times.

  12. The Statistical Evolution of Multiple Generations of Oxidation Products in the Photochemical Aging of Chemically Reduced Organic Aerosol

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Kevin R.; Smith, Jared D.; Kessler, Sean; Kroll, Jesse H.

    2011-10-03

    The heterogeneous reaction of hydroxyl radicals (OH) with squalane and bis(2-ethylhexyl) sebacate (BES) particles are used as model systems to examine how distributions of reactionproducts evolve during the oxidation of chemically reduced organic aerosol. A kinetic model of multigenerational chemistry, which is compared to previously measured (squalane) and new(BES) experimental data, reveals that it is the statistical mixtures of different generations of oxidation products that control the average particle mass and elemental composition during thereaction. The model suggests that more highly oxidized reaction products, although initially formed with low probability, play a large role in the production of gas phase reaction products.In general, these results highlight the importance of considering atmospheric oxidation as a statistical process, further suggesting that the underlying distribution of molecules could playimportant roles in aerosol formation as well as in the evolution of key physicochemical properties such as volatility and hygroscopicity.

  13. Critical effect of hydrogen peroxide concentration in photochemical oxidative degradation of C.I. Acid Red 27 (AR27).

    Science.gov (United States)

    Daneshvar, N; Rabbani, M; Modirshahla, N; Behnajady, M A

    2004-09-01

    The photochemical decolorization of C.I. Acid Red 27 (AR27), an anionic monoazo dye, was studied in the UV/H2O2 process by using a batch reactor with a UV-C lamp emitting at 254 nm (30 W). The decolorization rate follows pseudo-first order kinetic with respect to the AR27 concentration. The results indicate that the apparent reaction rate constant in the UV/H2O2 process is a function of H2O2 concentration. In this work, a mathematical relation between the apparent reaction rate constant of the AR27 removal and used H2O2 was established. The applied amount of H2O2 was performed in two forms: (i) the light fraction absorbed by H2O2 in 254 nm, (ii) the initial concentration ratio of H2O2 to AR27. The results obtained from this mathematical model are in good agreement with experimental results.

  14. Oxide Nanocrystal Model Catalysts.

    Science.gov (United States)

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified

  15. Preparation of conducting polymer patterns using photochemical reaction of oxidation polymerization agents; Sanka jugozai no hikarikagaku henka wo riyoshita dodensei kobunshi patan no seisaku hoho

    Energy Technology Data Exchange (ETDEWEB)

    Onishi, Yasushi; Naruse, Tsutomu; Yoshimoto, Shoji; Kimura, Kazuyuki [Aichi Prefectura Goverment, Aichi (Japan). Institute of Industrial Research; Natsume, Yukihiro [Aica Kogyo Corp., Aichi (Japan)

    1999-09-10

    Preparation of conducting polymer patterns using the photochemical oxidizing ability changes of an oxidation polymerization agent has been investigated. Photoreactive metal salts such as iron (3) chloride were used for oxidation polymerization of conducting polymers such as polymers such as polypyrrole. Metal salts were reduced by exposing to ultra-violet (UV) light and missed the ability of oxidation polymerization. Therefore, conducting polypyrrole patterns have been prepared on the unirradiated part by exposing films containing iron (3) chloride to UV light through the pattern mask and then contacting with pyrrole vapor or dipping in pyrrole solution. By this method, large and fine conducting polymer patterns can easily be prepared on plastics, ceramics, papers, clothes, woods, etc. In addition, it may be able to prepare patterns with partially different conductivity by controlling the irradiation time of UV light and/or shades of the pattern masks. (author)

  16. Kinetic and mechanistic studies of reactive intermediates in photochemical and transition metal-assisted oxidation, decarboxylation and alkyl transfer reactions

    Science.gov (United States)

    Carraher, Jack McCaslin

    Reactive species like high-valent metal-oxo complexes and carbon and oxygen centered radicals are important intermediates in enzymatic systems, atmospheric chemistry, and industrial processes. Understanding the pathways by which these intermediates form, their relative reactivity, and their fate after reactions is of the utmost importance. Herein are described the mechanistic detail for the generation of several reactive intermediates, synthesis of precursors, characterization of precursors, and methods to direct the chemistry to more desirable outcomes yielding 'greener' sources of commodity chemicals and fuels. High-valent Chromium from Hydroperoxido-Chromium(III). The decomposition of pentaaquahydroperoxido chromium(III) ion (hereafter Cr aqOOH2+) in acidic aqueous solutions is kinetically complex and generates mixtures of products (Craq3+, HCrO 4-, H2O2, and O2). The yield of high-valent chromium products (known carcinogens) increased from a few percent at pH 1 to 70 % at pH 5.5 (near biological pH). Yields of H 2O2 increased with acid concentration. The reproducibility of the kinetic data was poor, but became simplified in the presence of H2O2 or 2,2‧-azinobis(3-ethylbenzothiazoline-6-sulfonate) dianion (ABTS2-). Both are capable of scavenging strongly oxidizing intermediates). The observed rate constants (pH 1, [O2] ≤ 0.03 mM) in the presence of these scavengers are independent of [scavenger] and within the error are the same (k,ABTS2- = (4.9 +/- 0.2) x 10-4 s-1 and kH2O2 = (5.3 +/- 0.7) x 10-4 s-1); indicating involvement of the scavengers in post-rate determining steps. In the presence of either scavenger, decomposition of CrOOH2+ obeyed a two-term rate law, k obs / s-1 = (6.7 +/- 0.7) x 10-4 + (7.6 +/- 1.1) x 10-4 [H+]. Effect of [H+] on the kinetics and the product distribution, cleaner kinetics in the presence of scavengers, and independence of kobs on [scavenger] suggest a dual-pathway mechanism for the decay of Craq OOH2+. The H+-catalyzed path

  17. Effects of photochemical oxidation on the mixing state and light absorption of black carbon in the urban atmosphere of China

    Science.gov (United States)

    Wang, Qiyuan; Huang, Rujin; Zhao, Zhuzi; Cao, Junji; Ni, Haiyan; Tie, Xuexi; Zhu, Chongshu; Shen, Zhenxing; Wang, Meng; Dai, Wenting; Han, Yongming; Zhang, Ningning; Prévôt, André S. H.

    2017-04-01

    The relationship between the refractory black carbon (rBC) aerosol mixing state and the atmospheric oxidation capacity was investigated to assess the possible influence of oxidants on the particles’ light absorption effects at two large cities in China. The number fraction of thickly-coated rBC particles (F rBC) was positively correlated with a measure of the oxidant concentrations (OX = O3 + NO2), indicating an enhancement of coated rBC particles under more oxidizing conditions. The slope of a linear regression of F rBC versus OX was 0.58% ppb-1 for Beijing and 0.84% ppb-1 for Xi’an, and these relationships provide some insights into the evolution of rBC mixing state in relation to atmospheric oxidation processes. The mass absorption cross-section of rBC (MACrBC) increased with OX during the daytime at Xi’an, at a rate of 0.26 m2 g-1 ppb-1, suggesting that more oxidizing conditions lead to internal mixing that enhances the light-absorbing capacity of rBC particles. Understanding the dependence of the increasing rates of F rBC and MACrBC as a function of OX may lead to improvements of climate models that deal with the warming effects, but more studies in different cities and seasons are needed to gauge the broader implications of these findings.

  18. Photochirogenesis: photochemical models on the absolute asymmetric formation of amino acids in interstellar space.

    Science.gov (United States)

    Meinert, Cornelia; de Marcellus, Pierre; d'Hendecourt, Louis Le Sergeant; Nahon, Laurent; Jones, Nykola C; Hoffmann, Søren V; Bredehöft, Jan Hendrik; Meierhenrich, Uwe J

    2011-10-01

    Proteins of all living organisms including plants, animals, and humans are made up of amino acid monomers that show identical stereochemical L-configuration. Hypotheses for the origin of this symmetry breaking in biomolecules include the absolute asymmetric photochemistry model by which interstellar ultraviolet (UV) circularly polarized light (CPL) induces an enantiomeric excess in chiral organic molecules in the interstellar/circumstellar media. This scenario is supported by a) the detection of amino acids in the organic residues of UV-photo-processed interstellar ice analogues, b) the occurrence of L-enantiomer-enriched amino acids in carbonaceous meteorites, and c) the observation of CPL of the same helicity over large distance scales in the massive star-forming region of Orion. These topics are of high importance in topical biophysical research and will be discussed in this review. Further evidence that amino acids and other molecules of prebiotic interest are asymmetrically formed in space comes from studies on the enantioselective photolysis of amino acids by UV-CPL. Also, experiments have been performed on the absolute asymmetric photochemical synthesis of enantiomer-enriched amino acids from mixtures of astrophysically relevant achiral precursor molecules using UV-circularly polarized photons. Both approaches are based on circular dichroic transitions of amino acids that will be highlighted here as well. These results have strong implications on our current understanding of how life's precursor molecules were possibly built and how life selected the left-handed form of proteinogenic amino acids. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. Photochemical modeling in California with two chemical mechanisms: model intercomparison and response to emission reductions.

    Science.gov (United States)

    Cai, Chenxia; Kelly, James T; Avise, Jeremy C; Kaduwela, Ajith P; Stockwell, William R

    2011-05-01

    An updated version of the Statewide Air Pollution Research Center (SAPRC) chemical mechanism (SAPRC07C) was implemented into the Community Multiscale Air Quality (CMAQ) version 4.6. CMAQ simulations using SAPRC07C and the previously released version, SAPRC99, were performed and compared for an episode during July-August, 2000. Ozone (O3) predictions of the SAPRC07C simulation are generally lower than those of the SAPRC99 simulation in the key areas of central and southern California, especially in areas where modeled concentrations are greater than the federal 8-hr O3 standard of 75 parts per billion (ppb) and/or when the volatile organic compound (VOC)/nitrogen oxides (NOx) ratio is less than 13. The relative changes of ozone production efficiency (OPE) against the VOC/NOx ratio at 46 sites indicate that the OPE is reduced in SAPRC07C compared with SAPRC99 at most sites by as much as approximately 22%. The SAPRC99 and SAPRC07C mechanisms respond similarly to 20% reductions in anthropogenic VOC emissions. The response of the mechanisms to 20% NOx emissions reductions can be grouped into three cases. In case 1, in which both mechanisms show a decrease in daily maximum 8-hr O3 concentration with decreasing NOx emissions, the O3 decrease in SAPRC07C is smaller. In case 2, in which both mechanisms show an increase in O3 with decreasing NOx emissions, the O3 increase is larger in SAPRC07C. In case 3, SAPRC07C simulates an increase in O3 in response to reduced NOx emissions whereas SAPRC99 simulates a decrease in O3 for the same region. As a result, the areas where NOx controls would be disbeneficial are spatially expanded in SAPRC07C. Although the results presented here are valuable for understanding differences in predictions and model response for SAPRC99 and SAPRC07C, the study did not evaluate the impact of mechanism differences in the context of the U.S. Environmental Protection Agency's guidance for using numerical models in demonstrating air quality attainment

  20. Modeling electrodialysis and a photochemical process for their integration in saline wastewater treatment

    Directory of Open Access Journals (Sweden)

    F. J. Borges

    2010-09-01

    Full Text Available Oxidation processes can be used to treat industrial wastewater containing non-biodegradable organic compounds. However, the presence of dissolved salts may inhibit or retard the treatment process. In this study, wastewater desalination by electrodialysis (ED associated with an advanced oxidation process (photo-Fenton was applied to an aqueous NaCl solution containing phenol. The influence of process variables on the demineralization factor was investigated for ED in pilot scale and a correlation was obtained between the phenol, salt and water fluxes with the driving force. The oxidation process was investigated in a laboratory batch reactor and a model based on artificial neural networks was developed by fitting the experimental data describing the reaction rate as a function of the input variables. With the experimental parameters of both processes, a dynamic model was developed for ED and a continuous model, using a plug flow reactor approach, for the oxidation process. Finally, the hybrid model simulation could validate different scenarios of the integrated system and can be used for process optimization.

  1. Ligand-Assisted Co-Assembly Approach toward Mesoporous Hybrid Catalysts of Transition-Metal Oxides and Noble Metals: Photochemical Water Splitting.

    Science.gov (United States)

    Liu, Ben; Kuo, Chung-Hao; Chen, Jiejie; Luo, Zhu; Thanneeru, Srinivas; Li, Weikun; Song, Wenqiao; Biswas, Sourav; Suib, Steven L; He, Jie

    2015-07-27

    A bottom-up synthetic approach was developed for the preparation of mesoporous transition-metal-oxide/noble-metal hybrid catalysts through ligand-assisted co-assembly of amphiphilic block-copolymer micelles and polymer-tethered noble-metal nanoparticles (NPs). The synthetic approach offers a general and straightforward method to precisely tune the sizes and loadings of noble-metal NPs in metal oxides. This system thus provides a solid platform to clearly understand the role of noble-metal NPs in photochemical water splitting. The presence of trace amounts of metal NPs (≈0.1 wt %) can enhance the photocatalytic activity for water splitting up to a factor of four. The findings can conceivably be applied to other semiconductors/noble-metal catalysts, which may stand out as a new methodology to build highly efficient solar energy conversion systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Splitting and non splitting are pollution models photochemical reactions in the urban areas of greater Tehran area

    International Nuclear Information System (INIS)

    Heidarinasab, A.; Dabir, B.; Sahimi, M.; Badii, Kh.

    2003-01-01

    During the past years, one of the most important problems has been air pollution in urban areas. In this regards, ozone, as one of the major products of photochemical reactions, has great importance. The term 'photochemical' is applied to a number of secondary pollutants that appear as a result of sun-related reactions, ozone being the most important one. So far various models have been suggested to predict these pollutants. In this paper, we developed the model that has been introduced by Dabir, et al. [4]. In this model more than 48 chemical species and 114 chemical reactions are involved. The result of this development, showed good to excellent agreement across the region for compounds such as O 3 , NO, NO 2 , CO, and SO 2 with regard to VOC and NMHC. The results of the simulation were compared with previous work [4] and the effects of increasing the number of components and reactions were evaluated. The results of the operator splitting method were compared with non splitting solving method. The result showed that splitting method with one-tenth time step collapsed with non splitting method (Crank-Nicolson, under-relaxation iteration method without splitting of the equation terms). Then we developed one dimensional model to 3-D and were compared with experimental data

  3. Modeling the photochemical transformation of nitrobenzene under conditions relevant to sunlit surface waters: Reaction pathways and formation of intermediates.

    Science.gov (United States)

    Vione, Davide; De Laurentiis, Elisa; Berto, Silvia; Minero, Claudio; Hatipoglu, Arzu; Cinar, Zekiye

    2016-02-01

    Nitrobenzene (NB) would undergo photodegradation in sunlit surface waters, mainly by direct photolysis and triplet-sensitized oxidation, with a secondary role of the *OH reaction. Its photochemical half-life time would range from a few days to a couple of months under fair-weather summertime irradiation, depending on water chemistry and depth. NB phototransformation gives phenol and the three nitrophenol isomers, in different yields depending on the considered pathway. The minor *OH role in degradation would make NB unsuitable as *OH probe in irradiated natural water samples, but the selectivity towards *OH could be increased by monitoring the formation of phenol from NB+*OH. The relevant reaction would proceed through ipso-addition of *OH on the carbon atom bearing the nitro-group, forming a pre-reactive complex that would evolve into a transition state (and then into a radical addition intermediate) with very low activation energy barrier. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Reversible transformation between α-oxo acids and α-amino acids on ZnS particles: a photochemical model for tuning the prebiotic redox homoeostasis

    Science.gov (United States)

    Wang, Wei; Liu, Xiaoyang; Yang, Yanqiang; Su, Wenhui

    2013-01-01

    How prebiotic metabolic pathways could have formed is an essential question for the origins of life on early Earth. From the abiogenetic point of view, the emergence of primordial metabolism may be postulated as a continuum from Earth's geochemical processes to chemoautotrophic biochemical procedures on mineral surfaces. In the present study, we examined in detail the reversible amination of α-ketoglutarate on UV-irradiated ZnS particles under variable reaction conditions such as pH, temperature, hole scavenger species and concentrations, and different amino acids. It was observed that the reductive amination of α-ketoglutarate and the oxidative amination of glutamate were both effectively performed on ZnS surfaces in the presence and absence of a hole scavenger, respectively. Accordingly, a photocatalytic mechanism was proposed. The reversible photochemical reaction was more efficient under basic conditions but independent of temperature in the range of 30-60 °C. SO3 2- was more effective than S2- as the hole scavenger. Finally, we extended the glutamate dehydrogenase-like chemistry to a set of other α-amino acids and their corresponding α-oxo acids and found that hydrophobic amino acid side chains were more conducive to the reversible redox reactions. Since the experimental conditions are believed to have been prevalent in shallow water hydrothermal vent systems of early Earth, the results of this work not only suggest that the ZnS-assisted photochemical reaction can regulate the redox equilibrium between α-amino acids and α-oxo acids, but also provide a model of how prebiotic metabolic homoeostasis could have been developed and regulated. These findings can advance our understanding of the establishment of archaic non-enzymatic metabolic systems and the origins of autotrophy.

  5. Photochemical oxidant injury and bark beetle coleoptera scolytidae infestation of ponderosa pine. IV. Theory on the relationships between oxidant injury and bark beetle infestation

    Energy Technology Data Exchange (ETDEWEB)

    Cobb, F.W. Jr.; Wood, D.L.; Stark, R.W.; Parmeter, J.R. Jr.

    1968-05-01

    The authors suggest that a reduction of oleoresin exudation pressure, quantity, rate of flow, and an increase in the propensity of oleoresin to crystallize, and a reduction in phloem and sapwood moisture content enhance successful establishment of the western pine beetle and mountain pine beetle in ponderosa pine injured by photochemical atmospheric pollution. Hypotheses are presented which relate these results to host susceptibility.

  6. Summary of photochemical and radiative data used in the LLNL one-dimensional transport-kinetics model of the troposphere and stratosphere: 1982

    International Nuclear Information System (INIS)

    Connell, P.S.; Wuebbles, D.J.

    1983-01-01

    This report summarizes the contents and sources of the photochemical and radiative segment of the LLNL one-dimensional transport-kinetics model of the troposphere and stratosphere. Data include the solar flux incident at the top of the atmosphere, absorption spectra for O 2 , O 3 and NO 2 , and effective absorption coefficients for about 40 photolytic processes as functions of wavelength and, in a few cases, temperature and pressure. The current data set represents understanding of atmospheric photochemical processes as of late 1982 and relies largely on NASA Evaluation Number 5 of Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, JPL Publication 82-57 (DeMore et al., 1982). Implementation in the model, including the treatment of multiple scattering and cloud cover, is discussed in Wuebbles (1981)

  7. Modelling photochemical pollutants in a deep urban street canyon: Application of a coupled two-box model approximation

    Science.gov (United States)

    Zhong, Jian; Cai, Xiao-Ming; Bloss, William James

    2016-10-01

    Air pollution associated with road transport is a major environmental issue in urban areas. Buildings in urban areas are the artificial obstacles to atmospheric flow and cause reduced ventilation for street canyons. For a deep street canyon, there is evidence of the formation of multiple segregated vortices, which generate flow regimes such that pollutants exhibit a significant contrast between these vortices. This results in poor air ventilation conditions at pedestrian level, thereby leading to elevated pollutant levels and potential breaches of air quality limits. The hypothesis of a well-mixed deep street canyon in the practical one-box model approach is shown to be inappropriate. This study implements a simplified simulation of the canyon volume: a coupled two-box model with a reduced chemical scheme to represent the key photochemical processes with timescales similar to and smaller than the turbulent mixing timescale. The two-box model captures the significant pollutant contrast between the lower and upper parts of a deep street canyon, particularly for NO2. Core important parameters (i.e. heterogeneity coefficient, exchange velocity and box height ratio) in the two-box model approach were investigated through sensitivity tests. The two-box model results identify the emission regimes and the meteorological conditions under which NO2 in the lower canyon (i.e. the region of interest for the assessment of human health effects) is in breach of air quality standards. Higher NO2 levels were observed for the cases with higher heterogeneity coefficients (the two boxes are more segregated), with lower exchange velocities (worse ventilation conditions), or with smaller box height ratios (reduced dilution possibly due to secondary smaller eddies in the lower canyon). The performance of a one-box model using the same chemical scheme is also evaluated against the two-box model. The one-box model was found to systematically underestimate NO2 levels compared with those in

  8. Evaluation of Kinetic and Mechanistic Data for Modeling of Photochemical Smog

    International Nuclear Information System (INIS)

    Atkinson, R.; Lloyd, A.C.

    1984-01-01

    This review is a critical evaluation of the rate constants, mechanisms, and products of selected atmospheric reactions of hydrocarbons, nitrogen oxides, and sulfur oxides in air. The evaluation considers eight hydrocarbons (n-butane, 2,3-dimethylbutane, ethene, propene, 1-butene, trans-2-butene, toluene, and m-xylene) for which smog chamber irradiations have been carried out under carefully controlled conditions and which have been the subject of computer modeling studies by more than one research group. The reactions involved are treated in the following categories: inorganic reactions in organic-NO/sub x/-air irradiations; organic reactions of the formaldehyde-NO/sub x/-air system; organic reactions of the acetaldehyde-NO/sub x/-air system; organic reactions of the alkene-NO/sub x/-air systems; organic reactions of the alkane-NO/sub x/-air systems; organic reactions of selected carbonyl-NO/sub x/-air systems; organic reactions of the aromatic-NO/sub x/-air systems; combination reactions of peroxy radicals, and homogeneous gas phase SO 2 reactions. This report considers literature through early 1983

  9. Chemical and cellular oxidant production induced by naphthalene secondary organic aerosol (SOA): effect of redox-active metals and photochemical aging.

    Science.gov (United States)

    Tuet, Wing Y; Chen, Yunle; Fok, Shierly; Gao, Dong; Weber, Rodney J; Champion, Julie A; Ng, Nga L

    2017-11-09

    Exposure to air pollution is a leading global health risk. Secondary organic aerosol (SOA) constitute a large portion of ambient particulate matter (PM). In this study, the water-soluble oxidative potential (OP) determined by dithiothreitol (DTT) consumption and intracellular reactive oxygen and nitrogen species (ROS/RNS) production was measured for SOA generated from the photooxidation of naphthalene in the presence of iron sulfate and ammonium sulfate seed particles. The measured intrinsic OP varied for aerosol formed using different initial naphthalene concentrations, however, no trends were observed between OP and bulk aerosol composition or seed type. For all experiments, aerosol generated in the presence of iron-containing seed induced higher ROS/RNS production compared to that formed in the presence of inorganic seed. This effect was primarily attributed to differences in aerosol carbon oxidation state [Formula: see text]. In the presence of iron, radical concentrations are elevated via iron redox cycling, resulting in more oxidized species. An exponential trend was also observed between ROS/RNS and [Formula: see text] for all naphthalene SOA, regardless of seed type or aerosol formation condition. This may have important implications as aerosol have an atmospheric lifetime of a week, over which [Formula: see text] increases due to continued photochemical aging, potentially resulting in more toxic aerosol.

  10. Evaluation of emission control strategies to reduce ozone pollution in the Paso del Norte region using a photochemical air quality modeling system

    Science.gov (United States)

    Valenzuela, Victor Hugo

    Air pollution emissions control strategies to reduce ozone precursor pollutants are analyzed by applying a photochemical modeling system. Simulations of air quality conditions during an ozone episode which occurred in June, 2006 are undertaken by increasing or reducing area source emissions in Ciudad Juarez, Chihuahua, Mexico. Two air pollutants are primary drivers in the formation of tropospheric ozone. Oxides of nitrogen (NOx) and volatile organic compounds (VOC) undergo multiple chemical reactions under favorable meteorological conditions to form ozone, which is a secondary pollutant that irritates respiratory systems in sensitive individuals especially the elderly and young children. The U.S. Environmental Protection Agency established National Ambient Air Quality Standards (NAAQS) to limit ambient air pollutants such as ozone by establishing an 8-hour average concentration of 0.075 ppm as the threshold at which a violation of the standard occurs. Ozone forms primarily due reactions in the troposphere of NOx and VOC emissions generated primarily by anthropogenic sources in urban regions. Data from emissions inventories indicate area sources account for ˜15 of NOx and ˜45% of regional VOC emissions. Area sources include gasoline stations, automotive paint bodyshops and nonroad mobile sources. Multiplicity of air pollution emissions sources provides an opportunity to investigate and potentially implement air quality improvement strategies to reduce emissions which contribute to elevated ozone concentrations. A baseline modeling scenario was established using the CAMx photochemical air quality model from which a series of sensitivity analyses for evaluating air quality control strategies were conducted. Modifications to area source emissions were made by varying NOx and / or VOC emissions in the areas of particular interest. Model performance was assessed for each sensitivity analysis. Normalized bias (NB) and normalized error (NE) were used to identify

  11. Catalysis of Photochemical Reactions.

    Science.gov (United States)

    Albini, A.

    1986-01-01

    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  12. Mapping the Binding Interface of VEGF and a Monoclonal Antibody Fab-1 Fragment with Fast Photochemical Oxidation of Proteins (FPOP) and Mass Spectrometry

    Science.gov (United States)

    Zhang, Ying; Wecksler, Aaron T.; Molina, Patricia; Deperalta, Galahad; Gross, Michael L.

    2017-05-01

    We previously analyzed the Fab-1:VEGF (vascular endothelial growth factor) system described in this work, with both native top-down mass spectrometry and bottom-up mass spectrometry (carboxyl-group or GEE footprinting) techniques. This work continues bottom-up mass spectrometry analysis using a fast photochemical oxidation of proteins (FPOP) platform to map the solution binding interface of VEGF and a fragment antigen binding region of an antibody (Fab-1). In this study, we use FPOP to compare the changes in solvent accessibility by quantitating the extent of oxidative modification in the unbound versus bound states. Determining the changes in solvent accessibility enables the inference of the protein binding sites (epitope and paratopes) and a comparison to the previously published Fab-1:VEGF crystal structure, adding to the top-down and bottom-up data. Using this method, we investigated peptide-level and residue-level changes in solvent accessibility between the unbound proteins and bound complex. Mapping these data onto the Fab-1:VEGF crystal structure enabled successful characterization of both the binding region and regions of remote conformation changes. These data, coupled with our previous higher order structure (HOS) studies, demonstrate the value of a comprehensive toolbox of methods for identifying the putative epitopes and paratopes for biotherapeutic antibodies.

  13. Photochemical model estimated fire impacts on ozone and aerosol evaluated with field studies and routine data sources

    Science.gov (United States)

    Baker, K. R.

    2017-12-01

    Highly instrumented field studies provide a unique opportunity to evaluate multiple aspects of photochemical grid model representation of fire emissions, dispersion, and chemical evolution. Fuel information and burn area for a specific fire coupled with near-fire and downwind chemical measurements provides information needed to constrain model predicted fire plume transport and chemical evolution of important pollutants such as ozone and particulate matter (PM2.5) that have deleterious health effects. Most local to regional scale field campaigns to date have made relatively few transects through plumes from fires with well characterized fuel type and consumption. While more comprehensive field studies are being planned for 2018 and beyond (WE-CAN, FIREX, FIRE-CHEM, and FASMEE), existing measurement data from multiple field campaigns including 2013 SEAC4RS, satellite data, and routine surface networks are used to assess how a regulatory modeling system captures fire impacts on local to regional scale ozone and PM2.5. Key aspects of the regulatory modeling system include fire location and burn area from SMARTFIRE2, emissions from BlueSky framework, and predictions of ambient O3 and PM2.5 from the Community Multiscale Air Quality (CMAQ) photochemical transport model. A comparison of model estimated O3 from specific fires with routine surface measurements at rural locations in proximity to the 2013 Rim fire, 2011 Wallow fire, and 2011 Flint Hills fires suggest the modeling system over-estimates smoke impacts on hourly ozone. Sensitivity simulations where solar radiation and photolysis rates are more aggressively attenuated by smoke reduced O3 predictions but did not ameliorate the over prediction bias. PM2.5 organic carbon tends to be overpredicted at rural surface sites downwind from the 2011 Flint Hills prescribed fires while results were mixed at rural sites downwind of the 2013 Rim fire and 2011 Wallow fire suggesting differences in fuel characterization (e

  14. Photochemical methodologies for organic waste treatment: advanced oxidation process using uranyl ion with H2O2

    International Nuclear Information System (INIS)

    Naik, D.B.; Sarkar, S.K.; Mukherjee, T.

    2009-01-01

    Excited uranyl ion is able to degrade dyes such as thionine and methylene blue on irradiation with 254 nm/300 nm light. By adding H 2 O 2 along with uranyl ion, photodegradation takes place with visible light and also with enhanced rate. The hydroxyl radicals generated in the reoxidation of U(IV)/UO 2 + to UO 2 2+ are responsible for this enhanced degradation. The above advanced oxidation process (AOP) was applied to study the oxidation of 2-propanol to acetone. (author)

  15. Naval Research Laboratory Ecological -- Photochemical -- Bio-optical--Numerical Experiment (Neptune) Version 1: A Portable, Flexible Modeling Environment Designed to Resolve Time-dependent Feedbacks Between Upper Ocean Ecology, Photochemistry, and Optics

    National Research Council Canada - National Science Library

    Jolliff, Jason K; Kindle, John C

    2007-01-01

    A modeling system has been constructed that combines ecological element cycling, photochemical processes, and bio-optical processes into a single simulation that may be coupled to hydrodynamic models...

  16. Fast Photochemical Oxidation of Proteins Coupled to Multidimensional Protein Identification Technology (MudPIT): Expanding Footprinting Strategies to Complex Systems

    Science.gov (United States)

    Rinas, Aimee; Jones, Lisa M.

    2015-04-01

    Peptides containing the oxidation products of hydroxyl radical-mediated protein footprinting experiments are typically much less abundant than their unoxidized counterparts. This is inherent to the design of the experiment as excessive oxidation may lead to undesired conformational changes or unfolding of the protein, skewing the results. Thus, as the complexity of the systems studied using this method expands, the detection and identification of these oxidized species can be increasingly difficult with the limitations of data-dependent acquisition (DDA) and one-dimensional chromatography. Here we report the application of multidimensional protein identification technology (MudPIT) in combination with hydroxyl radical footprinting as a method to increase the identification of quantifiable peptides in these experiments. Using this method led to a 37% increase in unique peptide identifications as well as a 70% increase in protein group identifications over one-dimensional data-dependent acquisition on the same samples. Furthermore, we demonstrate the combination of these methods as a means to investigate megadalton complexes.

  17. Photochemical grid model estimates of lateral boundary contributions to ozone and particulate matter across the continental United States

    Science.gov (United States)

    Baker, Kirk R.; Emery, Chris; Dolwick, Pat; Yarwood, Greg

    2015-12-01

    Multiple approaches to characterize lateral boundary contributions to photochemical model predicted ozone (O3) and particulate matter less than 2.5 microns in diameter (PM2.5) are available in the Comprehensive Air quality Model with extensions (CAMx). Here, three approaches are used for O3: (1) a comprehensive source apportionment scheme for chemical boundary conditions and emissions (OSAT), (2) chemically reactive tracers (RTRAC), and (3) chemically inert tracers. Two approaches are used for PM2.5: (1) particulate source apportionment (PSAT) and (2) chemically inert tracers. The inert tracer approach resulted in higher O3 lateral boundary contribution estimates because the method does not account for any O3 destruction reactions. OSAT and RTRAC estimate generally similar monthly average contributions during the warmer months although RTRAC estimates higher urban area contribution during the cold months because this RTRAC implementation did not treat O3 titration by NO. Accurate representation of lateral boundary O3 impacts must include appropriate accounting for O3 destruction reactions. OSAT and RTRAC were configured to estimate the contribution to modeled O3 from each of the four lateral faces of the model domain. RTRAC was configured to further stratify the western and northern boundaries by groups of vertical layers. The RTRAC approach showed that the largest O3 contributions to the continental U.S. are from the mid-troposphere, with less contribution from the upper troposphere/lower stratosphere. Inert tracers compared more closely to reactive tracers on average for PM2.5 compared to O3. This close agreement for PM2.5 indicates most of the lateral boundary contribution is from PM2.5 rather than precursor inflow. A strong relationship exists between model predicted PM2.5 boundary contribution and model overestimates of nitrate and organic carbon at IMPROVE monitor locations suggesting global model estimates of these species were overestimated at some places

  18. An Integrative Study of Photochemical Air Pollution in Hong Kong: an Overview

    Science.gov (United States)

    Wang, T.

    2014-12-01

    Hong Kong is situated in the Pearl River delta of Southern China. This region has experienced phenomenal economic growth in the past 30 years. Emissions of large amount of pollutants from urban areas and various industries coupled with subtropical climate have led to frequent occurrences of severe photochemical air pollution. Despite the long-term control efforts of the Hong Kong government, the atmospheric levels of ozone have been increasing in the past decade. To obtain an updated and more complete understanding of photochemical smog, an integrative study has been conducted during 2010-2014. Several intensive measurement campaigns were carried out at urban, suburban and rural sites in addition to the routine observations at fourteen air quality monitoring stations in Hong Kong. Meteorological, photochemical, and chemical-transport modeling studies were conducted to investigate the causes/processes of elevated photochemical pollution . The main activities of this study were to (1) examine the situation and trends of photochemical air pollution in Hong Kong, (2) understand some underlying chemical processes in particular the poorly-understood heterogeneous processes of reactive nitrogen oxides, (3) quantify the local, regional, and super-regional contributions to the ozone pollution in Hong Kong, and (4) review the control policy and make further recommendations based on the science. This paper will give an overview of this study and present some key results on the trends and chemistry of the photochemical pollution in this polluted subtropical region.

  19. Engineering photochemical smog through convection towers

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, S.; Prueitt, M.L.; Bossert, J.E.; Mroz, E.J.; Krakowski, R.A.; Miller, R.L. [Los Alamos National Lab., NM (United States); Jacobson, M.Z.; Turco, R.P. [Los Alamos National Lab., NM (United States)]|[Univ. of California, Los Angeles, CA (United States). Atmospheric Sciences Dept.

    1995-02-01

    Reverse convection towers have attracted attention as a medium for cleansing modern cities. Evaporation of an aqueous mist injected at the tower opening could generate electrical power by creating descent, and simultaneously scavenge unsightly and unhealthful particulates. The study offered here assesses the influence to tower water droplets on the photochemical component of Los Angeles type smog. The primary radical chain initiator OH is likely removed into aqueous phases well within the residence time of air in the tower, and then reacts away rapidly. Organics do not dissolve, but nighttime hydrolysis of N{sub 2}O{sub 5} depletes the nitrogen oxides. A lack of HOx would slow hydrocarbon oxidation and so also ozone production. Lowering of NOx would also alter ozone production rates, but the direction is uncertain. SO{sub 2} is available in sufficient quantities in some urban areas to react with stable oxidants, and if seawater were the source of the mist, the high pH would lead to fast sulfur oxidation kinetics. With an accommodation coefficient of 10{sup {minus}3}, however, ozone may not enter the aqueous phase efficiently. Even if ozone is destroyed or its production suppressed, photochemical recovery times are on the order of hours, so that tower processing must be centered on a narrow midday time window. The cost of building the number of structures necessary for this brief turnover could be prohibitive. The increase in humidity accompanying mist evaporation could be controlled with condensers, but might otherwise counteract visibility enhancements by recreating aqueous aerosols. Quantification of the divergent forcings convection towers must exert upon the cityscape would call for coupled three dimensional modeling of transport, microphysics, and photochemistry. 112 refs.

  20. Application of Wavelet Filters in an Evaluation of Photochemical Model Performance

    Science.gov (United States)

    Air quality model evaluation can be enhanced with time-scale specific comparisons of outputs and observations. For example, high-frequency (hours to one day) time scale information in observed ozone is not well captured by deterministic models and its incorporation into model pe...

  1. Large-scale and green synthesis of octahedral flower-like cupric oxide nanocrystals with enhanced photochemical properties

    Science.gov (United States)

    Li, Shi-Kuo; Pan, Yu-Yi; Wu, Mi; Huang, Fang-Zhi; Li, Chuan-Hao; Shen, Yu-Hua

    2014-10-01

    In this work, a large-scale and green method is reported for the facile synthesis of octahedral flower-like CuO nanocrystals via a coordination-deposition route by using Fehling regents. Not any harmful organic chemicals were used during the reaction period. The obtained hierarchical nanostructure can be rationally tailored by varying the concentration of tartrate ions and reaction time. The typical flower-like CuO nanocrystals in the range of 200-250 nm are consisted of numerous small crystalline whiskers, which present a porous surface with a specific surface area of 32.12 m2/g and a narrow band gap of 1.5 eV. Importantly, the flower-like CuO nanocrystals show an enhanced photocatalytic activity toward decomposing Rhodamine B (RhB) molecules. The degradation rate is about 87.9% in 40 min under visible light irradiation, which is about 2.5 times for the commercial CuO powers (35.2%). Moreover, the uniform flower-like monolayered CuO film exhibits an excellent photoelectrochemical (PEC) performance with a maximum photocurrent density of 58.8 μA/cm2, which is nearly five times higher than the commercial CuO film. This novel synthesis approach provides a large-scale and green protocol for synthesizing hierarchical metal oxide nanocrystals that are useful for photocatalysis, PEC water splitting and photovoltaic device.

  2. Evaluating the regional-scale photochemical modeling systems and using them for regulatory policy-making

    Science.gov (United States)

    Hogrefe, Christian

    2000-10-01

    In this study, the concept of scale analysis is introduced to evaluate the performance of regional-scale air quality models. To this end, seasonal time series of observations and predictions from the RAMS/UAM-V modeling system for ozone and meteorological variables are spectrally decomposed into fluctuations on the intra-day, diurnal, synoptic and longer-term time scales. The results indicate that the modeling system underestimates the total variance of the ozone time series (energy) when compared with observations at most locations, but shows a higher mean value than the observations. Furthermore, for all components, the model predicts that the average spatial correlation for ozone extends over longer distances than that for the observations. It is shown that correlations between the model predictions and observations for ozone are insignificant for the intra-day component, high for the diurnal component because of the inherent diurnal cycle but low for the amplitude of the diurnal component, and highest for the synoptic and baseline components. Furthermore, analyses of ozone observations and model predictions reveal that only those components that contain fluctuations with periods equal to or greater than one day carry the information that distinguishes ozone episode days from non-episodic days. The magnitude of the intra-day fluctuations is nearly invariant in time. Which of the longer-term fluctuations is dominant in a particular episode varies from episode to episode. These results suggest that for regulatory purposes, modeling periods must be longer than one single episode and the modeling domain must cover the eastern United States to increase the confidence in model predictions. In addition, the effect of simulation length on the predicted ozone improvements stemming from emission reductions is examined. The results demonstrate that for regulatory purposes, model simulations need to cover for longer time periods than just the duration of a single ozone

  3. Estimation of emission adjustments from the application of four-dimensional data assimilation to photochemical air quality modeling

    International Nuclear Information System (INIS)

    Mendoza-Dominguez, A.; Russell, A.G.

    2001-01-01

    Four-dimensional data assimilation applied to photochemical air quality modeling is used to suggest adjustments to the emissions inventory of the Atlanta, Georgia metropolitan area. In this approach, a three-dimensional air quality model, coupled with direct sensitivity analysis, develops spatially and temporally varying concentration and sensitivity fields that account for chemical and physical processing, and receptor analysis is used to adjust source strengths. Proposed changes to domain-wide NO x , volatile organic compounds (VOCs) and CO emissions from anthropogenic sources and for VOC emissions from biogenic sources were estimated, as well as modifications to sources based on their spatial location (urban vs. rural areas). In general, domain-wide anthropogenic VOC emissions were increased approximately two times their base case level to best match observations, domain-wide anthropogenic NO x and biogenic VOC emissions (BEIS2 estimates) remained close to their base case value and domain-wide CO emissions were decreased. Adjustments for anthropogenic NO x emissions increased their level of uncertainty when adjustments were computed for mobile and area sources (or urban and rural sources) separately, due in part to the poor spatial resolution of the observation field of nitrogen-containing species. Estimated changes to CO emissions also suffer from poor spatial resolution of the measurements. Results suggest that rural anthropogenic VOC emissions appear to be severely underpredicted. The FDDA approach was also used to investigate the speciation profiles of VOC emissions, and results warrant revision of these profiles. In general, the results obtained here are consistent with what are viewed as the current deficiencies in emissions inventories as derived by other top-down techniques, such as tunnel studies and analysis of ambient measurements. (Author)

  4. Feedbacks between microphysics and photochemical aging in viscous aerosol

    Science.gov (United States)

    Dou, Jing; Corral Arroyo, Pablo; Alpert, Peter A.; Ammann, Markus; Peter, Thomas; Krieger, Ulrich K.

    2017-04-01

    Fe(III)-citrate complex photochemistry, which plays an important role in aerosol aging, especially in lower troposphere, has been widely recognized in both solution and solid states. It can get excited by light below about 500 nm, inducing the oxidation of carboxylate ligands and the production of peroxides (e.g., OH•, HO2•), which have a significant impact on the climate, air quality and health. Recently, there is literature reporting that aqueous aerosol particles may attain highly viscous, semi-solid or even glassy physical states under a wide range of atmospheric conditions. However, systematic studies on the effect of high viscosity on photochemical processes are scarce. In this research, mass and size changes of a single, aqueous Fe(III)-citrate/citric acid particle levitated in an electrodynamic balance (EDB) are tracked during photochemical processing. We observe an overall mass loss during photochemical processing due to evaporation of volatile (e.g., CO2) and semi-volatile (e.g., ketones) compounds. It is known that relative humidity and temperature strongly effects the viscosity of citric acid. Hence, under light intensities large enough not limiting photochemical processing (at a wavelength of either 375 nm or 473 nm), the quasi-steady state evaporation rate in our experiments depends on relative humidity and temperature. The same holds true for the characteristic time scale for reaching thermodynamic equilibrium after switching off the light source. We are focusing on the high viscosity case (i.e., reduced molecular mobility and low water content), which slows down the transport of products but can also affect chemical reaction rates (e.g., initial absorption process, charge and energy transfer). Data are compared to kinetic modeling and diffusivities for semi-volatile compounds are estimated aiming at a more detailed understanding of the feedbacks between microphysics and photochemical aging.

  5. Contribution of regional-scale fire events to ozone and PM2.5 air quality estimated by photochemical modeling approaches

    Science.gov (United States)

    Baker, K. R.; Woody, M. C.; Tonnesen, G. S.; Hutzell, W.; Pye, H. O. T.; Beaver, M. R.; Pouliot, G.; Pierce, T.

    2016-09-01

    Two specific fires from 2011 are tracked for local to regional scale contribution to ozone (O3) and fine particulate matter (PM2.5) using a freely available regulatory modeling system that includes the BlueSky wildland fire emissions tool, Spare Matrix Operator Kernel Emissions (SMOKE) model, Weather and Research Forecasting (WRF) meteorological model, and Community Multiscale Air Quality (CMAQ) photochemical grid model. The modeling system was applied to track the contribution from a wildfire (Wallow) and prescribed fire (Flint Hills) using both source sensitivity and source apportionment approaches. The model estimated fire contribution to primary and secondary pollutants are comparable using source sensitivity (brute-force zero out) and source apportionment (Integrated Source Apportionment Method) approaches. Model estimated O3 enhancement relative to CO is similar to values reported in literature indicating the modeling system captures the range of O3 inhibition possible near fires and O3 production both near the fire and downwind. O3 and peroxyacetyl nitrate (PAN) are formed in the fire plume and transported downwind along with highly reactive VOC species such as formaldehyde and acetaldehyde that are both emitted by the fire and rapidly produced in the fire plume by VOC oxidation reactions. PAN and aldehydes contribute to continued downwind O3 production. The transport and thermal decomposition of PAN to nitrogen oxides (NOX) enables O3 production in areas limited by NOX availability and the photolysis of aldehydes to produce free radicals (HOX) causes increased O3 production in NOX rich areas. The modeling system tends to overestimate hourly surface O3 at routine rural monitors in close proximity to the fires when the model predicts elevated fire impacts on O3 and Hazard Mapping System (HMS) data indicates possible fire impact. A sensitivity simulation in which solar radiation and photolysis rates were more aggressively attenuated by aerosol in the plume

  6. The application of photochemical modelling for the City of Johannesburg AQMP

    CSIR Research Space (South Africa)

    Naidoo, Mogesh

    2017-10-01

    Full Text Available to account for accurate transformation and interactions of the various pollutants within a single simulation (hence the term “one-atmosphere” as opposed to dispersion model simulations which are often separated by source categories). A similar study... input can be interpolated finer however this is not ideal). Figure 1 shows the model domains used for the CoJ AQMP. The 3 km resolution domain captures regional transport of pollutants to ensure inter-municipality impacts are represented; while a...

  7. In Situ Measurements of the NO2/NO Ratio for Testing Atmospheric Photochemical Models

    Science.gov (United States)

    Jaegle, L.; Webster, C. R.; May, R. D.; Fahey, D. W.; Woodbridge, E. L.; Keim, E. R.; Gao, R. S.; Proffitt, M. H.; Stimpfle, R. M.; Salawitch, R. J.

    1994-01-01

    Simultaneous in situ measurements of NO2, NO, O3, ClO, pressure and temperature have been made for the first time, presenting a unique opportunity to test our current understanding of the photochemistry of the lower stratosphere. Data were collected from several flights of the ER-2 aircraft at mid-latitudes in May 1993 during NASA's Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE). The daytime ratio of NO2/NO remains fairly constant at 19 km with a typical value of 0.68 and standard deviation of +/- 0.17. The ratio observations are compared with simple steady-state calculations based on laboratory-measured reaction rates and modeled NO2 photolysis rates. At each measurement point the daytime NO2/NO with its measurement uncertainty overlap the results of steady-state calculations and associated uncertainty. However, over all the ER-2 flights examined, the model systematically overestimates the ratio by 40% on average. Possible sources of error are examined in both model and measurements. It is shown that more accurate laboratory determinations of the NO + O3 reaction rate and of the NO2 cross-sections in the 200-220 K temperature range characteristic of the lower stratosphere would allow for a more robust test of our knowledge of NO(x) photochemistry by reducing significant sources of uncertainties in the interpretation of stratospheric measurements. The present measurements are compared with earlier observations of the ratio at higher altitudes.

  8. The solar flare of 18 August 1979: Incoherent scatter radar data and photochemical model comparisons

    International Nuclear Information System (INIS)

    Zinn, J.; Sutherland, C.D.; Fenimore, E.E.; Ganguly, S.

    1988-04-01

    Measurements of electron density at seven D-region altidues were made with the Arecibo radar during a Class-X solar flare on 18 August 1979. Measurements of solar x-ray fluxes during the same period were available from the GOES-2 satellite (0.5 to 4 /angstrom/ and 1 to 8 /angstrom/) and from ISEE-3 (in four bands between 26 and 400 keV). From the x-ray flux data we computed ionization rates in the D-region and the associated chemical changes, using a coupled atmospheric chemistry and diffusion model (with 836 chemical reactions and 19 vertical levels). The computed electron densities matched the data fairly well after we had adjusted the rate coefficients of two reactions. We discuss the hierarchies among the many flare-induced chemical reactions in two altitude ranges within the D-region and the effects of adjusting several other rate coefficients. 51 refs., 6 figs., 3 tabs

  9. Photochemically induced spinal ischaemia: a model of spinal cord trauma in the rat

    Science.gov (United States)

    Olby, Natasha J.; Blakemore, W. F.

    1995-05-01

    Focal thrombosis was induced in the dorsal funiculus of the rat spinal cord by exposing the cord to light following intravenous injection of the photoactive dye, rose bengal. The light source was a 599 standing wave dye laser, pumped by an Innova 70 - 4 argon ion laser (Coherent Ltd, Cambridge, UK) and the light was delivered to the operative site via an optical fiber. The histological characteristics of the development and resolution of the lesion have been studied. Forty rats were examined with light and electron microscopy at various time points between 30 minutes and one month after irradiation and the lesion length was measured. Platelet aggregation, increased extracellular space in the white matter and vacuolation of the neurones and glia of the grey matter were present 30 minutes after injury. Progressive necrosis of the white and grey matter developed over the subsequent 24 hours to produce a fusiform lesion that occupied the dorsal funiculus and dorsal horns of the spinal cord at its center and tapered cranially and caudally along the dorsal columns for a total distance of seven millimeters. By one month after injury the area of necrosis had become a cyst lined by astrocytes ventrolaterally and meningeal cells dorsally. Measurements of lesion length showed a variability of 26%. This model of spinal cord trauma produces a lesion that is sufficiently reproducible to be suitable for performing studies aimed at tissue preservation and repair.

  10. Photochemical effects of sunlight.

    Science.gov (United States)

    Daniels, F

    1972-07-01

    The importance of sunlight in bringing about not only photosynthesis in plants, but also other photochemical effects, is reviewed. More effort should be devoted to photochemical storage of the sun's energy without the living plant. There is no theoretical reason to believe that such reactions are impossible. Ground rules for searching for suitable solar photochemical reactions are given, and a few attempts are described, but nothing successful has yet been found. Future possibilities are suggested. Photogalvanic cells which convert sunlight into electricity deserve further research. Eugene Rabinowitch has been an active pioneer in these fields.

  11. Photochemical decomposition of catecholamines

    International Nuclear Information System (INIS)

    Mol, N.J. de; Henegouwen, G.M.J.B. van; Gerritsma, K.W.

    1979-01-01

    During photochemical decomposition (lambda=254 nm) adrenaline, isoprenaline and noradrenaline in aqueous solution were converted to the corresponding aminochrome for 65, 56 and 35% respectively. In determining this conversion, photochemical instability of the aminochromes was taken into account. Irradiations were performed in such dilute solutions that the neglect of the inner filter effect is permissible. Furthermore, quantum yields for the decomposition of the aminochromes in aqueous solution are given. (Author)

  12. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  13. Validation of the emission inventory in the Sao Paulo Metropolitan Area of Brazil, based on ambient concentrations ratios of CO, NMOG and NO x and on a photochemical model

    Science.gov (United States)

    Vivanco, Marta G.; Andrade, Maria de Fátima

    In recent years, photochemical air pollution has become a significant problem in the São Paulo Metropolitan Area (SPMA). For some air pollutants, especially ozone and particulate matter, concentrations in excess of national air quality standards have been registered. According to data published by the State Environmental Agency (CETESB), approximately 90% of ozone precursors are emitted into the atmosphere by the vehicle fleet [CETESB, 2000. Relatório de Qualidade do ar do Estado de Sao Paulo, 1999; CETESB, 2002. Relatório de Qualidade do ar do Estado de Sao Paulo, 2004]. The estimation of precursor emissions speciation is a rather complex task. Estimating spatial and temporal variation of vehicle emissions is the greatest source of uncertainty. As in other locales, data regarding motor vehicle emissions are scarce. Due to the considerable discrepancies in emission inventories reported in various regions of the world, we evaluated the official emission inventories of non-methane organic gas (NMOG) and nitrogen oxides (NO x) using an observation-based approach. Ratios of NO x/carbon monoxide (CO) and NMOG/CO were calculated from ambient measurements taken in the early morning (0700-0800) during July and August of 1999. This top-down approach assumes that early morning ambient concentrations of CO, NO x and NMOG are dominated by motor vehicle emissions, and that the photochemical process has not substantially affected the concentrations. Based on these ratios and on the assumption that official inventory of CO emissions is reasonably accurate, on-road motor vehicle emissions of NO x seem to be significantly overestimated and NMOG emissions slightly underestimated. An Eulerian photochemical model, using both the revised motor vehicle emission inventory and the original official emissions provided by CETESB, was applied to an episodic air pollution event in the SPMA (9-12 August 1999). Meteorology fields were obtained from the CALMET model. When the revised, rather

  14. Photochemical transformation of anionic 2-nitro-4-chlorophenol in surface waters: Laboratory and model assessment of the degradation kinetics, and comparison with field data

    Energy Technology Data Exchange (ETDEWEB)

    Sur, Babita [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Department of Chemical Engineering, Calcutta University, 92 Acharya P. C. Road, Kolkata 700009 (India); De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Vione, Davide [Dipartimento di Chimica, Universita di Torino, Via P. Giuria 5, 10125 Torino (Italy); Centro Interdipartimentale NatRisk, Universita di Torino, Via Leonardo da Vinci 44, 10095 Grugliasco (Italy)

    2012-06-01

    Anionic 2-nitro-4-chlorophenol (NCP) may occur in surface waters as a nitroderivative of 4-chlorophenol, which is a transformation intermediate of the herbicide dichlorprop. Here we show that NCP would undergo efficient photochemical transformation in environmental waters, mainly by direct photolysis and reaction with {center_dot}OH. NCP has a polychromatic photolysis quantum yield {Phi}{sub NCP} = (1.27 {+-} 0.22) {center_dot} 10{sup -5}, a rate constant with {center_dot}OH k{sub NCP,}{center_dot}{sub OH} = (1.09 {+-} 0.09) {center_dot} 10{sup 10} M{sup -1} s{sup -1}, a rate constant with {sup 1}O{sub 2}k{sub NCP,1O2} = (2.15 {+-} 0.38) {center_dot} 10{sup 7} M{sup -1} s{sup -1}, a rate constant with the triplet state of anthraquinone-2-sulphonate k{sub NCP,3AQ2S*} = (5.90 {+-} 0.43) {center_dot} 10{sup 8} M{sup -1} s{sup -1}, and is poorly reactive toward CO{sub 3}{sup -}{center_dot}. The k{sub NCP,3AQ2S*} value is representative of reaction with the triplet states of chromophoric dissolved organic matter. The inclusion of photochemical reactivity data into a model of surface-water photochemistry allowed the NCP transformation kinetics to be predicted as a function of water chemical composition and column depth. Very good agreement between model predictions and field data was obtained for the shallow lagoons of the Rhone delta (Southern France). Highlights: Black-Right-Pointing-Pointer Phototransformation kinetics of 2-nitro-4-chlorophenol, relevant to surface waters. Black-Right-Pointing-Pointer Determination of photochemical reactivity data in the laboratory. Black-Right-Pointing-Pointer Model approach to combine photochemical reactivity with environmental variables. Black-Right-Pointing-Pointer Good agreement with field data in lagoon water (Rhone delta, Southern France). Black-Right-Pointing-Pointer Direct photolysis and reaction with {center_dot}OH as main photoprocesses in the environment.

  15. Efficacy of photochemical internalisation using disulfonated chlorin and porphyrin photosensitisers: An in vitro study in 2D and 3D prostate cancer models.

    Science.gov (United States)

    Martinez de Pinillos Bayona, Alejandra; Woodhams, Josephine H; Pye, Hayley; Hamoudi, Rifat A; Moore, Caroline M; MacRobert, Alexander J

    2017-05-01

    This study shows the therapeutic outcome of Photochemical Internalisation (PCI) in prostate cancer in vitro surpasses that of Photodynamic Therapy (PDT) and could improve prostate PDT in the clinic, whilst avoiding chemotherapeutics side effects. In addition, the study assesses the potential of PCI with two different photosensitisers (TPCS 2a and TPPS 2a ) in prostate cancer cells (human PC3 and rat MatLyLu) using standard 2D monolayer culture and 3D biomimetic model. Photosensitisers were used alone for photodynamic therapy (PDT) or with the cytotoxin saporin (PCI). TPPS 2a and TPCS 2a were shown to be located in discrete cytoplasmic vesicles before light treatment and redistribute into the cytosol upon light excitation. PC3 cells exhibit a higher uptake than MatLyLu cells for both photosensitisers. In the 2D model, PCI resulted in greater cell death than PDT alone in both cell lines. In 3D model, morphological changes were also observed. Saporin-based toxicity was negligible in PC3 cells, but pronounced in MatLyLu cells (IC50 = 18 nM). In conclusion, the study showed that tumour features such as tumour cell growth rate or interaction with drugs determine therapeutic conditions for optimal photochemical treatment in metastatic prostate cancer. Crown Copyright © 2017. Published by Elsevier B.V. All rights reserved.

  16. Evidence for photochemical formation of H[sub 2]O[sub 2] and oxidation of SO[sub 2] in authentic fog water

    Energy Technology Data Exchange (ETDEWEB)

    Yuegang Zuo, Hoigne, J. (Swiss Federal Inst. of Technology, Duebendorf (Switzerland))

    1993-04-02

    When samples of rain and fog water were exposed to ultraviolet and visible light, reactive transients such as hydrogen peroxide were formed and dissolved organic matter and sulfur dioxide were depleated. These results, in conjunction with those from previous studies, imply that dissolved organic compounds and transition metals such as iron ions are involved in the photochemical formation of hydrogen peroxide and other photooxidants in atmospheric waters.

  17. Impact of interannual variability (1979-1986) of transport and temperature on ozone as computed using a two-dimensional photochemical model

    Science.gov (United States)

    Jackman, Charles H.; Douglass, Anne R.; Chandra, Sushil; Stolarski, Richard S.; Rosenfield, Joan E.; Kaye, Jack A.

    1991-01-01

    Values of the monthly mean heating rates and the residual circulation characteristics were calculated using NMC data for temperature and the solar backscattered UV ozone for the period between 1979 and 1986. The results were used in a two-dimensional photochemical model in order to examine the effects of temperature and residual circulation on the interannual variability of ozone. It was found that the calculated total ozone was more sensitive to variations in interannual residual circulation than in the interannual temperature. The magnitude of the modeled ozone variability was found to be similar to the observed variability, but the observed and modeled year-to-year deviations were, for the most part, uncorrelated, due to the fact that the model did not account for most of the QBO forcing and for some of the observed tropospheric changes.

  18. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

    Science.gov (United States)

    Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

    2015-12-01

    The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

  19. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W [Brookline, MA; Kochevar, Irene E [Charlestown, MA

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  20. Impact of genotypic and phenotypic differences in sarcoma models on the outcome of photochemical internalization (PCI) of bleomycin.

    Science.gov (United States)

    Olsen, Cathrine Elisabeth; Sellevold, Simen; Theodossiou, Theodossis; Patzke, Sebastian; Berg, Kristian

    2017-12-01

    The low curative response to current treatment regimens for most soft tissue sarcomas indicates a strong need for alternative treatment strategies and predictive markers for treatment outcome. PCI (photochemical internalization) is a novel treatment strategy to translocate drugs into cytosol that otherwise would have been degraded in lysosomes. Two highly geno-and phenotypically different uterine and vulvar leiomyosarcoma cell lines, MES-SA and SK-LMS-1, were treated with bleomycin (BLM) activated by PCI (PCI BLM ). The MES-SA cells were much more sensitive to PCI BLM than the SK-LMS-1 cells and the treatment induced a 7-8 fold higher increase in DNA double-strand breaks at the same dose of light as measure by γH2AX staining. A 3-fold higher induction of apoptosis and stronger activation of Bax and p21 was also measured in the P53WT MES-SA cells, compared to the P53mut SK-LMS-1 cells. The basal formation of reactive oxygen species (ROS) was 3-fold higher in SK-LMS-1 cells than in the MES-SA cells and SK-LMS-1 cells expressed glutathione peroxidase 1 (GPx1) and more superoxide dismutase 2 (SOD2) than the MES-SA cells. Glutathione depletion with the glutathione synthetase inhibitor buthionine sulfoximine increased the cytotoxic effect of the photochemical treatment (PDT) most strongly in the SK-LMS-1 cells, and reduced PCI BLM -induced H2AX activation in the MES-SA cells, but not in the SK-LMS-1 cells. The results indicate PCI BLM as a potential novel treatment strategy for soft tissue sarcomas, with antioxidant enzymes, in particular GPx1, and the P53 status as potential predictive markers for response to PCI BLM . Copyright © 2017 Elsevier B.V. All rights reserved.

  1. 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

  2. Additive and Photochemical Manufacturing of Copper

    Science.gov (United States)

    Yung, Winco K. C.; Sun, Bo; Meng, Zhengong; Huang, Junfeng; Jin, Yingdi; Choy, Hang Shan; Cai, Zhixiang; Li, Guijun; Ho, Cheuk Lam; Yang, Jinlong; Wong, Wai Yeung

    2016-12-01

    In recent years, 3D printing technologies have been extensively developed, enabling rapid prototyping from a conceptual design to an actual product. However, additive manufacturing of metals in the existing technologies is still cost-intensive and time-consuming. Herein a novel platform for low-cost additive manufacturing is introduced by simultaneously combining the laser-induced forward transfer (LIFT) method with photochemical reaction. Using acrylonitrile butadiene styrene (ABS) polymer as the sacrificial layer, sufficient ejection momentum can be generated in the LIFT method. A low-cost continuous wave (CW) laser diode at 405 nm was utilized and proved to be able to transfer the photochemically synthesized copper onto the target substrate. The wavelength-dependent photochemical behaviour in the LIFT method was verified and characterized by both theoretical and experimental studies compared to 1064 nm fiber laser. The conductivity of the synthesized copper patterns could be enhanced using post electroless plating while retaining the designed pattern shapes. Prototypes of electronic circuits were accordingly built and demonstrated for powering up LEDs. Apart from pristine PDMS materials with low surface energies, the proposed method can simultaneously perform laser-induced forward transfer and photochemical synthesis of metals, starting from their metal oxide forms, onto various target substrates such as polyimide, glass and thermoplastics.

  3. Stratospheric Ozone: Transport, Photochemical Production and Loss

    Science.gov (United States)

    Douglass, A. R.; Kawa, S. R.; Jackman, C. H.

    2003-01-01

    Observations from various satellite instruments (e.g., Total Ozone Mapping Spectrometer (TOMS), Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS)) specify the latitude and seasonal variations of total ozone and ozone as a function of altitude. These seasonal variations change with latitude and altitude partly due to seasonal variation in transport and temperature, partly due to differences in the balance between photochemical production and loss processes, and partly due to differences in the relative importance of the various ozone loss processes. Comparisons of modeled seasonal ozone behavior with observations test the following: the seasonal dependence of dynamical processes where these dominate the ozone tendency; the seasonal dependence of photochemical processes in the upper stratosphere; and the seasonal change in the balance between photochemical and dynamical processes.

  4. Photochemical reduction of uranyl nitrate

    Energy Technology Data Exchange (ETDEWEB)

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  5. Photochemical oxidant injury and bark beetle coleoptera scolytidae infestation of ponderosa pine. II. Effect of injury upon physical properties of oleoresin, moisture content, and phloem thickness

    Energy Technology Data Exchange (ETDEWEB)

    Cobb, F.W. Jr.; Wood, D.L.; Stark, R.W.; Miller, P.R.

    1968-05-01

    Studies were made during the summer, 1966, to determine the effects of air pollution injury (i.e., chlorotic decline) of ponderosa pine on various factors related to tree physiology. The results of these studies show that disease caused by photochemical atmospheric pollution affects certain physiological properties of ponderosa pine that may be related to increased susceptibility to bark beetles. Oleoresin exudation pressure, yield, and rate of flow were substantially reduced in severely affected trees, but crystallization of resin increased as the severity of the disease became greater. Both sapwood and phloem moisture contents were less in diseased trees. Phloem thickness in advanced-diseased trees was less than 60% of that in healthy trees.

  6. Assessing the sensitivity of the hydroxyl radical to model biases in composition and temperature using a single-column photochemical model for Lauder, New Zealand

    Science.gov (United States)

    López-Comí, Laura; Morgenstern, Olaf; Zeng, Guang; Masters, Sarah L.; Querel, Richard R.; Nedoluha, Gerald E.

    2016-11-01

    We assess the major factors contributing to local biases in the hydroxyl radical (OH) as simulated by a global chemistry-climate model, using a single-column photochemical model (SCM) analysis. The SCM has been constructed to represent atmospheric chemistry at Lauder, New Zealand, which is representative of the background atmosphere of the Southern Hemisphere (SH) mid-latitudes. We use long-term observations of variables essential to tropospheric OH chemistry, i.e. ozone (O3), water vapour (H2O), methane (CH4), carbon monoxide (CO), and temperature, and assess how using these measurements affect OH calculated in the SCM, relative to a reference simulation only using modelled fields. The analysis spans 1994 to 2010. Results show that OH responds approximately linearly to correcting biases in O3, H2O, CO, CH4, and temperature. The biggest impact on OH is due to correcting an overestimation by approximately 20 to 60 % of H2O, using radiosonde observations. Correcting this moist bias leads to a reduction of OH by around 5 to 35 %. This is followed by correcting predominantly overestimated O3. In the troposphere, the model biases are mostly in the range of -10 to 30 %. The impact of changing O3 on OH is due to two pathways; the OH responses to both are of similar magnitude but different seasonality: correcting in situ tropospheric ozone leads to changes in OH in the range -14 to 4 %, whereas correcting the photolysis rate of O3 in accordance with overhead column ozone changes leads to increases of OH of 8 to 16 %. The OH sensitivities to correcting CH4, CO, and temperature biases are all minor effects. The work demonstrates the feasibility of quantitatively assessing OH sensitivity to biases in longer-lived species, which can help explain differences in simulated OH between global chemistry models and relative to observations. In addition to clear-sky simulations, we have performed idealized sensitivity simulations to assess the impact of clouds (ice and liquid

  7. Use of Combined Observational- and Model-Derived Photochemical Indicators to Assess the O3-NOx-VOC System Sensitivity in Urban Areas

    Directory of Open Access Journals (Sweden)

    Edson R. Carrillo-Torres

    2017-01-01

    Full Text Available Tropospheric levels of O3 have historically exceeded the official annual Mexican standards within the Monterrey Metropolitan Area (MMA in NE Mexico. High-frequency and high-precision measurements of tropospheric O3, NOy, NO2, NO, CO, SO2, PM10 and PM2.5 were made at the Obispado monitoring site near the downtown MMA from September 2012 to August 2013. The seasonal cycles of O3 and NOy are driven by changes in meteorology and to a lesser extent by variations in primary emissions. The NOy levels were positively correlated with O3 precursors and inversely correlated with O3 and wind speed. Recorded data were used to assess the O3-Volatile Organic Compounds (VOC-NOx system’s sensitivity through an observational-based approach. The photochemical indicator O3/NOy was derived from measured data during the enhanced O3 production period (12:00–18:00 Central Daylight Time (CDT, GMT-0500. The O3/NOy ratios calculated for this time period showed that the O3 production within the MMA is VOC sensitive. A box model simulation of production rates of HNO3 (PHNO3 and total peroxides (Pperox carried out for O3 episodes in fall and spring confirmed the VOC sensitivity within the MMA environment. No significant differences were observed in O3/NOy from weekdays to weekends or for PHNO3/Pperox ratios, confirming the limiting role of VOCs in O3 production within the MMA. The ratified photochemical regime observed may allow the environmental authorities to revise and verify the current policies for air quality control within the MMA.

  8. Photochemical Assessment Monitoring Stations (PAMS)

    Data.gov (United States)

    U.S. Environmental Protection Agency — Photochemical Assessment Monitoring Stations (PAMS). This file provides information on the numbers and distribution (latitude/longitude) of air monitoring sites...

  9. Modelling oxide formation and growth on platinum

    Science.gov (United States)

    Baroody, Heather A.; Jerkiewicz, Gregory; Eikerling, Michael H.

    2017-04-01

    We present a mathematical model of oxide formation and growth on platinum. The motivation stems from the necessity to understand platinum dissolution in the cathode catalyst layer of polymer electrolyte fuel cells. As is known, platinum oxide formation and reduction are strongly linked to platinum dissolution processes. However, a consistent model of the oxidation processes on platinum does not exist. Our oxide growth model links interfacial exchange processes between platinum and oxygen ions with the transport of oxygen ion vacancies via diffusion and migration. A parametric analysis is performed to rationalize vital trends in oxide growth kinetics. The rate determining step of oxide formation and growth is identified as the extraction of platinum atoms at the metal-oxide interface. A kinetic effect is observed while adjusting the potential when growing the oxide layer, and the solution indicates that a structural change occurs at high potentials, around 1.5 VRHE. The model compares well to experimental data for various materials from various sources.

  10. Photochemical cutting of fabrics

    Science.gov (United States)

    Piltch, Martin S.

    1994-01-01

    Apparatus for the cutting of garment patterns from one or more layers of fabric. A laser capable of producing laser light at an ultraviolet wavelength is utilized to shine light through a pattern, such as a holographic phase filter, and through a lens onto the one or more layers of fabric. The ultraviolet laser light causes rapid photochemical decomposition of the one or more layers of fabric, but only along the pattern. The balance of the fabric of the one or more layers of fabric is undamaged.

  11. Investigation of the photochemical changes of chlorogenic acids induced by ultraviolet light in model systems and in agricultural practice with Stevia rebaudiana cultivation as an example.

    Science.gov (United States)

    Karaköse, Hande; Jaiswal, Rakesh; Deshpande, Sagar; Kuhnert, Nikolai

    2015-04-08

    Mono- and diacyl chlorogenic acids undergo photochemical trans-cis isomerization under ultraviolet (UV) irradiation. The photochemical equilibrium composition was established for eight selected derivatives. In contrast to all other dicaffeoylquinic acid derivatives, cynarin (1,3-dicaffeoylquinic acid) undergoes a [2 + 2] photochemical cycloaddition reaction, constituting a first example of Schmidt's law in a natural product family. The relevance of photochemical isomerization in agricultural practice was investigated using 120 samples of Stevia rebaudiana leave samples grown under defined cultivation conditions. Ratios of cis to trans chlorogenic acids were determined in leaf samples and correlated with climatic and harvesting conditions. The data indicate a clear correlation between the formation of cis-caffeoyl derivatives and sunshine hours prior to harvesting and illustrate the relevance of UV exposure to plant material affecting its phytochemical composition.

  12. Tropospheric Ozone and Photochemical Smog

    Science.gov (United States)

    Sillman, S.

    2003-12-01

    global background ozone can make the effects of local pollution events everywhere more acute, and can also cause ecological damage in remote locations that are otherwise unaffected by urban pollution. Ozone at the global scale is also related to greenhouse warming.This chapter provides an overview of photochemical smog at the urban and regional scale, focused primarily on ozone and including a summary of information about particulates. It includes the following topics: dynamics and extent of pollution events; health and ecological impacts; relation between ozone and precursor emissions, including hydrocarbons and nitrogen oxides (NOx); sources, composition, and fundamental properties of particulates; chemistry of ozone and related species; methods of interpretation based on ambient measurements; and the connection between air pollution events and the chemistry of the global troposphere. Because there are many similarities between the photochemistry of ozone during pollution events and the chemistry of the troposphere in general, this chapter will include some information about global tropospheric chemistry and the links between urban-scale and global-scale events. Additional treatment of the global troposphere is found in Volume 4 of this work. The chemistry of ozone formation discussed here is also related to topics discussed in greater detail elsewhere in this volume (see Chapters 9.10 and 9.12) and in Volume 4.

  13. Modelling of UO2 oxidation in steam

    International Nuclear Information System (INIS)

    Brito, A.C.; Iglesias, F.C.; Liu, Y.

    1996-01-01

    A computer model has been developed for calculating oxidation of UO 2 at high temperatures in steam oxidising conditions. Several methods to calculate the partial pressure of oxygen in the fuel and in the environment surrounding the fuel are available. The various methodologies have been compared and the best models have been compiled into a computer model which will be implemented into fuel thermal/mechanical behaviour codes such as FACTAR 2.0 (LOECI) and ELESIM/ELOCA. Calculations from the computer model have been compared to experimental results. The calculated oxidation reaction kinetics are in good agreement with the experimental data. (author)

  14. 77 FR 36534 - Third External Review Draft Integrated Science Assessment for Ozone and Related Photochemical...

    Science.gov (United States)

    2012-06-19

    ... AGENCY Third External Review Draft Integrated Science Assessment for Ozone and Related Photochemical...: EPA is announcing the availability of the third external review draft of a document titled, ``Third External Review Draft Integrated Science Assessment for Ozone and Related Photochemical Oxidants'' (EPA/600...

  15. Photochemical Water-Splitting with Organomanganese Complexes.

    Science.gov (United States)

    Kadassery, Karthika J; Dey, Suman Kr; Cannella, Anthony F; Surendhran, Roshaan; Lacy, David C

    2017-08-21

    Certain organometallic chromophores with water-derived ligands, such as the known [Mn(CO) 3 (μ 3 -OH)] 4 (1) tetramer, drew our attention as possible platforms to study water-splitting reactions. Herein, we investigate the UV irradiation of various tricarbonyl organomanganese complexes, including 1, and demonstrate that dihydrogen, CO, and hydrogen peroxide form as products in a photochemical water-splitting decomposition reaction. The organic and manganese-containing side products are also characterized. Labeling studies with 18 O-1 suggest that the source of oxygen atoms in H 2 O 2 originates from free water that interacts with 1 after photochemical dissociation of CO (1-CO) constituting the oxidative half-reaction of water splitting mediated by 1. Hydrogen production from 1 is the result of several different processes, one of which involves the protons derived from the hydroxido ligands in 1 constituting the reductive half-reaction of water splitting mediated by 1. Other processes that generate H 2 are also operative and are described. Collectively the results from the photochemical decomposition of 1 provide an opportunity to propose a mechanism, and it is discussed within the context of developing new strategies for water-splitting reactions with organomanganese complexes.

  16. Evaluating the impact of new observational constraints on P-S/IVOC emissions, multi-generation oxidation, and chamber wall losses on SOA modeling for Los Angeles, CA

    Science.gov (United States)

    Ma, Prettiny K.; Zhao, Yunliang; Robinson, Allen L.; Worton, David R.; Goldstein, Allen H.; Ortega, Amber M.; Jimenez, Jose L.; Zotter, Peter; Prévôt, André S. H.; Szidat, Sönke; Hayes, Patrick L.

    2017-08-01

    Secondary organic aerosol (SOA) is an important contributor to fine particulate matter (PM) mass in polluted regions, and its modeling remains poorly constrained. A box model is developed that uses recently published literature parameterizations and data sets to better constrain and evaluate the formation pathways and precursors of urban SOA during the CalNex 2010 campaign in Los Angeles. When using the measurements of intermediate-volatility organic compounds (IVOCs) reported in Zhao et al. (2014) and of semi-volatile organic compounds (SVOCs) reported in Worton et al. (2014) the model is biased high at longer photochemical ages, whereas at shorter photochemical ages it is biased low, if the yields for VOC oxidation are not updated. The parameterizations using an updated version of the yields, which takes into account the effect of gas-phase wall losses in environmental chambers, show model-measurement agreement at longer photochemical ages, even though some low bias at short photochemical ages still remains. Furthermore, the fossil and non-fossil carbon split of urban SOA simulated by the model is consistent with measurements at the Pasadena ground site. Multi-generation oxidation mechanisms are often employed in SOA models to increase the SOA yields derived from environmental chamber experiments in order to obtain better model-measurement agreement. However, there are many uncertainties associated with these aging mechanisms. Thus, SOA formation in the model is compared to data from an oxidation flow reactor (OFR) in order to constrain SOA formation at longer photochemical ages than observed in urban air. The model predicts similar SOA mass at short to moderate photochemical ages when the aging mechanisms or the updated version of the yields for VOC oxidation are implemented. The latter case has SOA formation rates that are more consistent with observations from the OFR though. Aging mechanisms may still play an important role in SOA chemistry, but the

  17. Rates and regimes of photochemical ozone production over Central East China in June 2006: a box model analysis using comprehensive measurements of ozone precursors

    Directory of Open Access Journals (Sweden)

    Y. Kanaya

    2009-10-01

    Full Text Available An observation-based box model approach was undertaken to estimate concentrations of OH, HO2, and RO2 radicals and the net photochemical production rate of ozone at the top of Mount Tai, located in the middle of Central East China, in June 2006. The model calculation was constrained by the measurements of O3, H2O, CO, NO, NO2, hydrocarbon, HCHO, and CH3CHO concentrations, and temperature and J values. The net production rate of ozone was estimated to be 6.4 ppb h−1 as a 6-h average (09:00–15:00 CST, suggesting 58±37 ppb of ozone is produced in one day. Thus the daytime buildup of ozone recorded at the mountain top as ~23 ppb on average is likely affected by in situ photochemistry as well as by the upward transport of polluted air mass in the daytime. On days with high ozone concentrations (hourly values exceeding 100 ppb at least once, in situ photochemistry was more active than it was on low ozone days, suggesting that in situ photochemistry is an important factor controlling ozone concentrations. Sensitivity model runs for which different NOx and hydrocarbon concentrations were assumed suggested that the ozone production occurred normally under NOx-limited conditions, with some exceptional periods (under volatile-organic-compound-limited conditions in which there was fresh pollution. We also examined the possible influence of the heterogeneous loss of gaseous HO2 radicals in contact with aerosol particle surfaces on the rate and regimes of ozone production.

  18. A KINETIC MODEL FOR H2O2/UV PROCESS IN A COMPLETELY MIXED BATCH REACTOR. (R825370C076)

    Science.gov (United States)

    A dynamic kinetic model for the advanced oxidation process (AOP) using hydrogen peroxide and ultraviolet irradiation (H2O2/UV) in a completely mixed batch reactor (CMBR) is developed. The model includes the known elementary chemical and photochemical reac...

  19. Anatomy of the Photochemical Reaction: Excited-State Dynamics Reveals the C-H Acidity Mechanism of Methoxy Photo-oxidation on Titania.

    Science.gov (United States)

    Kolesov, Grigory; Vinichenko, Dmitry; Tritsaris, Georgios A; Friend, Cynthia M; Kaxiras, Efthimios

    2015-05-07

    Light-driven chemical reactions on semiconductor surfaces have potential for addressing energy and pollution needs through efficient chemical synthesis; however, little is known about the time evolution of excited states that determine reaction pathways. Here, we study the photo-oxidation of methoxy (CH3O) derived from methanol on the rutile TiO2(110) surface using ab initio simulations to create a molecular movie of the process. The movie sequence reveals a wealth of information on the reaction intermediates, time scales, and energetics. The reaction is broken in three stages, described by Lewis structures directly derived from the "hole" wave functions that lead to the concept of "photoinduced C-H acidity". The insights gained from this work can be generalized to a set of simple rules that can predict the efficiency of photo-oxidation reactions in reactant-catalyst pairs.

  20. Reversible Association of Nitro Compounds with p-Nitrothiophenol Modified on Ag Nanoparticles/Graphene Oxide Nanocomposites through Plasmon Mediated Photochemical Reaction.

    Science.gov (United States)

    Lin, Tsung-Wu; Tasi, Ting-Ti; Chang, Po-Ling; Cheng, Hsiu-Yao

    2016-03-01

    Because localized surface plasmon resonance in nanostructures of noble metals is accompanied by interesting physical effects such as optical near-field enhancement, heat release, and the generation of hot electrons, it has been employed in a wide range of applications, including plasmon-assisted chemical reactions. Here, we use a composite of silver nanoparticles and graphene oxide (Ag@GO) as the catalytic as well as the analytic platform for plasmon-assisted chemical reactions. Through time-dependent surface-enhanced Raman scattering experiments, it is found that p-nitrothiophenol (pNTP) molecules on Ag@GO can be associated with nitro compounds such as nitrobenzene and 1-nitropropane to form azo compounds when aided by the plasmons. Furthermore, the reaction rate can be modulated by varying the wavelength and power of the excitation laser as well as the nitro compounds used. In addition, the aforementioned coupling reaction can be reversed. We demonstrate that the oxidation of azo compounds on Ag@GO using KMnO4 leads to the dissociation of the N═N double bond in the azo compounds and that the rate of bond dissociation can be accelerated significantly via laser irradiation. Furthermore, the pNTP molecules on Ag@GO can be recovered after the oxidation reaction. Finally, we demonstrate that the plasmon-assisted coupling reaction allows for the immobilization of nitro-group-containing fluorophores at specific locations on Ag@GO.

  1. Photochemically Synthesized Polyimides

    Science.gov (United States)

    Meador, Michael A.; Tyson, Daniel S.

    2008-01-01

    An alternative to the conventional approach to synthesis of polyimides involves the use of single monomers that are amenable to photopolymerization. Heretofore, the synthesis of polyimides has involved multiple-monomer formulations and heating to temperatures that often exceed 250 C. The present alternative approach enables synthesis under relatively mild conditions that can include room temperature. The main disadvantages of the conventional approach are the following: Elevated production temperatures can lead to high production costs and can impart thermal stresses to the final products. If the proportions of the multiple monomeric ingredients in a given batch are not exactly correct, the molecular weight and other physical properties of the final material could be reduced from their optimum or desired values. To be useful in the alternative approach, a monomer must have a molecular structure tailored to exploit Diels-Alder trapping of a photochemically generated ortho-quinodimethane. (In a Diels-Alder reaction, a diene combines with a dienophile to form molecules that contain six-membered rings.) In particular, a suitable monomer (see figure) contains ortho-methylbenzophenone connected to a dienophile (in this case, a maleimide) through a generic spacer group. Irradiation with ultraviolet light gives rise to a photochemical intermediate the aforementioned ortho-quinodimethane from the ortho-methylbenzophenone. This group may react with the dienophile on another such monomer molecule to produce an oligomer that, in turn may react in a stepgrowth manner to produce a polyimide. This approach offers several advantages in addition to those mentioned above: The monomer can be stored for a long time because it remains unreactive until exposed to light. Because the monomer is the only active starting ingredient, there is no need for mixing, no concern for ensuring correct proportions of monomers, and the purity of the final product material is inherently high. The use

  2. Photochemical reactions in dehydrated photosynthetic organisms, leaves, chloroplasts and photosystem II particles: reversible reduction of pheophytin and chlorophyll and oxidation of {beta}-carotene

    Energy Technology Data Exchange (ETDEWEB)

    Shuvalov, Vladimir A.; Heber, Ulrich

    2003-11-01

    Photoreactions of dehydrated leaves, isolated broken chloroplasts and PSII membrane fragments of spinach (Spinacia oleracea) were studied at different air humidities and compared with photoreactions of dry fronds of a fern, Polypodium vulgare, and a dry lichen, Parmelia sulcata, which in contrast to spinach are insensitive to photoinactivation in the dry state. Even in very dry air, P700 in the reaction center of photosystem I of dry leaves was oxidized, and the primary quinone acceptor Q{sub A} in the reaction center of photosystem II was photoreduced by low light. These reactions were only very slowly reversed in the dark and saturated under low light intensity. Light-minus-dark difference absorption spectra of the dry leaves, isolated chloroplasts and PSII membrane fragments measured at higher light intensities revealed absorbance changes of {beta}-carotene at 500 nm (light-dependent bleaching) and 980 nm (light-dependent band formation) and bleaching of chlorophyll at 436 and 680 nm with appearance of bands at 450 and 800 nm. Decrease of chlorophyll fluorescence upon strong illumination indicated photoaccumulation of a quencher. All these changes were kinetically related and readily reversible. They are interpreted to show light-induced oxidation of {beta}-carotene (Car) and reduction of chlorophyll-680 (Chl-680) in the reaction center of photosystem II of the dried leaves, chloroplasts and photosystem II particles. The fluorescence quencher was suggested to be Chl-680{sup -} or Car{sup +} in close proximity to P680, the primary electron donor. Appreciable photoaccumulation of reduced pheophytin was only observed in dry leaves after Q{sub A} reduction had been lost during heat treatment of hydrated leaves prior to dehydration. The observations are interpreted to show light-dependent cyclic electron flow within the reaction center of photosystem II in which Chl-680 (or Pheo) is reduced by P680* and Car is oxidized by P680{sup +} with consequent recombination of

  3. Photochemical reactions in dehydrated photosynthetic organisms, leaves, chloroplasts and photosystem II particles: reversible reduction of pheophytin and chlorophyll and oxidation of β-carotene

    International Nuclear Information System (INIS)

    Shuvalov, Vladimir A.; Heber, Ulrich

    2003-01-01

    Photoreactions of dehydrated leaves, isolated broken chloroplasts and PSII membrane fragments of spinach (Spinacia oleracea) were studied at different air humidities and compared with photoreactions of dry fronds of a fern, Polypodium vulgare, and a dry lichen, Parmelia sulcata, which in contrast to spinach are insensitive to photoinactivation in the dry state. Even in very dry air, P700 in the reaction center of photosystem I of dry leaves was oxidized, and the primary quinone acceptor Q A in the reaction center of photosystem II was photoreduced by low light. These reactions were only very slowly reversed in the dark and saturated under low light intensity. Light-minus-dark difference absorption spectra of the dry leaves, isolated chloroplasts and PSII membrane fragments measured at higher light intensities revealed absorbance changes of β-carotene at 500 nm (light-dependent bleaching) and 980 nm (light-dependent band formation) and bleaching of chlorophyll at 436 and 680 nm with appearance of bands at 450 and 800 nm. Decrease of chlorophyll fluorescence upon strong illumination indicated photoaccumulation of a quencher. All these changes were kinetically related and readily reversible. They are interpreted to show light-induced oxidation of β-carotene (Car) and reduction of chlorophyll-680 (Chl-680) in the reaction center of photosystem II of the dried leaves, chloroplasts and photosystem II particles. The fluorescence quencher was suggested to be Chl-680 - or Car + in close proximity to P680, the primary electron donor. Appreciable photoaccumulation of reduced pheophytin was only observed in dry leaves after Q A reduction had been lost during heat treatment of hydrated leaves prior to dehydration. The observations are interpreted to show light-dependent cyclic electron flow within the reaction center of photosystem II in which Chl-680 (or Pheo) is reduced by P680* and Car is oxidized by P680 + with consequent recombination of Car + and Chl-680 - (or Pheo

  4. Integrated photochemical and biological treatment of a commercial textile surfactant: Process optimization, process kinetics and COD fractionation

    International Nuclear Information System (INIS)

    Arslan-Alaton, Idil; Cokgor, Emine Ubay; Koban, Baris

    2007-01-01

    The biodegradability of surfactants is a frequent and complex issue arising both at domestic as well as industrial treatment facilities. In the present experimental study, the integrated photochemical (H 2 O 2 /UV-C) and biochemical (activated sludge) treatment of a commercial grade nonionic/anionic textile surfactant formulation was investigated. Photochemical baseline experiments have shown that once the initial pH and H 2 O 2 dose were optimized, practically complete COD removal (COD o = 500 ± 30 mg L -1 ) could be achieved. Once the COD was elevated to values being typical for the textile fabric preparation stage, treatment efficiency was seriously retarded provided that the photochemical treatment conditions remained constant. Moreover, a definite relationship existed between H 2 O 2 consumption and COD removal for H 2 O 2 /UV-C advanced oxidation of the textile surfactant. In the second part of the study, COD abatement was modeled for the biodegradation of untreated and photochemically pretreated textile surfactant formulation according to their COD fractions. Results have indicated that the readily biodegradable and rapidly hydrolysable COD fractions of the textile surfactant solution could be appreciably increased upon exposure to an optimum H 2 O 2 concentration (60 mM; i.e. 2.1 g H 2 O 2 (g COD o ) -1 ) and extended UV-C irradiation times (i.e. 90 and 120 min)

  5. Graphene oxide quantum dot-derived nitrogen-enriched hybrid graphene nanosheets by simple photochemical doping for high-performance supercapacitors

    Science.gov (United States)

    Xu, Yongjie; Li, Xinyu; Hu, Guanghui; Wu, Ting; Luo, Yi; Sun, Lang; Tang, Tao; Wen, Jianfeng; Wang, Heng; Li, Ming

    2017-11-01

    Nitrogen-enriched graphene was fabricated via a facile strategy. Graphene oxide (GO) nanosheets and graphene oxide quantum dots (GQDs) were used as a structure-directing agent and in situ activating agent, respectively, after photoreduction under NH3 atmosphere. The combination of photoreduction and NH3 not only reduced GO and GQD composites (GO/GQDs) within a shorter duration but also doped a high level of nitrogen on the composites (NrGO/GQDs). The nitrogen content of NrGO/GQDs reached as high as 18.86 at% within 5 min of irradiation. Benefiting from the nitrogen-enriched GO/GQDs hybrid structure, GQDs effectively prevent the agglomeration of GO sheets and increased the numbers of ion channels in the material. Meanwhile, the high levels of nitrogen improved electrical conductivity and strengthened the binding energy between GQD and GO sheets. Compared with reduced GO and low nitrogen-doped reduced GO, NrGO/GQD electrodes exhibited better electrochemical characteristics with a high specific capacitance of 344 F g-1 at a current density of 0.25 A g-1. Moreover, the NrGO/GQD electrodes exhibited 82% capacitance retention after 3000 cycles at a current density of 0.8 A g-1 in 6 M KOH electrolyte. More importantly, the NrGO/GQD electrodes deliver a high energy density of 43 Wh kg-1 at a power density of 417 W kg-1 in 1 M Li2SO4 electrolyte. The nitrogen-doped graphene and corresponding supercapacitor presented in this study are novel materials with potential applications in advanced energy storage systems.

  6. Tropospheric Ozone Research: Monitoring and modelling of photo-oxidants over Europe

    NARCIS (Netherlands)

    Beck JP; Roemer MGM; Vosbeek MEJP; Builtjes PJH; RIVM-LLO; TNO-MEP; KEMA

    1996-01-01

    The Dutch activities contributing to the EUROTRAC-TOR programme were set up to study and quantify the underlying chemical and transport processes important to the occurrence of photochemical oxidants in Europe. The project involved establishing an advanced monitoring site at Kollumerwaard,

  7. Photochemical Synthesis of Au@Pd Core-Shell Nanoparticles for Methanol Oxidation Reaction: the Promotional Effect of the Au Core

    Directory of Open Access Journals (Sweden)

    Dong Yingnan

    2016-01-01

    Full Text Available A novel method for synthesizing Au@Pd core-shell nanoparticles was proposed based on photochemistry. By irradiating the mixture of Au (III and Pd (II ions using ultraviolet light, the Au@Pd core-shell nanoparticles were prepared. The size of the nanoparticles and the thickness of the Pd shell could be efficiently adjusted by changing the molar ratio of Au (III to Pd (II ion. In this way, nanoparticles with diameter in the range of 5.6~4.6 nm were obtained. The core-shell structure of the synthesized nanoparticles was showed by the characterization using UV-Vis, TEM/HR-TEM and XPS. The paper investigated the electrocatalysis performance of Au@Pd nanoparticles in the methanol catalytic oxidation reaction, as well as the electron donating effect of Au core to Pd shell and the promotion of this effect on the catalytic activity of Pd shell. The experimental results provided reference for the development of non-platinum catalysts of low-temperature fuel cell anode.

  8. Photochemical oxidant injury and bark beetle coleoptera scolytidae infestation of ponderosa pine. I. Incidence of bark beetle infestation in injured trees

    Energy Technology Data Exchange (ETDEWEB)

    Stark, R.W.; Miller, P.R.; Cobb, F.W. Jr.; Wood, D.L.; Parmeter, J.R. Jr.

    1968-05-01

    A total of 107 beetle-killed and 963 nearest-neighbor ponderosa pines were examined to determine the association between severity of atmospheric pollution injury and infestation by bark beetles. Trees exhibiting advanced symptoms of pollution injury were most frequently infested by the western pine beetle, Dendroctonus brevicomis, and the mountain pine beetle, D. ponderosae. The degree of injury and incidence of bark beetle infestation were not related to total height, diameter, length of live and dead crown or crown class. As severity of oxidant injury increased, live crown ratio decreased and incidence of bark beetle infestation increased. One hundred noninfested trees in each of three disease categories, advanced, intermediate, and healthy, were examined for evidence of prior beetle attacks. Thirty-six percent of the advanced-diseased trees versus only 5% of the healthy trees were attacked. Thus, the beetles may discriminate between healthy and diseased trees at a distance, upon contact with the host, or both. These studies indicate strongly that atmospheric pollution injury predisposes ponderosa pine to bark beetle infestations. 3 references, 7 tables.

  9. Research opportunities in photochemical sciences

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-07-01

    The workshop entitled {open_quotes}Research Opportunities in Photochemical Sciences{close_quotes} was initiated by the U.S. Department of Energy (DOE), Office of Energy Research (ER), Office of Basic Energy Sciences (BES), Division of Chemical Sciences. The National Renewable Energy Laboratory (NREL) in Golden, Colorado was requested by ER to host the workshop. It was held February 5-8, 1996 at the Estes Park Conference Center, Estes Park, CO, and attended by about 115 leading scientists and engineers from the U.S., Japan, and Europe; program managers for the DOE ER and Energy Efficiency and Renewable Energy (EERE) programs also attended. The purpose of the workshop was to bridge the communication gap between the practioneers and supporters of basic research in photochemical science and the practioneers and supporters of applied research and development in technologies related to photochemical science. For the purposes of the workshop the definition of the term {open_quotes}photochemical science{close_quotes} was broadened to include homogeneous photochemistry, heterogeneous photochemistry, photoelectrochemistry, photocatalysis, photobiology (for example, the light-driven processes of biological photosynthesis and proton pumping), artificial photosynthesis, solid state photochemistry, and solar photochemistry. The technologies under development through DOE support that are most closely related to photochemical science, as defined above, are the renewable energy technologies of photovoltaics, biofuels, hydrogen energy, carbon dioxide reduction and utilization, and photocatalysis for environmental cleanup of water and air. Individual papers were processed separately for the United states Department of Energy databases.

  10. Photochemical Attenuation of Pesticides in Prairie Potholes

    Science.gov (United States)

    Zeng, T.; Arnold, W. A.

    2013-12-01

    DOM appeared to exert the largest effects on the overall photodegradation. Furthermore, a suite of second-order rate constants for reactions of pesticides with PPRIs were derived based on the quenching effect on observed reaction rate constants and measured steady-state concentrations of PPRIs. These rate constants may find practical utility for estimating DOM photochemical reaction rates in addition to data traditionally estimated from model compounds. Overall, our work contributed to a systematic evaluation of the potential for photochemical attenuation of pesticides in near-surface pothole water. Given recent incentives to expand agriculture in the PPR for production of organic crops and corn-based biofuels, this research also calls for the need to properly conserve prairie potholes and to develop regionally-specific, sustainable water resource management and land use strategies.

  11. The evolution of photochemical smog in a power plant plume

    Science.gov (United States)

    Luria, Menachem; Valente, Ralph J.; Tanner, Roger L.; Gillani, Noor V.; Imhoff, Robert E.; Mueller, Stephen F.; Olszyna, Kenneth J.; Meagher, James F. Present address: Aeronomy Laboratory, NOAA, 325 Broadway, Boulder CO 80303, USA.)

    The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study - Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west-northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50-60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O 3 that peaked at 120 ppbv at a short distance (15-25 km) downwind of Nashville. Ozone productivity (the ratio of excess O 3 to NO y and NO z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.

  12. The evolution of photochemical smog in a power plant plume

    International Nuclear Information System (INIS)

    Luria, M.; The Hebrew University, Jerusalem; Valente, R.J.; Tanner, R.L.; Imhoff, R.E.; Mueller, S.F.; Olszyna, K.J.; Meagher, J.F.; Gillani, N.V.; University of Alabama, Huntsville, AL

    1999-01-01

    The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study - Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west-northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50-60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O 3 that peaked at 120 ppbv at a short distance (15-25 km) downwind of Nashville. Ozone productivity (the ratio of excess O 3 to NO y and NO z ) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism. (author)

  13. In-situ BrO measurements in the upper troposphere / lower stratosphere. Validation of the ENVISAT satellite measurements and photochemical model studies

    Energy Technology Data Exchange (ETDEWEB)

    Hrechanyy, S.

    2007-04-15

    and SCOUT-O3 in the 15-20 km altitude regime are at the low side of comparable DOAS measurements a CLaMS study of the evolution of Bry from the source gases has been carried out. For this purpose an ensemble of trajectories rising from the lower troposphere to the TTL within 6 to more than 90 days were initialized with observed mixing ratios in the boundary layer of all important organic bromine source gases and the free-up of Bry by chemical and photochemical reactions was simulated. Bromoform, CHBr3, was found to be the main source of inorganic bromine at the tropopause. The derived tropospheric lifetime of bromoform is 33 days. The modelled BrO mixing ratio at the tropopause (less than 2.5 pptv) is consistent with HALOX measurements which do not detect significant amounts of BrO there (<1-2 pptv). Therefore measurements of more than 4 pptv (as retrieved from SCIAMACHY) can only be explained trough processes not included in the model. (orig.)

  14. Photochemical transformation of aircraft exhausts at their transition from the plume to the large scale dispersion in the Northern temperature belt

    Energy Technology Data Exchange (ETDEWEB)

    Karol, I.L.; Kiselev, A.A. [Main Geophysical Observatory, St.Petersburg (Russian Federation)

    1997-12-31

    The 2-D diurnally varying photochemical model of the Northern temperate zonal tropospheric belt with fixed (off line) temperature and air transport is used for the description of the formation of aircraft exhaust concentration distribution in the North Atlantic commercial flight corridor, based on actual flights in summer and winter. A strong diurnal and seasonal variation of emitted NO{sub x} oxidation rate is revealed and evaluated. (author) 11 refs.

  15. Photochemical Transformation Processes in Sunlit Surface Waters

    Science.gov (United States)

    Vione, D.

    2012-12-01

    Photochemical reactions are major processes in the transformation of hardly biodegradable xenobiotics in surface waters. They are usually classified into direct photolysis and indirect or sensitised degradation. Direct photolysis requires xenobiotic compounds to absorb sunlight, and to get transformed as a consequence. Sensitised transformation involves reaction with transient species (e.g. °OH, CO3-°, 1O2 and triplet states of chromophoric dissolved organic matter, 3CDOM*), photogenerated by so-called photosensitisers (nitrate, nitrite and CDOM). CDOM is a major photosensitiser: is it on average the main source of °OH (and of CO3-° as a consequence, which is mainly produced upon oxidation by °OH of carbonate and bicarbonate) and the only important source of 1O2 and 3CDOM* [1, 2]. CDOM origin plays a key role in sensitised processes: allochthonous CDOM derived from soil runoff and rich in fulvic and humic substances is usually more photoactive than autochthonous CDOM (produced by in-water biological processes and mainly consisting of protein-like material) or of CDOM derived from atmospheric deposition. An interesting gradual evolution of CDOM origin and photochemistry can be found in mountain lakes across the treeline, which afford a gradual transition of allochthonous- autochtonous - atmopheric CDOM when passing from trees to alpine meadows to exposed rocks [3]. Another important issue is the sites of reactive species photoproduction in CDOM. While there is evidence that smaller molecular weight fractions are more photoactive, some studies have reported considerable 1O2 reactivity in CDOM hydrophobic sites and inside particles [4]. We have recently addressed the problem and found that dissolved species in standard humic acids (hydrodynamic diameter pollutants to be assessed and modelled. For instance, it is possible to predict pollutant half-life times by knowing absorption spectrum, direct photolysis quantum yield and reaction rate constants with °OH, CO3

  16. Investigation of Zircaloy-2 oxidation model for SFP accident analysis

    Science.gov (United States)

    Nemoto, Yoshiyuki; Kaji, Yoshiyuki; Ogawa, Chihiro; Kondo, Keietsu; Nakashima, Kazuo; Kanazawa, Toru; Tojo, Masayuki

    2017-05-01

    The authors previously conducted thermogravimetric analyses on Zircaloy-2 in air. By using the thermogravimetric data, an oxidation model was constructed in this study so that it can be applied for the modeling of cladding degradation in spent fuel pool (SFP) severe accident condition. For its validation, oxidation tests of long cladding tube were conducted, and computational fluid dynamics analyses using the constructed oxidation model were proceeded to simulate the experiments. In the oxidation tests, high temperature thermal gradient along the cladding axis was applied and air flow rates in testing chamber were controlled to simulate hypothetical SFP accidents. The analytical outputs successfully reproduced the growth of oxide film and porous oxide layer on the claddings in oxidation tests, and validity of the oxidation model was proved. Influence of air flow rate for the oxidation behavior was thought negligible in the conditions investigated in this study.

  17. Modelling the Krebs cycle and oxidative phosphorylation.

    Science.gov (United States)

    Korla, Kalyani; Mitra, Chanchal K

    2014-01-01

    The Krebs cycle and oxidative phosphorylation are the two most important sets of reactions in a eukaryotic cell that meet the major part of the total energy demands of a cell. In this paper, we present a computer simulation of the coupled reactions using open source tools for simulation. We also show that it is possible to model the Krebs cycle with a simple black box with a few inputs and outputs. However, the kinetics of the internal processes has been modelled using numerical tools. We also show that the Krebs cycle and oxidative phosphorylation together can be combined in a similar fashion - a black box with a few inputs and outputs. The Octave script is flexible and customisable for any chosen set-up for this model. In several cases, we had no explicit idea of the underlying reaction mechanism and the rate determining steps involved, and we have used the stoichiometric equations that can be easily changed as and when more detailed information is obtained. The script includes the feedback regulation of the various enzymes of the Krebs cycle. For the electron transport chain, the pH gradient across the membrane is an essential regulator of the kinetics and this has been modelled empirically but fully consistent with experimental results. The initial conditions can be very easily changed and the simulation is potentially very useful in a number of cases of clinical importance.

  18. Modeling Nitrogen Oxides in the Lower Stratosphere

    Science.gov (United States)

    Kawa, S. Randy; Einaudi, Franco (Technical Monitor)

    2001-01-01

    This talk will focus on the status of current understanding (not a historical review) as regards modeling nitrogen oxides (NOy) in the lower stratosphere (LS). The presentation will be organized around three major areas of process understanding: 1) NOy sources, sinks, and transport to the LS, 2) NOy species partitioning, and 3) polar multiphase processes. In each area, process topics will be identified with an estimate of the degree of confidence associated with their representation in numerical models. Several exotic and/or speculative processes will also be discussed. Those topics associated with low confidence or knowledge gaps, weighted by their prospective importance in stratospheric chemical modeling, will be collected into recommendations for further study. Suggested approaches to further study will be presented for discussion.

  19. Mathematical modeling of solid oxide fuel cells

    Science.gov (United States)

    Lu, Cheng-Yi; Maloney, Thomas M.

    1988-01-01

    Development of predictive techniques, with regard to cell behavior, under various operating conditions is needed to improve cell performance, increase energy density, reduce manufacturing cost, and to broaden utilization of various fuels. Such technology would be especially beneficial for the solid oxide fuel cells (SOFC) at it early demonstration stage. The development of computer models to calculate the temperature, CD, reactant distributions in the tubular and monolithic SOFCs. Results indicate that problems of nonuniform heat generation and fuel gas depletion in the tubular cell module, and of size limitions in the monolithic (MOD 0) design may be encountered during FC operation.

  20. Participation of oxidized sulfur center in intramolecular free radical processes in the model organic compounds of biological importance

    International Nuclear Information System (INIS)

    Pogocki, D.M.

    2004-01-01

    The pathogenesis of neurodegenerative diseases such as prion diseases (Creutzfeldt-Jacob disease) and Alzheimer's disease is strongly associated with the presence of β-amyloid peptide (βA) and prion protein (hPrP) in the brain tissue. Both macromolecules contain methionine (Met) residues. Their presence seems to be responsible for unique redox properties of βA and hPrP. These residues may undergo relatively easy autooxidation and/or metal-catalysed oxidation. The presented studies were focused on the potential function of Met residues as antioxidants or pro-oxidants and on their role in radical-mediated oxidation of peptides and proteins. The role of S-, O-, N- and C-centered radicals generated in various oligopeptides containing Met and relevant model compounds has been examined in detail with respect to formation of 2c-3e bonds, redox processes, fragmentation and their mutual interconversion. In order to achieve these goals several experimental radiation, photochemical, and molecular modelling methods were applied. The experimental and molecular modelling results show significant influence of functional neighbouring groups and conformational flexibility of a peptide backbone on the oxidative reduction pathway in oligopeptides containing single and multiple Met residues. The results presented here allow for better understanding of the known propensities of βA and hPrP to reduce transition metals and to form reactive oxygen species and free radicals. (author)

  1. Photochemical pollution indicators; Les indicateurs de la pollution photochimique. La mesure des composes azotes

    Energy Technology Data Exchange (ETDEWEB)

    Perros, P.E.; Marion, T. [Paris-7 Univ., 75 (France). Laboratoire Interuniversitaire des Systemes Atmospheriques

    1998-11-01

    The number of photochemical pollution is generally based on the observation of ozone and nitrogen oxides concentration levels. So, the measurement of photochemical pollution indicators becomes essential to better understand the involved phenomena, and at the end to enable its reduction control and strategy. In this paper, we focus on the measurements of nitrogen compounds (NO{sub x} PAN, HNO{sub 3}). (authors) 24 refs.

  2. MARMOT update for oxide fuel modeling

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yongfeng [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schwen, Daniel [Idaho National Lab. (INL), Idaho Falls, ID (United States); Chakraborty, Pritam [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Chao [Idaho National Lab. (INL), Idaho Falls, ID (United States); Aagesen, Larry [Idaho National Lab. (INL), Idaho Falls, ID (United States); Ahmed, Karim [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, Wen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Biner, Bulent [Idaho National Lab. (INL), Idaho Falls, ID (United States); Bai, Xianming [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Tonks, Michael [Pennsylvania State Univ., University Park, PA (United States); Millett, Paul [Univ. of Arkansas, Fayetteville, AR (United States)

    2016-09-01

    This report summarizes the lower-length-scale research and development progresses in FY16 at Idaho National Laboratory in developing mechanistic materials models for oxide fuels, in parallel to the development of the MARMOT code which will be summarized in a separate report. This effort is a critical component of the microstructure based fuel performance modeling approach, supported by the Fuels Product Line in the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program. The progresses can be classified into three categories: 1) development of materials models to be used in engineering scale fuel performance modeling regarding the effect of lattice defects on thermal conductivity, 2) development of modeling capabilities for mesoscale fuel behaviors including stage-3 gas release, grain growth, high burn-up structure, fracture and creep, and 3) improved understanding in material science by calculating the anisotropic grain boundary energies in UO$_2$ and obtaining thermodynamic data for solid fission products. Many of these topics are still under active development. They are updated in the report with proper amount of details. For some topics, separate reports are generated in parallel and so stated in the text. The accomplishments have led to better understanding of fuel behaviors and enhance capability of the MOOSE-BISON-MARMOT toolkit.

  3. Approximate photochemical dynamics of azobenzene with reactive force fields

    Science.gov (United States)

    Li, Yan; Hartke, Bernd

    2013-12-01

    We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cis→trans- and trans→cis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work).

  4. Empirical soot formation and oxidation model

    Directory of Open Access Journals (Sweden)

    Boussouara Karima

    2009-01-01

    Full Text Available Modelling internal combustion engines can be made following different approaches, depending on the type of problem to be simulated. A diesel combustion model has been developed and implemented in a full cycle simulation of a combustion, model accounts for transient fuel spray evolution, fuel-air mixing, ignition, combustion, and soot pollutant formation. The models of turbulent combustion of diffusion flame, apply to diffusion flames, which one meets in industry, typically in the diesel engines particulate emission represents one of the most deleterious pollutants generated during diesel combustion. Stringent standards on particulate emission along with specific emphasis on size of emitted particulates have resulted in increased interest in fundamental understanding of the mechanisms of soot particulate formation and oxidation in internal combustion engines. A phenomenological numerical model which can predict the particle size distribution of the soot emitted will be very useful in explaining the above observed results and will also be of use to develop better particulate control techniques. A diesel engine chosen for simulation is a version of the Caterpillar 3406. We are interested in employing a standard finite-volume computational fluid dynamics code, KIVA3V-RELEASE2.

  5. Modeling Degradation in Solid Oxide Electrolysis Cells

    Energy Technology Data Exchange (ETDEWEB)

    Manohar S. Sohal; Anil V. Virkar; Sergey N. Rashkeev; Michael V. Glazoff

    2010-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic no equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, , within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, no equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  6. Complex Equilibria Changing in Photochemical Reaction: Computerized Evaluation and Simulation.

    Science.gov (United States)

    Horvath, Otto; Papp, Sandor

    1988-01-01

    States that if photochemical reactions can be followed spectrophotometrically, reactivities can be estimated by evaluating data from only one curve. Studies such a system using computerized evaluation and simulation. Uses chlorocuprate(II) complexes in acetonitrile solutions for the model systems. (MVL)

  7. A Highly Effective Photochemical System for Complex Treatment of Heavily Contaminated Wastewaters

    Czech Academy of Sciences Publication Activity Database

    Krystyník, Pavel; Klusoň, Petr; Hejda, S.; Mašín, P.; Tito, D.N.

    2014-01-01

    Roč. 86, č. 11 (2014), s. 2212-2220 ISSN 1061-4303 R&D Projects: GA MPO(CZ) FR-TI1/065 Institutional support: RVO:67985858 Keywords : advanced oxidation processes * photochemical oxidation * wastewater treatment Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.865, year: 2014

  8. Model alloy oxidation in oxyfuel characteristic environment

    International Nuclear Information System (INIS)

    Coelho, D.; Rizzo, F.; Kranzmann, A.; Monteiro, M.; Caminha, I.

    2014-01-01

    In the oxyfuel process, pure oxygen is burned in boilers with recycled gas producing a gas rich in CO 2 , making it easer to capture the CO 2 in the end of the process. The present work investigates the high temperature corrosion characteristics of a model Fe-Cr-Co alloy in typical oxyfuel process environment. Samples were oxidized at 600°C during 1000 hours in single atmosphere condition, where the samples is exposed to the same gas in all faces, and in a dual atmosphere condition, where the sample is exposed to water vapor in one side and to oxyfuel gas in the other. Samples where characterized by SEM and EDX. Results showed that corrosion is higher in a dual atmosphere condition than in single condition. (author)

  9. Monitoring Photochemical Reactions Using Marangoni Flows

    Science.gov (United States)

    2017-01-01

    We evaluated the sensitivity and time resolution of a technique for photochemical reaction monitoring based on the interferometric detection of the deformation of liquid films. The reaction products change the local surface tension and induce Marangoni flow in the liquid film. As a model system, we consider the irradiation of the aliphatic hydrocarbon squalane with broadband deep-UV light. We developed a numerical model that quantitatively reproduces the flow patterns observed in the experiments. Moreover, we present self-similarity solutions that elucidate the mechanisms governing different stages of the dynamics and their parametric dependence. Surface tension changes as small as Δγ = 10–6 N/m can be detected, and time resolutions of <1 s can be achieved. PMID:28319399

  10. Influence of humidity on photochemical ozone generation with 172nm xenon excimer lamps

    Science.gov (United States)

    Salvermoser, M. J.; Kogelschatz, U.; Murnick, D. E.

    2009-08-01

    The reaction kinetics of photochemical ozone (O{3}) generation in humid air and oxygen (O{2}) using efficient, narrow band vacuum ultra violet (VUV) 172 nm xenon excimer lamps is discussed. Trace amounts of water (H{2}O) vapor in the process gas leads to hydroxyl (OH) and hydroperoxy (HO{2}) radical formation. These radicals drive a catalytic O{3} destruction cycle limiting O{3} saturation concentration. This catalytic O{3} destruction cycle was included into a quantitative kinetic model describing photochemical O{3} production. Experimental O{3} saturation concentrations obtained with coaxial VUV driven photochemical O{3} generators compare satisfactorily with the models predictions.

  11. Model for low temperature oxidation during long term interim storage

    International Nuclear Information System (INIS)

    Desgranges, C.; Abbas, A.; Terlain, A.

    2003-01-01

    Low-alloyed steels or carbon steels are considered as candidate materials for the fabrication of some nuclear waste package containers for long term interim storage. The containers are required to remain retrievable for centuries. One factor limiting their performance on this time scale is corrosion. The estimation of the metal thickness lost by dry oxidation over such long periods requires the construction of reliable models from short-time experimental data. In a first step, models based on simplified oxidation theories have been derived from experimental data on iron and a low-alloy steel oxidation. Their extrapolation to long oxidation periods confirms that the expected damage due to dry oxidation could be small. In order to improve the reliability of these predictions advanced models taking into account the elementary processes involved in the whole oxidation mechanism, are under development. (authors)

  12. Photochemically induced oscillations of aromatic pentazadienes

    Energy Technology Data Exchange (ETDEWEB)

    Kunz, T.; Hahn, C.; Wokaun, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Aromatic pentazadienes are used to enhance the laser induced ablation of standard polymers with low absorption in the UV. Therefore the photochemistry of substituted 1,5-diaryl-3-alkyl-1,4-pentazadiene monomers was studied with a pulsed excimer laser as irradiation source. The net photochemical reaction proceeds in an overall one-step pathway A{yields}B. Quantum yields for the laser decomposition were determined to be up to 10%. An oscillating behaviour of the absorption was found during the dark period following the irradiation. The temperature dependence of this dark reaction has been studied. An attempt to model this behaviour in terms of a non-linear coupling between heat released, heat transfer, and reaction kinetics will be described. (author) 4 figs., 4 refs.

  13. Carbon monoxide oxidation over three different states of copper: Development of a model metal oxide catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Jernigan, Glenn Geoffrey [California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1994-10-01

    Carbon monoxide oxidation was performed over the three different oxidation states of copper -- metallic (Cu), copper (I) oxide (Cu2O), and copper (II) oxide (CuO) as a test case for developing a model metal oxide catalyst amenable to study by the methods of modern surface science and catalysis. Copper was deposited and oxidized on oxidized supports of aluminum, silicon, molybdenum, tantalum, stainless steel, and iron as well as on graphite. The catalytic activity was found to decrease with increasing oxidation state (Cu > Cu2O > CuO) and the activation energy increased with increasing oxidation state (Cu, 9 kcal/mol < Cu2O, 14 kcal/mol < CuO, 17 kcal/mol). Reaction mechanisms were determined for the different oxidation states. Lastly, NO reduction by CO was studied. A Cu and CuO catalyst were exposed to an equal mixture of CO and NO at 300--350 C to observe the production of N2 and CO2. At the end of each reaction, the catalyst was found to be Cu2O. There is a need to study the kinetics of this reaction over the different oxidation states of copper.

  14. Photochemical processes and ozone production in Finnish conditions

    Energy Technology Data Exchange (ETDEWEB)

    Laurila, T.; Hakola, H. [Finnish Meteorological Inst., Helsinki (Finland). Air Quality Dept.

    1996-12-31

    Photochemical ozone production is observed in March-September. Highest ozone concentrations and production efficiencies are observed in spring in the northern parts and in summer in the southern parts of the country. VOC concentrations are relatively low compared to continental areas in general. During the growing season a substantial part of the total reactive mass of VOCs is of biogenic origin. Large forest areas absorb ozone substantially, decreasing the ambient ozone concentrations in central and northern parts of Finland where long-range transport of ozone is relatively important compared to local production. The aim of the work conducted at Finnish Meteorological Institute has been to characterise concentrations of photochemically active species in the boundary layer and their photochemical formation and deposition including the effects on vegetation. Also interactions between the boundary layer and free troposphere of ozone have been studied. In the future, fluxes of both biogenic species and air pollutants will be measured and the models will be further developed so that the photochemical and micrometeorological processes could be better understood

  15. Photochemical Copper Coating on 3D Printed Thermoplastics

    Science.gov (United States)

    Yung, Winco K. C.; Sun, Bo; Huang, Junfeng; Jin, Yingdi; Meng, Zhengong; Choy, Hang Shan; Cai, Zhixiang; Li, Guijun; Ho, Cheuk Lam; Yang, Jinlong; Wong, Wai Yeung

    2016-08-01

    3D printing using thermoplastics has become very popular in recent years, however, it is challenging to provide a metal coating on 3D objects without using specialized and expensive tools. Herein, a novel acrylic paint containing malachite for coating on 3D printed objects is introduced, which can be transformed to copper via one-step laser treatment. The malachite containing pigment can be used as a commercial acrylic paint, which can be brushed onto 3D printed objects. The material properties and photochemical transformation processes have been comprehensively studied. The underlying physics of the photochemical synthesis of copper was characterized using density functional theory calculations. After laser treatment, the surface coating of the 3D printed objects was transformed to copper, which was experimentally characterized by XRD. 3D printed prototypes, including model of the Statue of Liberty covered with a copper surface coating and a robotic hand with copper interconnections, are demonstrated using this painting method. This composite material can provide a novel solution for coating metals on 3D printed objects. The photochemical reduction analysis indicates that the copper rust in malachite form can be remotely and photo-chemically reduced to pure copper with sufficient photon energy.

  16. Development of a photochemical reactor for the treatment of effluents in petroleum industry; Desenvolvimento de um reator fotoquimico para o tratamento de efluentes da industria do petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Mota, Andre Luis Novais; Chiavone-Filho, Osvaldo [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil); Muranaka, Cinthia Tiemi; Moraes, Jose Ermirio Ferreira de; Guardani, Roberto; Nascimento, Claudio Augusto Oller do [Universidade de Sao Paulo (USP), SP (Brazil). Dept. de Engenharia Quimica; Quina, Frank H. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica

    2004-07-01

    Advanced Oxidation Processes (AOP) have been largely studied for the treatment of wastewaters containing highly toxic organic compounds, being mainly indicated when the biologic process is inefficient. In some cases, AOP need the use of special UV lamps, which represent significant cost and electrical energy demand, consisting in the main problem related to the application these processes in industrial scale. Because this fact, the development of a photochemical reactor presenting a chip UV source is very important. In this present work, a new photochemical reactor was designed. The UV radiation source was a row of 12 fluorescent lamps (Sylvania, black light, 40 W). In these experiments, the photo-Fenton process, a combination of ferrous ions, hydrogen peroxide and UV light, was studied. This system was employed for the degradation of a simulated wastewater containing phenol as model pollutant, which presents an aromatic ring in its molecular structure, such as the BTEX group, one of the main pollutants of the petroleum industry. (author)

  17. Studies to the Field Applications of Advanced Oxidation Processes: A Case Study of Technology Transfer from Switzerland to Burkina Faso on the Field of Photochemical Detoxification of Bio recalcitrant Chemical Pollutants in Water

    International Nuclear Information System (INIS)

    Kenfack, S.; Klutse, A.; Sarria, V.; Wethe, J.; Maiga, A.H.; Cisse, G.; Pulgarin, C.

    2009-01-01

    The Fenton and photo-Fenton detoxification of non-biodegradable chemical pollution in water was investigated under simulated UV light in the laboratory and under direct sunlight in Ouagadougou, Burkina Faso. The laboratory experiments enable one to make a systematic diagnosis among three types of wastewaters, identifying a bio recalcitrant wastewater containing the Chloro-hydroxy-Pryridine (CHYPR). The application of the photo-Fenton process on effluent containing the CHYPR showed not to stimulate the generation of biodegradable by-products. Optimal conditions for detoxification of effluent containing the CHYPR were found at ph=2.8, [Fe 2+ ]=5.2 mM, initial [H 2 O 2 ]=768 mM, for an effluent concentrated at 2.2 mM of CHYPR. The application of the photochemical process on a field pilot solar photo reactor for the detoxification of water polluted with a pesticide made with Endosulfan showed very promising results, with potential biodegradable effluents obtained at the end of the photochemical treatment. Optimal conditions of the applied study were found at ph=3. [H 2 O 2 ]=8 mM and [Fe 2+ ]=0.18 mM for an initial concentration of 0.36 mM of Endosulfan.

  18. Modeling Manganese Sorption and Surface Oxidation During Filtration

    OpenAIRE

    Bierlein, Kevin Andrew

    2012-01-01

    Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the â natural greensand effect,â in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Mer...

  19. Non-photochemical Fluorescence Quenching in Photosystem II Antenna Complexes by the Reaction Center Cation Radical.

    Science.gov (United States)

    Paschenko, V Z; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Ivanov, M V; Maksimov, E G; Mamedov, M D

    2016-06-01

    In direct experiments, rate constants of photochemical (kP) and non-photochemical (kP(+)) fluorescence quenching were determined in membrane fragments of photosystem II (PSII), in oxygen-evolving PSII core particles, as well as in core particles deprived of the oxygen-evolving complex. For this purpose, a new approach to the pulse fluorometry method was implemented. In the "dark" reaction center (RC) state, antenna fluorescence decay kinetics were measured under low-intensity excitation (532 nm, pulse repetition rate 1 Hz), and the emission was registered by a streak camera. To create a "closed" [P680(+)QA(-)] RC state, a high-intensity pre-excitation pulse (pump pulse, 532 nm) of the sample was used. The time advance of the pump pulse against the measuring pulse was 8 ns. In this experimental configuration, under the pump pulse, the [P680(+)QA(-)] state was formed in RC, whereupon antenna fluorescence kinetics was measured using a weak testing picosecond pulsed excitation light applied to the sample 8 ns after the pump pulse. The data were fitted by a two-exponential approximation. Efficiency of antenna fluorescence quenching by the photoactive RC pigment in its oxidized (P680(+)) state was found to be ~1.5 times higher than that of the neutral (P680) RC state. To verify the data obtained with a streak camera, control measurements of PSII complex fluorescence decay kinetics by the single-photon counting technique were carried out. The results support the conclusions drawn from the measurements registered with the streak camera. In this case, the fitting of fluorescence kinetics was performed in three-exponential approximation, using the value of τ1 obtained by analyzing data registered by the streak camera. An additional third component obtained by modeling the data of single photon counting describes the P680(+)Pheo(-) charge recombination. Thus, for the first time the ratio of kP(+)/kP = 1.5 was determined in a direct experiment. The mechanisms of higher

  20. Photochemical organonitrate formation in wet aerosols

    Science.gov (United States)

    Lim, Yong Bin; Kim, Hwajin; Kim, Jin Young; Turpin, Barbara J.

    2016-10-01

    Water is the most abundant component of atmospheric fine aerosol. However, despite rapid progress, multiphase chemistry involving wet aerosols is still poorly understood. In this work, we report results from smog chamber photooxidation of glyoxal- and OH-containing ammonium sulfate or sulfuric acid particles in the presence of NOx and O3 at high and low relative humidity. Particles were analyzed using ultra-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS). During the 3 h irradiation, OH oxidation products of glyoxal that are also produced in dilute aqueous solutions (e.g., oxalic acids and tartaric acids) were formed in both ammonium sulfate (AS) aerosols and sulfuric acid (SA) aerosols. However, the major products were organonitrogens (CHNO), organosulfates (CHOS), and organonitrogen sulfates (CHNOS). These were also the dominant products formed in the dark chamber, indicating non-radical formation. In the humid chamber (> 70 % relative humidity, RH), two main products for both AS and SA aerosols were organonitrates, which appeared at m / z- 147 and 226. They were formed in the aqueous phase via non-radical reactions of glyoxal and nitric acid, and their formation was enhanced by photochemistry because of the photochemical formation of nitric acid via reactions of peroxy radicals, NOx and OH during the irradiation.

  1. Photo oxidative degradation of azure-B by sono-photo-Fenton and photo-Fenton reagents

    Directory of Open Access Journals (Sweden)

    Prahlad Vaishnave

    2014-12-01

    Full Text Available A model for the decomposition of azure-B by photo-Fenton reagent in the presence of ultrasound in homogeneous aqueous solution has been described. The photochemical decomposition rate of azure-B is markedly increased in the presence of ultrasound. It is a rather inexpensive reagent for wastewater treatment. The effect of different variables like the concentration of ferric ion, concentration of dye, hydrogen peroxide, pH, light intensity etc. on the reaction rate has been observed. The progress of the sono-photochemical degradation was monitored spectrophotometrically. The optimum sono-photochemical degradation conditions were experimentally determined. The results showed that the dye was completely oxidized and degraded into CO2 and H2O. A suitable tentative mechanism for sono-photochemical bleaching of azure-B by sono-photo-Fenton’s reaction has been proposed.

  2. Modeling Electronic Properties of Complex Oxides

    Science.gov (United States)

    Krishnaswamy, Karthik

    Complex oxides are a class of materials that have recently emerged as potential candidates for electronic applications owing to their interesting electronic properties. The goal of this dissertation is to develop a fundamental understanding of these electronic properties using a combination of first-principles approaches based on density functional theory (DFT), and Schrodinger-Poisson (SP) simulation (Abstract shortened by ProQuest.

  3. Ozone precursor levels and responses to emissions reductions: Analysis of regional oxidant model results

    Science.gov (United States)

    Milford, Jana B.; Gao, Dongfen; Zafirakou, Antigoni; Pierce, Thomas E.

    An analysis of results from the Regional Oxidant Modeling for Northeast Transport (ROMNET) study ( U.S. EPA, 1991, EPA-450/4-91-002a) has investigated the chemical conditions under which air quality was predicted to improve with reductions in ROG and/or NO ξ emissions, or with changes in the composition of ROG emissions. The ROMNET simulations used emissions projected to the year 2005, with meteorological conditions from July 1988. Predicted concentrations of PAN, HNO 3, H 2O 2 and HCHO are shown along with O 3 for the 2005 base case, allowing limited comparisons to be made with field observations and results from other modeling studies. Predicted secondary pollutant concentrations indicate an unusual degree of photochemical activity over much of the model domain, directionally consistent with the extreme nature of the July 1988 episode. Reducing NO ξ emissions was predicted to reduce O 3 in grid cells in which reactive nitrogen (NO y) concentrations were below about 25 ppb, but to be counterproductive for some cells with higher NO y. The New York City area where NO ξ control was predicted to be counterproductive was characterized by very high NO ξ to NO y ratios. Ozone was relatively insensitive to ROG controls in grid cells with NO y concentrations below 5-10 ppb. Comparison of unweighted ROG concentrations with concentrations weighted by HO rate constants (i.e. reactivity) showed that the latter varied less across locations. Predicted spatial gradients of NO y were generally sharper than those of reactivity-weighted ROG, supporting a dominant role for variations in NO y in controlling the sensitivity of ozone to its precursors. Reductions in reactivity-weighted ROG achieved with composition changes were similar to reductions achieved with ROG emissions cuts, explaining the similar response of ozone to these two control strategies.

  4. Model for low temperature oxidation during long term interim storage

    International Nuclear Information System (INIS)

    Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne; Poquillon, Dominique; Monceau, Daniel

    2004-01-01

    For high-level nuclear waste containers in long-term interim storage, dry oxidation will be the first and the main degradation mode during about one century. The metal lost by dry oxidation over such a long period must be evaluated with a good reliability. To achieve this goal, modelling of the oxide scale growth is necessary and this is the aim of the dry oxidation studies performed in the frame of the COCON program. An advanced model based on the description of elementary mechanisms involved in scale growth at low temperatures, like partial interfacial control of the oxidation kinetics and/or grain boundary diffusion, is developed in order to increase the reliability of the long term extrapolations deduced from basic models developed from short time experiments. Since only few experimental data on dry oxidation are available in the temperature range of interest, experiments have also been performed to evaluate the relevant input parameters for models like grain size of oxide scale, considering iron as simplified material. (authors)

  5. Water Treatment Process Intensification by Combination of Electrochemical and Photochemical Methods

    Czech Academy of Sciences Publication Activity Database

    Krystyník, Pavel; Klusoň, Petr; Tito, D.N.

    2015-01-01

    Roč. 94, SI (2015), s. 85-92 ISSN 0255-2701 R&D Projects: GA MPO(CZ) FR-TI1/065; GA TA ČR TA03010548 Institutional support: RVO:67985858 Keywords : electrocoagulation * photochemical oxidation * TOC removal Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.154, year: 2015

  6. Photochemically deoxygenating solvents for triplet-triplet annihilation photon upconversion operating in air.

    Science.gov (United States)

    Wan, Shigang; Lin, Jinxiong; Su, Huimin; Dai, Junfeng; Lu, Wei

    2018-04-03

    Sulfoxides and cyclic ureas are photochemically deoxygenating solvents in which the oxidative stress could be released and efficient triplet-triplet annihilation photon upconversion (TTA-UC) can operate in air. Such solvents can be practically screened out by harnessing the property of photo-activated phosphorescence.

  7. Air oxidation of Zircaloy, Part 2: New model for Zry-4 oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Stempniewicz, M.M., E-mail: stempniewicz@nrg.eu

    2016-05-15

    Highlights: • Recommended set of correlations proposed for air oxidation of Zircaloy-4. • New breakaway correlation for air oxidation of Zircaloy-4. • Improved accuracy of predicting air oxidation of Zircaloy-4. • Models applicable to analyses of accidents in Spent Fuel Pool. - Abstract: The accident in Fukushima brought up new issues in the area of safety of nuclear reactors. Among others, Spent Fuel Pool accidents gained new focus. The computer codes applicable for safety analyses of Nuclear Power Plants have limited verification and validation in this area and their applicability remains still to be proven. An important phenomenon occurring during loss of water in SFP is air oxidation of Zircaloy cladding material. Mathematical modeling of this phenomenon in computer codes has been under development during the last years. This document presents a review of models for air oxidation of Zircaloy, including: up to date models available in open literature, as well as models available in computer codes: ASTEC, MELCOR, and SPECTRA. The models were tested by performing simulations of a number air oxidation experiments from ANL, KIT, and IRSN. As a result of this work, a recommended set of correlations, applicable for wide range of temperatures, including pre- and post-breakaway reaction, has been selected. For the pre-breakaway (parabolic) regime the correlation of Benjamin et al. (Sandia National Laboratories, Albuquerque, NM, 1979) was selected for the low temperatures and a new correlation has been proposed for the high temperatures. For the post-breakaway (linear) regime, Boase and Vandergraaf (Nucl. Technol., 1977;32:60–71) were selected for the low temperatures and a new correlation has been proposed for the high temperatures. Furthermore, a new model for the breakaway transition has been proposed. The correlation set is applicable for Zircaloy-4, for practically the entire temperature range. The recommended set provides an improved accuracy of results

  8. Advanced methods of solid oxide fuel cell modeling

    CERN Document Server

    Milewski, Jaroslaw; Santarelli, Massimo; Leone, Pierluigi

    2011-01-01

    Fuel cells are widely regarded as the future of the power and transportation industries. Intensive research in this area now requires new methods of fuel cell operation modeling and cell design. Typical mathematical models are based on the physical process description of fuel cells and require a detailed knowledge of the microscopic properties that govern both chemical and electrochemical reactions. ""Advanced Methods of Solid Oxide Fuel Cell Modeling"" proposes the alternative methodology of generalized artificial neural networks (ANN) solid oxide fuel cell (SOFC) modeling. ""Advanced Methods

  9. Emissions from the petroleum related activity at Haltenbanken. Contribution to photochemical activity and acidification; Utslipp fra petroleumsrelatert aktivitet paa Haltenbanken. Bidrag til fotokjemisk oksidantdannelse og forsuring

    Energy Technology Data Exchange (ETDEWEB)

    Knudsen, S.; Johnsrud, M.; Solberg, S.; Walker, S.E.; Skjelkvaale, B.L.

    1996-01-01

    This work includes studies of effects from emissions of nitrogen oxides and hydrocarbons from Haltenbanken (Draugen, Heidrun, Njord, Norne) and Aasgard. It includes estimates of photochemical activity, air quality and deposition. 6 refs., 8 figs., 10 tabs.

  10. Single sheet iron oxides

    DEFF Research Database (Denmark)

    Yin, Zhou

    activity. LDH single sheets have been reported to be effective sorbents, catalysts in electrochemical and photochemical reactions, and building thin films together with other nanomaterials for designing new functionalities. Here we focus on the delamination of FeII-FeIII LDHs into single sheet iron oxide...... was rapid compared to other iron oxides, reaching equilibrium within 60 minutes. Arsenic sorption and acid-base titration data could be successfully described with a 1pk Basic Stern Model (BSM). The point of zero charge was around 8. The intrinsic surface complexation equilibrium constants (log K...... became abundant at low pH. (3) Electrochemical reduction of chlorinated compounds using an SSI modified electrode. Here, the electrochemical reactivity of SSIs coated on indium tin oxide coated glass electrodes was investigated. Iron on the SSI modified electrode showed a typical Cyclic Voltammetry...

  11. Assessing the poplar photochemical response to high zinc concentrations by image processing and statistical approach.

    Science.gov (United States)

    Sighicelli, Maria; Guarneri, Massimiliano

    2014-12-01

    Exposure of plants to high-heavy metals concentration inhibits multiple metabolic processes in plants and leads to an oxidative stress commonly referred as heavy metal ion toxicity. Chlorophyll a fluorescence has enhanced understanding of heavy metal ion action on the photosynthetic system. A rapid and non-invasive technique involving imaging of chlorophyll fluorescence is a useful tool for early detection of plant responses to heavy metal ion toxicity. In this work chlorophyll fluorescence emission and photochemical parameters in plants of Populus x euramericana clone I-214 were investigated by the portable Imaging PAM fluorometer at different days after soil treatment with zinc. Custom software for analysis of the photochemical parameters images has been developed in order to gain a better assessing of the plant performance in response of metal stress. The imaging analysis allowed visualizing heterogeneity in plant response to high zinc concentrations. The heterogeneity of images suggests spatial differences in photochemical activity and changes in the antenna down-regulation.

  12. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5-23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  13. Simplified kinetic models of methanol oxidation on silver

    DEFF Research Database (Denmark)

    Andreasen, Anders; Lynggaard, Hasse Harloff; Stegelmann, Carsten

    2005-01-01

    Recently the authors developed a microkinetic model of methanol oxidation on silver [A. Andreasen, H. Lynggaard, C. Stegelmann, P. Stoltze, Surf. Sci. 544 (2003) 5–23]. The model successfully explains both surface science experiments and kinetic experiments at industrial conditions applying...

  14. A mechanistic model on methane oxidation in the rice rhizosphere

    NARCIS (Netherlands)

    Bodegom, van P.M.; Leffelaar, P.A.; Goudriaan, J.

    2001-01-01

    A mechanistic model is presented on the processes leading to methane oxidation in rice rhizosphere. The model is driven by oxygen release from a rice root into anaerobic rice soil. Oxygen is consumed by heterotrophic and methanotrophic respiration, described by double Monod kinetics, and by iron

  15. Redox reaction in photochemical and ionizing irradiation systems

    International Nuclear Information System (INIS)

    Slama-Schwok, A.

    1985-09-01

    This work presents a basic study of electron transfer reactions which could be involved in appropriate systems for photochemical conversion and storage of solar energy. The aim was to extend the knowledge to new photosensitizers and quenchers and to compare them with the most popular photosensitizers-quenchers system, i.e. a rubidium complex. The photosensitizer studied here is an irridium complex. We studied in this work the air oxidation of bromide to Br 3 - and H 2 O 2 using the irridium complex as the sensitizer. The reducing properties of the reduced irridium complex photosensitizer were studied, using the pulse radiolysis techniques. In conclusion, the oxidation reduction properties of the irridium and its lowest excited state correspond to most of the photosensitizer for electron transfer reactions. The energy temporary present in the charge separation products can be stored using appropriate environment such as polyelectrolytes

  16. Modeling of thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode

    Science.gov (United States)

    Heydari, F.; Maghsoudipour, A.; Alizadeh, M.; Khakpour, Z.; Javaheri, M.

    2015-09-01

    Artificial intelligence models have the capacity to eliminate the need for expensive experimental investigation in various areas of manufacturing processes, including the material science. This study investigates the applicability of adaptive neuro-fuzzy inference system (ANFIS) approach for modeling the performance parameters of thermal expansion coefficient (TEC) of perovskite oxide for solid oxide fuel cell cathode. Oxides (Ln = La, Nd, Sm and M = Fe, Ni, Mn) have been prepared and characterized to study the influence of the different cations on TEC. Experimental results have shown TEC decreases favorably with substitution of Nd3+ and Mn3+ ions in the lattice. Structural parameters of compounds have been determined by X-ray diffraction, and field emission scanning electron microscopy has been used for the morphological study. Comparison results indicated that the ANFIS technique could be employed successfully in modeling thermal expansion coefficient of perovskite oxide for solid oxide fuel cell cathode, and considerable savings in terms of cost and time could be obtained by using ANFIS technique.

  17. Influence of the Radio-Oxidation Kinetic Model on the Critical Oxided Thickness

    International Nuclear Information System (INIS)

    Dely, N

    2006-01-01

    The diffusion-controlled oxidation (also named physical effect of the dose rate) is an unavoidable phenomenon that occurs in polymers under ionising radiation in presence of oxygen. Indeed, oxygen is consumed inside the polymer consecutively to radio-oxidative processes. When oxygen molecules are consumed faster than they can diffuse inside the sample, oxidation is not homogeneous within the sample thickness. This leads to a heterogeneous oxidation profile with a minimum of oxidation at the centre of the sample. In this context, the concept of critical thickness L c has been introduced. It corresponds to the thickness for which the cumulative oxygen consumption is equal to 90 % of the oxygen consumption which would occur if the oxidation was not limited by the oxygen diffusion. Gillen and Clough have determined a practical way to estimate the value of L c from several parameters linked to the experimental conditions in the frame of the homogeneous steady?state kinetic model simplified by a relation giving the reaction constant for the recombination between the macroradicals, P degree and the peroxyl radicals, POO degree. This common assumption has the unique purpose of providing an analytical solution of the oxidation rate but is in fact unfounded. Consequently, we reconsidered the calculus, still in the frame of the homogeneous steady-state kinetic model, but without this unrealistic hypothesis on the reaction rate between P degree and POO degree. We compared the results obtained in both cases. And it appears that, exception made of the very low oxygen pressure region, L c is not significantly affected by choosing the simplified kinetic model

  18. Developments in kinetic modelling of chalcocite particle oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Jaervi, J.; Ahokainen, T.; Jokilaakso, A. [Helsinki Univ. of Technology, Otaniemi (Finland). Lab. of Materials Processing and Powder Metallurgy

    1997-12-31

    A mathematical model for simulating chalcocite particle oxidation is presented. Combustion of pure chalcocite with oxygen is coded as a kinetic module which can be connected as a separate part of commercial CFD-package, PHOENICS. Heat transfer, fluid flow and combustion phenomena can be simulated using CFD-calculation together with the kinetic model. Interaction between gas phase and particles are taken into account by source terms. The aim of the kinetic model is to calculate the particle temperature, contents of species inside the particle, oxygen consumption and formation of sulphur dioxide. Four oxidation reactions are considered and the shrinking core model is used to describe the rate of the oxidation reactions. The model is verified by simulating the particle oxidation reactions in a laboratory scale laminar-flow furnace under different conditions and the model predicts the effects of charges correctly. In the future, the model validation will be done after experimental studies in the laminar flow-furnace. (author) 18 refs.

  19. Modeling the photochemical attenuation of down-the-drain chemicals during river transport by stochastic methods and field measurements of pharmaceuticals and personal care products.

    Science.gov (United States)

    Hanamoto, Seiya; Nakada, Norihide; Yamashita, Naoyuki; Tanaka, Hiroaki

    2013-01-01

    Existing stochastic models for predicting concentrations of down-the-drain chemicals in aquatic environments do not account for the diurnal variation of direct photolysis by sunlight, despite its being an important factor in natural attenuation. To overcome this limitation, we developed a stochastic model incorporating temporal variations in direct photolysis. To verify the model, we measured 57 pharmaceuticals and personal care products (PPCPs) in a 7.6-km stretch of an urban river, and determined their physical and biological properties in laboratory experiments. During transport along the river, 8 PPCPs, including ketoprofen and azithromycin, were attenuated by >20%, mainly owing to direct photolysis and adsorption to sediments. The photolabile PPCPs attenuated significantly in the daytime but persisted in the nighttime. The observations were similar to the values predicted by the photolysis model for the photolabile PPCPs (i.e., ketoprofen, diclofenac and furosemide) but not by the existing model. The stochastic model developed in this study was suggested to be a novel and useful stochastic model for evaluating direct photolysis of down-the-drain chemicals, which occurs during the river transport.

  20. Detailed chemical kinetic modeling of cyclohexane oxidation.

    Science.gov (United States)

    Silke, Emma J; Pitz, William J; Westbrook, Charles K; Ribaucour, Marc

    2007-05-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Rules for reaction rate constants are developed for the low-temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Because cyclohexane produces only one type of cyclohexyl radical, much of the low-temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical with O2 through five-, six-, and seven-membered-ring transition states. The direct elimination of cyclohexene and HO2 from RO2 is included in the treatment using a modified rate constant of Cavallotti et al. (Proc. Combust. Inst. 2007, 31, 201). Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data, are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments cannot be simulated according to the current understanding of low-temperature chemistry. Possible "alternative" H-atom isomerizations leading to different products from the parent O2QOOH radical were included in the low-temperature chemical kinetic mechanism and were found to play a significant role.

  1. Can polymer thermal oxidative ageing be modelled?

    International Nuclear Information System (INIS)

    Audouin, L.; Colin, X.; Fayolle, B.; Richaud, E.; Verdu, J.

    2010-01-01

    It has been supposed, for a long time, that kinetic modelling of polymer ageing for nonempirical lifetime prediction was out of reach for two main reasons: hyper-complexity of mechanisms and heterogeneity of reactions. The arguments relative to both aspects are examined here. It is concluded that, thanks to recent advances, especially the introduction of numerical methods, kinetic modelling is possible in various important practical cases. (authors)

  2. CLASSICAL AREAS OF PHENOMENOLOGY: Photochemical kinetics for holographic grating formation in phenanthrenequinone doped poly (methyl methacrylate) photopolymer

    Science.gov (United States)

    Wang, Jian; Sun, Xiu-Dong; Luo, Su-Hua; Jiang, Yong-Yuan; Meng, Qing-Xin

    2009-10-01

    The photochemical kinetics of phenanthrenequinone (PQ) doped poly (methyl methacrylate) photopolymer in holographic recording was studied theoretically and experimentally. The diffusion of PQ molecules during holographic recording was negligible because of its small diffusion coefficient at room temperature. A photochemical reaction kinetics model of PQ/PMMA was established. The analytical expressions for the temporal variations of transmittance and diffraction efficiency were derived. By fitting the experimental curves, some parameters related with the polymer components were obtained by the proposed model, which can be used to analyze the photochemical process and will be helpful to the optimization of material preparation.

  3. Modeling the viscosity of silicate melts containing manganese oxide

    Directory of Open Access Journals (Sweden)

    Kim Wan-Yi

    2013-01-01

    Full Text Available Our recently developed model for the viscosity of silicate melts is applied to describe and predict the viscosities of oxide melts containing manganese oxide. The model requires three pairs of adjustable parameters that describe the viscosities in three systems: pure MnO, MnO-SiO2 and MnO-Al2O3-SiO2. The viscosity of other ternary and multicomponent silicate melts containing MnO is then predicted by the model without any additional adjustable model parameters. Experimental viscosity data are reviewed for melts formed by MnO with SiO2, Al2O3, CaO, MgO, PbO, Na2O and K2O. The deviation of the available experimental data from the viscosities predicted by the model is shown to be within experimental error limits.

  4. Do Photochemical Hazes Cloud the Atmosphere of 51 Eri b?

    Science.gov (United States)

    Marley, Mark; Zahnle, Kevin; Moses, Julianne; Morley, Caroline

    2015-12-01

    The first young giant planet to be discovered by the Gemini Planet Imager was the ~ 2MJ planet 51 Eri b. This ~20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet’s mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. In the atmosphere of an object as cool as 700 K the global silicate and iron clouds would be expected to be found well below the photosphere, although strong vertical mixing in the low gravity atmosphere is a possibility. Instead, clouds of Na2S, as have been detected in brown dwarf atmospheres, are a likely source of particle opacity. As a third explanation we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. We also have explored whether photochemical products can alter the equilibrium temperature profile of the atmosphere. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet’s effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.

  5. Metal assisted photochemical etching of 4H silicon carbide

    Science.gov (United States)

    Leitgeb, Markus; Zellner, Christopher; Schneider, Michael; Schwab, Stefan; Hutter, Herbert; Schmid, Ulrich

    2017-11-01

    Metal assisted photochemical etching (MAPCE) of 4H-silicon carbide (SiC) in Na2S2O8/HF and H2O2/HF aqueous solutions is investigated with platinum as metallic cathode. The formation process of the resulting porous layer is studied with respect to etching time, concentration and type of oxidizing agent. From the experiments it is concluded that the porous layer formation is due to electron hole pairs generated in the semiconductor, which stem from UV light irradiation. The generated holes are consumed during the oxidation of 4H-SiC and the formed oxide is dissolved by HF. To maintain charge balance, the oxidizing agent has to take up electrons at the Pt/etching solution interface. Total dissolution of the porous layers is achieved when the oxidizing agent concentration decreases during MAPCE. In combination with standard photolithography, the definition of porous regions is possible. Furthermore chemical micromachining of 4 H-SiC at room temperature is possible.

  6. Quantum Chemical Modeling of Homogeneous Water Oxidation Catalysis.

    Science.gov (United States)

    Liao, Rong-Zhen; Siegbahn, Per E M

    2017-11-23

    The design of efficient and robust water oxidation catalysts has proven challenging in the development of artificial photosynthetic systems for solar energy harnessing and storage. Tremendous progress has been made in the development of homogeneous transition-metal complexes capable of mediating water oxidation. To improve the efficiency of the catalyst and to design new catalysts, a detailed mechanistic understanding is necessary. Quantum chemical modeling calculations have been successfully used to complement the experimental techniques to suggest a catalytic mechanism and identify all stationary points, including transition states for both O-O bond formation and O 2 release. In this review, recent progress in the applications of quantum chemical methods for the modeling of homogeneous water oxidation catalysis, covering various transition metals, including manganese, iron, cobalt, nickel, copper, ruthenium, and iridium, is discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Photochemical model evaluation of the ground-level ozone impacts on ambient air quality and vegetation health in the Alberta oil sands region: Using present and future emission scenarios

    Science.gov (United States)

    Vijayaraghavan, Krish; Cho, Sunny; Morris, Ralph; Spink, David; Jung, Jaegun; Pauls, Ron; Duffett, Katherine

    2016-09-01

    One of the potential environmental issues associated with oil sands development is increased ozone formation resulting from NOX and volatile organic compound emissions from bitumen extraction, processing and upgrading. To manage this issue in the Athabasca Oil Sands Region (AOSR) in northeast Alberta, a regional multi-stakeholder group, the Cumulative Environmental Management Association (CEMA), developed an Ozone Management Framework that includes a modelling based assessment component. In this paper, we describe how the Community Multi-scale Air Quality (CMAQ) model was applied to assess potential ground-level ozone formation and impacts on ambient air quality and vegetation health for three different ozone precursor cases in the AOSR. Statistical analysis methods were applied, and the CMAQ performance results met the U.S. EPA model performance goal at all sites. The modelled 4th highest daily maximum 8-h average ozone concentrations in the base and two future year scenarios did not exceed the Canada-wide standard of 65 ppb or the newer Canadian Ambient Air Quality Standards of 63 ppb in 2015 and 62 ppb in 2020. Modelled maximum 1-h ozone concentrations in the study were well below the Alberta Ambient Air Quality Objective of 82 ppb in all three cases. Several ozone vegetation exposure metrics were also evaluated to investigate the potential impact of ground-level ozone on vegetation. The chronic 3-months SUM60 exposure metric is within the CEMA baseline range (0-2000 ppb-hr) everywhere in the AOSR. The AOT40 ozone exposure metric predicted by CMAQ did not exceed the United Nations Economic Commission for Europe (UN/ECE) threshold of concern of 3000 ppb-hr in any of the cases but is just below the threshold in high-end future emissions scenario. In all three emission scenarios, the CMAQ predicted W126 ozone exposure metric is within the CEMA baseline threshold of 4000 ppb-hr. This study outlines the use of photochemical modelling of the impact of an industry (oil

  8. Diagnosis of Photochemical Ozone Production Rates and Limiting Factors based on Observation-based Modeling Approach over East Asia: Impact of Radical Chemistry Mechanism and Ozone-Control Implications

    Science.gov (United States)

    Kanaya, Y.

    2015-12-01

    Growth of tropospheric ozone, causing health and climate impacts, is concerned over East Asia, because emissions of precursors have dramatically increased. Photochemical production rates of ozone and limiting factors, primarily studied for urban locations, have been poorly assessed within a perspective of regional-scale air pollution over East Asia. We performed comprehensive observations of ozone precursors at several locations with regional representativeness and made such assessment based on the observation-based modeling approach. Here, diagnosis at Fukue Island (32.75°N, 128.68°E) remotely located in western Japan (May 2009) is highlighted, where the highest 10% of hourly ozone concentrations reached 72‒118 ppb during May influenced by Asian continental outflow. The average in-situ ozone production rate was estimated to be 6.8 ppb per day, suggesting that in-travel production was still active, while larger buildup must have occurred beforehand. Information on the chemical status of the air mass arriving in Japan is important, because it affects how further ozone production occurs after precursor addition from Japanese domestic emissions. The main limiting factor of ozone production was usually NOx, suggesting that domestic NOx emission control is important in reducing further ozone production and the incidence of warning issuance (>120 ppb). VOCs also increased the ozone production rate, and occasionally (14% of time) became dominant. This analysis implies that the VOC reduction legislation recently enacted should be effective. The uncertainty in the radical chemistry mechanism governing ozone production had a non-negligible impact, but the main conclusion relevant to policy was not altered. When chain termination was augmented by HO2-H2O + NO/NO2 reactions and by heterogeneous loss of HO2 on aerosol particle surfaces, the daily ozone production rate decreased by <24%, and the fraction of hours when the VOC-limited condition occurred varied from 14% to 13

  9. Oxide-supported metal clusters: models for heterogeneous catalysts

    International Nuclear Information System (INIS)

    Santra, A K; Goodman, D W

    2003-01-01

    Understanding the size-dependent electronic, structural and chemical properties of metal clusters on oxide supports is an important aspect of heterogeneous catalysis. Recently model oxide-supported metal catalysts have been prepared by vapour deposition of catalytically relevant metals onto ultra-thin oxide films grown on a refractory metal substrate. Reactivity and spectroscopic/microscopic studies have shown that these ultra-thin oxide films are excellent models for the corresponding bulk oxides, yet are sufficiently electrically conductive for use with various modern surface probes including scanning tunnelling microscopy (STM). Measurements on metal clusters have revealed a metal to nonmetal transition as well as changes in the crystal and electronic structures (including lattice parameters, band width, band splitting and core-level binding energy shifts) as a function of cluster size. Size-dependent catalytic reactivity studies have been carried out for several important reactions, and time-dependent catalytic deactivation has been shown to arise from sintering of metal particles under elevated gas pressures and/or reactor temperatures. In situ STM methodologies have been developed to follow the growth and sintering kinetics on a cluster-by-cluster basis. Although several critical issues have been addressed by several groups worldwide, much more remains to be done. This article highlights some of these accomplishments and summarizes the challenges that lie ahead. (topical review)

  10. Modelling toluene oxidation : Incorporation of mass transfer phenomena

    NARCIS (Netherlands)

    Hoorn, J.A.A.; van Soolingen, J.; Versteeg, G. F.

    The kinetics of the oxidation of toluene have been studied in close interaction with the gas-liquid mass transfer occurring in the reactor. Kinetic parameters for a simple model have been estimated on basis of experimental observations performed under industrial conditions. The conclusions for the

  11. Modelling the change in the oxidation coefficient during the aerobic ...

    African Journals Online (AJOL)

    In this work the aerobic degradation of phenol by acclimated activated sludge was studied. Results demonstrate that while the phenol removal rate by acclimated activated sludge follows the Monod model, the oxygen uptake rate obeys a Haldane-type equation. The phenol oxidation coefficient obtained at different intial ...

  12. Animation Model to Conceptualize ATP Generation: A Mitochondrial Oxidative Phosphorylation

    Science.gov (United States)

    Jena, Ananta Kumar

    2015-01-01

    Adenosine triphosphate (ATP) is the molecular unit of intracellular energy and it is the product of oxidative phosphorylation of cellular respiration uses in cellular processes. The study explores the growth of the misconception levels amongst the learners and evaluates the effectiveness of animation model over traditional methods. The data…

  13. Impedance Modeling of Solid Oxide Fuel Cell Cathodes

    DEFF Research Database (Denmark)

    Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

    2010-01-01

    A 1-dimensional impedance model for a solid oxide fuel cell cathode is formulated and applied to a cathode consisting of 50/50 wt% strontium doped lanthanum cobaltite and gadolinia doped ceria. A total of 42 impedance spectra were recorded in the temperature range: 555-852°C and in the oxygen...

  14. On the origin of the ionosphere at Moon : a study using results from Chandrayaan-I S-band radio occultation experiment and a photochemical model

    Science.gov (United States)

    Kailasam Madathil, Ambili; Bhardwaj, Anil; Choudhary, Raj Kumar

    2016-07-01

    Using Chandrayaan-1 communication link between orbiter and ground (S-band frequency), the presence of ionosphere at Moon has been explored using Radio Occultation technique. Results obtained from the observations conducted between July 30 and August 14, 2009 show evidence for a possible existence of the Ionosphere at Moon. A few seconds before the occultation of Chandrayaan-1 radio signals, extra fluctuation in the rate of change of difference between the theoretically estimated Doppler and observed Doppler was observed. The fluctuation was more pronounced when the probing radio waves were crossing through the day-night terminator. Using standard onion-peeling technique to invert the phase changes in radio signals to the refractivity of the medium, we estimated the bending angle and hence the electron density profiles for the Lunar medium. The estimated electron density near the Lunar surface was of the order of 400 - 1000 cm ^{-3} which decreased monotonically with increasing altitude till about 40 km above the surface where it became negligible. The observed electron density was compared with the results from a model which was developed based on CHACE measurements abroad Moon Impact Probe of Chandrayaan-I. The model included the photo chemical reactions and solar wind interactions of the lunar plasma. We propose that the ionosphere over Moon could have molecular origin with H _{2}O ^{+},CO_{2} ^{+} and H_{3}O ^{+} as dominant ions.

  15. Advanced impedance modeling of solid oxide electrochemical cells

    DEFF Research Database (Denmark)

    Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Impedance spectroscopy is a powerful technique for detailed study of the electrochemical and transport processes that take place in fuel cells and electrolysis cells, including solid oxide cells (SOCs). Meaningful analysis of impedance measurements is nontrivial, however, because a large number...... techniques to provide good guesses for the modeling parameters, like transforming the impedance data to the distribution of relaxation times (DRT), together with experimental parameter sensitivity studies, is the state-of-the-art approach to achieve good EC model fits. Here we present new impedance modeling......) constraining the parameter values during fitting to ranges of physically reasonable values. Using these methods, the number of fitting parameters for four impedance spectra measured with isolated changes to the fuel and oxidant gas compositions, has been reduced from 80 to 21-34 depending on the model...

  16. Photochemical Transformation Processes in Sunlit Surface Waters (Invited)

    Science.gov (United States)

    Vione, D.

    2013-12-01

    Photochemical reactions are major processes in the transformation of hardly biodegradable xenobiotics in surface waters. They are usually classified into direct photolysis and indirect or sensitised degradation. Direct photolysis requires xenobiotic compounds to absorb sunlight, and to get transformed as a consequence. Sensitised transformation involves reaction with transient species (e.g. °OH, CO3-°, 1O2 and triplet states of chromophoric dissolved organic matter, 3CDOM*), photogenerated by so-called photosensitisers (nitrate, nitrite and CDOM). CDOM is a major photosensitiser: is it on average the main source of °OH (and of CO3-° as a consequence, which is mainly produced upon oxidation by °OH of carbonate and bicarbonate) and the only important source of 1O2 and 3CDOM* [1, 2]. CDOM origin plays a key role in sensitised processes: allochthonous CDOM derived from soil runoff and rich in fulvic and humic substances is usually more photoactive than autochthonous CDOM (produced by in-water biological processes and mainly consisting of protein-like material) or of CDOM derived from atmospheric deposition. An interesting gradual evolution of CDOM origin and photochemistry can be found in mountain lakes across the treeline, which afford a gradual transition of allochthonous- autochtonous - atmopheric CDOM when passing from trees to alpine meadows to exposed rocks [3]. Another important issue is the sites of reactive species photoproduction in CDOM. While there is evidence that smaller molecular weight fractions are more photoactive, some studies have reported considerable 1O2 reactivity in CDOM hydrophobic sites and inside particles [4]. We have recently addressed the problem and found that dissolved species in standard humic acids (hydrodynamic diameter pollutants to be assessed and modelled. For instance, it is possible to predict pollutant half-life times by knowing absorption spectrum, direct photolysis quantum yield and reaction rate constants with °OH, CO3

  17. Oxidative stress of crystalline lens in rat menopausal model

    OpenAIRE

    Acer, Semra; Pekel, Gökhan; Küçükatay, Vural; Karabulut, Aysun; Yağcı, Ramazan; Çetin, Ebru Nevin; Akyer, Şahika Pınar; Şahin, Barbaros

    2016-01-01

    ABSTRACT Purpose: To evaluate lenticular oxidative stress in rat menopausal models. Methods: Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1). From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2), 10 were administered a daily injection of methylprednisolone until the end of the study (Gro...

  18. Model catalytic oxidation studies using supported monometallic and heterobimetallic oxides. Progress report, August 1, 1991--January 31, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Ekerdt, J.G.

    1992-02-03

    This research program is directed toward a more fundamental understanding of the effects of catalyst composition and structure on the catalytic properties of metal oxides. Metal oxide catalysts play an important role in many reactions bearing on the chemical aspects of energy processes. Metal oxides are the catalysts for water-gas shift reactions, methanol and higher alcohol synthesis, isosynthesis, selective catalytic reduction of nitric oxides, and oxidation of hydrocarbons. A key limitation to developing insight into how oxides function in catalytic reactions is in not having precise information of the surface composition under reaction conditions. To address this problem we have prepared oxide systems that can be used to study cation-cation effects and the role of bridging (-O-) and/or terminal (=O) surface oxygen anion ligands in a systematic fashion. Since many oxide catalyst systems involve mixtures of oxides, we selected a model system that would permit us to examine the role of each cation separately and in pairwise combinations. Organometallic molybdenum and tungsten complexes were proposed for use, to prepare model systems consisting of isolated monomeric cations, isolated monometallic dimers and isolated bimetallic dimers supported on silica and alumina. The monometallic and bimetallic dimers were to be used as models of more complex mixed- oxide catalysts. Our current program was to develop the systems and use them in model oxidation reactions.

  19. SOME REACTIONS OF OXYGEN ATOMS. VOLUME II: ETHYLENE OXIDE, DIMETHYL ETHER, N-C4H10, N-C7H16, AND ISOOCTANE.

    Science.gov (United States)

    REACTION KINETICS, OXYGEN), PRODUCTION, DECOMPOSITION, NITROGEN COMPOUNDS, OXIDES, PHOTOCHEMICAL REACTIONS, MERCURY, EXCITATION, PROPENES, FLUORINE COMPOUNDS, ETHYLENE OXIDE , ETHERS, BUTANES, ALKANES, INFRARED SPECTRA.

  20. A model of pyritic oxidation in waste rock dumps

    International Nuclear Information System (INIS)

    Davis, G.B.; Ritchie, A.I.M.

    1983-01-01

    The oxidation of pyrite can lead to high acid levels and high concentrations of trace metals in the water that runs off and percolates through pyritic material. This is the situation at the abandoned uranium mine at Rum Jungle in the Northern Territory of Australia, where pyritic oxidation in the waste rock dumps resulting from open cut mining of the uranium orebody has led to pollution of the nearby East Branch of the Finniss River, with trace metals such as copper, manganese and zinc. Mathematical equations are formulated which describe a model of pyritic oxidation within a waste rock dump, where it is assumed that oxygen transport is the rate limiting step in the oxidation process and that oxygen is transported by gaseous diffusion through the pore space of the dump, followed by diffusion into oxidation sites within the particles that comprise the dump. The equations have been solved numerically assuming values for such parameters as porosity, sulphur density and oxygen diffusion coefficients which are applicable to the waste rock dumps at Rum Jungle. An approximate solution to the equations is also presented. Calculations of the heat source distribution and the total SO 4 production rate are presented for both single size particles and for a range of particle sizes in the dump. The usefulness of the approximate solution, and of calculations based on single size particles in the dump in assessing the effectiveness of strategies to reduce pollution from such waste rock dumps are discussed

  1. A photochemically driven molecular-level abacus

    Science.gov (United States)

    Ashton; Ballardini; Balzani; Credi; Dress; Ishow; Kleverlaan; Kocian; Preece; Spencer; Stoddart; Venturi; Wenger

    2000-10-02

    sequence of photoinduced electron transfer processes? In order to find an answer to this question, the electrochemical, photophysical, and photochemical (under continuous and pulsed excitation) properties of the [2]rotaxane, its dumbbell-shaped component, and some model compounds containing electro- and photoactive units have been investigated. In an attempt to obtain the photoinduced abacus-like movement of the BPP34C10 macrocycle between the two stations, two strategies have been employed-one was based fully on processes that involved only the rotaxane components (intramolecular mechanism), while the other one required the help of external reactants (sacrificial mechanism). Both mechanisms imply a sequence of four steps (destabilization of the stable translational isomer, macrocyclic ring displacement, electronic reset, and nuclear reset) that have to compete with energy-wasteful steps. The results have demonstrated that photochemically driven switching can be performed successfully by the sacrificial mechanism, whereas, in the case of the intramolecular mechanism, it would appear that the electronic reset of the system is faster than the ring displacement.

  2. Photochemical welding of silica microspheres to silicone rubber by ArF excimer laser

    Science.gov (United States)

    Okoshi, Masayuki; Iyono, Minako; Inoue, Narumi; Yamashita, Tsugito

    2009-09-01

    Transparent fused silica (SiO 2) microspheres 2.5 μm in diameter were photochemically welded to transparent, flexible silicone rubber ([SiO(CH 3) 2] n) substrate by 193 nm ArF excimer laser induced photochemical modification of silicone into silicon oxide. Single layer of silica microspheres was easily formed on an adhesive silicone rubber before laser irradiation after dropping of silica microspheres dispersed in ethanol and subsequent tape peeling. The welding rate, the percentage of welded microspheres tested by ultrasonic cleaning with ethanol, was examined by varying the single pulse fluence and irradiation time of ArF excimer laser. The welding layer underneath microsphere, silicon oxide, was also found to emit white light of strong intensity under UV light illumination.

  3. A modelling approach for the heterogeneous oxidation of elastomers

    Science.gov (United States)

    Herzig, A.; Sekerakova, L.; Johlitz, M.; Lion, A.

    2017-09-01

    The influence of oxygen on elastomers, known as oxidation, is one of the most important ageing processes and becomes more and more important for nowadays applications. The interaction with thermal effects as well as antioxidants makes oxidation of polymers a complex process. Based on the polymer chosen and environmental conditions, the ageing processes may behave completely different. In a lot of cases the influence of oxygen is limited to the surface layer of the samples, commonly referred to as diffusion-limited oxidation. For the lifetime prediction of elastomer components, it is essential to have detailed knowledge about the absorption and diffusion behaviour of oxygen molecules during thermo-oxidative ageing and how they react with the elastomer. Experimental investigations on industrially used elastomeric materials are executed in order to develop and fit models, which shall be capable of predicting the permeation and consumption of oxygen as well as changes in the mechanical properties. The latter are of prime importance for technical applications of rubber components. Oxidation does not occur homogeneously over the entire elastomeric component. Hence, material models which include ageing effects have to be amplified in order to consider heterogeneous ageing, which highly depends on the ageing temperature. The influence of elevated temperatures upon accelerated ageing has to be critically analysed, and influences on the permeation and diffusion coefficient have to be taken into account. This work presents phenomenological models which describe the oxygen uptake and the diffusion into elastomers based on an improved understanding of ongoing chemical processes and diffusion limiting modifications. On the one side, oxygen uptake is modelled by means of Henry's law in which solubility is a function of the temperature as well as the ageing progress. The latter is an irreversible process and described by an inner differential evolution equation. On the other side

  4. The influence of aerosols on photochemical smog in Mexico City

    Energy Technology Data Exchange (ETDEWEB)

    Castro, T.; Mar, B. [UNAM, Mexico, Centro de Ciencias de la Atmosfera (Mexico); Madronich, S.; Rivale, S. [National Center for Atmospheric Research, Boulder, CO (United States); Muhlia, A. [UNAM, Mexico, Inst. de Geofysica (Mexico)

    2001-04-01

    Aerosols in the Mexico City atmosphere can have a non-negligible effect on the ultraviolet radiation field and hence on the formation of photochemical smog. We used estimates of aerosol optical depths from sun photometer observations in a detailed radiative transfer model, to calculate photolysis rate coefficients (J{sub NO2}) for the key reaction NO{sub 2}+h{nu}{yields}NO+O ({lambda}<430nm). The calculated values are in good agreement with previously published measurements of J{sub NO2} at two sites in Mexico City: Palacio de Mineria (19 degrees 25'59''N, 99 degrees 07'58''W, 2233masl), and IMP (19 degrees 28'48''N, 99 degrees 11'07''W, 2277masl) and in Tres Marias, a town near Mexico City (19 degrees 03'N, 99 degrees 14'W, 2810masl). In particular, the model reproduces very well the contrast between the two urban sites and the evidently much cleaner Tres Marias site. For the measurement days, reductions in surface J{sub NO2} by 10-30% could be attributed to the presence of aerosols, with considerable uncertainty due largely to lack of detailed data on aerosol optical properties at ultraviolet wavelengths (esp. the single scattering albedo). The potential impact of such large reductions in photolysis rates on surface ozone concentrations is illustrated with a simple zero-dimensional photochemical model. (Author)

  5. Modelling cloud effects on ozone on a regional scale : A case study

    NARCIS (Netherlands)

    Matthijsen, J.; Builtjes, P.J.H.; Meijer, E.W.; Boersen, G.

    1997-01-01

    We have investigated the influence of clouds on ozone on a regional scale (Europe) with a regional scale photochemical dispersion model (LOTOS). The LOTOS-model calculates ozone and other photo-oxidant concentrations in the lowest three km of the troposphere, using actual meteorologic data and

  6. Photochemical Haze Formation in the Atmospheres of Super-Earths and Mini-Neptunes

    Science.gov (United States)

    He, Chao; Hoerst, Sarah M.; Lewis, Nikole K.; Yu, Xinting; Moses, Julianne I.; Kempton, Eliza M.- R.; Marley, Mark S.; McGuiggan, Patricia; Morley, Caroline V.; Valenti, Jeff A.; hide

    2018-01-01

    UV (ultraviolet) radiation can induce photochemical processes in the atmospheres of exoplanet and produce haze particles. Recent transmission spectra of super-Earths and mini-Neptunes have demonstrated the possibility that exoplanets have haze/cloud layers at high altitudes in their atmospheres. Haze particles play an important role in planetary atmospheres because they affect the chemistry, dynamics, and radiation flux in planetary atmospheres, and may provide a source of organic material to the surface which may impact the origin or evolution of life. However, very little information is known about photochemical processes in cool, high-metallicity exoplanetary atmospheres. We present here photochemical haze formation in laboratory simulation experiments with UV radiation; we explored temperatures ranging from 300 to 600 degrees Kelvin and a range of atmospheric metallicities (100 times, 1000 times, and 10000 times solar metallicity). We find that photochemical hazes are generated in all simulated atmospheres, but the haze production rates appear to be temperature dependent: the particles produced in each metallicity group decrease as the temperature increases. The images taken with an atomic force microscope (AFM) show that the particle size (15 nanometers to 190 nanometers) varies with temperature and metallicity. Our results provide useful laboratory data on the photochemical haze formation and particle properties, which can serve as critical inputs for exoplanet atmosphere modeling, and guide future observations of exoplanets with the Transiting Exoplanet Survey Satellite (TESS), the James Webb Space Telescope (JWST), and the Wide-Field Infrared Survey Telescope (WFIRST).

  7. Laboratory Experiments and Modeling for Interpreting Field Studies of Secondary Organic Aerosol Formation Using an Oxidation Flow Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Jimenez, Jose-Luis [Univ. of Colorado, Boulder, CO (United States)

    2016-02-01

    This grant was originally funded for deployment of a suite of aerosol instrumentation by our group in collaboration with other research groups and DOE/ARM to the Ganges Valley in India (GVAX) to study aerosols sources and processing. Much of the first year of this grant was focused on preparations for GVAX. That campaign was cancelled due to political reasons and with the consultation with our program manager, the research of this grant was refocused to study the applications of oxidation flow reactors (OFRs) for investigating secondary organic aerosol (SOA) formation and organic aerosol (OA) processing in the field and laboratory through a series of laboratory and modeling studies. We developed a gas-phase photochemical model of an OFR which was used to 1) explore the sensitivities of key output variables (e.g., OH exposure, O3, HO2/OH) to controlling factors (e.g., water vapor, external reactivity, UV irradiation), 2) develop simplified OH exposure estimation equations, 3) investigate under what conditions non-OH chemistry may be important, and 4) help guide design of future experiments to avoid conditions with undesired chemistry for a wide range of conditions applicable to the ambient, laboratory, and source studies. Uncertainties in the model were quantified and modeled OH exposure was compared to tracer decay measurements of OH exposure in the lab and field. Laboratory studies using OFRs were conducted to explore aerosol yields and composition from anthropogenic and biogenic VOC as well as crude oil evaporates. Various aspects of the modeling and laboratory results and tools were applied to interpretation of ambient and source measurements using OFR. Additionally, novel measurement methods were used to study gas/particle partitioning. The research conducted was highly successful and details of the key results are summarized in this report through narrative text, figures, and a complete list of publications acknowledging this grant.

  8. Using of Photochemical H2O2/UVC Decontamination Cell for Heavily Polluted Waters

    Czech Academy of Sciences Publication Activity Database

    Žebrák, R.; Mašín, P.; Klusoň, Petr; Krystyník, Pavel

    2014-01-01

    Roč. 2014, č. 2 (2014), s. 55-62 ISSN 1804-0195. [Symposium ODPADOVÉ FÓRUM 2014. Hustopeče u Brna, 23.042014-23.04.2013] R&D Projects: GA MPO(CZ) FR-TI1/065 Institutional support: RVO:67985858 Keywords : photochemical oxidation * remediation * pilot scale Subject RIV: CI - Industrial Chemistry, Chemical Engineering http://www. waste forum.cz/

  9. Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

    DEFF Research Database (Denmark)

    Tritsaris, G. A.; Rossmeisl, J.

    2012-01-01

    Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat...... sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells....

  10. Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth.

    Science.gov (United States)

    Wei, Hehe; Huang, Kai; Wang, Da; Zhang, Ruoyu; Ge, Binghui; Ma, Jingyuan; Wen, Bo; Zhang, Shuai; Li, Qunyang; Lei, Ming; Zhang, Cheng; Irawan, Joshua; Liu, Li-Min; Wu, Hui

    2017-11-14

    Photochemical solution-phase reactions have been widely applied for the syntheses of nanocrystals. In particular, tuning of the nucleation and growth of solids has been a major area of focus. Here we demonstrate a facile approach to generate atomically dispersed platinum via photochemical reduction of frozen chloroplatinic acid solution using ultraviolet light. Using this iced-photochemical reduction, the aggregation of atoms is prevented, and single atoms are successfully stabilized. The platinum atoms are deposited on various substrates, including mesoporous carbon, graphene, carbon nanotubes, titanium dioxide nanoparticles, and zinc oxide nanowires. The atomically dispersed platinum on mesoporous carbon exhibits efficient catalytic activity for the electrochemical hydrogen evolution reaction, with an overpotential of only 65 mV at a current density of 100 mA cm -2 and long-time durability (>10 h), superior to state-of-the-art platinum/carbon. This iced-photochemical reduction may be extended to other single atoms, for example gold and silver, as demonstrated in this study.

  11. The efficiency of non-photochemical fluorescence quenching by cation radicals in photosystem II reaction centers.

    Science.gov (United States)

    Paschenko, V Z; Churin, A A; Gorokhov, V V; Grishanova, N P; Korvatovskii, B N; Maksimov, E G; Mamedov, M D

    2016-12-01

    In a direct experiment, the rate constants of photochemical k p and non-photochemical k p + quenching of the chlorophyll fluorescence have been determined in spinach photosystem II (PS II) membrane fragments, oxygen-evolving PS II core, as well as manganese-depleted PS II particles using pulse fluorimetry. In the dark-adapted reaction center(s) (RC), the fluorescence decay kinetics of the antenna were measured at low-intensity picosecond pulsed excitation. To create a "closed" P680 + Q A - state, RCs were illuminated by high-intensity actinic flash 8 ns prior to the measuring flash. The obtained data were approximated by the sum of two decaying exponents. It was found that the antennae fluorescence quenching efficiency by the oxidized photoactive pigment of RC P680 + was about 1.5 times higher than that of the neutral P680 state. These results were confirmed by a single-photon counting technique, which allowed to resolve the additional slow component of the fluorescence decay. Slow component was assigned to the charge recombination of P680 + Pheo - in PS II RC. Thus, for the first time, the ratio k p + /k p  ≅ 1.5 was found directly. The mechanism of the higher efficiency of non-photochemical quenching comparing to photochemical quenching is discussed.

  12. Quantification of oxide particle composition in model oxide dispersion strengthened steel alloys

    Energy Technology Data Exchange (ETDEWEB)

    London, A.J., E-mail: andrew.london@materials.ox.ac.uk [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Lozano-Perez, S.; Moody, M.P. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom); Amirthapandian, S.; Panigrahi, B.K.; Sundar, C.S. [Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102, TN (India); Grovenor, C.R.M. [Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH (United Kingdom)

    2015-12-15

    Oxide dispersion strengthened ferritic steels (ODS) are being considered for structural components of future designs of fission and fusion reactors because of their impressive high-temperature mechanical properties and resistance to radiation damage, both of which arise from the nanoscale oxide particles they contain. Because of the critical importance of these nanoscale phases, significant research activity has been dedicated to analysing their precise size, shape and composition (Odette et al., Annu. Rev. Mater. Res. 38 (2008) 471–503 [1]; Miller et al., Mater. Sci. Technol. 29(10) (2013) 1174–1178 [2]). As part of a project to develop new fuel cladding alloys in India, model ODS alloys have been produced with the compositions, Fe–0.3Y{sub 2}O{sub 3}, Fe–0.2Ti–0.3Y{sub 2}O{sub 3} and Fe–14Cr–0.2Ti–0.3Y{sub 2}O{sub 3}. The oxide particles in these three model alloys have been studied by APT in their as-received state and following ion irradiation (as a proxy for neutron irradiation) at various temperatures. In order to adequately quantify the composition of the oxide clusters, several difficulties must be managed, including issues relating to the chemical identification (ranging and variable peak-overlaps); trajectory aberrations and chemical structure; and particle sizing. This paper presents how these issues can be addressed by the application of bespoke data analysis tools and correlative microscopy. A discussion follows concerning the achievable precision in these measurements, with reference to the fundamental limiting factors.

  13. New System for Measuring the Photochemical Ozone Production Rate in the Atmosphere.

    Science.gov (United States)

    Sadanaga, Yasuhiro; Kawasaki, Shio; Tanaka, Yuki; Kajii, Yoshizumi; Bandow, Hiroshi

    2017-03-07

    We have developed a new system for measuring photochemical ozone production rates in the atmosphere. Specifically, the system measures the net photochemical oxidant (O x : the sum of ozone (O 3 ) and nitrogen dioxide (NO 2 )) production rates (P-L(O x )). Measuring O x avoids issues from perturbations to the photostationary states between nitrogen oxides (NO x ) and O 3 . This system has "reaction" and "reference" chambers. Ambient air is introduced into both chambers, and O x is photochemically produced in the reaction chamber and not generated in the reference chamber. Air from the chambers is alternately introduced into an NO-reaction (NO: nitric oxide) tube to convert O 3 to NO 2 , and then the O x concentration is measured as NO 2 using a laser-induced fluorescence technique. P-L(O x ) was obtained by dividing the difference in O x concentrations between air samples from the two chambers by the mean residence time of the air in the reaction chamber. In this study, the P-L(O x ) measurement system was characterized, and the current detection limit of P-L(O x ) was determined to be 0.54 ppbv h -1 with an integration time of 60 s (S/N = 2), assuming an ambient O x concentration of 100 ppbv. Field measurements of P-L(O x ) were conducted using the system at a remote forest location.

  14. Deposition versus photochemical removal of PBDEs from Lake Superior air.

    Science.gov (United States)

    Raff, Jonathan D; Hites, Ronald A

    2007-10-01

    Analysis of a sediment core collected from Siskiwit Lake, located on a remote island in Lake Superior, provides evidence that polybrominated diphenyl ethers (PBDEs) are removed effectively from the atmosphere via deposition processes during long-range transport. A mass balance model based on photochemical rate constants and data from atmospheric samples was created to understand the relative importance of various photochemical and deposition processes in removing PBDEs from the atmosphere. Photolysis rate constants were derived from UV absorption spectra of 25 PBDEs recorded in isooctane over the range of 280-350 nm at 298 K. Photolysis decays measured for BDE-3 and -7 in the gas phase were substantial compared to a well-defined chemical actinometer, indicating that their photolysis quantum yields are significant. Dibenzofuran production was observed when PBDE congeners containing ortho-bromines were photolyzed in helium. From estimates of removal rates of PBDEs from the lower troposphere, we find that wet and dry deposition accountfor >95% of the removal of BDE-209, while photolysis accounts for -90% of the removal of gas-phase congeners such as BDE-47. These results help explain the deposition patterns of PBDEs found in lake and river sediments and have important implications concerning the inclusion of photolysis as a fate process in multimedia models.

  15. NOx Effects on Photochemical Aging of Urban Wet Particles

    Science.gov (United States)

    Lim, Y. B.; Seo, J.; Kim, J. Y.; Turpin, B. J.

    2017-12-01

    Aqueous chemistry in aerosol liquid water (ALW) has been considered an important pathway of particle formation, which is expected to improve current models; however, little is known about NOx effects on aqueous chemistry in wet urban particulate matter (PM). Here we show photochemical aging of wet aerosols at modest urban conditions conducted in a smog chamber and provide atmospheric evidence of these chamber reactions. At high relative humidity, HNO3, the main sink of photochemistry of NOx, initiates water uptake into aerosols and ALW in turn facilitates aqueous chemistry. The hygroscopic growth was significant, and aqueous chemistry led to mainly non-radical products, such as organonitrates and oligomers. This multiphase chemistry contributes to particle aging during a haze event in Seoul, a megacity in East Asia. PM2.5 at Seoul, a downwind site at high NOx conditions, and reference PM2.5 at Deokjeok Island, an upwind site that has no emission source, during winter including the haze period were analyzed. Chemical components of Seoul haze particles can be explained by photochemical aging of transported particles in the presence of NOx. East Asian megacities including Seoul suffer from high concentration particles, yet the formation is poorly understood. Our finding of chemical aging and secondary formation highlights the importance of multiphase reactions, including gas-phase photochemistry at high NOx and aqueous chemistry in ALW, which need to be incorporated into air quality models to improve predictions for public health.

  16. A microkinetic model of the methanol oxidation over silver

    DEFF Research Database (Denmark)

    Andreasen, A.; Lynggaard, H.; Stegelmann, C.

    2003-01-01

    A simple microkinetic model for the oxidation of methanol on silver based on surface science studies at UHV and low temperatures has been formulated. The reaction mechanism is a simple Langmuir-Hinshelwood mechanism, with one type of active oxygen and one route to formaldehyde and carbon dioxide......, respectively. The model explains observed reaction orders, selectivity, apparent activation enthalpies and the choice of industrial reaction conditions. More interesting the model disproves the notion that the mechanism deduced from surface science in UHV cannot be responsible for formaldehyde synthesis...... at industrial steady-state conditions. The present work therefore seriously questions the prevailing models of formaldehyde synthesis in the literature. One of the reasons for this controversy is that many of the models in the literature are derived from transient experiments exhibiting dynamic effects...

  17. Photochemical stability of electrochromic polymers and devices

    DEFF Research Database (Denmark)

    Jensen, Jacob; Madsen, Morten Vesterager; Krebs, Frederik C

    2013-01-01

    The stability of fully printed flexible organic electrochromics based on 11 different conjugated polymers is explored from the fundamental chemical degradation level to the operational device level. The photochemical stability of the electrochromic polymers (ECPs) is studied enabling an analysis...... of the influence that the chemical constitution of the conjugated polymer backbone has on the photochemical stability. Based on changes in the UV-visible absorption and IR spectra, the polymers were categorized into two distinct groups, each with a separate degradation mechanism. During irradiation (1000 W m -2......, AM 1.5G) under ambient conditions the majority of the polymers degraded within 4-5 hours. Three polymers showed increased stability with degradation rates from 0.44 to 1.58% per hour measured as loss of absorption. Application of oxygen and UV barrier foils was found to drastically slow...

  18. Sunlight-Induced Photochemical Degradation of Methylene Blue by Water-Soluble Carbon Nanorods

    Directory of Open Access Journals (Sweden)

    Anshu Bhati

    2016-01-01

    Full Text Available Water-soluble graphitic hollow carbon nanorods (wsCNRs are exploited for their light-driven photochemical activities under outdoor sunlight. wsCNRs were synthesized by a simple pyrolysis method from castor seed oil, without using any metal catalyst or template. wsCNRs exhibited the light-induced photochemical degradation of methylene blue used as a model pollutant by the generation of singlet oxygen species. Herein, we described a possible degradation mechanism of methylene blue under the irradiation of visible photons via the singlet oxygen-superoxide anion pathway.

  19. Transgenic Mouse Model for Reducing Oxidative Damage in Bone

    Science.gov (United States)

    Schreurs, Ann-Sofie; Torres, S.; Truong, T.; Moyer, E. L.; Kumar, A.; Tahimic, Candice C. G.; Alwood, J. S.; Limoli, C. L.; Globus, R. K.

    2016-01-01

    Bone loss can occur due to many challenges such age, radiation, microgravity, and Reactive Oxygen Species (ROS) play a critical role in bone resorption by osteoclasts (Bartell et al. 2014). We hypothesize that suppression of excess ROS in skeletal cells, both osteoblasts and osteoclasts, regulates skeletal growth and remodeling. To test our hypothesis, we used transgenic mCAT mice which overexpress the human anti-oxidant catalase gene targeted to the mitochondria, the main site for endogenous ROS production. mCAT mice have a longer life-span than wildtype controls and have been used to study various age-related disorders. To stimulate remodeling, 16 week old mCAT mice or wildtype mice were exposed to treatment (hindlimb-unloading and total body-irradiation) or sham treatment conditions (control). Tissues were harvested 2 weeks later for skeletal analysis (microcomputed tomography), biochemical analysis (gene expression and oxidative damage measurements), and ex vivo bone marrow derived cell culture (osteoblastogenesis and osteoclastogenesis). mCAT mice expressed the transgene and displayed elevated catalase activity in skeletal tissue and marrow-derived osteoblasts and osteoclasts grown ex vivo. In addition, when challenged with treatment, bone tissues from wildtype mice showed elevated levels of malondialdehyde (MDA), indicating oxidative damage) whereas mCAT mice did not. Correlation analysis revealed that increased catalase activity significantly correlated with decreased MDA levels and that increased oxidative damage correlated with decreased percent bone volume (BVTV). In addition, ex-vivo cultured osteoblast colony growth correlated with catalase activity in the osteoblasts. Thus, we showed that these transgenic mice can be used as a model to study the relationship between markers of oxidative damage and skeletal properties. mCAT mice displayed reduced BVTV and trabecular number relative to wildtype mice, as well as increased structural model index in the

  20. Asymptotically exact solution of a local copper-oxide model

    International Nuclear Information System (INIS)

    Zhang Guangming; Yu Lu.

    1994-03-01

    We present an asymptotically exact solution of a local copper-oxide model abstracted from the multi-band models. The phase diagram is obtained through the renormalization-group analysis of the partition function. In the strong coupling regime, we find an exactly solved line, which crosses the quantum critical point of the mixed valence regime separating two different Fermi-liquid (FL) phases. At this critical point, a many-particle resonance is formed near the chemical potential, and a marginal-FL spectrum can be derived for the spin and charge susceptibilities. (author). 15 refs, 1 fig

  1. The Lightning Nitrogen Oxides Model (LNOM): Status and Recent Applications

    Science.gov (United States)

    Koshak, William; Khan, Maudood; Peterson, Harold

    2011-01-01

    Improvements to the NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) are discussed. Recent results from an August 2006 run of the Community Multiscale Air Quality (CMAQ) modeling system that employs LNOM lightning NOx (= NO + NO2) estimates are provided. The LNOM analyzes Lightning Mapping Array (LMA) data to estimate the raw (i.e., unmixed and otherwise environmentally unmodified) vertical profile of lightning NOx. The latest LNOM estimates of (a) lightning channel length distributions, (b) lightning 1-m segment altitude distributions, and (c) the vertical profile of NOx are presented. The impact of including LNOM-estimates of lightning NOx on CMAQ output is discussed.

  2. Photochemical tissue bonding with chitosan adhesive films

    OpenAIRE

    Lauto, Antonio; Mawad, Damia; Barton, Matthew; Gupta, Abhishek; Piller, Sabine C; Hook, James

    2010-01-01

    Abstract Background Photochemical tissue bonding (PTB) is a promising sutureless technique for tissue repair. PTB is often achieved by applying a solution of rose bengal (RB) between two tissue edges, which are irradiated by a green laser to crosslink collagen fibers with minimal heat production. In this study, RB has been incorporated in chitosan films to create a novel tissue adhesive that is laser-activated. Methods Adhesive films, based on chitosan and containing ~0.1 wt% RB were manufact...

  3. A Photochemical Route to Metal Chalcogenide Nanomaterials

    Science.gov (United States)

    Warwick, P. C. Temple

    Semiconducting nanoscale metal chaicogenides are an important class of materials used in optoelectronics, photovoltaics, and thermoelectric applications. The properties of nanomaterials are directly influenced by their size and shape. Because of this a great deal of research has been focused on the size-controllable synthesis of these materials. Metal chalcogenide nanomaterial:; have been synthesized using solvothermal, sonochemical, pyrolysis, and microwave heating methods, which require high temperature and pressure. Furthermore, the reactants, solvents, and reaction conditions are highly specific for each method as well as the desired nanomaterial. We have developed a unique photochemical method for the generalized synthesis of metal chalcogenide nanomateri GIs. The photolysis is conducted at 20° C, which is substantially lower than current solution based methods. Furthermore, the low temperature allows conventional solvents to be used. We have synthesized Culn2, InS, SbSe, and E2S3 (where E = Sb and Bi) nanopz,rticles with sizes ranging from 5 - 100 nm by photolysis of photoreactive single source precursors (SSPs). The SSPs are designed to photochemically decompose to yield the desired material with the proper stoichiometry. Our SSPs contain photoactive benzyl-X ligands (where X = S or Se), which are known to undergo bond homolysis at the benzyl-X bond. The results indicate that the reactions proceed by bond homolysis to produce reactive radicals species that self-assemble to yield the desired nanomaterials. Furthermore, we have used the same photochemical method as a route to functiorialize a Si surface with bismuth sulfide. We have also investigated the photochemistry of Ph2PBn (where Bn = CH2Ph). Upon photolysis, the P-Bn bond cleaves and yields tetraphenyl diphosphine (Ph4P2) and bibenzyl (PhCH2CH2Ph). These results support the observations made during the photochemical metal chalcogenide nanomaterials synthesis.

  4. A Structurally Based Viscosity Model for Oxide Melts

    Science.gov (United States)

    Zhang, Guo-Hua; Chou, Kuo-Chih; Mills, Ken

    2014-04-01

    A structurally based viscosity model is proposed to represent the viscosity of oxide melts as functions of both temperature and composition; The oxide melts cover the following constituents: Li2O, Na2O, K2O, MgO, CaO, SrO, BaO, FeO, MnO, Al2O3, SiO2, CaF2, TiO2, Fe2O3, and P2O5. The model describes the slag structure in terms of the various forms of oxygen ions which are classified according to the metal cations they bond with. Approximate methods for calculating the concentrations of these oxygen ions are proposed and are then used to describe the effect of melt structure on viscosity. The model provides a good description of the variations in viscosity with composition and temperature. The measured viscosities were compared with values calculated with the model, and the current model was found to provide reliable estimates of viscosities of slags used in various industrial processes ( e.g., blast furnace, basic oxygen steelmaking, ladle refining, continuous casting of steel, coal gasification, and electroslag remelting).

  5. Oxidative stress of crystalline lens in rat menopausal model

    Directory of Open Access Journals (Sweden)

    Semra Acer

    Full Text Available ABSTRACT Purpose: To evaluate lenticular oxidative stress in rat menopausal models. Methods: Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1. From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2, 10 were administered a daily injection of methylprednisolone until the end of the study (Group 3, and the remaining 10 rats were administered intraperitoneal streptozocin to induce diabetes mellitus (Group 4. Total oxidant status (TOS, total antioxidant capacity (TAC, and oxidative stress index (OSI measurements of the crystalline lenses were analyzed. Results: The mean OSI was the lowest in group 1 and highest in group 4. Nevertheless, the difference between the groups was not statistically significant in terms of OSI (p >0.05. The mean TOS values were similar between the groups (p >0.05, whereas the mean TAC of group 1 was significantly higher than that of the other groups (p <0.001. Conclusions: Our results indicate that menopause may not promote cataract formation.

  6. Oxidative stress of crystalline lens in rat menopausal model.

    Science.gov (United States)

    Acer, Semra; Pekel, Gökhan; Küçükatay, Vural; Karabulut, Aysun; Yağcı, Ramazan; Çetin, Ebru Nevin; Akyer, Şahika Pınar; Şahin, Barbaros

    2016-01-01

    To evaluate lenticular oxidative stress in rat menopausal models. Forty Wistar female albino rats were included in this study. A total of thirty rats underwent oophorectomy to generate a menopausal model. Ten rats that did not undergo oophorectomy formed the control group (Group 1). From the rats that underwent oophorectomy, 10 formed the menopause control group (Group 2), 10 were administered a daily injection of methylprednisolone until the end of the study (Group 3), and the remaining 10 rats were administered intraperitoneal streptozocin to induce diabetes mellitus (Group 4). Total oxidant status (TOS), total antioxidant capacity (TAC), and oxidative stress index (OSI) measurements of the crystalline lenses were analyzed. The mean OSI was the lowest in group 1 and highest in group 4. Nevertheless, the difference between the groups was not statistically significant in terms of OSI (p >0.05). The mean TOS values were similar between the groups (p >0.05), whereas the mean TAC of group 1 was significantly higher than that of the other groups (p <0.001). Our results indicate that menopause may not promote cataract formation.

  7. Simulations of photochemical smog formation in complex urban areas

    Science.gov (United States)

    Muilwijk, C.; Schrijvers, P. J. C.; Wuerz, S.; Kenjereš, S.

    2016-12-01

    In the present study we numerically investigated the dispersion of photochemical reactive pollutants in complex urban areas by applying an integrated Computational Fluid Dynamics (CFD) and Computational Reaction Dynamics (CRD) approach. To model chemical reactions involved in smog generation, the Generic Reaction Set (GRS) approach is used. The GRS model was selected since it does not require detailed modeling of a large set of reactive components. Smog formation is modeled first in the case of an intensive traffic emission, subjected to low to moderate wind conditions in an idealized two-dimensional street canyon with a building aspect ratio (height/width) of one. It is found that Reactive Organic Components (ROC) play an important role in the chemistry of smog formation. In contrast to the NOx/O3 photochemical steady state model that predicts a depletion of the (ground level) ozone, the GRS model predicts generation of ozone. Secondly, the effect of direct sunlight and shadow within the street canyon on the chemical reaction dynamics is investigated for three characteristic solar angles (morning, midday and afternoon). Large differences of up to one order of magnitude are found in the ozone production for different solar angles. As a proof of concept for real urban areas, the integrated CFD/CRD approach is applied for a real scale (1 × 1 km2) complex urban area (a district of the city of Rotterdam, The Netherlands) with high traffic emissions. The predicted pollutant concentration levels give realistic values that correspond to moderate to heavy smog. It is concluded that the integrated CFD/CRD method with the GRS model of chemical reactions is both accurate and numerically robust, and can be used for modeling of smog formation in complex urban areas.

  8. Solvent-free one-step photochemical hydroxylation of benzene derivatives by the singlet excited state of 2,3-Dichloro-5,6-dicyano-p-benzoquinone acting as a super oxidant.

    Science.gov (United States)

    Ohkubo, Kei; Hirose, Kensaku; Fukuzumi, Shunichi

    2015-02-09

    Photoinduced hydroxylation of neat deaerated benzene to phenol occurred under visible-light irradiation of 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), which acts as a super photooxidant in the presence of water. Photocatalytic solvent-free hydroxylation of benzene derivatives with electron-withdrawing substituents such as benzonitrile, nitrobenzene, and trifluoromethylbenzene used as neat solvents has been achieved for the first time by using DDQ as a super photooxidant to yield the corresponding phenol derivatives and 2,3-dichloro-5,6-dicyanohydroquinone (DDQH2 ) in the presence of water under deaerated conditions. In the presence of dioxygen and tert-butyl nitrite, the photocatalytic hydroxylation of neat benzene occurred with DDQ as a photocatalyst to produce phenol. The photocatalytic reactions are initiated by oxidation of benzene derivatives with the singlet and triplet excited states of DDQ to form the corresponding radical cations, which associate with benzene derivatives to produce the dimer radical cations, which were detected by the femto- and nanosecond laser flash photolysis measurements to clarify the photocatalytic reaction mechanisms. Radical cations of benzene derivatives react with water to yield the OH-adduct radicals. On the other hand, DDQ(.) (-) produced by the photoinduced electron transfer from benzene derivatives reacts with the OH-adduct radicals to yield the corresponding phenol derivatives and DDQH2 . DDQ is recovered by the reaction of DDQH2 with tert-butyl nitrite when DDQ acts as a photocatalyst for the hydroxylation of benzene derivatives by dioxygen. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Ab initio and kinetic modeling studies of formic acid oxidation

    DEFF Research Database (Denmark)

    Marshall, Paul; Glarborg, Peter

    2015-01-01

    A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism...... have been compared to the experimental results of de Wilde and van Tiggelen (1968) who measured the laminar burning velocities for HOCHO flames over a range of stoichiometries and dilution ratios. The modeling predictions are generally satisfactory. The governing reaction mechanisms are outlined based...... on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well...

  10. Advanced impedance modeling of solid oxide electrochemical cells

    DEFF Research Database (Denmark)

    Graves, Christopher R.; Hjelm, Johan

    2014-01-01

    Impedance spectroscopy is a powerful technique for detailed study of the electrochemical and transport processes that take place in fuel cells and electrolysis cells, including solid oxide cells (SOCs). Meaningful analysis of impedance measurements is nontrivial, however, because a large number...... of modeling parameters are fit to the many processes which often overlap in the same frequency ranges. Also, commonly used equivalent circuit (EC) models only provide zero-dimensional (0-D) approximations of the processes of the two electrodes, electrolyte and gas transport. Employing improved analytical...... electrode and 2-D gas transport models which have fewer unknown parameters for the same number of processes, (ii) use of a new model fitting algorithm, “multi-fitting”, in which multiple impedance spectra are fit simultaneously with parameters linked based on the variation of measurement conditions, (iii...

  11. LG Solid Oxide Fuel Cell (SOFC) Model Development

    Energy Technology Data Exchange (ETDEWEB)

    Haberman, Ben [LG Fuel Cell Systems Inc., North Canton, OH (United States); Martinez-Baca, Carlos [LG Fuel Cell Systems Inc., North Canton, OH (United States); Rush, Greg [LG Fuel Cell Systems Inc., North Canton, OH (United States)

    2013-05-31

    This report presents a summary of the work performed by LG Fuel Cell Systems Inc. during the project LG Solid Oxide Fuel Cell (SOFC) Model Development (DOE Award Number: DE-FE0000773) which commenced on October 1, 2009 and was completed on March 31, 2013. The aim of this project is for LG Fuel Cell Systems Inc. (formerly known as Rolls-Royce Fuel Cell Systems (US) Inc.) (LGFCS) to develop a multi-physics solid oxide fuel cell (SOFC) computer code (MPC) for performance calculations of the LGFCS fuel cell structure to support fuel cell product design and development. A summary of the initial stages of the project is provided which describes the MPC requirements that were developed and the selection of a candidate code, STAR-CCM+ (CD-adapco). This is followed by a detailed description of the subsequent work program including code enhancement and model verification and validation activities. Details of the code enhancements that were implemented to facilitate MPC SOFC simulations are provided along with a description of the models that were built using the MPC and validated against experimental data. The modeling work described in this report represents a level of calculation detail that has not been previously available within LGFCS.

  12. Fluorogenic, catalytic, photochemical reaction for amplified detection of nucleic acids.

    Science.gov (United States)

    Dutta, Subrata; Fülöp, Annabelle; Mokhir, Andriy

    2013-09-18

    Photochemical, nucleic acid-induced reactions, which are controlled by nontoxic red light, are well-suited for detection of nucleic acids in live cells, since they do not require any additives and can be spatially and temporally regulated. We have recently described the first reaction of this type, in which a phenylselenyl derivative of thymidine (5'-PhSeT-ODNa) is cleaved in the presence of singlet oxygen (Fülöp, A., Peng, X., Greenberg, M. M., Mokhir, A. (2010) A nucleic acid directed, red light-induced chemical reaction. Chem. Commun. 46, 5659-5661). The latter reagent is produced upon exposure of a photosensitizer 3'-PS-ODNb (PS = Indium(III)-pyropheophorbide-a-chloride: InPPa) to >630 nm light. In 2012 we reported on a fluorogenic version of this reaction (Dutta, S., Flottmann, B., Heilemann, M., Mokhir, A. (2012) Hybridization and reaction-based, fluorogenic nucleic acid probes. Chem. Commun. 47, 9664-9666), which is potentially applicable for the detection of nucleic acids in cells. Unfortunately, its yield does not exceed 25% and no catalytic turnover could be observed in the presence of substrate excess. This problem occurs due to the efficient, competing oxidation of the substrate containing an electron rich carbon-carbon double bonds (SCH═CHS) in the presence of singlet oxygen with formation of a noncleavable product (SCH═CHSO). Herein we describe a related, but substantially improved photochemical, catalytic transformation of a fluorogenic, organic substrate, which consists of 9,10-dialkoxyanthracene linked to fluorescein, with formation of a bright fluorescent dye. In highly dilute solution this reaction occurs only in the presence of a nucleic acid template. We developed three types of such a reaction and demonstrated that they are high yielding and generate over 7.7 catalytic turnovers, are sensitive to single mismatches in nucleic acid targets, and can be applied for determination of both the amount of nucleic acids and potentially their

  13. Effect of photochemical ageing on the ice nucleation properties of diesel and wood burning particles

    Directory of Open Access Journals (Sweden)

    C. Chou

    2013-01-01

    Full Text Available A measurement campaign (IMBALANCE conducted in 2009 was aimed at characterizing the physical and chemical properties of freshly emitted and photochemically aged combustion particles emitted from a log wood burner and diesel vehicles: a EURO3 Opel Astra with a diesel oxidation catalyst (DOC but no particle filter and a EURO2 Volkswagen Transporter TDI Syncro without emission aftertreatment. Ice nucleation experiments in the deposition and condensation freezing modes were conducted with the Portable Ice Nucleation Chamber (PINC at three nominal temperatures, −30 °C, −35 °C and −40 °C. Freshly emitted diesel particles showed ice formation only at −40 °C in the deposition mode at 137% relative humidity with respect to ice (RHi and 92% relative humidity with respect to water (RHw, and photochemical ageing did not play a role in modifying their ice nucleation behaviour. Only one diesel experiment where α-pinene was added for the ageing process, showed an ice nucleation enhancement at −35 °C. Wood burning particles also act as ice nuclei (IN at −40 °C in the deposition mode at the same conditions as for diesel particles and photochemical ageing also did not alter the ice formation properties of the wood burning particles. Unlike diesel particles, wood burning particles form ice via condensation freezing at −35 °C whereas no ice nucleation was observed at −30 °C. Photochemical ageing did not affect the ice nucleation ability of the diesel and wood burning particles at the three different temperatures investigated but a broader range of temperatures below −40 °C need to be investigated in order to draw an overall conclusion on the effect of photochemical ageing on deposition/condensation ice nucleation across the entire temperature range relevant to cold clouds.

  14. Magnetism-tuning strategies for graphene oxide based on magnetic oligoacene oxide patches model.

    Science.gov (United States)

    Wen, Yanjie; Yen, Chia-Liang; Yan, Linyin; Kono, Hirohiko; Lin, Sheng-Hsien; Ling, Yong-Chien

    2018-01-31

    Graphene oxide (GO) has wide application potential owing to its 2D structure and diverse modification sites for various targeted uses. The introduction of magnetism into GO structures has further advanced the controllability of the application of GO materials. Herein, the concept of modular design and modeling was applied to tune the magnetism of GO. To obtain desirable magnetic properties, diradical-structured GO patches were formed by the introduction of two functional groups to break the Kekule structure of the benzene ring. In these diradical GO patches, the energy of the triplet state was lower than those of the open-shell broken-symmetry singlet state and closed-shell singlet state. To create such multi-radical patches, a practical approach is to determine a substantial spatial separation of the α and β spin densities in the molecule. Thus, systematic design strategies and tests were evaluated. The first strategy was extending the distance between the distribution center of the α and β spin densities; the second was controlling the delocalization directions of the α and β electrons; the third was controlling the delocalization extension of the α and β electrons by oxidative modification, and finally introducing multi-radical structures into the molecular system and controlling the position of each radical. Herein, successful molecular models with a large magnetic coupling constant (∼3600 cm -1 ) were obtained. This study paves the way to explore ferromagnetic MGO guided by theoretical study, which may become reality soon.

  15. The chemical energy unit partial oxidation reactor operation simulation modeling

    Science.gov (United States)

    Mrakin, A. N.; Selivanov, A. A.; Batrakov, P. A.; Sotnikov, D. G.

    2018-01-01

    The chemical energy unit scheme for synthesis gas, electric and heat energy production which is possible to be used both for the chemical industry on-site facilities and under field conditions is represented in the paper. The partial oxidation reactor gasification process mathematical model is described and reaction products composition and temperature determining algorithm flow diagram is shown. The developed software product verification showed good convergence of the experimental values and calculations according to the other programmes: the temperature determining relative discrepancy amounted from 4 to 5 %, while the absolute composition discrepancy ranged from 1 to 3%. The synthesis gas composition was found out practically not to depend on the supplied into the partial oxidation reactor (POR) water vapour enthalpy and compressor air pressure increase ratio. Moreover, air consumption coefficient α increase from 0.7 to 0.9 was found out to decrease synthesis gas target components (carbon and hydrogen oxides) specific yield by nearly 2 times and synthesis gas target components required ratio was revealed to be seen in the water vapour specific consumption area (from 5 to 6 kg/kg of fuel).

  16. Prebiotic synthesis of carboxylic acids, amino acids and nucleic acid bases from formamide under photochemical conditions⋆

    Science.gov (United States)

    Botta, Lorenzo; Mattia Bizzarri, Bruno; Piccinino, Davide; Fornaro, Teresa; Robert Brucato, John; Saladino, Raffaele

    2017-07-01

    The photochemical transformation of formamide in the presence of a mixture of TiO2 and ZnO metal oxides as catalysts afforded a large panel of molecules of biological relevance, including carboxylic acids, amino acids and nucleic acid bases. The reaction was less effective when performed in the presence of only one mineral, highlighting the role of synergic effects between the photoactive catalysts. Taken together, these results suggest that the synthesis of chemical precursors for both the genetic and the metabolic apparatuses might have occurred in a simple environment, consisting of formamide, photoactive metal oxides and UV-radiation.

  17. Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment

    Science.gov (United States)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Lei, Yu; Wang, Jizhong; Chen, Tianhu

    2017-05-01

    Nitrous acid (HONO) is an important tropospheric pollutant and a major source of hydroxyl radical in the atmospheric gas phase. However, studies on the role of HONO in atmospheric aqueous phase chemistry processes are relatively few. The present work investigated the photochemical reaction of HONO with triclosan (TCS), which is an emerging contaminant, using a combination of laser flash photolysis spectrometry and gas chromatography mass spectrometry. With these techniques, the reaction pathway of HONO with TCS was proposed by directly monitoring the transient species and detecting the stable products. ·OH was generated from the photodissociation of the HONO aqueous solution and attacked TCS molecules on different sites to produce the TCS-OH adducts with a second-order rate constant of 1.11 × 109 L mol-1 s-1. The ·OH added a C atom adjacent to the ether bond in the aromatic ring of TCS and self-decayed when the ether bond broke. The intermediates generated from the addition of ·OH to the benzene ring of the TCS molecular structure were immediately nitrated by HONO, which played a key role in the formation process of nitrocompounds. An atmospheric model suggests that the aqueous oxidation of TCS by ·OH is a major reaction at high liquid water concentrations, and the photolysis of TCS dominates under low-humidity conditions.

  18. Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

    1998-12-31

    A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

  19. Application of the GRI 1.2 Methane Oxidation Model to Methane and Methanol Oxidation in Supercritical Water

    National Research Council Canada - National Science Library

    Rice, Steven

    1997-01-01

    The Gas Research Institute (GRI) has been leading an effort over the past few years to consolidate recent developments in the elementary reaction modeling of the oxidation of methane for combustion applications into a single...

  20. Participation of the Halogens in Photochemical Reactions in Natural and Treated Waters

    Directory of Open Access Journals (Sweden)

    Yi Yang

    2017-10-01

    Full Text Available Halide ions are ubiquitous in natural waters and wastewaters. Halogens play an important and complex role in environmental photochemical processes and in reactions taking place during photochemical water treatment. While inert to solar wavelengths, halides can be converted into radical and non-radical reactive halogen species (RHS by sensitized photolysis and by reactions with secondary reactive oxygen species (ROS produced through sunlight-initiated reactions in water and atmospheric aerosols, such as hydroxyl radical, ozone, and nitrate radical. In photochemical advanced oxidation processes for water treatment, RHS can be generated by UV photolysis and by reactions of halides with hydroxyl radicals, sulfate radicals, ozone, and other ROS. RHS are reactive toward organic compounds, and some reactions lead to incorporation of halogen into byproducts. Recent studies indicate that halides, or the RHS derived from them, affect the concentrations of photogenerated reactive oxygen species (ROS and other reactive species; influence the photobleaching of dissolved natural organic matter (DOM; alter the rates and products of pollutant transformations; lead to covalent incorporation of halogen into small natural molecules, DOM, and pollutants; and give rise to certain halogen oxides of concern as water contaminants. The complex and colorful chemistry of halogen in waters will be summarized in detail and the implications of this chemistry for global biogeochemical cycling of halogen, contaminant fate in natural waters, and water purification technologies will be discussed.

  1. Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

    Science.gov (United States)

    Levine, J. S.; Summers, M. E.; Ewell, M.

    2010-01-01

    The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

  2. Photochemical reactions of aqueous plutonium systems

    International Nuclear Information System (INIS)

    Friedman, H.A.; Toth, L.M.; Bell, J.T.

    1977-01-01

    The photochemical shift of the Pu 4+ disproportionation equilibrium in aqueous perchloric acid solutions has been measured and shown to be reversible. Ratios of equilibrium quotients between light and dark conditions have been measured for 0.01 M Pu ion concentrations in 0.53 to 1.24 N acid solutions exposed to 0.5 Watt of UV light. The photodecomposition of time- and temperature-aged Pu(IV) polymers in perchloric and nitric acid solutions have been examined as a function of aging conditions. Effects similar to those seen previously for fresh polymers have been observed in the aged perchloric acid solutions. (author)

  3. Photochemical Hexadehydro-Diels-Alder Reaction.

    Science.gov (United States)

    Xu, Feng; Xiao, Xiao; Hoye, Thomas R

    2017-06-28

    We demonstrate that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction to produce reactive benzyne derivatives can be initiated photochemically. As with the thermal variant of the HDDA process, the reactive intermediates are formed in the absence of reagents or the resulting byproducts required for the generation of benzynes by traditional methods. This photo-HDDA (or hν-HDDA) reaction occurs at much lower temperatures (including even at -70 °C) than the thermal HDDA, but the benzynes produced behave in the same fashion with respect to their trapping reactions, suggesting they are of the same electronic state.

  4. The photochemical stability of the Venus atmosphere against UV radiation

    International Nuclear Information System (INIS)

    Mills, F.P.; Slanger, T.G.; Allen, M.

    2004-01-01

    Full text: One unresolved question regarding the Venus atmosphere is what chemical mechanism(s) stabilize its primary constituent (CO 2 ) against UV radiation. CO 2 photolyzes on the day side into CO and O after absorbing photons at 2 rather than recombining with CO to form CO 2 , and the intense night side O 2 airglow observed quantitatively supports this. CO and O 2 are photochemically stable in an otherwise pure CO 2 atmosphere so significant abundances of CO and O 2 could accumulate on Venus if no catalytic mechanism existed to speed the reformation of CO 2 . However, the observational upper limit on ground state O 2 is equivalent to 2 from CO and O 2 . Recent laboratory work verified the existence of the ClC(O)OO catalytic mechanism that has been used in photochemical models since the early 1980s. However, there are significant uncertainties in the rates for the component steps of this catalytic mechanism. An alternative mechanism for production of CO 2 that has not previously been modeled but which could be competitive with the ClCO(O)O mechanism is the reaction CO + O 2 (c 1 Σ - u ) → CO 2 + O( 1 D) or O( 1 S), Reaction (1). A range of values for Reaction (1) will be examined in model calculations to compare with observational (UV to IR) constraints and to assess under what conditions this mechanism is competitive with the ClC(O)OO catalytic mechanism. The sensitivity of the results to uncertainties in the CO 2 UV absorption cross section also will be examined

  5. Photochemical and Spectroscopic Effects Resulting from Excimer Laser Excitation.

    Science.gov (United States)

    Wang, Xuan Xiao

    I. Photochemical production of ozone from pure oxygen using excimer lasers. Production of ozone was observed from experiments when oxygen was under a broadband pulsed KrF laser radiation. The production process was found to be autocatalytic. Mechanisms for the ozone formation were proposed. Experimental results over a range of oxygen pressure and laser pulse energy (irradiance) provided evidences in favor of the proposed mechanisms. Experiments were also numerically modeled. Good agreement between the experimental and the numerical results were observed, which provided further evidence to support the proposed mechanisms. Cross sections for some photochemical processes in the mechanisms were estimated. Production of ozone from pure oxygen under a ArF excimer laser radiation (193 nm) was also studied and numerically modeled. Effects of ambient water vapor on ozone production were investigated. Experimental results showed a fast ozone destruction when water vapor was present in the cell. However, numerical results obtained from the well-known OH and HO _2 chain ozone destruction mechanism predicted a slower ozone destruction. Possible reasons for the discrepancy are discussed. II. Resonance-enhanced multiphoton ionization of N_2 at 193 and 248 nm detected by N_sp{2}{+} fluorescence. Using a broadband excimer laser operating at 193 and 248 nm multiphoton ionization at high pressures in air and pure nitrogen has been detected by fluorescence from N_sp{2}{+} in the B-X firstnegative system. Measurements of the fluorescence intensity as a function of beam irradiance indicate resonance in N_2 at the energy of two 193 nm photons (2 + 1 REMPI) and three 248 nm photons (3 + 1 REMPI). Possible intermediate states are discussed. III. Excimer laser-induced fluorescence from some organic solvents. Fluorescence was observed from vapor phase benzene, toluene, p-xylene, benzyl chloride, methyl benzoate, acetic anhydride, ether, methanol, ethyl acetone, acetone, and 2-butanone using

  6. An experimental and modeling study of diethyl carbonate oxidation

    KAUST Repository

    Nakamura, Hisashi

    2015-04-01

    Diethyl carbonate (DEC) is an attractive biofuel that can be used to displace petroleum-derived diesel fuel, thereby reducing CO2 and particulate emissions from diesel engines. A better understanding of DEC combustion characteristics is needed to facilitate its use in internal combustion engines. Toward this goal, ignition delay times for DEC were measured at conditions relevant to internal combustion engines using a rapid compression machine (RCM) and a shock tube. The experimental conditions investigated covered a wide range of temperatures (660-1300K), a pressure of 30bar, and equivalence ratios of 0.5, 1.0 and 2.0 in air. To provide further understanding of the intermediates formed in DEC oxidation, species concentrations were measured in a jet-stirred reactor at 10atm over a temperature range of 500-1200K and at equivalence ratios of 0.5, 1.0 and 2.0. These experimental measurements were used to aid the development and validation of a chemical kinetic model for DEC.The experimental results for ignition in the RCM showed near negative temperature coefficient (NTC) behavior. Six-membered alkylperoxy radical (RO˙2) isomerizations are conventionally thought to initiate low-temperature branching reactions responsible for NTC behavior, but DEC has no such possible 6- and 7-membered ring isomerizations. However, its molecular structure allows for 5-, 8- and 9-membered ring RO˙2 isomerizations. To provide accurate rate constants for these ring structures, ab initio computations for RO˙2⇌Q˙OOH isomerization reactions were performed. These new RO˙2 isomerization rate constants have been implemented in a chemical kinetic model for DEC oxidation. The model simulations have been compared with ignition delay times measured in the RCM near the NTC region. Results of the simulation were also compared with experimental results for ignition in the high-temperature region and for species concentrations in the jet-stirred reactor. Chemical kinetic insights into the

  7. Photochemical tissue bonding with chitosan adhesive films

    Directory of Open Access Journals (Sweden)

    Piller Sabine C

    2010-09-01

    Full Text Available Abstract Background Photochemical tissue bonding (PTB is a promising sutureless technique for tissue repair. PTB is often achieved by applying a solution of rose bengal (RB between two tissue edges, which are irradiated by a green laser to crosslink collagen fibers with minimal heat production. In this study, RB has been incorporated in chitosan films to create a novel tissue adhesive that is laser-activated. Methods Adhesive films, based on chitosan and containing ~0.1 wt% RB were manufactured and bonded to calf intestine by a solid state laser (λ = 532 nm, Fluence~110 J/cm2, spot size~0.5 cm. A single-column tensiometer, interfaced with a personal computer, tested the bonding strength. K-type thermocouples recorded the temperature (T at the adhesive-tissue interface during laser irradiation. Human fibroblasts were also seeded on the adhesive and cultured for 48 hours to assess cell growth. Results The RB-chitosan adhesive bonded firmly to the intestine with adhesion strength of 15 ± 2 kPa, (n = 31. The adhesion strength dropped to 0.5 ± 0.1 (n = 8 kPa when the laser was not applied to the adhesive. The average temperature of the adhesive increased from 26°C to 32°C during laser exposure. Fibroblasts grew confluent on the adhesive without morphological changes. Conclusion A new biocompatible chitosan adhesive has been developed that bonds photochemically to tissue with minimal temperature increase.

  8. Evaluated kinetic and photochemical data for atmospheric chemistry

    Science.gov (United States)

    Baulch, D. L.; Cox, R. A.; Hampson, R. F., Jr.; Kerr, J. A.; Troe, J.; Watson, R. T.

    1980-01-01

    This paper contains a critical evaluation of the kinetics and photochemistry of gas phase chemical reactions of neutral species involved in middle atmosphere chemistry (10-55 km altitude). Data sheets have been prepared for 148 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each reaction a preferred value of the rate coefficient at 298 K is given together with a temperature dependency where possible. The selection of the preferred value is discussed, and estimates of the accuracies of the rate coefficients and temperature coefficients have been made for each reaction. The data sheets are intended to provide the basic physical chemical data needed as input for calculations which model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available data on enthalpies of formation of the reactant and product species.

  9. 40 CFR 52.777 - Control strategy: photochemical oxidants (hydrocarbons).

    Science.gov (United States)

    2010-07-01

    ..., industrial clean up solvents, industrial wastewater processes, offset lithography operations, business... wastewater processes, offset lithography operations, business plastics, automotive plastics, and synthetic.... Today's action finalizes approval of Indiana's 1-hour ozone attainment demonstration SIP revision. (z...

  10. WATER DEFICIT ENSURES THE PHOTOCHEMICAL EFFICIENCY OF Copaifera langsdorffii Desf1

    Directory of Open Access Journals (Sweden)

    Angélica Lino Rodrigues

    2017-02-01

    Full Text Available ABSTRACT The intensity and frequency of drought periods has increased according to climate change predictions. The fast overcome and recovery are important adaptive features for plant species found in regions presenting water shortage periods. Copaifera langsdorffii is a neotropical species that has developed leaves presenting physiological mechanisms and morphological adaptations that allow its survival under seasonal water stress. We aimed in this work to observe substantial physiological responses for water saving and damage representative to the photochemical reaction after exposed plants to water stress and to subsequent recovery. We found in plants mechanisms to control water loss through the lower stomatal conductance, even after rehydration. It goes against the rapid recovery of leaves, indicated by the relative water content values restored to previously unstressed plants. Stomatal conductance was the only variable presenting high plasticity index. In photochemical activity, the species presented higher photochemical quenching, electron transport rate and effective quantum yield of photosystem II when they were subjected to rehydration after water stress period. Our results suggest that C. langsdorffii presented rapid rehydration and higher photochemical efficiency even after water restriction. These data demonstrate that this species can be used as a model for physiological studies due to the adjustment developed in response to different environmental schemes.

  11. Modeling of Cd(II) sorption on mixed oxide

    International Nuclear Information System (INIS)

    Waseem, M.; Mustafa, S.; Naeem, A.; Shah, K.H.; Hussain, S.Y.; Safdar, M.

    2011-01-01

    Mixed oxide of iron and silicon (0.75 M Fe(OH)3:0.25 M SiO/sub 2/) was synthesized and characterized by various techniques like surface area analysis, point of zero charge (PZC), energy dispersive X-rays (EDX) spectroscopy, Thermogravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared spectroscopy (FTIR) and X-rays diffraction (XRD) analysis. The uptake of Cd/sup 2+/ ions on mixed oxide increased with pH, temperature and metal ion concentration. Sorption data have been interpreted in terms of both Langmuir and Freundlich models. The Xm values at pH 7 are found to be almost twice as compared to pH 5. The values of both DH and DS were found to be positive indicating that the sorption process was endothermic and accompanied by the dehydration of Cd/sup 2+/. Further, the negative value of DG confirms the spontaneity of the reaction. The ion exchange mechanism was suggested to take place for each Cd/sup 2+/ ions at pH 5, whereas ion exchange was found coupled with non specific adsorption of metal cations at pH 7. (author)

  12. From Mars Meteorites to Laboratory Investigations: Understanding Heterogeneous Photochemical Transformations Using Oxygen Triple Isotope Anomalies of Carbonates

    Science.gov (United States)

    Shaheen, R.; Smirnova, V.; Jackson, T. L.; Mang, L.; Thiemens, M. H.

    2016-12-01

    The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These observation will help refine Mars photochemistry models and also to constrain the past hydrological cycle and its coupling with the regolith. The observed inverse correlation between ozone and water vapor also suggests a dynamic role of hydroxyl radical chemistry in the atmosphere of Mars.

  13. Thermo-cleavable polymers: Materials with enhanced photochemical stability

    DEFF Research Database (Denmark)

    Manceau, Matthieu; Petersen, Martin Helgesen; Krebs, Frederik C

    2010-01-01

    Photochemical stability of three thermo-cleavable polymers was investigated as thin films under atmospheric conditions. A significant increase in lifetime was observed once the side-chain was cleaved emphasizing the detrimental effect of solubilizing groups on the photochemical stability...... of conjugated polymers. In addition to their ease of processing, thermo-cleavable polymers thus also offer a greater intrinsic stability under illumination....

  14. Trends in photochemical smog in the Cape Peninsula and the ...

    African Journals Online (AJOL)

    There has been growing public concern over reports of increasing air pollution in the Cape Peninsula. Attention has been focused on the 'brown haze' and on photochemical smog. Because of deficiencies in the monitoring equipment, information on trends in photochemical smog levels over the past decade is limited.

  15. Modeling Degradation in Solid Oxide Electrolysis Cells - Volume II

    Energy Technology Data Exchange (ETDEWEB)

    Manohar Motwani

    2011-09-01

    Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential,, within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, non-equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

  16. Dual wavelength asymmetric photochemical synthesis with circularly polarized light† †Electronic supplementary information (ESI) available: Full detailed methods used for the entire study; further discussion of the work not central to the main message of the paper; full derivation of the kinetics models used to predict the dual wavelength enantioselectivity; computational details and energy breakdown; more complete mechanism for the reaction. See DOI: 10.1039/c4sc03897e

    Science.gov (United States)

    Richardson, Robert D.; Baud, Matthias G. J.; Weston, Claire E.; Rzepa, Henry S.

    2015-01-01

    Asymmetric photochemical synthesis using circularly polarized (CP) light is theoretically attractive as a means of absolute asymmetric synthesis and postulated as an explanation for homochirality on Earth. Using an asymmetric photochemical synthesis of a dihydrohelicene as an example, we demonstrate the principle that two wavelengths of CP light can be used to control separate reactions. In doing so, a photostationary state (PSS) is set up in such a way that the enantiomeric induction intrinsic to each step can combine additively, significantly increasing the asymmetric induction possible in these reactions. Moreover, we show that the effects of this dual wavelength approach can be accurately determined by kinetic modelling of the PSS. Finally, by coupling a PSS to a thermal reaction to trap the photoproduct, we demonstrate that higher enantioselectivity can be achieved than that obtainable with single wavelength irradiation, without compromising the yield of the final product. PMID:29218156

  17. Reactor modeling and process analysis for partial oxidation of natural gas

    NARCIS (Netherlands)

    Albrecht, B.A.

    2004-01-01

    This thesis analyses a novel process of partial oxidation of natural gas and develops a numerical tool for the partial oxidation reactor modeling. The proposed process generates syngas in an integrated plant of a partial oxidation reactor, a syngas turbine and an air separation unit. This is called

  18. Radiolytic oxidation of propane: computer modeling of the reaction scheme

    International Nuclear Information System (INIS)

    Gupta, A.K.; Hanrahan, R.J.

    1991-01-01

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25 o C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases. (author)

  19. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.M.; Graaff, de C.M.; Bosch, van den P.L.F.; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.H.

    2013-01-01

    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was

  20. A mathematical model of aerobic methane oxidation coupled to denitrification.

    Science.gov (United States)

    Modin, Oskar

    2018-05-01

    Aerobic methanotrophic bacteria use methane as their only source of energy and carbon. They release organic compounds that can serve as electron donors for co-existing denitrifiers. This interaction between methanotrophs and denitrifiers is known to contribute to nitrogen losses in natural environments and has also been exploited by researchers for denitrification of nitrate-contaminated wastewater. The purpose of this study was to develop a mathematical model describing aerobic methane oxidation coupled to denitrification in suspended-growth reactors. The model considered the activities of three microbial groups: aerobic methanotrophs, facultative methylotrophs, and facultative heterotrophs. The model was tested against data from the scientific literature and used to explore the effects of the oxygen mass transfer coefficient, the solids retention time, and the fraction methane in the feed gas on nitrate removal. The fraction of methane in the feed gas was found to be critical for the nitrate removal rate. A value of about 15% in air was optimal. A lower methane fraction led to excess oxygen, which was detrimental for denitrification. A higher fraction led to oxygen-limitation, which restricted the growth rate of methanotrophs in the reactor.

  1. Ultrasound assisted synthesis of nanocrystalline zinc oxide: Experiments and modelling

    Energy Technology Data Exchange (ETDEWEB)

    Hosni, Mongia [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Farhat, Samir, E-mail: farhat@lspm.cnrs.fr [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Schoenstein, Frederic; Karmous, Farah; Jouini, Noureddine [Laboratoire des Sciences des Procédés et des Matériaux, LSPM-CNRS, Université Paris 13, 99 av. J.B. Clément, 93430 Villetaneuse (France); Viana, Bruno [LCMCP Chimie-Paristech, UPMC, Collège de France, 11 Rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France); Mgaidi, Arbi [Laboratoire de chimie minérale industrielle université Tunis el Manar (Tunisia)

    2014-12-05

    Highlights: • ZnO nanospheres and nanowires were grown using ultrasound and thermal activation techniques. • The growth uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). • A thermochemical model was developed based on thermodynamic equilibrium calculations. • We estimate species distribution in the bubble in temperature range from 5000 K to ambient. • We propose a new mechanism for ZnO growth assisted by ultrasound irradiation. - Abstract: A fast and green approach is proposed for the preparation of nanocrystalline zinc oxide (ZnO) via ultrasonic (US) irradiation in polyol medium. The process uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). The protocol is compared to thermal activation under the same chemical environment. The activation method is found to be playing a critical role in the selective synthesis of morphologically distinct nanostructures. As compared to thermally activated conventional polyol process, (US) permits to considerably reduce reaction time as well as size of particles. In addition, the shape of these nanoparticles was changed from long nanowires to small nanospheres, indicating different reaction mechanisms. To explain this difference, a thermochemical model was developed based on thermodynamic equilibrium calculations. The model estimate species distribution in the bubble in temperature range from 5000 K to ambient simulating quenching process during bubble formation and collapse. Our results indicate the presence of high density of zinc atoms that could be responsible of a high density of nucleation as compared to thermal activation.

  2. Ultrasound assisted synthesis of nanocrystalline zinc oxide: Experiments and modelling

    International Nuclear Information System (INIS)

    Hosni, Mongia; Farhat, Samir; Schoenstein, Frederic; Karmous, Farah; Jouini, Noureddine; Viana, Bruno; Mgaidi, Arbi

    2014-01-01

    Highlights: • ZnO nanospheres and nanowires were grown using ultrasound and thermal activation techniques. • The growth uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). • A thermochemical model was developed based on thermodynamic equilibrium calculations. • We estimate species distribution in the bubble in temperature range from 5000 K to ambient. • We propose a new mechanism for ZnO growth assisted by ultrasound irradiation. - Abstract: A fast and green approach is proposed for the preparation of nanocrystalline zinc oxide (ZnO) via ultrasonic (US) irradiation in polyol medium. The process uses forced hydrolysis of zinc acetate in diethylene glycol (DEG). The protocol is compared to thermal activation under the same chemical environment. The activation method is found to be playing a critical role in the selective synthesis of morphologically distinct nanostructures. As compared to thermally activated conventional polyol process, (US) permits to considerably reduce reaction time as well as size of particles. In addition, the shape of these nanoparticles was changed from long nanowires to small nanospheres, indicating different reaction mechanisms. To explain this difference, a thermochemical model was developed based on thermodynamic equilibrium calculations. The model estimate species distribution in the bubble in temperature range from 5000 K to ambient simulating quenching process during bubble formation and collapse. Our results indicate the presence of high density of zinc atoms that could be responsible of a high density of nucleation as compared to thermal activation

  3. A comprehensive experimental and modeling study of isobutene oxidation

    KAUST Repository

    Zhou, Chong-Wen

    2016-03-17

    Isobutene is an important intermediate in the pyrolysis and oxidation of higher-order branched alkanes, and it is also a component of commercial gasolines. To better understand its combustion characteristics, a series of ignition delay time (IDT) and laminar flame speed (LFS) measurements have been performed. In addition, flow reactor speciation data recorded for the pyrolysis and oxidation of isobutene is also reported. Predictions of an updated kinetic model described herein are compared with each of these data sets, as well as with existing jet-stirred reactor (JSR) species measurements. IDTs of isobutene oxidation were measured in four different shock tubes and in two rapid compression machines (RCMs) under conditions of relevance to practical combustors. The combination of shock tube and RCM data greatly expands the range of available validation data for isobutene oxidation models to pressures of 50 atm and temperatures in the range 666–1715 K. Isobutene flame speeds were measured experimentally at 1 atm and at unburned gas temperatures of 298–398 K over a wide range of equivalence ratios. For the flame speed results, there was good agreement between different facilities and the current model in the fuel-rich region. Ab initio chemical kinetics calculations were carried out to calculate rate constants for important reactions such as H-atom abstraction by hydroxyl and hydroperoxyl radicals and the decomposition of 2-methylallyl radicals. A comprehensive chemical kinetic mechanism has been developed to describe the combustion of isobutene and is validated by comparison to the presently considered experimental measurements. Important reactions, highlighted via flux and sensitivity analyses, include: (a) hydrogen atom abstraction from isobutene by hydroxyl and hydroperoxyl radicals, and molecular oxygen; (b) radical–radical recombination reactions, including 2-methylallyl radical self-recombination, the recombination of 2-methylallyl radicals with

  4. Biogenic emissions modeling for Southeastern Texas

    Energy Technology Data Exchange (ETDEWEB)

    Estes, M.; Jacob, D.; Jarvie, J. [Texas Natural Resource Conservation Commission, Austin, TX (United States)] [and others

    1996-12-31

    The Texas Natural Resource Conservation Commission (TNRCC) modeling staff performed biogenic hydrocarbon emissions modeling in support of gridded photochemical modeling for ozone episodes in 1992 and 1993 for the Coastal Oxidant Assessment for Southeast Texas (COAST) modeling domain. This paper summarizes the results of the biogenic emissions modeling and compares preliminary photochemical modeling results to ambient air monitoring data collected during the 1993 COAST study. Biogenic emissions were estimated using BIOME, a gridded biogenic emissions model that uses region-specific land use and biomass density data, and plant species-specific emission factor data. Ambient air monitoring data were obtained by continuous automated gas chromatography at two sites, one-hour canister samples at 5 sites, and 24-hour canister samples at 13 other sites. The concentrations of Carbon Bond-IV species (as determined from urban airshed modeling) were compared to measured hydrocarbon concentrations. In this paper, we examined diurnal and seasonal variations, as well as spatial variations.

  5. Phase-field modeling of corrosion kinetics under dual-oxidants

    Science.gov (United States)

    Wen, You-Hai; Chen, Long-Qing; Hawk, Jeffrey A.

    2012-04-01

    A phase-field model is proposed to simulate corrosion kinetics under a dual-oxidant atmosphere. It will be demonstrated that the model can be applied to simulate corrosion kinetics under oxidation, sulfidation and simultaneous oxidation/sulfidation processes. Phase-dependent diffusivities are incorporated in a natural manner and allow more realistic modeling as the diffusivities usually differ by many orders of magnitude in different phases. Simple free energy models are then used for testing the model while calibrated free energy models can be implemented for quantitative modeling.

  6. Unmetallated and metallated phthalocyanines bearing oxadiazole groups: Synthesis, photophysical and photochemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Nas, Asiye [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey); Kantekin, Halit, E-mail: halit@ktu.edu.tr [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey); Durmuş, Mahmut [Gebze Institute of Technology, Department of Chemistry, PO Box 141, Gebze, 41400 Kocaeli (Turkey); Gümrükçüoğlu, Nurhan [Department of Chemistry, Karadeniz Technical University, 61080 Trabzon (Turkey)

    2014-10-15

    Unmetallated (4) and metallated (zinc(II), cobalt(II), lead(II)) phthalocyanines (5–7) carrying four 4-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenoxy) groups on the peripheral positions were synthesized by cyclotetramerization of 4-(4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenoxy)phthalonitrile (3) in the presence of corresponding metal salts (zinc(II) acetate, cobalt(II) chloride, lead(II) oxide) for metallated and without any metal for unmetallated phthalocyanines. The obtained organo-soluble phthalocyanines were characterized by infrared, electronic absorption, nuclear magnetic resonance and mass spectral techniques and elemental analysis as well. The photophysical and photochemical properties of newly synthesized tetra-substituted unmetallated (4), zinc(II) (5) and lead(II) (7) phthalocyanines were reported in N,N-dimetilformamid (DMF). The synthesized phthalocyanine compound 6 was not evaluated for photophysical and photochemical studies due to open shell and paramagnetic behavior of cobalt(II) metal ions in the phthalocyanine cavity. - Highlights: • Synthesis of unmetallated and metallated phthalocyanines. • Photophysical and photochemical properties of tetra-substituted phthalocyanines. • Characterization of organosoluble phthalocyanines by several spectral techniques.

  7. A fresh look at the evolution and diversification of photochemical reaction centers.

    Science.gov (United States)

    Cardona, Tanai

    2015-10-01

    In this review, I reexamine the origin and diversification of photochemical reaction centers based on the known phylogenetic relations of the core subunits, and with the aid of sequence and structural alignments. I show, for example, that the protein folds at the C-terminus of the D1 and D2 subunits of Photosystem II, which are essential for the coordination of the water-oxidizing complex, were already in place in the most ancestral Type II reaction center subunit. I then evaluate the evolution of reaction centers in the context of the rise and expansion of the different groups of bacteria based on recent large-scale phylogenetic analyses. I find that the Heliobacteriaceae family of Firmicutes appears to be the earliest branching of the known groups of phototrophic bacteria; however, the origin of photochemical reaction centers and chlorophyll synthesis cannot be placed in this group. Moreover, it becomes evident that the Acidobacteria and the Proteobacteria shared a more recent common phototrophic ancestor, and this is also likely for the Chloroflexi and the Cyanobacteria. Finally, I argue that the discrepancies among the phylogenies of the reaction center proteins, chlorophyll synthesis enzymes, and the species tree of bacteria are best explained if both types of photochemical reaction centers evolved before the diversification of the known phyla of phototrophic bacteria. The primordial phototrophic ancestor must have had both Type I and Type II reaction centers.

  8. Mathematical modeling of oxygen transport in solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Svensson, Ann Mari

    1997-12-31

    This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

  9. Atmospheric photochemical degradation of 1,4-unsaturated dicarbonyls

    Energy Technology Data Exchange (ETDEWEB)

    Liu, X.; Jeffries, H.E.; Sexton, K.G.

    1999-12-01

    To better understand fates of aromatics hydrocarbon species in the atmosphere, the authors have investigated the transformation chemistry of butenedial (CHOCH{double{underscore}bond}CHCHO), 4-oxo-2-pentenal (CH{sub 3}COCH{double{underscore}bond}CHCHO), and 3-hexene-2, 5-dione (CH{sub 3}COCH{double{underscore}bond}CHCOCH{sub 3}). These 1,4-unsaturated dicarbonyls are known to be products of aromatic photochemical oxidation. Both hydroxyl radical (OH) and ozone (O{sub 3}) initiated smog chamber experiments under atmospheric conditions were conducted in the University of North Carolina outdoor smog chamber. Carbonyl intermediates and products were measured using the O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization method followed by gas chromatography/ion trap mass spectrometry analysis. Carbonyl products detected and identified by comparison with standards in the OH-initiated photooxidation of butenedial include formaldehyde, acrolein, glycolaldehyde, glyoxal, and malonaldehyde (CHOCH{sub 2}CHO). For 4-oxo-2-pentenal, the carbonyl products were formaldehyde, methyl vinyl ketone, glycolaldehyde, hydroxyacetone, glyoxal, methylglyoxal, and malonaldehyde. for 3-hexene-2,5-dione the products were formaldehyde, acetaldehyde, acetone, hydroxyacetone, and methylglyoxal. Carbonyl products detected in the P{sub 3}-initiated experiments with cyclohexane as the OH scavenger were formaldehyde and glyoxal in butenedial; formaldehyde, glyoxal, methyl-glyoxal, and malonaldehyde in 4-oxo-2-pentenal; and formaldehyde and methylglyoxal in 3-hexene-2,5-dione.

  10. Photochemical chlorine and bromine activation from artificial saline snow

    Directory of Open Access Journals (Sweden)

    S. N. Wren

    2013-10-01

    Full Text Available The activation of reactive halogen species – particularly Cl2 – from sea ice and snow surfaces is not well understood. In this study, we used a photochemical snow reactor coupled to a chemical ionization mass spectrometer to investigate the production of Br2, BrCl and Cl2 from NaCl/NaBr-doped artificial snow samples. At temperatures above the NaCl-water eutectic, illumination of samples (λ > 310 nm in the presence of gas phase O3 led to the accelerated release of Br2, BrCl and the release of Cl2 in a process that was significantly enhanced by acidity, high surface area and additional gas phase Br2. Cl2 production was only observed when both light and ozone were present. The total halogen release depended on [ozone] and pre-freezing [NaCl]. Our observations support a "halogen explosion" mechanism occurring within the snowpack, which is initiated by heterogeneous oxidation and propagated by Br2 or BrCl photolysis and by recycling of HOBr and HOCl into the snowpack. Our study implicates this important role of active chemistry occurring within the interstitial air of aged (i.e. acidic snow for halogen activation at polar sunrise.

  11. Transgenic Mouse Model for Reducing Oxidative Damage in Bone

    Science.gov (United States)

    Schreurs, A.-S.; Torres, S.; Truong, T.; Kumar, A.; Alwood, J. S.; Limoli, C. L.; Globus, R. K.

    2014-01-01

    Exposure to musculoskeletal disuse and radiation result in bone loss; we hypothesized that these catabolic treatments cause excess reactive oxygen species (ROS), and thereby alter the tight balance between bone resorption by osteoclasts and bone formation by osteoblasts, culminating in bone loss. To test this, we used transgenic mice which over-express the human gene for catalase, targeted to mitochondria (MCAT). Catalase is an anti-oxidant that converts the ROS hydrogen peroxide into water and oxygen. MCAT mice were shown previously to display reduced mitochondrial oxidative stress and radiosensitivity of the CNS compared to wild type controls (WT). As expected, MCAT mice expressed the transgene in skeletal tissue, and in marrow-derived osteoblasts and osteoclast precursors cultured ex vivo, and also showed greater catalase activity compared to wildtype (WT) mice (3-6 fold). Colony expansion in marrow cells cultured under osteoblastogenic conditions was 2-fold greater in the MCAT mice compared to WT mice, while the extent of mineralization was unaffected. MCAT mice had slightly longer tibiae than WT mice (2%, P less than 0.01), although cortical bone area was slightly lower in MCAT mice than WT mice (10%, p=0.09). To challenge the skeletal system, mice were treated by exposure to combined disuse (2 wk Hindlimb Unloading) and total body irradiation Cs(137) (2 Gy, 0.8 Gy/min), then bone parameters were analyzed by 2-factor ANOVA to detect possible interaction effects. Treatment caused a 2-fold increase (p=0.015) in malondialdehyde levels of bone tissue (ELISA) in WT mice, but had no effect in MCAT mice. These findings indicate that the transgene conferred protection from oxidative damage caused by treatment. Unexpected differences between WT and MCAT mice emerged in skeletal responses to treatment.. In WT mice, treatment did not alter osteoblastogenesis, cortical bone area, moment of inertia, or bone perimeter, whereas in MCAT mice, treatment increased these

  12. Modelling nitrous oxide emissions from grazed grassland systems

    International Nuclear Information System (INIS)

    Wang Junye; Cardenas, Laura M.; Misselbrook, Tom H.; Cuttle, Steve; Thorman, Rachel E.; Li Changsheng

    2012-01-01

    Grazed grassland systems are an important component of the global carbon cycle and also influence global climate change through their emissions of nitrous oxide and methane. However, there are huge uncertainties and challenges in the development and parameterisation of process-based models for grazed grassland systems because of the wide diversity of vegetation and impacts of grazing animals. A process-based biogeochemistry model, DeNitrification-DeComposition (DNDC), has been modified to describe N 2 O emissions for the UK from regional conditions. This paper reports a new development of UK-DNDC in which the animal grazing practices were modified to track their contributions to the soil nitrogen (N) biogeochemistry. The new version of UK-DNDC was tested against datasets of N 2 O fluxes measured at three contrasting field sites. The results showed that the responses of the model to changes in grazing parameters were generally in agreement with observations, showing that N 2 O emissions increased as the grazing intensity increased. - Highlights: ► Parameterisation of grazing system using grazing intensity. ► Modification of UK D NDC for the UK soil and weather conditions. ► Validation of the UK D NDC against measured data of N 2 O emissions in three UK sites. ► Estimating influence of animal grazing practises on N 2 O emissions. - Grazing system was parameterised using grazing intensity and UK-DNDC model was modified and validated against measured data of N 2 O emissions in three UK sites.

  13. Physical chemistry and modelling of the sintering of actinide oxides

    International Nuclear Information System (INIS)

    Lechelle, Jacques

    2013-01-01

    This report gives a synthesis of the work I have carried out or to which I have numerically contributed to from 1996 up to 2012 in the Department of Plutonium Uranium and minor Actinides in Cadarache CEA Center. Their main goal is the study and the modeling of the sintering process of nuclear fuels which is the unifying thread of this document. Both in order to take into account the physical and chemical features of the actinide bearing oxide material and in order to combine the different transport phenomena leading to sintering, a sub-granular scale model is under development. Extension to a varying chemical composition as well as exchanges with the gaseous phase are foreseen. A simulation on a larger scale (pellet scale) is ongoing in the framework of a PhD thesis. Validation means have been tested with (U,Pu)O 2 material on the scale of the pellet (Small Angle Neutron Diffusion), on the scale of powder granules (X-Ray High Resolution Micro-Tomography) and with CeO 2 at the 'Institut de Chimie Separative' in Marcoule on a single crystal scale (Environmental Scanning Electron Microscope). The required microstructure homogeneity for nuclear fuels has led to a campaign of experimental studies about the role of Cr 2 O 3 as a sintering aid. Whole of these studies improve our understanding of fuel sintering and hence leads to an improved mastering of this process. (author) [fr

  14. Effects of Photobiomodulation Therapy on Oxidative Stress in Muscle Injury Animal Models: A Systematic Review

    OpenAIRE

    dos Santos, Solange Almeida; Serra, Andrey Jorge; Stancker, Tatiane Garcia; Simões, Maíra Cecília Brandão; dos Santos Vieira, Marcia Ataíze; Leal-Junior, Ernesto Cesar; Prokic, Marko; Vasconsuelo, Andrea; Santos, Simone Silva; de Carvalho, Paulo de Tarso Camillo

    2017-01-01

    This systematic review was performed to identify the role of photobiomodulation therapy on experimental muscle injury models linked to induce oxidative stress. EMBASE, PubMed, and CINAHL were searched for studies published from January 2006 to January 2016 in the areas of laser and oxidative stress. Any animal model using photobiomodulation therapy to modulate oxidative stress was included in analysis. Eight studies were selected from 68 original articles targeted on laser irradiation and oxi...

  15. Effects of tempol and redox-cycling nitroxides in models of oxidative stress

    OpenAIRE

    Wilcox, Christopher S.

    2010-01-01

    Tempol is a redox cycling nitroxide that promotes the metabolism of many reactive oxygen species (ROS) and improves nitric oxide bioavailability. It has been studied extensively in animal models of oxidative stress. Tempol has been shown to preserve mitochondria against oxidative damage and improve tissue oxygenation. Tempol improved insulin responsiveness in models of diabetes mellitus and improved the dyslipidemia, reduced the weight gain and prevented diastolic dysfunction and heart failur...

  16. Experimental Study of Nonequilibrium Electrodeposition of Nanostructures on Copper and Nickel for Photochemical Fuel Cell Application

    Directory of Open Access Journals (Sweden)

    Rajesh K. Shanmugam

    2011-01-01

    Full Text Available To increase the performance of photochemical fuel cells, nonequilibrium electrodeposition has been performed on Cu and Ni to make photosensitive anodes. Processing parameters including electrolyte concentration, and electrode potential were studied using cyclic voltammetry. Scanning electron microscopy (SEM and X-ray Spectroscopy (EDS were performed to understand the formation of the nanostructures during the nonequilibrium deposition of copper fractals. An increase in the deposition rate was observed with the increase in electrolyte concentration (from 0.05 M to 1.0 M. Similar trend was found when the cathode potential was decreased from −0.5 V to −4.5 V. The effect of substrate material was also examined. Porous fractal structures on copper were achieved, while the deposited material showed high density of surface cracks on nickel. The fractal structures deposited on copper electrode with the increased surface area were converted into copper oxide by oxidation in air. Such oxide samples were made into anodes for photochemical fuel cell application. We demonstrated that an increase in the magnitude of open circuit output voltage is associated with the increase in the fractal surface area under the ultraviolet irradiation test conditions. However, the electrodeposited fractals on nickel showed very limited increase in the magnitude of open circuit voltage.

  17. Novel Magnetic Zinc Oxide Nanotubes for Phenol Adsorption: Mechanism Modeling

    Directory of Open Access Journals (Sweden)

    Marwa F. Elkady

    2017-11-01

    Full Text Available Considering the great impact of a material’s surface area on adsorption processes, hollow nanotube magnetic zinc oxide with a favorable surface area of 78.39 m2/g was fabricated with the assistance of microwave technology in the presence of poly vinyl alcohol (PVA as a stabilizing agent followed by sonic precipitation of magnetite nano-particles. Scanning electron microscopy (SEM and transmission electron microscopy (TEM micrographs identified the nanotubes’ morphology in the synthesized material with an average aspect ratio of 3. X-ray diffraction (XRD analysis verified the combination of magnetite material with the hexagonal wurtzite structure of ZnO in the prepared material. The immobilization of magnetite nanoparticles on to ZnO was confirmed using vibrating sample magnetometry (VSM. The sorption affinity of the synthesized magnetic ZnO nanotube for phenolic compounds from aqueous solutions was examined as a function of various processing factors. The degree of acidity of the phenolic solution has great influence on the phenol sorption process on to magnetic ZnO. The calculated value of ΔH0 designated the endothermic nature of the phenol uptake process on to the magnetic ZnO nanotubes. Mathematical modeling indicated a combination of physical and chemical adsorption mechanisms of phenolic compounds on to the fabricated magnetic ZnO nanotubes. The kinetic process correlated better with the second-order rate model compared to the first-order rate model. This result indicates the predominance of the chemical adsorption process of phenol on to magnetic ZnO nanotubes.

  18. Stoichiometric modeling of oxidation of reduced inorganic sulfur compounds (Riscs) in Acidithiobacillus thiooxidans.

    Science.gov (United States)

    Bobadilla Fazzini, Roberto A; Cortés, Maria Paz; Padilla, Leandro; Maturana, Daniel; Budinich, Marko; Maass, Alejandro; Parada, Pilar

    2013-08-01

    The prokaryotic oxidation of reduced inorganic sulfur compounds (RISCs) is a topic of utmost importance from a biogeochemical and industrial perspective. Despite sulfur oxidizing bacterial activity is largely known, no quantitative approaches to biological RISCs oxidation have been made, gathering all the complex abiotic and enzymatic stoichiometry involved. Even though in the case of neutrophilic bacteria such as Paracoccus and Beggiatoa species the RISCs oxidation systems are well described, there is a lack of knowledge for acidophilic microorganisms. Here, we present the first experimentally validated stoichiometric model able to assess RISCs oxidation quantitatively in Acidithiobacillus thiooxidans (strain DSM 17318), the archetype of the sulfur oxidizing acidophilic chemolithoautotrophs. This model was built based on literature and genomic analysis, considering a widespread mix of formerly proposed RISCs oxidation models combined and evaluated experimentally. Thiosulfate partial oxidation by the Sox system (SoxABXYZ) was placed as central step of sulfur oxidation model, along with abiotic reactions. This model was coupled with a detailed stoichiometry of biomass production, providing accurate bacterial growth predictions. In silico deletion/inactivation highlights the role of sulfur dioxygenase as the main catalyzer and a moderate function of tetrathionate hydrolase in elemental sulfur catabolism, demonstrating that this model constitutes an advanced instrument for the optimization of At. thiooxidans biomass production with potential use in biohydrometallurgical and environmental applications. Copyright © 2013 Wiley Periodicals, Inc.

  19. Internal oxidation and probabilistic fracture model of irradiation assisted stress corrosion cracking in stainless steels

    Science.gov (United States)

    Konstantinović, M. J.

    2017-11-01

    A probabilistic fracture model is applied to irradiation assisted stress corrosion cracking effect, assuming that the oxidized part of stainless steel sample plays an essential role in the crack initiation, propagation and the sample failure. The Weibull statistical distribution of time-to-failures, estimated through the correlation with the statistical distribution of oxide strengths, including both the surface oxide layer and oxidized grain boundaries, fully describe the experimental scatter obtained in the constant load time-to-failure tests. Large failure uncertainties in these type of tests originate from an intrinsic stochastic behavior of the oxide cracking due to subcritical crack propagation process.

  20. Introductory study of the chemical behavior of jet emissions in photochemical smog. [computerized simulation

    Science.gov (United States)

    Whitten, G. Z.; Hogo, H.

    1976-01-01

    Jet aircraft emissions data from the literature were used as initial conditions for a series of computer simulations of photochemical smog formation in static air. The chemical kinetics mechanism used in these simulations was an updated version which contains certain parameters designed to account for hydrocarbon reactivity. These parameters were varied to simulate the reaction rate constants and average carbon numbers associated with the jet emissions. The roles of surface effects, variable light sources, NO/NO2 ratio, continuous emissions, and untested mechanistic parameters were also assessed. The results of these calculations indicate that the present jet emissions are capable of producing oxidant by themselves. The hydrocarbon/nitrous oxides ratio of present jet aircraft emissions is much higher than that of automobiles. These two ratios appear to bracket the hydrocarbon/nitrous oxides ratio that maximizes ozone production. Hence an enhanced effect is seen in the simulation when jet exhaust emissions are mixed with automobile emissions.

  1. Localized Carbon Deposition in Solid Oxide Electrolysis Cells Studied By Multiphysics Modeling

    DEFF Research Database (Denmark)

    Navasa, Maria; Graves, Christopher R.; Frandsen, Henrik Lund

    2016-01-01

    Modeling for optimizing performance has attracted substantial research efforts in the last twenty years with special focus on solid oxide fuel cells (SOFCs). However, limited amount of the modeling work has been focused on the solid oxide electrolysis cell (SOEC) operation mode and even less...

  2. Identification of the Active Species in Photochemical Hole Scavenging Reactions of Methanol on TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Shen, Mingmin; Henderson, Michael A.

    2011-11-03

    Molecular and dissociative methanol adsorption species were prepared on rutile TiO2(110) surfaces to study photocatalytic oxidation of methanol in ultrahigh vacuum (UHV) using temperature-programmed desorption (TPD). Adsorbed methoxy groups (CH3O-) were found to be the photoactive form of adsorbed methanol converted to adsorbed formaldehyde and a surface OH group by hole-mediated C-H bond cleavage. These results suggest that adsorbed methoxy is the effective hole scavenger in photochemical reactions involving methanol.

  3. Thermodynamic and kinetic modeling of oxide precipitation in nanostructured ferritic alloys

    International Nuclear Information System (INIS)

    Barnard, L.; Cunningham, N.; Odette, G.R.; Szlufarska, I.; Morgan, D.

    2015-01-01

    The mechanical properties and radiation tolerance of nanostructured ferritic alloys rely on a dense population of nanometer-scale Y–Ti oxides. The stability of these nano-oxides during extended service is critical in high temperature applications. Here, a model framework is developed for the thermodynamics and kinetics of Y–Ti oxide nucleation, growth and coarsening. The model, which is based upon available thermodynamic and kinetic data as well as key density functional theory calculations, shows that nano-oxide nucleation and growth are highly driven and that pipe diffusion is the dominant mode of their coarsening, in agreement with previous analyses of experimental high temperature data. The model predicts that the nano-oxides are thermally stable for 80 or more years below 1175 K. This analysis also provides insights into the effect of O and Ti on nano-oxide sizes, and on optimization of alloy microstructure

  4. Impact of oxide thickness on gate capacitance – Modelling and ...

    Indian Academy of Sciences (India)

    of oxide thickness. The obtained threshold voltage is characteristic with the variation of oxide thickness and is in good agreement with the experimental results obtained by Bera et al [15]. Then, eq. (17) is plotted in MATLAB by using the necessary parameter values for. AlInN/GaN and AlGaN/GaN MOSHEMT to graphically ...

  5. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies: Evaluation Number 18

    Science.gov (United States)

    Burkholder, J. B.; Sander, S. P.; Abbatt, J. P. D.; Barker, J. R.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Orkin, V. L.; Wilmouth, D. M.; Wine, P. H.

    2015-01-01

    This is the eighteenth in a series of evaluated sets of rate constants, photochemical cross sections, heterogeneous parameters, and thermochemical parameters compiled by the NASA Panel for Data Evaluation. The data are used primarily to model stratospheric and upper tropospheric processes, with particular emphasis on the ozone layer and its possible perturbation by anthropogenic and natural phenomena. The evaluation is available in electronic form from the following Internet URL: http://jpldataeval.jpl.nasa.gov/

  6. Ignition in an Atomistic Model of Hydrogen Oxidation.

    Science.gov (United States)

    Alaghemandi, Mohammad; Newcomb, Lucas B; Green, Jason R

    2017-03-02

    Hydrogen is a potential substitute for fossil fuels that would reduce the combustive emission of carbon dioxide. However, the low ignition energy needed to initiate oxidation imposes constraints on the efficiency and safety of hydrogen-based technologies. Microscopic details of the combustion processes, ephemeral transient species, and complex reaction networks are necessary to control and optimize the use of hydrogen as a commercial fuel. Here, we report estimates of the ignition time of hydrogen-oxygen mixtures over a wide range of equivalence ratios from extensive reactive molecular dynamics simulations. These data show that the shortest ignition time corresponds to a fuel-lean mixture with an equivalence ratio of 0.5, where the number of hydrogen and oxygen molecules in the initial mixture are identical, in good agreement with a recent chemical kinetic model. We find two signatures in the simulation data precede ignition at pressures above 200 MPa. First, there is a peak in hydrogen peroxide that signals ignition is imminent in about 100 ps. Second, we find a strong anticorrelation between the ignition time and the rate of energy dissipation, suggesting the role of thermal feedback in stimulating ignition.

  7. Radiolytic oxidation of propane: Computer modeling of the reaction scheme

    Science.gov (United States)

    Gupta, Avinash K.; Hanrahan, Robert J.

    The oxidation of gaseous propane under gamma radiolysis was studied at 100 torr pressure and 25°C, at oxygen pressures from 1 to 15 torr. Major oxygen-containing products and their G-values with 10% added oxygen are as follows: acetone, 0.98; i-propyl alcohol, 0.86; propionaldehyde, 0.43; n-propyl alcohol, 0.11; acrolein, 0.14; and allyl alcohol, 0.038. Minor products include i-butyl alcohol, t-amyl alcohol, n-butyl alcohol, n-amyl alcohol, and i-amyl alcohol. Small yields of i-hexyl alcohol and n-hexyl alcohol were also observed. There was no apparent difference in the G-values at pressures of 50, 100 and 150 torr. When the oxygen concentration was decreased below 5%, the yields of acetone, i-propyl alcohol, and n-propyl alcohol increased, the propionaldehyde yield decreased, and the yields of other products remained constant. The formation of major oxygen-containing products was explained on the basis that the alkyl radicals combine with molecular oxygen to give peroxyl radicals; the peroxyl radicals react with one another to give alkoxyl radicals, which in turn react with one another to form carbonyl compounds and alcohols. The reaction scheme for the formation of major products was examined using computer modeling based on a mechanism involving 28 reactions. Yields could be brought into agreement with the data within experimental error in nearly all cases.

  8. Copper Oxide Nanoparticles for Advanced Refrigerant Thermophysical Properties: Mathematical Modeling

    Directory of Open Access Journals (Sweden)

    S. A. Fadhilah

    2014-01-01

    Full Text Available In modern days, refrigeration systems are important for industrial and domestic applications. The systems consume more electricity as compared to other appliances. The refrigeration systems have been investigated thoroughly in many ways to reduce the energy consumption. Hence, nanorefrigerant which is one kind of nanofluids has been introduced as a superior properties refrigerant that increased the heat transfer rate in the refrigeration system. Many types of materials could be used as the nanoparticles to be suspended into the conventional refrigerants. In this study, the effect of the suspended copper oxide (CuO nanoparticles into the 1,1,1,2-tetrafluoroethane, R-134a is investigated by using mathematical modeling. The investigation includes the thermal conductivity, dynamic viscosity, and heat transfer rate of the nanorefrigerant in a tube of evaporator. The results show enhanced thermophysical properties of nanorefrigerant compared to the conventional refrigerant. These advanced thermophysical properties increased the heat transfer rate in the tube. The nanorefrigerant could be a potential working fluid to be used in the refrigeration system to increase the heat transfer characteristics and save the energy usage.

  9. Towards a Predictive Thermodynamic Model of Oxidation States of Uranium Incorporated in Fe (hydr) oxides

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S. [Univ. of North Texas, Denton, TX (United States)

    2013-01-01

    -Level Excited States: Consequences For X-Ray Absorption Spectroscopy”, J. Elec. Spectros. and Related Phenom., 200, 174 (2015) describes our first application of these methods. As well as applications to problems and materials of direct interest for our PNNL colleagues, we have pursued applications of fundamental theoretical significance for the analysis and interpretation of XPS and XAS spectra. These studies are important for the development of the fields of core-level spectroscopies as well as to advance our capabilities for applications of interest to our PNNL colleagues. An excellent example is our study of the surface core-level shifts, SCLS, for the surface and bulk atoms of an oxide that provides a new approach to understanding how the surface electronic of oxides differs from that in the bulk of the material. This work has the potential to lead to a new key to understanding the reactivity of oxide surfaces. Our theoretical studies use cluster models with finite numbers of atoms to describe the properties of condensed phases and crystals. This approach has allowed us to focus on the local atomistic, chemical interactions. For these clusters, we obtain orbitals and spinors through the solution of the Hartree-Fock, HF, and the fully relativistic Dirac HF equations. These orbitals are used to form configuration mixing wavefunctions which treat the many-body effects responsible for the open shell angular momentum coupling and for the satellites of the core-level spectra. Our efforts have been in two complementary directions. As well as the applications described above, we have placed major emphasis on the enhancement and extension of our theoretical and computational capabilities so that we can treat complex systems with a greater range of many-body effects. Noteworthy accomplishments in terms of method development and enhancement have included: (1) An improvement in our treatment of the large matrices that must be handled when many-body effects are treated. (2

  10. Implementation of marine halogen chemistry into the Community Multiscale Air Quality (CMAQ) model

    Science.gov (United States)

    Gantt, B.; Sarwar, G.

    2017-12-01

    In two recent studies (Sarwar et al, 2015 and Gantt et al., 2017), the impact of marine halogen (bromine and iodine) chemistry on air quality has been evaluated using the Community Multiscale Air Quality (CMAQ) model. We found that marine halogen chemistry not only has the expected effect of reducing marine boundary layer ozone concentrations, but also reduces ozone in the free troposphere and inland from the coast. In Sarwar et al. (2015), the impact of the halogen chemistry without and with photochemical reactions of higher iodine oxides over the Northern Hemisphere was examined using the coarse horizontal grids of a hemispheric domain. Halogen chemistry without and with the photochemical reactions of higher iodine oxides reduces ozone over seawater by 15% and 48%, respectively. Using the results of the chemistry without the photochemical reactions of higher iodine oxides, we developed a simple first order ozone loss rate and implemented it into the public version of CMAQv52. In Gantt et al. (2017), the impact of the simple first order loss rate as well as the full halogen chemistry without photochemical reactions of higher iodine oxides over the continental United States was examined using finer horizontal grids of the regional domain and boundary conditions from the hemispheric domain with and without marine halogen chemistry. The boundary conditions obtained with the halogen chemistry as well as the simple halogen chemistry reduces ozone along the coast where CMAQ typically overpredicts the concentrations. Development of halogen chemistry in CMAQ has continued with the implementation of several heterogeneous reactions of bromine and iodine species, revised reactions of higher iodine oxides, and a refined marine halogen emissions inventory. Our latest version of halogen chemistry with photochemical reactions of higher iodine oxides reduces ozone by 23% over the seawater. This presentation will discuss the previous and ongoing implementation of revised halogen

  11. Method of making gold thiolate and photochemically functionalized microcantilevers

    Science.gov (United States)

    Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

    2009-08-25

    Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

  12. Photochemical Reaction Altered Cardiac Toxicity of Diesel Exhaust Inhalation

    Science.gov (United States)

    Rationale: Epidemiological studies have indicated an association between urban air pollution exposure and cardiovascular morbidity and mortality. The present study was designed to evaluate the cardiac effects of inhaled diesel exhaust and compared with photochemically altered d...

  13. Photochemical ozone budget during the BIBLE A and B campaigns

    Science.gov (United States)

    Ko, Malcolm; Hu, Wenjie; Rodríguez, José M.; Kondo, Yutaka; Koike, Makoto; Kita, Kazuyuki; Kawakami, Shuji; Blake, Donald; Liu, Shaw; Ogawa, Toshihiro

    2003-02-01

    Using the measured concentrations of NO, O3, H2O, CO, CH4, and NMHCs along the flight tracks, a photochemical box model is used to calculate the concentrations of the Ox radicals, the HOx radicals, and the nitrogen species at the sampling points. The calculations make use of the measurements from radiometers to scale clear sky photolysis rates to account for cloud cover and ground albedo at the sampling time/point. The concentrations of the nitrogen species in each of the sampled air parcels are computed assuming they are in instantaneous equilibrium with the measured NO and O3. The diurnally varying species concentrations are next calculated using the box model and used to estimate the diurnally averaged production and removal rates of ozone for the sampled air parcels. Clear sky photolysis rates are used in the diurnal calculations. The campaign also provided measured concentration of NOy. The observed NO/NOy ratio is usually larger than the model calculated equilibrium value. There are several possible explanations. It could be a result of recent injection of NO into the air parcel, recent removal of HNO3 from the parcel, recent rapid transport of an air parcel from another location, or a combination of all processes. Our analyses suggest that the local production rate of O3 can be used as another indicator of recent NO injection. However, more direct studies using air trajectory analyses and other collaborative evidences are needed to ascertain the roles played by individual process.

  14. Photochemical etching of GaAs using synchrotron radiation

    Energy Technology Data Exchange (ETDEWEB)

    Terakado, Shingo; Nishino, Jun-ichi; Morigami, Mitsuaki; Harada, Mitsuaki; Suzuki, Shigeo (SANYO Electric Co. Ltd., Tsukuba, Ibaraki (Japan). Tsukuba Research Center); Tanaka, Kenichiro; Chikawa, Jun-ichi

    1990-05-01

    The photochemical etching of gallium arsenide by chlorine was investigated using synchrotron radiation. At the substrate temperatures above 25degC, both the irradiated and nonirradiated regions were uniformly etched. In case of substrate temperatures below -25degC, highly selective etching was observed in the irradiated region. We considered that at low temperatures, etching reaction caused by gas-phase excitation is suppressed and photochemical surface reaction becomes dominant. (author).

  15. Aquatic photochemical kinetics of benzotriazole and structurally related compounds

    OpenAIRE

    Janssen Elisabeth M. L.; Marron Emily; McNeill Kristopher

    2015-01-01

    Benzotriazole corrosion inhibitors are not completely removed during wastewater treatment and are frequently detected in surface waters. Here the photochemical kinetics of benzotriazoles and structurally related compounds were assessed for natural aqueous environments. The direct photochemical half lives during exposure to simulated sunlight ranged from 1.3 to 1.8 days for benzotriazole and its derivatives (4 methyl 5 methyl 4 hydroxy substituted benzotriazoles). Benzotriazole is more resis...

  16. Ab Initio Thermodynamic Modeling of Electrified Metal-Oxide Interfaces

    DEFF Research Database (Denmark)

    Zeng, Zhenhua; Hansen, Martin Hangaard; Greeley, Jeff

    2015-01-01

    Solid oxide fuel cells are attractive devices in a sustainable energy context because of their fuel flexibility and potentially highly efficient conversion of chemical to electrical energy. The performance of the device is to a large extent determined by the atomic structure of the electrode...... the structural information can be used as a starting point for accurate calculations of the kinetics of fuel oxidation reactions, in particular the hydrogen oxidation reaction. More generally, we anticipate that the scheme will be a valuable theoretical tool to describe solid-solid interfaces. [Figure]...

  17. One-step surface selective modification of UV-curable hard coatings with photochemical metal organics

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yoon Kwang; Park, Chang-Sun; Park, Hyung-Ho, E-mail: hhpark@yonsei.ac.kr

    2016-12-15

    Graphical abstract: This study demonstrates suitable for exceptional hybrid film under UV exposure. A small quantity of the dispersive photochemical precursor Sr 2-ethylhexanoate was mixed and the composition altered from the surface to the bottom, forming an organic layer and a densely concentrated SrO surface layer. The surface-selective SrO strongly enhanced the surface flatness and hardness of the UV-curable organic coating film. - Highlights: • Hybrid bi-layer coating was synthesized through one-pot UV exposure chemical route. • The influence of additive and different reactivity formed densely concentrated SrO surface layer. • Chemical composition and continuous interface between organic and inorganic were analyzed. • Surface flatness and mechanical property were improved by inorganic material. - Abstract: An organic–inorganic hybrid bi-layer film with a selective distribution of inorganic components was synthesized from a one-pot process of UV irradiation. A photochemical metal oxide precursor (Sr 2-ethylhexanoate) varying from 0 to 4 wt% was dispersed in UV-curable coating materials. Under UV exposure, the bi-layer started reacting simultaneously but at different rates due to differences in the two UV-condensable components’ reactivity. The effects of the dispersed inorganic component on the surface morphology and mechanical properties were investigated by atomic force microscopy and nanoindentation, respectively. The reaction process and rates were studied from linkage change using Fourier transform infrared spectroscopy at various UV exposure times (0–30 min). The elemental distribution and the interface on the coating layer were characterized by X-ray photoelectron spectroscopy from Ar etching, revealing continuous and gradual composition changes in depth. The results showed that a flattened and surface-selectively hardened SrO containing the coating film could be obtained by this simple process. Consequently, a small ratio of photochemical

  18. Degradation of artificial sweeteners via direct and indirect photochemical reactions.

    Science.gov (United States)

    Perkola, Noora; Vaalgamaa, Sanna; Jernberg, Joonas; Vähätalo, Anssi V

    2016-07-01

    We studied the direct and indirect photochemical reactivity of artificial sweeteners acesulfame, saccharin, cyclamic acid and sucralose in environm entally relevant dilute aqueous solutions. Aqueous solutions of sweeteners were irradiated with simulated solar radiation (>290 nm; 96 and 168 h) or ultraviolet radiation (UVR; up to 24 h) for assessing photochemical reactions in surface waters or in water treatment, respectively. The sweeteners were dissolved in deionised water for examination of direct photochemical reactions. Direct photochemical reactions degraded all sweeteners under UVR but only acesulfame under simulated solar radiation. Acesulfame was degraded over three orders of magnitude faster than the other sweeteners. For examining indirect photochemical reactions, the sweeteners were dissolved in surface waters with indigenous dissolved organic matter or irradiated with aqueous solutions of nitrate (1 mg N/L) and ferric iron (2.8 mg Fe/L) introduced as sensitizers. Iron enhanced the photodegradation rates but nitrate and dissolved organic matter did not. UVR transformed acesulfame into at least three products: iso-acesulfame, hydroxylated acesulfame and hydroxypropanyl sulfate. Photolytic half-life was one year for acesulfame and more than several years for the other sweeteners in surface waters under solar radiation. Our study shows that the photochemical reactivity of commonly used artificial sweeteners is variable: acesulfame may be sensitive to photodegradation in surface waters, while saccharin, cyclamic acid and sucralose degrade very slowly even under the energetic UVR commonly used in water treatment.

  19. Study of the photochemical isomerization of ergosterol

    International Nuclear Information System (INIS)

    Mermet-Bouvier, Rene

    1972-01-01

    The photochemical reaction scheme of Ergosterol-Vitamin D 2 was studied. The schemes proposed in published literature are described together with earlier methods used for the analysis and determination. The method used is then discussed. In the first part, the factors concerning the changes occurring in molecular systems exposed to radiation, and the formalism used, are examined. Investigations of linear molecular systems and their applications to the reaction scheme of Ergosterol-Vitamin D 2 are discussed. The properties which enable the last three reaction schemes proposed in the literature to be distinguished are described. In the second part, the experimental analytical methods and the determinations made of the different isomers formed are presented. Chromatographic techniques (thin films, columns, gaseous phase) suitable for separating the various isomeric species are used. The existence of 8 isomers was established as well as a transformation occurring in one of them. The ultraviolet and infrared spectra were obtained. A reaction scheme is proposed (in which all the quantum yield values are given) from comparisons between the calculated and experimental values of the eigenvalue of the absolute minimum value λ m and the eigenvector corresponding to V m . (author) [fr

  20. Photochemical synthesis of polygonal gold nanoparticles

    International Nuclear Information System (INIS)

    Huang, W.-C.; Chen, Y.-C.

    2008-01-01

    In this paper, we propose a method to generate gold nanoparticles capable of absorbing near infrared light (NIR) radiation through a photochemical reaction. This approach does not require the use of either surfactants or polymers, reducing the difficulties that may arise in further chemical modifications for the gold nanoparticles. The gold nanoparticles with either triangular or hexagonal shapes were generated using the photo-reduction method, mixing hydrogen tetrachloroaurate with sodium oxalate, a reducing agent, in aqueous solution under illumination of a mercury lamp (λ max = 306 nm) for more than 10 min. The size of the gold nanoparticles varies from 25 to 200 nm, which mainly depends on the duration of light illumination and the concentration of sodium oxalate. Furthermore, we demonstrate that the presence of the gold nanoparticles in aqueous solutions can effectively elevate the temperature of the solutions under irradiation of NIR light (808 nm) within a few minutes. The gold nanoparticles can be potentially used as suitable photothermal agents for hyperthermia

  1. Photochemical synthesis of biomolecules under anoxic conditions

    Science.gov (United States)

    Folsome, Clair; Brittain, Andrew; Zelko, Michael

    1983-03-01

    We report the long-wavelength UV anoxic photosynthesis of uracil, various sugars (including deoxyribose and glycoaldehyde), amino acids, and other organic photoproducts. These reactions occur in mixtures of water, calcium carbonate, formaldehyde and hydrazine. Our data demonstrate that under several sets of conditions biomolecules can be formed in variety and abundance from reduced compounds (formaldehyde and hydrazine) derived from anoxic dinitrogen/carbon dioxide environments. The formaldehyde concentrations were varied from 10 mM to 0.005 mM, and the hydrazine concentrations were varied from 1 mM to 0.01 mM. The highest of these reactant concentrations were 500 and 6 times greater than those reported for earlier experiments upon the synthesis of these precursors from CO2 or N2, while the lowest of reactant concentrations employed here were 0.5 (formaldehyde) and 0.006 (hydrazine). Product yields were greatest when the hydrazine/formaldehyde ratio was 1, and when the reactant concentrations were low. These data suggest that organic products can be formed in variety from those amounts of formaldehyde and hydrazine precursors which are themselves formed under anoxic UV photochemical conditions. Hence these various reactions would seem to have prebiotic relevance. The UV 254 nm photon flux employed was 100 times higher than unattenuated solar flux. Durations of UV exposure were 24 hrs and 72 hrs. No experiments have been addressed to the possibility of UV flux dependency.

  2. Cladding oxidation model development based on diffusion equations and a simulation of the monoclinic-tetragonal phase transformation of zirconia during transient oxidation

    Science.gov (United States)

    He, Xiaoqiang; Yu, Hongxing; Jiang, Guangming; Dang, Gaojian; Wu, Dan; Zhang, Yu

    2014-08-01

    Zircaloy cladding oxidation is mostly represented by parabolic rate correlation. But the correlation approach is not suitable for long-term isothermal oxidation [4] or oxidation occurs under steam starvation conditions [5] and cannot obtain the detailed oxygen distribution which impacts the detailed mechanical behavior. To obtain the detailed oxygen distribution, a multi-phase diffusion problem with moving boundaries was introduced to simulate the cladding oxidation [9,10]. However, the hysteresis phenomenon related to the coexistence of monoclinic-tetragonal phases of zirconia which are very important to model the cladding oxidation during a LOCA, is not analyzed. In this study, a cladding oxidation model based on diffusion equations in the temperature range from 923 K to 2098 K which contains β-Zr, α-Zr, monoclinic-ZrO2, tetragonal-ZrO2, and cubic-ZrO2 is developed and the detailed oxygen distribution in the cladding could be obtained. It showed that the simulations of short-term and long-term isothermal oxidation, transient oxidation, and oxidation under steam starvation conditions were reasonable through comparing with the experimental data. We found that our model can give a reasonable simulation of the hysteresis phenomenon of monoclinic-tetragonal phase transformation during transient oxidation as well as a much better simulation of the hypothetical LOCA transient oxidation experiments [11] in ORNL than that by the code based on the parabolic rate correlation. This indicates that the developed model can accurately simulate the cladding oxidation during a LOCA transient.

  3. Modelling nitrous oxide emissions from cropland at the regional scale

    Directory of Open Access Journals (Sweden)

    Gabrielle Benoît

    2006-11-01

    Full Text Available Arable soils are a large source of nitrous oxide (N2O emissions, making up half of the biogenic emissions worldwide. Estimating their source strength requires methods capable of capturing the spatial and temporal variability of N2O emissions, along with the effects of crop management. Here, we applied a process-based model, CERES, with geo-referenced input data on soils, weather, and land use to map N2O emissions from wheat-cropped soils in three agriculturally intensive regions in France. Emissions were mostly controlled by soil type and local climate conditions, and only to a minor extent by the doses of fertilizer nitrogen applied. As a result, the direct emission factors calculated at the regional level were much smaller (ranging from 0.0007 to 0.0033 kg N2O-N kg–1 N than the value of 0.0125 kg N2O-N kg–1 N currently recommended in the IPCC Tier 1 methodology. Regional emissions were far more sensitive to the soil microbiological parameter s governing denitrification and its fraction evolved as N2O, soil bulk density, and soil initial inorganic N content. Mitigation measures should therefore target a reduction in the amount of soil inorganic N upon sowing of winter crops, and a decrease of the soil N2O production potential itself. From a general perspective, taking into account the spatial variability of soils and climate thereby appears necessary to improve the accuracy of national inventories, and to tailor mitigation strategies to regional characteristics. The methodology and results presented here may easily be transferred to winter oilseed rape, whose has growing cycle and fertilser requirements are similar.

  4. 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.

  5. Behaviour of defective CANDU fuel: fuel oxidation kinetic and thermodynamic modelling

    International Nuclear Information System (INIS)

    Higgs, J.

    2005-01-01

    The thermal performance of operating CANDU fuel under defect conditions is affected by the ingress of heavy water into the fuel element. A mechanistic model has been developed to predict the extent of fuel oxidation in defective fuel and its affect on fuel thermal performance. A thermodynamic treatment of such oxidized fuel has been performed as a basis for the boundary conditions in the kinetic model. Both the kinetic and thermodynamic models have been benchmarked against recent experimental work. (author)

  6. Sunlight technologies for photochemical deactivation of organic pollutants in water

    Energy Technology Data Exchange (ETDEWEB)

    Acher, A.; Fischer, E.; Tornheim, R. [The Volcani Center, Inst. of Soils and Water, Bet Dagan (Israel); Manor, Y. [Sheba Medical Center, Central Virology Lab., Ramat Gan (Israel)

    1997-12-31

    Sensitized-photochemical oxidation methods aimed at use in water treatment technologies for deactivation of biotic (microorganisms) and/or of xenobiotic (pesticides) pollutants in water were developed using global solar radiation or concentrated sunlight (up to 250 suns). The solar global radiation was used either for detoxification of industrial waste water from a pesticide factory to allow their discharge into the urban sewer, or for disinfection of domestric effluents to be used in crop irrigation. The disinfection process was eventually carried out in an experimental pilot-scale plant, capable of disinfection up to 50 m{sup 3}/h of effluent supplied by an activated sludge sewage treatment plant located in Tel-Aviv area. The treated effluents did not show any regrowth of the microorganisms during 7 days. The solar concentrated radiation experiments performed using facilities of the Sun Tower of The Weizman Institute of Science, Rehovot. The concentrated sunlight was provided by different combination of several computer controlled heliostates, up to 8, that track the sun and focus the received sunlight onto the target situated on the roof of the sun-tower. The sunlight intensities measured on the target reached up to 200 kW/m{sup 2}. The experiments were performed either batch- or continuous-wise. The water-samples exposed to disinfection were the above effluent, filtered and supplemented with vaccine strain poliovirus or with different concentrations of an industrial potential pollutant (bromacil), MB 2 mg/L and two concentrations of dissolved oxygen (8.0 or 40.0 mg O{sub 2}/L). An exposure time of 2-3 seconds at 150 kW/m{sup 2} was decreased the microorganisms alive (counts) by five orders of magnitude. A comparison between the two above water treatment technologies is presented. (orig./SR)

  7. The role of lager beer yeast in oxidative stability of model beer

    DEFF Research Database (Denmark)

    Berner, Torben Sune; Arneborg, Nils

    2012-01-01

    AIMS: In this study, we investigated the relationship between the ability of lager brewing yeast strains to tolerate oxidative stress and their ability to produce oxidative stable model beer. METHODS AND RESULTS: Screening of 21 lager brewing yeast strains against diamide and paraquat showed...

  8. Experimental kinetic study and modeling of calcium oxide carbonation

    International Nuclear Information System (INIS)

    Rouchon, L.

    2012-01-01

    Anthropogenic carbon dioxide (CO 2 ) emissions, major contributors to the greenhouse effect, are considered as the main cause of global warming. So, decrease of CO 2 emitted by large industrial combustion sources or power plants, is an important scientific goal. One of the approaches is based on CO 2 separation and capture from flue gas, followed by sequestration in a wide range of geological formations. In this aim, CO 2 is captured by sorbents like calcium oxide (CaO) in multi-cycle process of carbonation/de-carbonation. However, it was shown that the most important limitations of such process are related to the reversibility of reaction. CaO rapidly loses activity towards CO 2 , so the maximum extent of carbonation decreases as long as the number of cycles increases. In order to well understand the processes and parameters influencing the capture capacity of CaO-based sorbents, it appears important to get details on the kinetic law governing the reaction, which have not been really studied up to now. To investigate this reaction, CaO carbonation kinetics was followed by means of thermogravimetric analysis (TGA) on divided materials. Special care was given to the validation of the usual kinetic assumptions such as steady state and rate-determining step assumptions. The aim was to obtain a model describing the reaction in order to explain the influence of intensive variables such as carbonation temperature and CO 2 partial pressure. TGA curves obtained under isothermal and isobaric conditions showed an induction period linked to the nucleation process and a strong slowing down of the reaction rate once a given fractional conversion was reached. Both phenomena were observed to depend on carbonation temperature and CO 2 partial pressure. To explain these results, the evolution of texture and microstructure of the solid during the reaction was regarded as essential. Reaction at the grain scale induces a volume increase from CaO to CaCO 3 which causes a change in the

  9. Mesozeaxanthin Protects Retina from Oxidative Stress in a Rat Model.

    Science.gov (United States)

    Orhan, Cemal; Akdemir, Fatih; Tuzcu, Mehmet; Sahin, Nurhan; Yilmaz, Ismet; Deshpande, Jayant; Juturu, Vijaya; Sahin, Kazim

    2016-11-01

    Mesozeaxanthin (MZ) is able to protect against chronic and cumulative eye damage and neutralize free radicals produced by oxidative stress. The objective of the present study was to evaluate the protective potential of MZ against retinal oxidative damage and growth and transcription factors of the retina in rats fed with high-fat diet (HFD). Twenty-eight Sprague Dawley rats were randomly divided into the following 4 groups: (1) Control, (2) MZ (100 mg/kg bw/d), (3) HFD (42% of calories as fat), and (4) HFD+MZ (100 mg/kg bw/d) group rats were administered daily as supplement for 12 weeks. Consumption of HFD was associated with hyperglycemia and oxidative stress as reflected by increased serum MDA concentration (P retina of rats fed with HFD had increased levels of vascular endothelial growth factor (VEGF), inducible nitric oxide (iNOS), intercellular adhesion molecule-1 (ICAM-1), and nuclear factor-kappa B (NF-κB) levels and decreased nuclear factor erythroid 2-related factor 2 (Nrf2) and heme-oxygenase 1(HO-1) levels compared to the healthy rat retina (P retina of rats fed (P retina and the ability to modulate oxidative stress of retina in rats fed an HFD by suppressing retinal lipid peroxidation and regulating growth and transcription factors.

  10. In vitro model suggests oxidative stress involved in keratoconus disease

    Science.gov (United States)

    Karamichos, D.; Hutcheon, A. E. K.; Rich, C. B.; Trinkaus-Randall, V.; Asara, J. M.; Zieske, J. D.

    2014-04-01

    Keratoconus (KC) affects 1:2000 people and is a disorder where cornea thins and assumes a conical shape. Advanced KC requires surgery to maintain vision. The role of oxidative stress in KC remains unclear. We aimed to identify oxidative stress levels between human corneal keratocytes (HCKs), fibroblasts (HCFs) and keratoconus cells (HKCs). Cells were cultured in 2D and 3D systems. Vitamin C (VitC) and TGF-β3 (T3) were used for 4 weeks to stimulate self-assembled extracellular matrix (ECM). No T3 used as controls. Samples were analyzed using qRT-PCR and metabolomics. qRT-PCR data showed low levels of collagen I and V, as well as keratocan for HKCs, indicating differentiation to a myofibroblast phenotype. Collagen type III, a marker for fibrosis, was up regulated in HKCs. We robustly detected more than 150 metabolites of the targeted 250 by LC-MS/MS per condition and among those metabolites several were related to oxidative stress. Lactate levels, lactate/malate and lactate/pyruvate ratios were elevated in HKCs, while arginine and glutathione/oxidized glutathione ratio were reduced. Similar patterns found in both 2D and 3D. Our data shows that fibroblasts exhibit enhanced oxidative stress compared to keratocytes. Furthermore the HKC cells exhibit the greatest level suggesting they may have a myofibroblast phenotype.

  11. Models for the Configuration and Integrity of Partially Oxidized Fuel Rod Cladding at High Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Siefken, L.J.

    1999-01-01

    Models were designed to resolve deficiencies in the SCDAP/RELAP5/MOD3.2 calculations of the configuration and integrity of hot, partially oxidized cladding. These models are expected to improve the calculations of several important aspects of fuel rod behavior. First, an improved mapping was established from a compilation of PIE results from severe fuel damage tests of the configuration of melted metallic cladding that is retained by an oxide layer. The improved mapping accounts for the relocation of melted cladding in the circumferential direction. Then, rules based on PIE results were established for calculating the effect of cladding that has relocated from above on the oxidation and integrity of the lower intact cladding upon which it solidifies. Next, three different methods were identified for calculating the extent of dissolution of the oxidic part of the cladding due to its contact with the metallic part. The extent of dissolution effects the stress and thus the integrity of the oxidic part of the cladding. Then, an empirical equation was presented for calculating the stress in the oxidic part of the cladding and evaluating its integrity based on this calculated stress. This empirical equation replaces the current criterion for loss of integrity which is based on temperature and extent of oxidation. Finally, a new rule based on theoretical and experimental results was established for identifying the regions of a fuel rod with oxidation of both the inside and outside surfaces of the cladding. The implementation of these models is expected to eliminate the tendency of the SCDAP/RELAP5 code to overpredict the extent of oxidation of the upper part of fuel rods and to underpredict the extent of oxidation of the lower part of fuel rods and the part with a high concentration of relocated material. This report is a revision and reissue of the report entitled, Improvements in Modeling of Cladding Oxidation and Meltdown.

  12. Metal Oxide Nanomaterial QNAR Models: Available Structural Descriptors and Understanding of Toxicity Mechanisms

    Directory of Open Access Journals (Sweden)

    Jiali Ying

    2015-10-01

    Full Text Available Metal oxide nanomaterials are widely used in various areas; however, the divergent published toxicology data makes it difficult to determine whether there is a risk associated with exposure to metal oxide nanomaterials. The application of quantitative structure activity relationship (QSAR modeling in metal oxide nanomaterials toxicity studies can reduce the need for time-consuming and resource-intensive nanotoxicity tests. The nanostructure and inorganic composition of metal oxide nanomaterials makes this approach different from classical QSAR study; this review lists and classifies some structural descriptors, such as size, cation charge, and band gap energy, in recent metal oxide nanomaterials quantitative nanostructure activity relationship (QNAR studies and discusses the mechanism of metal oxide nanomaterials toxicity based on these descriptors and traditional nanotoxicity tests.

  13. An atmospheric photochemical source of the persistent greenhouse gas CF4

    Science.gov (United States)

    Jubb, Aaron M.; McGillen, Max R.; Portmann, Robert W.; Daniel, John S.; Burkholder, James B.

    2015-11-01

    A previously uncharacterized atmospheric source of the persistent greenhouse gas tetrafluoromethane, CF4, has been identified in the UV photolysis of trifluoroacetyl fluoride, CF3C(O)F, which is a degradation product of several halocarbons currently present in the atmosphere. CF4 quantum yields in the photolysis of CF3C(O)F were measured at 193, 214, 228, and 248 nm, wavelengths relevant to stratospheric photolysis, to be (75.3 ± 1) × 10-4, (23.7 ± 0.4) × 10-4, (6.6 ± 0.2) × 10-4, and ≤0.4 × 10-4, respectively. A 2-D atmospheric model was used to estimate the contribution of the photochemical source to the global CF4 budget. The atmospheric photochemical production of CF4 from CF3CH2F (HFC-134a), CF3CHFCl (HCFC-124), and CF3CCl2F (CFC-114a) per molecule emitted was calculated to be (1-2.5) × 10-5, 1.0 × 10-4, and 2.8 × 10-3, respectively. Although CF4 photochemical production was found to be relatively minor at the present time, the identified mechanism demonstrates that long-lived products with potential climate impacts can be formed from the atmospheric breakdown of shorter-lived source gases.

  14. Models for solid oxide fuel cell systems exploitation of models hierarchy for industrial design of control and diagnosis strategies

    CERN Document Server

    Marra, Dario; Polverino, Pierpaolo; Sorrentino, Marco

    2016-01-01

    This book presents methodologies for optimal design of control and diagnosis strategies for Solid Oxide Fuel Cell systems. A key feature of the methodologies presented is the exploitation of modelling tools that balance accuracy and computational burden.

  15. Could clinical photochemical internalisation be optimised to avoid neuronal toxicity?

    Science.gov (United States)

    O'Rourke, Caitriona; Hopper, Colin; MacRobert, Alexander J; Phillips, James B; Woodhams, Josephine H

    2017-08-07

    Photochemical Internalisation (PCI) is a novel drug delivery technology in which low dose photodynamic therapy (PDT) can selectively rupture endo/lysosomes by light activation of membrane-incorporated photosensitisers, facilitating intracellular drug release in the treatment of cancer. For PCI to be developed further, it is important to understand whether nerve damage is an impending side effect when treating cancers within or adjacent to nervous system tissue. Dorsal root ganglion (DRG) neurons and their associated satellite glia were subjected to PCI treatment in a 3D co-culture system following incubation with photosensitisers: meso-tetraphenylporphine (TPPS 2a ) or tetraphenylchlorin disulfonate (TPCS 2 a) and Bleomycin. Results from the use of 3D co-culture models demonstrate that a cancer cell line PCI30 and satellite glia were more sensitive to PCI than neurons and mixed glial cells, athough neurite length was affected. Neurons in culture survived PCI treatment under conditions sufficient to kill tumour cells, suggesting cancers within or adjacent to nervous system tissue could be treated with this novel technology. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  16. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  17. Arsenate and phosphate adsorption in relation to oxides composition in soils: LCD modeling.

    Science.gov (United States)

    Cui, Yanshan; Weng, Liping

    2013-07-02

    The pH dependent solid-solution distribution of arsenate and phosphate in five Dutch agricultural soil samples was measured in the pH range 4-8, and the results were interpreted using the LCD (ligand and charge distribution) adsorption modeling. The pH dependency is similar for both oxyanions, with a minimum soluble concentration observed around pH 6-8. This pH dependency can be successfully described with the LCD model and it is attributed mainly to the synergistic effects from Ca adsorption. The solubility of phosphate is much lower than that of arsenate. This big difference cannot be sufficiently explained by the reduction of small amount of As(V) into As(III), neither by slow desorption/adsorption. The difference between phosphate and arsenate in their solid-solution distribution becomes larger with the increase of aluminum (hydr)oxides (Al-oxides) contribution to the total amount of metal (Al and Fe) (hydr)oxides. The influence of Al-oxides is much larger than its relative amount extracted from the soils. When Al-oxides account for >40% of the soil oxides, the whole adsorbents behave apparently similarly to that of pure Al-oxides. These results indicated that surface coating and substitution may have modified significantly oxyanion adsorption to Fe-oxides in soils, and how to account for this complexity is a challenge for geochemical modeling.

  18. Impact of oxide thickness on gate capacitance – Modelling and ...

    Indian Academy of Sciences (India)

    approaches the nanometer regime, the oxide capacitance Cox becomes comparable to the inversion layer capacitance Cinv which means that the quantum capacitance CQ and the centroid capacitance Ccent start to affect the gate capacitance [8]. The centroid capacitance. Ccent is related to the average physical distance ...

  19. Ammonia-oxidizing bacteria: A model for molecular microbial ecology

    NARCIS (Netherlands)

    Kowalchuk, G.A.; Stephen, J.R.

    2001-01-01

    The eutrophication of many ecosystems in recent decades has led to an increased interest in the ecology of nitrogen transformation. Chemolitho-autotrophic ammonia-oxidizing bacteria are responsible for the rate-limiting step of nitrification in a wide variety of environments, making them important

  20. SO2 oxidation catalyst model systems characterized by thermal methods

    DEFF Research Database (Denmark)

    Hatem, G; Eriksen, Kim Michael; Gaune-Escard, M

    2002-01-01

    ) and Differential Scanning Calorimetry (DSC). Fundamental thermodynamic data like temperatures and molar heats of solid-solid transition and fusion, phase diagrams, heat capacities of solids and liquids, heat of mixing and heats of complex formation have been obtained and the results are discussed in relation...... to the mechanism Of SO2 oxidation by V2O5 based industrial catalysts....

  1. Studies on energy consumption patterns for improving air quality in the seoul metropolitan area. pt. 3 Status of photochemical air pollution and control technologies

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Seong Soo; Son, Jae Ik; Park, Young Ok; Kim, Hong Yong; Cho, Sung Ho [Korea Inst. of Energy Research, Taejon (Korea, Republic of)

    1995-12-01

    1. Status of photochemical air pollution in the capital area and control strategy. The results of this study show that the air quality in the capital area has an indication of regional photochemical air pollution. Primary pollutants can be controlled at the emission sources, but it is not easy to find the target of photochemical pollution control. For effective photochemical pollution control, basic studies on the fraction of VOCs in total hydrocarbon emissions, the composition of VOCs, and non-traditional emissions such as those from solvent use should be conducted. Comprehensive studies on photochemical pollution control strategies in this report would be useful for identifying essential factors on devising strategies. 2. Air quality modelling using STEM-II. Modelling domain in the last year was confined to the capital area that was too small for a regional-scale model. Modeling domain in this year covered the east of China to the East Sea. The results of modeling in this year were much better than those of the last year. However, the limitations associated with incomplete input data and modeling domain that was too large for the capital area would not be overcome without sufficient basic studies. (author). 29 refs., 34 figs., 21 tabs.

  2. Effects of Photobiomodulation Therapy on Oxidative Stress in Muscle Injury Animal Models: A Systematic Review.

    Science.gov (United States)

    Dos Santos, Solange Almeida; Serra, Andrey Jorge; Stancker, Tatiane Garcia; Simões, Maíra Cecília Brandão; Dos Santos Vieira, Marcia Ataíze; Leal-Junior, Ernesto Cesar; Prokic, Marko; Vasconsuelo, Andrea; Santos, Simone Silva; de Carvalho, Paulo de Tarso Camillo

    2017-01-01

    This systematic review was performed to identify the role of photobiomodulation therapy on experimental muscle injury models linked to induce oxidative stress. EMBASE, PubMed, and CINAHL were searched for studies published from January 2006 to January 2016 in the areas of laser and oxidative stress. Any animal model using photobiomodulation therapy to modulate oxidative stress was included in analysis. Eight studies were selected from 68 original articles targeted on laser irradiation and oxidative stress. Articles were critically assessed by two independent raters with a structured tool for rating the research quality. Although the small number of studies limits conclusions, the current literature indicates that photobiomodulation therapy can be an effective short-term approach to reduce oxidative stress markers (e.g., thiobarbituric acid-reactive) and to increase antioxidant substances (e.g., catalase, glutathione peroxidase, and superoxide dismutase). However, there is a nonuniformity in the terminology used to describe the parameters and dose for low-level laser treatment.

  3. Efficacy of chitosan in inhibiting the oxidation of (+)-catechin in white wine model solutions.

    Science.gov (United States)

    Chinnici, Fabio; Natali, Nadia; Riponi, Claudio

    2014-10-08

    The efficacy of chitosan and sulfites in inhibiting the oxidation of (+)-catechin in aerated model white wines has been compared by monitoring the browning development and the generation of oxidized phenolic compounds. In addition, the protecting effects of these two additives toward the oxidative decay of varietal thiols were investigated. Chitosan effectively contrasted the browning onset in model solutions all along the entire duration of the experimentation. Color development was limited and comparable in both the sulfite and chitosan added samples. Thanks to its polyelectrolyte behavior, chitosan adsorbed up to 80% of the more hydrophilic oxidized phenolic species and chelated 70 and 30% of Fe and Cu added to the solutions, respectively. Thiol oxidation was significantly lowered by chitosan, suggesting that this additive could contribute to maintain the varietal character of wines coming from aromatic grapes and vinified with reduced sulfite amounts.

  4. Modelling ionising radiation induced defect generation in bipolar oxides with gated diodes

    International Nuclear Information System (INIS)

    Barnaby, H.J.; Cirba, C.; Schrimpf, R.D.; Kosier, St.; Fouillat, P.; Montagner, X.

    1999-01-01

    Radiation-induced oxide defects that degrade electrical characteristics of bipolar junction transistor (BJTs) can be measured with the use of gated diodes. The buildup of defects and their effect on device radiation response are modeled with computer simulation. (authors)

  5. NASA MSFC LIGHTNING NITROGEN OXIDES MODEL (LNOM) DATA FOR DC METROPOLITAN REGION V1

    Data.gov (United States)

    National Aeronautics and Space Administration — The NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) combines detailed, flash-specific measurements of lightning with both theoretical and...

  6. Self-Assembly of Mono- and Dinuclear Metal Complexes; Oxidation Catalysis and Metalloenzyme Models

    NARCIS (Netherlands)

    Gelling, Onko-Jan; Rispens, Minze T.; Lubben, Marcel; Feringa, Bernard

    1994-01-01

    In this chapter several approaches to achieve assembly of mono- and dinuclear metal complexes, which can be considered structural and functional models for metalloenzymes, are described. The emphasis lies on oxidation chemistry, summarizing O2 binding, hydroxylation, demethylation, dehalogenation

  7. NASA MSFC LIGHTNING NITROGEN OXIDES MODEL (LNOM) DATA FOR NORTH ALABAMA REGION V1

    Data.gov (United States)

    National Aeronautics and Space Administration — The NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) combines detailed, flash-specific measurements of lightning with both theoretical and...

  8. Mathematical Modelling to Predict Oxidative Behaviour of Conjugated Linoleic Acid in the Food Processing Industry

    Directory of Open Access Journals (Sweden)

    Aitziber Ojanguren

    2013-06-01

    Full Text Available Industrial processes that apply high temperatures in the presence of oxygen may compromise the stability of conjugated linoleic acid (CLA bioactive isomers. Statistical techniques are used in this study to model and predict, on a laboratory scale, the oxidative behaviour of oil with high CLA content, controlling the limiting factors of food processing. This modelling aims to estimate the impact of an industrial frying process (140 °C, 7 L/h air on the oxidation of CLA oil for use as frying oil instead of sunflower oil. A factorial design was constructed within a temperature (80–200 °C and air flow (7–20 L/h range. Oil stability index (Rancimat method was used as a measure of oxidation. Three-level full factorial design was used to obtain a quadratic model for CLA oil, enabling the oxidative behaviour to be predicted under predetermined process conditions (temperature and air flow. It is deduced that temperatures applied in food processes affect the oxidation of CLA to a greater extent than air flow. As a result, it is estimated that the oxidative stability of CLA oil is less resistant to industrial frying than sunflower oil. In conclusion, thanks to the mathematical model, a good choice of the appropriate industrial food process can be selected to avoid the oxidation of the bioactive isomers of CLA, ensuring its functionality in novel applications.

  9. The NASA Lightning Nitrogen Oxides Model (LNOM): Application to Air Quality Modeling

    Science.gov (United States)

    Koshak, William; Peterson, Harold; Khan, Maudood; Biazar, Arastoo; Wang, Lihua

    2011-01-01

    Recent improvements to the NASA Marshall Space Flight Center Lightning Nitrogen Oxides Model (LNOM) and its application to the Community Multiscale Air Quality (CMAQ) modeling system are discussed. The LNOM analyzes Lightning Mapping Array (LMA) and National Lightning Detection Network(TradeMark)(NLDN) data to estimate the raw (i.e., unmixed and otherwise environmentally unmodified) vertical profile of lightning NO(x) (= NO + NO2). The latest LNOM estimates of lightning channel length distributions, lightning 1-m segment altitude distributions, and the vertical profile of lightning NO(x) are presented. The primary improvement to the LNOM is the inclusion of non-return stroke lightning NOx production due to: (1) hot core stepped and dart leaders, (2) stepped leader corona sheath, K-changes, continuing currents, and M-components. The impact of including LNOM-estimates of lightning NO(x) for an August 2006 run of CMAQ is discussed.

  10. A Model for the Oxidation of Carbon Silicon Carbide Composite Structures

    Science.gov (United States)

    Sullivan, Roy M.

    2004-01-01

    A mathematical theory and an accompanying numerical scheme have been developed for predicting the oxidation behavior of carbon silicon carbide (C/SiC) composite structures. The theory is derived from the mechanics of the flow of ideal gases through a porous solid. The result of the theoretical formulation is a set of two coupled nonlinear differential equations written in terms of the oxidant and oxide partial pressures. The differential equations are solved simultaneously to obtain the partial vapor pressures of the oxidant and oxides as a function of the spatial location and time. The local rate of carbon oxidation is determined using the map of the local oxidant partial vapor pressure along with the Arrhenius rate equation. The nonlinear differential equations are cast into matrix equations by applying the Bubnov-Galerkin weighted residual method, allowing for the solution of the differential equations numerically. The numerical method is demonstrated by utilizing the method to model the carbon oxidation and weight loss behavior of C/SiC specimens during thermogravimetric experiments. The numerical method is used to study the physics of carbon oxidation in carbon silicon carbide composites.

  11. Correlation of Vascular Endothelial Growth Factor Production with Photochemical Reaction-induced Retinal Edema.

    Science.gov (United States)

    Shan, Liang; Zheng, Mi; Zhang, Yuan; Qu, Yuan; Niu, Tian; Gu, Qing; Liu, Kun; Xia, Xin

    2016-12-20

    Retinal edema is the major complication of retinal vein occlusion and diabetic retinopathy; it can damage visual function by influencing macular region. This study was to establish a rat retinal edema model and explore the related VEGF expression and observe the responses to anti-VEGF drugs in this model. A rat retinal edema model was established by inducing photochemical reaction using a 532 nm laser after the intravenous injection of Erythrosin B. Immediately after the laser treatment, models were given intravitreal injections of Ranibizumab or Conbercept to inhibit VEGF expression, and the changes of retinal thickness were measured. Retinal edema was observed using fundus photography (FP), optical coherence tomography (OCT), and fluoresce in fundus angiography (FFA) at 0, 1, 2, 4, 7 and 14 days after intervention. The retinal VEGF expression was measured using enzyme-linked immunosorbent assay (ELISA) and western blotting at each time point. The rat retinal edema model was also used to verify the function of anti-VEGF polypeptide ZY1. Both retinal edema and vascular leakage were clearly observed at 1, 2 and 4 days after photochemical induction and the retinal thickness increased notably over the same period. The retinal VEGF expression peaked at day 1 and retina became thickening simultaneously. After the interventions, the VEGF expression of the Ranibizumab and Conbercept groups decreased at each time point compared to the edema group (26.90 ± 3.57 vs. 40.29 ± 6.68, F = 31.269 on day 1 and 22.36 ± 1.12 vs. 29.92 ± 0.93 F = 163.789 on day 2, both P photochemical reaction is reliable and repeatable. Induced edema increases expression of VEGF. This model can be used to test new drugs.

  12. Nitric oxide synthase and nitric oxide alterations in chronically stressed rats: a model for nitric oxide in major depressive disorder.

    Science.gov (United States)

    Gao, Shang-Feng; Lu, Yun-Rong; Shi, Li-Gen; Wu, Xue-Yan; Sun, Bo; Fu, Xin-Yan; Luo, Jian-Hong; Bao, Ai-Min

    2014-09-01

    Nitric oxide (NO) and NO synthase-1 (NOS1) are involved in the stress response and in depression. We compared NOS-NO alterations in rats exposed to chronic unpredictable stress (CUS) with alterations in major depressive disorder (MDD) in humans. In the hypothalamus of male CUS rats we determined NOS activity, and in the paraventricular nucleus (PVN) we determined NOS1-immunoreactive (ir) cell densities and co-localization of NOS1 with stress-related neuropeptides corticotropin-releasing hormone (CRH), vasopressin (AVP) or oxytocin (OXT). We measured plasma NO levels and cortisol in male medicine-naïve MDD patients and plasma NO and corticosterone (CORT) in CUS rats. In the CUS rat total NOS activity in the hypothalamus (P=0.018) and NOS1-ir cell density in the PVN were both significantly decreased (P=0.018), while NOS1 staining was mainly expressed in OXT-ir neurons in this nucleus. Interestingly, plasma NO levels were significantly increased both in male CUS rats (P=0.001) and in male MDD patients (Pdepression. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Optimization of a new flow design for solid oxide cells using computational fluid dynamics modelling

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig

    2016-01-01

    Design of a gas distributor to distribute gas flow into parallel channels for Solid Oxide Cells (SOC) is optimized, with respect to flow distribution, using Computational Fluid Dynamics (CFD) modelling. The CFD model is based on a 3d geometric model and the optimized structural parameters include...

  14. Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

    Science.gov (United States)

    2016-01-01

    The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis. PMID:27120289

  15. Photochemical recovery of europium from non-aqueous solutions.

    Science.gov (United States)

    Van den Bogaert, Bart; Gheeraert, Lore; Leblebici, Mumin Enis; Binnemans, Koen; Van Gerven, Tom

    2016-11-21

    The photochemical recovery of europium from non-aqueous media, more specifically alcohols, is studied. The recovery was performed by photochemical reduction of europium(iii) to europium(ii) and subsequent removal as the insoluble EuCl 2 . Two charge transfer bands are present in the UV-C region, one originating from the alcohol (around 230 nm) and the other from the chloride anion (at 271 nm), which are responsible for the photochemical reduction when the solution is illuminated by a medium-pressure mercury lamp. When using different alcohol solvents, a trend is observed with regards to the removal rate and efficiency, following methanol (MeOH) lamp phosphors (Y 2 O 3 :Eu 3+ ), which consist entirely of europium and yttrium with a Eu/Y molar ratio of 1/20-1/30.

  16. The Oxides of Nitrogen in Air Pollution.

    Science.gov (United States)

    California State Air Resources Board, Sacramento.

    Research on the health effects of oxides of nitrogen and on the role of oxides of nitrogen in producing photochemical smog effects is presented in this report. Prepared by the California State Department of Public Health at the request of the State Legislature, it gives a comprehensive review of available information, as well as the need for air…

  17. Photochemical preparation of ZnO nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Gbur, T.; Čuba, V.; Múčka, V.; Nikl, Martin; Knížek, Karel; Pospíšil, M.; Jakubec, Ivo

    2011-01-01

    Roč. 13, č. 10 (2011), 4529-4537 ISSN 1388-0764 R&D Projects: GA AV ČR KAN300100802 Institutional research plan: CEZ:AV0Z10100521; CEZ:AV0Z40320502 Keywords : zinc oxide * UV radiation * nanoparticles * scintillation materials * doping * synthesis Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.287, year: 2011

  18. Numerical modelling of emissions of nitrogen oxides in solid fuel combustion.

    Science.gov (United States)

    Bešenić, Tibor; Mikulčić, Hrvoje; Vujanović, Milan; Duić, Neven

    2018-06-01

    Among the combustion products, nitrogen oxides are one of the main contributors to a negative impact on the environment, participating in harmful processes such as tropospheric ozone and acid rains production. The main source of emissions of nitrogen oxides is the human combustion of fossil fuels. Their formation models are investigated and implemented with the goal of obtaining a tool for studying the nitrogen-containing pollutant production. In this work, numerical simulation of solid fuel combustion was carried out on a three-dimensional model of a drop tube furnace by using the commercial software FIRE. It was used for simulating turbulent fluid flow and temperature field, concentrations of the reactants and products, as well as the fluid-particles interaction by numerically solving the integro-differential equations describing these processes. Chemical reactions mechanisms for the formation of nitrogen oxides were implemented by the user functions. To achieve reasonable calculation times for running the simulations, as well as efficient coupling with the turbulent mixing process, the nitrogen scheme is limited to sufficiently few homogeneous reactions and species. Turbulent fluctuations that affect the reaction rates of nitrogen oxides' concentration are modelled by probability density function approach. Results of the implemented model for nitrogen oxides' formation from coal and biomass are compared to the experimental data. Temperature, burnout and nitrogen oxides' concentration profiles are compared, showing satisfactory agreement. The new model allows the simulation of pollutant formation in the real-world applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Cladding oxidation during air ingress. Part II: Synthesis of modelling results

    International Nuclear Information System (INIS)

    Beuzet, E.; Haurais, F.; Bals, C.; Coindreau, O.; Fernandez-Moguel, L.; Vasiliev, A.; Park, S.

    2016-01-01

    Highlights: • A state-of-the-art for air oxidation modelling in the frame of severe accident is done. • Air oxidation models from main severe accident codes are detailed. • Simulations from main severe accident codes are compared against experimental results. • Perspectives in terms of need for further model development and experiments are given. - Abstract: Air ingress is a potential risk in some low probable situations of severe accidents in a nuclear power plant. Air is a highly oxidizing atmosphere that can lead to an enhanced Zr-based cladding oxidation and core degradation affecting the release of fission products. This is particularly true speaking about ruthenium release, due to its high radiotoxicity and its ability to form highly volatile oxides in a significant manner in presence of air. The oxygen affinity is decreasing from the Zircaloy cladding, fuel and ruthenium inclusions. It is consequently of great need to understand the phenomena governing cladding oxidation by air as a prerequisite for the source term issues in such scenarios. In the past years, many works have been done on cladding oxidation by air under severe accident conditions. This paper with in addition the paper “Cladding oxidation during air ingress – Part I: Synthesis of experimental results” of this journal issue aim at assessing the state of the art on this phenomenon. In this paper, the modelling of air ingress phenomena in the main severe accident codes (ASTEC, ATHLET-CD, MAAP, MELCOR, RELAP/SCDAPSIM, SOCRAT) is described in details, as well as the validation against the integral experiments QUENCH-10, QUENCH-16 and PARAMETER-SF4. A full review of cladding oxidation by air is thus established.

  20. Iminium and enamine catalysis in enantioselective photochemical reactions

    Science.gov (United States)

    Hörmann, Fabian M.

    2018-01-01

    Although enantioselective catalysis under thermal conditions has been well established over the last few decades, the enantioselective catalysis of photochemical reactions is still a challenging task resulting from the complex enantiotopic face differentiation in the photoexcited state. Recently, remarkable achievements have been reported by a synergistic combination of organocatalysis and photocatalysis, which have led to the expedient construction of a diverse range of enantioenriched molecules which are generally not easily accessible under thermal conditions. In this tutorial review, we summarize and highlight the most significant advances in iminium and enamine catalysis of enantioselective photochemical reactions, with an emphasis on catalytic modes and reaction types. PMID:29155908

  1. Egg white hydrolysate inhibits oxidation in mayonnaise and a model system.

    Science.gov (United States)

    Kobayashi, Hideaki; Sasahara, Ryou; Yoda, Shoichi; Kotake-Nara, Eiichi

    2017-06-01

    The flavor deterioration of mayonnaise is induced by iron, which is released from egg yolk phosvitin under acidic conditions and promotes lipid oxidation. To prevent oxidative deterioration, natural components, rather than synthetic chemicals such as ethylenediaminetetraacetic acid have been required by consumers. In the present study, we evaluated the inhibitory effects of three egg white components with the same amino acid composition, namely egg white protein, hydrolysate, and the amino acid mixture, on lipid oxidation in mayonnaise and an acidic egg yolk solution as a model system. We found that the hydrolysate had the strongest inhibitory effect on lipid oxidation among the three components. The mechanism underlying the antioxidant effect was associated with Fe 2+ -chelating activity. Thus, egg white hydrolysate may have the potential as natural inhibitors of lipid oxidation in mayonnaise.

  2. Fatty acid oxidation changes and the correlation with oxidative stress in different preeclampsia-like mouse models.

    Directory of Open Access Journals (Sweden)

    Xiaoyan Ding

    Full Text Available BACKGROUND: Long-chain 3-hydroxyacyl-CoA dehydrogenase (LCHAD expression is decreased in placenta of some cases of preeclampsia (PE which may result in free fatty acid (FFA increased. High FFA level will induce oxidative stress, so abnormal long-chain fatty acid-oxidation may participate in the pathogenesis of PE through oxidative stress pathway. METHODS: PE-like groups were ApoC3 transgenic mice with abnormal fatty acid metabolism, classical PE-like models with injection of Nw-nitro-L-arginine-methyl ester (L-NA or lipopolysaccharide (LPS and the antiphospholipid syndrome (APS mouse model with β2GPI injection (ApoC3+NS, ApoC3+L-NA, L-NA, LPS and β2GPI groups. The control group was wild-type mice with normal saline injection. Except for β2GPI mice, the other mice were subdivided into pre-implantation (Pre and mid-pregnancy (Mid subgroups by injection time. RESULTS: All PE-like groups showed hypertension and proteinuria except ApoC3+NS mice only showed hypertension. Serum FFA levels increased significantly except in LPS group compared to controls (P<0.05. LCHAD mRNA and protein expression in the liver and placenta was significantly higher for ApoC3+NS, ApoC3+L-NA and β2GPI mice and lower for L-NA mice than controls (P<0.05 but did not differ between LPS mice and controls. P47phox mRNA and protein expression in the liver significantly increased in all PE-like groups except LPS group, while P47phox expression in the placenta only significantly increased in L-NA and β2GPI groups. CONCLUSIONS: Abnormal long-chain fatty acid-oxidation may play a different role in different PE-like models and in some cases participate in the pathogenesis of PE through oxidative stress pathway.

  3. Development of 3D Oxide Fuel Mechanics Models

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, B. W. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Casagranda, A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Pitts, S. A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Jiang, W. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2017-07-27

    This report documents recent work to improve the accuracy and robustness of the mechanical constitutive models used in the BISON fuel performance code. These developments include migration of the fuel mechanics models to be based on the MOOSE Tensor Mechanics module, improving the robustness of the smeared cracking model, implementing a capability to limit the time step size based on material model response, and improving the robustness of the return mapping iterations used in creep and plasticity models.

  4. Generic Top-Functionalization of Patterned Antifouling Zwitterionic Polymers on Indium Tin Oxide

    NARCIS (Netherlands)

    Li, Y.; Giesbers, M.; Zuilhof, H.

    2012-01-01

    This paper presents a novel surface engineering approach that combines photochemical grafting and surface-initiated atom transfer radical polymerization (SI-ATRP) to attach zwitterionic polymer brushes onto indium tin oxide (ITO) substrates. The photochemically grafted hydroxyl-terminated organic

  5. Distinguishing homogeneous-heterogeneous degradation of norfloxacin in a photochemical Fenton-like system (Fe3O4/UV/oxalate) and the interfacial reaction mechanism.

    Science.gov (United States)

    Huang, Mingjie; Zhou, Tao; Wu, Xiaohui; Mao, Juan

    2017-08-01

    This study demonstrated the efficient degradation of a typical bio-refractory antibiotic norfloxacin (NOR) in a photochemical iron oxides/oxalate system adopting magnetic catalyst (Fe 3 O 4 /UV/Ox). It was found that the in-situ generated HO was the main reactive oxygen species (ROS) but CO 2 - could also participate in the NOR degradation to form formylate organic intermediates. Besides, NOR would be degraded via an interesting pathway comprising an initial lag and a subsequent rapid period, where the former could be eliminated by introducing the pre-dissolution of Fe 3 O 4 particles. Furthermore, specific comparative investigations and surface characterizations of pre-adsorbed Fe 3 O 4 particles had evidenced that the existence of surface-bound iron-Ox complexes would be critical for the heterogeneous photochemical dissolution of Fe 3 O 4 and effectively initiated the subsequent homogeneous-heterogeneous NOR degradation. Finally, a comprehensive distinguishing reaction mechanism was proposed including a homogeneous-heterogeneous iron cycle on the solid-water interface and a series of homogeneous radical reactions. Therein, complexation instead of photochemical reduction would be dominant during the whole dissolution process even under UV irradiation. Rapid electrons exchange would occur photochemically between Fe II and Fe III in the octahedral sites, further weakening the surface Fe-O bonds and accelerating its breakaway from the bulk Fe 3 O 4 structure. This work could distinguish the complex heterogeneous/homogeneous reactions in the photochemical in-situ chemical oxidation systems that utilize naturally abundant iron oxides and polycarboxylic acids. Copyright © 2017. Published by Elsevier Ltd.

  6. Role of nitrite in the photochemical formation of radicals in the snow.

    Science.gov (United States)

    Jacobi, Hans-Werner; Kleffmann, Jörg; Villena, Guillermo; Wiesen, Peter; King, Martin; France, James; Anastasio, Cort; Staebler, Ralf

    2014-01-01

    Photochemical reactions in snow can have an important impact on the composition of the atmosphere over snow-covered areas as well as on the composition of the snow itself. One of the major photochemical processes is the photolysis of nitrate leading to the formation of volatile nitrogen compounds. We report nitrite concentrations determined together with nitrate and hydrogen peroxide in surface snow collected at the coastal site of Barrow, Alaska. The results demonstrate that nitrite likely plays a significant role as a precursor for reactive hydroxyl radicals as well as volatile nitrogen oxides in the snow. Pollution events leading to high concentrations of nitrous acid in the atmosphere contributed to an observed increase in nitrite in the surface snow layer during nighttime. Observed daytime nitrite concentrations are much higher than values predicted from steady-state concentrations based on photolysis of nitrate and nitrite indicating that we do not fully understand the production of nitrite and nitrous acid in snow. The discrepancy between observed and expected nitrite concentrations is probably due to a combination of factors, including an incomplete understanding of the reactive environment and chemical processes in snow, and a lack of consideration of the vertical structure of snow.

  7. Photochemical reactions in the tropospheric aqueous phase and on particulate matter.

    Science.gov (United States)

    Vione, Davide; Maurino, Valter; Minero, Claudio; Pelizzetti, Ezio; Harrison, Mark A J; Olariu, Romeo-Iulian; Arsene, Cecilia

    2006-05-01

    This paper is a tutorial review in the field of atmospheric chemistry. It describes some recent developments in tropospheric photochemistry in the aqueous phase and on particulate matter. The main focus is regarding the transformation processes that photochemical reactions induce on organic compounds. The relevant reactions can take place both on the surface of dispersed particles and within liquid droplets (e.g. cloud, fog, mist, dew). Direct and sensitised photolysis and the photogeneration of radical species are the main processes involved. Direct photolysis can be very important in the transformation of particle-adsorbed compounds. The significance of direct photolysis depends on the substrate under consideration and on the colour of the particle: dark carbonaceous material shields light, therefore protecting the adsorbed molecules from photodegradation, while a much lower protection is afforded for the light-shaded mineral fraction of particulate. Particulate matter is also rich in photosensitisers (e.g. quinones and aromatic carbonyls), partially derived from PAH photodegradation. These compounds can induce degradation of other molecules upon radiation absorption. Interestingly, substrates such as methoxyphenols, major constituents of wood-smoke aerosol, can also enhance the degradation of some sensitisers. Photosensitised processes in the tropospheric aqueous phase have been much less studied: it will be interesting to assess the photochemical properties of Humic-Like Substances (HULIS) that are major components of liquid droplets. The main photochemical sources of reactive radical species in aqueous solution and on particulate matter are hydrogen peroxide, nitrate, nitrite, and Fe(iii) compounds and oxides. The photogeneration of hydroxyl radicals can be important in polluted areas, while their transfer from the gas phase and dark generation are usually prevailing on an average continental scale. The reactions involving hydroxyl radicals can induce very

  8. Optical modeling of nickel-base alloys oxidized in pressurized water reactor

    Energy Technology Data Exchange (ETDEWEB)

    Clair, A. [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France); Foucault, M.; Calonne, O. [Areva ANP, Centre Technique Departement Corrosion-Chimie, 30 Bd de l' industrie, BP 181, 71205 Le Creusot (France); Finot, E., E-mail: Eric.Finot@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France)

    2012-10-01

    The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution-precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude-Lorentz model. A robust optical stratification model was determined using focused ion beam cross-section of thin foils examined by transmission electron microscopy. Dielectric constants of the inner oxide layer depleted in chromium were assimilated to those of the nickel thin film. The optical constants of both the spinels and extern layer were determined. - Highlights: Black-Right-Pointing-Pointer Spectroscopic ellipsometry of Ni-base alloy oxidation in pressurized water reactor Black-Right-Pointing-Pointer Measurements of the dielectric constants of the alloys Black-Right-Pointing-Pointer Optical simulation of the mixed oxidation process using a three stack model Black-Right-Pointing-Pointer Scattered crystallites cationic outer layer; linear Ni-gradient bottom layer Black-Right-Pointing-Pointer Determination of the refractive index of the spinel and the Cr{sub 2}O{sub 3} layers.

  9. Optical modeling of nickel-base alloys oxidized in pressurized water reactor

    International Nuclear Information System (INIS)

    Clair, A.; Foucault, M.; Calonne, O.; Finot, E.

    2012-01-01

    The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution–precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude–Lorentz model. A robust optical stratification model was determined using focused ion beam cross-section of thin foils examined by transmission electron microscopy. Dielectric constants of the inner oxide layer depleted in chromium were assimilated to those of the nickel thin film. The optical constants of both the spinels and extern layer were determined. - Highlights: ► Spectroscopic ellipsometry of Ni-base alloy oxidation in pressurized water reactor ► Measurements of the dielectric constants of the alloys ► Optical simulation of the mixed oxidation process using a three stack model ► Scattered crystallites cationic outer layer; linear Ni-gradient bottom layer ► Determination of the refractive index of the spinel and the Cr 2 O 3 layers

  10. Model simulating oxidation of Zircalot-4 at 400 (C in water vapor. Influence of thermal cycling and structure

    International Nuclear Information System (INIS)

    Garcia, Eduardo A.; Beranguer, G.

    1998-01-01

    This work gives a model simulating the oxidation of Zircaloy-4 in water vapor at 400 (C with different precipitates and granular sizes. The model combines diffusion with inter linked porosity, defining also an interface in the oxide separating phases of inter linked porosity from non inter linked porosity in the (PI/PnL) oxide, which spreads in a discrete way in time and is capable of reproducing kinetics of experimental oxidation

  11. The Adsorption of Cd(II on Manganese Oxide Investigated by Batch and Modeling Techniques

    Directory of Open Access Journals (Sweden)

    Xiaoming Huang

    2017-09-01

    Full Text Available Manganese (Mn oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999. The adsorption of Cd(II on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd at low pH and inner-sphere surface complexation sites (SOCd+ and (SO2CdOH− species at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface.

  12. The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

    Science.gov (United States)

    Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

    2017-09-28

    Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

  13. Bisphenol A Induces Hepatotoxicity through Oxidative Stress in Rat Model

    Directory of Open Access Journals (Sweden)

    Zeinab K. Hassan

    2012-01-01

    Full Text Available Reactive oxygen species (ROS are cytotoxic agents that lead to significant oxidative damage. Bisphenol A (BPA is a contaminant with increasing exposure to it and exerts both toxic and estrogenic effects on mammalian cells. Due to limited information concerning the effect of BPA on liver, this study investigates whether BPA causes hepatotoxicity by induction of oxidative stress in liver. Rats were divided into five groups: The first four groups, BPA (0.1, 1, 10, 50 mg/kg/day were administrated orally to rats for four weeks. The fifth group was taken water with vehicle. The final body weights in the 0.1 mg group showed a significant decrease compared to control group. Significant decreased levels of reduced glutathione, superoxide dismutase, glutathione peroxidase, glutathione-S-transferase, glutathione reductase and catalase activity were found in the 50 mg BPA group compared to control groups. High dose of BPA (50 mg/kg significantly increased the biochemical levels of ALT, ALP and total bilirubin. BPA effect on the activity of antioxidant genes was confirmed by real time PCR in which the expression levels of these genes in liver tissue were significantly decrease compared to control. Data from this study demonstrate that BPA generate ROS and reduce the antioxidant gene expression that causes hepatotoxicity.

  14. Coordinated HArd Sphere Model (CHASM): A Simplified Model for Silicate and Oxide Liquids at Mantle Conditions

    Science.gov (United States)

    Wolf, A. S.; Asimow, P. D.; Stevenson, D. J.

    2013-12-01

    Recent first-principles theoretical calculations (Stixrude 2009) and experimental shock-wave investigations (Mosenfelder 2009) indicate that melting perovskite requires significantly less energy than previously thought, supporting the idea of a deep-mantle magma ocean early in Earth's history. The modern-day solid Earth is thus likely the result of crystallization from an early predominantly molten state, a process that is primarily controlled by the poorly understood behavior of silicate melts at extreme pressures and temperatures. Probing liquid thermodynamics at mantle conditions is difficult for both theory and experiment, and further challenges are posed by the large relevant compositional space including at least MgO, SiO2, and FeO. First-principles molecular dynamics has been used with great success to determine the high P-T properties of a small set of fixed composition silicate-oxide liquids including MgO (Karki 2006), SiO2 (Karki 2007), Mg2SiO4 (de Koker 2008), MgSiO3 (Stixrude 2005), and Fe2SiO4 (Ramo 2012). While extremely powerful, this approach has limitations including high computational cost, lower bounds on temperature due to relaxation constraints, as well as restrictions to length scales and time scales that are many orders of magnitude smaller than those relevant to the Earth or experimental methods. As a compliment to accurate first-principles calculations, we have developed the Coordinated HArd Sphere Model (CHASM). We extend the standard hard sphere mixture model, recently applied to silicate liquids by Jing (2011), by accounting for the range of oxygen coordination states available to liquid cations. Utilizing approximate analytic expressions for the hard sphere model, the method can predict complex liquid structure and thermodynamics while remaining computationally efficient. Requiring only minutes on standard desktop computers rather than months on supercomputers, the CHASM approach is well-suited to providing an approximate thermodynamic

  15. Preliminary evaluation of a model of stimulant use, oxidative damage and executive dysfunction.

    Science.gov (United States)

    Winhusen, Theresa; Walker, Jessica; Brigham, Gregory; Lewis, Daniel; Somoza, Eugene; Theobald, Jeff; Somoza, Veronika

    2013-07-01

    Illicit stimulant use increases oxidative stress and oxidative stress has been found to be associated with deficits in memory, attention and problem-solving. To test a model of the association among oxidative DNA damage, a severe form of oxidative stress, and stimulant use, executive function and stimulant-use outcomes. Six sites evaluating 12-step facilitation for stimulant abusers obtained peripheral blood samples from methamphetamine-dependent (n = 45) and cocaine-dependent (n = 120) participants. The blood samples were submitted to a comet assay to assess oxidative DNA damage. Executive Dysfunction was assessed with the Frontal Systems Behavior Scale (FrSBe), which is a reliable and valid self-report assessment of executive dysfunction, disinhibition and apathy. Stimulant-use measures included self-reported stimulant use and stimulant urine drug screens (UDS). While more recent cocaine use (executive dysfunction and stimulant use outcomes for cocaine-dependent patients. Support for the model was found for methamphetamine-dependent patients, with oxidative DNA damage significantly greater in methamphetamine-dependent patients with executive dysfunction (W = 2.2, p executive dysfunction being a significant mediator of oxidative DNA damage and stimulant use during active treatment (ab = 0.089, p executive dysfunction, which in turn increases vulnerability to future stimulant use.

  16. Modeling electron competition among nitrogen oxides reduction and N2 O accumulation in hydrogenotrophic denitrification.

    Science.gov (United States)

    Liu, Yiwen; Ngo, Huu H; Guo, Wenshan; Peng, Lai; Chen, Xueming; Wang, Dongbo; Pan, Yuting; Ni, Bing-Jie

    2018-04-01

    Hydrogenotrophic denitrification is a novel and sustainable process for nitrogen removal, which utilizes hydrogen as electron donor, and carbon dioxide as carbon source. Recent studies have shown that nitrous oxide (N 2 O), a highly undesirable intermediate and potent greenhouse gas, can accumulate during this process. In this work, a new mathematical model is developed to describe nitrogen oxides dynamics, especially N 2 O, during hydrogenotrophic denitrification for the first time. The model describes electron competition among the four steps of hydrogenotrophic denitrification through decoupling hydrogen oxidation and nitrogen reduction processes using electron carriers, in contrast to the existing models that couple these two processes and also do not consider N 2 O accumulation. The developed model satisfactorily describes experimental data on nitrogen oxides dynamics obtained from two independent hydrogenotrophic denitrifying cultures under various hydrogen and nitrogen oxides supplying conditions, suggesting the validity and applicability of the model. The results indicated that N 2 O accumulation would not be intensified under hydrogen limiting conditions, due to the higher electron competition capacity of N 2 O reduction in comparison to nitrate and nitrite reduction during hydrogenotrophic denitrification. The model is expected to enhance our understanding of the process during hydrogenotrophic denitrification and the ability to predict N 2 O accumulation. © 2017 Wiley Periodicals, Inc.

  17. Effects of tempol and redox-cycling nitroxides in models of oxidative stress

    Science.gov (United States)

    Wilcox, Christopher S.

    2010-01-01

    Tempol is a redox cycling nitroxide that promotes the metabolism of many reactive oxygen species (ROS) and improves nitric oxide bioavailability. It has been studied extensively in animal models of oxidative stress. Tempol has been shown to preserve mitochondria against oxidative damage and improve tissue oxygenation. Tempol improved insulin responsiveness in models of diabetes mellitus and improved the dyslipidemia, reduced the weight gain and prevented diastolic dysfunction and heart failure in fat-fed models of the metabolic syndrome. Tempol protected many organs, including the heart and brain, from ischemia/reperfusion damage. Tempol prevented podocyte damage, glomerulosclerosis, proteinuria and progressive loss of renal function in models of salt and mineralocorticosteroid excess. It reduced brain or spinal cord damage after ischemia or trauma and exerted a spinal analgesic action. Tempol improved survival in several models of shock. It protected normal cells from radiation while maintaining radiation sensitivity of tumor cells. Its paradoxical pro-oxidant action in tumor cells accounted for a reduction in spontaneous tumor formation. Tempol was effective in some models of neurodegeneration. Thus, tempol has been effective in preventing several of the adverse consequences of oxidative stress and inflammation that underlie radiation damage and many of the diseases associated with aging. Indeed, tempol given from birth prolonged the life span of normal mice. However, presently tempol has been used only in human subjects as a topical agent to prevent radiation-induced alopecia. PMID:20153367

  18. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  19. Configurational Model for Conductivity of Stabilized Fluorite Structure Oxides

    DEFF Research Database (Denmark)

    Poulsen, Finn Willy

    1981-01-01

    The formalism developed here furnishes means by which ionic configurations, solid solution limits, and conductivity mechanisms in doped fluorite structures can be described. The present model differs markedly from previous models but reproduces qualitatively reality. The analysis reported...

  20. Oxidative Stress Associated with Neuronal Apoptosis in Experimental Models of Epilepsy

    Directory of Open Access Journals (Sweden)

    Marisela Méndez-Armenta

    2014-01-01

    Full Text Available Epilepsy is considered one of the most common neurological disorders worldwide. Oxidative stress produced by free radicals may play a role in the initiation and progression of epilepsy; the changes in the mitochondrial and the oxidative stress state can lead mechanism associated with neuronal death pathway. Bioenergetics state failure and impaired mitochondrial function include excessive free radical production with impaired synthesis of antioxidants. This review summarizes evidence that suggest what is the role of oxidative stress on induction of apoptosis in experimental models of epilepsy.

  1. Model support for an out-reactor-instrumented-defected-fuel-experiment to validate the RMC fuel oxidation model

    Energy Technology Data Exchange (ETDEWEB)

    Quastel, A.D.; Corcoran, E.C.; Lewis, B.J. [Royal Military College of Canada, Chemistry and Chemical Engineering Dept., Kingston, Ontario (Canada); Thiriet, C. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Hadaller, G. [Stern Laboratories Inc., Hamilton, Ontario (Canada)

    2011-07-01

    An out-reactor fuel oxidation experiment with controlled parameters is being planned to provide data for validation of the Royal Military College (RMC) mechanistic fuel oxidation model. In support of this work, fuel oxidation 2D r-θ and 3D models are presented. The 2D r-θ model with radial cracks provides the radial temperature distribution in the test fuel element and also provides heating power information. The 3D model with radial cracks and a pellet-pellet gap under a defected sheath indicate that an oxygen stoichiometry deviation of 0.057 could result within one week of heating a defected UO{sub 2} fuel element with a 5-mm{sup 2} sheath defect. (author)

  2. Modeling Nitrous Oxide Production during Biological Nitrogen Removal via Nitrification and Denitrification: Extensions to the General ASM Models

    DEFF Research Database (Denmark)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer i Nàcher, Carles

    2011-01-01

    Nitrous oxide (N2O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N2O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N2O...

  3. Modelling of Physical, Chemical, and Material Properties of Solid Oxide Fuel Cells

    Directory of Open Access Journals (Sweden)

    Jakub Kupecki

    2015-01-01

    Full Text Available This paper provides a review of modelling techniques applicable for system-level studies to account for physical, chemical, and material properties of solid oxide fuel cells. Functionality of 0D to 3D models is discussed and selected examples are given. Author provides information on typical length scales in evaluation of power systems with solid oxide fuel cells. In each section, proper examples of previous studies done in the field of 0D–3D modelling are recalled and discussed.

  4. Modeling explicit tropospheric oxidation through identifying volatile organic compound (VOC) sources, their impact on air quality and their signatures in South China

    Science.gov (United States)

    Cheng, Hairong

    Photochemical smog, characterized by high concentrations of ozone (O 3) and fine particles, is of great concern in the urban areas like the Pearl River Delta (PRD). Ambient O3 and its precursors were simultaneously measured for the first time at a site within the inland PRD region (WQS) and a site in Hong Kong (TC) from 22 October to 01 December 2007, in order to improve our understanding of the interplay of O3 pollution between Hong Kong and the inland PRD region, to explore the relationships between O3 and its precursors, and to identify the key volatile organic compound (VOC) species and emission source categories contributing to the O3 formation. Ratio analyses for trace gases and VOCs and back trajectory calculation revealed that the air masses arriving at WQS were more aged due to regional influence, whereas the air masses at TC were mainly affected by local emissions and/or regional transport. An observation-Based Model (OBM) was employed to determine the O 3-precursor relationship. At both sites, O3 production was found to be VOC-limited. Anthropogenic hydrocarbons played a key role in O 3 production, while reducing NO emissions aided the build up of O 3 concentrations. The contribution of carbonyls to O3 formation was firstly input in the OBM by using measured data, the results showed that the net O3 production derived from the OBM agreed better with the observed O3 increment after hourly carbonyl concentrations were included. A photochemical trajectory model was developed and used for the first time to simulate the formation of photochemical pollutants at WQS, Guangzhou during photochemical pollution episodes between 12 and 17 November, 2007. Calculated photochemical ozone creation potential (POCP) indices indicated that alkanes and oxygenated organic compounds had relatively low reactivity, while alkenes and aromatics presented high reactivity. Analysis of the emission inventory found that the sum of 60 of the 139 VOC species accounted for 91% of the

  5. Oxidative Stress in Genetic Mouse Models of Parkinson’s Disease

    Directory of Open Access Journals (Sweden)

    Mustafa Varçin

    2012-01-01

    Full Text Available There is extensive evidence in Parkinson’s disease of a link between oxidative stress and some of the monogenically inherited Parkinson’s disease-associated genes. This paper focuses on the importance of this link and potential impact on neuronal function. Basic mechanisms of oxidative stress, the cellular antioxidant machinery, and the main sources of cellular oxidative stress are reviewed. Moreover, attention is given to the complex interaction between oxidative stress and other prominent pathogenic pathways in Parkinson’s disease, such as mitochondrial dysfunction and neuroinflammation. Furthermore, an overview of the existing genetic mouse models of Parkinson’s disease is given and the evidence of oxidative stress in these models highlighted. Taken into consideration the importance of ageing and environmental factors as a risk for developing Parkinson’s disease, gene-environment interactions in genetically engineered mouse models of Parkinson’s disease are also discussed, highlighting the role of oxidative damage in the interplay between genetic makeup, environmental stress, and ageing in Parkinson’s disease.

  6. Solid-state Photochemical [2+ 2] Cycloaddition Reaction of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 2. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds. ABDUL MALIK P PEEDIKAKKAL. Regular Article Volume 129 Issue 2 February 2017 pp 239-247 ...

  7. Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen.

    Science.gov (United States)

    Scrano, Laura; Bufo, Sabino A; Cataldi, Tommaso R I; Albanis, Triantafyllos A

    2004-01-01

    The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.

  8. A comprehensive approach to the photochemical synthesis of ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 114; Issue 6. A comprehensive approach to the photochemical synthesis of bioactive compounds by the reaction of oxazolidine, thiazolidine and pyrazolidine derivatives with indol-2,3-diones. I Sharma A Saxena C K Ojha P Pardasani R T Pardasani T Mukherjee.

  9. Photochemical synthesis of benzoyl spiro[2.2]pentanes.

    Science.gov (United States)

    Muehling, Olaf; Wessig, Pablo

    2006-11-01

    In the present study, we describe the photochemical behaviour of 2-mesyloxy phenyl ketones 8 and 12 bearing a cyclopropane moiety in the side-chain. Irradiation of 8 and 12 leads to the corresponding benzoyl spiro[2.2]pentanes as a consequence of an initial gamma-H-shift, subsequent elimination of MsOH (accompanied by a spin-center shift) and cyclization of the resulting 1,3-diradicals. In contrast, a corresponding phenyl ketone without a mesyloxy group in the 2-position, and thus a potential reactant of the "classical" Norrish-Yang reaction, shows no photochemical reaction. By means of quantum chemical calculations we discovered that in the presence of a mesyloxy group the activation barrier for the photochemical gamma-H-shift is substantially decreased. Furthermore, a photoinduced skeletal rearrangement of benzoyl spiro[2.2]pentane to 2-cyclobutylidene-acetophenone could be observed. Compared to the common methods used to synthesize spiro[2.2]pentanes, the photochemical preparation of benzoyl spiro[2.2]pentane presented herein is the first example where a bond between the spiro atom and an adjacent atom is formed.

  10. Photochemically induced emission tuning of conductive polumers used in OLEDs

    Science.gov (United States)

    Vasilopoulou, M.; Pistolis, G.; Argitis, P.

    2005-01-01

    The present work focuses on the use of novel patterning technology schemes for the fabrication of OLED-based displays and in particular on the definition of two colour emitting pixels in one polymeric conducting layer. The approach adopted to this end is based on photochemically induced emition tuning. On the basis of this approach a novel photolithographic patterning technique was developed, aiming at the considerable simplification of the display fabrication process and on the performance improvement. We prepared electroluminescent devices that are emitting blue colour (λmax = 413 nm) with a turnon voltage about 12-15 V. In other devices we introduce a dispersed dye (1-[4-(dimethylamino)phenyl]-6-phenylhexatriene) and a series of photoacid generators (onium salts) in the polymeric layer and, by using an appropriate photochemical transformation through a photomask in a single layer, we were able to change the colour to desirable direction, since the parent compound and its photochemical product have distinguishable luminescence spectra (green and blue colour respectively). We were able to produce two of the three primary colours in a single layer of a conductive polymer by using a photochemical transformation based on photoacid induced emission change. A series of photoacid generators were evaluated.

  11. Photochemically induced hydrogen isotope exchange between anthracene and aliphatic amines

    International Nuclear Information System (INIS)

    Gebicki, J.; Reimschuessel, W.; Nowicki, T.

    1978-01-01

    The kinetics of photochemically induced deuterium and tritium isotope exchange between anthracene and diethylamine labelled in NH group or triethylamine-labelled water mixture was studied in acetonitrile and n-heptane. The rate constants of isotope exchange were calculated and ksub(D)/ksub(T) isotope effect was found. A mechanism for isotope exchange involving exciplex formation was proposed. (Auth.)

  12. A comprehensive approach to the photochemical synthesis of ...

    Indian Academy of Sciences (India)

    Unknown

    Indol-2,3-dione (isatin) derivatives 1a–c have been long known for a wide spectrum of biological activities.1–3 It is a core constituent of many naturally occurring alkaloids and drugs. We have investigated the photochemical reactions of indol-2,3-dione derivatives with various five-membered heterocycles containing O–C–N, ...

  13. Selection of antioxidants against ovarian oxidative stress in mouse model.

    Science.gov (United States)

    Li, Bojiang; Weng, Qiannan; Liu, Zequn; Shen, Ming; Zhang, Jiaqing; Wu, Wangjun; Liu, Honglin

    2017-12-01

    Oxidative stress (OS) plays an important role in the process of ovarian granulosa cell apoptosis and follicular atresia. The aim of this study was to select antioxidant against OS in ovary tissue. Firstly, we chose the six antioxidants and analyzed the reactive oxygen species (ROS) level in the ovary tissue. The results showed that proanthocyanidins, gallic acid, curcumin, and carotene decrease the ROS level compared with control group. We further demonstrated that both proanthocyanidins and gallic acid increase the antioxidant enzymes activity. Moreover, change in the ROS level was not observed in proanthocyanidins and gallic acid group of brain, liver, spleen, and kidney tissues. Finally, we found that proanthocyanidins and gallic acid inhibit pro-apoptotic genes expression in granulosa cells. Taken together, proanthocyanidins and gallic acid may be the most acceptable and optimal antioxidants specifically against ovarian OS and also may be involved in the inhibition of granulosa cells apoptosis in mouse ovary. © 2017 Wiley Periodicals, Inc.

  14. Dynamic modelling of nitrous oxide emissions from three Swedish sludge liquor treatment systems

    DEFF Research Database (Denmark)

    Lindblom, E.; Arnell, M.; Flores-Alsina, X.

    2014-01-01

    The objective of this paper is to model the dynamics and validate the results of nitrous oxide (N2O)emissions from three Swedish nitrifying/denitrifying, nitritation and anammox systems treating real anaerobic digester sludge liquor. The Activated Sludge Model No. 1 is extended to describe N2O pr...

  15. Application of the Generic Modeling Template Approach to Unsaturated Fatty Acid Oxidation and Crystallization Systems

    DEFF Research Database (Denmark)

    Fedorova, Marina; Papadakis, Emmanouil; Meisler, Kresten Troelstrup

    2014-01-01

    for following the modelling workflow steps, guidance through the steps , as well as providing additional information and comments. The application of the tool is highlighted with two case studies: oxidation of unsaturated acid with hydrogen peroxide and modeling of a crystal lization operation...

  16. Simulation of photochemical pollutants in summer 2013 in China

    Science.gov (United States)

    Zhang, H.; Guo, H.; Hu, J.

    2016-12-01

    Rapid economic growth and associated emissions increase in China have led to severe air pollution in recent decades. Photochemical pollutants are secondary formed pollutants in the atmosphere with the existence of sunlight. Ozone (O3) is adverse to human health and ecosystems and secondary organic aerosol (SOA) is a major component of fine particulate matter (PM2.5) that affects human health, visibility, and climate. In this work, the Community Multi-scale Air Quality (CMAQ) model was used to investigate the formation of O3 and SOA in three episodes from June to August 2013. Compared with observation data, O3 performance meets the EPA criteria of mean normalized bias (MNB) within ± 0.15 in major parts of China including five megacities. The diurnal variation of O3 had similar trend with the temperature. The August episode has the highest O3 concentrations of 100 ppb in North China Plain while the July episode has the lowest concentrations of 50 ppb. SOA concentrations were up to 35-40 μgm-3 at different cities in different episodes. Biogenic SOA was the majority with the contributions from glyoxal (GLY), methylglyoxal (MGLY), isoprene epoxydiol (IEPOX) and oligomers (OLGM) of 70%. Isopleth found that NOx controls O3 concentration in most areas of China. Reducing VOC would have minor effects on O3 concentrations while reducing NOx could largely reduce O3 concentration except for urban areas such as Shanghai and Guangzhou. On the contrary, SOA was controlled by VOCs in cities such as Beijing, Shanghai, and Xi'an. This study provides valuable information for designing effective control strategies for O3 and particulate matter in China.

  17. Kinetic modeling of nitric oxide removal by ultraviolet/H2O2 advanced oxidation process

    Directory of Open Access Journals (Sweden)

    Masoumeh Moheb Shahrestani

    2016-01-01

    Full Text Available Aims: In present study, the mass transfer-reaction kinetic parameters of nitric oxide (NO removal by ultraviolet (UV/H 2 O 2 process in a bubble column reactor in the presence of SO 2 are calculated. Materials and Methods: The mass balance equation for NO through a layer thickness of δ, under the steady state condition is solved, and NO absorption rate is calculated. The value of rate constants and Ha numbers are obtained based on experimental data under different conditions. Results: The calculations indicate that the values of Ha number are >3. The values of rate constants (k obs are fitted to some empirical equations for different operating conditions. It is observed that the value of k obs increases with an increase in H 2 O 2 concentration and UV radiation intensity while it decreases with an increase in NO and SO 2 inlet concentrations. The values of rate constants are in order of 10−5 , expect for SO 2 , which are in order of 10−7 . The results reveal that there is a good agreement between calculated and experimental values where the maximum absolute error is 16.18% related to UV light intensities between 0 and 0.012 W/m 3 . Conclusion: The obtained values of Ha numbers under different condition confirm that the absorption process of gas in the liquid phase is a fast reaction. The maximum error values resulted from a comparison between the calculated NO absorption rates and the experimental ones are acceptable.

  18. Photochemical fate of beta-blockers in NOM enriched waters

    International Nuclear Information System (INIS)

    Wang, Ling; Xu, Haomin; Cooper, William J.; Song, Weihua

    2012-01-01

    Beta-blockers, prescribed for the treatment of high blood pressure and for long-term use after a heart attack, have been detected in surface and ground waters. This study examines the photochemical fate of three beta-blockers, atenolol, metoprolol, and nadolol. Hydrolysis accounted for minor losses of these beta-blockers in the pH range 4–10. The rate of direct photolysis at pH 7 in a solar simulator varied from 6.1 to 8.9 h −1 at pH 7. However, the addition of a natural organic matter (NOM) isolate enhanced the photochemical loss of all three compounds. Indirect photochemical fate, generally described by reactions with hydroxyl radical (·OH) and singlet oxygen ( 1 ΔO 2 ), and, the direct reaction with the triplet excited state, 3 NOM ⁎ , also varied but collectively appeared to be the major loss factor. Bimolecular reaction rate constants of the three beta-blockers with 1 ΔO 2 and ·OH were measured and accounted for 0.02–0.04% and 7.2–38.9% of their loss, respectively. These data suggest that the 3 NOM ⁎ contributed 50.6–85.4%. Experiments with various 3 NOM ⁎ quenchers supported the hypothesis that it was singly the most important reaction. Atenolol was chosen for more detailed investigation, with the photoproducts identified by LC–MS analysis. The results suggested that electron-transfer could be an important mechanism in photochemical fate of beta-blockers in the presence of NOM. - Highlights: ► Photochemical degradation of beta-blockers in the simulated natural waters. ► Reactive Oxygen Species play a minor role in the indirect photodegradation. ► The loss of beta-blockers results from direct reaction with 3 DOM ⁎ .

  19. Electrochemical Impedance Modeling of a Solid Oxide Fuel Cell Anode

    DEFF Research Database (Denmark)

    Mohammadi, R.; Søgaard, Martin; Ramos, Tania

    2014-01-01

    A simulation package for the impedance response of SOFC anodes is presented here. The model couples the gas transport in gas channels and within a porous electrode with the electrochemical kinetics. The gas phase mass transport is modeled using mass conservation equations. A transmission line mod...

  20. The effect of various environmental and design parameters on methane oxidation in a model biofilter.

    Science.gov (United States)

    Park, Soyoung; Brown, Kirk W; Thomas, James C

    2002-10-01

    Methane from landfills built with RCRA (Resource Conservation and Recovery Act) covers is frequently vented directly to the atmosphere. Alternatively, landfill gasses could be vented through a layer of soil that could serve as a biofilter to oxidize CH4 to carbon dioxide and water. Properly designed soil biofilters may reduce atmospheric CH4 emissions from landfills and help reduce the accumulation of greenhouse gasses in the atmosphere. This study was conducted to investigate the performance of a lab-scale model biofilter system using soil as the filterbed medium in packed columns to measure the effect of a variety of environmental and design factors on the CH4 oxidation capacity of a soil biofilter. Biofilter performance was tested under a variety of environmental and design conditions. The optimum soil moisture content for CH4 oxidation in a loamy sand was 13% by weight. Addition of NO3-N did not affect the CH4 oxidation rate. Soil depths of 30 cm and 60 cm were equally efficient in CH4 oxidation. When the CH4 loading rate was decreased, the percentage of CH4 oxidized increased. The maximum CH4 oxidation rate was 27.2 mol m(-2) d(-1) under optimum conditions.

  1. Water oxidation catalysis: an amorphous quaternary Ba-Sr-Co-Fe oxide as a promising electrocatalyst for the oxygen-evolution reaction.

    Science.gov (United States)

    Zhang, Cuijuan; Berlinguette, Curtis P; Trudel, Simon

    2016-01-25

    We present an amorphous quaternary Ba-Sr-Co-Fe oxide (a-BSCF) with a specific stoichiometry, readily fabricated via a photochemical decomposition method. a-BSCF demonstrates high catalytic activity towards the oxygen-evolution reaction (OER).

  2. Photophysical and photochemical effects in ultrafast laser patterning of CVD graphene

    International Nuclear Information System (INIS)

    Bobrinetskiy, Ivan; Otero, Nerea; Romero, Pablo M; Emelianov, Aleksei; Komarov, Ivan; Nasibulin, Albert

    2016-01-01

    The micro-scale patterns in graphene on Si/SiO 2 substrate were fabricated using ultrashort 515 nm laser pulses. For both picosecond and femtosecond laser pulses two competitive processes, based on photo-thermal (ablation) and photochemical (oxidation/etching) effects, were observed. The laser-induced etching of graphene starts just below the threshold energy of graphene ablation: 1.7 nJ per 280 fs pulse and 2.7 µ J per 30 ps pulse. Whilst etching is not sensitive to thermal properties of graphene and provides uniform patterns, the ablation, in contrast, is highly affected by defects in the graphene structure like wrinkles and bilayer islands. The mechanisms of ultrafast laser interaction with graphene are discussed. (letter)

  3. Light-induced changes in bottled white wine and underlying photochemical mechanisms.

    Science.gov (United States)

    Grant-Preece, Paris; Barril, Celia; Schmidtke, Leigh M; Scollary, Geoffrey R; Clark, Andrew C

    2017-03-04

    Bottled white wine may be exposed to UV-visible light for considerable periods of time before it is consumed. Light exposure may induce an off-flavor known as "sunlight" flavor, bleach the color of the wine, and/or increase browning and deplete sulfur dioxide. The changes that occur in bottled white wine exposed to light depend on the wine composition, the irradiation conditions, and the light exposure time. The light-induced changes in the aroma, volatile composition, color, and concentrations of oxygen and sulfur dioxide in bottled white wine are reviewed. In addition, the photochemical reactions thought to have a role in these changes are described. These include the riboflavin-sensitized oxidation of methionine, resulting in the formation of methanethiol and dimethyl disulfide, and the photodegradation of iron(III) tartrate, which gives rise to glyoxylic acid, an aldehyde known to react with flavan-3-ols to form yellow xanthylium cation pigments.

  4. Chemical degradation of proteins in the solid state with a focus on photochemical reactions.

    Science.gov (United States)

    Mozziconacci, Olivier; Schöneich, Christian

    2015-10-01

    Protein pharmaceuticals comprise an increasing fraction of marketed products but the limited solution stability of proteins requires considerable research effort to prepare stable formulations. An alternative is solid formulation, as proteins in the solid state are thermodynamically less susceptible to degradation. Nevertheless, within the time of storage a large panel of kinetically controlled degradation reactions can occur such as, e.g., hydrolysis reactions, the formation of diketopiperazine, condensation and aggregation reactions. These mechanisms of degradation in protein solids are relatively well covered by the literature. Considerably less is known about oxidative and photochemical reactions of solid proteins. This review will provide an overview over photolytic and non-photolytic degradation reactions, and specially emphasize mechanistic details on how solid structure may affect the interaction of protein solids with light. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Modeling Electrocatalysis -- Electro-oxidation of Pt(111)

    Science.gov (United States)

    Jacob, Timo; Scheffler, Matthias

    2006-03-01

    Electrochemical reactions (such as in fuel cells) usually occur under conditions of finite temperature, pressure, and electrode potential, implying a very involved situation, possibly leading to novel surface materials. Especially the presence of an electrode potential, which results in the formation of an electric double-layer, affects the composition and structure of the electrode/electrolyte-interface. Towards a more realistic treatment of electrocatalysis we developed an appropriate theory in which the electrode of the interface is assumed to be in contact with a bulk-electrode reservoir (at chemical potential μel) while the electrolyte is in contact with a bulk-electrolyte reservoir. Although we are in the process of simulating the entire electric-double layer self-consistently, the present approach already allows us to estimate the limites of the expected effects. As a first application we studied the electro-oxidation of Pt(111) by calculating the p/T/φ-phase diagram. The obtained behavior, that positive electrode potentials stabilize higher oxygen coverages, is in qualitative agreement with cyclic-voltammetry experiments.

  6. Genome-Scale, Constraint-Based Modeling of Nitrogen Oxide Fluxes during Coculture of Nitrosomonas europaea and Nitrobacter winogradskyi.

    Science.gov (United States)

    Mellbye, Brett L; Giguere, Andrew T; Murthy, Ganti S; Bottomley, Peter J; Sayavedra-Soto, Luis A; Chaplen, Frank W R

    2018-01-01

    Nitrification, the aerobic oxidation of ammonia to nitrate via nitrite, emits nitrogen (N) oxide gases (NO, NO 2 , and N 2 O), which are potentially hazardous compounds that contribute to global warming. To better understand the dynamics of nitrification-derived N oxide production, we conducted culturing experiments and used an integrative genome-scale, constraint-based approach to model N oxide gas sources and sinks during complete nitrification in an aerobic coculture of two model nitrifying bacteria, the ammonia-oxidizing bacterium Nitrosomonas europaea and the nitrite-oxidizing bacterium Nitrobacter winogradskyi . The model includes biotic genome-scale metabolic models (iFC578 and iFC579) for each nitrifier and abiotic N oxide reactions. Modeling suggested both biotic and abiotic reactions are important sources and sinks of N oxides, particularly under microaerobic conditions predicted to occur in coculture. In particular, integrative modeling suggested that previous models might have underestimated gross NO production during nitrification due to not taking into account its rapid oxidation in both aqueous and gas phases. The integrative model may be found at https://github.com/chaplenf/microBiome-v2.1. IMPORTANCE Modern agriculture is sustained by application of inorganic nitrogen (N) fertilizer in the form of ammonium (NH 4 + ). Up to 60% of NH 4 + -based fertilizer can be lost through leaching of nitrifier-derived nitrate (NO 3 - ), and through the emission of N oxide gases (i.e., nitric oxide [NO], N dioxide [NO 2 ], and nitrous oxide [N 2 O] gases), the latter being a potent greenhouse gas. Our approach to modeling of nitrification suggests that both biotic and abiotic mechanisms function as important sources and sinks of N oxides during microaerobic conditions and that previous models might have underestimated gross NO production during nitrification.

  7. Modelling of Zircaloy-steam-oxidation under severe fuel damage conditions

    International Nuclear Information System (INIS)

    Malang, S.; Neitzel, H.J.

    1983-01-01

    Small break loss-of-coolant accidents and special transients in an LWR, in combination with loss of required safety systems, may lead to an uncovered core for an extended period of time. As a consequence, the cladding temperature could rise up to the melting point due to the decay heat, resulting in severely damaged fuel rods. During heat-up the claddings oxidize due to oxygen uptake from the steam atmosphere in the core. The modeling and assessment of the Zircaloy-steam oxidation under such conditions is important, mainly for two reasons: The oxidation of the cladding influences the temperature transients due to the exothermic heat of reaction; the amount of liquified fuel depends on the oxide layer thickness and the oxygen content of the remaining Zircaloy metal when the melting point is reached. (author)

  8. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    C. W. Spicer

    1994-08-01

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  9. Chemical composition and photochemical reactivity of exhaust from aircraft turbine engines

    Directory of Open Access Journals (Sweden)

    T. F. Lyon

    Full Text Available Assessment of the environmental impact of aircraft emissions is required by planners and policy makers. Seveal areas of concern are: 1. exposure of airport workers and urban residents to toxic chemicals emitted when the engines operate at low power (idle and taxi on the ground; 2. contributions to urban photochemical air pollution of aircraft volatile organic and nitrogen oxides emissions from operations around airports; and 3. emissions of nitrogen oxides and particles during high-altitude operation. The environmental impact of chemicals emitted from jet aircraft turbine engines has not been firmly established due to lack of data regarding emission rates and identities of the compounds emitted. This paper describes an experimental study of two different aircraft turbine engines designed to determine detailed organic emissions, as well as emissions of inorganic gases. Emissions were measured at several engine power settings. Measurements were made of detailed organic composition from C1 through C17, CO, CO2, NO, NOx, and polycyclic aromatic hydrocarbons. Measurements were made using a multi-port sampling pro be positioned directly behind the engine in the exhaust exit plane. The emission measurements have been used to determine the organic distribution by carbon number and the distribution by compound class at each engine power level. The sum of the organic species was compared with an independent measurement of total organic carbon to assess the carbon mass balance. A portion of the exhaust was captured and irradiated in outdoor smog chambers to assess the photochemical reactivity of the emissions with respect to ozone formation. The reactivity of emissions from the two engines was apportioned by chemical compound class.

  10. Photochemical Production of Hydrogen from Water

    International Nuclear Information System (INIS)

    Broda, E.

    1978-01-01

    The energy flux in sunlight is 40 000 kW per head of the world population. Theoretically much of this energy can be used to photolyze water, in presence of a sensitizer, to H2 (and 02) for a hydrogen economy. The main difficulty in a homogeneous medium is the back-reaction of the primary products. According to the 'membrane principle', the reducing and the oxidizing primary products are released on opposite sides of asymmetric membranes, and so prevented from back-reacting. In essence, this is the mechanism of the photosynthetic machinery in plants and bacteria. This therefore serves as an example in the artificial construction of suitable asymmetric, 'vectorial', membranes. Relatively small areas of photolytic collectors, e.g. in tropical deserts, could cover the energy needs of large populations through hydrogen. (author)

  11. Oxidative Damage and Cellular Defense Mechanisms in Sea Urchin Models of Aging

    Science.gov (United States)

    Du, Colin; Anderson, Arielle; Lortie, Mae; Parsons, Rachel; Bodnar, Andrea

    2013-01-01

    The free radical or oxidative stress theory of aging proposes that the accumulation of oxidative cellular damage is a major contributor to the aging process and a key determinant of species longevity. This study investigates the oxidative stress theory in a novel model for aging research, the sea urchin. Sea urchins present a unique model for the study of aging due to the existence of species with tremendously different natural life spans including some species with extraordinary longevity and negligible senescence. Cellular oxidative damage, antioxidant capacity and proteasome enzyme activities were measured in the tissues of three sea urchin species: short-lived Lytechinus variegatus, long-lived Strongylocentrotus franciscanus and Strongylocentrotus purpuratus which has an intermediate lifespan. Levels of protein carbonyls and 4-hydroxynonenal (HNE) measured in tissues (muscle, nerve, esophagus, gonad, coelomocytes, ampullae) and 8-hydroxy-2’-deoxyguanosine (8-OHdG) measured in cell-free coelomic fluid showed no general increase with age. The fluorescent age-pigment lipofuscin measured in muscle, nerve and esophagus, increased with age however it appeared to be predominantly extracellular. Antioxidant mechanisms (total antioxidant capacity, superoxide dismutase) and proteasome enzyme activities were maintained with age. In some instances, levels of oxidative damage were lower and antioxidant activity higher in cells or tissues of the long-lived species compared to the short-lived species, however further studies are required to determine the relationship between oxidative damage and longevity in these animals. Consistent with the predictions of the oxidative stress theory of aging, the results suggest that negligible senescence is accompanied by a lack of accumulation of cellular oxidative damage with age and maintenance of antioxidant capacity and proteasome enzyme activities may be important mechanisms to mitigate damage. PMID:23707327

  12. Scale-Up Design Analysis and Modelling of Cobalt Oxide Silica Membrane Module for Hydrogen Processing

    OpenAIRE

    Guozhao Ji; Guoxiong Wang; Kamel Hooman; Suresh K. Bhatia; João C. Diniz da Costa

    2013-01-01

    This work shows the application of a validated mathematical model for gas permeation at high temperatures focusing on demonstrated scale-up design for H2 processing. The model considered the driving force variation with spatial coordinates and the mass transfer across the molecular sieve cobalt oxide silica membrane to predict the separation performance. The model was used to study the process of H2 separation at 500 °C in single and multi-tube membrane modules. Parameters of interest include...

  13. Experimental and modeling study of the oxidation of n- and iso-butanal

    KAUST Repository

    Veloo, Peter S.

    2013-09-01

    Understanding the kinetics of large molecular weight aldehydes is essential in the context of both conventional and alternative fuels. For example, they are key intermediates formed during the low-temperature oxidation of hydrocarbons as well as during the high-temperature oxidation of oxygenated fuels such as alcohols. In this study, an experimental and kinetic modeling investigation of n-butanal (. n-butyraldehyde) and iso-butanal (. iso-butyraldehyde or 2-methylpropanal) oxidation kinetics was performed. Experiments were performed in a jet stirred reactor and in counterflow flames over a wide range of equivalence ratios, temperatures, and pressures. The jet stirred reactor was utilized to observe the evolution of stable intermediates and products for the oxidation of n- and iso-butanal at elevated pressures and low to intermediate temperatures. The counterflow configuration was utilized for the determination of laminar flame speeds. A detailed chemical kinetic interpretative model was developed and validated consisting of 244 species and 1198 reactions derived from a previous study of the oxidation of propanal (propionaldehyde). Extensive reaction pathway and sensitivity analysis was performed to provide detailed insight into the mechanisms governing low-, intermediate-, and high-temperature reactivity. The simulation results using the present model are in good agreement with the experimental laminar flame speeds and well within a factor of two of the speciation data obtained in the jet stirred reactor. © 2013 The Combustion Institute.

  14. Atmospheric Dissolved Iron Depostiion to the Global Oceans: Effects of Oxalate-Promoted Fe Dissolution, Photochemical Redox Cycling, and Dust Mineralogy

    Science.gov (United States)

    Johnson, M. S.; Meskhidze, N.

    2013-01-01

    Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fed) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fed production during the atmospheric transport of mineral dust taking into account inorganic and organic (oxalate)-promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of windblown dust from the major desert regions. Our calculations suggest that during the yearlong simulation is approximately 0.26 Tg (1 Tg = 1012 g) of Fed was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate to the dust-Fe mobilization scheme increased total annual model-predicted Fed deposition to global oceanic regions by approximately 75%. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model allows for the distinction between different oxidation states of deposited Fed. Our calculations suggest that during the daytime, large fractions of Fed deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fed are largely in Fe(III) form. Model simulations also show that atmospheric fluxes of Fed can be strongly influenced by the mineralogy of Fe-containing compounds. This study shows that Fed deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the

  15. Detailed kinetic modeling study of n-pentanol oxidation

    KAUST Repository

    Heufer, Karl Alexander

    2012-10-18

    To help overcome the world\\'s dependence upon fossil fuels, suitable biofuels are promising alternatives that can be used in the transportation sector. Recent research on internal combustion engines shows that short alcoholic fuels (e.g., ethanol or n-butanol) have reduced pollutant emissions and increased knock resistance compared to fossil fuels. Although higher molecular weight alcohols (e.g., n-pentanol and n-hexanol) exhibit higher reactivity that lowers their knock resistance, they are suitable for diesel engines or advanced engine concepts, such as homogeneous charge compression ignition (HCCI), where higher reactivity at lower temperatures is necessary for engine operation. The present study presents a detailed kinetic model for n-pentanol based on modeling rules previously presented for n-butanol. This approach was initially validated using quantum chemistry calculations to verify the most stable n-pentanol conformation and to obtain C-H and C-C bond dissociation energies. The proposed model has been validated against ignition delay time data, speciation data from a jet-stirred reactor, and laminar flame velocity measurements. Overall, the model shows good agreement with the experiments and permits a detailed discussion of the differences between alcohols and alkanes. © 2012 American Chemical Society.

  16. Mouse models for disorders of mitochondrial fatty acid beta-oxidation.

    Science.gov (United States)

    Schuler, A Michele; Wood, Philip A

    2002-01-01

    Mitochondrial beta-oxidation of fatty acids is vital for energy production in periods of fasting and other metabolic stress. Human patients have been identified with inherited disorders of mitochondrial beta-oxidation of fatty acids with enzyme deficiencies identified at many of the steps in this pathway. Although these patients exhibit a range of disease processes, Reye-like illness (hypoketotic-hypoglycemia, hyperammonemia and fatty liver) and cardiomyopathy are common findings. There have been several mouse models developed to aid in the study of these disease conditions. The characterized mouse models include inherited deficiencies of very long-chain acyl-CoA dehydrogenase, long-chain acyl-CoA dehydrogenase, short-chain acyl-CoA dehydrogenase, mitochondrial trifunctional protein-alpha, and medium-/short-chain hydroxyacyl-CoA dehydrogenase. Mouse mutants developed, but presently incompletely characterized as models, include carnitine palmitoyltransferase-1a and medium-chain acyl-CoA dehydrogenase deficiencies. In general, the mouse models of disorders of mitochondrial fatty acid beta-oxidation have shown clinical signs that include Reye-like syndrome and cardiomyopathy, and many are cold intolerant. It is expected that these mouse models will provide vital contributions in understanding the mechanisms of disease pathogenesis of fatty acid oxidation disorders and the development of appropriate treatments and supportive care.

  17. Modeling selenate adsorption behavior on oxides, clay minerals, and soils using the triple layer model

    Science.gov (United States)

    Selenate adsorption behavior was investigated on amorphous aluminum oxide, amorphous iron oxide, goethite, clay minerals: kaolinites, montmorillonites, illite, and 18 soil samples from Hawaii, and the Southwestern and the Midwestern regions of the US as a function of solution pH. Selenate adsorpti...

  18. Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

    International Nuclear Information System (INIS)

    Crist, K.C.

    1984-10-01

    An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables

  19. Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

    Energy Technology Data Exchange (ETDEWEB)

    Crist, K.C.

    1984-10-01

    An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables.

  20. Hydrogen oxidation at high pressure and intermediate temperatures: experiments and kinetic modeling

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Christensen, Jakob Munkholt; Gersen, Sander

    2015-01-01

    , and the present data sup- port recent values for the rate constant. In addition to the current experiments, the mechanism was evaluated against ignition delay time measurements from rapid compression machines and shock tubes. The model was used to analyze the complex dependence of the ignition delay for H 2...... for the reactions HO 2 + OH, OH + OH, and HO 2 +HO 2 were updated based on recent determinations. The modeling pre- dictions were in good agreement with the measurements in the flow reactor. The predicted H 2 oxidation rate was sensitive to the rate of the HO 2 + OH reaction, particularly at lean conditions......Hydrogen oxidation at 50 bar and temperatures of 700–900 K was investigated in a high pressure laminar flow reactor under highly diluted conditions. The experiments provided information about H 2 oxidation at pressures above the third explosion limit. The fuel–air equivalence ratio of the reactants...

  1. Numerical modeling of nitrogen oxide emission and experimental verification

    Directory of Open Access Journals (Sweden)

    Szecowka Lech

    2003-12-01

    Full Text Available The results of nitrogen reduction in combustion process with application of primary method are presented in paper. The reduction of NOx emission, by the recirculation of combustion gasses, staging of fuel and of air was investigated, and than the reduction of NOx emission by simultaneous usage of the mentioned above primary method with pulsatory disturbances.The investigations contain numerical modeling of NOx reduction and experimental verification of obtained numerical calculation results.

  2. Chemometrics models for assessment of oxidative stress risk in chrome-electroplating workers.

    Science.gov (United States)

    Zendehdel, Rezvan; Shetab-Boushehri, Seyed Vahid; Azari, Mansoor R; Hosseini, Vajihe; Mohammadi, Hamidreza

    2015-04-01

    Oxidative stress is the main cause of hexavalant chromium-induced damage in chrome electroplating workers. The main goal of this study is toxicity analysis and the possibility of toxicity risk categorizing in the chrome electroplating workers based on oxidative stress parameters as prognostic variables. We assessed blood chromium levels and biomarkers of oxidative stress such as lipid peroxidation, thiol (SH) groups and antioxidant capacity of plasma. Data were subjected to principle component analysis (PCA) and artificial neuronal network (ANN) to obtain oxidative stress pattern for chrome electroplating workers. Blood chromium levels increased from 4.42 ppb to 10.6 ppb. Induction of oxidative stress was observed by increased in lipid peroxidation (22.38 ± 10.47 μM versus 14.74 ± 4.82 μM, p chrome electroplaters. The result showed multivariate modeling can be interpreted as the induced biochemical toxicity in the workers exposed to hexavalent chromium. Different occupation groups were assessed on the basis of risk level of oxidative stress which could further justify proceeding engineering control measures.

  3. Cholesterol photo-oxidation: A chemical reaction network for kinetic modeling.

    Science.gov (United States)

    Barnaba, Carlo; Rodríguez-Estrada, Maria Teresa; Lercker, Giovanni; García, Hugo Sergio; Medina-Meza, Ilce Gabriela

    2016-12-01

    In this work we studied the effect of polyunsaturated fatty acids (PUFAs) methyl esters on cholesterol photo-induced oxidation. The oxidative routes were modeled with a chemical reaction network (CRN), which represents the first application of CRN to the oxidative degradation of a food-related lipid matrix. Docosahexaenoic acid (DHA, T-I), eicosapentaenoic acid (EPA, T-II) and a mixture of both (T-III) were added to cholesterol using hematoporphyrin as sensitizer, and were exposed to a fluorescent lamp for 48h. High amounts of Type I cholesterol oxidation products (COPs) were recovered (epimers 7α- and 7β-OH, 7-keto and 25-OH), as well as 5β,6β-epoxy. Fitting the experimental data with the CRN allowed characterizing the associated kinetics. DHA and EPA exerted different effects on the oxidative process. DHA showed a protective effect to 7-hydroxy derivatives, whereas EPA enhanced side-chain oxidation and 7β-OH kinetic rates. The mixture of PUFAs increased the kinetic rates several fold, particularly for 25-OH. With respect to the control, the formation of β-epoxy was reduced, suggesting potential inhibition in the presence of PUFAs. Copyright © 2016 Elsevier Inc. All rights reserved.

  4. Extending the models for iron and sulfur oxidation in the extreme Acidophile Acidithiobacillus ferrooxidans

    Directory of Open Access Journals (Sweden)

    Holmes David S

    2009-08-01

    Full Text Available Abstract Background Acidithiobacillus ferrooxidans gains energy from the oxidation of ferrous iron and various reduced inorganic sulfur compounds at very acidic pH. Although an initial model for the electron pathways involved in iron oxidation has been developed, much less is known about the sulfur oxidation in this microorganism. In addition, what has been reported for both iron and sulfur oxidation has been derived from different A. ferrooxidans strains, some of which have not been phylogenetically characterized and some have been shown to be mixed cultures. It is necessary to provide models of iron and sulfur oxidation pathways within one strain of A. ferrooxidans in order to comprehend the full metabolic potential of the pangenome of the genus. Results Bioinformatic-based metabolic reconstruction supported by microarray transcript profiling and quantitative RT-PCR analysis predicts the involvement of a number of novel genes involved in iron and sulfur oxidation in A. ferrooxidans ATCC23270. These include for iron oxidation: cup (copper oxidase-like, ctaABT (heme biogenesis and insertion, nuoI and nuoK (NADH complex subunits, sdrA1 (a NADH complex accessory protein and atpB and atpE (ATP synthetase F0 subunits. The following new genes are predicted to be involved in reduced inorganic sulfur compounds oxidation: a gene cluster (rhd, tusA, dsrE, hdrC, hdrB, hdrA, orf2, hdrC, hdrB encoding three sulfurtransferases and a heterodisulfide reductase complex, sat potentially encoding an ATP sulfurylase and sdrA2 (an accessory NADH complex subunit. Two different regulatory components are predicted to be involved in the regulation of alternate electron transfer pathways: 1 a gene cluster (ctaRUS that contains a predicted iron responsive regulator of the Rrf2 family that is hypothesized to regulate cytochrome aa3 oxidase biogenesis and 2 a two component sensor-regulator of the RegB-RegA family that may respond to the redox state of the quinone pool

  5. Sinapic acid prevents hypertension and cardiovascular remodeling in pharmacological model of nitric oxide inhibited rats.

    Science.gov (United States)

    Silambarasan, Thangarasu; Manivannan, Jeganathan; Krishna Priya, Mani; Suganya, Natarajan; Chatterjee, Suvro; Raja, Boobalan

    2014-01-01

    Hypertensive heart disease is a constellation of abnormalities that includes cardiac fibrosis in response to elevated blood pressure, systolic and diastolic dysfunction. The present study was undertaken to examine the effect of sinapic acid on high blood pressure and cardiovascular remodeling. An experimental hypertensive animal model was induced by L-NAME intake on rats. Sinapic acid (SA) was orally administered at a dose of 10, 20 and 40 mg/kg body weight (b.w.). Blood pressure was measured by tail cuff plethysmography system. Cardiac and vascular function was evaluated by Langendorff isolated heart system and organ bath studies, respectively. Fibrotic remodeling of heart and aorta was assessed by histopathologic analyses. Oxidative stress was measured by biochemical assays. mRNA and protein expressions were assessed by RT-qPCR and western blot, respectively. In order to confirm the protective role of SA on endothelial cells through its antioxidant property, we have utilized the in vitro model of H2O2-induced oxidative stress in EA.hy926 endothelial cells. Rats with hypertension showed elevated blood pressure, declined myocardial performance associated with myocardial hypertrophy and fibrosis, diminished vascular response, nitric oxide (NO) metabolites level, elevated markers of oxidative stress (TBARS, LOOH), ACE activity, depleted antioxidant system (SOD, CAT, GPx, reduced GSH), aberrant expression of TGF-β, β-MHC, eNOS mRNAs and eNOS protein. Remarkably, SA attenuated high blood pressure, myocardial, vascular dysfunction, cardiac fibrosis, oxidative stress and ACE activity. Level of NO metabolites, antioxidant system, and altered gene expression were also repaired by SA treatment. Results of in vitro study showed that, SA protects endothelial cells from oxidative stress and enhance the production of NO in a concentration dependent manner. Taken together, these results suggest that SA may have beneficial role in the treatment of hypertensive heart disease by

  6. Sinapic acid prevents hypertension and cardiovascular remodeling in pharmacological model of nitric oxide inhibited rats.

    Directory of Open Access Journals (Sweden)

    Thangarasu Silambarasan

    Full Text Available Hypertensive heart disease is a constellation of abnormalities that includes cardiac fibrosis in response to elevated blood pressure, systolic and diastolic dysfunction. The present study was undertaken to examine the effect of sinapic acid on high blood pressure and cardiovascular remodeling.An experimental hypertensive animal model was induced by L-NAME intake on rats. Sinapic acid (SA was orally administered at a dose of 10, 20 and 40 mg/kg body weight (b.w.. Blood pressure was measured by tail cuff plethysmography system. Cardiac and vascular function was evaluated by Langendorff isolated heart system and organ bath studies, respectively. Fibrotic remodeling of heart and aorta was assessed by histopathologic analyses. Oxidative stress was measured by biochemical assays. mRNA and protein expressions were assessed by RT-qPCR and western blot, respectively. In order to confirm the protective role of SA on endothelial cells through its antioxidant property, we have utilized the in vitro model of H2O2-induced oxidative stress in EA.hy926 endothelial cells.Rats with hypertension showed elevated blood pressure, declined myocardial performance associated with myocardial hypertrophy and fibrosis, diminished vascular response, nitric oxide (NO metabolites level, elevated markers of oxidative stress (TBARS, LOOH, ACE activity, depleted antioxidant system (SOD, CAT, GPx, reduced GSH, aberrant expression of TGF-β, β-MHC, eNOS mRNAs and eNOS protein. Remarkably, SA attenuated high blood pressure, myocardial, vascular dysfunction, cardiac fibrosis, oxidative stress and ACE activity. Level of NO metabolites, antioxidant system, and altered gene expression were also repaired by SA treatment. Results of in vitro study showed that, SA protects endothelial cells from oxidative stress and enhance the production of NO in a concentration dependent manner.Taken together, these results suggest that SA may have beneficial role in the treatment of hypertensive heart

  7. Mitochondrial Alterations and Oxidative Stress in an Acute Transient Mouse Model of Muscle Degeneration

    Science.gov (United States)

    Ramadasan-Nair, Renjini; Gayathri, Narayanappa; Mishra, Sudha; Sunitha, Balaraju; Mythri, Rajeswara Babu; Nalini, Atchayaram; Subbannayya, Yashwanth; Harsha, Hindalahalli Chandregowda; Kolthur-Seetharam, Ullas; Bharath, Muchukunte Mukunda Srinivas

    2014-01-01

    Muscular dystrophies (MDs) and inflammatory myopathies (IMs) are debilitating skeletal muscle disorders characterized by common pathological events including myodegeneration and inflammation. However, an experimental model representing both muscle pathologies and displaying most of the distinctive markers has not been characterized. We investigated the cardiotoxin (CTX)-mediated transient acute mouse model of muscle degeneration and compared the cardinal features with human MDs and IMs. The CTX model displayed degeneration, apoptosis, inflammation, loss of sarcolemmal complexes, sarcolemmal disruption, and ultrastructural changes characteristic of human MDs and IMs. Cell death caused by CTX involved calcium influx and mitochondrial damage both in murine C2C12 muscle cells and in mice. Mitochondrial proteomic analysis at the initial phase of degeneration in the model detected lowered expression of 80 mitochondrial proteins including subunits of respiratory complexes, ATP machinery, fatty acid metabolism, and Krebs cycle, which further decreased in expression during the peak degenerative phase. The mass spectrometry (MS) data were supported by enzyme assays, Western blot, and histochemistry. The CTX model also displayed markers of oxidative stress and a lowered glutathione reduced/oxidized ratio (GSH/GSSG) similar to MDs, human myopathies, and neurogenic atrophies. MS analysis identified 6 unique oxidized proteins from Duchenne muscular dystrophy samples (n = 6) (versus controls; n = 6), including two mitochondrial proteins. Interestingly, these mitochondrial proteins were down-regulated in the CTX model thereby linking oxidative stress and mitochondrial dysfunction. We conclude that mitochondrial alterations and oxidative damage significantly contribute to CTX-mediated muscle pathology with implications for human muscle diseases. PMID:24220031

  8. Matrix isolation study of the photochemical reaction of cyclohexane, cyclohexene, and cyclopropane with ozone

    Science.gov (United States)

    Hoops, Michael D.; Ault, Bruce S.

    2009-07-01

    The matrix isolation technique, combined with infrared spectroscopy, has been used to characterize the products of the photochemical reactions of cyclohexane, cyclohexene, and cyclopropane with ozone. While initial twin jet deposition of the reagents led to no visible changes in the recorded spectra, strong product bands were noted following irradiation with light of λ > 200 nm. Irradiation of matrices containing ozone and cyclohexane led to O atom reactions with insertion into a C sbnd H bond and a C sbnd C bond to form cyclohexanol and oxacycloheptane, respectively. Irradiation of matrices containing ozone and cyclohexene led to a mixture of products formed through oxidation of the double bond, including cyclohexanone and cyclohexene oxide. Cyclopropane and ozone were codeposited into argon matrices followed by irradiation, leading to the formation of both cyclopropanal through insertion into a C sbnd H bond and aldehydes through ring-opening and oxidation. These conclusions were supported by isotopic labeling ( 18O), by comparison to authentic infrared spectra, and by B3LYP/6-311G++(d,2p) density functional calculations.

  9. Spectroscopic studies on the photochemical decarboxylation mechanisms of synthetic pyrethroids.

    Science.gov (United States)

    Suzuki, Yusuke; Ishizaka, Shoji; Kitamura, Noboru

    2012-12-01

    A novel radical trapping technique combined with a fluorescence spectroscopic analysis has been employed to investigate the radical intermediates produced by photodecarboxylation of four synthetic pyrethroids: fenvalerate (SMD), fenpropathrin (DTL), cyphenothrin (GKL), and cypermethrin (AGT). Under photoirradiation at >290 nm, all pyrethroids underwent direct photolysis via homolytic cleavage of the carbon-oxygen bonds in the ester groups. The consumed amount of a nitroxide free radical, as a trapping agent for the intermediate radical of a pyrethroid, was determined by ESR, which was the measure of the reaction yield of a photochemically generated α-cyano-3-phenoxybenzyl radical common to all pyrethroids. The reactivities of the pyrethroids studied was in the sequence of SMD > DTL > GKL > AGT. Furthermore, nanosecond transient absorption spectroscopy demonstrated that geminate recombination of the radical pair within a solvent cage is the main deactivation route of the photochemically generated α-cyano-3-phenoxybenzyl radical common for all pyrethroids studied.

  10. Photochemical selectivity in guanine–cytosine base-pair structures

    Science.gov (United States)

    Abo-Riziq, Ali; Grace, Louis; Nir, Eyal; Kabelac, Martin; Hobza, Pavel; de Vries, Mattanjah S.

    2005-01-01

    Prebiotic chemistry presumably took place before formation of an oxygen-rich atmosphere and thus under conditions of intense short wavelength UV irradiation. Therefore, the UV photochemical stability of the molecular building blocks of life may have been an important selective factor in determining the eventual chemical makeup of critical biomolecules. To investigate the role of UV irradiation in base-pairing we have studied guanine (G) and cytosine (C) base pairs in the absence of the RNA backbone. We distinguished base-pair structures by IR–UV hole-burning spectroscopy as well as by high-level correlated ab initio calculations. The Watson–Crick structure exhibits broad UV absorption, in stark contrast to other GC structures and other base-pair structures. This broad absorption may be explained by a rapid internal conversion that makes this specific base pair arrangement uniquely photochemically stable. PMID:15618394

  11. Effects of Photobiomodulation Therapy on Oxidative Stress in Muscle Injury Animal Models: A Systematic Review

    Directory of Open Access Journals (Sweden)

    Solange Almeida dos Santos

    2017-01-01

    Full Text Available This systematic review was performed to identify the role of photobiomodulation therapy on experimental muscle injury models linked to induce oxidative stress. EMBASE, PubMed, and CINAHL were searched for studies published from January 2006 to January 2016 in the areas of laser and oxidative stress. Any animal model using photobiomodulation therapy to modulate oxidative stress was included in analysis. Eight studies were selected from 68 original articles targeted on laser irradiation and oxidative stress. Articles were critically assessed by two independent raters with a structured tool for rating the research quality. Although the small number of studies limits conclusions, the current literature indicates that photobiomodulation therapy can be an effective short-term approach to reduce oxidative stress markers (e.g., thiobarbituric acid-reactive and to increase antioxidant substances (e.g., catalase, glutathione peroxidase, and superoxide dismutase. However, there is a nonuniformity in the terminology used to describe the parameters and dose for low-level laser treatment.

  12. Endothelin receptor antagonist attenuates oxidative stress in a neonatal sepsis piglet model.

    Science.gov (United States)

    Goto, Tatenobu; Hussein, Mohamed Hamed; Kato, Shin; Daoud, Ghada Abdel-Hamid; Kato, Takenori; Sugiura, Takahiro; Kakita, Hiroki; Nobata, Masanori; Kamei, Michi; Mizuno, Haruo; Imai, Masaki; Ito, Tetsuya; Kato, Ineko; Suzuki, Satoshi; Okada, Noriko; Togari, Hajime; Okada, Hidechika

    2012-12-01

    Oxidative stress (oxidant-antioxidant imbalance) plays an important role in the pathophysiology of neonatal sepsis. This study evaluated whether an antisense peptide endothelin receptor antagonist, ETR-P1/fl, could attenuate oxidative stress in a neonatal sepsis model. A total of 18 3-d-old piglets were anesthetized and mechanically ventilated. Six piglets received cecal ligation and perforation (CLP group) for induction of sepsis. Six piglets also received continuous infusion (0.05 mg/kg/h) of ETR-P1/fl 30 min after CLP (ETR-P1/fl group). Six piglets received a sham operation. Serum total hydroperoxide (TH), biological antioxidant potentials (BAPs), oxidative stress index (OSI, calculated as TH/BAP), interleukin (IL)-6, serum glutamic oxaloacetic transaminase (GOT), and creatinine were measured before CLP and at 1, 3, and 6 h after CLP. CLP evoked a state of shock resulting in elevated TH, OSI, and IL-6 levels. ETR-P1/fl administration after CLP resulted in lower serum TH at 1 and 3 h after CLP, OSI at 1 and 3 h after CLP, IL-6 at 1 and 3 h after CLP, and GOT at 3 and 6 h after CLP as compared with the CLP group. ETR-P1/fl treatment significantly attenuated the elevation of serum oxidative stress markers (TH and OSI), IL-6, and GOT in a progressive neonatal sepsis CLP model.

  13. Oxidative stress in a rat model of cotton smoke inhalation-induced ...

    African Journals Online (AJOL)

    Background: Smoke inhalation injury refers to airway and lung parenchyma injury and general chemical damage caused by inhaling toxic gases and substances. The aim of this study was to explore the oxidative stress mechanism of cotton smoke inhalation-induced pulmonary injury in a rat model. Materials and Methods: ...

  14. NITROUS OXIDE EMISSIONS FROM SOUTHERN HIGH PLAINS BEEF CATTLE FEEDYARDS: MEASUREMENT AND MODELING

    Science.gov (United States)

    Predictive models for nitrous oxide emission are crucial for assessing the greenhouse gas footprint of beef cattle production. The Texas Panhandle produces approximately 42% of finished beef in the U.S. and cattle production is estimated to contribute 8 Tg carbon dioxide equivalents from nitrous oxi...

  15. Characterization of subcritical water oxidation with in situ monitoring and self-modeling curve resolution

    International Nuclear Information System (INIS)

    Gemperline, Paul J.; Yang Yu; Bian Zhihui

    2003-01-01

    In this paper, a subcritical water oxidation (SBWO) process was monitored using self-modeling curve resolution (SMCR) of in situ UV-Vis measurements to estimate time-dependant composition profiles of reactants, intermediates and products. A small laboratory scale reactor with UV-Vis fiber-optic probes and a flow cell was used to demonstrate the usefulness of SMCR for monitoring the destruction of model compounds phenol, benzoic acid, and aniline in a dilute aqueous solutions. Hydrogen peroxide was used as the oxidizing reagent at moderate temperature (150-250 deg. C) and pressure (60-90 atm) in a single phase. By use of in situ monitoring, reaction times were easily determined and conditions for efficient oxidations were easily diagnosed without the need for time consuming off-line reference measurements. For selected runs, the destruction of the model compound was confirmed by gas chromatography and chemical oxygen demand (COD) measurements. Suspected intermediate oxidation products were easily detected by the use of UV-Vis spectrometry and self-modeling curve resolution, but could not be detected by gas chromatography

  16. Quantitative analysis of anaerobic oxidation of methane (AOM) in marine sediments: a modeling perspective

    NARCIS (Netherlands)

    Regnier, P.; Dale, A.W.; Arndt, S.; LaRowe, D.E.; Mogollon, J.M.; Van Cappellen, P.

    2011-01-01

    Recent developments in the quantitativemodeling of methane dynamics and anaerobic oxidation of methane (AOM) in marine sediments are critically reviewed. The first part of the review begins with a comparison of alternative kinetic models for AOM. The roles of bioenergetic limitations, intermediate

  17. Manipulation of nitric oxide in an animal model of acute liver injury ...

    African Journals Online (AJOL)

    We evaluated the impact of altering nitric oxide release on acute liver injury, the associated gut injury and bacterial translocation, at different time intervals. Methods: An acute rat liver injury model induced by D-galactosamine was used. Sprague Dawley rats were divided into four main groups: normal control, acute liver ...

  18. A model for the release of low-volatility fission products in oxidizing conditions

    International Nuclear Information System (INIS)

    Cox, D.S.; Hunt, C.E.L.; Liu, Z.; Keller, N.A.; Barrand, R.D.; O'Connor, R.F.

    1991-07-01

    A thermodynamic and kinetic model has been developed for calculating low-volatility fission-product releases from UO 2 at high temperatures in oxidizing conditions. Volatilization of the UO 2 matrix is assumed to be the rate controlling process. Oxidation kinetics of the UO 2 are modelled by either interfacial rate control, gas phase oxidant transport control, or solid-state diffusion of oxygen. The vapour pressure of UO 3 in equilibrium with the oxidizing fuel is calculated from thermodynamic data, and volatilization rates are determined using a model for forced convective mass transport. Low-volatility fission-product releases are calculated from the volume of vapourized fuel. Model calculations are conservative compared to experimental data for Zr, La, Ce and Nb fission-product releases from irradiated UO 2 exposed to air at 1973-2350 K. The implications of this conservatism are discussed in terms of possible rate control by processes other than convective mass transport of UO 3 . Coefficients for effective surface area (based on experimental data) and for heterogeneous rate controlling reaction kinetics are introduced to facilitate agreement between calculations and the experimental data.

  19. Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Aranda, V.; Christensen, J. M.; Alzueta, Maria

    2013-01-01

    the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were...

  20. Land use regression modelling estimating nitrogen oxides exposure in industrial south Durban, South Africa.

    NARCIS (Netherlands)

    Muttoo, Sheena; Ramsay, Lisa; Brunekreef, Bert; Beelen, Rob; Meliefste, Kees; Naidoo, Rajen N

    2018-01-01

    The South Durban (SD) area of Durban, South Africa, has a history of air pollution issues due to the juxtaposition of low-income communities with industrial areas. This study used measurements of oxides of nitrogen (NOx) to develop a land use regression (LUR) model to explain the spatial variation

  1. CO2 Reduction: From the Electrochemical to Photochemical Approach

    OpenAIRE

    Wu, Jinghua; Huang, Yang; Ye, Wen; Li, Yanguang

    2017-01-01

    Abstract Increasing CO2 concentration in the atmosphere is believed to have a profound impact on the global climate. To reverse the impact would necessitate not only curbing the reliance on fossil fuels but also developing effective strategies capture and utilize CO2 from the atmosphere. Among several available strategies, CO2 reduction via the electrochemical or photochemical approach is particularly attractive since the required energy input can be potentially supplied from renewable source...

  2. Molecular-beam studies of primary photochemical processes

    International Nuclear Information System (INIS)

    Lee, Y.T.

    1982-12-01

    Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser

  3. Molecular-beam studies of primary photochemical processes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y.T.

    1982-12-01

    Application of the method of molecular-beam photofragmentation translational spectroscopy to the investigation of primary photochemical processes of polyatomic molecules is described. Examples will be given to illustrate how information concerning the energetics, dynamics, and mechanism of dissociation processes can be obtained from the precise measurements of angular and velocity distributions of products in an experiment in which a well-defined beam of molecules is crossed with a laser.

  4. Heptacoordinate Coii complex: a new architecture for photochemical hydrogen production

    OpenAIRE

    Lucarini, Fiorella; Pastore, Mariachiara; Vasylevskyi, Serhii; Varisco, Massimo; Solari, Euro; Crochet, Aurelien; Fromm, Katharina M.; Zobi, Fabio; Ruggi, Albert

    2017-01-01

    The first heptacoordinate cobalt catalyst for light-driven hydrogen production in water has been synthesized and characterized. Photochemical experiments using [Ru(bpy)₃]²⁺ as photosensitizer gave a turnover number (TON) of 16300 mol H₂ (mol  cat.)⁻¹ achieved in 2 hours of irradiation with visible (475 nm) light. This promising result provides a path forward in the development of new structures to improve the efficiency of the catalysis.

  5. Photochemical Degradation of Polybrominated Diphenyl Ethers in Microreactor

    Czech Academy of Sciences Publication Activity Database

    Vajglová, Zuzana; Veselý, M.; Hejda, S.; Vondráčková, Magdalena; Křišťál, Jiří; Cajthaml, Tomáš; Křesinová, Zdena; Tříska, Jan; Klusoň, Petr; Jiřičný, Vladimír

    2015-01-01

    Roč. 41, č. 12 (2015), s. 9373-9381 ISSN 0922-6168. [Pannonian Symposium on Catalysis /12./. Castle Trest, 16.09.2014-20.09.2014] R&D Projects: GA ČR(CZ) GAP105/12/0664; GA ČR GA104/09/0880 Institutional support: RVO:67985858 ; RVO:61388971 ; RVO:67179843 Keywords : polybrominated diphenyl ethers * photochemical microreactor * debromination * photo degradation Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.833, year: 2015

  6. Synthesis of 3-heteroarylchromones via a photochemical reaction.

    Science.gov (United States)

    Yang, Qian; He, Yun; Wang, Tao; Zeng, Lingyu; Zhang, Zunting

    2016-02-01

    The direct coupling of 3-iodochromen-4-ones with heteroaromatics has been achieved via a photochemical reaction. A variety of 3-heteroarylchromones was obtained in moderate to good yields from the corresponding 3-iodochromen-4-ones and heteroaromatics, such as pyrrole, furan, thiophene, and benzofuran. The reaction worked smoothly in acetonitrile under a mercury lamp without any additives, providing a catalyst- and base-free approach for the synthesis of 3-heteroarylchromones.

  7. A plasmaless, photochemical etch process for porous organosilicate glass films

    Science.gov (United States)

    Ryan, E. Todd; Molis, Steven E.

    2017-12-01

    A plasmaless, photochemical etch process using ultraviolet (UV) light in the presence of NH3 or O2 etched porous organosilicate glass films, also called pSiCOH films, in a two-step process. First, a UV/NH3 or UV/O2 treatment removed carbon (mostly methyl groups bonded to silicon) from a pSiCOH film by demethylation to a depth determined by the treatment exposure time. Second, aqueous HF was used to selectively remove the demethylated layer of the pSiCOH film leaving the methylated layer below. UV in the presence of inert gas or H2 did not demethylate the pSiCOH film. The depth of UV/NH3 demethylation followed diffusion limited kinetics and possible mechanisms of demethylation are presented. Unlike reactive plasma processes, which contain ions that can damage surrounding structures during nanofabrication, the photochemical etch contains no damaging ions. Feasibility of the photochemical etching was shown by comparing it to a plasma-based process to remove the pSiCOH dielectric from between Cu interconnect lines, which is a critical step during air gap fabrication. The findings also expand our understanding of UV photon interactions in pSiCOH films that may contribute to plasma-induced damage to pSiCOH films.

  8. Oxidative stress contributes to outcome severity in a Drosophila melanogaster model of classic galactosemia

    Directory of Open Access Journals (Sweden)

    Patricia P. Jumbo-Lucioni

    2013-01-01

    Classic galactosemia is a genetic disorder that results from profound loss of galactose-1P-uridylyltransferase (GALT. Affected infants experience a rapid escalation of potentially lethal acute symptoms following exposure to milk. Dietary restriction of galactose prevents or resolves the acute sequelae; however, many patients experience profound long-term complications. Despite decades of research, the mechanisms that underlie pathophysiology in classic galactosemia remain unclear. Recently, we developed a Drosophila melanogaster model of classic galactosemia and demonstrated that, like patients, GALT-null Drosophila succumb in development if exposed to galactose but live if maintained on a galactose-restricted diet. Prior models of experimental galactosemia have implicated a possible association between galactose exposure and oxidative stress. Here we describe application of our fly genetic model of galactosemia to the question of whether oxidative stress contributes to the acute galactose sensitivity of GALT-null animals. Our first approach tested the impact of pro- and antioxidant food supplements on the survival of GALT-null and control larvae. We observed a clear pattern: the oxidants paraquat and DMSO each had a negative impact on the survival of mutant but not control animals exposed to galactose, and the antioxidants vitamin C and α-mangostin each had the opposite effect. Biochemical markers also confirmed that galactose and paraquat synergistically increased oxidative stress on all cohorts tested but, interestingly, the mutant animals showed a decreased response relative to controls. Finally, we tested the expression levels of two transcripts responsive to oxidative stress, GSTD6 and GSTE7, in mutant and control larvae exposed to galactose and found that both genes were induced, one by more than 40-fold. Combined, these results implicate oxidative stress and response as contributing factors in the acute galactose sensitivity of GALT-null Drosophila and, by

  9. Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

    Directory of Open Access Journals (Sweden)

    Linxu Chen

    Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

  10. Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

    Science.gov (United States)

    Chen, Linxu; Ren, Yilin; Lin, Jianqun; Liu, Xiangmei; Pang, Xin; Lin, Jianqiang

    2012-01-01

    Acidithiobacillus caldus (A. caldus) is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs) for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox) system (omitting SoxCD), non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR). The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system. An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor) was created and its growth abilities were measured in media using elemental sulfur (S(0)) and tetrathionate (K(2)S(4)O(6)) as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR) of the wild type and the Δsor mutant in S(0) and K(2)S(4)O(6) media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO) and heterodisulfide reductase (HDR), the truncated Sox pathway, and the S(4)I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media. An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

  11. Modeling nitrous oxide production during biological nitrogen removal via nitrification and denitrification: extensions to the general ASM models.

    Science.gov (United States)

    Ni, Bing-Jie; Ruscalleda, Maël; Pellicer-Nàcher, Carles; Smets, Barth F

    2011-09-15

    Nitrous oxide (N(2)O) can be formed during biological nitrogen (N) removal processes. In this work, a mathematical model is developed that describes N(2)O production and consumption during activated sludge nitrification and denitrification. The well-known ASM process models are extended to capture N(2)O dynamics during both nitrification and denitrification in biological N removal. Six additional processes and three additional reactants, all involved in known biochemical reactions, have been added. The validity and applicability of the model is demonstrated by comparing simulations with experimental data on N(2)O production from four different mixed culture nitrification and denitrification reactor study reports. Modeling results confirm that hydroxylamine oxidation by ammonium oxidizers (AOB) occurs 10 times slower when NO(2)(-) participates as final electron acceptor compared to the oxic pathway. Among the four denitrification steps, the last one (N(2)O reduction to N(2)) seems to be inhibited first when O(2) is present. Overall, N(2)O production can account for 0.1-25% of the consumed N in different nitrification and denitrification systems, which can be well simulated by the proposed model. In conclusion, we provide a modeling structure, which adequately captures N(2)O dynamics in autotrophic nitrification and heterotrophic denitrification driven biological N removal processes and which can form the basis for ongoing refinements.

  12. Antisickling properties, thermal and photochemical degradations of ...

    African Journals Online (AJOL)

    Anthocyanin crude extracts and fractions of Annona senegalensis leaves were screened for their antisickling properties using a validated in vitro bioassay model of sickle cell anaemia. Preparative thin layer chromatography of acetylated anthocyanin crude extracts carried out with chloroform as solvent provided two active ...

  13. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Directory of Open Access Journals (Sweden)

    Elena Lima-Cabello

    2016-01-01

    Full Text Available Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome.

  14. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability

    Science.gov (United States)

    Lima-Cabello, Elena; Garcia-Guirado, Francisco; Calvo-Medina, Rocio; el Bekay, Rajaa; Perez-Costillas, Lucia; Quintero-Navarro, Carolina; Sanchez-Salido, Lourdes

    2016-01-01

    Background. Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. Methods. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Results. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. Conclusions. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome. PMID:26788253

  15. An Abnormal Nitric Oxide Metabolism Contributes to Brain Oxidative Stress in the Mouse Model for the Fragile X Syndrome, a Possible Role in Intellectual Disability.

    Science.gov (United States)

    Lima-Cabello, Elena; Garcia-Guirado, Francisco; Calvo-Medina, Rocio; el Bekay, Rajaa; Perez-Costillas, Lucia; Quintero-Navarro, Carolina; Sanchez-Salido, Lourdes; de Diego-Otero, Yolanda

    2016-01-01

    Fragile X syndrome is the most common genetic cause of mental disability. Although many research has been performed, the mechanism underlying the pathogenesis is unclear and needs further investigation. Oxidative stress played major roles in the syndrome. The aim was to investigate the nitric oxide metabolism, protein nitration level, the expression of NOS isoforms, and furthermore the activation of the nuclear factor NF-κB-p65 subunit in different brain areas on the fragile X mouse model. This study involved adult male Fmr1-knockout and wild-type mice as controls. We detected nitric oxide metabolism and the activation of the nuclear factor NF-κBp65 subunit, comparing the mRNA expression and protein content of the three NOS isoforms in different brain areas. Fmr1-KO mice showed an abnormal nitric oxide metabolism and increased levels of protein tyrosine nitrosylation. Besides that, nuclear factor NF-κB-p65 and inducible nitric oxide synthase appeared significantly increased in the Fmr1-knockout mice. mRNA and protein levels of the neuronal nitric oxide synthase appeared significantly decreased in the knockout mice. However, the epithelial nitric oxide synthase isoform displayed no significant changes. These data suggest the potential involvement of an abnormal nitric oxide metabolism in the pathogenesis of the fragile X syndrome.

  16. Validação de poluentes fotoquímicos e inclusão do inventário de emissões no modelo de qualidade do ar WRF/CHEM, para a região metropolitana de São Paulo Prediction of photochemical pollutants in metropolitan area of São Paulo using air quality model (WRF/CHEM and the CETESP pollutants emmission inventory

    Directory of Open Access Journals (Sweden)

    Rosiberto Salustiano da Silva Junior

    2013-03-01

    the results of an approximation and transformation made on the Sao Paulo Metropolitan Region (SPMR pollutant emission inventory, required to be used as input data on the WRF/Chem model ("Weather Research This paper shows the results of an approximation and transformation made on the Sao Paulo Metropolitan Region (SPMR pollutant emission inventory, required to be used as input data on the WRF/Chem model ("Weather Research and Forecasting / CHEMistry". Therefore, the purpose is to evaluate the efficiency of the WRF/Chem model to simulate photochemical pollutants on the SPMR, using as parameters the inclusion of the emission inventory and measurements of carbon monoxide (CO and tropospheric ozone (O3 concentrations. The WRF/Chem is a forecast, weather climate and air quality model, which solves simultaneously the meteorology and chemistry modules. SPMR is considered one of the largest cities in the world, and like other big cities suffer with atmospheric pollution. Researches made in SPMR show that vehicles are the main sources of Carbon monoxide (CO, Hydrocarbon (HC and Nitrogen oxide (NOx. When it comes to Sulphur oxides (SOx and inhalable particles (PM10 the main sources of emission fundamentally are industries and vehicles. Another crucial factor is the resuspension of particles from the ground (soil and the formation of secondary aerosols. A 2006 Companhia Ambiental do Estado de São Paulo (CETESB inventory of emissions will be used as input data to the WRF/CHEM model. Since the annual CETESB inventory of emissions integrates the whole SPMR some approximation is required to match the model input data format. It was proposed some approximation methods in which the inventory of annual emissions was representatively distributed in time and space as required by the model. The results show that these methods improved the forecasting of the ozone (O3 and of CO concentration by approximately 25%, reaching a correlation coefficients of 0,79% for the ozone and 0,49% for

  17. Thermodynamic parameters of oxides by the example of periclase in representations of the equilibrium model

    Science.gov (United States)

    Maevskii, K. K.; Kinelovskii, S. A.

    2017-12-01

    The results of numerical modeling of thermodynamic parameters of oxides are presented by the example of periclase MgO and its mixtures under shock wave loading. The mixture of components experiencing the phase transition is investigated: quartz, SiO2, silicon nitride Si3N4, aluminum nitride AlN. The calculation results obtained by thermodynamic equilibrium component (TEC) models are compared with both the experimental data and the simulation results obtained by other authors.

  18. Experimental and Kinetic Modeling Study of C2H2Oxidation at High Pressure

    DEFF Research Database (Denmark)

    Lopez, Jorge Gimenez; Rasmussen, Christian Tihic; Hashemi, Hamid

    2016-01-01

    A detailed chemical kinetic model for oxidation of acetylene at intermediate temperatures and high pressure has been developed and evaluated experimentally. The rate coefficients for the reactions of C2H2 with HO2 and O2 were investigated, based on the recent analysis of the potential energy...... vinyl (reducing conditions) or with OH to form a CHCHOH adduct (stoichiometric to lean conditions). Both C2H3 and CHCHOH then react primarily with O2. The CHCHOH + O2 reaction leads to formation of significant amounts of glyoxal (OCHCHO) and formic acid (HOCHO), and the oxidation chemistry...

  19. Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul

    2017-01-01

    constants for HNC + O2 and HNC + OH, it is possible to reconcile the modeling issues and provide a satisfactory prediction of a wide range of experimental results on HCN oxidation. In the burned gases of fuel-rich flames, HCN and the CN radical are partially equilibrated and the sequence HCN →+M HNC →+OH...... HNCO is the major consumption path for HCN. Under lean conditions, HNC is shown to be less important than indicated by the early work by Lin and co-workers, but it acts to accelerate HCN oxidation and promotes the formation of HNCO....

  20. Recent advances in mathematical modeling of nitrous oxides emissions from wastewater treatment processes.

    Science.gov (United States)

    Ni, Bing-Jie; Yuan, Zhiguo

    2015-12-15

    Nitrous oxide (N2O) can be emitted from wastewater treatment contributing to its greenhouse gas footprint significantly. Mathematical modeling of N2O emissions is of great importance toward the understanding and reduction of the environmental impact of wastewater treatment systems. This article reviews the current status of the modeling of N2O emissions from wastewater treatment. The existing mathematical models describing all the known microbial pathways for N2O production are reviewed and discussed. These included N2O production by ammonia-oxidizing bacteria (AOB) through the hydroxylamine oxidation pathway and the AOB denitrification pathway, N2O production by heterotrophic denitrifiers through the denitrification pathway, and the integration of these pathways in single N2O models. The calibration and validation of these models using lab-scale and full-scale experimental data is also reviewed. We conclude that the mathematical modeling of N2O production, while is still being enhanced supported by new knowledge development, has reached a maturity that facilitates the estimation of site-specific N2O emissions and the development of mitigation strategies for a wastewater treatment plant taking into the specific design and operational conditions of the plant. Copyright © 2015 Elsevier Ltd. All rights reserved.

  1. Reassessing the atmospheric oxidation mechanism of toluene

    Science.gov (United States)

    Ji, Yuemeng; Zhao, Jun; Terazono, Hajime; Misawa, Kentaro; Levitt, Nicholas P.; Li, Yixin; Lin, Yun; Peng, Jianfei; Wang, Yuan; Duan, Lian; Pan, Bowen; Zhang, Fang; Feng, Xidan; An, Taicheng; Marrero-Ortiz, Wilmarie; Secrest, Jeremiah; Zhang, Annie L.; Shibuya, Kazuhiko; Molina, Mario J.; Zhang, Renyi

    2017-08-01

    Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH (ortho) addition, the pathway of H extraction by O2 to form the cresol proceeds with a smaller barrier than O2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

  2. Reassessing the atmospheric oxidation mechanism of toluene.

    Science.gov (United States)

    Ji, Yuemeng; Zhao, Jun; Terazono, Hajime; Misawa, Kentaro; Levitt, Nicholas P; Li, Yixin; Lin, Yun; Peng, Jianfei; Wang, Yuan; Duan, Lian; Pan, Bowen; Zhang, Fang; Feng, Xidan; An, Taicheng; Marrero-Ortiz, Wilmarie; Secrest, Jeremiah; Zhang, Annie L; Shibuya, Kazuhiko; Molina, Mario J; Zhang, Renyi

    2017-08-01

    Photochemical oxidation of aromatic hydrocarbons leads to tropospheric ozone and secondary organic aerosol (SOA) formation, with profound implications for air quality, human health, and climate. Toluene is the most abundant aromatic compound under urban environments, but its detailed chemical oxidation mechanism remains uncertain. From combined laboratory experiments and quantum chemical calculations, we show a toluene oxidation mechanism that is different from the one adopted in current atmospheric models. Our experimental work indicates a larger-than-expected branching ratio for cresols, but a negligible formation of ring-opening products (e.g., methylglyoxal). Quantum chemical calculations also demonstrate that cresols are much more stable than their corresponding peroxy radicals, and, for the most favorable OH ( ortho ) addition, the pathway of H extraction by O 2 to form the cresol proceeds with a smaller barrier than O 2 addition to form the peroxy radical. Our results reveal that phenolic (rather than peroxy radical) formation represents the dominant pathway for toluene oxidation, highlighting the necessity to reassess its role in ozone and SOA formation in the atmosphere.

  3. Photochemical fate of beta-blockers in NOM enriched waters

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Ling; Xu, Haomin; Cooper, William J. [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA 92697-2175 (United States); Song, Weihua, E-mail: wsong@fudan.edu.cn [Department of Environmental Science and Engineering, Fudan University, Shanghai 200433 (China)

    2012-06-01

    Beta-blockers, prescribed for the treatment of high blood pressure and for long-term use after a heart attack, have been detected in surface and ground waters. This study examines the photochemical fate of three beta-blockers, atenolol, metoprolol, and nadolol. Hydrolysis accounted for minor losses of these beta-blockers in the pH range 4-10. The rate of direct photolysis at pH 7 in a solar simulator varied from 6.1 to 8.9 h{sup -1} at pH 7. However, the addition of a natural organic matter (NOM) isolate enhanced the photochemical loss of all three compounds. Indirect photochemical fate, generally described by reactions with hydroxyl radical ({center_dot}OH) and singlet oxygen ({sup 1}{Delta}O{sub 2}), and, the direct reaction with the triplet excited state, {sup 3}NOM{sup Low-Asterisk }, also varied but collectively appeared to be the major loss factor. Bimolecular reaction rate constants of the three beta-blockers with {sup 1}{Delta}O{sub 2} and {center_dot}OH were measured and accounted for 0.02-0.04% and 7.2-38.9% of their loss, respectively. These data suggest that the {sup 3}NOM{sup Low-Asterisk} contributed 50.6-85.4%. Experiments with various {sup 3}NOM{sup Low-Asterisk} quenchers supported the hypothesis that it was singly the most important reaction. Atenolol was chosen for more detailed investigation, with the photoproducts identified by LC-MS analysis. The results suggested that electron-transfer could be an important mechanism in photochemical fate of beta-blockers in the presence of NOM. - Highlights: Black-Right-Pointing-Pointer Photochemical degradation of beta-blockers in the simulated natural waters. Black-Right-Pointing-Pointer Reactive Oxygen Species play a minor role in the indirect photodegradation. Black-Right-Pointing-Pointer The loss of beta-blockers results from direct reaction with {sup 3}DOM{sup Low-Asterisk }.

  4. Methanol oxidation at platinum electrodes in acid solution: comparison between model and real catalysts

    Directory of Open Access Journals (Sweden)

    A. V. TRIPKOVIC

    2006-12-01

    Full Text Available Methanol oxidation in acid solution was studied at platinum single crystals, Pt(hkl, as the model catalyst, and at nanostructural platinum supported on high surface area carbon, Pt/C, as the real catalyst. The linear extrapolation method was used to determine the beginning of hydroxyl anion adsorption. Structural sensitivity of the adsorption was proved and a correlation with the onset of the methanol oxidation current was established at all catalysts. Bisulfate and chloride anions were found to decrease the methanol oxidation rate, but probably did not influence the reaction parth. The specific activity for the reaction increased in the sequence Pt(110 < Pt/C < Pt(111, suggesting that the activity of the supported Pt catalyst can be correlated with the activities of the dominating crystal planes on its surface.

  5. Modelling study of boundary-layer ozone over northern China - Part II: Responses to emission reductions during the Beijing Olympics

    Science.gov (United States)

    Tang, Guiqian; Zhu, Xiaowan; Xin, Jinyuan; Hu, Bo; Song, Tao; Sun, Yang; Wang, Lili; Wu, Fangkun; Sun, Jie; Cheng, Mengtian; Chao, Na; Li, Xin; Wang, Yuesi

    2017-09-01

    The implementation of emission reduction measures during the Olympics provided a valuable opportunity to study regional photochemical pollution over northern China. In this study, the fifth-generation Pennsylvania State University/National Centre for Atmospheric Research Mesoscale Model and Community Multiscale Air Quality model system was applied to conduct two sets of modelling analyses of the period from July 20 to September 20, 2008, to illustrate the influences of emission reduction measures on regional photochemical pollution over northern China during the Beijing Olympics. The results indicated that the implementation of emission control measures decreased the concentrations of ozone (O3) precursors, namely nitrogen oxide (NOx) and volatile organic compounds (VOCs), throughout the boundary layer. The concentrations of these compounds were reduced by 45% in the central urban area of Beijing at the ground level. Although the average O3 concentration in the central urban area increased by more than 8 ppbv, the total oxidant concentration decreased significantly by more than 5 ppbv. Greater O3 concentrations mainly occurred during periods with weak photochemical reactions. During periods of strong photochemical production, the O3 concentration decreased significantly due to a weakening vertical circulation between the lower and upper boundary layer. Consequently, the number of days when the O3 concentration exceeded 100 ppbv decreased by 25% in Beijing. The emission control measures altered the sensitivity of the regional O3 production. The coordinated control region of NOx and VOCs expanded, and the control region of VOCs decreased in size. The reduction of non-point-source emissions, such as fugitive VOCs and vehicles, was more useful for controlling regional photochemical pollution over northern China.

  6. Oxidation of organics in water in microfluidic electrochemical reactors: Theoretical model and experiments

    International Nuclear Information System (INIS)

    Scialdone, Onofrio; Guarisco, Chiara; Galia, Alessandro

    2011-01-01

    The electrochemical oxidation of organics in water performed in micro reactors on boron doped diamond (BDD) anode was investigated both theoretically and experimentally in order to find the influence of various operative parameters on the conversion and the current efficiency CE of the process. The electrochemical oxidation of formic acid (FA) was selected as a model case. High conversions for a single passage of the electrolytic solution inside the cell were obtained by operating with proper residence times and low distances between cathode and anode. The effect of initial concentration, flow rate and current density was investigated in detail. Theoretical predictions were in very good agreement with experimental results for both mass transfer control, oxidation reaction control and mixed kinetic regimes in spite of the fact that no adjustable parameters was used. Mass transfer process was successfully modelled by considering for simplicity a constant Sh number (e.g., a constant mass transfer coefficient k m ) for a process performed with no high values of the current intensity to minimize the effect of the gas bubbling on the flowdynamic pattern. For mixed kinetic regimes, two different modelling approaches were used. In the first one, the oxidation of organics at BDD was assumed to be mass transfer controlled and to occur with an intrinsic 100% CE when applied current density is higher than the limiting current density. In the second case, the CE of the process was modelled assuming that the competition between organic and water oxidation depends only on the electrodic material and on the nature and the concentration of the organic. In the latter case a better agreement between experimental data and theoretical predictions was observed.

  7. Modelling the effect of oxide fuel fracturing on the mechanical behaviour of fuel rods

    International Nuclear Information System (INIS)

    Helfer, T.; Garcia, P.; Ricaud, J.M.; Plancq, D.; Sidoroff, F.; Bernard, L.

    2005-01-01

    Computing stress and strain fields in fuel pellets is essential to modelling the in-pile behaviour of PWR fuel rods, especially under pellet-cladding interaction conditions. Fuel cracking occurs immediately after reactor start-up and is effective in relaxing stresses in the pellet. It is therefore important that the brittle behaviour of oxide fuels be modelled. A first attempt to take into account fuel cracking involved describing radial and axial fuel cracks in the pellet through a phenomenological modification of Hooke's law. A description of the model is given along with its two-dimensional extension applied to axisymmetrical fuel pellet simulations. The first results pertaining to this model are discussed. Another approach to modelling the damage to pellets induced by cracking involves the use of so-called cohesive models. These models describe the progressive loss of cohesion of the material in the damaged area ahead of the crack tip. A short review of these models is presented. (authors)

  8. Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

    Science.gov (United States)

    Jimenez, Jose L.; Yung, Yuk L.; Toon, Owen B.; Tolbert, Margaret A.

    2012-01-01

    Abstract Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λphotochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N2 in the irradiated gas. The aerosol mass greatly decreases when N2 is removed, which indicates that N2 plays a major role in aerosol production. Because direct dissociation of N2 is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N2 must occur via another pathway. Any chemical activation of N2 at wavelengths >120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH4 photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets. Key Words: Titan—Photochemical aerosol—CH4-N2 photolysis—Far UV—Nitrogen activation. Astrobiology 12, 315–326. PMID:22519972

  9. Non-animal photosafety screening for complex cosmetic ingredients with photochemical and photobiochemical assessment tools.

    Science.gov (United States)

    Nishida, Hayato; Hirota, Morihiko; Seto, Yoshiki; Suzuki, Gen; Kato, Masashi; Kitagaki, Masato; Sugiyama, Mariko; Kouzuki, Hirokazu; Onoue, Satomi

    2015-08-01

    Previously, a non-animal screening approach was proposed for evaluating photosafety of cosmetic ingredients by means of in vitro photochemical and photobiochemical assays; however, complex cosmetic ingredients, such as plant extracts and polymers, could not be evaluated because their molecular weight is often poorly defined and so their molar concentration cannot be calculated. The aim of the present investigation was to establish a photosafety screen for complex cosmetic ingredients by using appropriately modified in vitro photosafety assays. Twenty plant extracts were selected as model materials on the basis of photosafety information, and their phototoxic potentials were assessed by means of ultraviolet (UV)/visible light (VIS) spectral analysis, reactive oxygen species (ROS)/micellar ROS (mROS) assays, and 3T3 neutral red uptake phototoxicity testing (3T3 NRU PT). The maximum UV/VIS absorption value was employed as a judgment factor for evaluating photoexcitability of samples, and the value of 1.0 was adopted as a tentative criterion for photosafety identification. The ROS/mROS assays were conducted at 50 μg/mL, and no false negative prediction was obtained. Furthermore, the ROS/mROS assays at 50 μg/mL had a similar predictive capacity to the ROS/mROS assays in the previous study. A systematic tiered approach for simple and rapid non-animal photosafety evaluation of complex cosmetic ingredients can be constructed using these modified in vitro photochemical assays. Copyright © 2015 Elsevier Inc. All rights reserved.

  10. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  11. Wastewater remediation using a spiral shaped reactor for photochemical reduction of hexavalent chromium.

    Science.gov (United States)

    Machado, Tiele Caprioli; Lansarin, Marla Azário; Ribeiro, Camila Silva

    2015-03-01

    The hexavalent chromium contained in wastewater of some industries is toxic to most microorganisms and potentially harmful to human health. The application of photochemical reduction of Cr(VI) in the treatment of wastewater from the electroplating industry was studied, and a continuous reactor in spiral shape made of borosilicate was designed and constructed (SSR). The statistical model of a circumscribed central composite design (CCCD) was used to investigate the influence of the amount of ethanol and the initial concentration of hexavalent chromium on total Cr(VI) reduction. A total Cr(VI) reduction of 46.0% was achieved under the optimal conditions established by the experimental design, using a synthetic Cr(VI) solution. In addition, the photochemical reduction of Cr(VI) follows pseudo first-order kinetics. The SSR exhibited similar behavior to that of the plug flow reactor (PFR), and presented higher photonic efficiency than the batch reactor. Finally, the designed reactor was effective when applied to real wastewater, showing a total Cr(VI) reduction of 51.8%, and its configuration is suitable for scale up.

  12. The photochemical origins of life and photoreaction of ferrous ion in the archaean oceans

    Science.gov (United States)

    Mauzerall, David C.

    1990-01-01

    A general argument is made for the photochemical origins of life. A constant flux of free energy is required to maintain the organized state of matter called life. Solar photons are the unique source of the large amounts of energy probably required to initiate this organization and certainly required for the evolution of life to occur. The completion of this argument will require the experimental determination of suitable photochemical reactions. It is shown that biogenetic porphyrins readily photooxidize substrates and emit hydrogen in the presence of a catalyst. These results are consistent with the Granick hypothesis, which relates a biosynthetic pathway to its evolutionary origin. It has been shown that photoexcitation of ferrous ion at neutral pH with near ultraviolet light produces hydrogen with high quantum yield. This same simple system may reduce carbon dioxide to formaldehyde and further products. These reactions offer a solution to the dilemma confronting the Oparin-Urey-Miller model of the chemical origin of life. If carbon dioxide is the main form of carbon on the primitive earth, the ferrous photoreaction may provide the reduced carbon necessary for the formation of amino acids and other biogenic molecules. These results suggest that this progenitor of modern photosynthesis may have contributed to the chemical origins of life.

  13. A 3d Regional Scale Photochemical Air Quality Model. Application to a 3 Day Summertime Episode over Paris Un modèle photochimique 3D de qualité de l'air à l'échelle régionale. Application à un épisode de 3 jours à Paris en été

    Directory of Open Access Journals (Sweden)

    Carissimo B.

    2006-12-01

    Full Text Available This paper presents AZUR, a 3D Eulerian photochemical air quality model for the simulation of air pollution in urban and semi-urban areas. The model tracks gas pollutant species emitted into the atmosphere by transportation and industrial sources, it computes the chemical reactions of these species under varying meteorological conditions (photolysis, pressure, temperature, humidity, their transport by wind and their turbulent diffusion as a function of air stability. It has a modular software structure which includes several components dedicated to specific processes :-MERCURE, a meso-scale meteorological model to compute the wind field, turbulent diffusion coefficients, and other meteorological parameters. It is a 3D regional scale model accounting for different ground types and urban densities. It includes a complete set of physical parameterizations in clear sky. -MIEL, an emission inventory model describing the pollutant fluxes from automotive transportation, domestic and industrial activities. This model includes a mobile source inventory based on road vehicle countings together with global information on transportation fluxes extracted from statistical population data. It uses specific emission factors representative of the vehicle fleet and real driving patterns. -MoCA a photochemical gas phase model describing the chemistry of ozone, NOx, and hydrocarbon compounds. This model, with 83 species and 191 reactions, is a reduced mechanism well adapted to various air quality conditions (ranging from urban to rural conditions. For interpretative reasons, the identity of primary hydrocarbons is preserved. -AIRQUAL, a 3D Eulerian model describing the transport by mean wind flux and air turbulent diffusion of species in the atmosphere, associated with a Gear type chemical equation solver. The model has been applied to a 3-day summertime episode over Paris area. Simulation results are compared to ground level concentration measurements performed by

  14. Oxidative Damage Compromises Energy Metabolism in the Axonal Degeneration Mouse Model of X-Adrenoleukodystrophy

    Science.gov (United States)

    Galino, Jorge; Ruiz, Montserrat; Fourcade, Stéphane; Schlüter, Agatha; López-Erauskin, Jone; Guilera, Cristina; Jove, Mariona; Naudi, Alba; García-Arumí, Elena; Andreu, Antoni L.; Starkov, Anatoly A.; Pamplona, Reinald; Ferrer, Isidre; Portero-Otin, Manuel

    2011-01-01

    Abstract Aims Chronic metabolic impairment and oxidative stress are associated with the pathogenesis of axonal dysfunction in a growing number of neurodegenerative conditions. To investigate the intertwining of both noxious factors, we have chosen the mouse model of adrenoleukodystrophy (X-ALD), which exhibits axonal degeneration in spinal cords and motor disability. The disease is caused by loss of function of the ABCD1 transporter, involved in the import and degradation of very long-chain fatty acids (VLCFA) in peroxisomes. Oxidative stress due to VLCFA excess appears early in the neurodegenerative cascade. Results In this study, we demonstrate by redox proteomics that oxidative damage to proteins specifically affects five key enzymes of glycolysis and TCA (Tricarboxylic acid) cycle in spinal cords of Abcd1− mice and pyruvate kinase in human X-ALD fibroblasts. We also show that NADH and ATP levels are significantly diminished in these samples, together with decrease of pyruvate kinase activities and GSH levels, and increase of NADPH. Innovation Treating Abcd1− mice with the antioxidants N-acetylcysteine and α-lipoic acid (LA) prevents protein oxidation; preserves NADH, NADPH, ATP, and GSH levels; and normalizes pyruvate kinase activity, which implies that oxidative stress provoked by VLCFA results in bioenergetic dysfunction, at a presymptomatic stage. Conclusion Our results provide mechanistic insight into the beneficial effects of antioxidants and enhance the rationale for translation into clinical trials for X-adrenoleukodystrophy. Antioxid. Redox Signal. 15, 2095–2107. PMID:21453200

  15. Titanium oxide modeling and design for innovative biomedical surfaces: a concise review.

    Science.gov (United States)

    De Nardo, Luigi; Raffaini, Giuseppina; Ebramzadeh, Edward; Ganazzoli, Fabio

    2012-09-01

    The natural oxide layer on implantable alloys insulates the reactive underlying metal from the physiological environment, preventing substrate corrosion and device failure. This type of oxide film has had a major role in the minimization of functional failure and toxic response after implantation in the first generation biomaterials. Recent advances in theoretical, computational, and experimental surface engineering tools provide the foundation for the design of novel devices with improved performances in this regard based on conventional implantable metal alloys. An increasing number of technologies provide the possibility of tailoring chemico-physical and morphological parameters of the surface oxide layers. For some applications, such as dental implants, surface modifications result in substantial innovation and economic success. However, the selection of novel surfaces is in general based on experimental studies and has a limited theoretical and computational foundation. In this review, we offer a perspective analysis of the correlation between theoretical studies and chemical surface modification technologies, with a special emphasis on titanium oxide on Ti alloys. Theoretical approaches for the surface behavior at an atomistic level of description are presented, together with some adsorption studies on a rutile surface. The role of chemical and electrochemical surface modification technologies in modifying the TiO(2) structure, morphology, and chemistry to tailor in vivo biological response is then briefly reviewed. Finally, we discuss the role of surface modeling as a powerful design tool for a new generation of implantable devices in which metal oxide surface can be tuned to yield specific biological response.

  16. Impacts of Combustion Conditions and Photochemical Processing on the Light Absorption of Biomass Combustion Aerosol.

    Science.gov (United States)

    Martinsson, J; Eriksson, A C; Nielsen, I Elbæk; Malmborg, V Berg; Ahlberg, E; Andersen, C; Lindgren, R; Nyström, R; Nordin, E Z; Brune, W H; Svenningsson, B; Swietlicki, E; Boman, C; Pagels, J H

    2015-12-15

    The aim was to identify relationships between combustion conditions, particle characteristics, and optical properties of fresh and photochemically processed emissions from biomass combustion. The combustion conditions included nominal and high burn rate operation and individual combustion phases from a conventional wood stove. Low temperature pyrolysis upon fuel addition resulted in "tar-ball" type particles dominated by organic aerosol with an absorption Ångström exponent (AAE) of 2.5-2.7 and estimated Brown Carbon contributions of 50-70% to absorption at the climate relevant aethalometer-wavelength (520 nm). High temperature combustion during the intermediate (flaming) phase was dominated by soot agglomerates with AAE 1.0-1.2 and 85-100% of absorption at 520 nm attributed to Black Carbon. Intense photochemical processing of high burn rate flaming combustion emissions in an oxidation flow reactor led to strong formation of Secondary Organic Aerosol, with no or weak absorption. PM1 mass emission factors (mg/kg) of fresh emissions were about an order of magnitude higher for low temperature pyrolysis compared to high temperature combustion. However, emission factors describing the absorption cross section emitted per kg of fuel consumed (m(2)/kg) were of similar magnitude at 520 nm for the diverse combustion conditions investigated in this study. These results provide a link between biomass combustion conditions, emitted particle types, and their optical properties in fresh and processed plumes which can be of value for source apportionment and balanced mitigation of biomass combustion emissions from a climate and health perspective.

  17. Improved stratospheric atmosphere forecasts in the general circulation model through a methane oxidation parametrization

    Science.gov (United States)

    Wang, S.; Jun, Z.

    2017-12-01

    Climatic characteristics of tropical stratospheric methane have been well researched using various satellite data, and numerical simulations have furtherly conducted using chemical climatic models, while the impact of stratospheric methane oxidation on distribution of water vapor is not paid enough attention in general circulation models. Simulated values of water vapour in the tropical upper stratosphere, and throughout much of the extratropical stratosphere, were too low. Something must be done to remedy this deficiency in order to producing realistic stratospheric water vapor using a general circulation model including the whole stratosphere. Introduction of a simple parametrization of the upper-stratospheric moisture source due to methane oxidation and a sink due to photolysis in the mesosphere was conducted. Numerical simulations and analysis of the influence of stratospheric methane on the prediction of tropical stratospheric moisture and temperature fields were carried out. This study presents the advantages of methane oxidation parametrization in producing a realistic distribution of water vapour in the tropical stratosphere and analyzes the impact of methane chemical process on the general circulation model using two storm cases including a heavy rain in South China and a typhoon caused tropical storm.It is obvious that general circulation model with methane oxidation parametrization succeeds in simulating the water vapor and temperature in stratosphere. The simulating rain center value of contrast experiment is increased up to 10% than that of the control experiment. Introduction of methane oxidation parametrization has modified the distribution of water vapour and then producing a broadly realistic distribution of temperature. Objective weather forecast verifications have been performed using simulating results of one month, which demonstrate somewhat positive effects on the model skill. There is a certain extent impact of methane oxidation