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

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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...

A Model Study of the Photochemical Fate of As(III in Paddy-Water

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Luca Carena

2017-03-01

Full Text Available The APEX (Aqueous Photochemistry of Environmentally-occurring Xenobiotics software previously developed by one of us was used to model the photochemistry of As(III in paddy-field water, allowing a comparison with biotic processes. The model included key paddy-water variables, such as the shielding effect of the rice canopy on incident sunlight and its monthly variations, water pH, and the photochemical parameters of the chromophoric dissolved organic matter (CDOM occurring in paddy fields. The half-life times (t1/2 of As(III photooxidation to As(V would be ~20–30 days in May. In contrast, the photochemical oxidation of As(III would be much slower in June and July due to rice-canopy shading of radiation because of plant growth, despite higher sunlight irradiance. At pH < 8 the photooxidation of As(III would mainly be accounted for by reaction with transient species produced by irradiated CDOM (here represented by the excited triplet states 3CDOM*, neglecting the possibly more important reactions with poorly known species such as the phenoxy radicals and, to a lesser extent, with the hydroxyl radicals (HO•. However, the carbonate radicals (CO3•− could be key photooxidants at pH > 8.5 provided that the paddy-water 3CDOM* is sufficiently reactive toward the oxidation of CO32−. In particular, if paddy-water 3CDOM* oxidizes the carbonate anion with a second-order reaction rate constant near (or higher than 106 M−1·s−1, the photooxidation of As(III could be quite fast at pH > 8.5. Such pH conditions can be produced by elevated photosynthetic activity that consumes dissolved CO2.

Photochemical air pollution

International Nuclear Information System (INIS)

Te Winkel, B.H.

1992-01-01

During periods of severe photochemical air pollution (smog) the industry in the Netherlands is recommended by the Dutch government to strongly reduce the emissions of air pollutants. For the electric power generating companies it is important to investigate the adequacy of this policy. The purpose of this investigation is to determine the contribution of electric power plants to photochemical air pollution and to assess the efficacy of emission reducing measures. A literature survey on the development of photochemical air pollution was carried out and modelled calculations concerning the share of the electric power plants to the photochemical air pollution were executed

Dispersion and photochemical evolution of reactive pollutants in street canyons

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Kwak, Kyung-Hwan; Baik, Jong-Jin; Lee, Kwang-Yeon

2013-05-01

Dispersion and photochemical evolution of reactive pollutants in street canyons with canyon aspect ratios of 1 and 2 are investigated using a computational fluid dynamics (CFD) model coupled with the carbon bond mechanism IV (CBM-IV). Photochemical ages of NOx and VOC are expressed as a function of the NO2-to-NOx and toluene-to-xylene ratios, respectively. These are found to be useful for analyzing the O3 and OH oxidation processes in the street canyons. The OH oxidation process (O3 oxidation process) is more pronounced in the upper (lower) region of the street canyon with a canyon aspect ratio of 2, which is characterized by more (less) aged air. In the upper region of the street canyon, O3 is chemically produced as well as transported downward across the roof level, whereas O3 is chemically reduced in the lower region of the street canyon. The O3 chemical production is generally favorable when the normalized photochemical ages of NOx and VOC are larger than 0.55 and 0.28, respectively. The sensitivities of O3 chemical characteristics to NOx and VOC emission rates, photolysis rate, and ambient wind speed are examined for the lower and upper regions of the street canyon with a canyon aspect ratio of 2. The O3 concentration and the O3 chemical production rate divided by the O3 concentration increase as the NOx emission rate decreases and the VOC emission rate and photolysis rate increase. The O3 concentration is less sensitive to the ambient wind speed than to other factors considered. The relative importance of the OH oxidation process compared to the O3 oxidation process increases with increasing NOx emission rate and photolysis rate and decreasing VOC emission rate. In this study, both O3 and OH oxidation processes are found to be important in street-canyon scale chemistry. The methodology of estimating the photochemical ages can potentially be adopted to neighborhood scale chemistry.

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

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.

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

1998-12-31

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.

Photochemical smog and plants

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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.

Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data

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A. P. Grieshop

2009-03-01

Full Text Available Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit-mass-resolution quadrupole Aerosol Mass Spectrometer (AMS. The results highlight how photochemical processing can lead to considerable evolution of the mass, volatility and level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the OA mass after a few hours of aging under typical summertime conditions. Aging also decreased the volatility of the OA and made it progressively more oxygenated. The results also illustrate strengths of, and challenges with, using AMS data for source apportionment analysis. For example, the mass spectra of fresh and aged BBOA are distinct from fresh motor-vehicle emissions. The mass spectra of the secondary OA produced from aging wood smoke are very similar to those of the oxygenated OA (OOA that dominates ambient AMS datasets, further reinforcing the connection between OOA and OA formed from photo-chemistry. In addition, aged wood smoke spectra are similar to those from OA created by photo-oxidizing dilute diesel exhaust. This demonstrates that the OOA observed in the atmosphere can be produced by photochemical aging of dilute emissions from different types of combustion systems operating on fuels with modern or fossil carbon. Since OOA is frequently the dominant component of ambient OA, the similarity of spectra of aged emissions from different sources represents an important challenge for AMS-based source apportionment studies.

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

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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

Photochemical preparation of aluminium oxide layers via vacuum ultraviolet irradiation of a polymeric hexanoato aluminium complex

International Nuclear Information System (INIS)

Wennrich, L.; Khalil, H.; Bundesmann, C.; Decker, U.; Gerlach, J.W.; Helmstedt, U.; Manova, D.; Naumov, S.; Prager, L.

2013-01-01

By means of photochemical conversion of thin layers of a polymeric hexanoato aluminium complex as the precursor, thin aluminium oxide layers were prepared onto silicon wafers. The precursor compound was synthesized and characterized by several analytical techniques like NMR, FTIR, XPS, ICP, and found to be a polymeric aluminium-containing coordination compound which has been proposed to be a hydroxo-bridged aluminium chain with pendant hexanoyl side-chains ascertained as catena-poly[{di(κ-O,O-hexanoato)aluminium}(μ-hydroxo)] (PHAH). Thin layers deposited from a solution of PHAH in toluene onto silicon wafers were irradiated using VUV radiation from a xenon excimer lamp. The layers were characterized by XPS, XRD, XRR, and spectroscopic ellipsometry. VUV radiation with a radiant exposure of E = 36 J cm −2 led to almost carbon-free amorphous layers with a composition close to that of alumina having a density of about 2.1 g cm −3 . Thus, using the example of a polymeric aluminium complex, the potential of the photochemical conversion of metal complexes into oxides could be shown as an alternative method, in addition to sol–gel techniques, for the generation of thin plane metal-oxide layers at normal temperature and pressure. Highlights: ► A polymeric aluminium complex was synthesized and characterized by NMR, FTIR, XPS and ICP. ► Thin layers of the compound were irradiated using vacuum-UV radiation and converted to AlO x . ► Quantum-chemical calculations explain the conversion mechanism.

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

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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.

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.

Photochemical production of ozone and control strategy for Southern Taiwan

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Shiu, Chein-Jung; Liu, Shaw Chen; Chang, Chih-Chung; Chen, Jen-Ping; Chou, Charles C. K.; Lin, Chuan-Yao; Young, Chea-Yuan

An observation-based method (OBM) is developed to evaluate the ozone (O 3) production efficiency (O 3 molecules produced per NO x molecule consumed) and O 3 production rate ( P(O 3)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m, p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO x and NMHCs by OH. In addition, total oxidant (O 3+NO 2) instead of O 3 itself turns out to be very useful for representing ozone production in the OBM approach. The average O 3 production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O 3) with NO x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O 3) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O 3 production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O 3 precursors. The 3D OBM O 3 production diagram suggests that reducing emissions of NMHCs are more effective in controlling O 3 than reducing NO x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O 3 and formulating O 3 control strategy in urban and suburban environments.

Total OH reactivity study from VOC photochemical oxidation in the SAPHIR chamber

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Yu, Z.; Tillmann, R.; Hohaus, T.; Fuchs, H.; Novelli, A.; Wegener, R.; Kaminski, M.; Schmitt, S. H.; Wahner, A.; Kiendler-Scharr, A.

2015-12-01

It is well known that hydroxyl radicals (OH) act as a dominant reactive species in the degradation of VOCs in the atmosphere. In recent field studies, directly measured total OH reactivity often showed poor agreement with OH reactivity calculated from VOC measurements (e.g. Nölscher et al., 2013; Lu et al., 2012a). This "missing OH reactivity" is attributed to unaccounted biogenic VOC emissions and/or oxidation products. The comparison of total OH reactivity being directly measured and calculated from single component measurements of VOCs and their oxidation products gives us a further understanding on the source of unmeasured reactive species in the atmosphere. This allows also the determination of the magnitude of the contribution of primary VOC emissions and their oxidation products to the missing OH reactivity. A series of experiments was carried out in the atmosphere simulation chamber SAPHIR in Jülich, Germany, to explore in detail the photochemical degradation of VOCs (isoprene, ß-pinene, limonene, and D6-benzene) by OH. The total OH reactivity was determined from the measurement of VOCs and their oxidation products by a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS) with a GC/MS/FID system, and directly measured by a laser-induced fluorescence (LIF) at the same time. The comparison between these two total OH reactivity measurements showed an increase of missing OH reactivity in the presence of oxidation products of VOCs, indicating a strong contribution to missing OH reactivity from uncharacterized oxidation products.

Seasonal photochemical transformations of nitrogen species in a forest stream and lake.

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Petr Porcal

Full Text Available The photochemical release of inorganic nitrogen from dissolved organic matter is an important source of bio-available nitrogen (N in N-limited aquatic ecosystems. We conducted photochemical experiments and used mathematical models based on pseudo-first-order reaction kinetics to quantify the photochemical transformations of individual N species and their seasonal effects on N cycling in a mountain forest stream and lake (Plešné Lake, Czech Republic. Results from laboratory experiments on photochemical changes in N speciation were compared to measured lake N budgets. Concentrations of organic nitrogen (Norg; 40-58 µmol L-1 decreased from 3 to 26% during 48-hour laboratory irradiation (an equivalent of 4-5 days of natural solar insolation due to photochemical mineralization to ammonium (NH4+ and other N forms (Nx; possibly N oxides and N2. In addition to Norg mineralization, Nx also originated from photochemical nitrate (NO3- reduction. Laboratory exposure of a first-order forest stream water samples showed a high amount of seasonality, with the maximum rates of Norg mineralization and NH4+ production in winter and spring, and the maximum NO3- reduction occurring in summer. These photochemical changes could have an ecologically significant effect on NH4+ concentrations in streams (doubling their terrestrial fluxes from soils and on concentrations of dissolved Norg in the lake. In contrast, photochemical reactions reduced NO3- fluxes by a negligible (<1% amount and had a negligible effect on the aquatic cycle of this N form.

Photochemical reduction of uranyl ion with triphenylphosphine

International Nuclear Information System (INIS)

Brar, A.S.; Sidhu, M.S.; Sandhu, S.S.

1981-01-01

Photochemical reduction of uranyl ion with triphenylphosphine has been studied in acetone-water medium in the presence of sulphuric acid at 346nm, 400nm and 434nm wavelengths. The photochemical reduction is of second order and increases with increase in hydrogen ion concentration. Absorption spectra of uranyl ion in acidic medium and uranyl ion with triphenylphosphine do not show any ground state complex formation. The value of quantum yield increases with the wavelength of the radiation increase from 346 to 434nm. Plots of reciprocal of quantum yield for the formation of U(IV) versus reciprocal [triphenylphosphine] are linear. Products characterized by UV and visible, IR and TLC show the formation of U(IV) and triphenylphosphine oxide. On the basis of above observations mechanism of the photochemical reduction has been proposed. (author)

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

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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

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.

Photochemical reactions of actinide ions

International Nuclear Information System (INIS)

Tomiyasu, Hiroshi

1995-01-01

This paper reviews the results of photochemical studies of actinide ions, which have been performed in our research group for past several years as follows: I) behavior of the excited uranyl(VI) ion; II) photo-reductions of the uranyl ion with organic and inorganic compounds; III) photo-oxidations of uranium(IV) and plutonium(III) in nitric acid solutions. (author)

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.

Modelling the photochemical pollution over the metropolitan area of Porto Alegre, Brazil

Science.gov (United States)

Borrego, C.; Monteiro, A.; Ferreira, J.; Moraes, M. R.; Carvalho, A.; Ribeiro, I.; Miranda, A. I.; Moreira, D. M.

2010-01-01

The main purpose of this study is to evaluate the photochemical pollution over the Metropolitan Area of Porto Alegre (MAPA), Brazil, where high concentrations of ozone have been registered during the past years. Due to the restricted spatial coverage of the monitoring air quality network, a numerical modelling technique was selected and applied to this assessment exercise. Two different chemistry-transport models - CAMx and CALGRID - were applied for a summer period, driven by the MM5 meteorological model. The meteorological model performance was evaluated comparing its results to available monitoring data measured at the Porto Alegre airport. Validation results point out a good model performance. It was not possible to evaluate the chemistry models performance due to the lack of adequate monitoring data. Nevertheless, the model intercomparison between CAMx and CALGRID shows a similar behaviour in what concerns the simulation of nitrogen dioxide, but some discrepancies concerning ozone. Regarding the fulfilment of the Brazilian air quality targets, the simulated ozone concentrations surpass the legislated value in specific periods, mainly outside the urban area of Porto Alegre. The ozone formation is influenced by the emission of pollutants that act as precursors (like the nitrogen oxides emitted at Porto Alegre urban area and coming from a large refinery complex) and by the meteorological conditions.

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.

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

Quantitative assessment on the contribution of direct photolysis and radical oxidation in photochemical degradation of 4-chlorophenol and oxytetracycline.

Science.gov (United States)

Liu, Yiqing; He, Xuexiang; Fu, Yongsheng; Dionysiou, Dionysios D

2016-07-01

In UV-254 nm/H2O2 advanced oxidation process (AOP), the potential degradation pathways for organic pollutants include (1) hydrolysis, (2) direct H2O2 oxidation, (3) UV direct photolysis, and (4) hydroxyl radical (HO(•)) reaction. In this study, the contribution of these pathways was quantitatively assessed in the photochemical destruction of 4-chlorophenol (4-CP), demonstrating pathways (3) and (4) to be predominantly responsible for the removal of 4-CP by UV/H2O2 in 50 mM phosphate buffer solution. Increasing reaction pH could significantly enhance the contribution of direct photolysis in UV/H2O2 process. The contribution of HO(•) oxidation was improved with increasing initial H2O2 concentration probably due to the increased formation of HO(•). Presence of sodium carbonate (Na2CO3) as in UV/H2O2/Na2CO3 system promoted the degradation of 4-CP, with carbonate radical (CO3 (•-)) reaction and direct photolysis identified to be the main contributing pathways. The trends in the contribution of each factor were further evaluated and validated on the degradation of the antibiotic compound oxytetracycline (OTC). This study provides valuable information on the relative importance of different reaction pathways on the photochemical degradation of organic contaminants such as 4-CP and OTC in the presence and absence of a CO3 (•-) precursor.

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.

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

International Nuclear Information System (INIS)

Lan, Nguyen Thi; Chi, Do Thi; Dinh, Ngo Xuan; Hung, Nguyen Duy; Lan, Hoang; Tuan, Pham Anh; Thang, Le Hong; Trung, Nguyen Ngoc; Hoa, Nguyen Quang; Huy, Tran Quang; Quy, Nguyen Van; Duong, Thanh-Tung; Phan, Vu Ngoc; Le, Anh-Tuan

2014-01-01

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

Applications of the Regional Atmospheric Modeling System (RAMS) to provide input to photochemical grid models for the Lake Michigan Ozone Study (LMOS)

Energy Technology Data Exchange (ETDEWEB)

Lyons, W.A.; Tremback, C.J.; Pielke, R.A. [ASTeR, Inc., Ft. Collins, CO (United States); Eastman, J.L. [Colorado State Univ., Ft. Collins, CO (United States)

1994-12-31

In spite of stringent emission controls, numerous exceedances of the US ozone air quality standard have continued in the Lake Michigan region, especially during the very hot summers of 1987 and 1988. Analyses revealed that exceedances of the 120 PPB hourly standard were 400% more likely at monitors located within 20 km of the lakeshore. While the role of Lake Michigan in exacerbating regional air quality problems has been investigated for almost 20 years, the relative impacts of various phenomena upon regional photochemical air quality have yet to be quantified. In order to design a defensible regional emission control policy, LMOS sponsored the development of a comprehensive regional photochemical modeling system. This is comprised of an emission model, an advanced regional photochemical model, and a prognostic meteorological model.

Facile photoreduction of graphene oxide by an NAD(P)H model: Hantzsch 1,4-dihydropyridine.

Science.gov (United States)

Zhang, Hui-Hui; Liu, Qiang; Feng, Ke; Chen, Bin; Tung, Chen-Ho; Wu, Li-Zhu

2012-05-29

To make "clean" reduced GO sheets in high quality and in large scale, a natural reduced nicotinamine adenine dinucleotide NAD(P)H model, Hantzsch 1,4-dihydropyridine (HEH), is used as a mild organic photoreductant in this work. Benefiting from the intense absorption of HEH in the range of 300-420 nm, the graphene oxide (GO) can be readily reduced by HEH under UV light irradiation (λ > 320 nm) to afford single or few-layer reduced graphene oxide at room temperature. Studies on reduction extent reveal that both irradiation time and concentration ratio of HEH to GO are important for effective reduction of GO under UV light. The as-prepared photochemically reduced graphene oxide (PRGO) dispersion is stable without the need for any polymeric or surfactant stabilizers. Simply by extraction treatment, the "clean" PRGO sheets can be obtained in large quantities, and its conductivity approaches to 4680 S·m(-1) that is the highest value reported by photochemical approaches so far.

Photochemical epoxidation of olefins by visible light in a redox system involving Sb(V) tetraphenylporphyrin and water

Energy Technology Data Exchange (ETDEWEB)

Inoue, Haruo; Hida, Mitsuhiko (Tokyo Metropolitan Univ. (Japan))

1989-03-25

The authors explore electron donors from the viewpoint of solar energy storage. Much attention has been focused on how a water molecule can be incorporated into electron donor system. In this paper, the authors describe a photochemical epoxidation of alkene sensitized by Sb(V)-, P(V)-, Sn(IV)-, Ge(IV)- tetraphenylporphyrin (TPP) with higher oxidation potential than 1.0 Volts vs. NHE in redox systems with a water molecule as an electron donor. The water molecule acts as an electron donor, and alkene acts as an oxygen atom acceptor in this photoredox system. Epoxidation of alkenes usually requires strong oxidizing agents either by the thermal or photochemical method. This is the first example of the photochemical epoxide formation from alkene and water without any strong oxidizing agent. 1 fig.

Factors controlling the redox potential of ZnCe6 in an engineered bacterioferritin photochemical 'reaction centre'.

Science.gov (United States)

Mahboob, Abdullah; Vassiliev, Serguei; Poddutoori, Prashanth K; van der Est, Art; Bruce, Doug

2013-01-01

Photosystem II (PSII) of photosynthesis has the unique ability to photochemically oxidize water. Recently an engineered bacterioferritin photochemical 'reaction centre' (BFR-RC) using a zinc chlorin pigment (ZnCe6) in place of its native heme has been shown to photo-oxidize bound manganese ions through a tyrosine residue, thus mimicking two of the key reactions on the electron donor side of PSII. To understand the mechanism of tyrosine oxidation in BFR-RCs, and explore the possibility of water oxidation in such a system we have built an atomic-level model of the BFR-RC using ONIOM methodology. We studied the influence of axial ligands and carboxyl groups on the oxidation potential of ZnCe6 using DFT theory, and finally calculated the shift of the redox potential of ZnCe6 in the BFR-RC protein using the multi-conformational molecular mechanics-Poisson-Boltzmann approach. According to our calculations, the redox potential for the first oxidation of ZnCe6 in the BRF-RC protein is only 0.57 V, too low to oxidize tyrosine. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. We discuss the possibilities for modifying the BFR-RC to achieve this goal.

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

Ozone modeling for compliance planning: A synopsis of ''The Use of Photochemical Air Quality Models for Evaluating Emission Control Strategies: A Synthesis Report''

International Nuclear Information System (INIS)

Blanchard, C.L.

1992-12-01

The 1990 federal Clean Air Act Amendments require that many nonattainment areas use gridded, photochemical air quality models to develop compliance plans for meeting the ambient ozone standard. Both industry and regulatory agencies will need to consider explicitly the strengths and limitations of the models. Photochemical air quality models constitute the principal tool available for evaluating the relative effectiveness of alternative emission control strategies. Limitations in the utility of modeling results stem from the uncertainty and bias of predictions for modeled episodes, possible compensating errors, limitations in the number of modeled episodes, and incompatibility between deterministic model predictions and the statistical form of the air quality standard for ozone. If emissions estimates (including naturally produced ''biogenic'' emissions) are accurate, intensive aerometric data are available, and an evaluation of performance (including diagnostic evaluations) is successfully completed, gridded photochemical airquality models can determine (1) the types of emission controls - VOC, NO x , or both - that would be most effective for reducing ozone concentrations, and (2) the approximate magnitudes - to within about 20--40% - of the estimated ozone reductions

Photochemical Hydrogen Doping Induced Embedded Two-Dimensional Metallic Channel Formation in InGaZnO at Room Temperature.

Science.gov (United States)

Kim, Myeong-Ho; Lee, Young-Ahn; Kim, Jinseo; Park, Jucheol; Ahn, Seungbae; Jeon, Ki-Joon; Kim, Jeong Won; Choi, Duck-Kyun; Seo, Hyungtak

2015-10-27

The photochemical tunability of the charge-transport mechanism in metal-oxide semiconductors is of great interest since it may offer a facile but effective semiconductor-to-metal transition, which results from photochemically modified electronic structures for various oxide-based device applications. This might provide a feasible hydrogen (H)-radical doping to realize the effectively H-doped metal oxides, which has not been achieved by thermal and ion-implantation technique in a reliable and controllable way. In this study, we report a photochemical conversion of InGaZnO (IGZO) semiconductor to a transparent conductor via hydrogen doping to the local nanocrystallites formed at the IGZO/glass interface at room temperature. In contrast to thermal or ionic hydrogen doping, ultraviolet exposure of the IGZO surface promotes a photochemical reaction with H radical incorporation to surface metal-OH layer formation and bulk H-doping which acts as a tunable and stable highly doped n-type doping channel and turns IGZO to a transparent conductor. This results in the total conversion of carrier conduction property to the level of metallic conduction with sheet resistance of ∼16 Ω/□, room temperature Hall mobility of 11.8 cm(2) V(-1) sec(-1), the carrier concentration at ∼10(20) cm(-3) without any loss of optical transparency. We demonstrated successful applications of photochemically highly n-doped metal oxide via optical dose control to transparent conductor with excellent chemical and optical doping stability.

Application of a Three-Layer Photochemical Box Model in an Athens Street Canyon.

Science.gov (United States)

Proyou, Athena G; Ziomas, Loannis C; Stathopoulos, Antony

1998-05-01

The aim of this paper is to show that a photochemical box model could describe the air pollution diurnal profiles within a typical street canyon in the city of Athens. As sophisticated three-dimensional dispersion models are computationally expensive and they cannot serve to simulate pollution levels in the scale of an urban street canyon, a suitably modified three-layer photochemical box model was applied. A street canyon of Athens with heavy traffic was chosen to apply the aforementioned model. The model was used to calculate pollutant concentrations during two days with meteorological conditions favoring pollutant accumulation. Road traffic emissions were calculated based on existing traffic load measurements. Meteorological data, as well as various pollutant concentrations, in order to compare with the model results, were provided by available measurements. The calculated concentrations were found to be in good agreement with measured concentration levels and show that, when traffic load and traffic composition data are available, this model can be used to predict pollution episodes. It is noteworthy that high concentrations persisted, even after additional traffic restriction measures were taken on the second day because of the high pollution levels.

New electrochemical and photochemical systems for water and wastewater treatment

International Nuclear Information System (INIS)

Sarria, Victor M; Parra, Sandra; Rincon, Angela G; Torres, Ricardo A; Pulgarin, Cesar

2005-01-01

With the increasing pressure on a more effective use of water resources, the development of appropriate water treatment technologies become more and more important. Photochemical and electrochemical oxidation processes have been proposed in recent years as an attractive alternative for the treatment of contaminated water containing anthropogenic substances hardly biodegradable as well as to purify and disinfect drinking waters. The aim of this paper is to present some of our last results demonstrating that electrochemical, photochemical, and the coupling of these processes with biological systems are very promising alternatives for the improvement of the water quality

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.

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

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.

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

Oxidation of Fe(II) in rainwater.

Science.gov (United States)

Willey, J D; Whitehead, R F; Kieber, R J; Hardison, D R

2005-04-15

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

APPLICATION OF BAYESIAN MONTE CARLO ANALYSIS TO A LAGRANGIAN PHOTOCHEMICAL AIR QUALITY MODEL. (R824792)

Science.gov (United States)

Uncertainties in ozone concentrations predicted with a Lagrangian photochemical air quality model have been estimated using Bayesian Monte Carlo (BMC) analysis. Bayesian Monte Carlo analysis provides a means of combining subjective "prior" uncertainty estimates developed ...

Results of photochemical modeling sensitivity analyses in the Lake Michigan region: Current status of Lake Michigan Ozone Control Program (LMOP) modeling

Energy Technology Data Exchange (ETDEWEB)

Dolwick, P.D. [Lake Michigan Air Directors Consortium, Des Plaines, IL (United States); Kaleel, R.J. [Illinois Environmental Protection Agency, Springfield, IL (United States); Majewski, M.A. [Wisconsin Dept. of Natural Resources, Madison, WI (United States)

1994-12-31

The four states that border Lake Michigan are cooperatively applying a state-of-the-art nested photochemical grid model to assess the effects of potential emission control strategies on reducing elevated tropospheric ozone concentrations in the region to levels below the national ambient air quality standard. In order to provide an extensive database to support the application of the photochemical model, a substantial data collection effort known as the Lake Michigan Ozone Study (LMOS) was completed during the summer of 1991. The Lake Michigan Ozone Control Program (LMOP) was established by the States of Illinois, Wisconsin, Michigan, and Indiana to carry out the application of the modeling system developed from the LMOS, in terms of developing the attainment demonstrations required from this area by the Clean Air Act Amendments of 1990.

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)

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.

Photochemical oxidation of short-chain polychlorinated n-alkane mixtures using H2O2/UV and the photo-Fenton reaction

OpenAIRE

Ken J. Friesen; Taha M. El-Morsi; Alaa S. Abd-El-Aziz

2004-01-01

The photochemical oxidation of a series of short-chain polychlorinated n-alkane (PCA) mixtures was investigated using H2O2/UV and modified photo-Fenton conditions (Fe3+/H2O2/UV) in both Milli-Q and lake water. All PCA mixtures, including chlorinated (Cl5 to Cl8) decanes, undecanes, dodecanes and tridecanes degraded in 0.02 M H2O2/UV at pH 2.8 in pure water, with 80±4% disappearance after 3 h of irradiation using a 300 nm light source. Degradation was somewhat enhanced under similar conditions...

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,

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

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.

Photochemical reactions of neptunium in nitric acid solution containing photocatalyst

International Nuclear Information System (INIS)

Fukasawa, Tetsuo; Kawamura, Fumio

1991-01-01

Photochemical oxidation and reduction behaviors of neptunium were preliminarily investigated in 3 mol/l nitric acid solution. Nitric acid of 3 mol/l simulated the high level waste solution from a spent fuel reprocessing process. Concentrations of Np(V), Np(VI) and nitrous acid were determined with a photospectrometer, and solution potential with an electrode. Without additives, Np(VI) was reduced to Np(V) by nitrous acid which was photolytically generated from nitric acid. With a scavenger for nitrous acid, Np(V) was oxidized to extractable Np(VI) by a photolytically generated oxidizing reagent which were predicted by the solution potential measurement. The reduction rate was higher than the oxidation rate because of the larger quantity and higher reactivity of nitrous acid than an oxidizing reagent. Photocatalyst was proved to be effective for the oxidation of Np(V) to Np(VI). (author)

The Social Network of Tracer Variations and O(100) Uncertain Photochemical Parameters in the Community Atmosphere Model

Science.gov (United States)

Lucas, D. D.; Labute, M.; Chowdhary, K.; Debusschere, B.; Cameron-Smith, P. J.

2014-12-01

Simulating the atmospheric cycles of ozone, methane, and other radiatively important trace gases in global climate models is computationally demanding and requires the use of 100's of photochemical parameters with uncertain values. Quantitative analysis of the effects of these uncertainties on tracer distributions, radiative forcing, and other model responses is hindered by the "curse of dimensionality." We describe efforts to overcome this curse using ensemble simulations and advanced statistical methods. Uncertainties from 95 photochemical parameters in the trop-MOZART scheme were sampled using a Monte Carlo method and propagated through 10,000 simulations of the single column version of the Community Atmosphere Model (CAM). The variance of the ensemble was represented as a network with nodes and edges, and the topology and connections in the network were analyzed using lasso regression, Bayesian compressive sensing, and centrality measures from the field of social network theory. Despite the limited sample size for this high dimensional problem, our methods determined the key sources of variation and co-variation in the ensemble and identified important clusters in the network topology. Our results can be used to better understand the flow of photochemical uncertainty in simulations using CAM and other climate models. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344 and supported by the DOE Office of Science through the Scientific Discovery Through Advanced Computing (SciDAC).

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:NO_x 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.

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.

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...

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.

1997-12-31

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

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

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.

Photochemical Internalization of Bleomycin Before External-Beam Radiotherapy Improves Locoregional Control in a Human Sarcoma Model

International Nuclear Information System (INIS)

Norum, Ole-Jacob; Bruland, Oyvind Sverre; Gorunova, Ludmila; Berg, Kristian

2009-01-01

Purpose: The aim of this study was to explore the tumor growth response of the combination photochemical internalization and external-beam radiotherapy. Photochemical internalization is a technology to improve the utilization of therapeutic macromolecules in cancer therapy by photochemical release of endocytosed macromolecules into the cytosol. Methods and Materials: A human sarcoma xenograft TAX-1 was inoculated subcutaneously into nude mice. The photosensitizer AlPcS 2a and bleomycin were intraperitoneally administrated 48 h and 30 min, respectively, before diode laser light exposure at 670 nm (20 J/cm 2 ). Thirty minutes or 7 days after photochemical treatment, the animals were subjected to 4 Gy of ionizing radiation. Results: Using photochemical internalization of bleomycin as an adjunct to ionizing radiation increased the time to progression for the tumors from 17 to 33 days as compared with that observed with photodynamic therapy combined with ionizing radiation as well as for radiochemotherapy with bleomycin. The side effects observed when photochemical internalization of bleomycin was given shortly before ionizing radiation were eliminated by separating the treatment modalities in time. Conclusion: Photochemical internalization of bleomycin combined with ionizing radiation increased the time to progression and showed minimal toxicity and may therefore reduce the total radiation dose necessary to obtain local tumor control while avoiding long-term sequelae from radiotherapy.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-07-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

Photochemical smog incident on June 30, 1973

Energy Technology Data Exchange (ETDEWEB)

Hata, S

1973-01-01

The first photochemical smog incident in Shizuoka prefecture (June 30, 1973) started in Hamamatsu and extended 100 km northeast as far as Fujinomiya city. This not only involved an extraordinarily large area, but the type of smog was different from that in Tokyo and Osaka. The victims were all pupils exercising at the time in the playgrounds. In Hamamatsu, 1050 children were involved and complained of eye irritation and pain, throat pain, coughs, and headaches between 2 and 3 pm, but there were no serious effects. The damages to agricultural produce were extensive and 70% of the total rice fields (1656 hectares), and 40 hectares of green scallions were affected. In Shizuoka, 716 children were affected about 5:30 pm, but in Fujinomiya, which is located further northeast, 16 children were affected about 4 pm. The movement of the damages, the locations, the extent of damages, and the direction of the wind, were puzzling in the light of the normal pattern of photochemical smogs, and the pollution sources could not be the coastal industrial area or automobile exhaust gases. Meteorological factors were similar to the usual photochemical smog conditions, but the locations of the cities involved and the wind direction from the sea suggested that the pollution source was the Pacific Ocean. Since the wind above 1000 m was northeast, circulation of industrial pollutants by the sea breeze is a possible explanation. The maximum concentration of oxidants was about 0.2 ppm in all areas except for Hamamatsu, where it was a little over 0.2 ppm.

Photochemical Pollution Modeling of Ozone at Metropolitan Area of Porto Alegre - RS/Brazil using WRF/Chem

Science.gov (United States)

Cuchiara, G. C.; Carvalho, J.

2013-05-01

One of the main problems related to air pollution in urban areas is caused by photochemical oxidants, particularly troposphere ozone (O3), which is considered a harmful substance. The O3 precursors (carbon monoxide CO, nitrogen oxides NOx and hydrocarbons HCs) are predominantly of anthropogenic origin in these areas, and vehicles are the main emission sources. Due to the increased urbanization and industrial development in recent decades, air pollutant emissions have increased likewise, mainly by mobile sources in the highly urbanized and developed areas, such as the Metropolitan Area of Porto Alegre-RS (MAPA). According to legal regulations implemented in Brazil in 2005, which aimed at increasing the fraction of biofuels in the national energy matrix, 2% biodiesel were supposed to be added to the fuel mixture within three years, and up to 5% after eight years of implementation of these regulations. Our work performs an analysis of surface concentrations for O3, NOx, CO, and HCs through numerical simulations with WRF/Chem (Weather Research and Forecasting model with Chemistry). The model is validated against observational data obtained from the local urban air quality network for the period from January 5 to 9, 2009 (96 hours). One part of the study focused on the comparison of simulated meteorological variables, to observational data from two stations in MAPA. The results showed that the model simulates well the diurnal evolution of pressure and temperature at the surface, but is much less accurate for wind speed. Another part included the evaluation of model results of WRF/Chem for O3 versus observed data at air quality stations Esteio and Porto Alegre. Comparisons between simulated and observed O3 revealed that the model simulates well the evolution of the observed values, but on many occasions the model did not reproduce well the maximum and minimum concentrations. Finally, a preliminary quantitative sensitivity study on the impact of biofuel on the

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)

1998-12-31

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.

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.

Preparation of photoelectrodes with spectral response in the visible without applied bias based on photochemically deposited copper oxide inside a porous titanium dioxide film

Energy Technology Data Exchange (ETDEWEB)

Vigil, Elena [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Gonzalez, Bernardo [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Zumeta, Inti [Institute of Materials-Physics Faculty, University of Havana, Colina Universitaria, C. Habana 10 400 (Cuba); Domingo, Concepcion [Institut de Ciencia de Materials de Barcelona (ICMAB), CSIC, 08290 Cerdanyola del Valles (Spain); Domenech, Xavier [Department of Chemistry, Universitat Autonoma de Barcelona, 08290 Cerdanyola del Valles (Spain); Ayllon, Jose A. [Department of Chemistry, Universitat Autonoma de Barcelona, 08290 Cerdanyola del Valles (Spain)]. E-mail: JoseAntonio.Ayllon@uab.es

2005-10-01

A soft and simple photochemical technique is proposed for the incorporation of copper oxide to nanoporous TiO{sub 2} with the purpose of sensitizing the TiO{sub 2} to wavelengths in the visible range. An aqueous solution of copper formate is employed as precursor. The light intensity value needed for the process, as well as its spectral range, is readily attainable with solar light. Because of the importance of heterojunctions of porous semiconductors in solar energy application, like extremely thin absorber solar cells, experimental conditions have been studied in order to obtain a thin absorption layer of copper oxide covering the TiO{sub 2}. Selection of copper formate solution concentration, irradiation time and previous immersion time in the precursor solution has been studied using X-ray diffraction, scanning electron microscopy and optical spectral transmission. Direction and wavelength dependence of photocurrent show that photons are absorbed by the copper oxide and electrons injected to the TiO{sub 2}.

Ice-nucleating particle emissions from photochemically aged diesel and biodiesel exhaust

Science.gov (United States)

Schill, G. P.; Jathar, S. H.; Kodros, J. K.; Levin, E. J. T.; Galang, A. M.; Friedman, B.; Link, M. F.; Farmer, D. K.; Pierce, J. R.; Kreidenweis, S. M.; DeMott, P. J.

2016-05-01

Immersion-mode ice-nucleating particle (INP) concentrations from an off-road diesel engine were measured using a continuous-flow diffusion chamber at -30°C. Both petrodiesel and biodiesel were utilized, and the exhaust was aged up to 1.5 photochemically equivalent days using an oxidative flow reactor. We found that aged and unaged diesel exhaust of both fuels is not likely to contribute to atmospheric INP concentrations at mixed-phase cloud conditions. To explore this further, a new limit-of-detection parameterization for ice nucleation on diesel exhaust was developed. Using a global-chemical transport model, potential black carbon INP (INPBC) concentrations were determined using a current literature INPBC parameterization and the limit-of-detection parameterization. Model outputs indicate that the current literature parameterization likely overemphasizes INPBC concentrations, especially in the Northern Hemisphere. These results highlight the need to integrate new INPBC parameterizations into global climate models as generalized INPBC parameterizations are not valid for diesel exhaust.

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.

Photochemical hydrogen production system

International Nuclear Information System (INIS)

Copeland, R.J.

1990-01-01

Both technical and economic factors affect the cost of producing hydrogen by photochemical processes. Technical factors include the efficiency and the capital and operating costs of the renewable hydrogen conversion system; economic factors include discount rates, economic life, credit for co-product oxygen, and the value of the energy produced. This paper presents technical and economic data for a system that generates on-peak electric power form photochemically produced hydrogen

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)

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.

Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light emitting diodes

Science.gov (United States)

Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

2015-01-01

Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90%). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize products yields and to identify side products. The use of UV-LED arrays offers many advantages over conventional Hg lamp setups, including greater light output over a narrower wavelength range, lower power consumption, and minimal generation of heat.

Simulation of photoreactive transients and of photochemical transformation of organic pollutants in sunlit boreal lakes across 14 degrees of latitude: A photochemical mapping of Sweden.

Science.gov (United States)

Koehler, Birgit; Barsotti, Francesco; Minella, Marco; Landelius, Tomas; Minero, Claudio; Tranvik, Lars J; Vione, Davide

2018-02-01

Lake water constituents, such as chromophoric dissolved organic matter (CDOM) and nitrate, absorb sunlight which induces an array of photochemical reactions. Although these reactions are a substantial driver of pollutant degradation in lakes they are insufficiently understood, in particular on large scales. Here, we provide for the first time comprehensive photochemical maps covering a large geographic region. Using photochemical kinetics modeling for 1048 lakes across Sweden we simulated the steady-state concentrations of four photoreactive transient species, which are continuously produced and consumed in sunlit lake waters. We then simulated the transient-induced photochemical transformation of organic pollutants, to gain insight into the relevance of the different photoreaction pathways. We found that boreal lakes were often unfavorable environments for photoreactions mediated by hydroxyl radicals (OH) and carbonate radical anions (CO 3 - ), while photoreactions mediated by CDOM triplet states ( 3 CDOM*) and, to a lesser extent, singlet oxygen ( 1 O 2 ) were the most prevalent. These conditions promote the photodegradation of phenols, which are used as plastic, medical drug and herbicide precursors. When CDOM concentrations increase, as is currently commonly the case in boreal areas such as Sweden, 3 CDOM* will also increase, promoting its importance in photochemical pathways even more. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

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).

Photochemical degradation of alachlor in water

Directory of Open Access Journals (Sweden)

Tajana Đurkić

2017-01-01

Full Text Available This study investigates the photochemical degradation of alachlor, a chloroacetanilide herbicide. All experiments were conducted in ultra-pure deionized water (ASTM Type I quality using direct ultraviolet (UV photolysis and the UV/H2O2 advanced oxidation process. The direct UV photolysis and UV/H2O2 experiments were conducted in a commercial photochemical reactor with a quartz reaction vessel equipped with a 253.7 nm UV low pressure mercury lamp (Philips TUV 16 W. The experimental results demonstrate that UV photolysis was very effective for alachlor degradation (up to 97% removal using a high UV fluence of 4200 mJ/cm2. The UV/H2O2 process promoted alachlor degradation compared to UV photolysis alone, with a high degree of decomposition (97% achieved at a significantly lower UV fluence of 600 mJ/cm2 when combined with 1 mg H2O2/L. The application of UV photolysis alone with a UV fluence of 600 mJ/cm2 gave a negligible 4% alachlor degradation. The photo degradation of alachlor, in both direct UV photolysis and the UV/H2O2 process, followed pseudo first-order kinetics. The degradation rate constant was about 6 times higher for the UV/H2O2 process than for UV photolysis alone.

Test Concept for Advanced Oxidation Techniques

DEFF Research Database (Denmark)

Bennedsen, Lars Rønn; Søgaard, Erik Gydesen; Mortensen, Lars

advanced on-site oxidation tests. The remediation techniques included are electrochemical oxidation, photochemical/photocatalytic oxidation, ozone, hydrogen peroxide, permanganate, and persulfate among others. A versatile construction of the mobile test unit makes it possible to combine different...

Testing a Conceptual Model of Soil Emissions of Nitrous and Nitric Oxides

Science.gov (United States)

Eric A. Davidson; Michael Keller; Heather E. Erickson; Verchot NO-VALUE; Edzo Veldkamp

2000-01-01

Nitrous and nitric oxides are often studied separately by atmospheric chemists because they play such different roles in the atmosphere. N2O is a stable greenhouse gas in the lower atmosphere (the troposphere; Ramanathan et al. 1985), but it participates in photochemical reactions in the upper atmosphere (the stratosphere) that destroy ozone (Crutzen 1970). In contrast...

Photochemical sensitization by azathioprine and its metabolites. Part 3. A direct EPR and spin-trapping study of light-induced free radicals from 6-mercaptopurine and its oxidation products.

Science.gov (United States)

Moore, D E; Sik, R H; Bilski, P; Chignell, C F; Reszka, K J

1994-12-01

Sunlight has been implicated in the high incidence of skin cancer found in patients receiving 6-mercaptopurine (PSH) in the form of its pro-drug azathioprine. In this study we have used EPR spectroscopy in conjunction with the spin-trapping technique to determine whether PSH and its metabolic or photochemical oxidation products generate highly reactive free radicals upon UV irradiation. When an aqueous anaerobic solution (pH 5 or 9) of PSH (pKa = 7.7) and either 2-methyl-2-nitrosopropane (MNP) or nitromethane (NM) were irradiated (lambda > 300 nm) with a Xe arc lamp, the corresponding purine-6-thiyl (PS.) radical adduct and the reduced form of the spin trap (MNP/H. or CH3NO2.-) were observed. However, no radical adducts were detected when PSH and 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) were irradiated (lambda = 320 nm) in oxygen-free buffer. These findings suggest that PSH does not photoionize but that instead MNP and NM are reduced by direct electron transfer from excited state PSH, 1.3(PSH)*. In aerobic solution, oxygen can act as an electron acceptor and the O2.- and PS. radicals are formed and trapped by DMPO. 6-Mercaptopurine did photoionize when irradiated with a Nd:YAG laser at 355 nm as evidenced by the appearance of the DMPO/H.(eq- + H+) adduct, which decreased in intensity in the presence of N2O. 1.3(6-Mercaptopurine)* oxidized ascorbate, formate and reduced glutathione to the corresponding ascorbyl, CO2.- or glutathiyl radicals. The photochemical behavior of 6-thioxanthine and 6-thiouric acid was similar to PSH. However, the excited states of these metabolic oxidation products exhibited stronger reducing properties than 1.3(PSH)*.(ABSTRACT TRUNCATED AT 250 WORDS)

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.

Modelling horizontal and vertical concentration profiles of ozone and oxides of nitrogen within high-latitude urban areas

International Nuclear Information System (INIS)

Nicholson, J.P.; Weston, K.J.

2001-01-01

Urban ozone concentrations are determined by the balance between ozone destruction, chemical production and supply through advection and turbulent down-mixing from higher levels. At high latitudes, low levels of solar insolation and high horizontal advection speeds reduce the photochemical production and the spatial ozone concentration patterns are largely determined by the reaction of ozone with nitric oxide and dry deposition to the surface. A Lagrangian column model has been developed to simulate the mean (monthly and annual) three-dimensional structure in ozone and nitrogen oxides (NO x ) concentrations in the boundary-layer within and immediately around an urban area. The short-time-scale photochemical processes of ozone and NO x , as well as emissions and deposition to the ground, are simulated. The model has a horizontal resolution of 1x1km and high resolution in the vertical. It has been applied over a 100x100km domain containing the city of Edinburgh (at latitude 56 o N) to simulate the city-scale processes of pollutants. Results are presented, using averaged wind-flow frequencies and appropriate stability conditions, to show the extent of the depletion of ozone by city emissions. The long-term average spatial patterns in the surface ozone and NO x concentrations over the model domain are reproduced quantitatively. The model shows the average surface ozone concentrations in the urban area to be lower than the surrounding rural areas by typically 50% and that the areas experiencing a 20% ozone depletion are generally restricted to within the urban area. The depletion of the ozone concentration to less than 50% of the rural surface values extends only 20m vertically above the urban area. A series of monitoring sites for ozone, nitric oxide and nitrogen dioxide on a north-south transect through the city - from an urban, through a semi-rural, to a remote rural location - allows the comparison of modelled with observed data for the mean diurnal cycle of ozone

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

Action spectrum for photochemical retinal pigment epithelium (RPE) disruption in an in vivo monkey model

Science.gov (United States)

Zhang, Jie; Sabarinathan, Ranjani; Bubel, Tracy; Williams, David R.; Hunter, Jennifer J.

2016-03-01

Observations of RPE disruption and autofluorescence (AF) photobleaching at light levels below the ANSI photochemical maximum permissible exposure (MPE) (Morgan et al., 2008) indicates a demand to modify future light safety standards to protect the retina from harm. To establish safe light exposures, we measured the visible light action spectrum for RPE disruption in an in vivo monkey model with fluorescence adaptive optics retinal imaging. Using this high resolution imaging modality can provide insight into the consequences of light on a cellular level and allow for longitudinal monitoring of retinal changes. The threshold retinal radiant exposures (RRE) for RPE disruption were determined for 4 wavelengths (460, 488, 544, and 594 nm). The anaesthetized macaque retina was exposed to a uniform 0.5° × 0.5° field of view (FOV). Imaging within a 2° × 2° FOV was performed before, immediately after and at 2 week intervals for 10 weeks. At each wavelength, multiple RREs were tested with 4 repetitions each to determine the threshold for RPE disruption. For qualitative analysis, RPE disruption is defined as any detectable change from the pre exposure condition in the cell mosaic in the exposed region relative to the corresponding mosaic in the immediately surrounding area. We have tested several metrics to evaluate the RPE images obtained before and after exposure. The measured action spectrum for photochemical RPE disruption has a shallower slope than the current ANSI photochemical MPE for the same conditions and suggests that longer wavelength light is more hazardous than other measurements would suggest.

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)

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.wasteforum.cz/

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.

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

Lagrangian Photochemical Box-Model Calculations of Asian Pacific Rim Outflow During TRACE-P

Science.gov (United States)

Hamlin, A.; Crawford, J.; Olson, J.; Avery, M.; Sachse, G.; Barrick, J.; Blake, D.; Tan, D.; Sandholm, S.; Kondo, Y.; Singh, H.; Eisele, F.; Zondlo, M.; Flocke, F.; Talbot, R.

2006-12-01

NASA's TRACE-P (TRAnsport and Chemical Evolution over the Pacific) mission was conducted over the northwestern Pacific February-April, 2001. During two transit flights across the Pacific, extensive pollution was observed from an Asian outflow event that split into two branches over the central Pacific, one subsiding and moving southward over the central Pacific and the other continuing eastward in the upper troposphere. The subsiding branch was observed as a widespread stagnant pollution layer between 2 and 4 km over the central Pacific during transit flights from Kona, HI to Guam. In this region, high levels of O3 (70 ppbv), CO (217 ppbv), and NOx (114 pptv) were well in excess of typical values observed during TRACE-P along the Asian coast. Evidence suggests that the subsiding branch experienced extensive photochemical processing compared to the branch that remained at altitude. To examine the processes controlling the chemical evolution of ozone and its precursors in this outflow event, data collected during the TRACE-P mission have been combined with lagrangian photochemical box model calculations. One of the largest sources of uncertainty in these calculations was associated with predicted water vapor levels along the transport trajectories calculated using the HYSPLIT model. Water vapor levels predicted by HYSPLIT trajectory calculations in the subsiding layer ranged from 3390 to 4880 ppm, while the median level observed in the pollution layer was only 637 ppm. Simulations of ozone production and associated radical chemistry differed dramatically when using water vapor levels based on trajectory calculations versus observed water vapor levels. Levels of PAN and HO2NO2, NOx reservoir species, are also influenced by uncertainties in temperature along the trajectories. These results highlight the importance of accurately representing the humidification and warming of subsiding air masses in 3-D chemical- transport models.

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 conju......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....

Effects of Edaravone, a Free Radical Scavenger, on Photochemically Induced Cerebral Infarction in a Rat Hemiplegic Model

OpenAIRE

Ikeda, Satoshi; Harada, Katsuhiro; Ohwatashi, Akihiko; Kamikawa, Yurie

2013-01-01

Edaravone is a free radical scavenger that protects the adjacent cortex during cerebral infarction. We created a hemiparetic model of cerebral thrombosis from a photochemically induced infarction with the photosensitive dye, rose bengal, in rats. We examined the effects of edaravone on recovery in the model. A total of 36 adult Wistar rats were used. The right sensorimotor area was irradiated with green light with a wavelength of 533?nm (10?mm diameter), and the rose bengal was injected intra...

Photochemical dynamics of surface oriented molecules

International Nuclear Information System (INIS)

Ho, W.

1992-01-01

The period 8/01/91-7/31/92 is the first year of a new project titled ''Photochemical Dynamics of Surface Oriented Molecules'', initiated with DOE Support. The main objective of this project is to understand the dynamics of elementary chemical reactions by studying photochemical dynamics of surface-oriented molecules. In addition, the mechanisms of photon-surface interactions need to be elucidated. The strategy is to carry out experiments to measure the translational energy distribution, as a function of the angle from the surface normal, of the photoproducts by time-of-flight (TOF) technique by varying the photon wavelength, intensity, polarization, and pulse duration. By choosing adsorbates with different bonding configuration, the effects of adsorbate orientation on surface photochemical dynamics can be studied

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.

Photochemical transformation of phenylurea herbicides in surface waters: a model assessment of persistence, and implications for the possible generation of hazardous intermediates.

Science.gov (United States)

Fabbri, Debora; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2015-01-01

This work models the phototransformation kinetics in surface waters of five phenylurea herbicides (diuron, fenuron, isoproturon, metoxuron and chlortoluron), for which important photochemical parameters are available in the literature (direct photolysis quantum yields and reaction rate constants with ·OH, CO3(-·) and the triplet states of chromophoric dissolved organic matter, (3)CDOM*). Model calculations suggest that isoproturon and metoxuron would be the least photochemically persistent and diuron the most persistent compound. Reactions with ·OH and (3)CDOM* would be the main phototransformation pathways for all compounds in the majority of environmental conditions. Reaction with CO3(-) could be important in waters with low dissolved organic carbon (DOC), while direct photolysis would be negligible for fenuron, quite important for chlortoluron, and somewhat significant for the other compounds. The direct photolysis of metoxuron and diuron is known to increase toxicity, and such a photoreaction pathway would be enhanced at intermediate DOC values (1-4 mg C L(1)). The reaction between phenylureas and ·OH is known to produce toxic intermediates, differently from (3)CDOM*. Therefore, the shift of reactivity from ·OH to (3)CDOM* with increasing DOC could reduce the environmental impact of photochemical transformation. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

Coupled Photochemical and Condensation Model for the Venus Atmosphere

Science.gov (United States)

Bierson, Carver; Zhang, Xi; Mendonca, Joao; Liang, Mao-Chang

2017-10-01

Ground based and Venus Express observations have provided a wealth of information on the vertical and latitudinal distribution of many chemical species in the Venus atmosphere [1,2]. Previous 1D models have focused on the chemistry of either the lower [3] or middle atmosphere [4,5]. Photochemical models focusing on the sulfur gas chemistry have also been independent from models of the sulfuric acid haze and cloud formation [6,7]. In recent years sulfur-bearing particles have become important candidates for the observed SO2 inversion above 80 km [5]. To test this hypothesis it is import to create a self-consistent model that includes photochemistry, transport, and cloud condensation.In this work we extend the domain of the 1D chemistry model of Zhang et al. (2012) [5] to encompass the region between the surface to 110 km. This model includes a simple sulfuric acid condensation scheme with gravitational settling. It simultaneously solves for the chemistry and condensation allowing for self-consistent cloud formation. We compare the resulting chemical distributions to observations at all altitudes. We have also validated our model cloud mass against pioneer Venus observations [8]. This updated full atmosphere chemistry model is also being applied in our 2D solver (altitude and altitude). With this 2D model we can model how the latitudinal distribution of chemical species depends on the meridional circulation. This allows us to use the existing chemical observations to place constraints on Venus GCMs [9-11].References: [1] Arney et al., JGR:Planets, 2014 [2] Vandaele et al., Icarus 2017 (pt. 1 & 2) [3] Krasnopolsky, Icarus, 2007 [4] Krasnopolsky, Icarus, 2012 [5] Zhang et al., Icarus 2012 [6] Gao et al., Icarus, 2014 [7] Krasnopolsky, Icarus, 2015 [8] Knollenberg and Hunten, JGR:Space Physics, 1980 [9] Lee et al., JGR:Planets, 2007 [10] Lebonnois et al., Towards Understanding the Climate of Venus, 2013 [11] Mendoncca and Read, Planetary and Space Science, 2016

Sulfidic photochemical passivation of GaAs surfaces in alcoholic solutions

International Nuclear Information System (INIS)

Simonsmeier, T.; Ivankov, A.; Bauhofer, W.

2005-01-01

We report on a remarkable enhancement of the passivation effect of sulfidic solutions through illumination with above band gap light. Luminescence measurements on GaAs surfaces which have been illuminated during chemical passivation reveal in comparison to nonilluminated samples a further reduction of their surface density of states as well as a significantly increased stability of the passivation. Investigations with photoelectron spectroscopy show that illumination leads to a nearly complete removal of oxides on the surface. Measurements on Schottky diodes which have been manufactured with photochemically passivated GaAs indicate a noticeable decrease in band bending and a depinning of the Fermi level

Photochemical degradation of PCBs in snow.

Science.gov (United States)

Matykiewiczová, Nina; Klánová, Jana; Klán, Petr

2007-12-15

This work represents the first laboratory study known to the authors describing photochemical behavior of persistent organic pollutants in snow at environmentally relevant concentrations. The snow samples were prepared by shock freezing of the corresponding aqueous solutions in liquid nitrogen and were UV-irradiated in a photochemical cold chamber reactor at -25 degrees C, in which simultaneous monitoring of snow-air exchange processeswas also possible. The main photodegradation pathway of two model snow contaminants, PCB-7 and PCB-153 (c approximately 100 ng kg(-1)), was found to be reductive dehalogenation. Possible involvement of the water molecules of snow in this reaction has been excluded by performing the photolyses in D2O snow. Instead, trace amounts of volatile organic compounds have been proposed to be the major source of hydrogen atom in the reduction, and this hypothesis was confirmed by the experiments with deuterated organic cocontaminants, such as d6-ethanol or d8-tetrahydrofuran. It is argued that bimolecular photoreduction of PCBs was more efficient or feasible than any other phototransformations under the experimental conditions used, including the coupling reactions. The photodegradation of PCBs, however, competed with a desorption process responsible for the pollutant loss from the snow samples, especially in case of lower molecular-mass congeners. Organic compounds, apparently largely located or photoproduced on the surface of snow crystals, had a predisposition to be released to the air but, at the same time, to react with other species in the gas phase. It is concluded that physicochemical properties of the contaminants and trace co-contaminants, their location and local concentrations in the matrix, and the wavelength and intensity of radiation are the most important factors in the evaluation of organic contaminants' lifetime in snow. Based on the results, it has been estimated that the average lifetime of PCBs in surface snow, connected

Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

Science.gov (United States)

Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

2015-05-05

Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

Photochemical degradation of atenolol, carbamazepine, meprobamate, phenytoin and primidone in wastewater effluents

Energy Technology Data Exchange (ETDEWEB)

Dong, Mei Mei [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States); Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Trenholm, Rebecca [Southern Nevada Water Authority (SNWA), P.O. Box 99954, Las Vegas, NV 89193-9954 (United States); Rosario-Ortiz, Fernando L., E-mail: Fernando.rosario@colorado.edu [Civil, Environmental and Architectural Engineering, 428 UCB, University of Colorado, Boulder, CO 80309 (United States)

2015-01-23

Highlights: • The photochemical degradation of 5 compounds was evaluated in wastewater effluents. • Attenuation by sensitized photolysis was the most important degradation pathway. • Hydroxyl radical accounted for most of the degradation for aliphatic compounds. • Other transient oxidants could also significantly impact the degradation of the compounds. - Abstract: The photochemical degradation of five pharmaceuticals was examined in two secondary wastewater effluents. The compounds, which included atenolol, carbamazepine, meprobamate, phenytoin and primidone, were evaluated for both direct and sensitized photolysis. In the two wastewaters, direct photolysis did not lead to significant compound degradation; however, sensitized photolysis was an important removal pathway for the five pharmaceuticals. Upon solar irradiation, hydroxyl radical (HO·) was quantified using the hydroxylation of benzene and singlet oxygen ({sup 1}O{sub 2}) formation was monitored following the degradation of furfuryl alcohol. Degradation via sensitized photolysis was observed following five-day exposures for atenolol (69–91%), carbamazepine (67–98%), meprobamate (16–52%), phenytoin (44–85%), and primidone (34–88%). Varying removal is likely a result of the differences in reactivity with transient oxidants. Averaged steady state HO· concentrations ranged from 1.2 to 4.0 × 10{sup −16} M, whereas the concentrations of {sup 1}O{sub 2} were 6.0–7.6 × 10{sup −14} M. Partial removal due to presence of HO· indicates it was not the major sink for most compounds examined. Other transient oxidants, such as {sup 1}O{sub 2} and triplet state effluent organic matter, are likely to play important roles in fates of these compounds.

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.

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 (RH_i and 92% relative humidity with respect to water (RH_w, 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.

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

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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.

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.;

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

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)

On the influence of meteorological input on photochemical modelling of a severe episode over a coastal area

Science.gov (United States)

Pirovano, G.; Coll, I.; Bedogni, M.; Alessandrini, S.; Costa, M. P.; Gabusi, V.; Lasry, F.; Menut, L.; Vautard, R.

The modelling reconstruction of the processes determining the transport and mixing of ozone and its precursors in complex terrain areas is a challenging task, particularly when local-scale circulations, such as sea breeze, take place. Within this frame, the ESCOMPTE European campaign took place in the vicinity of Marseille (south-east of France) in summer 2001. The main objectives of the field campaign were to document several photochemical episodes, as well as to constitute a detailed database for chemistry transport models intercomparison. CAMx model has been applied on the largest intense observation periods (IOP) (June 21-26, 2001) in order to evaluate the impacts of two state-of-the-art meteorological models, RAMS and MM5, on chemical model outputs. The meteorological models have been used as best as possible in analysis mode, thus allowing to identify the spread arising in pollutant concentrations as an indication of the intrinsic uncertainty associated to the meteorological input. Simulations have been deeply investigated and compared with a considerable subset of observations both at ground level and along vertical profiles. The analysis has shown that both models were able to reproduce the main circulation features of the IOP. The strongest discrepancies are confined to the Planetary Boundary Layer, consisting of a clear tendency to underestimate or overestimate wind speed over the whole domain. The photochemical simulations showed that variability in circulation intensity was crucial mainly for the representation of the ozone peaks and of the shape of ozone plumes at the ground that have been affected in the same way over the whole domain and all along the simulated period. As a consequence, such differences can be thought of as a possible indicator for the uncertainty related to the definition of meteorological fields in a complex terrain area.

Characterization of photochemical pollution at different elevations in mountainous areas in Hong Kong

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H. Guo

2013-04-01

Full Text Available To advance our understanding on the factors that affect photochemical pollution at different elevations in mountainous areas, concurrent systematic field measurements (September to November 2010 were conducted at a mountain site and at an urban site at the foot of the mountain in Hong Kong. The mixing ratios of air pollutants were greater at the foot of the mountain (i.e., Tsuen Wan urban site, TW than near the summit (i.e., Tai Mao Shan mountain site, TMS, expect for ozone. In total, only one O3 episode day was observed at TW, whereas twenty-one (21 O3 episode days were observed at TMS. The discrepancy of O3 at the two sites was attributed to the mixed effects of NO titration, vertical meteorological conditions, regional transport and mesoscale circulations. The lower NO levels at TMS and the smaller differences of "oxidant" Ox (O3 + NO2 between the two sites suggested that variations of O3 at the two sites were partly attributed to different degree of NO titration. In addition, analysis of vertical structure of meteorological variables revealed that the inversion layer at the range of altitudes of 500–1000 m might be another factor that caused the high O3 levels at TMS. Furthermore, analyses of the wind fields, the levels of air pollutants in different air flows, ratios of different trace gases and the correlation between variability and the lifetime of VOCs (volatile organic compounds indicated that high O3 concentrations at TMS were somewhat influenced by regional air masses from the highly polluted Pearl River delta (PRD region. In particular, the diurnal profiles and correlations of gaseous pollutants suggested influence of mesoscale circulations, which is confirmed using the Master Chemical Mechanism moving box model (Mbox and the Weather Research and Forecasting (WRF model. By investigating the correlations of observed O3 and NOx* and the relationships of O3 and its precursors by an observation-based model (OBM, as well as the ratios

Photochemical alteration of organic carbon draining permafrost soils shifts microbial metabolic pathways and stimulates respiration.

Science.gov (United States)

Ward, Collin P; Nalven, Sarah G; Crump, Byron C; Kling, George W; Cory, Rose M

2017-10-03

In sunlit waters, photochemical alteration of dissolved organic carbon (DOC) impacts the microbial respiration of DOC to CO 2 . This coupled photochemical and biological degradation of DOC is especially critical for carbon budgets in the Arctic, where thawing permafrost soils increase opportunities for DOC oxidation to CO 2 in surface waters, thereby reinforcing global warming. Here we show how and why sunlight exposure impacts microbial respiration of DOC draining permafrost soils. Sunlight significantly increases or decreases microbial respiration of DOC depending on whether photo-alteration produces or removes molecules that native microbial communities used prior to light exposure. Using high-resolution chemical and microbial approaches, we show that rates of DOC processing by microbes are likely governed by a combination of the abundance and lability of DOC exported from land to water and produced by photochemical processes, and the capacity and timescale that microbial communities have to adapt to metabolize photo-altered DOC.The role of dissolved organic carbon (DOC) photo-alteration in the microbial respiration of DOC to CO 2 is unclear. Here, the authors show that the impact of this mechanism depends on whether photo-alteration of DOC produces or removes molecules used by native microbial communities prior to light exposure.

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.

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)

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface.

Science.gov (United States)

Tinel, Liselotte; Rossignol, Stéphanie; Ciuraru, Raluca; George, Christian

2015-04-01

Investigating the pathway for the photochemical formation of VOCs in presence of an organic monolayer at the air/water interface. Liselotte Tinel, Stéphanie Rossignol, Raluca Ciuraru and Christian George Université de Lyon, Université Lyon 1, CNRS, UMR5256, IRCELYON, Institut de recherches sur la catalyse et l'environnement de Lyon, Villeurbanne, F-69626, France Recently the surface microlayer (SML) has received growing attention for its role in the deposition and emission of trace gases. This SML is presumably a highly efficient environment for photochemical reactions thanks to its physical and chemical properties, showing enrichment in chromophores [1]. Still, little is known about the possible photochemical processes that could influence the emission and deposition of volatile organic compounds (VOCs) in the SML. A recent study underlines the particularity of the presence of an organic microlayer, showing enhanced formation of peptide bonds at the air-water interface, although this reaction is thermodynamically disfavoured in bulk water [2]. Also, emissions of small gas phase carbonyl compounds formed photochemically by dissolved organic matter have been measured above natural water and glyoxal, for example, measured above the open ocean is thought to be photochemically produced [3, 4]. This study presents the results of a set of laboratory studies set up in order to better understand the role of the SML in the photochemical production of VOCs. Recently, our group has shown the formation of VOCs by light driven reactions in a small quartz reactor (14mL) containing aqueous solutions of humic acids (HA) in the presence of an organic (artificial or natural) microlayer [5]. The main VOCs produced were oxidized species, such as aldehydes, ketones and alcohols, as classically can be expected by the oxidation of the organics present at the interface initiated by triplet excited chromophores present in the HA. But also alkenes, dienes, including isoprene and

Interaction of light and atmospheric photochemical products (smog) within plants. [Phaseolius vulgaris; Petunia hydrida

Energy Technology Data Exchange (ETDEWEB)

Taylor, O C; Dugger, W M; Cardiff, E A; Darley, E F

1961-12-02

Damage to plants from ozone and peroxyacetyl nitrate, two photochemically formed components of smog, has been described. However, variations in symptom expression and the degree of damage caused by a given concentration of these components, whether of synthetic or natural origin, have complicated development of an adequate biological assay method for these materials. These observed variations in symptomatology have implicated stomatal action, inorganic nutrition temperature, genetics, ascorbic acid content, physiological age of tissue and photoperiod. Plants grown under artificial illumination differ in their response to the photochemically formed pollutants as compared with plants grown in the greenhouse. Interactions between light and oxidants from the polluted atmosphere within plants, as reported here, might well explain some of the variabilities in symptomatology observed in earlier controlled experiments as well as the unexplained natural variability observed in the Los Angeles area. The results presented also emphasize the importance of standardizing plant growth conditions for future work of this nature. 10 references.

Development and first evaluation of micro-calgrid: a 3-D, urban-canopy-scale photochemical model

International Nuclear Information System (INIS)

Stern, R.; Yamartino, R.J.

2001-01-01

This paper details the development and first application of the MICRO-CALGRID (MCG), micro-scale photochemical model. The MCG model treats individual buildings as obstacles with impenetrable surfaces, rather than as roughness elements; is driven by the flow and turbulence fields generated by the MISKAM Navier-Stokes model, the emissions generated by the German MOBILEV model, and the concentration inflow boundary conditions generated by the urban-scale CALGRID model; includes a detailed treatment of vehicle-induced turbulence; and is equipped with three chemistry schemes (SAPRC-93, CB-4, and an analytic solution for Chapman cycle chemistry). The MCG model is exercised in both its 2-D and 3-D modes. Also described is a MCG application to a 5-day episode measured within a busy street canyon in Berlin, Germany. Concentrations of all measured pollutants (CO, NO, NO 2 , benzene, SO 2 and TSP) were well reproduced by the MCG model. NO 2 performance appeared adequate using the simpler analytic chemistry solution; however, inclusion of vehicle-induced turbulence was found to improve model performance statistics. (Author)

Global atmospheric model for mercury including oxidation by bromine atoms

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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 Hg^II 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 Hg^II 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 Hg^II 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

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...

Photochemical degradation of 1,3-dichloro-2-propanol aqueous solutions

International Nuclear Information System (INIS)

Nikolaki, M.D.; Philippopoulos, C.J.

2007-01-01

The photochemical oxidation of 1,3-dichloro-2-propanol (1,3-DCP) was studied by following the target compound degradation, the total carbon removal rate by a total organic carbon (TOC) analyzer and by identifying the oxidation products by gas chromatography-mass spectrometry (GC-MS). The reaction was performed in a batch recycle reactor, at room temperature, using UV radiation provided by a low pressure 12 W Hg lamp and H 2 O 2 as oxidant. Chloride ions, formic, acetic and chloroacetic acid were measured by ion chromatography. Apart from the chloride ions and the organic acids, the presence of 1,3-dichloro-2-propanone and chloroacetyl chloride was also detected and a possible pathway is proposed for the degradation of the parent compound. Complete degradation of 1,3-dichloro-2-propanol was achieved and the TOC removal reached as much as 80% at the end of the reaction time. The effect of the initial concentration of hydrogen peroxide was investigated and it was established that higher concentrations of H 2 O 2 slow down the reaction rate. Finally, the effect of the initial concentration of 1,3-DCP was investigated

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.

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.

Photochemical oxidants injury in rice plants. III. Effect of ozone on physiological activities in rice plants

Energy Technology Data Exchange (ETDEWEB)

Nakamura, H; Saka, H

1978-01-01

Experiments were made to determine the effect of photochemical oxidants on physiological activities of rice plants. Rice plants were fumigated with ozone at concentrations of 0.12-0.20 ppm for 2-3 hr to investigate acute injury and at 0.05 and 0.09 ppm for daily exposure from 3.0 leaf stage to assess the effect of ozone on growth. It was observed that malondialdehyde produced by disruption of the components of the membrane increased in the leaves exposed to ozone. Ozone reduced the RuBP-carboxylase activity in both young and old leaves 12-24 hr after fumigation. In the young leaves the activity of this enzyme recovered to some extent after 48 hr, but it did not show any recovery in the old leaves. On the other hand, ozone remarkably increased the peroxidase activity and slightly increased acid phosphatase in all leaves. Abnormally high ethylene evolution and oxygen uptake were detected in leaves soon after ozone fumigation. In general, high molecular protein and chlorophyll contents in the detached leaves decreased with incubation in dark, particularly in the old ones. These phenomena were more accelerated by ozone fumigation. Kinetin and benzimidazole showed significant effects on chlorophyll retention in ozone-exposed leaves. Reduction of plant growth and photosynthetic rate was recognized even in low concentration of ozone in daily exposure at 0.05 and 0.09 ppm. From these results it was postulated that ozone may cause the senescence of leaves in rice plants.

Reassessing the atmospheric oxidation mechanism of toluene

OpenAIRE

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

2017-01-01

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 atmo...

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.

Photocatalytic Iron Oxide Micro-Swimmers for Environmental Remediation

Science.gov (United States)

Richard, Cynthia; Simmchen, Juliane; Eychmüller, Alexander

2018-05-01

Harvesting energy from photochemical reactions has long been studied as an efficient means of renewable energy, a topic that is increasingly gaining importance also for motion at the microscale. Iron oxide has been a material of interest in recent studies. Thus, in this work different synthesis methods and encapsulation techniques were used to try and optimize the photo-catalytic properties of iron oxide colloids. Photodegradation experiments were carried out following the encapsulation of the nanoparticles and the Fenton effect was also verified. The end goal would be to use the photochemical degradation of peroxide to propel an array of swimmers in a controlled manner while utilizing the Fenton effect for the degradation of dyes or waste in wastewater remediation.

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.

Photochemical key steps in the synthesis of surfactants from furfural-derived intermediates.

Science.gov (United States)

Gassama, Abdoulaye; Ernenwein, Cédric; Hoffmann, Norbert

2009-01-01

Furfural is oxidized to 2[5H]-furanone by using hydrogen peroxide or to 5-hydroxy-2[5H]-furanone by using photo-oxygenation. An amine function is introduced by photochemically induced radical addition of tertiairy amines, some of which carry an n-alkyl side chain as hydrophobic moiety. These amines are produced from fatty aldehydes and cyclic secondary amines. The resulting adducts are transformed into amphoteric surfactants possessing an ammonium and a carboxylate function. Amphoteric (pK(N) and isoelectric point) and surfactant properties such as the critical micelle concentration and the adsorption efficiency are determined.

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...

Potential biosignatures in super-Earth atmospheres II. Photochemical responses.

Science.gov (United States)

Grenfell, J L; Gebauer, S; Godolt, M; Palczynski, K; Rauer, H; Stock, J; von Paris, P; Lehmann, R; Selsis, F

2013-05-01

Spectral characterization of super-Earth atmospheres for planets orbiting in the habitable zone of M dwarf stars is a key focus in exoplanet science. A central challenge is to understand and predict the expected spectral signals of atmospheric biosignatures (species associated with life). Our work applies a global-mean radiative-convective-photochemical column model assuming a planet with an Earth-like biomass and planetary development. We investigated planets with gravities of 1g and 3g and a surface pressure of 1 bar around central stars with spectral classes from M0 to M7. The spectral signals of the calculated planetary scenarios have been presented by in an earlier work by Rauer and colleagues. The main motivation of the present work is to perform a deeper analysis of the chemical processes in the planetary atmospheres. We apply a diagnostic tool, the Pathway Analysis Program, to shed light on the photochemical pathways that form and destroy biosignature species. Ozone is a potential biosignature for complex life. An important result of our analysis is a shift in the ozone photochemistry from mainly Chapman production (which dominates in Earth's stratosphere) to smog-dominated ozone production for planets in the habitable zone of cooler (M5-M7)-class dwarf stars. This result is associated with a lower energy flux in the UVB wavelength range from the central star, hence slower planetary atmospheric photolysis of molecular oxygen, which slows the Chapman ozone production. This is important for future atmospheric characterization missions because it provides an indication of different chemical environments that can lead to very different responses of ozone, for example, cosmic rays. Nitrous oxide, a biosignature for simple bacterial life, is favored for low stratospheric UV conditions, that is, on planets orbiting cooler stars. Transport of this species from its surface source to the stratosphere where it is destroyed can also be a key process. Comparing 1g with

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

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.

The composition dependence of the photochemical reactivity of strontium barium titanate

Science.gov (United States)

Bhardwaj, Abhilasha

The efficiency of particulate water photolysis catalysts is impractically low due to the recombination of intermediate species and charge carriers. The back reaction can occur easily if the oxidation and reduction sites on the surface of the catalyst are not far enough apart. It is hypothesized that it will be possible to increase the separation of the sites of the two half reactions and reduce the recombination of photogenerated charge carriers by using a ferroelectric material with permanent internal dipolar fields. This separation of the reaction sites may significantly increase the efficiency of the process. The present work compares the photochemical reactivities of ferroelectric and nonferroelectric materials (SrxBa1-xTiO 3, 0.0≤ x ≤1.0) with similar composition and structure. The reactivities are compared by measuring the color change of methylene blue dye after the aqueous dye solution reacts on the surface of ceramic sample pellets as a result of exposure to UV light. The reactivities are also compared by measuring the amount of silver that is formed when an aqueous AgNO3 solution photochemically reacts on the surface. The change in the color of the dye is measured by diffuse reflectance spectroscopy and absorbance measurements. The amount of silver is measured by atomic force microscopy. The photochemical reactivity of SrxBa1-xTiO3 shows a local maximum at the composition of the ferroelectric to non-ferroelectric transition. Also, the reactivities decrease as BaTiO3 and SrTiO3 become less pure. The dominant factors causing this trend in reactivities of SrxBa1-xTiO3 are the dielectric constant and alloy scattering. It is found that higher values of the dielectric constant increase the photochemical reactivity by enlarging the space charge region. The increase in alloy scattering in SrxBa1-xTiO 3 solid solutions as x increases from zero or decreases from 1, has adverse effect on reactivity. There are other factors such as ferroelectric polarization

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.

Photochemical stability of lipoic acid and its impact on skin ageing.

Science.gov (United States)

Matsugo, Seiichi; Bito, Toshinori; Konishi, Tetsuya

2011-08-01

It is well known that α-lipoic acid (LA) functions as an essential co-factor of the mitochondrial multi-enzyme complex and thus plays an important role in energy metabolism. Currently, it is attracting attention as a nutritional supplement because of its unique antioxidant properties and broad spectra of cellular functions. Skin protection from photodamage and ageing is one of the functional applications of LA. Medical and cosmetic application has been widely realized in the world. However, LA has a unique structure bearing a distorted five membered 1, 2-dithiolane ring, making it quite vulnerable to UV radiation. The present article briefly reviews skin ageing from the viewpoint of oxidative stress and sun exposure and analyses the photochemical properties of LA. It also discusses the effect of LA to cellular signalling and its adequate applications to treat skin ageing caused by oxidation. Data presented in this review suggest that LA is a powerful anti-ageing agent under the appropriate usage.

Development of a mouse model of neuropathic pain following photochemically induced ischemia in the sciatic nerve.

Science.gov (United States)

Hao, J X; Blakeman, K H; Yu, W; Hultenby, K; Xu, X J; Wiesenfeld-Hallin, Z

2000-05-01

A mouse model of neuropathic pain was developed by a photochemically induced ischemic nerve injury in normal male C57/BL6 mice. The ischemia was induced by unilateral irradiation of the sciatic nerve with an argon ion laser after intravenous administration of a photosensitizing dye, erythrosin B. The nerve injury resulted in a significant decrease in withdrawal threshold of the hindpaws to mechanical stimulation with von Frey hairs, as well as increased responsiveness to cold and heat stimulation. The mice, however, did not exhibit overt spontaneous pain-like behaviors. The evoked pain-related behaviors were observed bilaterally, although the ipsilateral changes were greater than on the contralateral side. The extent and time course of the behavioral changes were related to the duration of laser irradiation, with 1-min exposure producing the most consistent effect. Morphological examination at the light microscopic level revealed partial demyelination and axonal degeneration of the large myelinated fibers at the epicenter of the lesion 1 week postirradiation. The extent of the damage was correlated with the duration of irradiation. Injury and loss of unmyelinated fibers were also observed at the electronmicroscopic level. We conclude that an intravascular photochemical reaction leading to ischemia results in graded damage to the sciatic nerve in mice. Moreover, the nerve injury is associated with the development of abnormal pain-related behaviors. Both the behavioral and the morphological changes are correlated with the duration of irradiation. These results establish a mouse model of partial nerve injury with neuropathic pain-like behaviors which may be useful in studies using genetically modified mice. Copyright 2000 Academic Press.

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…

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

Preparation of UO{sub 2}, ThO{sub 2} and (Th,U)O{sub 2} pellets from photochemically-prepared nano-powders

Energy Technology Data Exchange (ETDEWEB)

Pavelková, Tereza [Czech Technical University in Prague, Faculty of Nuclear Sciences and Physical Engineering, Břehová 7, 115 19 Praha 1 (Czech Republic); Čuba, Václav, E-mail: vaclav.cuba@fjfi.cvut.cz [Czech Technical University in Prague, Faculty of Nuclear Sciences and Physical Engineering, Břehová 7, 115 19 Praha 1 (Czech Republic); Visser-Týnová, Eva de [Nuclear Research and Consultancy Group (NRG), Research & Innovation, Westerduinweg 3, 1755 LE Petten (Netherlands); Ekberg, Christian [Nuclear Chemistry/Industrial Materials Recycling, Chalmers University of Technology, SE-412 96 Göteborg (Sweden); Persson, Ingmar [Department of Chemistry and Biotechnology, Swedish University of Agricultural Sciences, P.O. Box 7015, SE-750 07 Uppsala (Sweden)

2016-02-15

Photochemically-induced preparation of nano-powders of crystalline uranium and/or thorium oxides and their subsequent pelletizing has been investigated. The preparative method was based on the photochemically induced formation of amorphous solid precursors in aqueous solution containing uranyl and/or thorium nitrate and ammonium formate. The EXAFS analyses of the precursors shown that photon irradiation of thorium containing solutions yields a compound with little long-range order but likely “ThO{sub 2} like” and the irradiation of uranium containing solutions yields the mixture of U(IV) and U(VI) compounds. The U-containing precursors were carbon free, thus allowing direct heat treatment in reducing atmosphere without pre-treatment in the air. Subsequent heat treatment of amorphous solid precursors at 300–550 °C yielded nano-crystalline UO{sub 2}, ThO{sub 2} or solid (Th,U)O{sub 2} solutions with high purity, well-developed crystals with linear crystallite size <15 nm. The prepared nano-powders of crystalline oxides were pelletized without any binder (pressure 500 MPa), the green pellets were subsequently sintered at 1300 °C under an Ar:H{sub 2} (20:1) mixture (UO{sub 2} and (Th,U)O{sub 2} pellets) or at 1600 °C in ambient air (ThO{sub 2} pellets). The theoretical density of the sintered pellets varied from 91 to 97%. - Highlights: • Photochemically prepared UO{sub 2}/ThO{sub 2} nano-powders were pelletized. • The nano-powders of crystalline oxides were pelletized without any binder. • Pellets were sintered at 1300 °C (UO{sub 2} and (Th,U)O{sub 2}) or 1600 °C (ThO{sub 2} pellets). • The theoretical density of the sintered pellets varies from 91 to 97%.

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, NO_x, 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.

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)

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

40 CFR 52.2426 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.2426 Section 52.2426 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... § 52.2426 Photochemical Assessment Monitoring Stations (PAMS) Program. On November 23, 1994 Virginia's... Photochemical Assessment Monitoring Stations (PAMS) Program as a state implementation plan (SIP) revision, as...

A photochemical proposal for the preparation of ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films from β-diketonate complex precursors

Energy Technology Data Exchange (ETDEWEB)

Cabello, G., E-mail: gerardocabelloguzman@hotmail.com [Departamento de Ciencias Básicas, Facultad de Ciencias, Universidad del Bío-Bío, Chillán (Chile); Lillo, L.; Caro, C.; Seguel, M.; Sandoval, C. [Departamento de Ciencias Básicas, Facultad de Ciencias, Universidad del Bío-Bío, Chillán (Chile); Buono-Core, G.E. [Instituto de Química, Pontificia Universidad Católica de Valparaíso, Valparaíso (Chile); Chornik, B.; Flores, M. [Deparamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Santiago 8370415 (Chile)

2016-05-15

Highlights: • ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were prepared by photo-chemical method. • The Zn(II), Mg(II) and Al(III) β-diketonate complexes were used as precursors. • The photochemical reaction was monitored by UV–vis and FT-IR spectroscopy. • The results reveal spinel oxide formation and the generation of intermediate products. - Abstract: ZnAl{sub 2}O{sub 4} and MgAl{sub 2}O{sub 4} thin films were grown on Si(100) and quartz plate substrates using a photochemical method in the solid phase with thin films of β-diketonate complexes as the precursors. The films were deposited by spin-coating and subsequently photolyzed at room temperature using 254 nm UV light. The photolysis of these films results in the deposition of metal oxide thin films and fragmentation of the ligands from the coordination sphere of the complexes. The obtained samples were post-annealed at different temperatures (350–1100 °C) for 2 h and characterized by FT-Infrared spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force miscroscopy (AFM), and UV–vis spectroscopy. The results indicate the formation of spinel-type structures and other phases. These characteristics determined the quality of the films, which were obtained from the photodeposition of ternary metal oxides.

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.

Bioavialability of Dom Photochemically Released from Resuspended Sediments

Science.gov (United States)

Avery, G. B., Jr.; Rainey, D. H.; Mead, R. N.; Skrabal, S. A.; Kieber, R. J.; Felix, J. D.; Helms, J. R.

2016-02-01

Little is known regarding the bioavailability of dissolved organic matter (DOM) released photochemically from resuspended estuarine sediments. Sediments were collected from two sites along the Cape Fear River estuary, NC, USA, size fractionated in 0.2 µm filtered Gulf Stream seawater and exposed to simulated sunlight for six hours. Light exposed samples resulted in increases of dissolved organic carbon (DOC) (34 ± 3 µM), chromophoric dissolved organic matter (CDOM) (a300nm, 2.7 m-1), and fluorescent dissolved organic matter (FDOM) (78.6 quinine sulfate equivalents (QSE)) compared to dark controls. Ultra high resolution mass spectrometric characterization indicated the photoreleased DOM was more oxidized and condensed based upon van Kreevlan analysis. Samples were then filtered and inoculated to a final ratio of 4% with coastal water sample filtered through a100 µm net to remove larger grazing organisms and particles while keeping most of bacterial community intact. All three parameters were monitored during a 30 day-long incubation in the dark to assess biological consumption and alteration. Previously light exposed samples had double (20 vs. 9 µM) the amount of DOC consumed compared to samples not previously exposed to light and twice the loss of CDOM (a300nm, 0.6 vs. 0.3 m-1) compared to samples not previously exposed to light. Previously light exposed samples resulted in a threefold loss of FDOM (9.5 QSE) compared to samples not previously exposed to light (2.8 QSE). Results of this study are important because they demonstrate dissolved organic matter released photochemically from resuspended sediments is more bioavailable than ambient material likely fueling secondary productivity and impacting ecosystem functioning in coastal regions.

Photochemical Synthesis and Properties of Colloidal Copper, Silver and Gold Adsorbed on Quartz

International Nuclear Information System (INIS)

Loginov, Anatoliy V.; Gorbunova, Valentina V.; Boitsova, Tatiana B.

2002-01-01

Original methods for the photochemical production of stable copper, silver and gold colloids in the form of films on quartz, and dispersion in liquids were devised. It is shown that photochemical synthesis of colloidal metals is a difficult multiphase process, and includes the formation of low-valence forms of Cu(I), Au(I) and nonmetal clusters, colloidal particles and their agglomerates. Cluster stabilization and further growth to colloidal particles are achieved by adsorption onto the solid surface (quartz) or by increasing the viscosity of photolyte. In the absence of these methods of stabilization, the processes of intermediate reoxidation to Cu(II) and Au(III) and agglomeration of Ag and Au colloids proceed in a photolyte. Adsorption and the rate of cluster growth on a quartz surface are speeded up by the action of monochromatic UV light. Experimental models of the mechanism of colloidal formation are suggested. The dependence of the growth rate and the properties of the colloids on conditions of the photochemical procedure (energy and light intensity, concentration of initial complex) has been established

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.

Sensitivity testing of the model set-up used for calculation of photochemical ozone creation potentials (POCP) under European conditions

Energy Technology Data Exchange (ETDEWEB)

Altenstedt, J.; Pleijel, K.

1998-02-01

Photochemical Ozone Creation Potentials (POCP) is a method to rank VOC, relative to other VOC, according to their ability to produce ground level ozone. To obtain POCP values valid under European conditions, a critical analysis of the POCP concept has been performed using the IVL photochemical trajectory model. The critical analysis has concentrated on three VOC (ethene, n-butane and o-xylene) and has analysed the effect on their POCP values when different model parameters were varied. The three species were chosen because of their different degradation mechanisms in the atmosphere and thus their different abilities to produce ozone. The model parameters which have been tested include background emissions, initial concentrations, dry deposition velocities, the features of the added point source and meteorological parameters. The critical analysis shows that the background emissions of NO{sub x} and VOC have a critical impact on the POCP values. The hour of the day for the point source emission also shows a large influence on the POCP values. Other model parameters which have been studied have not shown such large influence on the POCP values. Based on the critical analysis a model set-up for calculation of POCP is defined. The variations in POCP values due to changes in the background emissions of NO{sub x} and VOC are so large that they can not be disregarded in the calculation of POCP. It is recommended to calculate POCP ranges based on the extremes in POCP values instead of calculating site specific POCP values. Four individual emission scenarios which produced the extremes in POCP values in the analysis have been selected for future calculation of POCP ranges. The scenarios are constructed based on the emissions in Europe and the resulting POCP ranges are thus intended to be applicable within Europe 67 refs, 61 figs, 16 tabs

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.

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

Energy Technology Data Exchange (ETDEWEB)

Mann, E.A. [Department of Environmental Science, Acadia University, Wolfville, NS (Canada); Environmental Science Programme, Memorial University of Newfoundland, St. John' s, NL (Canada); Mallory, M.L. [Department of Biology, Acadia University, Wolfville, NS (Canada); Ziegler, S.E. [Environmental Science Programme, Memorial University of Newfoundland, St. John' s, NL (Canada); Tordon, R. [Environment Canada, Dartmouth, NS (Canada); O' Driscoll, N.J., E-mail: nelson.odriscoll@acadiau.ca [Department of Environmental Science, Acadia University, Wolfville, NS (Canada)

2015-03-15

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{sup −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.

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

Testing the early Mars H2-CO2 greenhouse hypothesis with a 1-D photochemical model

Science.gov (United States)

Batalha, Natasha; Domagal-Goldman, Shawn D.; Ramirez, Ramses; Kasting, James F.

2015-09-01

A recent study by Ramirez et al. (Ramirez, R.M. et al. [2014]. Nat. Geosci. 7(1), 59-63. http://www.nature.com/doifinder/10.1038/ngeo2000 (accessed 16.09.14)) demonstrated that an atmosphere with 1.3-4 bar of CO2 and H2O, in addition to 5-20% H2, could have raised the mean annual and global surface temperature of early Mars above the freezing point of water. Such warm temperatures appear necessary to generate the rainfall (or snowfall) amounts required to carve the ancient martian valleys. Here, we use our best estimates for early martian outgassing rates, along with a 1-D photochemical model, to assess the conversion efficiency of CO, CH4, and H2S to CO2, SO2, and H2. Our outgassing estimates assume that Mars was actively recycling volatiles between its crust and interior, as Earth does today. H2 production from serpentinization and deposition of banded iron-formations is also considered. Under these assumptions, maintaining an H2 concentration of ˜1-2% by volume is achievable, but reaching 5% H2 requires additional H2 sources or a slowing of the hydrogen escape rate below the diffusion limit. If the early martian atmosphere was indeed H2-rich, we might be able to see evidence of this in the rock record. The hypothesis proposed here is consistent with new data from the Curiosity Rover, which show evidence for a long-lived lake in Gale Crater near Mt. Sharp. It is also consistent with measured oxygen fugacities of martian meteorites, which show evidence for progressive mantle oxidation over time.

Radioactive intermediate products in the photolysis of the system [1-14C] tributyltin oxide cellulose

International Nuclear Information System (INIS)

Kloetzer, D.

1982-01-01

Interactions between matrix and applied biocide in the photochemical degradation of the system [1- 14 C] tributyltin oxide/cellulose have been investigated. The intermediate formation of [1- 14 C] tributylstannyl cellulose ethers was found to be the most important step. The photochemical preparation of bis [8- 14 C] tributylstannyl glucose ether is described. (author)

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.

Assessment of diphenylcyclopropenone for photochemically induced mutagenicity in the Ames assay

Energy Technology Data Exchange (ETDEWEB)

Wilkerson, M.G.; Connor, T.H.; Henkin, J.; Wilkin, J.K.; Matney, T.S.

1987-10-01

The photochemical conversion of diphenylcyclopropenone to diphenylacetylene has recently been reported. Diphenylcyclopropenone is used in the treatment of alopecia areata and is nonmutagenic in a limited Ames assay. We examined diphenylcyclopropenone and diphenylacetylene, as well as synthetic precursors of diphenylcyclopropenone--dibenzylketone and alpha,alpha'-dibromodibenzylketone--for mutagenicity against TA100, TA98, TA102, UTH8413, and UTH8414. All compounds were nonmutagenic except alpha,alpha'-dibromodibenzylketone, which was a potent mutagen in TA100 with and without S-9 activation. The effect of photochemical activation of diphenylcyclopropenone in the presence of bacteria demonstrated mutagenicity in UTH8413 (two times background) at 10 micrograms/plate with S-9 microsomal activation. 8-Methoxypsoralen produces a mutagenic response in TA102 at 0.1 microgram/plate with 60 seconds of exposure to 350 nm light. In vitro photochemically activated Ames assay with S-9 microsomal fraction may enhance the trapping of short-lived photochemically produced high-energy mutagenic intermediates. This technique offers exciting opportunities to trap high-energy intermediates that may play an important role in mutagenesis. This method can be applied to a variety of topically applied dermatologic agents, potentially subjected to photochemical changes in normal use.

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...

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

Photochemical reduction of CO{sub 2} to fuels and chemicals

Energy Technology Data Exchange (ETDEWEB)

DuBois, D. [National Renewable Energy Lab., Golden, CO (United States); Eisenberg, R. [Univ. of Rochester, NY (United States); Fujita, E. [Brookhaven National Lab., Upton, NY (United States)

1996-09-01

Photochemical reduction of CO{sub 2} represents a potentially useful approach to developing a sustainable source of carbon-based chemicals, fuels, and materials. In this report the present status of photochemical CO{sub 2} reduction is assessed, areas that need to be better understood for advancement are identified, and approaches to overcoming barriers are suggested. Because of the interdisciplinary nature of this field, assessments of three closely interrelated areas are given including integrated photochemical systems for catalytic CO{sub 2} reduction, thermal catalytic CO{sub 2} reactions, and electrochemical CO{sub 2} reduction. The report concludes with a summary and assessment of potential impacts of this area on chemical and energy technologies.

PHOTOCHEMICAL HEATING OF DENSE MOLECULAR GAS

Energy Technology Data Exchange (ETDEWEB)

Glassgold, A. E. [Astronomy Department, University of California, Berkeley, CA 94720 (United States); Najita, J. R. [National Optical Astronomy Observatory, 950 North Cherry Avenue, Tucson, AZ 85719 (United States)

2015-09-10

Photochemical heating is analyzed with an emphasis on the heating generated by chemical reactions initiated by the products of photodissociation and photoionization. The immediate products are slowed down by collisions with the ambient gas and then heat the gas. In addition to this direct process, heating is also produced by the subsequent chemical reactions initiated by these products. Some of this chemical heating comes from the kinetic energy of the reaction products and the rest from collisional de-excitation of the product atoms and molecules. In considering dense gas dominated by molecular hydrogen, we find that the chemical heating is sometimes as large, if not much larger than, the direct heating. In very dense gas, the total photochemical heating approaches 10 eV per photodissociation (or photoionization), competitive with other ways of heating molecular gas.

Photo-oxidative damage to isolated rat liver mitochondria induced by phenothiazines

Directory of Open Access Journals (Sweden)

T. RODRIGUES

2009-01-01

Full Text Available

Photosensitization is a well-known side-effect of phenothiazines that could involve photochemically promoted oxidative damage to mitochondria, leading to the impairment of metabolic functions and apoptosis. In this work, for the first time, we investigated the effects of photoexcited thioridazine (TR, trifluoperazine (TFP and fluphenazine (FP on isolated rat liver mitochondria. Under UV irradiation, the presence of these phenothiazines led to a dose-dependent lack of the respiratory control ratio. These effects were not accompanied by significant swelling and oxidation of protein thiol groups but were accompanied by lipid peroxidation. Lycopene and sorbate, well-known quenchers of singlet oxygen and triplet species, respectively, were ineffective at protecting mitochondrial lipids against the damage promoted by the excited phenothiazines, suggesting that photochemically-produced cation radicals were the prooxidant species. Corroborating this proposal, butylated hydroxytoluene (BHT completely inhibited the lipid peroxidation induced by UV irradiation in the presence of phenothiazines. These novel results make a significant contribution to the understanding of the photochemical properties of phenothiazines in biological systems. Keywords: Trifluoperazine, thioridazine, fluphenazine, rat liver mitochondria, oxidative stress, photochemistry, photodamage, respiratory chain.

APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

Science.gov (United States)

Bodrato, Marco; Vione, Davide

2014-04-01

The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

Photochemical heavy-atom effects

International Nuclear Information System (INIS)

Koziar, J.C.; Cowan, D.O.

1978-01-01

The effects of halogenated solvents such as n-butyl chloride, n-propyl bromide, and ethyl iodide, on the photochemistry of several aromatic compounds are reviewed. Dimerization of acenaphthylene is discussed in terms of spin -orbit coupling induced by the solvents. Appropriate wave functions are given for both the solvents and the compound. Cycloaddition reactions, electrocyclic rearrangements, and photochemical cis-trans isomerization are also considered

Determination of thiomersal by flow injection coupled with microwave-assisted photochemical online oxidative decomposition of organic mercury and cold vapor atomic fluorescence spectroscopy

International Nuclear Information System (INIS)

Campanella, Beatrice; Onor, Massimo; Mascherpa, Marco Carlo; D’Ulivo, Alessandro; Ferrari, Carlo; Bramanti, Emilia

2013-01-01

Graphical abstract: -- Highlights: •Thiomersal was determined on line using FI-MW/UV-CVGAFS. •MW/UV allows a “green” on line oxidation of organic mercury to Hg II . •Each measure requires less than 5 min with a LOD of 3 ng mL −1 (as mercury). •Hg concentration in commercial ophthalmic solutions ranges between 7.5 and 59.0 μg mL −1 . -- Abstract: We developed a flow injection (FI) method for the determination of thiomersal (sodium ethylmercurithiosalicylate, C 9 H 9 HgNaO 2 S) based on the UV/microwave (MW) photochemical, online oxidation of organic mercury, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. Thiomersal was quantitatively converted in the MW/UV process to Hg(II), with a yield of 97 ± 3%. This reaction was followed by the reduction of Hg(II) to Hg(0) performed in a knotted reaction coil with NaBH 4 solution, and AFS detection in an Ar/H 2 miniaturized flame. The method was linear in the 0.01–2 μg mL −1 range, with a LOD of 0.003 μg mL −1 . This method has been applied to the determination of thiomersal in ophthalmic solutions, with recoveries ranging between 97% and 101%. We found a mercury concentration in commercial ophthalmic solutions ranging between 7.5 and 59.0 μg mL −1

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.

Photochemical transformations accelerated in continuous-flow reactors: basic concepts and applications.

Science.gov (United States)

Su, Yuanhai; Straathof, Natan J W; Hessel, Volker; Noël, Timothy

2014-08-18

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable photochemical microreactor for a given reaction. In this review, we provide an up-to-date overview of both technological and chemical aspects associated with photochemical processes in microreactors. Important design considerations, such as light sources, material selection, and solvent constraints are discussed. In addition, a detailed description of photon and mass-transfer phenomena in microreactors is made and fundamental principles are deduced for making a judicious choice for a suitable photomicroreactor. The advantages of microreactor technology for photochemistry are described for UV and visible-light driven photochemical processes and are compared with their batch counterparts. In addition, different scale-up strategies and limitations of continuous-flow microreactors are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Numerical investigation of influence thermal preparation coal on nitric oxides formation in combustion process

Energy Technology Data Exchange (ETDEWEB)

Chernetskaya, N. [Siberian Federal Univ., Krasnoyarsk (Russian Federation); Chernetsky, M.; Dekterev, A. [Siberian Federal Univ., Krasnoyarsk (Russian Federation); Kutateladze Institute of Thermophysics, Novosibirsk (Russian Federation)

2013-07-01

Emissions of nitrogen oxides from coal combustion are a major environmental problem because they have been shown to contribute to the formation of acid rain and photochemical smog. Coal thermalpreparation before furnace delivery is effective method to reduce NOx emissions, shown by experiments in small-scale facilities (Babiy VI, Alaverdov PI, Influence of thermal preparation pulverized coal on nitric oxides outlet for combustion different metamorphized coal. ATI, 1983). This paper presents the mathematical model of burning thermal preparation coal. Validation of the model was carried out on laboratory-scale plant of All-Russia thermal engineering institute. Modeling of low-emissive burner with preliminary heating coal dust is made for the purpose of search of burner optimal constructions which provides low concentration of nitric oxides in the boiler. For modeling are used in-house CFD code ''{sigma}Flow'' (Dekterev AA, Gavrilov AA, Harlamov EB, Litvintcev KY, J Comput Technol 8(Part 1):250-255, 2003).

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 ⁎ .

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.

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.

Carbon nanostructures reduced from graphite oxide as electrode materials for supercapacitors

Directory of Open Access Journals (Sweden)

Yurii M. Shulga

2015-03-01

Full Text Available In this review we present information about obtaining and properties of carbon nanomaterials (graphite oxide, grapheme oxide, reduced graphene oxide, which are used as electrodes for supercapacitors (SC. This review describes methods of obtaining graphite oxide, followed by separation of graphene oxide and reducing graphene oxide by thermal, photochemical and chemical methods. Information on the composition and concentration of functional groups in graphene oxide and the elemental composition is described in detail. Results of the analysis of еру physical, electrochemical, thermal and optical properties of the graphene oxide and its derivatives are shown. The ratio of oxygen-containing functional groups was estimated by XPS. The presence of partial surface reduction is found. Hydroge-containing functional groups are characterized by IR spectroscopy. Method of estimating the size of graphene crystallites by Raman spectroscopy is shown. Mass loss upon heating is analyzed by thermogravimetry. The gassing of graphene oxide at thermal and photochemical reduction is studied by mass spectrometry. The difference between the abovementioned reduction methods is clearly demonstrated by the difference in the composition of the evolved gases. Also the chemical method of graphene oxide reduction with hydrazine is described. Review considers the literature data which illustrate the most interesting, from the Authors׳ point of view, aspects of that field of research.

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.

Plasmon mediated non-photochemical nucleation of nanoparticles by circularly polarized light

OpenAIRE

Karpov, Victor G.; Grigorchuk, Nicholas I.

2014-01-01

We predict nucleation of pancake shaped metallic nanoparticles having plasmonic frequencies in resonance with a non-absorbed circularly polarized electromagnetic field. We show that the same field can induce nucleation of randomly oriented needle shaped particles. The probabilities of these shapes are estimated vs. field frequency and strength, material parameters, and temperature. This constitutes a quantitative model of non-photochemical laser induced nucleation (NPLIN) consistent with the ...

Electro- and photochemical switching of dithienylethene self-assembled monolayers on gold electrodes

DEFF Research Database (Denmark)

Browne, W.R.; Kudernac, T.; Katsonis, N.

2008-01-01

forms of the dithienylethene SAMs is examined and found to be sensitive to the molecular structure of the switch. For the three dithienylethenes, the electrochemical behavior with respect to electrochemical ring opening/closing is retained in the SAMs. In contrast, a marked dependence on the nature...... of the anchoring group is observed upon immobilization in terms of the retention of the photochemical properties observed in solution. For the meta-thiophenol anchor both photochemical ring opening and closing are observed in the SAM, while for the thienyl-thiol-anchored switches the photochemically properties...

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

Modeling study of vibrational photochemical isotope enrichment. [HBr + Cl/sub 2/; HCl + Br/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Badcock, C.C.; Hwang, W.C.; Kalsch, J.F.

1978-09-29

Chemical kinetic modeling studies of vibrational-photochemical isotope enrichment have been performed on two systems: Model (I), H/sup 79/Br(H/sup 81/Br) + Cl/sub 2/ and, Model (II), H/sup 37/Cl(H/sup 35/Cl) + Br. Pulsed laser excitation was modeled to the first excited vibrational level of H/sup 79/Br in Model I and the first and second excited vibrational levels of both HCl isotopes in Model II. These are prototype systems of exoergic (Model I) and endoergic (Model II) reactions. The effects on enrichment of varying the external parameters (pressure, laser intensity) and the internal parameters (rate constants for V-V exchange and excited-state reactions) were examined. Studies of these prototype systems indicate that a favorable reaction for enrichment, with isotopically-specific excitation and a significantly accelerated vibrationally-excited-state reaction should have the following properties: the reaction from v = 0 should be only moderately exoergic, and the most favorable coreactant should be a polyatomic species, such as alkyl radical. Direct excitation of the reacting vibrational level is at least an order of magnitude more favorable for enrichment than is population by energy transfer. Enrichment of the minor isotope by these processes is more effective than is major isotope enrichment. Within limits, increased laser intensity is beneficial. However, for sequential excitation of a second vibrational level, major isotope enrichment can be diminished by high populations of the first vibrational level.

Southern Africa - a giant natural photochemical reactor

CSIR Research Space (South Africa)

Diab, RD

2006-04-01

Full Text Available photochemical reactor’ are abundant sources of ozone precursors (biomass burning, lightning, biogenic and urban-industrial sources), and meteorological conditions that promote anticyclonic recirculation on a subhemispheric scale....

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)

Relationships between ozone and other photochemical products at Ll. Valby, Denmark

DEFF Research Database (Denmark)

Skov, H.; Egeløv, A.H.; Granby, K.

1997-01-01

literature results it is estimated that the non-photochemical background mixing ratio of O-3 in the Northern Hemisphere is 24+/-6 ppbv. The correlation of HCOOH and CH3COOH with Ox indicates that these acids are of photochemical origin. A high correlation of HNO3 with Ox is also found. The anti-correlation...

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.

Photochemical Formation and Transformation of Birnessite: Effects of Cations on Micromorphology and Crystal Structure.

Science.gov (United States)

Zhang, Tengfei; Liu, Lihu; Tan, WenFeng; Suib, Steven L; Qiu, Guohong; Liu, Fan

2018-05-24

As important components with excellent oxidation and adsorption activity in soils and sediments, manganese oxides affect the transportation and fate of nutrients and pollutants in natural environments. In this work, birnessite was formed by photocatalytic oxidation of Mn2+aq in the presence of nitrate under solar irradiation. The effects of concentrations and species of interlayer cations (Na+, Mg2+, and K+) on birnessite crystal structure and micromorphology were investigated. The roles of adsorbed Mn2+ and pH in the transformation of the photosynthetic birnessite were further studied. The results indicated that Mn2+aq was oxidized to birnessite by superoxide radicals (O2•-) generated from the photolysis of NO3- under UV irradiation. The particle size and thickness of birnessite decreased with increasing cation concentration. The birnessite showed a plate-like morphology in the presence of K+, while exhibited a rumpled sheet-like morphology when Na+ or Mg2+ was used. The different micromorphologies of birnessites could be ascribed to the position of cations in the interlayer. The adsorbed Mn2+ and high pH facilitated the reduction of birnessite to low-valence manganese oxides including hausmannite, feitknechtite, and manganite. This study suggests that interlayer cations and Mn2+ play essential roles in the photochemical formation and transformation of birnessite in aqueous environments.

Photochemical decomposition of perfluorooctanoic acid mediated by iron in strongly acidic conditions

Energy Technology Data Exchange (ETDEWEB)

Ohno, Masaki, E-mail: mohno@hiroshima-u.ac.jp [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Ito, Masataka; Ohkura, Ryouichi [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Mino A, Esteban R. [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Kose, Tomohiro [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Okuda, Tetsuji [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan); Nakai, Satoshi [Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527 (Japan); Kawata, Kuniaki [Faculty of Applied Life Sciences, Niigata University of Pharmacy and Applied Life Sciences, 265-1, Higashijima, Akiha-ku, Niigata 956-8603 (Japan); Nishijima, Wataru [Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513 (Japan)

2014-03-01

Highlights: • Perfluorooctanoic acid (PFOA) was decomposed based on ferric ion performance. • Complete decomposition of PFOA was confirmed in strongly acidic conditions. • Fe{sup 2+} changed to Fe{sup 3+} to restore chemical equilibrium in this condition. • Fe{sup 3+} was only produced from Fe{sup 2+} by hydroxyl radical in weakly acidic conditions. • The Fe{sup 3+} regeneration mechanisms resulted in the performance of Fe{sup 3+} for PFOA. - Abstract: The performance of a ferric ion mediated photochemical process for perfluorooctanoic acid (PFOA) decomposition in strongly acidic conditions of pH 2.0 was evaluated in comparison with those in weakly acidic conditions, pH 3.7 or pH 5.0, based on iron species composition and ferric ion regeneration. Complete decomposition of PFOA under UV irradiation was confirmed at pH 2.0, whereas perfluoroheptanoic acid (PFHpA) and other intermediates were accumulated in weakly acidic conditions. Iron states at each pH were evaluated using a chemical equilibrium model, Visual MINTEQ. The main iron species at pH 2.0 is Fe{sup 3+} ion. Although Fe{sup 3+} ion is consumed and is transformed to Fe{sup 2+} ion by photochemical decomposition of PFOA and its intermediates, the produced Fe{sup 2+} ion will change to Fe{sup 3+} ion to restore chemical equilibrium. Continuous decomposition will occur at pH 2.0. However, half of the iron cannot be dissolved at pH 3.7. The main species of dissolved iron is Fe(OH){sup 2+}. At pH 3.7 or higher pH, Fe{sup 3+} ion will only be produced from the oxidation of Fe{sup 2+} ion by hydroxyl radical produced by Fe(OH){sup 2+} under UV irradiation. These different mechanisms of Fe{sup 3+} regeneration that prevail in strongly and weakly acidic conditions will engender different performances of the ferric ion.

Photochemically induced emission tuning of conductive polumers used in OLEDs

Energy Technology Data Exchange (ETDEWEB)

Vasilopoulou, M [NCSR ' Demokritos' , Institute of Microelectronics, POB 60228, 153 10 Agia Paraskevi, Attiki (Greece); Pistolis, G [Institute of Physical Chemistry, NCSR ' Demokritos' Athens 153 10 (Greece); Argitis, P [NCSR ' Demokritos' , Institute of Microelectronics, POB 60228, 153 10 Agia Paraskevi, Attiki (Greece)

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 ({lambda}{sub max} 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.

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.

Determination of thiomersal by flow injection coupled with microwave-assisted photochemical online oxidative decomposition of organic mercury and cold vapor atomic fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Campanella, Beatrice; Onor, Massimo; Mascherpa, Marco Carlo; D’Ulivo, Alessandro [National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo Metallici-ICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy); Ferrari, Carlo [National Research Council of Italy, C.N.R., Istituto Nazionale di Ottica, INO–UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy); Bramanti, Emilia, E-mail: bramanti@pi.iccom.cnr.it [National Research Council of Italy, C.N.R., Istituto di Chimica dei Composti Organo Metallici-ICCOM-UOS Pisa, Area di Ricerca, Via G. Moruzzi 1, 56124 Pisa (Italy)

2013-12-04

Graphical abstract: -- Highlights: •Thiomersal was determined on line using FI-MW/UV-CVGAFS. •MW/UV allows a “green” on line oxidation of organic mercury to Hg{sup II}. •Each measure requires less than 5 min with a LOD of 3 ng mL{sup −1} (as mercury). •Hg concentration in commercial ophthalmic solutions ranges between 7.5 and 59.0 μg mL{sup −1}. -- Abstract: We developed a flow injection (FI) method for the determination of thiomersal (sodium ethylmercurithiosalicylate, C{sub 9}H{sub 9}HgNaO{sub 2}S) based on the UV/microwave (MW) photochemical, online oxidation of organic mercury, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. Thiomersal was quantitatively converted in the MW/UV process to Hg(II), with a yield of 97 ± 3%. This reaction was followed by the reduction of Hg(II) to Hg(0) performed in a knotted reaction coil with NaBH{sub 4} solution, and AFS detection in an Ar/H{sub 2} miniaturized flame. The method was linear in the 0.01–2 μg mL{sup −1} range, with a LOD of 0.003 μg mL{sup −1}. This method has been applied to the determination of thiomersal in ophthalmic solutions, with recoveries ranging between 97% and 101%. We found a mercury concentration in commercial ophthalmic solutions ranging between 7.5 and 59.0 μg mL{sup −1}.

Photosynthesis by isolated chloroplasts. IV. General concept and comparison of three photochemical reactions

Energy Technology Data Exchange (ETDEWEB)

Arnon, D I; Allen, M B; Whatley, F R

1956-01-01

Procedures are described for the preparation of chloroplasts capable of carrying out three photochemical reactions, each representing an increasingly complex phase of photosynthesis: photolysis of water (Hill reaction), esterification of inorganic phosphate into adenosine triphosphate (photosynthetic phosphorylation) and the reduction of carbon dioxide to the level of carbohydrates with a simultaneous evolution of oxygen. The three photochemical reactions were separable by variations in the technique for preparation of chloroplasts and by differential inhibition by several reagents. Inhibition of a more complex phase of photosynthesis does not affect the simpler one which precedes it and, conversely, the inhibition of a simpler phase of photosynthesis is paralleled by an inhibition of the more complex phase which follows. Reversible inhibition of CO/sub 2/ fixation and photosynthetic phosphorylation, but not of photolysis, by sulfhydryl group inhibitors suggests that sulfhydryl compounds (enzymes, cofactors, or both) are involved in phosphorylation and CO/sub 2/ fixation, but not in the primary conversion of light into chemical energy as measured by the Hill reaction. Evidence is presented in support of the conclusion that the synthesis of ATP by green cells occurs at two distinct sites: anaerobically in chloroplasts by photosynthetic phosphorylation, and acrobically in smaller cytoplasmic particles, presumably mitochondria, by oxidative phosphorylation independent of light. A general scheme of photosynthesis by chloroplasts, consistent with these findings, is presented. 44 references, 8 figures, 4 tables.

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

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.

Photochemical synthesis of UO2 nanoparticles

International Nuclear Information System (INIS)

Rath, M.C.; Keny, Sangeeta; Naik, D.B.

2014-01-01

UO 2 nanoparticles have been recently synthesized by us from aqueous solutions of uranyl nitrate through radiolytic method on high-energy electron beam irradiation. In this study, the synthesis of UO 2 nanoparticles through photochemical method is reported which is a complementary route to radiation chemical method

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 }.

Photochemical reactions of nucleic acids and their constituents of photobiological relevance

International Nuclear Information System (INIS)

Saito, I.; Sugiyama, H.; Matsuura, T.

1983-01-01

A review is given of the papers published from 1977 to May 1983 on the UV-induced photochemical reactions of nucleic acids and their constituents of photobiological relevance where the structures of photoproducts have been fully characterized. Among the topics discussed are photoadditions relevant to nucleic acid-protein photocrosslinking, photoreactions with psoralens and nucleic acids and photochemical reactions of polynucleotides. (U.K.)

Clumped isotope effects during OH and Cl oxidation of methane

DEFF Research Database (Denmark)

Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan Albrecht

2017-01-01

A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produ......A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH...... effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE...... reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane...

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.

Photochirogenesis: Photochemical Models on the Origin of Biomolecular Homochirality

Directory of Open Access Journals (Sweden)

Cornelia Meinert

2010-05-01

Full Text Available Current research focuses on a better understanding of the origin of biomolecular asymmetry by the identification and detection of the possibly first chiral molecules that were involved in the appearance and evolution of life on Earth. We have reasons to assume that these molecules were specific chiral amino acids. Chiral amino acids have been identified in both chondritic meteorites and simulated interstellar ices. Present research reasons that circularly polarized electromagnetic radiation was identified in interstellar environments and an asymmetric interstellar photon-molecule interaction might have triggered biomolecular symmetry breaking. We review on the possible prebiotic interaction of ‘chiral photons’ in the form of circularly polarized light, with early chiral organic molecules. We will highlight recent studies on enantioselective photolysis of racemic amino acids by circularly polarized light and experiments on the asymmetric photochemical synthesis of amino acids from only one C and one N containing molecules by simulating interstellar environments. Both approaches are based on circular dichroic transitions of amino acids that will be presented as well.

Probability density functions of photochemicals over a coastal area of Northern Italy

International Nuclear Information System (INIS)

Georgiadis, T.; Fortezza, F.; Alberti, L.; Strocchi, V.; Marani, A.; Dal Bo', G.

1998-01-01

The present paper surveys the findings of experimental studies and analyses of statistical probability density functions (PDFs) applied to air pollutant concentrations to provide an interpretation of the ground-level distributions of photochemical oxidants in the coastal area of Ravenna (Italy). The atmospheric-pollution data set was collected from the local environmental monitoring network for the period 1978-1989. Results suggest that the statistical distribution of surface ozone, once normalised over the solar radiation PDF for the whole measurement period, follows a log-normal law as found for other pollutants. Although the Weibull distribution also offers a good fit of the experimental data, the area's meteorological features seem to favour the former distribution once the statistical index estimates have been analysed. Local transport phenomena are discussed to explain the data tail trends

Oxidation Products of Biogenic Emissions Contribute to Nucleation of Atmospheric Particles

CERN Document Server

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

2014-01-01

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

A review of post-column photochemical reaction systems coupled to electrochemical detection in HPLC

International Nuclear Information System (INIS)

Fedorowski, Jennifer; LaCourse, William R.

2010-01-01

Post-column photochemical reaction systems have developed into a common approach for enhancing conventional methods of detection in HPLC. Photochemical reactions as a means of 'derivatization' have a significant number of advantages over chemical reaction-based methods, and a significant effort has been demonstrated to develop an efficient photochemical reactor. When coupled to electrochemical (EC) detection, the technique allows for the sensitive and selective determination of a variety of compounds (e.g., organic nitro explosives, beta-lactam antibiotics, sulfur-containing antibiotics, pesticides and insecticides). This review will focus on developments and methods using post-column photochemical reaction systems followed by EC detection in liquid chromatography. Papers are presented in chronological order to emphasize the evolution of the approach and continued importance of the application.

Highly efficient destruction of squamous carcinoma cells of the head and neck by photochemical internalization of Ranpirnase.

Science.gov (United States)

Liebers, Nora; Holland-Letz, Tim; Welschof, Mona; Høgset, Anders; Jäger, Dirk; Arndt, Michaela A E; Krauss, Jürgen

2017-11-01

Photochemical Internalization is a novel drug delivery technology for cancer treatment based on the principle of Photodynamic Treatment. Using a photosensitizer that locates in endocytic vesicles membranes of tumor cells, Photochemical internalization enables cytosolic release of endocytosed antitumor agents in a site-specific manner. The purpose of the present in-vitro study was to explore whether Photochemical Internalization is able to enhance the efficacy of Ranpirnase, a cytotoxic amphibian ribonuclease, for eradication of squamous cell carcinoma of the head and neck. Cell viability was measured in 8 primary human cell lines of squamous cell carcinoma of the head and neck after treatment with Ranpirnase and Photochemical Internalization. For Photochemical Internalization the photosensitizer disulfonated tetraphenyl porphine was incubated with tumor cells followed by exposure to blue light (435 nm). Our study demonstrates significant enhancement of antitumor activity of Ranpirnase by Photochemical Internalization. Treatment responses were heterogeneous between the primary cancer cell lines. Combining Photochemical Internalization with Ranpirnase resulted in 4.6 to 1,940-fold increased cytotoxicity when compared with the ribonuclease alone (P Internalization in squamous cell carcinoma of the head and neck.

International conference on the photochemical conversion and storage of solar energy

Energy Technology Data Exchange (ETDEWEB)

Hofman, M.Z.

1977-01-31

Abstracts are given for the eight formal lectures and the contributed papers from delegates which were presented in the form of posters. There were seven sessions divided by subject as follows: (1) photochemistry, (2) electron transfer mechanisms in photochemical energy conversion processes, (3) photoelectrolysis, (4) photogalvanics, (5) photochemical production of fuels in homogeneous solutions, (6) membranes for photosynthesis reactions, and (7) non-biological systems for organic molecular energy storage. (WHK)

Path-integral method for the source apportionment of photochemical pollutants

Science.gov (United States)

Dunker, A. M.

2015-06-01

A new, path-integral method is presented for apportioning the concentrations of pollutants predicted by a photochemical model to emissions from different sources. A novel feature of the method is that it can apportion the difference in a species concentration between two simulations. For example, the anthropogenic ozone increment, which is the difference between a simulation with all emissions present and another simulation with only the background (e.g., biogenic) emissions included, can be allocated to the anthropogenic emission sources. The method is based on an existing, exact mathematical equation. This equation is applied to relate the concentration difference between simulations to line or path integrals of first-order sensitivity coefficients. The sensitivities describe the effects of changing the emissions and are accurately calculated by the decoupled direct method. The path represents a continuous variation of emissions between the two simulations, and each path can be viewed as a separate emission-control strategy. The method does not require auxiliary assumptions, e.g., whether ozone formation is limited by the availability of volatile organic compounds (VOCs) or nitrogen oxides (NOx), and can be used for all the species predicted by the model. A simplified configuration of the Comprehensive Air Quality Model with Extensions (CAMx) is used to evaluate the accuracy of different numerical integration procedures and the dependence of the source contributions on the path. A Gauss-Legendre formula using three or four points along the path gives good accuracy for apportioning the anthropogenic increments of ozone, nitrogen dioxide, formaldehyde, and nitric acid. Source contributions to these increments were obtained for paths representing proportional control of all anthropogenic emissions together, control of NOx emissions before VOC emissions, and control of VOC emissions before NOx emissions. There are similarities in the source contributions from the

Photochemical aging of aerosol particles in different air masses arriving at Baengnyeong Island, Korea

Science.gov (United States)

Kang, Eunha; Lee, Meehye; Brune, William H.; Lee, Taehyoung; Park, Taehyun; Ahn, Joonyoung; Shang, Xiaona

2018-05-01

Atmospheric aerosol particles are a serious health risk, especially in regions like East Asia. We investigated the photochemical aging of ambient aerosols using a potential aerosol mass (PAM) reactor at Baengnyeong Island in the Yellow Sea during 4-12 August 2011. The size distributions and chemical compositions of aerosol particles were measured alternately every 6 min from the ambient air or through the highly oxidizing environment of a potential aerosol mass (PAM) reactor. Particle size and chemical composition were measured by using the combination of a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). Inside the PAM reactor, O3 and OH levels were equivalent to 4.6 days of integrated OH exposure at typical atmospheric conditions. Two types of air masses were distinguished on the basis of the chemical composition and the degree of aging: air transported from China, which was more aged with a higher sulfate concentration and O : C ratio, and the air transported across the Korean Peninsula, which was less aged with more organics than sulfate and a lower O : C ratio. For both episodes, the particulate sulfate mass concentration increased in the 200-400 nm size range when sampled through the PAM reactor. A decrease in organics was responsible for the loss of mass concentration in 100-200 nm particles when sampled through the PAM reactor for the organics-dominated episode. This loss was especially evident for the m/z 43 component, which represents less oxidized organics. The m/z 44 component, which represents further oxidized organics, increased with a shift toward larger sizes for both episodes. It is not possible to quantify the maximum possible organic mass concentration for either episode because only one OH exposure of 4.6 days was used, but it is clear that SO2 was a primary precursor of secondary aerosol in northeast Asia, especially during long-range transport from China. In addition

Organic Aerosols in the Presence of CO{sub 2} in the Early Earth and Exoplanets: UV–Vis Refractive Indices of Oxidized Tholins

Energy Technology Data Exchange (ETDEWEB)

Gavilan, Lisseth; Carrasco, Nathalie; Vettier, Ludovic [LATMOS, Université Versailles St Quentin, UPMC Université Paris 06, CNRS, 11 blvd d’Alembert, F-78280 Guyancourt (France); Broch, Laurent [LCP-A2MC, Institut Jean Barriol, Université de Lorraine, Metz (France); Fleury, Benjamin, E-mail: lisseth.gavilan@latmos.ipsl.fr [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States)

2017-10-10

In this experimental study we investigate the role of atmospheric CO{sub 2} on the optical properties of organic photochemical aerosols. To this end, we add CO{sub 2} to a N{sub 2}:CH{sub 4} gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO{sub 2}/CH{sub 4} ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc–Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV–visible (270–600 nm). All samples present a significant absorption band in the UV. According to the Tauc–Lorentz model, as the CO{sub 2}/CH{sub 4} ratio is quadrupled, the position of the UV band is shifted from ∼177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV–vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.

Quantifying effects of oxidant air pollutants on agricultural crops

Energy Technology Data Exchange (ETDEWEB)

Medeiros, W H; Moskowitz, P D

1983-01-01

Estimating risks of air pollution damage to agricultural crops requires identifying crop location and size, likely doses, models for translating dose to response, and measures of response appropriate for economic analysis. Assessment of risk requires compatible data sets for each of these variables. Analysis of air pollution mixtures suggests that oxidant crop damage is caused by three compounds: ozone, nitrogen oxides, and peroxyacetylnitrates. The phytotoxicity of ozone, the most prevalent photochemical oxidant, has been studied more extensively than the other two oxidants, and its effects on vegetation are best understood. Response of vegetation to air pollutants was first characterized by foliar or visible injury. Subsequent research indicated that foliar injury did not translate directly into reduced plant growth or yield, which can be measured. Response to air pollutants may be influenced by physical, biological, and environmental factors. Inherent genetic resistance is probably the most important single factor affecting plant response, although environmental factors influencing stomatal aperture may also be important. For several crops open-top chamber studies and cross sectional analyses of field data provide adequate information to develop dose-response functions. All of these studies have both strengths and weaknesses. Although a number of different models exist for selected crops, there is no single biological or statistical criterion which identifies the best or most accurate model.

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

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

Science.gov (United States)

Ortega, Amber M.; Hayes, Patrick L.; Peng, Zhe; Palm, Brett B.; Hu, Weiwei; Day, Douglas A.; Li, Rui; Cubison, Michael J.; Brune, William H.; Graus, Martin; Warneke, Carsten; Gilman, Jessica B.; Kuster, William C.; de Gouw, Joost; Gutiérrez-Montes, Cándido; Jimenez, Jose L.

2016-06-01

Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA) that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR) was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS) and a scanning mobility particle sizer (SMPS) alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days-6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA) from aging showed a maximum net SOA production between 0.8-6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH ˜ 0.3 day) SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs) in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope ˜ -0.65). Oxidation state of carbon (OSc) in reactor SOA increased steeply with age and remained elevated (OSC ˜ 2) at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background) vs. photochemical age is similar to previous studies at low to moderate ages and also extends to

Real-time measurements of secondary organic aerosol formation and aging from ambient air in an oxidation flow reactor in the Los Angeles area

Directory of Open Access Journals (Sweden)

A. M. Ortega

2016-06-01

Full Text Available Field studies in polluted areas over the last decade have observed large formation of secondary organic aerosol (SOA that is often poorly captured by models. The study of SOA formation using ambient data is often confounded by the effects of advection, vertical mixing, emissions, and variable degrees of photochemical aging. An oxidation flow reactor (OFR was deployed to study SOA formation in real-time during the California Research at the Nexus of Air Quality and Climate Change (CalNex campaign in Pasadena, CA, in 2010. A high-resolution aerosol mass spectrometer (AMS and a scanning mobility particle sizer (SMPS alternated sampling ambient and reactor-aged air. The reactor produced OH concentrations up to 4 orders of magnitude higher than in ambient air. OH radical concentration was continuously stepped, achieving equivalent atmospheric aging of 0.8 days–6.4 weeks in 3 min of processing every 2 h. Enhancement of organic aerosol (OA from aging showed a maximum net SOA production between 0.8–6 days of aging with net OA mass loss beyond 2 weeks. Reactor SOA mass peaked at night, in the absence of ambient photochemistry and correlated with trimethylbenzene concentrations. Reactor SOA formation was inversely correlated with ambient SOA and Ox, which along with the short-lived volatile organic compound correlation, indicates the importance of very reactive (τOH  ∼  0.3 day SOA precursors (most likely semivolatile and intermediate volatility species, S/IVOCs in the Greater Los Angeles Area. Evolution of the elemental composition in the reactor was similar to trends observed in the atmosphere (O : C vs. H : C slope  ∼  −0.65. Oxidation state of carbon (OSc in reactor SOA increased steeply with age and remained elevated (OSC  ∼  2 at the highest photochemical ages probed. The ratio of OA in the reactor output to excess CO (ΔCO, ambient CO above regional background vs. photochemical age is similar to

Oxidation products of biogenic emissions contribute to nucleation of atmospheric particles.

Science.gov (United States)

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

2014-05-16

Atmospheric new-particle formation affects climate and is one of the least understood atmospheric aerosol processes. The complexity and variability of the atmosphere has hindered elucidation of the fundamental mechanism of new-particle formation from gaseous precursors. We show, in experiments performed with the CLOUD (Cosmics Leaving Outdoor Droplets) chamber at CERN, that sulfuric acid and oxidized organic vapors at atmospheric concentrations reproduce particle nucleation rates observed in the lower atmosphere. The experiments reveal a nucleation mechanism involving the formation of clusters containing sulfuric acid and oxidized organic molecules from the very first step. Inclusion of this mechanism in a global aerosol model yields a photochemically and biologically driven seasonal cycle of particle concentrations in the continental boundary layer, in good agreement with observations. Copyright © 2014, American Association for the Advancement of Science.

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

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.

Photochemical reaction products in air pollution

Energy Technology Data Exchange (ETDEWEB)

Stephens, E R; Darley, E F; Taylor, O C; Scott, W E

1961-01-01

Isolation and purification of peroxyacetyl nitrate (PAN) from artificial photochemical reaction of olefins and NO/sub x/ in air are analyzed. Olefin splits at the double bond, one end forming carbonyl compound and the other yielding PAN, among others. At concentrations below 1 ppM, PAN causes plant damage. At a concentration of about 1 ppM, PAN is a strong eye irritant.

Scavenging ratios, wet deposition, and in-cloud oxidation: An application to the oxides of sulphur and nitrogen

International Nuclear Information System (INIS)

Barrie, L.A.

1985-01-01

With special regard to the class of substances in precipitation that potentially originate from both gaseous and particulate precursors, the process of precipitation scavenging is discussed. A model relating daily average ground level scavenging ratios (W) to nucleation scavenging and in-cloud chemical transformation is introduced and is used as guidance in the regression analysis of 3 years of SO 4 = and NO 3 - scavenging-ratio observations made at six locations in eastern Canada. It was found that W of SO 4 = -, NO 3 = -, and SO 4 = -bearing particles is inversely proportional to the one-third power of the precipitation amount in the event. The best regression model explained 41% of the variance in log W for SO 4 = . It included the effects of location, precipitation amount, precipitation type, and in-cloud SO 2 oxidation. The last effect accounted for 50% of the variance explained. The analysis predicts that, on average, in-cloud SO 2 oxidation accounts for 42--79% of the SO 4 = observed in rain and with the exception of one site, less than 20% of the SO 4 = observed in snow. These results are consistent with a mechanism of SO 2 oxidation involving photochemically produced H 2 O 2 . A similar analysis for NO 3 - supports the hypothesis that throughout the year much of the NO 3 - in precipitation originates from in-cloud NO 2 oxidation. It suggests that, depending on location, oxidation of 0.5--1.2 ppbv of NO 2 is sufficient to explain observations. One possible mechanism of oxidation is the reaction with O 3 to form NO 3 and hence soluble N 2 O 5

A 3 D regional scale photochemical air quality model application to a 3 day summertime episode over Paris; Un modele photochimique 3D de qualite de l`air a l`echelle regionale. Application a un episode de 3 jours a Paris en ete

Energy Technology Data Exchange (ETDEWEB)

Jaecker-Voirol, A.; Lipphardt, M.; Martin, B.; Quandalle, Ph.; Salles, J. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France); Carissimo, B.; Dupont, P.M.; Musson-Genon, L.; Riboud, P.M. [Electricite de France (EDF), 78 - Chatou (France). Direction des Etudes et Recherches; Aumont, B.; Bergametti, G.; Bey, I.; Toupanse, G. [Paris-12 Univ., 94 - Creteil (France). Laboratoire interuniversitaire des systemes atmospheriques]|[Paris-7 Univ., 75 (France)

1998-03-01

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; MIEL, an emission inventory model describing the pollutant fluxes from automotive transportation, domestic and industrial activities; MoCA a photochemical gas phase model describing the chemistry of ozone, NO{sub x}, an hydrocarbon compounds; 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 the local monitoring network (Airparif). (authors) 22 refs.

Water oxidation catalysts and methods of use thereof

Energy Technology Data Exchange (ETDEWEB)

Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

2017-12-05

Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

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)

Carrier-lifetime-controlled selective etching process for semiconductors using photochemical etching

International Nuclear Information System (INIS)

Ashby, C.I.H.; Myers, D.R.

1992-01-01

This patent describes a process for selectively photochemically etching a semiconductor material. It comprises introducing at least one impurity into at least one selected region of a semiconductor material to be etched to increase a local impurity concentration in the at least one selected region relative to an impurity concentration in regions of the semiconductor material adjacent thereto, for reducing minority carrier lifetimes within the at least one selected region relative to the adjacent regions for thereby providing a photochemical etch-inhibiting mask at the at least one selected region; and etching the semiconductor material by subjecting the surface of the semiconductor material to a carrier-driven photochemical etching reaction for selectively etching the regions of the semiconductor material adjacent the at least one selected region having the increase impurity concentration; wherein the step of introducing at least one impurity is performed so as not to produce damage to the at least one selected region before any etching is performed

Photochemically Powered AgCl Janus Micromotors as a Model System to Understand Ionic Self-Diffusiophoresis.

Science.gov (United States)

Zhou, Chao; Zhang, H P; Tang, Jinyao; Wang, Wei

2018-03-13

Micromotors are an emerging class of micromachines that could find potential applications in biomedicine, environmental remediation, and microscale self-assembly. Understanding their propulsion mechanisms holds the key to their future development. This is especially true for a popular category of micromotors that are driven by asymmetric surface photochemical reactions. Many of these micromotors release ionic species and are propelled via a mechanism termed "ionic self-diffusiophoresis". However, exactly how it operates remains vague. To address this fundamental yet important issue, we have developed a dielectric-AgCl Janus micromotor that clearly moves away from the AgCl side when exposed to UV or strong visible light. Taking advantage of numerical simulations and acoustic levitation techniques, we have provided tentative explanations for its speed decay over time as well as its directionality. In addition, photoactive AgCl micromotors demonstrate interesting gravitactic behaviors that hint at three-dimensional transport or sensing applications. The current work presents a well-controlled and easily fabricated model system to understand chemically powered micromotors, highlighting the usefulness of acoustic levitation for studying active matter free from the effect of boundaries.

Anodic oxidation with doped diamond electrodes: a new advanced oxidation process

International Nuclear Information System (INIS)

Kraft, Alexander; Stadelmann, Manuela; Blaschke, Manfred

2003-01-01

Boron-doped diamond anodes allow to directly produce OH· radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included

Effects of the antioxidant moieties of dissolved organic matter on triplet-sensitized phototransformation processes: Implications for the photochemical modeling of sulfadiazine.

Science.gov (United States)

Vione, Davide; Fabbri, Debora; Minella, Marco; Canonica, Silvio

2018-01-01

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ - (pK a  = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ - than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and OH reaction would account for the majority of both HSDZ and SDZ - photodegradation in waters having low dissolved organic carbon (DOC DOC values (>3-4 mgC L -1 ) and despite the back-reduction processes, the 3 CDOM* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ - at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ - and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ - with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions. Copyright © 2017

Evaluation of multisectional and two-section particulate matter photochemical grid models in the Western United States.

Science.gov (United States)

Morris, Ralph; Koo, Bonyoung; Yarwood, Greg

2005-11-01

Version 4.10s of the comprehensive air-quality model with extensions (CAMx) photochemical grid model has been developed, which includes two options for representing particulate matter (PM) size distribution: (1) a two-section representation that consists of fine (PM2.5) and coarse (PM2.5-10) modes that has no interactions between the sections and assumes all of the secondary PM is fine; and (2) a multisectional representation that divides the PM size distribution into N sections (e.g., N = 10) and simulates the mass transfer between sections because of coagulation, accumulation, evaporation, and other processes. The model was applied to Southern California using the two-section and multisection representation of PM size distribution, and we found that allowing secondary PM to grow into the coarse mode had a substantial effect on PM concentration estimates. CAMx was then applied to the Western United States for the 1996 annual period with a 36-km grid resolution using both the two-section and multisection PM representation. The Community Multiscale Air Quality (CMAQ) and Regional Modeling for Aerosol and Deposition (REMSAD) models were also applied to the 1996 annual period. Similar model performance was exhibited by the four models across the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Clean Air Status and Trends Network monitoring networks. All four of the models exhibited fairly low annual bias for secondary PM sulfate and nitrate but with a winter overestimation and summer underestimation bias. The CAMx multisectional model estimated that coarse mode secondary sulfate and nitrate typically contribute nitrate when averaged across the more rural IMPROVE monitoring network.

Advanced oxidation in waste water treatment; Oxidacion avanzada en el tratamiento de aguas residuales

Energy Technology Data Exchange (ETDEWEB)

Baraza, J.; Esplugas, S. [Universitat de Barcelona (Spain)

2000-07-01

The treatment of waste waters and, sometimes, drinking water, using advanced oxidation processes is reviewed on the basis of the studies carried out in which the hydroxyl radical plays an important part, with different techniques and reagents offering a broad range of possibilities. A distinction is made between photochemical an non-photochemical processes. A simple presentation of the fundamentals of each method is made together with a wide-ranging review of the literature and the results obtained in the degradation of certain contaminants resistant to conventional chemical treatments. (Author) 43 refs.

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.

Repair processes for photochemical damage in mammalian cells

International Nuclear Information System (INIS)

Cleaver, J.E.

1974-01-01

Repair processes for photochemical damage in cells following uv irradiation are reviewed. Cultured fibroblast cells from human patients with xeroderma pigmentosum were used as an example to illustrate aspects of repair of injuries to DNA and proteins. (250 references) (U.S.)

Volatile organic compounds (VOCs) in photochemically aged air from the eastern and western Mediterranean

Science.gov (United States)

Derstroff, Bettina; Hüser, Imke; Bourtsoukidis, Efstratios; Crowley, John N.; Fischer, Horst; Gromov, Sergey; Harder, Hartwig; Janssen, Ruud H. H.; Kesselmeier, Jürgen; Lelieveld, Jos; Mallik, Chinmay; Martinez, Monica; Novelli, Anna; Parchatka, Uwe; Phillips, Gavin J.; Sander, Rolf; Sauvage, Carina; Schuladen, Jan; Stönner, Christof; Tomsche, Laura; Williams, Jonathan

2017-08-01

During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014) in the eastern Mediterranean, multiple volatile organic compounds (VOCs) were measured from a 650 m hilltop site in western Cyprus (34° 57' N/32° 23' E). Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy) and eastern (Turkey, Greece) Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80-100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs) methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5-3 ppbv median level by day, range: ca. 1-8 ppbv) than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days) of air masses originating from eastern and western Europe. Ozone and many OVOC levels were ˜ 20 and ˜ 30-60 % higher, respectively, in air arriving from the east. Using the FLEXPART calculated transport time, the contribution of photochemical

Open burning of rice, corn and wheat straws: primary emissions, photochemical aging, and secondary organic aerosol formation

Science.gov (United States)

Fang, Zheng; Deng, Wei; Zhang, Yanli; Ding, Xiang; Tang, Mingjin; Liu, Tengyu; Hu, Qihou; Zhu, Ming; Wang, Zhaoyi; Yang, Weiqiang; Huang, Zhonghui; Song, Wei; Bi, Xinhui; Chen, Jianmin; Sun, Yele; George, Christian; Wang, Xinming

2017-12-01

Agricultural residues are among the most abundant biomass burned globally, especially in China. However, there is little information on primary emissions and photochemical evolution of agricultural residue burning. In this study, indoor chamber experiments were conducted to investigate primary emissions from open burning of rice, corn and wheat straws and their photochemical aging as well. Emission factors of NOx, NH3, SO2, 67 non-methane hydrocarbons (NMHCs), particulate matter (PM), organic aerosol (OA) and black carbon (BC) under ambient dilution conditions were determined. Olefins accounted for > 50 % of the total speciated NMHCs emission (2.47 to 5.04 g kg-1), indicating high ozone formation potential of straw burning emissions. Emission factors of PM (3.73 to 6.36 g kg-1) and primary organic carbon (POC, 2.05 to 4.11 gC kg-1), measured at dilution ratios of 1300 to 4000, were lower than those reported in previous studies at low dilution ratios, probably due to the evaporation of semi-volatile organic compounds under high dilution conditions. After photochemical aging with an OH exposure range of (1.97-4.97) × 1010 molecule cm-3 s in the chamber, large amounts of secondary organic aerosol (SOA) were produced with OA mass enhancement ratios (the mass ratio of total OA to primary OA) of 2.4-7.6. The 20 known precursors could only explain 5.0-27.3 % of the observed SOA mass, suggesting that the major precursors of SOA formed from open straw burning remain unidentified. Aerosol mass spectrometry (AMS) signaled that the aged OA contained less hydrocarbons but more oxygen- and nitrogen-containing compounds than primary OA, and carbon oxidation state (OSc) calculated with AMS resolved O / C and H / C ratios increased linearly (p < 0.001) with OH exposure with quite similar slopes.

Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

Directory of Open Access Journals (Sweden)

Ulrich C. Fischer

2014-09-01

Full Text Available A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM of (3-aminopropyltriethoxysilane (APTES is explored with three different processes: 1 a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2 a chemical process induced by oxygen plasma etching as well as 3 a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL, which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern.

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/

Effects of Edaravone, a Free Radical Scavenger, on Photochemically Induced Cerebral Infarction in a Rat Hemiplegic Model

Directory of Open Access Journals (Sweden)

Satoshi Ikeda

2013-01-01

Full Text Available Edaravone is a free radical scavenger that protects the adjacent cortex during cerebral infarction. We created a hemiparetic model of cerebral thrombosis from a photochemically induced infarction with the photosensitive dye, rose bengal, in rats. We examined the effects of edaravone on recovery in the model. A total of 36 adult Wistar rats were used. The right sensorimotor area was irradiated with green light with a wavelength of 533 nm (10 mm diameter, and the rose bengal was injected intravenously to create an infarction. The edaravone group was injected intraperitoneally with edaravone (3 mg/kg, and the control group was injected with saline. The recovery process of the hemiplegia was evaluated with the 7-step scale of Fenny. The infarcted areas were measured after fixation. The recovery of the paralysis in the edaravone-treated group was significantly earlier than that in the untreated group. Seven days later, both groups were mostly recovered and had scores of 7, and the infarction region was significantly smaller in the edaravone-treated group. Edaravone reduced the infarction area and promoted the functional recovery of hemiparesis from cerebral thrombosis in a rat model. These findings suggest that edaravone treatment would be effective in clinical patients recovering from cerebral infarction.

Effects of edaravone, a free radical scavenger, on photochemically induced cerebral infarction in a rat hemiplegic model.

Science.gov (United States)

Ikeda, Satoshi; Harada, Katsuhiro; Ohwatashi, Akihiko; Kamikawa, Yurie

2013-01-01

Edaravone is a free radical scavenger that protects the adjacent cortex during cerebral infarction. We created a hemiparetic model of cerebral thrombosis from a photochemically induced infarction with the photosensitive dye, rose bengal, in rats. We examined the effects of edaravone on recovery in the model. A total of 36 adult Wistar rats were used. The right sensorimotor area was irradiated with green light with a wavelength of 533 nm (10 mm diameter), and the rose bengal was injected intravenously to create an infarction. The edaravone group was injected intraperitoneally with edaravone (3 mg/kg), and the control group was injected with saline. The recovery process of the hemiplegia was evaluated with the 7-step scale of Fenny. The infarcted areas were measured after fixation. The recovery of the paralysis in the edaravone-treated group was significantly earlier than that in the untreated group. Seven days later, both groups were mostly recovered and had scores of 7, and the infarction region was significantly smaller in the edaravone-treated group. Edaravone reduced the infarction area and promoted the functional recovery of hemiparesis from cerebral thrombosis in a rat model. These findings suggest that edaravone treatment would be effective in clinical patients recovering from cerebral infarction.

UV photodissociation spectroscopy of oxidized undecylenic acid films.

Science.gov (United States)

Gomez, Anthony L; Park, Jiho; Walser, Maggie L; Lin, Ao; Nizkorodov, Sergey A

2006-03-16

Oxidation of thin multilayered films of undecylenic (10-undecenoic) acid by gaseous ozone was investigated using a combination of spectroscopic and mass spectrometric techniques. The UV absorption spectrum of the oxidized undecylenic acid film is significantly red-shifted compared to that of the initial film. Photolysis of the oxidized film in the tropospheric actinic region (lambda > 295 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 observed photochemical activity. The presence of peroxides is confirmed by mass-spectrometric analysis of the oxidized sample and an iodometric test. Significant polymerization resulting from secondary reactions of Criegee radicals during ozonolysis of the film is observed. The data strongly imply the importance of photochemistry in aging of atmospheric organic aerosol particles.

Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

Energy Technology Data Exchange (ETDEWEB)

Xu, Songchen [Ames Laboratory; Manna, Kuntal [Ames Laboratory; Ellern, Arkady [Ames Laboratory; Sadow, Aaron D [Ames Laboratory

2014-12-08

In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbene–bis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(η4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(η4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(η4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(η4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(μ-Cl)(η2-C8H14)2]2 (M = Rh, Ir) provide {κ4-PhB(OxMe2)2ImMes'CH2}Rh(μ-H)(μ-Cl)Rh(η2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(η3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in C–H bond oxidative addition providing the compounds {κ4-PhB(OxMe2)2ImMes'CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis

Fluorescence studies of Rhodamine 6G functionalized silicon oxide nanostructures

International Nuclear Information System (INIS)

Baumgaertel, Thomas; Borczyskowski, Christian von; Graaf, Harald

2010-01-01

Selective anchoring of optically active molecules on nanostructured surfaces is a promising step towards the creation of nanoscale devices with new functionalities. Recently we have demonstrated the electrostatic attachment of charged fluorescent molecules on silicon oxide nanostructures prepared by atomic force microscopy (AFM) nanolithography via local anodic oxidation (LAO) of dodecyl-terminated silicon. In this paper we report on our findings from a more detailed optical investigation of the bound dye Rhodamine 6G. High sensitivity optical wide field microscopy as well as confocal laser microscopy have been used to characterize the Rhodamine fluorescence emission. A highly interesting question concerns the interaction between an emitter close to a silicon surface because mechanisms such as energy transfer and fluorescence quenching will occur which are still not fully understood. Since the oxide thickness can be varied during preparation continuously from 1 to ∼ 5 nm, it is possible to investigate the fluorescence of the bound dye in close proximity to the underlying silicon. Using confocal laser microscopy we were also able to obtain optical spectra from the bound molecules. Together with the results from an analysis of their photochemical bleaching behaviour, we conjecture that some of the Rhodamine 6G molecules on the structure are interacting with the oxide, causing a spectral shift and differences in their photochemical properties.

PHOTOCHEMISTRY IN TERRESTRIAL EXOPLANET ATMOSPHERES. I. PHOTOCHEMISTRY MODEL AND BENCHMARK CASES

Energy Technology Data Exchange (ETDEWEB)

Hu Renyu; Seager, Sara; Bains, William, E-mail: hury@mit.edu [Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)

2012-12-20

We present a comprehensive photochemistry model for exploration of the chemical composition of terrestrial exoplanet atmospheres. The photochemistry model is designed from the ground up to have the capacity to treat all types of terrestrial planet atmospheres, ranging from oxidizing through reducing, which makes the code suitable for applications for the wide range of anticipated terrestrial exoplanet compositions. The one-dimensional chemical transport model treats up to 800 chemical reactions, photochemical processes, dry and wet deposition, surface emission, and thermal escape of O, H, C, N, and S bearing species, as well as formation and deposition of elemental sulfur and sulfuric acid aerosols. We validate the model by computing the atmospheric composition of current Earth and Mars and find agreement with observations of major trace gases in Earth's and Mars' atmospheres. We simulate several plausible atmospheric scenarios of terrestrial exoplanets and choose three benchmark cases for atmospheres from reducing to oxidizing. The most interesting finding is that atomic hydrogen is always a more abundant reactive radical than the hydroxyl radical in anoxic atmospheres. Whether atomic hydrogen is the most important removal path for a molecule of interest also depends on the relevant reaction rates. We also find that volcanic carbon compounds (i.e., CH{sub 4} and CO{sub 2}) are chemically long-lived and tend to be well mixed in both reducing and oxidizing atmospheres, and their dry deposition velocities to the surface control the atmospheric oxidation states. Furthermore, we revisit whether photochemically produced oxygen can cause false positives for detecting oxygenic photosynthesis, and find that in 1 bar CO{sub 2}-rich atmospheres oxygen and ozone may build up to levels that have conventionally been accepted as signatures of life, if there is no surface emission of reducing gases. The atmospheric scenarios presented in this paper can serve as the

Photochemical Creation of Fluorescent Quantum Defects in Semiconducting Carbon Nanotube Hosts.

Science.gov (United States)

Wu, Xiaojian; Kim, Mijin; Kwon, Hyejin; Wang, YuHuang

2018-01-15

Quantum defects are an emerging class of synthetic single-photon emitters that hold vast potential for near-infrared imaging, chemical sensing, materials engineering, and quantum information processing. Herein, we show that it is possible to optically direct the synthetic creation of molecularly tunable fluorescent quantum defects in semiconducting single-walled carbon nanotube hosts through photochemical reactions. By exciting the host semiconductor with light that resonates with its electronic transition, we find that halide-containing aryl groups can covalently bond to the sp 2 carbon lattice. The introduced quantum defects generate bright photoluminescence that allows tracking of the reaction progress in situ. We show that the reaction is independent of temperature but correlates strongly with the photon energy used to drive the reaction, suggesting a photochemical mechanism rather than photothermal effects. This type of photochemical reactions opens the possibility to control the synthesis of fluorescent quantum defects using light and may enable lithographic patterning of quantum emitters with electronic and molecular precision. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Utility of Photochemical Traits as Diagnostics of Thermal Tolerance amongst Great Barrier Reef Corals

Directory of Open Access Journals (Sweden)

Matthew R. Nitschke

2018-02-01

Full Text Available Light availability is considered a key factor regulating the thermal sensitivity of reef building corals, where excessive excitation of photosystem II (PSII further exacerbates pressure on photochemical pathways already compromised by heat stress. Coral symbionts acclimate to changes in light availability (photoacclimation by continually fine-tuning the photochemical operating efficiency of PSII. However, how this process adjusts throughout the warmest months in naturally heat-tolerant or sensitive species is unknown, and whether this influences the capacity to tolerate transient heat stress is untested. We therefore examined the PSII photophysiology of 10 coral species (with known thermal tolerances from shallow reef environments at Heron Island (Great Barrier Reef, Australia, in spring (October-November, 2015 vs. summer (February-March, 2016. Corals were maintained in flow-through aquaria and rapid light curve (RLC protocols using pulse amplitude modulated (PAM fluorometry captured changes in the PSII photoacclimation strategy, characterized as the minimum saturating irradiance (Ek, and the extent of photochemical ([1 – C], operating efficiency vs. non-photochemical ([1 – Q] energy dissipation. Values of Ek across species were >2-fold higher in all coral species in spring, consistent with a climate of higher overall light exposure (i.e., higher PAR from lower cloud cover, rainfall and wind speed compared with summer. Summer decreases in Ek were combined with a shift toward preferential photochemical quenching in all species. All coral species were subsequently subjected to thermal stress assays. An equivalent temperature-ramping profile of 1°C increase per day and then maintenance at 32°C was applied in each season. Despite the significant seasonal photoacclimation, the species hierarchy of thermal tolerance [maximum quantum yields of PSII (Fv/Fm, monitored at dawn and dusk] did not shift between seasons, except for Pocillopora

Suppression of new particle formation from monoterpene oxidation by NOx

Science.gov (United States)

Wildt, J.; Mentel, T. F.; Kiendler-Scharr, A.; Hoffmann, T.; Andres, S.; Ehn, M.; Kleist, E.; Müsgen, P.; Rohrer, F.; Rudich, Y.; Springer, M.; Tillmann, R.; Wahner, A.

2014-03-01

The impact of nitrogen oxides (NOx = NO + NO2) on new particle formation (NPF) and on photochemical ozone production from real plant volatile organic compound (BVOC) emissions was studied in a laboratory setup. At high NOx conditions ([BVOC] / [NOx] 23 ppb) new particle formation was suppressed. Instead, photochemical ozone formation was observed resulting in higher hydroxyl radical (OH) and lower nitrogen monoxide (NO) concentrations. When [NO] was reduced back to levels below 1 ppb by OH reactions, NPF was observed. Adding high amounts of NOx caused NPF to be slowed by orders of magnitude compared to analogous experiments at low NOx conditions ([NOx] ~300 ppt), although OH concentrations were higher. Varying NO2 photolysis enabled showing that NO was responsible for suppression of NPF. This suggests that peroxy radicals are involved in NPF. The rates of NPF and photochemical ozone production were related by power law dependence with an exponent approaching -2. This exponent indicated that the overall peroxy radical concentration must have been similar when NPF occurred. Thus, permutation reactions of first-generation peroxy radicals cannot be the rate limiting step in NPF from monoterpene oxidation. It was concluded that permutation reactions of higher generation peroxy-radical-like intermediates limit the rate of new particle formation. In contrast to the strong effects on the particle numbers, the formation of particle mass was substantially less sensitive to NOx concentrations. If at all, yields were reduced by about an order of magnitude only at very high NOx concentrations.

THE EFFECTS OF OXIDANT AIR POLLUTANTS ON SOYBEANS, SNAP BEANS AND POTATOES

Science.gov (United States)

During the past 5 years the impact of photochemical oxidants on soybeans and snap beans in Maryland and on potatoes in Virginia and Delaware was assessed with open-top chambers. The mean yields of four selected soybean varieties grown in open-top chambers with carbon-filtered air...

A Simplified Model for Volatile-N Oxidation

DEFF Research Database (Denmark)

Hansen, Stine; Glarborg, Peter

2010-01-01

In solid fuel flames, NO is largely formed from the oxidation of volatile nitrogen compounds such as HCN and NH3. To be able to model the nitrogen chemistry in these flames, it is necessary to have an adequate model for volatile-N oxidation. Simple global models for oxidation of HCN and NH3 from...... the literature should be used cautiously, since their predictive capabilities are limited, particularly under reducing conditions. Models for HCN/NH3/NO conversion based on the systematic reduction of a detailed chemical kinetic model offer high accuracy but rely on input estimates of combustion intermediates...... for the sub-bituminous and bituminous coals, especially at lower temperatures. The semiempirical correlations for estimating radical concentrations may also be useful in combination with models for other trace species, such as sulfur oxides, organic species, etc....

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.

Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode.

Science.gov (United States)

Schauer, James J; Fraser, Matthew P; Cass, Glen R; Simoneit, Bernd R T

2002-09-01

A comprehensive organic compound-based receptor model is developed that can simultaneously apportion the source contributions to atmospheric gas-phase organic compounds, semivolatile organic compounds, fine particle organic compounds, and fine particle mass. The model is applied to ambient data collected at four sites in the south coast region of California during a severe summertime photochemical smog episode, where the model determines the direct primary contributions to atmospheric pollutants from 11 distinct air pollution source types. The 11 sources included in the model are gasoline-powered motor vehicle exhaust, diesel engine exhaust, whole gasoline vapors, gasoline headspace vapors, organic solvent vapors, whole diesel fuel, paved road dust, tire wear debris, meat cooking exhaust, natural gas leakage, and vegetative detritus. Gasoline engine exhaust plus whole gasoline vapors are the predominant sources of volatile organic gases, while gasoline and diesel engine exhaust plus diesel fuel vapors dominate the emissions of semivolatile organic compounds from these sources during the episode studied at all four air monitoring sites. The atmospheric fine particle organic compound mass was composed of noticeable contributions from gasoline-powered motor vehicle exhaust, diesel engine exhaust, meat cooking, and paved road dust with smaller but quantifiable contributions from vegetative detritus and tire wear debris. In addition, secondary organic aerosol, which is formed from the low-vapor pressure products of gas-phase chemical reactions, is found to be a major source of fine particle organic compound mass under the severe photochemical smog conditions studied here. The concentrations of secondary organic aerosol calculated in the present study are compared with previous fine particle source apportionment results for less intense photochemical smog conditions. It is shown that estimated secondary organic aerosol concentrations correlate fairly well with the

Photoinduced Oxidation of Arsenite to Arsenate on Ferrihydrite

Energy Technology Data Exchange (ETDEWEB)

N Bhandari; R Reeder; D Strongin

2011-12-31

The photochemistry of an aqueous suspension of the iron oxyhydroxide, ferrihydrite, in the presence of arsenite has been investigated using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray absorption near edge structure (XANES), and solution phase analysis. Both ATR-FTIR and XANES show that the exposure of ferrihydrite to arsenite in the dark leads to no change in the As oxidation state, but the exposure of this arsenite-bearing surface, which is in contact with pH 5 water, to light leads to the conversion of the majority of the adsorbed arsenite to the As(V) bearing species, arsenate. Analysis of the solution phase shows that ferrous iron is released into solution during the oxidation of arsenite. The photochemical reaction, however, shows the characteristics of a self-terminating reaction in that there is a significant suppression of this redox chemistry before 10% of the total iron making up the ferrihydrite partitions into solution as ferrous iron. The self-terminating behavior exhibited by this photochemical arsenite/ferrihydrite system is likely due to the passivation of the ferrihydrite surface by the strongly bound arsenate product.

Photochemical decomposition of perfluorooctanoic acid in aqueous periodate with VUV and UV light irradiation

International Nuclear Information System (INIS)

Cao, M.H.; Wang, B.B.; Yu, H.S.; Wang, L.L.; Yuan, S.H.; Chen, J.

2010-01-01

The photochemical decomposition of perfluorooctanoic acid (PFOA) in aqueous periodate (IO 4 - ) was investigated under two types of low-pressure mercury lamps: one emits at 254 nm light (UV light) and the other emits both 254 nm and 185 nm light (VUV light). PFOA decomposed efficiently under VUV light irradiation while it decomposed poorly under UV light irradiation. The addition of IO 4 - significantly increased the rate of decomposition and defluorination of PFOA irradiated with UV light whereas it decreased both processes under VUV irradiation. Reactive radical (IO 3 ·) generated by photolysis of IO 4 - initiated the oxidation of PFOA in UV process. Aquated electrons (e aq - ), generated from water homolysis, scavenged IO 4 - resulting in decrease of reactive radical species production and PFOA decomposition. The shorter-chain perfluorocarboxylic acids (PFCAs) formed in a stepwise manner from long-chain PFCAs.

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.

From small aromatic molecules to functional nanostructured carbon by pulsed laser-induced photochemical stitching

Directory of Open Access Journals (Sweden)

R. R. Gokhale

2012-06-01

Full Text Available A novel route employing UV laser pulses (KrF Excimer, 248 nm to cleave small aromatic molecules and stitch the generated free radicals into functional nanostructured forms of carbon is introduced. The process differs distinctly from any strategies wherein the aromatic rings are broken in the primary process. It is demonstrated that this pulsed laser-induced photochemical stitching (PLPS process when applied to routine laboratory solvents (or toxic chemical wastes when discarded Chlorobenzene and o-Dichlorobenzene yields Carbon Nanospheres (CNSs comprising of graphene-like sheets assembled in onion-like configurations. This room temperature process implemented under normal laboratory conditions is versatile and clearly applicable to the whole family of haloaromatic compounds without and with additions of precursors or other nanomaterials. We further bring out its applicability for synthesis of metal-oxide based carbon nanocomposites.

Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States

Directory of Open Access Journals (Sweden)

R. Sommariva

2011-07-01

Full Text Available Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM. The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60 % for all species, except acetic acid.

The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28 % and i-propanol (<15 % and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK is mostly produced from the oxidation of n-butane (20–30 % and 3-methylpentane (<40 %. Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23 % and 5–25 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.

Volatile organic compounds (VOCs in photochemically aged air from the eastern and western Mediterranean

Directory of Open Access Journals (Sweden)

B. Derstroff

2017-08-01

Full Text Available During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014 in the eastern Mediterranean, multiple volatile organic compounds (VOCs were measured from a 650 m hilltop site in western Cyprus (34° 57′ N/32° 23′ E. Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy and eastern (Turkey, Greece Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80–100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5–3 ppbv median level by day, range: ca. 1–8 ppbv than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days of air masses originating from eastern and western Europe. Ozone and many OVOC levels were  ∼  20 and  ∼  30–60 % higher, respectively, in air arriving from the east. Using the FLEXPART

The chitosan - Porphyrazine hybrid materials and their photochemical properties.

Science.gov (United States)

Chełminiak-Dudkiewicz, Dorota; Ziegler-Borowska, Marta; Stolarska, Magdalena; Sobotta, Lukasz; Falkowski, Michal; Mielcarek, Jadwiga; Goslinski, Tomasz; Kowalonek, Jolanta; Węgrzynowska-Drzymalska, Katarzyna; Kaczmarek, Halina

2018-04-01

Three magnesium sulfanyl porphyrazines differing in the size of peripheral substituents (3,5-dimethoxybenzylsulfanyl, (3,5-dimethoxybenzyloxy)benzylsulfanyl, 3,5-bis[(3,5-bis[(3,5-dimethoxybenzyloxy)benzyloxy]benzylsulfanyl) were exposed to visible and ultraviolet radiation (UV A + B + C) in order to determine their photochemical properties. The course of photochemical reactions in dimethylformamide solutions and the ability of the systems to generate singlet oxygen were studied by UV-Vis spectroscopy, which additionally gave information on aggregation processes. The porphyrazines were found to be stable upon visible light irradiation conditions, but when exposed to high energy UV radiation, the efficient photodegradation of these macrocycles was observed. Therefore, these three magnesium sulfanyl porphyrazines were incorporated into chitosan matrix. The obtained thin films of chitosan doped with porphyrazines were subjected to polychromatic UV-radiation and studied by spectroscopic methods (UV-Vis, FTIR), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Application of chitosan as a polymer matrix for porphyrazines was found to be successful method that effectively stopped the unwelcome degradation of macrocycles, thus worth considering for their photoprotection. In addition, the surface properties of the hybrid material were determined by contact angle measurements and calculation of surface free energy. Intermolecular interactions between these novel porphyrazines and chitosan were detected. The mechanism of photochemical reactions occurring in studied systems has been discussed. Copyright © 2018 Elsevier B.V. All rights reserved.

Investigation of Zircaloy-2 oxidation model for SFP accident analysis

Energy Technology Data Exchange (ETDEWEB)

Nemoto, Yoshiyuki, E-mail: nemoto.yoshiyuki@jaea.go.jp [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Kaji, Yoshiyuki; Ogawa, Chihiro; Kondo, Keietsu [Japan Atomic Energy Agency, 2-4 Shirakata, Ohaza, Tokai-mura, Naka-gun, Ibaraki, 319-1195 (Japan); Nakashima, Kazuo; Kanazawa, Toru; Tojo, Masayuki [Global Nuclear Fuel – Japan Co., Ltd., 2-3-1, Uchikawa, Yokosuka-shi, Kanagawa, 239-0836 (Japan)

2017-05-15

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. - Highlights: •An oxidation model of Zircaloy-2 in air environment was developed. •The oxidation model was validated by the comparison with oxidation tests using long cladding tubes in hypothetical spent fuel pool accident condition. •The oxidation model successfully reproduced the typical oxidation behavior in air.

Nitrous oxide metabolism in nitrate-reducing bacteria: Physiology and regulatory mechanisms

OpenAIRE

Torres, Maria; Simon, Jorg; Rowley, Gary; Bedmar, Eulogio; Richardson, David; Gates, Andrew; Delgado, Maria

2016-01-01

Nitrous oxide (N2O) is an important greenhouse gas (GHG) with substantial global warming potential and also contributes to ozone depletion through photochemical nit- ric oxide (NO) production in the stratosphere. The negative effects of N2O on climate and stratospheric ozone make N2O mitigation an international challenge. More than 60% of global N2O emissions are emitted from agricultural soils mainly due to the appli- cation of synthetic nitrogen-containing fertilizers. Thus, mitigation stra...

Facile synthesis of polymer-enveloped ultrasmall superparamagnetic iron oxide for magnetic resonance imaging

International Nuclear Information System (INIS)

Hong Jun; Xu Dongmei; Yu Jiahui; Gong Peijun; Ma Hongjuan; Yao Side

2007-01-01

Ultrasmall superparamagnetic iron oxide (USPIO) with synthetic polymer, based on magnetite core, was synthesized via facile photochemical in situ polymerization. A possible mechanism of photochemical in situ polymerization was proposed. The obtained polymer-enveloped UPSIO was characterized by transmission electron microscopy (TEM), photo-correlation spectroscopy (PCS), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric (TG) analysis and vibrating sampling magnetometer (VSM) measurement. Properties such as ultrasmall particle size, hydrophilicity, strong magnetization and surface characteristics, which are desirable for magnetic resonance imaging (MRI) contrast agents, were evaluated in detail. The resultant USPIO-based MRI contrast agent holds considerable promise in molecular MR tracking, MR immune imaging, cell tracking and targeted intracellular hyperthermia, etc

SITE - EMERGING TECHNOLOGIES: LASER INDUCED PHOTO- CHEMICAL OXIDATIVE DESTRUCTION OF TOXIC ORGANICS IN LEACHATES AND GROUNDWATERS

Science.gov (United States)

The technology described in this report has been developed under the Emerging Technology Program of the Superfund Innovative Technology Evaluation (SITE) Program to photochemically oxidize organic compounds in wastewater by applying ultraviolet radiation using an excimer laser. T...

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

Photochemical exchange reactions of thymine, uracil and their nucleosides with selected amino acids

International Nuclear Information System (INIS)

Shetlar, M.D.; Taylor, J.A.; Hom, K.

1984-01-01

The photoinduced exchange reactions of thymine with lysine at basic pH, using 254 nm light, have been studied. Three products have been isolated, namely, 6-amino-2-(1-thyminyl)hexanoic acid (Ia), 2-amino-6-(1-thyminyl)hexanoic acid (IIa) and 1-amino-5-(1-thyminyl)pentane (IIIa). Compound IIIa was shown to be a secondary product, produced by photochemical decarboxylation of Ia. Photochemical reaction of thymine with glycine and alanine at basic pH led, respectively, to formation of 2-(1-thyminyl)acetic acid (Ic) and 2-(1-thyminyl)propionic acid (Id). Compounds Ic and Id underwent photolysis to produce the decarboxylated secondary products 1-methylthymine and 1-ethylthymine, respectively. Thymidine reacts photochemically with glycine and alanine to produce the same products. Irradiation of DNA in the presence of lysine at basic pH led to the formation of the same products formed in the thymine-lysine system, namely Ia, IIa and IIIa. Uracil was found to undergo analogous photochemical exchange reactions with lysine to form 6-amino-2-(1-uracilyl)hexanoic acid (Ib), and 2-amino-6-(1-uracilyl)hexanoic acid (IIb). Compound Ib was found to undergo photodecarboxylation to form 1-amino-5-(1-uracilyl)pentane (IIIb), analogous to the secondary photoreaction of Ia. Photoreaction of uracil with 1,5-diaminopentane (cadaverine) likewise led to formation of IIIb. (author)

Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

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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.

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

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

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.

Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?

Science.gov (United States)

Marley, Mark Scott; Zahnle, Kevin; Moses, J.; Morley, C.

2015-01-01

The first young giant planet to be discovered by the Gemini Planet Imager was the (is) approximately 2MJ planet 51 Eri b. This approximately 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. However for an object as cool as 700 K, the origin of the cloud coverage is somewhat puzzling, as the global silicate and iron clouds would be expected to have sunk well below the photosphere by this effective temperature. While strong vertical mixing in these low gravity atmospheres remains a plausible 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. 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.

Oxide behaviour modelling progress in COMETHE

International Nuclear Information System (INIS)

Vliet, J. van; Hoppe, N.

1983-01-01

An attempt has been made to develop a global model which simultaneously describes many important aspects of uranium oxide under irradiation. The individual models describing fuel structural changes, swelling and gas release, which were earlier separate from one another, are now part of a more realistic integral fuel model. Fission gas release depends now on an explicitely calculated open porosity, which is generated by fuel swelling; the latter is in turn connected to fission gas release. The paper describes the individual oxide models and how they are linked together. (author)

Photochemical ozone production in tropical squall line convection during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A

Science.gov (United States)

Pickering, Kenneth E.; Thompson, Anne M.; Tao, Wei-Kuo; Simpson, Joanne; Scala, John R.

1991-01-01

The role of convection was examined in trace gas transport and ozone production in a tropical dry season squall line sampled on August 3, 1985, during NASA Global Tropospheric Experiment/Amazon Boundary Layer Experiment 2A (NASA GTE/ABLE 2A) in Amazonia, Brazil. Two types of analyses were performed. Transient effects within the cloud are examined with a combination of two-dimensional cloud and one-dimensional photochemical modeling. Tracer analyses using the cloud model wind fields yield a series of cross sections of NO(x), CO, and O3 distribution during the lifetime of the cloud; these fields are used in the photochemical model to compute the net rate of O3 production. At noon, when the cloud was mature, the instantaneous ozone production potential in the cloud is between 50 and 60 percent less than in no-cloud conditions due to reduced photolysis and cloud scavenging of radicals. Analysis of cloud inflows and outflows is used to differentiate between air that is undisturbed and air that has been modified by the storm. These profiles are used in the photochemical model to examine the aftereffects of convective redistribution in the 24-hour period following the storm. Total tropospheric column O3 production changed little due to convection because so little NO(x) was available in the lower troposphere. However, the integrated O3 production potential in the 5- to 13-km layer changed from net destruction to net production as a result of the convection. The conditions of the August 3, 1985, event may be typical of the early part of the dry season in Amazonia, when only minimal amounts of pollution from biomass burning have been transported into the region.

Modeling the radical chemistry in an oxidation flow reactor: radical formation and recycling, sensitivities, and the OH exposure estimation equation.

Science.gov (United States)

Li, Rui; Palm, Brett B; Ortega, Amber M; Hlywiak, James; Hu, Weiwei; Peng, Zhe; Day, Douglas A; Knote, Christoph; Brune, William H; de Gouw, Joost A; Jimenez, Jose L

2015-05-14

Oxidation flow reactors (OFRs) containing low-pressure mercury (Hg) lamps that emit UV light at both 185 and 254 nm ("OFR185") to generate OH radicals and O3 are used in many areas of atmospheric science and in pollution control devices. The widely used potential aerosol mass (PAM) OFR was designed for studies on the formation and oxidation of secondary organic aerosols (SOA), allowing for a wide range of oxidant exposures and short experiment duration with reduced wall loss effects. Although fundamental photochemical and kinetic data applicable to these reactors are available, the radical chemistry and its sensitivities have not been modeled in detail before; thus, experimental verification of our understanding of this chemistry has been very limited. To better understand the chemistry in the OFR185, a model has been developed to simulate the formation, recycling, and destruction of radicals and to allow the quantification of OH exposure (OHexp) in the reactor and its sensitivities. The model outputs of OHexp were evaluated against laboratory calibration experiments by estimating OHexp from trace gas removal and were shown to agree within a factor of 2. A sensitivity study was performed to characterize the dependence of the OHexp, HO2/OH ratio, and O3 and H2O2 output concentrations on reactor parameters. OHexp is strongly affected by the UV photon flux, absolute humidity, reactor residence time, and the OH reactivity (OHR) of the sampled air, and more weakly by pressure and temperature. OHexp can be strongly suppressed by high OHR, especially under low UV light conditions. A OHexp estimation equation as a function of easily measurable quantities was shown to reproduce model results within 10% (average absolute value of the relative errors) over the whole operating range of the reactor. OHexp from the estimation equation was compared with measurements in several field campaigns and shows agreement within a factor of 3. The improved understanding of the OFR185 and

Photochemical Reactions of Particulate Organic Matter: Deciphering the Role of Direct and Indirect Processes

Science.gov (United States)

Carrasquillo, A. J.; Gelfond, C. E.; Kocar, B. D.

2016-12-01

Photochemical reactions of natural organic matter (NOM) represent potentially important pathways for biologically recalcitrant material to be chemically altered in aquatic systems. Irradiation can alter the physical state of organic matter by facilitating the cycling between the particulate (POM) and dissolved (DOM) pools, however, a molecular level understanding of this chemically dynamic system is currently lacking. Photochemical reactions of a target molecule proceed by the direct absorption of a photon, or through reaction with a second photolytically generated species (i.e. the hydroxyl radical, singlet oxygen, excited triplet state NOM, hydrogen peroxide, etc.). Here, we isolate the major direct and indirect photochemical reactions of a lignocellulose-rich POM material (Phragmites australis) to determine their relative importance in changing the the chemical structure of the parent POM, and in the production of DOM. We measured POM molecular structure using a combination of NMR and FTIR for bulk analyses and scanning transmission x-ray microscopy (STXM) for spatially resolved chemistry, while the chemical composition of photo-produced DOM was measured using ultra-high resolution mass spectrometry. Results are discussed in the context of the differences in chemical composition of both NOM pools resulting from the isolated photochemical pathways. All treatments result in an increase in DOM with reaction time, indicating that the larger POM matrix is likely fragmenting into smaller more soluble species. Spectroscopic measurements, on the other hand, point to functionalization reactions which increase the abundance of alcohol, acid, and carbonyl moieties in both carbon pools. This unique dataset provides new insight into how photochemical reactions alter the chemical composition of NOM while highlighting the relative importance of indirect pathways.

Ammonia removal from leachate by photochemical process using H2O2

Directory of Open Access Journals (Sweden)

Giovani Archanjo Brota

2010-08-01

Full Text Available In this work, it was studied the optimization of the photochemical process using H2O2/UV in order to reduce the concentration of ammonia in leachate. It was used landfills leachate previously treated in the development of studies. A photochemical reactor with the capacity of 1.7 liters equipped with refrigeration system and recirculation of leachate was employed in the research. The influence of temperature, the light bulb power, the concentration of H2O2 and treatment time were tested during the study. A removal of 97% of ammonia was observed at 90 min.

Photochemical Aryl Radical Cyclizations to Give (E-3-Ylideneoxindoles

Directory of Open Access Journals (Sweden)

Michael Gurry

2014-09-01

Full Text Available (E-3-Ylideneoxindoles are prepared in methanol in reasonable to good yields, as adducts of photochemical 5-exo-trig of aryl radicals, in contrast to previously reported analogous radical cyclizations initiated by tris(trimethylsilylsilane and azo-initiators that gave reduced oxindole adducts.

Laser induced photochemical and photophysical processes in fuel reprocessing: present scenario and future prospects

International Nuclear Information System (INIS)

Bhowmick, G.K.; Sarkar, S.K.; Ramanujam, A.

2001-01-01

State-of-art lasers can meet the very stringent requirements of nuclear technology and hence find application in varied areas of nuclear fuel cycle. Here, we discuss two specific applications in nuclear fuel reprocessing namely (a) add-on photochemical modifications of PUREX process where photochemical reactors replace the chemical reactors, and (b) fast, matrix independent sensitive laser analytical techniques. The photochemical modifications based on laser induced valency adjustment offers efficient separation, easy maintenance and over all reduction in the volume of radioactive waste. The analytical technique of time resolved laser induced fluorescence (TRLIF) has several attractive features like excellent sensitivity, element selective, and capability of on line remote process monitoring. For optically opaque solutions, optical excitation is detected by its conversion into thermal energy by non-radiative relaxation processes using the photo-thermal spectroscopic techniques. (author)

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.

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

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.

Gas-phase Precursors to Anthropogenic SOA: Using the MCM to Probe Detailed Observations of Aromatic Photo-oxidation

Science.gov (United States)

Rickard, A. R.; Wyche, K. P.; Metzger, A.; Monks, P. S.; Ellis, A. M.; Baltensperger, U.; Pilling, M. J.; Jenkin, M. E.

2008-12-01

The formation of photochemical ozone and particulate matter are major priorities in the determination of European air quality policies. Predictions of the future state of the atmosphere and the development of appropriate mitigation strategies rely on models, which necessarily incorporate chemistry. The Master Chemical Mechanism (MCM, http://mcm.leeds.ac.uk/MCM) is a near-explicit chemical mechanism originally conceived to model ozone formation in Europe but now also employed as a benchmark mechanism in a wide variety of applications where chemical detail is required. The MCM currently describes the detailed gas- phase tropospheric degradation of a 135 primary emitted volatile organic compounds (VOCs) leading to a mechanism containing ca. 5900 species and 13500 reactions. In order that the MCM continues to be a state-of-the-art resource for the atmospheric science community it resides under a constant regime of evaluation, development and improvement. Individual VOC photochemical mechanisms are evaluated using data obtained, under a variety of atmospheric conditions, from highly instrumented smog chambers. Smog chamber experiments are crucial, not only for mechanism evaluation, but also for mechanism development. Findings obtained from combined model and chamber studies can additionally provide key insight for guiding the directions of future laboratory experiments. Recently, the MCM was updated to MCMv3.1 in order to take into account recent advancements in the understanding of aromatic photo-oxidation, an important class of anthropogenic VOCs. As well as constituting precursors to secondary organic aerosol (SOA), aromatics generally have high photochemical ozone creation potentials (POCPs) and hence contribute significantly towards tropospheric ozone formation. In the work presented, a detailed gas-phase photochemical chamber box model, incorporating the MCMv3.1 degradation mechanism for 1,3,5-trimethylbenzene (TMB), has been used to simulate data measured during

PHOTOCHEMICAL AIR POLLUTION IN THE NORTH OF PORTUGAL: A HIGH TROPOSHERIC OZONE EPISODE

Science.gov (United States)

Monteiro, A.; Carvalho, A.; Tchepel, O.; Ferreira, J.; Martins, H.; Miranda, A.; Borrego, C.; Saavedra, S.; Rodríguez, A.; Souto, J. A.

2009-12-01

Very high concentrations of ozone are continuously measured at the monitoring station at Lamas d’Olo, located at the North of Portugal,. A particular high photochemical episode occurred between 11 and 13 of July 2005, registering ozone hourly maximum values above 350 µg.m-3. This ozone-rich episode is investigated in this paper, in order to identify its origin and formation. Besides the analysis of both meteorological and air quality monitoring datasets, a numerical modelling approach, based on MM5-CAMx system, was used to simulate the dispersion and transport (horizontal and vertical) of the photochemical pollutants and its precursors. A cross spectrum analysis of the meteorological and air quality time series was performed, in the frequency domain, to establish the relationships between ozone data measured at Lamas d’Olo with air quality data from neighbourhood stations and meteorological parameters. Results point out different behaviour/contribution between the analysed sites. Moreover, different contributions of the u and v wind component on the ozone concentration fluctuations were found suggesting the presence a mountain breeze circulation and a north synoptic transport. The preliminary modelling results pointed out that the vertical transport of pollutants are responsible for the measured high concentrations, combined with particular meteorological conditions, related to the planetary boundary layer (PBL) development. The pollutants transported and existent at high vertical levels are captured/trapped when the PBL height reaches its daily maximum, and extremely high ozone ground level concentrations are consequently measured.

Complex catalysts from self-repairing ensembles to highly reactive air-based oxidation systems

Science.gov (United States)

Craig L. Hill; Laurent Delannoy; Dean C. Duncan; Ira A. Weinstock; Roman F. Renneke; Richard S. Reiner; Rajai H. Atalla; Jong Woo Han; Daniel A. Hillesheim; Rui Cao; Travis M. Anderson; Nelya M. Okun; Djamaladdin G. Musaev; Yurii V. Geletii

2007-01-01

Progress in four interrelated catalysis research efforts in our laboratory are summarized: (1) catalytic photochemical functionalization of unactivated CeH bonds by polyoxometalates (POMs); (2) self-repairing catalysts; (3) catalysts for air-based oxidations under ambient conditions; and (4) terminal oxo complexes of the late-transition metal elements and their...

High formation of secondary organic aerosol from the photo-oxidation of toluene

Directory of Open Access Journals (Sweden)

L. Hildebrandt

2009-05-01

Full Text Available Toluene and other aromatics have long been viewed as the dominant anthropogenic secondary organic aerosol (SOA precursors, but the SOA mass yields from toluene reported in previous studies vary widely. Experiments conducted in the Carnegie Mellon University environmental chamber to study SOA formation from the photo-oxidation of toluene show significantly larger SOA production than parameterizations employed in current air-quality models. Aerosol mass yields depend on experimental conditions: yields are higher under higher UV intensity, under low-NO_x conditions and at lower temperatures. The extent of oxidation of the aerosol also varies with experimental conditions, consistent with ongoing, progressive photochemical aging of the toluene SOA. Measurements using a thermodenuder system suggest that the aerosol formed under high- and low-NO_x conditions is semi-volatile. These results suggest that SOA formation from toluene depends strongly on ambient conditions. An approximate parameterization is proposed for use in air-quality models until a more thorough treatment accounting for the dynamic nature of this system becomes available.

Highly uniform resistive switching properties of amorphous InGaZnO thin films prepared by a low temperature photochemical solution deposition method.

Science.gov (United States)

Hu, Wei; Zou, Lilan; Chen, Xinman; Qin, Ni; Li, Shuwei; Bao, Dinghua

2014-04-09

We report on highly uniform resistive switching properties of amorphous InGaZnO (a-IGZO) thin films. The thin films were fabricated by a low temperature photochemical solution deposition method, a simple process combining chemical solution deposition and ultraviolet (UV) irradiation treatment. The a-IGZO based resistive switching devices exhibit long retention, good endurance, uniform switching voltages, and stable distribution of low and high resistance states. Electrical conduction mechanisms were also discussed on the basis of the current-voltage characteristics and their temperature dependence. The excellent resistive switching properties can be attributed to the reduction of organic- and hydrogen-based elements and the formation of enhanced metal-oxide bonding and metal-hydroxide bonding networks by hydrogen bonding due to UV irradiation, based on Fourier-transform-infrared spectroscopy, X-ray photoelectron spectroscopy, and Field emission scanning electron microscopy analysis of the thin films. This study suggests that a-IGZO thin films have potential applications in resistive random access memory and the low temperature photochemical solution deposition method can find the opportunity for further achieving system on panel applications if the a-IGZO resistive switching cells were integrated with a-IGZO thin film transistors.

The photochemical reaction of hydrocarbons under extreme thermobaric conditions

Science.gov (United States)

Serovaiskii, Aleksandr; Kolesnikov, Anton; Mukhina, Elena; Kutcherov, Vladimir

2017-10-01

The photochemical reaction of hydrocarbons was found to play an important role in the experiments with the synthetic petroleum conducted in Diamond Anvil Cell (DAC). Raman spectroscopy with a green laser (514.5 nm) was used for in situ sample analysis. This photochemical effect was investigated in the pressure range of 0.7-5 GPa, in the temperature interval from the ambient conditions to 450°C. The power of laser used in these experiment series was from 0.05 W to 0.6 W. The chemical transformation was observed when the necessary threshold pressure (~2.8 GPa) was reached. This transformation correlated with the luminescence appearance on the Raman spectra and a black opaque spot in the sample was observed in the place where the laser focus was forwarded. The exposure time and laser power (at least in the 0.1-0.5 W range) did not play a role in the 0.1-0.5 GPa range.

Formaldehyde production from isoprene oxidation across NOx regimes

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2016-03-01

Full Text Available The chemical link between isoprene and formaldehyde (HCHO is a strong, nonlinear function of NOx (i.e., NO + NO2. This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons. Over the range of observed NOx values (roughly 0.1–2 ppbv, the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1, while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv. We apply the same method to evaluate the performance of both a global chemical transport model (AM3 and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.

Tracking Oxidation During Transport of Trace Gases in Air from the Northern to Southern Hemisphere

Science.gov (United States)

Montzka, S. A.; Moore, F. L.; Atlas, E. L.; Parrish, D. D.; Miller, B. R.; Sweeney, C.; McKain, K.; Hall, B. D.; Siso, C.; Crotwell, M.; Hintsa, E. J.; Elkins, J. W.; Blake, D. R.; Barletta, B.; Meinardi, S.; Claxton, T.; Hossaini, R.

2017-12-01

Trace gas mole fractions contain the imprint of recent influences on an air mass such as sources, transport, and oxidation. Covariations among the many gases measured from flasks during ATom and HIPPO, and from the ongoing NOAA cooperative air sampling program enable recent influences to be identified from a wide range of sources including industrial activity, biomass burning, emissions from wetlands, and uptake by terrestrial ecosystems. In this work we explore the evolution of trace gas concentrations owing to atmospheric oxidation as air masses pass through the tropics, the atmospheric region with the highest concentrations of the hydroxyl radical. Variations in C2-C5 hydrocarbon concentrations downwind of source regions provide a measure of photochemical ageing in an air mass since emission, but they become less useful when tracking photochemical ageing as air is transported from the NH into the SH owing to their low mixing ratios, lifetimes that are very short relative to transport times, non-industrial sources in the tropics (e.g., biomass burning), and southern hemispheric sources. Instead, we consider a range of trace gases and trace gas pairs that provide a measure of photochemical processing as air transits the tropics. To be useful in this analysis, these trace gases would have lifetimes comparable to interhemispheric transport times, emissions arising from only the NH at constant relative magnitudes, and concentrations sufficient to allow precise and accurate measurements in both hemispheres. Some anthropogenically-emitted chlorinated hydrocarbons meet these requirements and have been measured during ATom, HIPPO, and from NOAA's ongoing surface sampling efforts. Consideration of these results and their implications for tracking photochemical processing in air as it is transported across the tropics will be presented.

Measurements and Modelling of Reactive Iodine Oxides in the Coastal MBL

Science.gov (United States)

Najera, J. J.; Bloss, W. J.

2012-04-01

The release of iodine compounds into the marine atmosphere can affect a number of aspects of atmospheric composition: Iodine species can participate in catalytic ozone destruction cycles, which may be augmented by bromine species; reactions of iodine compounds can perturb the OH:HO2 and NO:NO2 ratios, heterogeneous loss of reservoir compounds such as HOI and INO3 can lead to removal of HOx and NOx, and higher iodine oxides can contribute to the formation and/or growth of aerosol particles. In this work, we focus upon understanding the effect of the spatial distribution of iodine emissions upon local HOx and NOx levels in the immediate vicinity of a coastal sites, using new observations to re-evaluate previous field campaign data. We present an analysis of results from a new instruments which measures point inorganic iodine species concentrations. The technique of resonance fluorescence (RF) is employed for the detection of iodine atoms, and the total photolabile iodine content. Measurements made at Mace Head, Ireland during July-August 2007 and May 2011 are presented. A detailed 1-dimensional photochemical box model is employed in a lagrangian sense to simulate the evolving chemical composition of an air column advected across the coastal margin. The model is compared with the observed iodine species, and then used to explore the transient response of the NOx and HOx families at the Mace Head site to heterogeneous iodine emissions: The transit time between the intertidal iodine emission zone and the shoreline site where previous measurements of HOx, NOx etc. have been made is insufficient for steady-state to become established, although this assumption has been used in earlier model studies of such data. Finally, we consider the limitations in our ability to quantify the impacts of iodine chemistry, which arise from uncertainties in the iodine kinetics and photochemistry - for example, what is the atmospheric lifetime of inorganic iodine ? - and explore their

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

1998-12-31

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.

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.

Photochemical Reactivity of Dissolved Organic Matter in Boreal Lakes

Science.gov (United States)

Gu, Y.; Vuorio, K.; Tiirola, M.; Perämäki, S.; Vahatalo, A.

2016-12-01

Boreal lakes are rich in dissolved organic matter (DOM) that terrestrially derived from forest soil and wetland, yet little is known about potential for photochemical transformation of aquatic DOM in boreal lakes. Transformation of chromophoric dissolved organic matter (CDOM) can decrease water color and enhance microbial mineralization, affecting primary production and respiration, which both affect the CO2 balance of the lakes. We used laboratory solar radiation exposure experiments with lake water samples collected from 54 lakes located in Finland and Sweden, representing different catchment composition and watershed location to assess photochemical reactivity of DOM. The pH of water samples ranged from 5.4 to 8.3, and the concentrations of dissolved iron (Fe) were between samples received simulated solar radiation corresponding to a daily dose of sunlight, and photomineralization of dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) was measured for determination of spectral apparent quantum yields (AQY). During irradiation, photobleaching decreased the absorption coefficients of CDOM at 330 nm between 4.9 and 79 m-1 by 0.5 to 11 m-1. Irradiation generated DIC from 2.8 to 79 μmol C L-1. The AQY at 330 nm ranged between 31 and 273 ×10-6 mol C mol photons-1 h-1, which was correlated positively with concentration of dissolved Fe, and negatively with pH. Further statistical analyze indicated that the interaction between pH and Fe may explain much of the photochemical reactivity of DOM in the examined lakes, and land cover concerns main catchment areas also can have impact on the photoreaction process. This study may suggest how environmental conditions regulate DOM photomineralization in boreal lakes.

A model assessment of the ability of lake water in Terra Nova Bay, Antarctica, to induce the photochemical degradation of emerging contaminants.

Science.gov (United States)

Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2016-11-01

The shallow lakes located in Terra Nova Bay, Antarctica, are free from ice for only up to a couple of months (mid December to early/mid February) during the austral summer. In the rest of the year, the ice cover shields the light and inhibits the photochemical processes in the water columns. Previous work has shown that chromophoric dissolved organic matter (CDOM) in these lakes is very reactive photochemically. A model assessment is here provided of lake-water photoreactivity in field conditions, based on experimental data of lake water absorption spectra, chemistry and photochemistry obtained previously, taking into account the water depth and the irradiation conditions of the Antarctic summer. The chosen sample contaminants were the solar filter benzophenone-3 and the antimicrobial agent triclosan, which have very well known photoreactivity and have been found in a variety of environmental matrices in the Antarctic continent. The two compounds would have a half-life time of just a few days or less in the lake water during the Antarctic summertime, largely due to reaction with CDOM triplet states ((3)CDOM*). In general, pollutants that occur in the ice and could be released to lake water upon ice melting (around or soon after the December solstice) would be quickly photodegraded if they undergo fast reaction with (3)CDOM*. With some compounds, the important (3)CDOM* reactions might favour the production of harmful secondary pollutants, such as 2,8-dichlorodibenzodioxin from the basic (anionic) form of triclosan. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

-olefins selectively. This process is made catalytic by the introduction of O2. Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu +. Longer-chain acids also yield alpha olefins as exclusive products. In the absence of continued purging with O2 to aid removal of olefin, Cu+(olefin) complexes accumulate and catalytic activity slows dramatically due to depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids. Free Oxygen Atom in Solution from 4-Benzoylpyridine N-Oxide Excited Singlet. Photolysis of 4-benzoylpyridine N-oxide (BPyO) in the presence of quenchers of the triplet excited state produces up to 41% O(3P) (as determined by generation of ethylene upon scavenging with cyclopentene). In the absence of 3BPyO* quenchers a maximum of 13% O(3P) relative to consumed BPyO is obtained. The remaining products are hydroxylated-4-benzoylpyridine and 4-benzoylpyridine. Additionally, the rate of BPyO consumption (as determined by UV-vis) decreases in the presence of 3BPyO* quenching agents. Second order rate constants for 3BPyO* quenching were determined. A mechanism for photochemical deoxygenation of BPyO is proposed on the basis of kinetic data and product distribution under various conditions. Additionally, comparisons are made between the observed intermediates and similar triplet excited states and radical anions.

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.

Effect of latitude on the potential for formation of photochemical smog

Energy Technology Data Exchange (ETDEWEB)

Neiboer, H [Central Laboratorium TNO, Delft, Netherlands; Carter, W P.L.; Lloyd, A C; Pitts, Jr, J N

1976-01-01

The effect of latitude on the potential for the formation of photochemical smog has been assessed. Calculations suggest that at the summer solstice, the integrated sunlight intensity at Rotterdam or Fairbanks (Alaska) is very similar to that in Los Angeles. Computations carried out, assuming the same pollutant emission inventory for the three locations, showed that ozone and PAN dosages depend more on the integrated light intensity than on the nature of the light intensity distribution with time. Therefore, if factors such as emissions and meteorological conditions are equal, the potential for significant photochemical smog formation during the summer months is similar for Los Angeles (34/sup 0/N) and northern cities such as Rotterdam (52/sup 0/N) and Nome or Fairbanks, Alaska (65/sup 0/N).

Heterogeneous OH oxidation of motor oil particles causes selective depletion of branched and less cyclic hydrocarbons.

Science.gov (United States)

Isaacman, Gabriel; Chan, Arthur W H; Nah, Theodora; Worton, David R; Ruehl, Chris R; Wilson, Kevin R; Goldstein, Allen H

2012-10-02

Motor oil serves as a useful model system for atmospheric oxidation of hydrocarbon mixtures typical of anthropogenic atmospheric particulate matter, but its complexity often prevents comprehensive chemical speciation. In this work we fully characterize this formerly "unresolved complex mixture" at the molecular level using recently developed soft ionization gas chromatography techniques. Nucleated motor oil particles are oxidized in a flow tube reactor to investigate the relative reaction rates of observed hydrocarbon classes: alkanes, cycloalkanes, bicycloalkanes, tricycloalkanes, and steranes. Oxidation of hydrocarbons in a complex aerosol is found to be efficient, with approximately three-quarters (0.72 ± 0.06) of OH collisions yielding a reaction. Reaction rates of individual hydrocarbons are structurally dependent: compared to normal alkanes, reaction rates increased by 20-50% with branching, while rates decreased ∼20% per nonaromatic ring present. These differences in rates are expected to alter particle composition as a function of oxidation, with depletion of branched and enrichment of cyclic hydrocarbons. Due to this expected shift toward ring-opening reactions heterogeneous oxidation of the unreacted hydrocarbon mixture is less likely to proceed through fragmentation pathways in more oxidized particles. Based on the observed oxidation-induced changes in composition, isomer-resolved analysis has potential utility for determining the photochemical age of atmospheric particulate matter with respect to heterogeneous oxidation.

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.

Photochemical and other air pollutions in the Netherlands

Energy Technology Data Exchange (ETDEWEB)

Floor, H.

1975-01-01

Together with the State Institute of Public Health and the Royal Dutch Meteorological Institute, the Institute of Phytopathological Research continued investigations on incidence of air pollution in the country. The main purpose is to measure the effects of air pollution on indicator plants and to detect over the years which components separately or perhaps together damage indicator plants. In 1974, the network of experimental fields in the Netherlands was completed. From April until October, 29 fields were inspected weekly for typical symptoms of air pollution. Just as in the preceding year O3 caused most injury of the photochemical air pollutants, as shown by Spinacia oleracea and Nicotiana tabacum. Other photochemical air pollutants like PAN, and the pollutants SO2, NO/sub x/ and ethylene caused little injury to the indicator plants Urtica urens, Poa annua, Medicago sativa, Petunia nyctaginiflora and Solanum tuberosum. Symptoms of damage on Tulipa gesneriana, Gladiolus gandavensis and Freesia refracta indicated air pollution by HF in all experimental fields, but especially in the south of the country. The F determination in the air by means of the limed paper method established the results with the indicator plants.

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 ...... based on flexible barrier substrates exhibit increased stability and are indeed viable in devices such as shading elements, light management systems, displays with low switching speed requirements and signage. © 2013 The Royal Society of Chemistry....

Cherenkov light as a source of photochemical reactions in irradiated solutions of nitrile of malachite green

Energy Technology Data Exchange (ETDEWEB)

Stuglik, Z; Grodkowski, J

1986-10-01

Experimental data on photochemical activity of Cherenkov light are presented. Malachite green leucocyanide was used to detect the photochemical effects. The G value of Cherenkov light from the region 200-330 nm (number of quanta formed per 100 eV absorbed energy of ionizing radiation) in ethanol was estimated to be in the range of 0.0027-0.049. 14 references.

Cherenkov light as a source of photochemical reactions in irradiated solutions of nitrile of malachite green

International Nuclear Information System (INIS)

Stuglik, Z.; Grodkowski, J.

1986-01-01

Experimental data on photochemical activity of Cherenkov light are presented. Malachite green leucocyanide was used to detect the photochemical effects. The G value of Cherenkov light from the region 200-330 nm (number of quanta formed per 100 eV absorbed energy of ionizing radiation) in ethanol was estimated to be in the range of 0.0027-0.049. (author)

40 CFR 52.430 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... 40 Protection of Environment 3 2010-07-01 2010-07-01 false Photochemical Assessment Monitoring Stations (PAMS) Program. 52.430 Section 52.430 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Natural Resources & Environmental Control submitted a plan for the establishment and implementation of a...

40 CFR 52.480 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... of Columbia's Department of Consumer and Regulatory Affairs submitted a plan for the establishment... 40 Protection of Environment 3 2010-07-01 2010-07-01 false Photochemical Assessment Monitoring Stations (PAMS) Program. 52.480 Section 52.480 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...

40 CFR 52.1080 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.1080 Section 52.1080 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... § 52.1080 Photochemical Assessment Monitoring Stations (PAMS) Program. On March 24, 1994 Maryland's... Assessment Monitoring Stations (PAMS) Program as a state implementation plan (SIP) revision, as required by...

Impact of VOC Composition and Reactor Conditions on the Aging of Biomass Cookstove Emissions in an Oxidation Flow Reactor

Science.gov (United States)

Oxidation flow reactor (OFR) experiments in our lab have explored secondary organic aerosol (SOA) production during photochemical aging of emissions from cookstoves used by billions in developing countries. Previous experiments, conducted with red oak fuel under conditions of hig...

Photochemical technique for reduction of uranium and subsequently plutonium in the Purex process

International Nuclear Information System (INIS)

Goldstein, M.; Barker, J.J.; Gangwer, T.

1976-09-01

A photochemical modification of the Purex process is described in which a purified side stream of UO 2 ++ ion is reduced to U +4 outside the radioactive area of the reprocessing plant. The U +4 is then cycled back to step 2 of the Purex process to reduce the plutonium and effect separation within the partitioning column. This process is shown to be very energy efficient and compatible with existing conventional lamp technology. Preliminary cost estimates of the energy requirements for photon production are essentially negligible. Conceptual systems and photochemical reactor designs are presented. Potential benefits of this system are discussed

Influence of photochemical transformations upon optic-spectral characteristics of iodine cadmium crystals with copper dopant

International Nuclear Information System (INIS)

Novosad, S.S.

2000-01-01

The influence of photochemical transformations upon absorption. X-ray, photo- and thermostimulated luminescence of crystals CdI 2 :CuI, CdI 2 :CuI and CdI 2 :CuO grown by Stockbarger - Czochralski method has been studied. The photochemical reactions in crystals of iodine cadmium with the dopant of copper leads to reducing the intensity of X-ray, photo- and thermostimulated luminescence, the appearance of new luminescent centers is not observed

Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VIII, halogen species evaluation for atmospheric chemistry

International Nuclear Information System (INIS)

Atkinson, R.; Baulch, D.L.; Cox, R.A.; Hampson, R.F. Jr.; Kerr, J.A.; Rossi, M.J.; Troe, J.

2000-01-01

This paper updates and extends part of the previous data base of critical evaluations of the kinetics and photochemistry of gas-phase chemical reactions of neutral species involved in atmospheric chemistry [J. Phys. Chem. Ref. Data 9, 295 (1980); 11, 327 (1982); 13, 1259 (1984); 18, 881 (1989); 21, 1125 (1992); 26, 521 (1997); 26, 1329 (1997); 28, 191 (1999)]. The present evaluation is limited to the inorganic halogen family of atmospherically important reactions. The work has been carried out by the authors under the auspices of the IUPAC Subcommittee on Gas Phase Kinetic Data Evaluation for Atmospheric Chemistry. Data sheets have been prepared for 102 thermal and photochemical reactions, containing summaries of the available experimental data with notes giving details of the experimental procedures. For each thermal reaction, a preferred value of the rate coefficient at 298 K is given together with a temperature dependence 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. For each photochemical reaction the data sheets list the preferred values of the photoabsorption cross sections and the quantum yields of the photochemical reactions together with comments on how they were selected. The data sheets are intended to provide the basic physical chemical data needed as input for calculations that model atmospheric chemistry. A table summarizing the preferred rate data is provided, together with an appendix listing the available values of enthalpies of formation of the reactant and product species

Controlled nitric oxide production via O(1D) + N2O reactions for use in oxidation flow reactor studies

Science.gov (United States)

Lambe, Andrew; Massoli, Paola; Zhang, Xuan; Canagaratna, Manjula; Nowak, John; Daube, Conner; Yan, Chao; Nie, Wei; Onasch, Timothy; Jayne, John; Kolb, Charles; Davidovits, Paul; Worsnop, Douglas; Brune, William

2017-06-01

Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH) radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3) is photolyzed at 254 nm to produce O(1D) radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA) formation pathways. Simple addition of nitric oxide (NO) results in fast conversion of NOx (NO + NO2) to nitric acid (HNO3), making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2) radicals as a sink for organic peroxy (RO2) radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D) + N2O → 2NO, followed by the reaction NO + O3 → NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D) + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) measurements with nitrate (NO3-) reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

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.

Reductive and oxidative degradation of iopamidol, iodinated X-ray contrast media, by Fe(III)-oxalate under UV and visible light treatment.

Science.gov (United States)

Zhao, Cen; Arroyo-Mora, Luis E; DeCaprio, Anthony P; Sharma, Virender K; Dionysiou, Dionysios D; O'Shea, Kevin E

2014-12-15

Iopamidol, widely employed as iodinated X-ray contrast media (ICM), is readily degraded in a Fe(III)-oxalate photochemical system under UV (350 nm) and visible light (450 nm) irradiation. The degradation is nicely modeled by pseudo first order kinetics. The rates of hydroxyl radical (OH) production for Fe(III)-oxalate/H2O2/UV (350 nm) and Fe(III)-oxalate/H2O2/visible (450 nm) systems were 1.19 ± 0.12 and 0.30 ± 0.01 μM/min, respectively. The steady-state concentration of hydroxyl radical (OH) for the Fe(III)-oxalate/H2O2/UV (350 nm) conditions was 10.88 ± 1.13 × 10(-14) M and 2.7 ± 0.1 × 10(-14) M for the Fe(III)-oxalate/H2O2/visible (450 nm). The rate of superoxide anion radical (O2(-)) production under Fe(III)-oxalate/H2O2/UV (350 nm) was 0.19 ± 0.02 μM/min with a steady-state concentration of 5.43 ± 0.473 × 10(-10) M. Detailed product studies using liquid chromatography coupled to Q-TOF/MS demonstrate both reduction (multiple dehalogenations) and oxidation (aromatic ring and side chains) contribute to the degradation pathways. The reduction processes appear to be initiated by the carbon dioxide anion radical (CO2(-)) while oxidation processes are consistent with OH initiated reaction pathways. Unlike most advanced oxidation processes the Fe(III)-oxalate/H2O2/photochemical system can initiate to both reductive and oxidative degradation processes. The observed reductive dehalogenation is an attractive remediation strategy for halogenated organic compounds as the process can dramatically reduce the formation of the problematic disinfection by-products often associated with oxidative treatment processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

The study on laser photochemical process of Diazonaphthoquinon-Cresol system

International Nuclear Information System (INIS)

Wei Jie; Huang Yu Li; Wang Wenke

1999-01-01

The kinetic process of laser photochemical reaction of diazonaphthoquinon-cresol system was studied by using laser spectrophotofluorimetry and laser induced fluorescence attenuation method. The nonlinear relationship between photodecomposition rate of the sensitizer and laser power, exposure time and concentration of solutions was discussed in detail

Photochemical reduction of uranyl ion by acetonitrile and propionitrile

International Nuclear Information System (INIS)

Brar, A.S.; Chander, R.; Sandhu, S.S.

1979-01-01

The photochemical reduction of uranyl ion by acetonitrile, propionitrile, benzonitrile, phenylacetonitrile, cyanoacetic acid and malononitrile in aqueous or aq. acetone medium using radiations >= 400 nm from a medium pressure mercury vapour lamp has been investigated. Except acetonitrile and propionitrile all other nitriles fail to bring about the reduction of uranyl ion. The reduction with aceto- and propionitriles has been found to obey pseudo-first order kinetics. The magnitude of rate of reduction with propionitrile is higher than that with acetonitrile. The pseudo-first order rate constants and quenching constant have been calculated from the kinetic data. It has been found that physical and chemical quenching compete with each other. The plot of reciprocal of quantum yield versus reciprocal (nitrile) is linear with a small intercept on the ordinate axis. Absorption spectra of uranyl ion in pure water, in the presence of acid and in the presence of acid+nitrile reveal that there is no ground state interaction between uranyl ion and the nitrile. A mechanism of photochemical reduction of uranyl ion based on α-hydrogen abstraction from the nitrile has been proposed. (auth.)

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)

A physiologically based kinetic model for bacterial sulfide oxidation.

Science.gov (United States)

Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

2013-02-01

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 concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Seasonal variations of C1-C4 alkyl nitrates at a coastal site in Hong Kong: Influence of photochemical formation and oceanic emissions.

Science.gov (United States)

Song, Junwei; Zhang, Yingyi; Huang, Yu; Ho, Kin Fai; Yuan, Zibing; Ling, Zhenhao; Niu, Xiaojun; Gao, Yuan; Cui, Long; Louie, Peter K K; Lee, Shun-Cheng; Lai, Senchao

2018-03-01

Five C 1 -C 4 alkyl nitrates (RONO 2 ) were measured at a coastal site in Hong Kong in four selected months of 2011 and 2012. The total mixing ratios of C 1 -C 4 RONO 2 (Σ 5 RONO 2 ) ranged from 15.4 to 143.7 pptv with an average of 65.9 ± 33.0 pptv. C 3 -C 4 RONO 2 (2-butyl nitrate and 2-propyl nitrate) were the most abundant RONO 2 during the entire sampling period. The mixing ratios of C 3 -C 4 RONO 2 were higher in winter than those in summer, while the ones of methyl nitrate (MeONO 2 ) were higher in summer than those in winter. Source analysis suggests that C 2 -C 4 RONO 2 were mainly derived from photochemical formation along with biomass burning (58.3-71.6%), while ocean was a major contributor to MeONO 2 (53.8%) during the whole sampling period. The photochemical evolution of C 2 -C 4 RONO 2 was investigated, and found to be dominantly produced by the parent hydrocarbon oxidation. The notable enrichment of MeONO 2 over C 3 -C 4 RONO 2 was observed in a summer episode when the air masses originating from the South China Sea (SCS) and MeONO 2 was dominantly derived from oceanic emissions. In order to improve the accuracy of ozone (O 3 ) prediction in coastal environment, the relative contribution of RONO 2 from oceanic emissions versus photochemical formation and their coupling effects on O 3 production should be taken into account in future studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabrication of self-written waveguide in photosensitive polyimide resin by controlling photochemical reaction of photosensitizer

International Nuclear Information System (INIS)

Yamashita, K.; Kuro, T.; Oe, K.; Mune, K.; Tagawa, K.; Naitou, R.; Mochizuki, A.

2004-01-01

We have investigated optical properties of photosensitive polyimide appropriating for long self-written waveguide fabrication. From systematic measurements of absorption properties, it was found that photochemical reaction of photosensitizer dissolved in the photosensitive polyimide resins relates to transparency after the exposure, which limits the length of the fabricated self-written waveguide. By controlling the photochemical reaction, in which the photosensitive polyimide resin has sufficient transparency during exposure, four times longer self-written waveguide core was fabricated

Kinetic analysis of photochemical sterilization of thermoduric bacterial spores in slurry of semiconductor catalyst particles with aeration. Handotai shokubai ryushi no tsuki kendakukei ni okeru tainetsusei saikin hoshi no hikari sakkin to sono sokudoronteki kaiseki

Energy Technology Data Exchange (ETDEWEB)

Tone, S; Taya, M; Kato, S; Horie, Y; Ashikaga, Y [Osaka Univ., Osaka (Japan). Faculty of Engineering and Science; Joo, Hyunkyu [Konkuk Univ., Seoul (Korea, Republic of)

1993-11-10

To study the utilization of the photochemical sterilization of thermoduric bacterial spores B. stearothermophilus with photocatalysis of TiO2 particles, light irradiation experiments are conducted under various operational conditions. TiO2 particles and dissolved oxygen resulting from aeration must coexist to accelerate the rate of spore sterilization under light irradiation of a high pressure mercury lamp. The sterilization rate increases with larger average light intensity in the reactor, and it is estimated that the dissolved oxygen contributes to the formation of oxidative radicals which become the attacking species. The maximal rate of spore sterilization is obtained under the condition of TiO2 concentration of 5[times]10[sup -2]kg[center dot]m[sup -3]. By combining a second-order rate equation, wherein the spores' death caused by the oxidative radicals formed by TiO2 photocatalysis is taken into consideration, and single-hit multitarget model, wherein the target damaged by the oxidizer in the spores is assumed, the sterilization velocity can be described well, and the effect of light intensity and the obtained rate parameters are correlated well. 13 refs., 7 figs., 3 tabs.

Contribution of atmospheric processes affecting the dynamics of air pollution in South-Western Europe during a typical summertime photochemical episode

Directory of Open Access Journals (Sweden)

M. Gonçalves

2009-02-01

Full Text Available The southern Mediterranean region frequently experiences critical levels of photochemical pollutants during summertime. In order to account for the contribution of different atmospheric processes during this type of episodes, the WRF-ARW/HERMES/CMAQ modelling system was applied with high resolution (1 km², 33 sigma vertical layers, 1 h to assess the different dynamics in a coastal environment and an inland-continental zone: the North-Eastern and Central Iberian Peninsula (NEIP and CIP, respectively. The former is characterized by a very complex terrain, while the latter behaves as a flat area, which clearly affects the pattern of local flows. A representative type of photochemical pollution episode (occurring over 78% of summer days which occurred during 17–18 June, 2004 is selected as the study period. The CMAQ Integrated Process Rate provides the hourly contributions of atmospheric processes to net O₃, NO_x and NMVOCs concentrations. The O₃ photochemical formation occurs mainly in downwind areas from the main NO_x emission sources during midday. At surface level it accounts for 50 to 75 μg m⁻³ h⁻¹. The urban areas and main roads, as main sources of NO_x emissions, act as O₃ sinks, quenching up to −200 μg m⁻³ per hour during the traffic circulation peaks. The O₃ concentration gradient generated, larger during daytime, increases the contribution of diffusion processes to ground-level O₃ (up to 200 μg m⁻³ h⁻¹ fluxes, mainly from upper vertical layers. The maximum positive contributions of gas-phase chemistry to O₃ occur in the coastal domain at high levels (around 500 to 1500 m a.g.l., while in the continental domain they take place in the whole atmospheric column under the PBL. The transport of ozone precursors by advective flows determines the location of the maximum O

The oxidation of PET track-etched membranes by hydrogen peroxide as an effective method to increase efficiency of UV-induced graft polymerization

OpenAIRE

Il'ya Korolkov; Abzal Taltenov; Anastassiya Mashentseva; Olgun Guven

2015-01-01

In this article, we report on functionalization of track-etched membrane based on poly(ethylene terephthalate) (PET TeMs) oxidized by advanced oxidation systems and by grafting of acrylic acid using photochemical initiation technique for the purpose of increasing functionality thus expanding its practical application. Among advanced oxidation processes (H2O2/UV) system had been chosen to introduce maximum concentration of carboxylic acid groups. Benzophenone (BP) photo-initiator was first im...

40 CFR 52.2035 - Photochemical Assessment Monitoring Stations (PAMS) Program.

Science.gov (United States)

2010-07-01

... Stations (PAMS) Program. 52.2035 Section 52.2035 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY...) Pennsylvania § 52.2035 Photochemical Assessment Monitoring Stations (PAMS) Program. On September 23, 1994... (PAMS) Program as a state implementation plan (SIP) revision, as required by section 182(c)(1) of the...

Oxidative degradation of lignin by photochemical and chemical radical generating systems

International Nuclear Information System (INIS)

Gold, M.H.; Kutsuki, H.; Morgan, M.A.

1983-01-01

Oxidation of specifically radiolabeled 14 C-lignins by UV/H 2 O 2 , Fenton's reagent, photosensitizing riboflavin, UV- and γ-irradiation was examined. In the presence of UV/H 2 O 2 , a hydroxyl radical (radicalOH) generating system, 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin were rapidly and extensively degraded as measured by gel filtration of the reaction products on Sephadex LH-20. This suggested that exposure to radicalOH leads to rapid, nonspecific lignin degradation. Rapid degradation of 14 C-methoxy, 2-[ 14 C-sidechain] and 14 C-ring labeled lignin also occurred in the presence of the radicalOH generating system, Fenton's reagent, confirming the primary role of radicalOH in these reactions. Photosensitizing riboflavin, also capable of effecting transformation of organic compounds via Type I hydrogen radical abstractions, caused extensive oxidative degradation of 14 C-methoxy labeled lignin and significant degradation of 2-[ 14 C-sidechain] and 14 C-ring labeled lignin. In addition, UV- and γ-irradiation caused slower but extensive degradation of the polymers, probably via radical type mechanisms. All of these results indicate that radicalOH as well as organic radical generating systems are effective agents for the purpose of degrading this heterogeneous, optically inactive and random biopolymer. (author)

Heparin Assisted Photochemical Synthesis of Gold Nanoparticles and Their Performance as SERS Substrates

Science.gov (United States)

Rodríguez-Torres, Maria del Pilar; Díaz-Torres, Luis Armando; Romero-Servin, Sergio

2014-01-01

Reactive and pharmaceutical-grade heparins were used as biologically compatible reducing and stabilizing agents to photochemically synthesize colloidal gold nanoparticles. Aggregates and anisotropic shapes were obtained photochemically under UV black-light lamp irradiation (λ = 366 nm). Heparin-functionalized gold nanoparticles were characterized by Scanning Electron Microscopy and UV-Vis spectroscopy. The negatively charged colloids were used for the Surface Enhanced Raman Spectroscopy (SERS) analysis of differently charged analytes (dyes). Measurements of pH were taken to inspect how the acidity of the medium affects the colloid-analyte interaction. SERS spectra were taken by mixing the dyes and the colloidal solutions without further functionalization or addition of any aggregating agent. PMID:25342319

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

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)

Enhanced Ga2O3-photocatalyzed and photochemical degradation of the Fipronil insecticide by UVC irradiation in mixed aqueous/organic media under an inert atmosphere.

Science.gov (United States)

Hidaka, Hisao; Tsukamoto, Tohru; Mitsutsuka, Yoshihiro; Oyama, Toshiyuki; Serpone, Nick

2015-05-01

Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent). After 3 h of UVC irradiation (50 vol% mixed media) defluorination with Ga2O3/N2 was ∼65% greater than in aqueous media, and ca. 80% greater than the direct photolysis of Fipronil under inert (N2) conditions; under air-equilibrated conditions both Ga2O3-photocatalyzed and photochemical defluorination were significantly lower than in aqueous media. Dechlorination of Fipronil was ∼160% (Ga2O3/N2) and 140% (photochemically, N2) greater than in aqueous media; under air-equilibrated conditions, both photocatalyzed and photochemical formation of Cl(-) ions in mixed media fell rather short relative to aqueous media. The photocatalyzed (Ga2O3/N2) and photochemical (N2) conversion of the sulfur group in Fipronil to SO4(2(-)) ions was ca. 20% and 30% greater, respectively, in mixed media, while under air-equilibrated conditions photocatalyzed desulfonation was nearly twofold less than in the aqueous phase; direct photolysis showed little variations in mixed media. Denitridation of the nitrogens in Fipronil occurred mostly through the formation of ammonia (as NH4(+)) under all conditions with negligible quantities of NO3(-); again mixed media

Consequences of thermo- and photo-oxidation on end-use properties of pure PE

International Nuclear Information System (INIS)

Tireau, Jonathan; Van Schoors, Laetitia; Benzarti, Karim; Colin, Xavier

2010-01-01

Thin films of polyethylene have been exposed to thermal and photochemical accelerated agings at different temperatures and different UV intensities. In both cases, mechanical tests performed on aged samples revealed a severe embrittlement of the PE material. However, a multi-scale analysis showed that i) under thermal oxidative conditions, such embrittlement mainly resulted from a reduction of molecular mobility of the amorphous phase due to annealing phenomena, while ii) it was rather associated to a competition between chain scission and cross-linking processes under photo-oxidative conditions. As regards the oxidation mechanisms, it was found that thermo-oxidation is clearly initiated by a bimolecular decomposition of hydroperoxides, while photo-oxidation seems rather initiated by the photolysis of ketones and hydroperoxides. Over a critical threshold of the hydroperoxide concentration, thermolysis of hydroperoxides seems to predominate and even to control the overall photo-oxidation kinetics.

Model for low temperature oxidation during long term interim storage

Energy Technology Data Exchange (ETDEWEB)

Desgranges, Clara; Bertrand, Nathalie; Gauvain, Danielle; Terlain, Anne [Service de la Corrosion et du Comportement des Materiaux dans leur Environnement, CEA/Saclay - 91191 Gif-sur-Yvette Cedex (France); Poquillon, Dominique; Monceau, Daniel [CIRIMAT UMR 5085, ENSIACET-INPT, 31077 Toulouse Cedex 4 (France)

2004-07-01

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)

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)

Synthesis of fluorescent metal nanoparticles in aqueous solution by photochemical reduction

KAUST Repository

Kshirsagar, Prakash; Sangaru, Shiv; Brunetti, Virgilio; Malvindi, Maria Ada Da; Pompa, Pier Paolo

2014-01-01

A facile green chemistry approach for the synthesis of sub-5 nm silver and gold nanoparticles is reported. The synthesis was achieved by a photochemical method using tyrosine as the photoreducing agent. The size of the gold and silver nanoparticles

Photochemical transformations accelerated in continuous-flow reactors : basic concepts and applications

NARCIS (Netherlands)

Su, Y.; Straathof, N.J.W.; Hessel, V.; Noel, T.

2014-01-01

Continuous-flow photochemistry is used increasingly by researchers in academia and industry to facilitate photochemical processes and their subsequent scale-up. However, without detailed knowledge concerning the engineering aspects of photochemistry, it can be quite challenging to develop a suitable

The possible effect of solar soft X rays on thermospheric nitric oxide

International Nuclear Information System (INIS)

Siskind, D.E.; Barth, C.A.; Cleary, D.D.

1990-01-01

A rocket measurement of thermospheric nitric oxide (NO) is used to evaluate the production of odd nitrogen by solar soft X rays (18-50 angstrom). The rocket observation was performed over White Sands Missile Range on November 9, 1981, at 1500 LT for solar maximum conditions (F10.7 = 233). The peak observed NO density was 6.3 x 10 7 cm -3 at 102 km. A photochemical model which included soft X rays was used for comparison with the data. The soft X rays create photoelectrons which lead to enhanced ionization of N 2 and thus increased odd nitrogen production. A good fit to the data was achieved using a soft X ray flux of 0.75 erg cm -2 s -1

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

Science.gov (United States)

Palm, Brett B.; Campuzano-Jost, Pedro; Ortega, Amber M.; Day, Douglas A.; Kaser, Lisa; Jud, Werner; Karl, Thomas; Hansel, Armin; Hunter, James F.; Cross, Eben S.; Kroll, Jesse H.; Peng, Zhe; Brune, William H.; Jimenez, Jose L.

2016-03-01

An oxidation flow reactor (OFR) is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen-Rocky Mountain Biogenic Aerosol Study) field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq.) atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs) onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m-3 when LVOC fate corrected) compared to daytime (average 0.9 µg m-3 when LVOC fate corrected), with maximum formation observed at 0.4-1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days) led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70), similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production of small oxidized organic

In situ secondary organic aerosol formation from ambient pine forest air using an oxidation flow reactor

Directory of Open Access Journals (Sweden)

B. B. Palm

2016-03-01

Full Text Available An oxidation flow reactor (OFR is a vessel inside which the concentration of a chosen oxidant can be increased for the purpose of studying SOA formation and aging by that oxidant. During the BEACHON-RoMBAS (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics & Nitrogen–Rocky Mountain Biogenic Aerosol Study field campaign, ambient pine forest air was oxidized by OH radicals in an OFR to measure the amount of SOA that could be formed from the real mix of ambient SOA precursor gases, and how that amount changed with time as precursors changed. High OH concentrations and short residence times allowed for semicontinuous cycling through a large range of OH exposures ranging from hours to weeks of equivalent (eq. atmospheric aging. A simple model is derived and used to account for the relative timescales of condensation of low-volatility organic compounds (LVOCs onto particles; condensational loss to the walls; and further reaction to produce volatile, non-condensing fragmentation products. More SOA production was observed in the OFR at nighttime (average 3 µg m−3 when LVOC fate corrected compared to daytime (average 0.9 µg m−3 when LVOC fate corrected, with maximum formation observed at 0.4–1.5 eq. days of photochemical aging. SOA formation followed a similar diurnal pattern to monoterpenes, sesquiterpenes, and toluene+p-cymene concentrations, including a substantial increase just after sunrise at 07:00 local time. Higher photochemical aging (> 10 eq. days led to a decrease in new SOA formation and a loss of preexisting OA due to heterogeneous oxidation followed by fragmentation and volatilization. When comparing two different commonly used methods of OH production in OFRs (OFR185 and OFR254-70, similar amounts of SOA formation were observed. We recommend the OFR185 mode for future forest studies. Concurrent gas-phase measurements of air after OH oxidation illustrate the decay of primary VOCs, production

Photochemical model evaluation of 2013 California wild fire air quality impacts using surface, aircraft, and satellite data.

Science.gov (United States)

Baker, K R; Woody, M C; Valin, L; Szykman, J; Yates, E L; Iraci, L T; Choi, H D; Soja, A J; Koplitz, S N; Zhou, L; Campuzano-Jost, Pedro; Jimenez, Jose L; Hair, J W

2018-10-01

The Rim Fire was one of the largest wildfires in California history, burning over 250,000 acres during August and September 2013 affecting air quality locally and regionally in the western U.S. Routine surface monitors, remotely sensed data, and aircraft based measurements were used to assess how well the Community Multiscale Air Quality (CMAQ) photochemical grid model applied at 4 and 12 km resolution represented regional plume transport and chemical evolution during this extreme wildland fire episode. Impacts were generally similar at both grid resolutions although notable differences were seen in some secondary pollutants (e.g., formaldehyde and peroxyacyl nitrate) near the Rim fire. The modeling system does well at capturing near-fire to regional scale smoke plume transport compared to remotely sensed aerosol optical depth (AOD) and aircraft transect measurements. Plume rise for the Rim fire was well characterized as the modeled plume top was consistent with remotely sensed data and the altitude of aircraft measurements, which were typically made at the top edge of the plume. Aircraft-based lidar suggests O 3 downwind in the Rim fire plume was vertically stratified and tended to be higher at the plume top, while CMAQ estimated a more uniformly mixed column of O 3 . Predicted wildfire ozone (O 3 ) was overestimated both at the plume top and at nearby rural and urban surface monitors. Photolysis rates were well characterized by the model compared with aircraft measurements meaning aerosol attenuation was reasonably estimated and unlikely contributing to O 3 overestimates at the top of the plume. Organic carbon was underestimated close to the Rim fire compared to aircraft data, but was consistent with nearby surface measurements. Periods of elevated surface PM 2.5 at rural monitors near the Rim fire were not usually coincident with elevated O 3 . Published by Elsevier B.V.

Photochemical synthesis of biomolecules under anoxic conditions

Science.gov (United States)

Folsome, C.; Brittain, A.; Zelko, M.

1983-01-01

The long-wavelength UV anoxic photosynthesis of uracil, various sugars (including deoxyribose and glycoaldehyde), amino acids, and other organic photoproducts is reported. The reactions were conducted in a mixture of water, calcium carbonate, hydrazine, and formaldehyde which were subjected to 24 hr or 72 hr radiation. Product yields were greatest when the hydrazine/formaldehyde ratio was one, and when the reactant concentrations were low. These data suggest that organic products can be formed in variety from those amounts of formaldehyde and hydazine precursors which are themselves formed under anoxic UV photochemical conditions.

Accounting for the decrease of photosystem photochemical efficiency with increasing irradiance to estimate quantum yield of leaf photosynthesis.

Science.gov (United States)

Yin, Xinyou; Belay, Daniel W; van der Putten, Peter E L; Struik, Paul C

2014-12-01

Maximum quantum yield for leaf CO2 assimilation under limiting light conditions (Φ CO2LL) is commonly estimated as the slope of the linear regression of net photosynthetic rate against absorbed irradiance over a range of low-irradiance conditions. Methodological errors associated with this estimation have often been attributed either to light absorptance by non-photosynthetic pigments or to some data points being beyond the linear range of the irradiance response, both causing an underestimation of Φ CO2LL. We demonstrate here that a decrease in photosystem (PS) photochemical efficiency with increasing irradiance, even at very low levels, is another source of error that causes a systematic underestimation of Φ CO2LL. A model method accounting for this error was developed, and was used to estimate Φ CO2LL from simultaneous measurements of gas exchange and chlorophyll fluorescence on leaves using various combinations of species, CO2, O2, or leaf temperature levels. The conventional linear regression method under-estimated Φ CO2LL by ca. 10-15%. Differences in the estimated Φ CO2LL among measurement conditions were generally accounted for by different levels of photorespiration as described by the Farquhar-von Caemmerer-Berry model. However, our data revealed that the temperature dependence of PSII photochemical efficiency under low light was an additional factor that should be accounted for in the model.

Non-animal photosafety assessment approaches for cosmetics based on the photochemical and photobiochemical properties.

Science.gov (United States)

Onoue, Satomi; Suzuki, Gen; Kato, Masashi; Hirota, Morihiko; Nishida, Hayato; Kitagaki, Masato; Kouzuki, Hirokazu; Yamada, Shizuo

2013-12-01

The main purpose of the present study was to establish a non-animal photosafety assessment approach for cosmetics using in vitro photochemical and photobiochemical screening systems. Fifty-one cosmetics, pharmaceutics and other chemicals were selected as model chemicals on the basis of animal and/or clinical photosafety information. The model chemicals were assessed in terms of photochemical properties by UV/VIS spectral analysis, reactive oxygen species (ROS) assay and 3T3 neutral red uptake phototoxicity testing (3T3 NRU PT). Most phototoxins exhibited potent UV/VIS absorption with molar extinction coefficients of over 1000M(-1)cm(-1), although false-negative prediction occurred for 2 cosmetic phototoxins owing to weak UV/VIS absorption. Among all the cosmetic ingredients, ca. 42% of tested chemicals were non-testable in the ROS assay because of low water solubility; thereby, micellar ROS (mROS) assay using a solubilizing surfactant was employed for follow-up screening. Upon combination use of ROS and mROS assays, the individual specificity was 88.2%, and the positive and negative predictivities were estimated to be 94.4% and 100%, respectively. In the 3T3 NRU PT, 3 cosmetics and 4 drugs were incorrectly predicted not to be phototoxic, although some of them were typical photoallergens. Thus, these in vitro screening systems individually provide false predictions; however, a systematic tiered approach using these assays could provide reliable photosafety assessment without any false-negatives. The combined use of in vitro assays might enable simple and fast non-animal photosafety evaluation of cosmetic ingredients. Copyright © 2013 Elsevier Ltd. All rights reserved.

Nickel films: Nonselective and selective photochemical deposition and properties

International Nuclear Information System (INIS)

Smirnova, N.V.; Boitsova, T.B.; Gorbunova, V.V.; Alekseeva, L.V.; Pronin, V.P.; Kon'uhov, G.S.

2006-01-01

Nickel films deposited on quartz surfaces by the photochemical reduction of a chemical nickel plating solution were studied. It was found that the deposition of the films occurs after an induction period, the length of which depends on the composition of the photolyte and the light intensity. Ni particles with a mean diameter of 20-30 nm were detected initially by transmission electron microscopy. The particles then increased in size (50 nm) upon irradiation and grouped into rings consisting of 4-5 particles. Irradiation with high-intensity light produces three-dimensional films. The calculated extinction coefficient of the nickel film was found to be 4800 L mol -1 cm -1 . Electron diffraction revealed that the prepared amorphous nickel films crystallize after one day of storage. It was determined that the films exhibit catalytic activity in the process of nickel deposition from nickel plating solution. The catalytic action remains for about 5-7 min after exposure of the films to air. The processes of selective and nonselective deposition of the nickel films are discussed. The use of poly(butoxy titanium) in the process of selective photochemical deposition enables negative and positive images to be prepared on quartz surfaces

Products of BVOC oxidation: ozone and organic aerosols

Science.gov (United States)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to

L-Cysteine Capped CdSe Quantum Dots Synthesized by Photochemical Route.

Science.gov (United States)

Singh, Avinash; Kunwar, Amit; Rath, M C

2018-05-01

L-cysteine capped CdSe quantum dots were synthesized via photochemical route in aqueous solution under UV photo-irradiation. The as grown CdSe quantum dots exhibit broad fluorescence at room temperature. The CdSe quantum dots were found to be formed only through the reactions of the precursors, i.e., Cd(NH3)2+4 and SeSO2-3 with the photochemically generated 1-hydroxy-2-propyl radicals, (CH3)2COH radicals, which are formed through the process of H atom abstraction by the photoexcited acetone from 2-propanol. L-Cysteine was found to act as a suitable capping agent for the CdSe quantum dots and increases their biocompatability. Cytotoxicty effects of these quantum dots were evaluated in Chinese Hamster Ovary (CHO) epithelial cells, indicated a significant lower level for the L-cysteine capped CdSe quantum dots as compare to the bare ones.

Photochemical immobilization of anthraquinone conjugated oligonucleotides and PCR amplicons on solid surfaces

DEFF Research Database (Denmark)

Koch, T.; Jacobsen, N.; Fensholdt, J.

2000-01-01

Ligand immobilization on solid surfaces is an essential step in fields such as diagnostics, bio sensor manufacturing, and new material sciences in general. In this paper a photochemical approach based on anthraquinone as the chromophore is presented. Photochemical procedures offer special...... advantages as they are able to generate highly reactive species in an orientation specific manner. As presented here, anthraquinone (AQ) mediated covalent DNA immobilization appears to be superior to currently known procedures. A synthetic procedure providing AQ-phosphoramidites is presented. These reagents...... facilitate AQ conjugation during routine DNA synthesis, thus enabling the AQ-oligonucleotides to be immobilized in a very convenient and efficient manner. AQ-conjugated PCR primers can be used directly in PCR. When the PCR is performed in solution, the amplicons can be immobilized after the PCR. Moreover...

Fingerprinting DNA oxidation processes: IR characterization of the 5-methyl-2'-deoxycytidine radical cation.

Science.gov (United States)

Bucher, Dominik B; Pilles, Bert M; Pfaffeneder, Toni; Carell, Thomas; Zinth, Wolfgang

2014-02-24

Methylated cytidine plays an important role as an epigenetic signal in gene regulation. Its oxidation products are assumed to be involved in active demethylation processes but also in damaging DNA. Here, we report the photochemical production of the 5-methyl-2'-deoxycytidine radical cation via a two-photon ionization process. The radical cation is detected by time-resolved IR spectroscopy and identified by band assignment using density functional theory calculations. Two final oxidation products are characterized with liquid chromatography coupled to mass spectrometry. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies on the photochemical and thermal dissociation synthesis of krypton difluoride

Energy Technology Data Exchange (ETDEWEB)

Kinkead, S.A.; FitzPatrick, J.R.; Foropoulos, J. Jr.; Kissane, R.J.; Purson, J.D.

1993-08-01

Like dioxygen difluoride (O{sub 2}F{sub 2}), KrF{sub 2} can be produced by thermal dissociation or photochemical synthesis from the elements; however, the yields are invariably much less than those obtained for O{sub 2}F{sub 2}. For example, while irradiation of liquid O{sub 2}/F{sub 2} mixtures at {minus}196{degrees}C through a sapphire window with an unfiltered 1,000W uv lamp provides in excess of 3g of O{sub 2}F{sub 2} per hour, the yield of KrF{sub 2} under identical circumstances is approximately 125 mg/hr. In this report, the yield of KrF{sub 2} in quartz and Pyrex{trademark} photochemical reactors has been examined as a function of irradiation wavelength, irradiation power, and Kr: F{sub 2} mole ratio. The uv-visible spectrum of KrF{sub 2} has also been recorded for comparison with earlier work, and the quantum yield for photodissociation at two wavelengths determined. The synthesis of KrF{sub 2} using large thermal gradients has also been examined using resistively heated nickel filaments to thermally dissociate the F{sub 2} in close proximity to liquid nitrogen-cooled metal surfaces. As a net result, KrF{sub 2} has been produced in yields in excess of 1.75 g/hr for extended periods in photochemical systems, and 2.3 g/hr for shorter periods in thermally dissociative reactors. This paper summarizes the results of examining parametrically several different types of reactors for efficiency of producing krypton difluoride.

Windows(Registered Trademark)-Based Software Models Cyclic Oxidation Behavior

Science.gov (United States)

Smialek, J. L.; Auping, J. V.

2004-01-01

Oxidation of high-temperature aerospace materials is a universal issue for combustion-path components in turbine or rocket engines. In addition to the question of the consumption of material due to growth of protective scale at use temperatures, there is also the question of cyclic effects and spallation of scale on cooldown. The spallation results in the removal of part of the protective oxide in a discontinuous step and thereby opens the way for more rapid oxidation upon reheating. In experiments, cyclic oxidation behavior is most commonly characterized by measuring changes in weight during extended time intervals that include hundreds or thousands of heating and cooling cycles. Weight gains occurring during isothermal scale-growth processes have been well characterized as being parabolic or nearly parabolic functions of time because diffusion controls reaction rates. In contrast, the net weight change in cyclic oxidation is the sum of the effects of the growth and spallation of scale. Typically, the net weight gain in cyclic oxidation is determined only empirically (that is, by measurement), with no unique or straightforward mathematical connection to either the rate of growth or the amount of metal consumed. Thus, there is a need for mathematical modeling to infer spallation mechanisms. COSP is a computer program that models the growth and spallation processes of cyclic oxidation on the basis of a few elementary assumptions that were discussed in COSP: A Computer Model of Cyclic Oxidation, Oxidation of Metals, vol. 36, numbers 1 and 2, 1991, pages 81-112. Inputs to the model include the selection of an oxidation-growth law and a spalling geometry, plus oxide-phase, growth-rate, cycle-duration, and spall-constant parameters. (The spalling fraction is often shown to be a constant factor times the existing amount of scale.) The output of COSP includes the net change in weight, the amounts of retained and spalled oxide, the total amounts of oxygen and metal

Photochemical versus biological production of methyl iodide during Meteor 55

Science.gov (United States)

Richter, U.; Wallace, D.

2003-04-01

The flux of methyl iodide from sea to air represents the largest flux of iodine from the ocean to the atmosphere. Surface water concentrations and hence fluxes are particularly high in tropical regions. This flux may be responsible for the enrichment of iodine in the marine aerosol and may contribute to important processes in the marine boundary layer, including particle formation. Methyl iodide is commonly referred to as a biogenic gas, with both macroalgae and phytoplankton identified as important sources. On the other hand experimental and field data have shown the importance of photochemical production that is not necessarily associated directly with biological activity. During the Meteor cruise 55 along 11°N in the tropical Atlantic Ocean, a series of experiments were conducted to examine the biological vs. photochemical production of methyl iodide. A total of eight separate experiments were conducted. Production of CH3I in quartz glass flasks during 24 hour incubations (dark and natural sunlight) was measured under three experimental treatments: untreated seawater, filtered seawater (0.1 um pore size filter to exclude most phytoplankton and bacteria), and seawater that was poisoned with mercuric chloride. There were two clear findings from these experiments: (1) methyl iodide production was significantly higher in all the incubations that were exposed to the light than in the dark incubations; (2) there was no significant difference between CH3I production under the three experimental treatments. These results argue very strongly for the primary importance of photochemical production of CH3I as opposed to biogenic production at least for the tropical open ocean surface waters. Further experiments are required to investigate the reactants involved, their sources, the wavelength and depth dependence of production, etc. as well as (possibly related) sink processes.

Electrochemical advanced oxidation processes: today and tomorrow. A review.

Science.gov (United States)

Sirés, Ignasi; Brillas, Enric; Oturan, Mehmet A; Rodrigo, Manuel A; Panizza, Marco

2014-01-01

In recent years, new advanced oxidation processes based on the electrochemical technology, the so-called electrochemical advanced oxidation processes (EAOPs), have been developed for the prevention and remediation of environmental pollution, especially focusing on water streams. These methods are based on the electrochemical generation of a very powerful oxidizing agent, such as the hydroxyl radical ((•)OH) in solution, which is then able to destroy organics up to their mineralization. EAOPs include heterogeneous processes like anodic oxidation and photoelectrocatalysis methods, in which (•)OH are generated at the anode surface either electrochemically or photochemically, and homogeneous processes like electro-Fenton, photoelectro-Fenton, and sonoelectrolysis, in which (•)OH are produced in the bulk solution. This paper presents a general overview of the application of EAOPs on the removal of aqueous organic pollutants, first reviewing the most recent works and then looking to the future. A global perspective on the fundamentals and experimental setups is offered, and laboratory-scale and pilot-scale experiments are examined and discussed.

Quenching of excited uranyl ion during its photochemical reduction with triphenyl-phosphine : Part IV - effect of heterocyclic molecules

International Nuclear Information System (INIS)

Sidhu, M.S.; Bhatia, P.V.K.

1994-01-01

The presence of heterocyclic compounds triggers off a competition between photophysical and photochemical annihilation of excited uranyl ion during its photochemical reduction with triphenylphosphine. This competition is used to measure Stern-Volmer constant using UV visible spectrophotometer for quenching the uranyl ion luminescence with a number of heterocyclic molecules viz., pyridine, thiophene bipyridyl, tetrahydrofuran and piperidine. (author). 7 refs., 2 figs., 1 tab

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

Oxidation capacity of the city air of Santiago, Chile

Directory of Open Access Journals (Sweden)

Y. F. Elshorbany

2009-03-01

Full Text Available The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8–20 March 2005. The hydroxyl (OH radical budget was evaluated employing a simple quasi-photostationary-state model (PSS constrained with simultaneous measurements of HONO, HCHO, O₃, NO, NO₂, j(O¹D, j(NO₂, 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1 has been used to estimate production rates and total free radical budgets, including OH, HO₂ and RO₂. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8–7 ppbv (HONO, 0.9–11 ppbv (HCHO and 0–125 ppbv (O₃. The alkenes average mixing ratio was ~58 ppbC accounting for ~12% of the total identified non-methane hydrocarbons (NMHCs. During the daytime (08:00 h–19:00 h, HONO photolysis was shown to be the most important primary OH radical source comprising alone ~55% of the total initial production rate, followed by alkene ozonolysis (~24% and photolysis of HCHO (~16% and O₃ (~5%. The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h⁻¹ and 3.1 ppbv h⁻¹, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out.

Capturing the Stratosphere’s Influence on Seasonal and Intraseasonal Predictability in a State-of-the-Art Navy Global Environmental Model (NAVGEM)

Science.gov (United States)

2013-09-30

NRL water vapor chemistry scheme of McCormack et al. (2008). The new scheme uses updated photochemical equilibrium states and chemical production ...replenished through production via methane oxidation. The new code has been extensively tested in the single column model, was ported to NAVGEM and...tested (see below), and is currently in the process of being fully intergrated into the developmental NAVGEM code for use by NRL’s entire NAVGEM

Controlled nitric oxide production via O(1D  + N2O reactions for use in oxidation flow reactor studies

Directory of Open Access Journals (Sweden)

A. Lambe

2017-06-01

Full Text Available Oxidation flow reactors that use low-pressure mercury lamps to produce hydroxyl (OH radicals are an emerging technique for studying the oxidative aging of organic aerosols. Here, ozone (O3 is photolyzed at 254 nm to produce O(1D radicals, which react with water vapor to produce OH. However, the need to use parts-per-million levels of O3 hinders the ability of oxidation flow reactors to simulate NOx-dependent secondary organic aerosol (SOA formation pathways. Simple addition of nitric oxide (NO results in fast conversion of NOx (NO + NO2 to nitric acid (HNO3, making it impossible to sustain NOx at levels that are sufficient to compete with hydroperoxy (HO2 radicals as a sink for organic peroxy (RO2 radicals. We developed a new method that is well suited to the characterization of NOx-dependent SOA formation pathways in oxidation flow reactors. NO and NO2 are produced via the reaction O(1D + N2O  →  2NO, followed by the reaction NO + O3  →  NO2 + O2. Laboratory measurements coupled with photochemical model simulations suggest that O(1D + N2O reactions can be used to systematically vary the relative branching ratio of RO2 + NO reactions relative to RO2 + HO2 and/or RO2 + RO2 reactions over a range of conditions relevant to atmospheric SOA formation. We demonstrate proof of concept using high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS measurements with nitrate (NO3− reagent ion to detect gas-phase oxidation products of isoprene and α-pinene previously observed in NOx-influenced environments and in laboratory chamber experiments.

Photochemical immobilization of bovine serum albumin on Ti-O and evaluations in vitro and in vivo

International Nuclear Information System (INIS)

Weng, Y.J.; Qi, F.; Huang, N.; Wang, J.; Cheng, J.Y.; Leng, Y.X.

2008-01-01

Antithrombogenic biomaterials have been of great interest in the development of artificial organs and devices. In this study, titanium oxide coatings were used as the basis for covalent immobilization of a BSA layer by a photochemical method. BSA was first modified with azidophenyl group on the side chain, so it (AZ-BSA) has the property of photo-reactivity. Simultaneously, an organic monolayer of 3-aminopropylphosphonic acid (APP) was introduced on the Ti-O film by self-assembling, and then UV irradiation was used to couple AZ-BSA with APP. FTIR, XPS and contact angle measurements confirmed the occurrence of the modification. Additionally, a surface with both BSA immobilized and non-BSA immobilized regions was prepared by using a mask when irradiating, thus the interactions of materials and platelets were visualized. Platelet experiments of both qualitative and quantitative analysis showed that BSA immobilized surface was effective to inhibit platelet adhesion in vitro. In vivo study also confirmed better hemocompatibility of BSA immobilized surface after 90 days implantation

Enhanced Oxidation of Isoprene and Monoterpenes in High and Low NOx Conditions

Science.gov (United States)

Tokarek, T. W.; Gilman, J.; Lerner, B. M.; Koss, A.; Yuan, B.; Taha, Y. M.; Osthoff, H. D.; Warneke, C.; De Gouw, J. A.

2015-12-01

In the troposphere, the photochemical oxidation of volatile organic compounds (VOCs) is primarily initiated by their reactions with the hydroxyl radical (OH) which yields peroxy radicals (HO2 and RO2). Concentrations of OH and the rates of VOC oxidation depend on the efficiency of peroxy radical recycling to OH. Radical recycling mainly occurs through reaction of HO2 with NO to produce NO2 and, ultimately, ozone (O3). Hence, the rate of VOC oxidation is dependent on NOx (=NO+NO2) concentration. The Shale Oil and Natural Gas Nexus (SONGNEX) campaign was conducted from March 17 to April 29, 2015 with the main goal of identifying and quantifying industrial sources of pollutants throughout the United States, in particular those associated with the production of oil and natural gas. In this work, a case study of biogenic VOC oxidation within and outside a power plant plume in the Haynesville basin near the border of Texas and Louisiana is presented. Isoprene, monoterpenes and their oxides were measured by H3O+ chemical ionization mass spectrometry (H3O+ CIMS) in high time resolution (1 s). Further, an improved Whole Air Sampler (iWAS) was used to collect samples for post-flight analysis by gas chromatography mass spectrometric detection (GC-MS) and yielded speciated quantification of biogenic VOCs. The monoterpene oxide to monoterpene ratio follows the spatial extent of the plume as judged by another tracer (NOx), tracking the enhancement of oxidation rates by NOx. The observations are rationalized with the aid of box modeling using the Master Chemical Mechanism (MCM).

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

Science.gov (United States)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

DNA bulky adducts in a Mediterranean population correlate with environmental ozone concentration, an indicator of photochemical smog.

Science.gov (United States)

Palli, Domenico; Saieva, Calogero; Grechi, Daniele; Masala, Giovanna; Zanna, Ines; Barbaro, Antongiulio; Decarli, Adriano; Munnia, Armelle; Peluso, Marco

2004-03-01

Ozone (O(3)), the major oxidant component in photochemical smog, mostly derives from photolysis of nitrogen dioxide. O(3) may have biologic effects directly and/or via free radicals reacting with other primary pollutants and has been reported to influence daily mortality and to increase lung cancer risk. Although DNA damage may be caused by ozone itself, only other photochemical reaction products (as oxidised polycyclic aromatic hydrocarbons) may form bulky DNA adducts, a reliable biomarker of genotoxic damage and cancer risk, showing a seasonal trend. In a large series consisting of 320 residents in the metropolitan area of Florence, Italy, enrolled in a prospective study for the period 1993-1998 (206 randomly sampled volunteers, 114 traffic-exposed workers), we investigated the correlation between individual levels of DNA bulky adducts and a cumulative O(3) exposure score. The average O(3) concentrations were calculated for different time windows (0-5 to 0-90 days) prior to blood drawing for each participant, based on daily measurements provided by the local monitoring system. Significant correlations between DNA adduct levels and O3 cumulative exposure scores in the last 2-8 weeks before enrollment emerged in never smokers. Correlations were highest in the subgroup of never smokers residing in the urban area and not occupationally exposed to vehicle traffic pollution, with peak values for average concentrations 4-6 weeks before enrollment (r = 0.34). Our current findings indicate that DNA adduct formation may be modulated by individual characteristics and by the cumulative exposure to environmental levels of ozone in the last 4-6 weeks, possibly through ozone-associated reactive pollutants. Copyright 2003 Wiley-Liss, Inc.

Analysis of the unresolved organic fraction in atmospheric aerosols with ultrahigh-resolution mass spectrometry and nuclear magnetic resonance spectroscopy: organosulfates as photochemical smog constituents.

Science.gov (United States)

Schmitt-Kopplin, Philippe; Gelencsér, Andras; Dabek-Zlotorzynska, Ewa; Kiss, Gyula; Hertkorn, Norbert; Harir, Mourad; Hong, Yang; Gebefügi, Istvan

2010-10-01

Complementary molecular and atomic signatures obtained from Fourier transform ion cyclotron resonance (FTICR) mass spectra and NMR spectra provided unequivocal attribution of CHO, CHNO, CHOS, and CHNOS molecular series in secondary organic aerosols (SOA) and high-resolution definition of carbon chemical environments. Sulfate esters were confirmed as major players in SOA formation and as major constituents of its water-soluble fraction (WSOC). Elevated concentrations of SO(2), sulfate, and photochemical activity were shown to increase the proportion of SOA sulfur-containing compounds. Sulfonation of CHO precursors by means of heterogeneous reactions between carbonyl derivatives and sulfuric acid in gas-phase photoreactions was proposed as a likely formation mechanism of CHOS molecules. In addition, photochemistry induced oligomerization processes of CHOS molecules. Methylesters found in methanolic extracts of a SOA subjected to strong photochemical exposure were considered secondary products derived from sulfate esters by methanolysis. The relative abundance of nitrogen-containing compounds (CHNO and CHNOS series) appeared rather dependent on local effects such as biomass burning. Extensive aliphatic branching and disruption of extended NMR spin-systems by carbonyl derivatives and other heteroatoms were the most significant structural motifs in SOA. The presence of heteroatoms in elevated oxidation states suggests a clearly different SOA formation trajectory in comparison with established terrestrial and aqueous natural organic matter.

Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

Science.gov (United States)

Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

2016-06-30

A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

Impact of future nitrous oxide and carbon dioxide emissions on the stratospheric ozone layer

International Nuclear Information System (INIS)

Stolarski, Richard S; Waugh, Darryn W; Douglass, Anne R; Oman, Luke D

2015-01-01

The atmospheric levels of human-produced chlorocarbons and bromocarbons are projected to make only small contributions to ozone depletion by 2100. Increases in carbon dioxide (CO 2 ) and nitrous oxide (N 2 O) will become increasingly important in determining the future of the ozone layer. N 2 O increases lead to increased production of nitrogen oxides (NO x ), contributing to ozone depletion. CO 2 increases cool the stratosphere and affect ozone levels in several ways. Cooling decreases the rate of many photochemical reactions, thus slowing ozone loss rates. Cooling also increases the chemical destruction of nitrogen oxides, thereby moderating the effect of increased N 2 O on ozone depletion. The stratospheric ozone level projected for the end of this century therefore depends on future emissions of both CO 2 and N 2 O. We use a two-dimensional chemical transport model to explore a wide range of values for the boundary conditions for CO 2 and N 2 O, and find that all of the current scenarios for growth of greenhouse gases project the global average ozone to be larger in 2100 than in 1960. (letter)

Gas and particle phase chemical characterization of photochemical smog in Beijing and Hong Kong

Science.gov (United States)

Hallquist, Mattias; Le Breton, Michael; Guo, Song; Zhen Yu, Jian; Hallquist, Åsa. M.; Pathak, Ravi K.; Liu, Qianyun; Wang, Yuchen; Li, Jinjian; Chan, Chak K.; Wang, Yujue; Zheng, Jing; Yang, Yudong; Lu, Keding; Wu, Zhijun; Hu, Min

2017-04-01

Secondary chemistry transforming primary pollutants is of high relevance for Chinese photochemical smog. In particular, formation of ozone (O3) and particulate matter (PM), including Secondary Organic Aerosols (SOA), are of major concern regarding impacts on health, climate and ecosystems. The atmospheric oxidation processes leading to SOA formation are complex and involves thousands of different compounds, both of biogenic and anthropogenic origin. Furthermore, for a thorough understanding both the gas and the particle phase need to be considered. As part of an intercollaborative project to assess the photochemical smog in China, two major field campaigns were arranged in 2016; in Changping, Bejing during springtime and at HKUST, Hong Kong during the autumn. Alongside with other advanced instrumentations, a Time of Flight Chemical Ionisation Mass Spectrometer (ToF CIMS) utilising the Filiter Inlet for Gases and AEROsols (FIGAERO) was used to chemically characterize the gas and the particle phase. This specific instrument applies soft ionization limiting the fragmentation and one can usually identify molecular composition of hundreds of different parent molecules. In both Beijing and Hong Kong the iodide ionization scheme was utilised, making it possible to specifically detect oxygenated compounds such as carboxylic acids, organic nitrates and sulphates as well as some inorganic compounds e.g. N2O5, ClNO2, and HONO. For numerous compounds significant levels were detected in both the gas and particle phase enabling evaluation of partitioning and gas-to-particle transformation and its relationship to atmospheric conditions and estimated vapour pressures. Furthermore, the detection of molecular markers such as levoglucosan, C6H5NO3, C10H16NSO7, C5H8SO7, C5H8O4 can support source apportionment and atmospheric process description. In order to further investigate atmospheric ageing/processing a portable laminar flow reactor (Go:PAM) was for selected periods utilized to

A Universal Protocol for Photochemical Covalent Immobilization of Intact Carbohydrates for the Preparation of Carbohydrate Microarrays

Science.gov (United States)

Wang, Huibin; Zhang, Yiming; Yuan, Xun; Chen, Yi; Yan, Mingdi

2010-01-01

A universal photochemical method has been established for the immobilization of intact carbohydrates and their analogues, and for the fabrication of carbohydrate microarrays. The method features the use of perfluorophenyl azide (PFPA)-modified substrates and the photochemical reaction of surface azido groups with printed carbohydrates. Various aldoses, ketoses, non-reducing sugars such as alditols and their derivatives can be directly arrayed on the PFPA-modified chips. The lectin-recognition ability of arrayed mannose, glucose and their oligo- and polysaccharides were confirmed using surface plasmon resonance imaging and laser-induced fluorescence imaging. PMID:21138274

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

Kinetic modeling of antimony(III) oxidation and sorption in soils.

Science.gov (United States)

Cai, Yongbing; Mi, Yuting; Zhang, Hua

2016-10-05

Kinetic batch and saturated column experiments were performed to study the oxidation, adsorption and transport of Sb(III) in two soils with contrasting properties. Kinetic and column experiment results clearly demonstrated the extensive oxidation of Sb(III) in soils, and this can in return influence the adsorption and transport of Sb. Both sorption capacity and kinetic oxidation rate were much higher in calcareous Huanjiang soil than in acid red Yingtan soil. The results indicate that soil serve as a catalyst in promoting oxidation of Sb(III) even under anaerobic conditions. A PHREEQC model with kinetic formulations was developed to simulate the oxidation, sorption and transport of Sb(III) in soils. The model successfully described Sb(III) oxidation and sorption data in kinetic batch experiment. It was less successful in simulating the reactive transport of Sb(III) in soil columns. Additional processes such as colloid facilitated transport need to be quantified and considered in the model. Copyright © 2016 Elsevier B.V. All rights reserved.

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.)

DIAGNOSTIC EVALUATION OF NUMBERICAL AIR QUALITY MODELS WITH SPECIALIZED AMBIENT OBSERVATIONS: TESTING THE COMMUNITY MULTISCALE AIR QUALITY MODELING SYSTEM (CMAQ) AT SELECTED SOS 95 GROUND SITES

Science.gov (United States)

Three probes for diagnosing photochemical dynamics are presented and applied to specialized ambient surface-level observations and to a numerical photochemical model to better understand rates of production and other process information in the atmosphere and in the model. Howeve...

Intraspecific variation in Pinus pinaster PSII photochemical efficiency in response to winter stress and freezing temperatures.

Directory of Open Access Journals (Sweden)

Leyre Corcuera

Full Text Available As part of a program to select maritime pine (Pinus pinaster Ait. genotypes for resistance to low winter temperatures, we examined variation in photosystem II activity by chlorophyll fluorescence. Populations and families within populations from contrasting climates were tested during two consecutive winters through two progeny trials, one located at a continental and xeric site and one at a mesic site with Atlantic influence. We also obtained the LT₅₀, or the temperature that causes 50% damage, by controlled freezing and the subsequent analysis of chlorophyll fluorescence in needles and stems that were collected from populations at the continental trial site.P. pinaster showed sensitivity to winter stress at the continental site, during the colder winter. The combination of low temperatures, high solar irradiation and low precipitation caused sustained decreases in maximal photochemical efficiency (F(v/F(m, quantum yield of non-cyclic electron transport (Φ(PSII and photochemical quenching (qP. The variation in photochemical parameters was larger among families than among populations, and population differences appeared only under the harshest conditions at the continental site. As expected, the environmental effects (winter and site on the photochemical parameters were much larger than the genotypic effects (population or family. LT₅₀ was closely related to the minimum winter temperatures of the population's range. The dark-adapted F(v/F(m ratio discriminated clearly between interior and coastal populations.In conclusion, variations in F(v/F(m, Φ(PSII, qP and non-photochemical quenching (NPQ in response to winter stress were primarily due to the differences between the winter conditions and the sites and secondarily due to the differences among families and their interactions with the environment. Populations from continental climates showed higher frost tolerance (LT₅₀ than coastal populations that typically experience mild

Intraspecific variation in Pinus pinaster PSII photochemical efficiency in response to winter stress and freezing temperatures.

Science.gov (United States)

Corcuera, Leyre; Gil-Pelegrin, Eustaquio; Notivol, Eduardo

2011-01-01

As part of a program to select maritime pine (Pinus pinaster Ait.) genotypes for resistance to low winter temperatures, we examined variation in photosystem II activity by chlorophyll fluorescence. Populations and families within populations from contrasting climates were tested during two consecutive winters through two progeny trials, one located at a continental and xeric site and one at a mesic site with Atlantic influence. We also obtained the LT₅₀, or the temperature that causes 50% damage, by controlled freezing and the subsequent analysis of chlorophyll fluorescence in needles and stems that were collected from populations at the continental trial site.P. pinaster showed sensitivity to winter stress at the continental site, during the colder winter. The combination of low temperatures, high solar irradiation and low precipitation caused sustained decreases in maximal photochemical efficiency (F(v)/F(m)), quantum yield of non-cyclic electron transport (Φ(PSII)) and photochemical quenching (qP). The variation in photochemical parameters was larger among families than among populations, and population differences appeared only under the harshest conditions at the continental site. As expected, the environmental effects (winter and site) on the photochemical parameters were much larger than the genotypic effects (population or family). LT₅₀ was closely related to the minimum winter temperatures of the population's range. The dark-adapted F(v)/F(m) ratio discriminated clearly between interior and coastal populations.In conclusion, variations in F(v)/F(m), Φ(PSII), qP and non-photochemical quenching (NPQ) in response to winter stress were primarily due to the differences between the winter conditions and the sites and secondarily due to the differences among families and their interactions with the environment. Populations from continental climates showed higher frost tolerance (LT₅₀) than coastal populations that typically experience mild winters

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

DEFF Research Database (Denmark)

Berner, Torben Sune; Arneborg, Nils

2012-01-01

that the oxidative stress resistance was strain dependent. Fermentation of model wort in European Brewing Convention tubes using three yeast strains with varying oxidative stress resistances resulted in three model beers with different rates of radical formation as measured by electron spin resonance in forced......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...... in the model beers. CONCLUSIONS: A more oxidative stable beer is not obtained by a more-oxidative-stress-tolerant lager brewing yeast strain, exhibiting a higher secretion of thioredoxin, but rather by a less-oxidative-stress-tolerant strain, exhibiting a higher iron uptake. SIGNIFICANCE AND IMPACT...

Atmospheric Production of Perchlorate on Earth and Mars

Science.gov (United States)

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

2009-12-01

Natural production and preservation of perchlorate on Earth occurs only in arid environments. Isotopic evidence suggests a strong role for atmospheric oxidation of chlorine species via pathways including ozone or its photochemical derivatives. As the Martian atmosphere is both oxidizing and drier than the driest places on Earth, we propose an atmospheric origin for the Martian perchlorates measured by NASA's Phoenix Lander. A variety of hypothetical formation pathways can be proposed including atmospheric photochemical reactions, electrostatic discharge, and gas-solid reactions. Here, we investigate gas phase formation pathways using a 1-D photochemical model (Catling et al. 2009, accepted by JGR). Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we start with a study of the means to produce Atacama perchlorate. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. These results are sensitive to estimated reaction rates for ClO3 species. The feasibility of gas phase production for the Atacama provides justification for further investigations of gas phase photochemistry as a possible source for Martian perchlorate. In addition to the Atacama results, we will present a preliminary study incorporating chlorine chemistry into an existing Martian photochemical model (Zahnle et al. JGR 2008).

Model of dopant action in oxide cathodes

International Nuclear Information System (INIS)

Engelsen, Daniel den; Gaertner, Georg

2005-01-01

The paper describes an electrochemical model, which largely explains the formation of Ba in the oxide cathode at activation and normal operation. In a non-doped oxide cathode electrolysis of BaO is, besides the exchange reaction from the activators in the cathode nickel, an important source of Ba. By doping with rare earth oxides the conductivity of the oxide layer increases, which implies that the potential difference during current drawing over the oxide layer becomes lower and electrolysis of BaO is suppressed. This implies that the part of the electronic conductivity of the (Ba,Sr)O layer induced by the dopants also controls the sensitivity for poisoning: the higher the dopant level, the larger the sensitivity for poisoning. Furthermore, the suppression of electrolysis during normal operation largely explains why doped oxide cathodes have a better life performance than non-doped cathodes. Finally a hypothesis on the enhancement of sintering upon doping is presented

Finite element modelling of the oxidation kinetics of Zircaloy-4 with a controlled metal-oxide interface and the influence of growth stress

International Nuclear Information System (INIS)

Zumpicchiat, Guillaume; Pascal, Serge; Tupin, Marc; Berdin-Méric, Clotilde

2015-01-01

Highlights: We developed two finite element models of zirconium-based alloy oxidation using the CEA Cast3M code to simulate the oxidation kinetics of Zircaloy-4: the diffuse interface model and the sharp interface model. We also studied the effect of stresses on the oxidation kinetics. The main results are: • Both models lead to parabolic oxidation kinetics in agreement with the Wagner’s theory. • The modellings enable to calculate the stress distribution in the oxide as well as in the metal. • A strong effect of the hydrostatic stress on the oxidation kinetics has been evidenced. • The stress gradient effect changes the parabolic kinetics into a sub-parabolic law closer to the experimental kinetics because of the stress gradient itself, but also because of the growth stress increase with the oxide thickness. - Abstract: Experimentally, zirconium-based alloys oxidation kinetics is sub-parabolic, by contrast with the Wagner theory which predicts a parabolic kinetics. Two finite element models have been developed to simulate this phenomenon: the diffuse interface model and the sharp interface model. Both simulate parabolic oxidation kinetics. The growth stress effects on oxygen diffusion are studied to try to explain the gap between theory and experience. Taking into account the influence of the hydrostatic stress and its gradient into the oxygen flux expression, sub-parabolic oxidation kinetics have been simulated. The sub-parabolic behaviour of the oxidation kinetics can be explained by a non-uniform compressive stress level into the oxide layer.

Modeling of nitrous oxide production by autotrophic ammonia-oxidizing bacteria with multiple production pathways.

Science.gov (United States)

Ni, Bing-Jie; Peng, Lai; Law, Yingyu; Guo, Jianhua; Yuan, Zhiguo

2014-04-01

Autotrophic ammonia oxidizing bacteria (AOB) have been recognized as a major contributor to N2O production in wastewater treatment systems. However, so far N2O models have been proposed based on a single N2O production pathway by AOB, and there is still a lack of effective approach for the integration of these models. In this work, an integrated mathematical model that considers multiple production pathways is developed to describe N2O production by AOB. The pathways considered include the nitrifier denitrification pathway (N2O as the final product of AOB denitrification with NO2(-) as the terminal electron acceptor) and the hydroxylamine (NH2OH) pathway (N2O as a byproduct of incomplete oxidation of NH2OH to NO2(-)). In this model, the oxidation and reduction processes are modeled separately, with intracellular electron carriers introduced to link the two types of processes. The model is calibrated and validated using experimental data obtained with two independent nitrifying cultures. The model satisfactorily describes the N2O data from both systems. The model also predicts shifts of the dominating pathway at various dissolved oxygen (DO) and nitrite levels, consistent with previous hypotheses. This unified model is expected to enhance our ability to predict N2O production by AOB in wastewater treatment systems under varying operational conditions.

Photochemical charges separation and photoelectric properties of flexible solar cells with two types of heterostructures

Energy Technology Data Exchange (ETDEWEB)

Liu, Xiangyang, E-mail: lxy081276@126.com, E-mail: yzgu@henu.edu.cn; Wang, Shun; Zheng, Haiwu; Cheng, Xiuying; Gu, Yuzong, E-mail: lxy081276@126.com, E-mail: yzgu@henu.edu.cn [Institute of Microsystems Physics and School of Physics and Electronics, Henan University, Kaifeng 475004 (China)

2015-12-14

Photochemical charges generation, separation, and transport at nanocrystal interfaces are central to energy conversion for solar cells. Here, Zn{sub 2}SnO{sub 4} nanowires/Cu{sub 4}Bi{sub 4}S{sub 9} (ZTO/CBS), ZTO nanowires/CBS-reduced graphene oxide (ZTO/CBS-RGO), and bulk heterojunction (BHJ) solar cells were measured. The signals of steady state and electric field-induced surface photovoltage indicate that RGO with high electron mobility can evidently improve the photovoltaic response. Besides, ZTO/CBS and ZTO/CBS-RGO cells exhibit the excellent performance and the highest efficiencies of 1.2% and 2.8%, respectively. The internal relations of photoelectric properties to some factors, such as film thickness, direct paths, RGO conductive network, energy level matching, etc., were discussed in detail. Qualitative and quantitative analyses further verified the comprehensive effect of RGO and other factors. Importantly, the fine bendable characteristic of BHJ solar cells with excellent efficiency and facile, scalable production gives the as-made flexible solar cells device potential for practical application in future.

Testing fast photochemical theory during TRACE-P based on measurements of OH, HO2, and CH2O

Science.gov (United States)

Olson, Jennifer R.; Crawford, J. H.; Chen, G.; Fried, A.; Evans, M. J.; Jordan, C. E.; Sandholm, S. T.; Davis, D. D.; Anderson, B. E.; Avery, M. A.; Barrick, J. D.; Blake, D. R.; Brune, W. H.; Eisele, F. L.; Flocke, F.; Harder, H.; Jacob, D. J.; Kondo, Y.; Lefer, B. L.; Martinez, M.; Mauldin, R. L.; Sachse, G. W.; Shetter, R. E.; Singh, H. B.; Talbot, R. W.; Tan, D.

2004-08-01

Measurements of several short-lived photochemical species (e.g., OH, HO2, and CH2O) were obtained from the DC-8 and P3-B aircraft during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) campaign. To assess fast photochemical theory over the east Asian coast and western Pacific, these measurements are compared to predictions using a photochemical time-dependent box model constrained by coincident measurements of long-lived tracers and physical parameters. Both OH and HO2 are generally overpredicted by the model throughout the troposphere, which is a different result from previous field campaigns. The calculated-to-observed ratio of OH shows an altitude trend, with OH overpredicted by 80% in the upper troposphere and by 40-60% in the middle troposphere. Boundary layer and lower tropospheric OH ratios decrease from middle tropospheric values to 1.07 for the DC-8 and to 0.70 for the P3-B. HO2 measured on the DC-8 is overpredicted by a median of 23% and shows no trend in the agreement with altitude. Three subsets of data which compose 12% of the HO2 measurements represent outliers with respect to calculated-to-observed ratios: stratospherically influenced air, upper tropospheric data with NO > 135 pptv, and data from within clouds. Pronounced underpredictions of both HO2 and OH were found for stratospherically influenced air, which is in contrast to previous studies showing good agreement of predicted and observed HOx in the stratosphere. Observational evidence of heterogeneous uptake of HO2 within low and middle tropospheric clouds is presented, though there is no indication of significant HO2 uptake within higher-altitude clouds. Model predictions of CH2O are in good agreement with observations in the median for background concentrations, but a large scatter exists. Factors contributing to this scatter are examined, including the limited availability of some important constraining measurements, particularly CH3OOH. Some high concentrations of CH2O

Organic photochemical reactions on solid surfaces: Enrichment and separation of isotopes. Final report. SBIR-1988, Phase 2

International Nuclear Information System (INIS)

Ruderman, W.; Fehlner, J.; Spencer, J.

1988-01-01

The objectives of the Phase II program were to: (1) investigate organic photochemical reactions on solid porous silica surfaces, (2) utilize the magnetic isotope effect to develop a (13)C enrichment process using a fluidized bed reactor, and (3) investigate the possibility of enrichment of heavier isotopes having a nuclear spin. Although researchers were able to demonstrate a continuous fluidized bed (13)C enrichment process, analysis showed that the process could not compete with low temperature distillation of CO because of the high cost of the starting material, dibenzylketone (DBK), and the difficulty of converting the photochemical decomposition products back to DBK. However, the process shows promise for the separation of heavier isotopes such as (29)Si. The photochemical studies led to the discovery that the selectivity for terminal chlorination of alkanes can be increased more than 25 fold by sorbing the alkanes on ZSM-5 zeolites in a fluidized bed. The selectivity is ascribed to the presence of interfaces within the crystals

Particle number concentration, size distribution and chemical composition during haze and photochemical smog episodes in Shanghai.

Science.gov (United States)

Wang, Xuemei; Chen, Jianmin; Cheng, Tiantao; Zhang, Renyi; Wang, Xinming

2014-09-01

The aerosol number concentration and size distribution as well as size-resolved particle chemical composition were measured during haze and photochemical smog episodes in Shanghai in 2009. The number of haze days accounted for 43%, of which 30% was severe (visibilitysmog episodes, about 5.89 times and 4.29 times those of clean days. The particle volume concentration and surface concentration in haze, photochemical smog and clean days were 102, 49, 15μm(3)/cm(3) and 949, 649, 206μm(2)/cm(3), respectively. As haze events got more severe, the number concentration of particles smaller than 50nm decreased, but the particles of 50-200nm and 0.5-1μm increased. The diurnal variation of particle number concentration showed a bimodal pattern in haze days. All soluble ions were increased during haze events, of which NH4(+), SO4(2-) and NO3(-) increased greatly, followed by Na(+), K(+), Ca(2+) and Cl(-). These ions were very different in size-resolved particles during haze and photochemical smog episodes. Copyright © 2014. Published by Elsevier B.V.

Photochemical recombination of deep centers in silicon: decay of donor-acceptor pairs

International Nuclear Information System (INIS)

Adilov, K.A.

1991-01-01

Processes of photochemical recombination of deep impurity centers (DIC) in p-Si alloyed by Te, Zn and Fe occuring at 300-350 K under irradiation by super-low-energy light from δ 14 -10 17 quantum/cm 2 )Xs intensity impurity absorption range, are considered

Photochemical reactions in biological systems: probing the effect of the environment by means of hybrid quantum chemistry/molecular mechanics simulations.

Science.gov (United States)

Boggio-Pasqua, Martial; Burmeister, Carl F; Robb, Michael A; Groenhof, Gerrit

2012-06-14

Organisms have evolved a wide variety of mechanisms to utilize and respond to light. In many cases, the biological response is mediated by structural changes that follow photon absorption in a protein complex. The initial step in such cases is normally the photoisomerization of a highly conjugated prosthetic group. To understand better the factors controlling the isomerization, we perform atomistic molecular dynamics simulations. In this perspective article we briefly review the key theoretical concepts of photochemical reactions and present a practical simulation scheme for simulating photochemical reactions in biomolecular systems. In our scheme, a multi-configurational quantum mechanical description is used to model the electronic rearrangement for those parts of the system that are involved in the photon absorption. For the remainder, typically consisting of the apo-protein and the solvent, a simple force field model is used. The interactions in the systems are thus computed within a hybrid quantum/classical framework. Forces are calculated on-the-fly, and a diabatic surface hopping procedure is used to model the excited-state decay. To demonstrate how this method is used we review our studies on photoactivation of the photoactive yellow protein, a bacterial photoreceptor. We will show what information can be obtained from the simulations, and, by comparing to recent experimental findings, what the limitations of our simulations are.

Fundamental Studies of Butane Oxidation over Model-Supported Vanadium Oxide Catalysts: Molecular Structure-Reactivity Relationships

NARCIS (Netherlands)

Wachs, I.E.; Jehng, J.M.; Deo, G.; Weckhuysen, B.M.; Guliants, V.V.; Benziger, J.B.; Sundaresan, S.

1997-01-01

The oxidation of n-butane to maleic anhydride was investigated over a series of model-supported vanadia catalysts where the vanadia phase was present as a two-dimensional metal oxide overlayer on the different oxide supports (TiO2, ZrO2, CeO2, Nb2O5, Al2O3, and SiO2). No correlation was found

Emissions inventories for urban airshed model application in the Philadelphia Aqcr (Air Quality Control Region)

Energy Technology Data Exchange (ETDEWEB)

1982-04-01

This report documents the procedures used to develop emissions input required by the Urban Airshed photochemical oxidant model. Ambient air quality data were gathered as part of another effort during the summer of 1979 in Philadelphia to be used in the model validation effort. For 1979 and the 1987 projection year, ES compiled hour by hour emissions data for a representative weekday in the oxidant season. The pollutants inventoried are five categories of VOC required by the Airshed model, four categories of VOC defined in RAPS, NO, NO2, CO, SO2, and TSP. Point and area sources were considered with the highway vehicle portion of the inventory being subcontracted to DVRPC. County level area source data were allocated to a 502-cell grid system. Projections were made so that ozone air quality in 1987 could be investigated. ES developed annualized EIS/PandR data and data files containing temporal and VOC/NOx profiles in order to generate the data packets required by the Airshed model.

Water-Mediated Photochemical Treatments for Low-Temperature Passivation of Metal-Oxide Thin-Film Transistors.

Science.gov (United States)

Heo, Jae Sang; Jo, Jeong-Wan; Kang, Jingu; Jeong, Chan-Yong; Jeong, Hu Young; Kim, Sung Kyu; Kim, Kwanpyo; Kwon, Hyuck-In; Kim, Jaekyun; Kim, Yong-Hoon; Kim, Myung-Gil; Park, Sung Kyu

2016-04-27

The low-temperature electrical passivation of an amorphous oxide semiconductor (AOS) thin-film transistor (TFT) is achieved by a deep ultraviolet (DUV) light irradiation-water treatment-DUV irradiation (DWD) method. The water treatment of the first DUV-annealed amorphous indium-gallium-zinc-oxide (a-IGZO) thin film is likely to induce the preferred adsorption of water molecules at the oxygen vacancies and leads to subsequent hydroxide formation in the bulk a-IGZO films. Although the water treatment initially degraded the electrical performance of the a-IGZO TFTs, the second DUV irradiation on the water-treated devices may enable a more complete metal-oxygen-metal lattice formation while maintaining low oxygen vacancies in the oxide films. Overall, the stable and dense metal-oxygen-metal (M-O-M) network formation could be easily achieved at low temperatures (below 150 °C). The successful passivation of structural imperfections in the a-IGZO TFTs, such as hydroxyl group (OH-) and oxygen vacancies, mainly results in the enhanced electrical performances of the DWD-processed a-IGZO TFTs (on/off current ratio of 8.65 × 10(9), subthreshold slope of 0.16 V/decade, an average mobility of >6.94 cm(2) V(-1) s(-1), and a bias stability of ΔVTH IGZO TFTs.

Selective Oxidation of Lignin Model Compounds.

Science.gov (United States)

Gao, Ruili; Li, Yanding; Kim, Hoon; Mobley, Justin K; Ralph, John

2018-05-02

Lignin, the planet's most abundant renewable source of aromatic compounds, is difficult to degrade efficiently to welldefined aromatics. We developed a microwave-assisted catalytic Swern oxidation system using an easily prepared catalyst, MoO 2 Cl 2 (DMSO) 2 , and DMSO as the solvent and oxidant. It demonstrated high efficiency in transforming lignin model compounds containing the units and functional groups found in native lignins. The aromatic ring substituents strongly influenced the selectivity of β-ether phenolic dimer cleavage to generate sinapaldehyde and coniferaldehyde, monomers not usually produced by oxidative methods. Time-course studies on two key intermediates provided insight into the reaction pathway. Owing to the broad scope of this oxidation system and the insight gleaned with regard to its mechanism, this strategy could be adapted and applied in a general sense to the production of useful aromatic chemicals from phenolics and lignin. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

Energy Technology Data Exchange (ETDEWEB)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan [Pusan National University, Busan (Korea, Republic of); Kim, Dong Uk [Daegu National University of Education, Daegu (Korea, Republic of); Xue, Jin Ying [Harbin Normal University, Harbin (China); Mariano, Patrick S. [University of New Mexico, Albuquerque (United States)

2010-09-15

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways.

Studies of Silyl-Transfer Photochemical Reactions of N-[(Trimethylsilyl)alkyl]saccharins

International Nuclear Information System (INIS)

Cho, Dae Won; Oh, Sun Wha; Park, Hea Jung; Yoon, Ung Chan; Kim, Dong Uk; Xue, Jin Ying; Mariano, Patrick S.

2010-01-01

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and γ-hydrogen abstraction pathways

Photochemical Cyclopolymerization of Polyimides in Ultraviolet Ridgidizing Composites for Use in Inflatable Structures, Phase I

Data.gov (United States)

National Aeronautics and Space Administration — This innovation uses photochemical cyclopolymerization of polyimides to manufacture ultraviolet rigidizable composites for use in RIS (ridgidizing inflatable)...

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)

Multiscale model of metal alloy oxidation at grain boundaries

International Nuclear Information System (INIS)

Sushko, Maria L.; Alexandrov, Vitaly; Schreiber, Daniel K.; Rosso, Kevin M.; Bruemmer, Stephen M.

2015-01-01

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr 2 O 3 . This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl 2 O 4 . Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3–10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr 2 O 3 has a plate-like structure with 1.2–1.7 nm wide pores running along the grain boundary, while NiAl 2 O 4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional

Ozone modeling

International Nuclear Information System (INIS)

McIllvaine, C.M.

1994-01-01

Exhaust gases from power plants that burn fossil fuels contain concentrations of sulfur dioxide (SO 2 ), nitric oxide (NO), particulate matter, hydrocarbon compounds and trace metals. Estimated emissions from the operation of a hypothetical 500 MW coal-fired power plant are given. Ozone is considered a secondary pollutant, since it is not emitted directly into the atmosphere but is formed from other air pollutants, specifically, nitrogen oxides (NO), and non-methane organic compounds (NMOQ) in the presence of sunlight. (NMOC are sometimes referred to as hydrocarbons, HC, or volatile organic compounds, VOC, and they may or may not include methane). Additionally, ozone formation Alternative is a function of the ratio of NMOC concentrations to NO x concentrations. A typical ozone isopleth is shown, generated with the Empirical Kinetic Modeling Approach (EKMA) option of the Environmental Protection Agency's (EPA) Ozone Isopleth Plotting Mechanism (OZIPM-4) model. Ozone isopleth diagrams, originally generated with smog chamber data, are more commonly generated with photochemical reaction mechanisms and tested against smog chamber data. The shape of the isopleth curves is a function of the region (i.e. background conditions) where ozone concentrations are simulated. The location of an ozone concentration on the isopleth diagram is defined by the ratio of NMOC and NO x coordinates of the point, known as the NMOC/NO x ratio. Results obtained by the described model are presented

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.

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.

Polymers designed for laser ablation-influence of photochemical properties

International Nuclear Information System (INIS)

Lippert, T.; Dickinson, J.T.; Hauer, M.; Kopitkovas, G.; Langford, S.C.; Masuhara, H.; Nuyken, O.; Robert, J.; Salmio, H.; Tada, T.; Tomita, K.; Wokaun, A.

2002-01-01

The ablation characteristics of various polymers were studied at low and high fluences. The polymers can be divided into three groups, i.e. polymers containing triazene and ester groups, the same polymers without the triazene group, and polyimide as reference polymer. At high fluences similar ablation parameters, i.e. etch rates and effective absorption coefficients, were obtained for all polymers. The main difference is the absence of carbon deposits for the designed polymers. At low fluences (at 308 nm) very pronounced differences are detected. The polymers containing the photochemically most active group (triazene) exhibit the lowest threshold of ablation (as low as 25 mJ cm -2 ) and the highest etch rates (up to 3 μm/pulse), followed by the designed polyesters and then polyimide. The laser-induced decomposition of the designed polymers was studied by nanosecond-interferometry. Only the triazene-polymer reveals etching without any sign of surface swelling, which is observed for all other polymers. The etching of the triazene-polymer starts and ends with the laser pulse, clearly indicating photochemical etching. The triazene-polymer was also studied by time-of-flight mass spectrometry (TOF-MS). The intensities of the ablation fragments show pronounced differences between irradiation at the absorption band of the triazene group (308 nm) and irradiation at a shorter wavelength (248 nm)

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

Science.gov (United States)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Photochemical degradation of the carbapenem antibiotics imipenem and meropenem in aqueous solutions under solar radiation.

Science.gov (United States)

Reina, Alejandro Cabrera; Martínez-Piernas, Ana B; Bertakis, Yannis; Brebou, Christina; Xekoukoulotakis, Nikolaos P; Agüera, Ana; Sánchez Pérez, José Antonio

2018-01-01

This paper deals with the photochemical fate of two representative carbapenem antibiotics, namely imipenem and meropenem, in aqueous solutions under solar radiation. The analytical method employed for the determination of the target compounds in various aqueous matrices, such as ultrapure water, municipal wastewater treatment plant effluents, and river water, at environmentally relevant concentrations, was liquid chromatography coupled with hybrid triple quadrupole-linear ion trap-mass spectrometry. The absorption spectra of both compounds were measured in aqueous solutions at pH values from 6 to 8, and both compounds showed a rather strong absorption band centered at about 300 nm, while their molar absorption coefficient was in the order from 9 × 10 3 -10 4  L mol -1  cm -1 . The kinetics of the photochemical degradation of the target compounds was studied in aqueous solutions under natural solar radiation in a solar reactor with compound parabolic collectors. It was found that the photochemical degradation of both compounds at environmentally relevant concentrations follows first order kinetics and the quantum yield was in the order of 10 -3  mol einsten -1 . Several parameters were studied, such as solution pH, the presence of nitrate ions and humic acids, and the effect of water matrix. In all cases, it was found that the presence of various organic and inorganic constituents in the aqueous matrices do not contribute significantly, either positively or negatively, to the photochemical degradation of both compounds under natural solar radiation. In a final set of photolysis experiments, the effect of the level of irradiance was studied under simulated solar radiation and it was found that the quantum yield for the direct photodegradation of both compounds remained practically constant by changing the incident solar irradiance from 28 to 50 W m -2 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Photochemical reaction of Si-substituted ethynylsilanes with 1,2-ethanedithiol

Energy Technology Data Exchange (ETDEWEB)

Voronkov, M.G.; Brodskaya, E.I.; Kalabin, G.A.; Vlasova, N.N.; Yarosh, O.G.; Zhila, G.Y.

1985-12-01

The authors investigate the chief products of the photochemical reactions of Si-substituted ethynylsilanes with 1,2,-ethanedithiol at 60-70 C. It is found that the chief products are 2-triorganylsilyl-substituted 1,4-dithiacyclopentanes and 1,4-dithiacyclohexanes. On lowering the temperature to -30 C, formation of bis (triorganylsilyl)-substituted 1,4,7,10-tetrathiacyclododecanes occurs along with the abo ve-mentioned five- and six-membered heterocycles.

Profiling the biological activity of oxide nanomaterials with mechanistic models

NARCIS (Netherlands)

Burello, E.

2013-01-01

In this study we present three mechanistic models for profiling the potential biological and toxicological effects of oxide nanomaterials. The models attempt to describe the reactivity, protein adsorption and membrane adhesion processes of a large range of oxide materials and are based on properties

Data assimilation in atmospheric chemistry models using Kalman filtering

NARCIS (Netherlands)

Segers, A.

2002-01-01

The problem of air pollution around urbanized area across Europe is strongly related to ozone. Ozone is a result of photo-chemical oxidation, and therefore an indication of the presence of pollutants. Overexposure to ozone is harmful to the health, and the concentrations are therefore measured on a

A case study of ozone production, nitrogen oxides, and the radical budget in Mexico City

Directory of Open Access Journals (Sweden)

E. C. Wood

2009-04-01

Full Text Available Observations at a mountain-top site within the Mexico City basin are used to characterize ozone production and destruction, nitrogen oxide speciation and chemistry, and the radical budget, with an emphasis on a stagnant air mass observed on one afternoon. The observations compare well with the results of recent photochemical models. An ozone production rate of ~50 ppbv/h was observed in a stagnant air mass during the afternoon of 12 March 2006, which is among the highest observed anywhere in the world. Approximately half of the ozone destruction was due to the oxidation of NO₂. During this time period ozone production was VOC-limited, deduced by a comparison of the radical production rates and the formation rate of NO_x oxidation products (NO_z. For [NO_x]/[NO_y] values between 0.2 and 0.8, gas-phase HNO₃ typically accounted for less than 10% of NO_z and accumulation-mode particulate nitrate (NO_3(PM1⁻ accounted for 20%–70% of NO_z, consistent with high ambient NH₃ concentrations. The fraction of NO_z accounted for by the sum of HNO_3(g and NO_3(PM1⁻ decreased with photochemical processing. This decrease is apparent even when dry deposition of HNO₃ is accounted for, and indicates that HNO₃ formation decreased relative to other NO_x "sink" processes during the first 12 h of photochemistry and/or a significant fraction of the nitrate was associated with the coarse aerosol size mode. The ozone production efficiency of NO_x on 11 and 12 March 2006 was approximately 7 on a time scale of one day. A new metric for ozone production efficiency that relates the dilution-adjusted ozone mixing ratio to cumulative OH exposure is proposed.

The contribution of the european project loop to the photochemical pollution in Lombardy; Il contributo del progetto europeo loop allo studio dell'inquinamento fotochimico in Lombardia

Energy Technology Data Exchange (ETDEWEB)

Longoni, M G; Maffeis, G [TerrAria S.r.l., Milan (Italy); De Martini, A [Regione Lombardia, Ufficio Prevenzione Rischi, Milan, (Italy); Balasso, A; Borelli,; Rimoldi, A; Zabot, S; Zanella, G [Regione Lombardia, Direzione Generale Tutela Ambientale, Milan (Italy); Lanzani, G [Amministrazione Provinciale di Como, Settore Ecologia, Como (Italy); Tamponi, M [Azienda Sanitaria Locale, Lecco (Italy); Cattaneo, R; Ghezzi, F; Toscani, D

2000-06-01

During the last years, in Lombardy, the concentrations of primary pollutants such as CO and SO{sub 2} have diminished thanks to some acts to abate emissions. On the other hand, the concentrations of pollutants, belonging to the photochemical mixture, have increased. The continual monitoring of photochemical pollutants and their measure on the ground level, but also along the vertical profile, present costs so high that they become no utilizable in a wide area. The experimental campaign PIPAPO (PIanura PAdana Produzione Ozono) has been carried on in the late spring in 1998 and it belongs to the European project LOOP (Limitation Of Oxidant Production). This campaign is an example of intensive campaign of measurement in which institutions of a lot of nationalities have collaborated. In this way the problem of a lot of nationalities have collaborated. In this way the problem of costs in continual monitoring has been obviated. PIPAPO has confirmed the criticity of photochemical smog in the Lombardy area. A modellistic approach, complementary to that of measurements, permits to verify the territory representativity of the points of measurement and to carry on evaluations of the politics to abate emissions. [Italian] In Lombardia durante gli ultimi anni le concentrazioni di inquinanti primari quali CO ed SO{sub 2} hanno subito una diminuzione grazie all'efficacia di alcuni interventi di abbattimento delle emissioni. D'altro lato si e' avuto un incremento delle concentrazioni degli inquinanti appartenenti alla miscela fotochimica di cui l'ozono e' considerato il principale tracciante. Il monitoraggio in continuo di tutti gli inquinanti fotochimici e la loro misura a livello sia del suolo, ma anche lungo la verticale, avrebbero dei costi per quanto riguarda le risorse strumentali e umane tali da renderli irrealizzabili su un'area estesa come quella lombarda. La campagna sperimentale PIPAPO (PIanura PAdana Produzione Ozono), avvenuta nella tarda primavera 1998 ed avviata all

Probing and exploiting the chaotic dynamics of a hydrodynamic photochemical oscillator to implement all the basic binary logic functions

Energy Technology Data Exchange (ETDEWEB)

Hayashi, Kenta [Department of Mechanical Engineering, Ritsumeikan University, 1-1-1 Nojihigashi, Kusatsu-shi, Shiga 525-8577 (Japan); Department of Chemistry, Biology, and Biotechnology, University of Perugia, 06123 Perugia (Italy); Gotoda, Hiroshi [Department of Mechanical Engineering, Tokyo University of Science, 6-3-1 Niijuku, Katsushika-ku, Tokyo 125-8585 (Japan); Gentili, Pier Luigi, E-mail: pierluigi.gentili@unipg.it [Department of Chemistry, Biology, and Biotechnology, University of Perugia, 06123 Perugia (Italy)

2016-05-15

The convective motions within a solution of a photochromic spiro-oxazine being irradiated by UV only on the bottom part of its volume, give rise to aperiodic spectrophotometric dynamics. In this paper, we study three nonlinear properties of the aperiodic time series: permutation entropy, short-term predictability and long-term unpredictability, and degree distribution of the visibility graph networks. After ascertaining the extracted chaotic features, we show how the aperiodic time series can be exploited to implement all the fundamental two-inputs binary logic functions (AND, OR, NAND, NOR, XOR, and XNOR) and some basic arithmetic operations (half-adder, full-adder, half-subtractor). This is possible due to the wide range of states a nonlinear system accesses in the course of its evolution. Therefore, the solution of the convective photochemical oscillator results in hardware for chaos-computing alternative to conventional complementary metal-oxide semiconductor-based integrated circuits.

Molecular distributions of dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in biomass burning aerosols: implications for photochemical production and degradation in smoke layers

Directory of Open Access Journals (Sweden)

A. Hoffer

2010-03-01

Full Text Available Aerosols in the size class <2.5 μm (6 daytime and 9 nighttime samples were collected at a pasture site in Rondônia, Brazil, during the intensive biomass burning period of 16–26 September 2002 as part of the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Smoke, Aerosols, Clouds, Rainfall and Climate (LBA-SMOCC. Homologous series of dicarboxylic acids (C2–C11 and related compounds (ketocarboxylic acids and α-dicarbonyls were identified using gas chromatography (GC and GC/mass spectrometry (GC/MS. Among the species detected, oxalic acid was found to be the most abundant, followed by succinic, malonic and glyoxylic acids. Average concentrations of total dicarboxylic acids, ketocarboxylic acids and α-dicarbonyls in the aerosol samples were 2180, 167 and 56 ng m−3, respectively. These are 2–8, 3–11 and 2–16 times higher, respectively, than those reported in urban aerosols, such as in 14 Chinese megacities. Higher ratios of dicarboxylic acids and related compounds to biomass burning tracers (levoglucosan and K+ were found in the daytime than in the nighttime, suggesting the importance of photochemical production. On the other hand, higher ratios of oxalic acid to other dicarboxylic acids and related compounds normalized to biomass burning tracers (levoglucosan and K+ in the daytime provide evidence for the possible degradation of dicarboxylic acids (≥C3 in this smoke-polluted environment. Assuming that these and related compounds are photo-chemically oxidized to oxalic acid in the daytime, and given their linear relationship, they could account for, on average, 77% of the formation of oxalic acid. The remaining portion of oxalic acid may have been directly emitted from biomass burning as suggested by a good correlation with the biomass burning tracers (K+, CO and ECa and organic carbon (OC. However, photochemical production from other precursors could not be excluded.

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

International Nuclear Information System (INIS)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz; Durmuş, Mahmut; Bulut, Mustafa

2015-01-01

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, 1 H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn 2+ , Mg 2+ , In +3 ) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

A review of photochemical approaches for the treatment of a wide range of pesticides.

Science.gov (United States)

Reddy, P Venkata Laxma; Kim, Ki-Hyun

2015-03-21

Pesticides are renowned as some of the most pernicious chemicals known to humankind. Nine out of twelve most hazardous and persistent organic chemicals on planet have been identified as pesticides and their derivatives. Because of their strong recalcitrant nature, it often becomes a difficult task to treat them by conventional approaches. It is well perceived that many factors can interfere with the degradation of pesticides under ambient conditions, e.g., media, light intensity, humic content, and other biological components. However, for the effective treatment of pesticides, photochemical methods are viewed as having clear and perceivable advantages. In this article, we provide a review of the fundamental characteristics of photochemical approaches for pesticide treatment and the factors governing their capacity and potential in such a process. Copyright © 2014 Elsevier B.V. All rights reserved.

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...

Modeling C1-C4 Alkyl Nitrate Photochemistry and Their Impacts on O3 Production in Urban and Suburban Environments of Hong Kong

Science.gov (United States)

Lyu, X. P.; Guo, H.; Wang, N.; Simpson, I. J.; Cheng, H. R.; Zeng, L. W.; Saunders, S. M.; Lam, S. H. M.; Meinardi, S.; Blake, D. R.

2017-10-01

As intermediate products of photochemical reactions, alkyl nitrates (RONO2) regulate ozone (O3) formation. In this study, a photochemical box model incorporating master chemical mechanism well reproduced the observed RONO2 at an urban and a mountainous site, with index of agreement in the range of 0.66-0.73. The value 0.0003 was identified to be the most appropriate branching ratio for C1 RONO2, with the error less than 50%. Although levels of the parent hydrocarbons and nitric oxide (NO) were significantly higher at the urban site than the mountainous site, the production of C2-C3 RONO2 was comparable to or even lower than at the mountainous site, due to the lower concentrations of oxidative radicals in the urban environment. Based on the profiles of air pollutants at the mountainous site, the formation of C2-C4 RONO2 was limited by NOx (volatile organic compounds (VOCs)) when total volatile organic compounds (TVOCs)/NOx was higher (lower) than 10.0 ± 0.4 parts per billion by volume (ppbv)/ppbv. This dividing ratio decreased (p controlling O3 formation and the relative abundances of TVOCs and NOx.

Facilitated beam-walking recovery during acute phase by kynurenic acid treatment in a rat model of photochemically induced thrombosis causing focal cerebral ischemia.

Science.gov (United States)

Abo, Masahiro; Yamauchi, Hideki; Suzuki, Masahiko; Sakuma, Mio; Urashima, Mitsuyoshi

We previously demonstrated the presence of activated areas in the non-injured contralateral sensorimotor cortex in addition to the ipsilateral sensorimotor cortex of the area surrounding a brain infarction, using a rat model of focal photochemically induced thrombosis (PIT) and functional magnetic resonance imaging. Using this model, we next applied gene expression profiling to screen key molecules upregulated in the activated area. RNA was extracted from the ipsilateral and contralateral sensorimotor cortex to the focal brain infarction and from the sham controlled cortex, and hybridized to gene-expression profiling arrays containing 1,322 neurology-related genes. Results showed that glycine receptors were upregulated in both the ipsilateral and contralateral cortex to the focal ischemic lesion. To prove the preclinical significance of upregulated glycine receptors, kynurenic acid, an endogenous antagonist to glycine receptors on neuronal cells, was administered intrathecally. As a result, the kynurenic acid significantly improved behavioral recovery within 10 days from paralysis induced by the focal PIT (p beam walking. These results suggest that intrathecal administration of a glycine receptor antagonist may facilitate behavioral recovery during the acute phase after brain infarction. Copyright (c) 2006 S. Karger AG, Basel.

Determination of Insulator-to-Semiconductor Transition in Sol-Gel Oxide Semiconductors Using Derivative Spectroscopy.

Science.gov (United States)

Lee, Woobin; Choi, Seungbeom; Kim, Kyung Tae; Kang, Jingu; Park, Sung Kyu; Kim, Yong-Hoon

2015-12-23

We report a derivative spectroscopic method for determining insulator-to-semiconductor transition during sol-gel metal-oxide semiconductor formation. When an as-spun sol-gel precursor film is photochemically activated and changes to semiconducting state, the light absorption characteristics of the metal-oxide film is considerable changed particularly in the ultraviolet region. As a result, a peak is generated in the first-order derivatives of light absorption ( A' ) vs. wavelength (λ) plots, and by tracing the peak center shift and peak intensity, transition from insulating-to-semiconducting state of the film can be monitored. The peak generation and peak center shift are described based on photon-energy-dependent absorption coefficient of metal-oxide films. We discuss detailed analysis method for metal-oxide semiconductor films and its application in thin-film transistor fabrication. We believe this derivative spectroscopy based determination can be beneficial for a non-destructive and a rapid monitoring of the insulator-to-semiconductor transition in sol-gel oxide semiconductor formation.

Human nitric oxide biomarker as potential NO donor in conjunction with superparamagnetic iron oxide @ gold core shell nanoparticles for cancer therapeutics.

Science.gov (United States)

Singh, Nimisha; Patel, Khushbu; Sahoo, Suban K; Kumar, Rajender

2018-03-01

Nitric oxide releasing superparamagnetic (Fe 3 O 4 -Au@NTHP) nanoparticles were synthesized by conjugation of human biomarker of nitric oxide, N-nitrosothioproline with iron oxide-gold (Fe 3 O 4 -Au) core shell nanoparticles. The structure and morphology of the prepared nanoparticles were confirmed by ATR-FTIR, HR-TEM, EDAX, XPS, DLS and VSM measurements. N-nitrosothioproline is a natural molecule and nontoxic to humans. Thus, the core shell nanoparticles prepared were highly biocompatible. The prepared Fe 3 O 4 -Au@NTHP nanoparticles also provided an excellent release of nitric oxide in dark and upon light irradiation for cancer treatment. The amount of NO release was controllable with the wavelength of light and time of irradiation. The developed nanoparticles provided efficient cellular uptake and good cytotoxicity in picomolar range when tested on HeLa cancerous cells. These nanoparticles on account of their controllable NO release can also be used to release small amount of NO for killing cancerous cells without any toxic effect. Furthermore, the magnetic and photochemical properties of these nanoparticles provides dual platform for magneto therapy and phototherapy for cancer treatment. Copyright © 2017 Elsevier B.V. All rights reserved.

Eco-toxicity and human estrogenic exposure risks from "·OH-initiated photochemical transformation of four phthalates in water: A computational study

International Nuclear Information System (INIS)

Gao, Yanpeng; An, Taicheng; Ji, Yuemeng; Li, Guiying; Zhao, Cunyuan

2015-01-01

Transformation products (TPs) of emerging organic contaminates (EOCs) in water are still rarely considered in environmental risk assessment, although some have been found to be concern. "·OH is believed as an important reactive species both in indirect phototransformation and advanced oxidation technology. Thus, eco-toxicity and human estrogenic exposure risks of four phthalates and TPs during the "·OH-initiated photochemical process were investigated using computational approach. Four phthalates can be degraded through "·OH-addition and H-transfer pathways. The "·OH-addition TPs were predominant for dimethyl phthalates, while H-transfer TPs were predominant for other three phthalates. Compared with phthalates, "·OH-addition TPs (o-OH-phthalates) were one level more toxic to aquatic organisms, and m-OH-phthalates exhibit higher estrogenic activity. Although H-transfer TPs were less harmful than "·OH-addition TPs, some of them still have aquatic toxicity and estrogenic activity. Therefore, more attentions should be paid to photochemical TPs and original EOCs, particularly those exhibiting high estrogenic activity to humans. - Highlights: • Phthalates can be degraded with "·OH-addition and H-transfer pathways. • "·OH-addition products are mainly formed during DMP transformation. • H-transfer products were predominant for the transformation of DEP, DPP and DBP. • o-"·OH-addition products have greater eco-toxicity than corresponding phthalates. • m-"·OH-addition products have higher estrogenic activity than corresponding phthalates. - Computational approach could provide valuable information on the mechanisms, kinetics, eco-toxicity as well as human estrogenic exposure risks of EOCs and their transformation products.

Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

Science.gov (United States)

Singh, Dharmendra Kumar; Kawamura, Kimitaka; Yanase, Ayako; Barrie, Leonard A

2017-08-15

The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

The contribution of the european project loop to the photochemical pollution in Lombardy; Il contributo del progetto europeo loop allo studio dell'inquinamento fotochimico in Lombardia

Energy Technology Data Exchange (ETDEWEB)

Longoni, M.G.; Maffeis, G. [TerrAria S.r.l., Milan (Italy); De Martini, A. [Regione Lombardia, Ufficio Prevenzione Rischi, Milan, (Italy); Balasso, A.; Borelli; Rimoldi, A.; Zabot, S.; Zanella, G. [Regione Lombardia, Direzione Generale Tutela Ambientale, Milan (Italy); Lanzani, G. [Amministrazione Provinciale di Como, Settore Ecologia, Como (Italy); Tamponi, M. [Azienda Sanitaria Locale, Lecco (Italy); Cattaneo, R.; Ghezzi, F.; Toscani, D.

2000-06-01

During the last years, in Lombardy, the concentrations of primary pollutants such as CO and SO{sub 2} have diminished thanks to some acts to abate emissions. On the other hand, the concentrations of pollutants, belonging to the photochemical mixture, have increased. The continual monitoring of photochemical pollutants and their measure on the ground level, but also along the vertical profile, present costs so high that they become no utilizable in a wide area. The experimental campaign PIPAPO (PIanura PAdana Produzione Ozono) has been carried on in the late spring in 1998 and it belongs to the European project LOOP (Limitation Of Oxidant Production). This campaign is an example of intensive campaign of measurement in which institutions of a lot of nationalities have collaborated. In this way the problem of a lot of nationalities have collaborated. In this way the problem of costs in continual monitoring has been obviated. PIPAPO has confirmed the criticity of photochemical smog in the Lombardy area. A modellistic approach, complementary to that of measurements, permits to verify the territory representativity of the points of measurement and to carry on evaluations of the politics to abate emissions. [Italian] In Lombardia durante gli ultimi anni le concentrazioni di inquinanti primari quali CO ed SO{sub 2} hanno subito una diminuzione grazie all'efficacia di alcuni interventi di abbattimento delle emissioni. D'altro lato si e' avuto un incremento delle concentrazioni degli inquinanti appartenenti alla miscela fotochimica di cui l'ozono e' considerato il principale tracciante. Il monitoraggio in continuo di tutti gli inquinanti fotochimici e la loro misura a livello sia del suolo, ma anche lungo la verticale, avrebbero dei costi per quanto riguarda le risorse strumentali e umane tali da renderli irrealizzabili su un'area estesa come quella lombarda. La campagna sperimentale PIPAPO (PIanura PAdana Produzione Ozono), avvenuta nella tarda

Ozone Production and Control Strategies for Southern Taiwan

Science.gov (United States)

Shiu, C.; Liu, S.; Chang, C.; Chen, J.; Chou, C. C.; Lin, C.

2006-12-01

An observation-based modeling (OBM) approach is used to estimate the ozone production efficiency and production rate of O3 (P(O3)) in southern Taiwan. The approach can also provide an indirect estimate of the concentration of OH. Measured concentrations of two aromatic hydrocarbons, i.e. ethylbenzene/m,p-xylene, are used to estimate the degree of photochemical processing and the amounts of photochemically consumed NOx and NMHCs. In addition, a one-dimensional (1d) photochemical model is used to compare with the OBM results. The average ozone production efficiency during the field campaign in Kaohsiung-Pingtung area in Fall 2003 is found to be about 5, comparable to previous works. The relationship of P(O3) with NOx is examined in detail and compared to previous studies. The derived OH concentrations from this approach are in fair agreement with values calculated from the 1d photochemical model. The relationship of total oxidants (e.g. O3+NO2) versus initial NOx and NMHCs suggests that reducing NMHCs are more effective in controlling total oxidants than reducing NOx. For O3 control, reducing NMHC is even more effective than NOx due to the NO titration effect. This observation-based approach provides a good alternative for understanding the production of ozone and formulating ozone control strategy in urban and suburban environment without measurements of peroxy radicals.

Photochemical redox reactions of copper(II)-alanine complexes in aqueous solutions.

Science.gov (United States)

Lin, Chen-Jui; Hsu, Chao-Sheng; Wang, Po-Yen; Lin, Yi-Liang; Lo, Yu-Shiu; Wu, Chien-Hou

2014-05-19

The photochemical redox reactions of Cu(II)/alanine complexes have been studied in deaerated solutions over an extensive range of pH, Cu(II) concentration, and alanine concentration. Under irradiation, the ligand-to-metal charge transfer results in the reduction of Cu(II) to Cu(I) and the concomitant oxidation of alanine, which produces ammonia and acetaldehyde. Molar absorptivities and quantum yields of photoproducts for Cu(II)/alanine complexes at 313 nm are characterized mainly with the equilibrium Cu(II) speciation where the presence of simultaneously existing Cu(II) species is taken into account. By applying regression analysis, individual Cu(I) quantum yields are determined to be 0.094 ± 0.014 for the 1:1 complex (CuL) and 0.064 ± 0.012 for the 1:2 complex (CuL2). Individual quantum yields of ammonia are 0.055 ± 0.007 for CuL and 0.036 ± 0.005 for CuL2. Individual quantum yields of acetaldehyde are 0.030 ± 0.007 for CuL and 0.024 ± 0.007 for CuL2. CuL always has larger quantum yields than CuL2, which can be attributed to the Cu(II) stabilizing effect of the second ligand. For both CuL and CuL2, the individual quantum yields of Cu(I), ammonia, and acetaldehyde are in the ratio of 1.8:1:0.7. A reaction mechanism for the formation of the observed photoproducts is proposed.

Cellular Automata Modelling of Photo-Induced Oxidation Processes in Molecularly Doped Polymers

Directory of Open Access Journals (Sweden)

David M. Goldie

2016-11-01

Full Text Available The possibility of employing cellular automata (CA to model photo-induced oxidation processes in molecularly doped polymers is explored. It is demonstrated that the oxidation dynamics generated using CA models exhibit stretched-exponential behavior. This dynamical characteristic is in general agreement with an alternative analysis conducted using standard rate equations provided the molecular doping levels are sufficiently low to prohibit the presence of safe-sites which are impenetrable to dissolved oxygen. The CA models therefore offer the advantage of exploring the effect of dopant agglomeration which is difficult to assess from standard rate equation solutions. The influence of UV-induced bleaching or darkening upon the resulting oxidation dynamics may also be easily incorporated into the CA models and these optical effects are investigated for various photo-oxidation product scenarios. Output from the CA models is evaluated for experimental photo-oxidation data obtained from a series of hydrazone-doped polymers.

High throughput photo-oxidations in a packed bed reactor system.

Science.gov (United States)

Kong, Caleb J; Fisher, Daniel; Desai, Bimbisar K; Yang, Yuan; Ahmad, Saeed; Belecki, Katherine; Gupton, B Frank

2017-12-01

The efficiency gains produced by continuous-flow systems in conducting photochemical transformations have been extensively demonstrated. Recently, these systems have been used in developing safe and efficient methods for photo-oxidations using singlet oxygen generated by photosensitizers. Much of the previous work has focused on the use of homogeneous photocatalysts. The development of a unique, packed-bed photoreactor system using immobilized rose bengal expands these capabilities as this robust photocatalyst allows access to and elaboration from these highly useful building blocks without the need for further purification. With this platform we were able to demonstrate a wide scope of singlet oxygen ene, [4+2] cycloadditions and heteroatom oxidations. Furthermore, we applied this method as a strategic element in the synthesis of the high-volume antimalarial artemisinin. Copyright © 2017. Published by Elsevier Ltd.

Plant injury due to air pollution - similar symptoms. Part I

Energy Technology Data Exchange (ETDEWEB)

Matsuoka, Y

1976-01-01

Many plant diseases cause injuries to leaves which mimic the damage inflicted by air pollution. The relationship between air pollution injuries and those caused by meteorological conditions are discussed. Rice plants often contract akagare which causes reddish-brown spots on leaves similar to the symptoms caused by photochemical oxidants. Spider mites produce leaf damage in kidney beans which mimics the spotting caused by photochemical oxidants. Lace bugs produce minute white spots on azaleas similar to those caused by photochemical oxidants.

Photochemical and photocatalytic evaluation of 1D titanate/TiO{sub 2} based nanomaterials

Energy Technology Data Exchange (ETDEWEB)

Conceição, D.S.; Ferreira, D.P. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Graça, C.A.L. [Universidade de São Paulo, Avenida Prof. Luciano Gualberto, tr. 3, 380 São Paulo (Brazil); Júlio, M.F.; Ilharco, L.M. [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Velosa, A.C. [Instituto Nacional de Tecnologia, Av. Venezuela 82, Rio de Janeiro (Brazil); Santos, P.F. [Centro de Química, Vila Real Universidade de Trás-os-Montes e Alto Douro, 5001-801 Vila Real (Portugal); Vieira Ferreira, L.F., E-mail: lfvieiraferreira@tecnico.ulisboa.pt [Centro de Química-Física Molecular and IN-Institute of Nanoscience and Nanotechnology Instituto Superior Técnico, Universidade de Lisboa Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

2017-01-15

Highlights: • 1D titanate based nanomaterials were prepared via a hydrothermal approach. • The structural and photochemical evaluation of the nanomaterials was performed. • A fluorescent dye was used as a surface probe in visible excitation conditions. • Amicarbazone was used as the model contaminant for photodegradation studies. - Abstract: One-dimensional (1D) titanate based nanomaterials were synthesized following an alkaline hydrothermal approach of commercial TiO{sub 2} nanopowder. The morphological features of all materials were monitored by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), and also Brunauer-Emmett-Teller (BET) technique. In addition the photochemical behaviour of these nanostructured materials were evaluated with the use of laser induced luminescence (LIL), ground-state diffuse reflectance (GSDR), and laser-flash photolysis in diffuse reflectance mode (DRLFP). The mixed titanate/TiO{sub 2} nanowires presented the least intense fluorescence spectra, suggesting the presence of surficial defects that can extend the lifetime of the excited charge carriers. A fluorescent ‘rhodamine-like’ dye was adsorbed onto different materials and examined via photoexcitation in the visible range to study the self-photosensitization mechanism. The presence of the radical cation of the dye and the degradation kinetics, when compared with a neutral substrate—cellulose, provided significant evidences regarding the photoactivity of the different materials. Regarding all the materials under study, the nanowires exhibited a strong photocatalytic efficiency, for the adsorbed fluorescent probe. The photocatalytic mechanism was also considered by studying the photodegradation capability of the titanate based materials in the presence of an herbicide, Amicarbazone, after ultraviolet (UVA) photoexcitation.

Unified computational model of transport in metal-insulating oxide-metal systems

Science.gov (United States)

Tierney, B. D.; Hjalmarson, H. P.; Jacobs-Gedrim, R. B.; Agarwal, Sapan; James, C. D.; Marinella, M. J.

2018-04-01

A unified physics-based model of electron transport in metal-insulator-metal (MIM) systems is presented. In this model, transport through metal-oxide interfaces occurs by electron tunneling between the metal electrodes and oxide defect states. Transport in the oxide bulk is dominated by hopping, modeled as a series of tunneling events that alter the electron occupancy of defect states. Electron transport in the oxide conduction band is treated by the drift-diffusion formalism and defect chemistry reactions link all the various transport mechanisms. It is shown that the current-limiting effect of the interface band offsets is a function of the defect vacancy concentration. These results provide insight into the underlying physical mechanisms of leakage currents in oxide-based capacitors and steady-state electron transport in resistive random access memory (ReRAM) MIM devices. Finally, an explanation of ReRAM bipolar switching behavior based on these results is proposed.

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.

Modelling of oxidation and hydriding behaviour of Zircaloy-2 pressure tubes in PHWR

International Nuclear Information System (INIS)

Sah, D.N.; Sunil Kumar; Khan, K.B.

2002-01-01

A computer model named DOCTOR (Deuteriding of Coolant Tubes during Operation of Reactor) has been developed for predicting the axial profile of oxide thickness and hydrogen (Deuterium) concentration in PHWR pressure tubes. This model is applicable to single channel or full core analysis. The main source of hydrogen is considered to be oxidation of pressure tube on the i.d. surface by high temperature coolant water. Three stages of oxidation is considered namely, pre- transition, post transition and accelerated. Oxidation rate is considered to be dependent on channel power, axial power/flux distribution, coolant temperature and pre-existing oxide thickness at the location. The kinetics parameters for oxidation model are derived from the actual measurement of oxide thickness on a number of pressure tubes examined in PIE Division. The input data required for the model are: channel power, channel power factor, axial flux distribution, coolant inlet temperature, critical oxide thickness, hydrogen pick up fraction, initial hydrogen in the material and time of operation (efpy). The model calculates the oxide layer thickness on the inside surface of the pressure tube along the length. The amount of hydrogen picked up by the pressure tube is calculated from the oxide thickness using hydrogen pick up fraction determined from the PIE data. The pressure tube length is divided into a number of axial segments for calculation. The temperature and fast neutron flux assumed to be constant in a given segment. The axial temperature profile calculated from the axial power profile in the channel is used for calculating the oxidation rate at various locations in the pressure tube. The model has been validated with PIE data of hydrogen equivalent measurement on a number of irradiated Zircaloy-2 pressure tubes of various PHWRs. The performance of the model in predicting the axial profile of hydrogen in the pressure tubes has been found to be good. (author)

Separation of the mercury isotopes by the indirect photochemical method

International Nuclear Information System (INIS)

Botter nee Bergheaud, F.; Scaringella nee Desnoyer, M.; Wacongne, M.

1976-01-01

A method of photochemical separation of the mercury isotopes by the so-called indirect route in which a gas stream of oxygen and butadiene containing a mixture of mercury isotopes is passed through one or a number of vessels placed in series. The gas stream is irradiated by a lamp containing mercury which is depleted in one or a number of the isotopes and said isotopes are recovered in a trap placed downstream of the vessel or vessels

Photophysical and photochemical properties of novel metallophthalocyanines bearing 7-oxy-3-(m-methoxyphenyl)coumarin groups

Energy Technology Data Exchange (ETDEWEB)

Taştemel, Ayşegül; Karaca, Birsen Yılmaz [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey); Durmuş, Mahmut [Gebze Technical University, Department of Chemistry, P.O. Box 141, Gebze 41400, Kocaeli (Turkey); Bulut, Mustafa, E-mail: mbulut@marmara.edu.tr [Marmara University, Faculty of Art and Science, Department of Chemistry, 34722 Kadıkoy-Istanbul (Turkey)

2015-12-15

Tetra-peripherally and non-peripherally 7-oxy-3-(m-methoxyphenyl)coumarin-substituted zinc(II) (4a and 5a), indium(III)acetate (4b and 5b) and magnesium(II) (4c and 5c) phthalocyanines were synthesized for the first time. These phthalocyanines were characterized by elemental analysis, FT-IR, {sup 1}H NMR, UV–vis spectroscopy and mass spectra. The novel phthalocyanines showed excellent solubility in general organic solvents, such as dichloromethane, chloroform, tetrahydrofuran (THF), N,N-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The photophysical and photochemical properties of these phthalocyanines were investigated in DMF. The effects of the central metal ions (Zn{sup 2+}, Mg{sup 2+}, In{sup +3}) and the position (peripheral or non-peripheral) of the substituents on the photophysical and photochemical parameters were reported for comparison. The singlet oxygen quantum yield values of novel phthalocyanines ranged from 0.29 to 0.82 in DMF. In this study, the fluorescence quenching behavior of the studied zinc(II) and magnesium(II) phthalocyanine complexes was also described by the addition of 1,4-benzoquinone. - Highlights: • 7-oxy-3-(m-methoxyphenyl)coumarin-substituted Zn, In(III)OAc and Mg phthalocyanines. • Investigation of their photophysical and photochemical properties in DMF. • The effects of metal types and position of the substituents on these properties.

Enhanced fluorescence detection of dansyl derivatives of phenolic compounds using a postcolumn photochemical reactor and application to chlorophenols in river water

Energy Technology Data Exchange (ETDEWEB)

de Ruiter, C.; Bohle, J.F.; de Jong, G.J.; Brinkman, U.A.T.; Frei, R.W.

1988-04-01

Photochemical decomposition by ultraviolet (UV) irradiation of dansyl derivatives of phenolic compounds in methanol-water mixtures leads to the formation of highly fluorescent dansyl-OH and dansyl-OCH/sub 3/. With substituted phenols as model compounds, it is demonstrated that inductive effects, caused by the substituents, play a major role in the gain in fluorescence signal (up to 8000-fold) that is obtained after postcolumn UV irradiation of the dansyl derivative, compared to that of the nonirradiated derivative. The optimal irradiation time for the dansyl derivatives is about 5.5 s. All monosubstituted phenolic dansyl derivatives now have a comparable limit of detection of approximately 200 pg (S/N = 3). The calibration curve of dansylated pentachlorophenol, using the postcolumn photochemical reactor under optimal conditions, is linear over at least 3 orders of magnitude with a correlation coefficient of 0.9999 (n = 9). Application of the system to the liquid chromatographic determination of highly chlorinated phenols in river water is presented. The repeatability of the system for a river water sample, spiked with 1 ppb pentachlorophenol, is 2.4% relative standard deviation (n = 5).

Enhanced cellular delivery of cell-penetrating peptide-peptide nucleic acid conjugates by photochemical internalization

DEFF Research Database (Denmark)

Shiraishi, Takehiko; Nielsen, Peter E

2011-01-01

(antisense activity) is still limited by endocytotic entrapment. We have shown that this low bioavailability can be greatly improved by combining CPP-PNA conjugate administration with a photochemical internalization technique using photosensitizers such as aluminum phthalocyanine (AlPcS(2a...

Ultra-trace determination of iodine in sediments and biological material using UV photochemical generation-inductively coupled plasma mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Grinberg, Patricia [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada)], E-mail: patricia.grinberg@nrc.ca; Sturgeon, Ralph E. [Institute for National Measurements Standards, National Research Council Canada, Ottawa, Ontario, K1A 0R6 (Canada)

2009-03-15

Several sample preparation techniques have been evaluated for the determination of iodine using UV-photochemical generation-quadrupole inductively coupled plasma mass spectrometry. Thermal decomposition of samples at 1000 {sup o}C followed by capture of the liberated iodine in dilute acetic acid permitted subsequent UV-photochemical generation of a volatile iodine species that serves to enhance sensitivity 25-fold over conventional solution nebulization, delivering reagent blank detection limits of 8.75 pg g{sup -1127}I and 0.075 pg g{sup -1129}I for solid samples (400 mg test mass). The methodology was validated through determination of total iodine in several Standard Reference Materials, including NIST 1572 Citrus leaves, NIST 1549 Non-fat milk powder, NIST 1566a Oyster tissue and NIST 2709 San Joaquin Soil. Liberation of iodine from samples and its collection as well as photochemical generation were quantitative, permitting calibration to be achieved using standards prepared in dilute acetic acid.

Photochemically induced carbon dioxide production as a mechanism for carbon loss from plant litter in arid ecosystems

Science.gov (United States)

Brandt, L. A.; Bohnet, C.; King, J. Y.

2009-06-01

We investigated the potential for abiotic mineralization to carbon dioxide (CO2) via photodegradation to account for carbon (C) loss from plant litter under conditions typical of arid ecosystems. We exposed five species of grass and oak litter collected from arid and mesic sites to a factorial design of ultraviolet (UV) radiation (UV pass, UV block), and sterilization under dry conditions in the laboratory. UV pass treatments produced 10 times the amount of CO2 produced in UV block treatments. CO2 production rates were unaffected by litter chemistry or sterilization. We also exposed litter to natural solar radiation outdoors on clear, sunny days close to the summer solstice at midlatitudes and found that UV radiation (280-400 nm) accounted for 55% of photochemically induced CO2 production, while shortwave visible radiation (400-500 nm) accounted for 45% of CO2 production. Rates of photochemically induced CO2 production on a per-unit-mass basis decreased with litter density, indicating that rates depend on litter surface area. We found no evidence for leaching, methane production, or facilitation of microbial decomposition as alternative mechanisms for significant photochemically induced C loss from litter. We conclude that abiotic mineralization to CO2 is the primary mechanism by which C is lost from litter during photodegradation. We estimate that CO2 production via photodegradation could be between 1 and 4 g C m-2 a-1 in arid ecosystems in the southwestern United States. Taken together with low levels of litter production in arid systems, photochemical mineralization to CO2 could account for a significant proportion of annual carbon loss from litter in arid ecosystems.

Highly stable and imperceptible electronics utilizing photoactivated heterogeneous sol-gel metal-oxide dielectrics and semiconductors.

Science.gov (United States)

Jo, Jeong-Wan; Kim, Jaekyun; Kim, Kyung-Tae; Kang, Jin-Gu; Kim, Myung-Gil; Kim, Kwang-Ho; Ko, Hyungduk; Kim, Jiwan; Kim, Yong-Hoon; Park, Sung Kyu

2015-02-18

Incorporation of Zr into an AlOx matrix generates an intrinsically activated ZAO surface enabling the formation of a stable semiconducting IGZO film and good interfacial properties. Photochemically annealed metal-oxide devices and circuits with the optimized sol-gel ZAO dielectric and IGZO semiconductor layers demonstrate the high performance and electrically/mechanically stable operation of flexible electronics fabricated via a low-temperature solution process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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)

Determination of total mercury and methylmercury in biological samples by photochemical vapor generation

Energy Technology Data Exchange (ETDEWEB)

Vieira, Mariana A.; Ribeiro, Anderson S.; Curtius, Adilson J. [Universidade Federal de Santa Catarina, Departamento de Quimica, Florianopolis, SC (Brazil); Sturgeon, Ralph E. [National Research Council Canada, Institute for National Measurement Standards, Ottawa, ON (Canada)

2007-06-15

Cold vapor atomic absorption spectrometry (CV-AAS) based on photochemical reduction by exposure to UV radiation is described for the determination of methylmercury and total mercury in biological samples. Two approaches were investigated: (a) tissues were digested in either formic acid or tetramethylammonium hydroxide (TMAH), and total mercury was determined following reduction of both species by exposure of the solution to UV irradiation; (b) tissues were solubilized in TMAH, diluted to a final concentration of 0.125% m/v TMAH by addition of 10% v/v acetic acid and CH{sub 3}Hg{sup +} was selectively quantitated, or the initial digests were diluted to 0.125% m/v TMAH by addition of deionized water, adjusted to pH 0.3 by addition of HCl and CH{sub 3}Hg{sup +} was selectively quantitated. For each case, the optimum conditions for photochemical vapor generation (photo-CVG) were investigated. The photochemical reduction efficiency was estimated to be {proportional_to}95% by comparing the response with traditional SnCl{sub 2} chemical reduction. The method was validated by analysis of several biological Certified Reference Materials, DORM-1, DORM-2, DOLT-2 and DOLT-3, using calibration against aqueous solutions of Hg{sup 2+}; results showed good agreement with the certified values for total and methylmercury in all cases. Limits of detection of 6 ng/g for total mercury using formic acid, 8 ng/g for total mercury and 10 ng/g for methylmercury using TMAH were obtained. The proposed methodology is sensitive, simple and inexpensive, and promotes ''green'' chemistry. The potential for application to other sample types and analytes is evident. (orig.)

Effect of Organic Matter on Cyanide Removal by Illuminated Titanium Dioxide or Zinc Oxide Nanoparticles

Directory of Open Access Journals (Sweden)

Mehdi Shirzad-Siboni

2013-08-01

Full Text Available Effect of different type of organic compounds (humic acid, oxalate, ethylenediaminetetraacetic acid, nitrilotriacetic acid, phenol on the photocatalytic removal of cyanide with TiO2 or ZnO was studied in this work with variation of the solution pH, contact time, initial cyanide concentration and type of organic compounds. Photocatalytic oxidation efficiency of cyanide with TiO2 was greatly affected by the solution pH. It increased as the solution pH decreased. Also maximum removal of cyanide by ZnO was observed near at neutral pH because of the reduced photocatalytic activity of ZnO at exceedingly low and high pH values originated from either acidic/photochemical corrosion of the catalyst and/or surface passivation with Zn(OH2. Removal efficiency of cyanide greatly decreased in the presence of humic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid compared to that without presence of organic compound because of the competitive oxidation as well as surface blocking by relatively large organic compounds. The oxidation pattern of cyanide was better described by first-order kinetic model. Finally photocatalytic reaction with TiO2 or ZnO can be effectively applied to treat synthetic wastewater contaminated with cyanide.

Photochemical fate and eco-genotoxicity assessment of the drug etodolac

Energy Technology Data Exchange (ETDEWEB)

Passananti, Monica [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF) UMR 6296, BP 10448, F-63000 Clermont-Ferrand (France); Lavorgna, Margherita [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy); Iesce, Maria Rosaria, E-mail: iesce@unina.it [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); DellaGreca, Marina [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Brigante, Marcello [Clermont Université, Université Blaise Pascal, Institut de Chimie de Clermont-Ferrand (ICCF) UMR 6296, BP 10448, F-63000 Clermont-Ferrand (France); Criscuolo, Emma [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy); Cermola, Flavio [Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario Monte S. Angelo, via Cintia, 4, 80126 Napoli (Italy); Isidori, Marina, E-mail: marina.isidori@unina2.it [Dipartimento di Scienze e Tecnologie Ambientali, Biologiche e Farmaceutiche, Seconda Università di Napoli, Via Vivaldi 43, I-81100 Caserta (Italy)

2015-06-15

The photochemical behavior of etodolac was investigated under various irradiation conditions. Kinetic data were obtained after irradiation of 10{sup −4} M aqueous solutions by UVB, UVA and direct exposure to sunlight. The Xenon lamp irradiation was used in order to determine the photodegradation quantum yield under sun-simulated condition (ϕ{sub sun}). The value was determined to be = 0.10 ± 0.01. In order to obtain photoproducts and for mechanistic purposes, experiments were carried out on more concentrated solutions by exposure to sunlight and to UVA and UVB lamps. The drug underwent photooxidative processes following an initial oxygen addition to the double bond of the five membered ring and was mainly converted into a spiro compound and a macrolactam. Ecotoxicity tests were performed on etodolac, its photostable spiro derivative and its sunlight irradiation mixture on two different aquatic trophic levels, plants (algae) and invertebrates (rotifers and crustaceans). Mutagenesis and genotoxicity were detected on bacterial strains. The results showed that only etodolac had long term effects on rotifers although at concentrations far from environmental detection values. A mutagenic and genotoxic potential was found for its derivative. - Highlights: • Photochemical transformation of etodolac occurs in the environment. • Etodolac was slightly toxic in the long term for some aquatic organisms. • A mutagenic and genotoxic potential was found for etodolac photostable derivative.

The photochemistry of the paleoatmosphere

Science.gov (United States)

Levine, J. S.

1982-01-01

Recent progress in the understanding of the chemistry and photochemistry of the paleoatmosphere is reviewed with emphasis on the application of photochemical models to the investigation of the evolution of the atmosphere. Photochemical calculations are presented which show that a primordial highly reducing atmosphere composed of methane and ammonia, if it formed at all, would be short-lived in the presence of solar ultraviolet radiation, giving way rapidly to a more mildly reducing atmosphere of carbon dioxide and nitrogen. Estimations of O2 produced from the photolysis of water vapor prior to the emergence of photosynthesis range from less than 10 to the -14th to 0.1 times the present atmospheric level, indicating the need for further research. A series of photochemical models of increasing complexity has been developed to study the evolution of atmospheric ozone taking into account reactions with O atoms, hydrogen oxides, nitrogen oxides, and chlorine as well as vertical transport, temperature and tropospheric chemistry so that the total content and vertical distribution of O3 may be determined for a specified level of paleoatmospheric O2.

Atmospheric origins of perchlorate on Mars and in the Atacama

Science.gov (United States)

Catling, D. C.; Claire, M. W.; Zahnle, K. J.; Quinn, R. C.; Clark, B. C.; Hecht, M. H.; Kounaves, S.

2010-01-01

Isotopic studies indicate that natural perchlorate is produced on Earth in arid environments by the oxidation of chlorine species through pathways involving ozone or its photochemical products. With this analogy, we propose that the arid environment on Mars may have given rise to perchlorate through the action of atmospheric oxidants. A variety of hypothetical pathways can be proposed including photochemical reactions, electrostatic discharge, and gas-solid reactions. Because perchlorate-rich deposits in the Atacama desert are closest in abundance to perchlorate measured at NASA's Phoenix Lander site, we made a preliminary study of the means to produce Atacama perchlorate to help shed light on the origin of Martian perchlorate. We investigated gas phase pathways using a 1-D photochemical model. We found that perchlorate can be produced in sufficient quantities to explain the abundance of perchlorate in the Atacama from a proposed gas phase oxidation of chlorine volatiles to perchloric acid. The feasibility of gas phase production for the Atacama provides justification for future investigations of gas phase photochemistry as a possible source for Martian perchlorate.

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.

A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

Science.gov (United States)

Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

2015-12-15

Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

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

Science.gov (United States)

London, A J; Lozano-Perez, S; Moody, M P; Amirthapandian, S; Panigrahi, B K; Sundar, C S; Grovenor, C R M

2015-12-01

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-0.3Y2O3, Fe-0.2Ti-0.3Y2O3 and Fe-14Cr-0.2Ti-0.3Y2O3. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

Ozone modeling

Energy Technology Data Exchange (ETDEWEB)

McIllvaine, C M

1994-07-01

Exhaust gases from power plants that burn fossil fuels contain concentrations of sulfur dioxide (SO{sub 2}), nitric oxide (NO), particulate matter, hydrocarbon compounds and trace metals. Estimated emissions from the operation of a hypothetical 500 MW coal-fired power plant are given. Ozone is considered a secondary pollutant, since it is not emitted directly into the atmosphere but is formed from other air pollutants, specifically, nitrogen oxides (NO), and non-methane organic compounds (NMOQ) in the presence of sunlight. (NMOC are sometimes referred to as hydrocarbons, HC, or volatile organic compounds, VOC, and they may or may not include methane). Additionally, ozone formation Alternative is a function of the ratio of NMOC concentrations to NO{sub x} concentrations. A typical ozone isopleth is shown, generated with the Empirical Kinetic Modeling Approach (EKMA) option of the Environmental Protection Agency's (EPA) Ozone Isopleth Plotting Mechanism (OZIPM-4) model. Ozone isopleth diagrams, originally generated with smog chamber data, are more commonly generated with photochemical reaction mechanisms and tested against smog chamber data. The shape of the isopleth curves is a function of the region (i.e. background conditions) where ozone concentrations are simulated. The location of an ozone concentration on the isopleth diagram is defined by the ratio of NMOC and NO{sub x} coordinates of the point, known as the NMOC/NO{sub x} ratio. Results obtained by the described model are presented.

A single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice

Science.gov (United States)

The data presented here shows that a single exposure to photochemical smog causes airway irritation and cardiac dysrhythmia in mice. Smog, which is a complex mixture of particulate matter and gaseous irritants (ozone, sulfur dioxide, reactive aldehydes), as well as components whi...

Large-scale Modeling of Nitrous Oxide Production: Issues of Representing Spatial Heterogeneity

Science.gov (United States)

Morris, C. K.; Knighton, J.

2017-12-01

Nitrous oxide is produced from the biological processes of nitrification and denitrification in terrestrial environments and contributes to the greenhouse effect that warms Earth's climate. Large scale modeling can be used to determine how global rate of nitrous oxide production and consumption will shift under future climates. However, accurate modeling of nitrification and denitrification is made difficult by highly parameterized, nonlinear equations. Here we show that the representation of spatial heterogeneity in inputs, specifically soil moisture, causes inaccuracies in estimating the average nitrous oxide production in soils. We demonstrate that when soil moisture is averaged from a spatially heterogeneous surface, net nitrous oxide production is under predicted. We apply this general result in a test of a widely-used global land surface model, the Community Land Model v4.5. The challenges presented by nonlinear controls on nitrous oxide are highlighted here to provide a wider context to the problem of extraordinary denitrification losses in CLM. We hope that these findings will inform future researchers on the possibilities for model improvement of the global nitrogen cycle.

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...

Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies Evaluation Number 16. Supplement to Evaluation 15: Update of Key Reactions

Science.gov (United States)

Sander, S. P.; Friedl, R. R.; Barker, J. R.; Golden, D. M.; Kurylo, M. J.; Wine, P. H.; Abbatt, J.; Burkholder, J. B.; Kolb, C. E.; Moortgat, G. K.;

Will Organic Synthesis Within Icy Grains or on Dust Surfaces in the Primitive Solar Nebula Completely Erase the Effects of Photochemical Self Shielding?

Science.gov (United States)

Nuth, Joseph A., III; Johnson, Natasha M.

2012-01-01

There are at least 3 separate photochemical self-shielding models with different degrees of commonality. All of these models rely on the selective absorption of (12))C(16)O dissociative photons as the radiation source penetrates through the gas allowing the production of reactive O-17 and O-18 atoms within a specific volume. Each model also assumes that the undissociated C(16)O is stable and does not participate in the chemistry of nebular dust grains. In what follows we will argue that this last, very important assumption is simply not true despite the very high energy of the CO molecular bond.

Photochemical cycle of bacteriorhodopsin studied by resonance Raman spectroscopy.

Science.gov (United States)

Stockburger, M; Klusmann, W; Gattermann, H; Massig, G; Peters, R

1979-10-30

Individual species of the photochemical cycle of bacteriorhodopsin, a retinal-protein complex of Halobacteria, were studied in aqueous suspensions of the "purple membrane" at room temperature by resonance Raman (RR) spectroscopy with flow systems. Two pronounced deuterium shifts were found in the RR spectra of the all-trans complex BR-570 in H2O-D2O suspensions. The first is ascribed to C=NH+ (C=ND+) stretching vibrations of the protonated Schiff base which links retinal to opsin. The second is assigned tentatively to an "X-H" ("X-D") bending mode, where "X" is an atom which carries an exchangeable proton. A RR spectrum of the 13-cis-retinal complex "BR-548" could be deduced from spectra of the dark-adapted purple membrane. The RR spectrum of the M-412 intermediate was monitored in a double-beam pump-probe experiment. The main vibrational features of the intermediate M' in the reaction M-412 in equilibrium hv M' leads to delta BR-570 could be deduced from a photostationary mixture of M-412 and M'. Difference procedures were applied to obtain RR spectra of the L-550 intermediate and of two new long-lived species, R1'-590 and R2-550. From kinetic data it is suggested that T1'-590 links the proton-translocating cycle to the "13-cis" cycle of BR-548. The protonation and isomeric states of the different species are discussed in light of the new spectroscopic and kinetic data. It is found that conformational changes during the photochemical cycle play an important role.

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.

Carotenoid-induced non-photochemical quenching in the cyanobacterial chlorophyll synthase-HliC/D complex

Czech Academy of Sciences Publication Activity Database

Niedzwiedzki, D.M.; Tronina, T.; Liu, H.; Staleva, H.; Komenda, Josef; Sobotka, Roman; Blankenship, R.E.; Polívka, T.

2016-01-01

Roč. 1857, č. 9 (2016), s. 1430-1439 ISSN 0005-2728 R&D Projects: GA ČR GBP501/12/G055 Institutional support: RVO:61388971 Keywords : Carotenoids * Non-photochemical quenching * Energy transfer Subject RIV: CE - Biochemistry Impact factor: 4.932, year: 2016

Effects of Biological and Photochemical Degradation on the Optical Properties of CDOM Exported to Coastal Marine Environments

National Research Council Canada - National Science Library

Moran, Mary

2004-01-01

.... This project quantitatively assessed the ability of coastal ocean bacteria to degrade and produce CDOM and investigated the synergistic interactions between bacterial degradation and photochemical...

Photochemical Formation of C1-C5 Alkyl Nitrates in Suburban Hong Kong and over the South China Sea.

Science.gov (United States)

Zeng, Lewei; Lyu, Xiaopu; Guo, Hai; Zou, Shichun; Ling, Zhenhao

2018-04-24

Alkyl nitrates (RONO 2 ) are important reservoirs of atmospheric nitrogen, regulating nitrogen cycling and ozone (O 3 ) formation. In this study, we found that propane and n-butane were significantly lower at the offshore site (WSI) in Hong Kong ( p 0.05). Stronger oxidative capacity at WSI led to more efficient RONO 2 formation. Relative incremental reactivity (RIR) was for the first time used to evaluate RONO 2 -precursor relationships. In contrast to a consistently volatile organic compounds (VOC)-limited regime at TC, RONO 2 formation at WSI switched from VOC-limited regime during O 3 episodes to VOC and nitrogen oxides (NO x ) colimited regime during nonepisodes. Furthermore, unlike the predominant contributions of parent hydrocarbons to C 4 -C 5 RONO 2 , the production of C 1 -C 3 RONO 2 was more sensitive to other VOCs like aromatics and carbonyls, which accounted for ∼40-90% of the productions of C 1 -C 3 alkylperoxy (RO 2 ) and alkoxy radicals (RO) at both sites. This resulted from the decomposition of larger RO 2 /RO and the change of OH abundance under the photochemistry of other VOCs. This study advanced our understanding of the photochemical formation of RONO 2 , particularly the relationships between RONO 2 and their precursors, which were not confined to the parent hydrocarbons.

Photochemical reduction of water-soluble C60 derivatives (EPR study)

International Nuclear Information System (INIS)

Brezova, V.; Stasko, A.; Dvoranova, D.; Asmus, K.D.; Guldi, D.M.

1999-01-01

The photochemical reduction of three bis-functionalized C 60 derivatives resulted in the formation of a single radical product, characterized by relatively narrow EPR line (g M = 2.0007, pp < 0.02 mT). In the irradiated aqueous solutions containing L-ascorbic acid, in the addition to the EPR line related to bis-adduct mono-anion, also 6-line EPR spectrum of ascorbyl radical was observed. Consequently, the photoinduced formation of ascorbyl radical was attributed to the intermolecular quenching of fullerenes excited states. (authors)

Suppression of non-photochemical quenching in Arabidopsis leaves to a ionizing radiation

International Nuclear Information System (INIS)

Yu Ran Moon; Jin-Hong Kim; Min Hee Lee; Byung Yeoup Chung; Jae-Sung Kim

2007-01-01

Complete text of publication follows. Non-photochemical quenching (NPQ) of chlorophyll fluorescence has been known to be involved in a protection of photosystems against photoinhibition through a dissipation of excess light absorbed by photosynthetic pigments. In the present study, we aimed to elucidate the effects of a ionizing radiation on NPQ by comparing alterations in the development and release of NPQ after gamma-irradiation between the wild-type (WT) and the npq1-2 mutant of Arabidopsis. The npq1-2 mutant can't develop with a normal NPQ under excess light, since it is defective in its de-epoxidase activity for conversion of violaxanthin to zeaxanthin. Gamma-irradiation with a dose of 200 Gy inhibited the development of NPQ in both the WT and mutant but more noticeably in the latter. Moreover, Fv/Fm as an indice of the photochemical efficiency of photosystem II (PSII) was almost the same in both the WT and npq1-2 mutant throughout the post-irradiation period of 5 d. The obtained results will be also discussed with those from photoinhibition induced by non-ionizing radiations such as visible light and UV-B.

Systems and methods for solar energy storage, transportation, and conversion utilizing photochemically active organometallic isomeric compounds and solid-state catalysts

Science.gov (United States)

Vollhardt, K. Peter C.; Segalman, Rachel A; Majumdar, Arunava; Meier, Steven

2015-02-10

A system for converting solar energy to chemical energy, and, subsequently, to thermal energy includes a light-harvesting station, a storage station, and a thermal energy release station. The system may include additional stations for converting the released thermal energy to other energy forms, e.g., to electrical energy and mechanical work. At the light-harvesting station, a photochemically active first organometallic compound, e.g., a fulvalenyl diruthenium complex, is exposed to light and is photochemically converted to a second, higher-energy organometallic compound, which is then transported to a storage station. At the storage station, the high-energy organometallic compound is stored for a desired time and/or is transported to a desired location for thermal energy release. At the thermal energy release station, the high-energy organometallic compound is catalytically converted back to the photochemically active organometallic compound by an exothermic process, while the released thermal energy is captured for subsequent use.

Photochemical internalization enhanced macrophage delivered chemotherapy.

Science.gov (United States)

Shin, Diane; Christie, Catherine; Ju, David; Nair, Rohit Kumar; Molina, Stephanie; Berg, Kristian; Krasieva, Tatiana B; Madsen, Steen J; Hirschberg, Henry

2018-03-01

Macrophage (Ma) vectorization of chemotherapeutic drugs has the advantage for cancer therapy in that it can actively target and maintain an elevated concentration of drugs at the tumor site, preventing their spread into healthy tissue. A potential drawback is the inability to deliver a sufficient number of drug-loaded Ma into the tumor, thus limiting the amount of active drug delivered. This study examined the ability of photochemical internalization (PCI) to enhance the efficacy of released drug by Ma transport. Tumor spheroids consisting of either F98 rat glioma cells or F98 cells combined with a subpopulation of empty or doxorubicin (DOX)-loaded mouse Ma (RAW264.7) were used as in vitro tumor models. PCI was performed with the photosensitizer AlPcS 2a and laser irradiation at 670 nm. RAW264.7 Ma pulsed with DOX released the majority of the incorporated DOX within two hours of incubation. PCI significantly increased the toxicity of DOX either as pure drug or derived from monolayers of DOX-loaded Ma. Significant growth inhibition of hybrid spheroids was also observed with PCI even at subpopulations of DOX-loaded Ma as low as 11% of the total initial hybrid spheroid cell number. Results show that RAW264.7 Ma, pulsed with DOX, could effectively incorporate and release DOX. PCI significantly increased the ability of both free and Ma-released DOX to inhibit the growth of tumor spheroids in vitro. The growth of F98 + DOX loaded Ma hybrid spheroids were synergistically reduced by PCI, compared to either photodynamic therapy or released DOX acting alone. Copyright © 2017 Elsevier B.V. All rights reserved.

Performance analysis of a solar photochemical photovoltaic hybrid system for decolorization of Acid Red 26 (AR 26)

International Nuclear Information System (INIS)

Cui, Lingyun; Zhu, Li; Huang, Qunwu; Wang, Yiping; Jin, Yanchao; Sun, Yong; Cui, Yong; Chen, Miao; Fan, Jiangyang

2017-01-01

To reduce the power energy consumption of wastewater treatment and make full use of the solar spectrum, a new water purification system that integrated homogeneous solar photochemical (SPC) and photovoltaics (PV) was constructed to treat wastewater and generate electricity for the first time. Hydrogen peroxide (H_2O_2) and potassium persulfate (K_2S_2O_8) were chosen as oxidants in the system and have a comparative analysis. The results show that solar/K_2S_2O_8 has a higher decolorization efficiency than solar/H_2O_2, the accumulated ultraviolet energy in solar/K_2S_2O_8, needed for complete decolorization, is far lower than in solar/H_2O_2. Also temperature has a positive effect on the dark-K_2S_2O_8 processes especially in the range of 40–60 °C, and it follows pseudo-first-order kinetic relationship. Meanwhile, to investigate the influence of flow channel on PV, the short circuit current (I_s_c) and maximum output power (P_m) were monitored. It indicates that the presence of flow channel effectively decreases the working temperature of PV modules, while the I_s_c and P_m have a different degree reduce. Luckily, the impact is not big. Additionally, P_m in experiment system, though lower than reference system, is sufficient to drive the whole system. - Highlights: • The hybrid system combing homogenous photochemical with photovoltaics was firstly performed. • Solar/K_2S_2O_8 and solar/H_2O_2 is comparative analysis in the decolorization of AR 26. • K_2S_2O_8 can be activated by heat and irradiation simultaneously in the hybrid system. • The PV panel of the hybrid system could work under lower temperature. • Solar spectrum could be made full use for power generation and water purification.

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

Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

Science.gov (United States)

Anderson, I. C.; Levine, J. S.

1986-01-01

An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

Proposal to realize a cost breakthrough in carbon-13 production by photochemical separation

International Nuclear Information System (INIS)

Marling, J.B.

1979-10-01

A cost breakthrough can now be made in photochemical production of the rare stable isotope carbon-13. This cost breakthrough is achieved by CO 2 laser infrared multiple-photon dissociation of any of several halocarbons (Freon derivatives) such as CF 3 Cl, CF 3 Br, or CF 2 Cl 2 . The single-step carbon-13 enrichment factor for this process is approximately 50, yielding 30% pure C-13 in one step, or up to 97% pure C-13 in two steps. A three-fold carbon-13 cost reduction to below $20/gram is expected to be achieved in a small laboratory-scale demonstration facility capable of producing 4 to 8 kg/year of carbon-13, using presently available pulsed CO 2 TEA lasers at an average power level of 50 watts. Personnel costs dominate the attainable C-13 production costs in a small photochemical enrichment facility. A price reduction to $2/gm carbon-13 is feasible at carbon-13 production levels of 100 to 1000 kg/year, dominated by the Freon raw material costs

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.

Chemical kinetic models for combustion of hydrocarbons and formation of nitric oxide

Science.gov (United States)