Uranium Oxide Rate Summary for the Spent Nuclear Fuel (SNF) Project (OCRWM)

International Nuclear Information System (INIS)

PAJUNEN, A.L.

2000-01-01

The purpose of this document is to summarize the uranium oxidation reaction rate information developed by the Hanford Spent Nuclear Fuel (SNF) Project and describe the basis for selecting reaction rate correlations used in system design. The selection basis considers the conditions of practical interest to the fuel removal processes and the reaction rate application during design studies. Since the reaction rate correlations are potentially used over a range of conditions, depending of the type of evaluation being performed, a method for transitioning between oxidation reactions is also documented. The document scope is limited to uranium oxidation reactions of primary interest to the SNF Project processes. The reactions influencing fuel removal processes, and supporting accident analyses, are: uranium-water vapor, uranium-liquid water, uranium-moist air, and uranium-dry air. The correlation selection basis will consider input from all available sources that indicate the oxidation rate of uranium fuel, including the literature data, confirmatory experimental studies, and fuel element observations. Trimble (2000) summarizes literature data and the results of laboratory scale experimental studies. This document combines the information in Trimble (2000) with larger scale reaction observations to describe uranium oxidation rate correlations applicable to conditions of interest to the SNF Project

Tritium breeding and release-rate kinetics from neutron-irradiated lithium oxide

International Nuclear Information System (INIS)

Quanci, J.F.

1989-01-01

The research encompasses the measurement of the tritium breeding and release-rate kinetics from lithium oxide, a ceramic tritium-breeding material. A thermal extraction apparatus which allows the accurate measurement of the total tritium inventory and release rate from lithium oxide samples under different temperatures, pressures and carrier-gas compositions with an uncertainty not exceeding 3% was developed. The goal of the Lithium Blanket Module program was to determine if advanced computer codes could accurately predict the tritium production in the lithium oxide blanket of a fusion power plant. A fusion blanket module prototype, was built and irradiated with a deuterium-tritium fusion-neutron source. The tritium production throughout the module was modeled with the MCNP three dimensional Monte Carlo code and was compared to the assay of the tritium bred in the module. The MCNP code accurately predicted tritium-breeding trends but underestimated the overall tritium breeding by 30%. The release rate of tritium from small grain polycrystalline sintered lithium oxide with a helium carrier gas from 300 to 450 C was found to be controlled by the first order surface desorption of mono-tritiated water. When small amounts of hydrogen were added to the helium carrier gas, the first order rate constant increased from the isotopic exchange of hydrogen for tritium at the lithium oxide surface occurring in parallel with the first order desorption process. The isotopic-exchange first order rate constant temperature dependence and hydrogen partial pressure dependence were evaluated. Large single crystals of lithium oxide were fabricated by the vacuum fusion technique. The release rate of tritium from the large single crystals was found to be controlled by diffusion, and the mixed diffusion-desorption controlled release regime

Tritium breeding and release-rate kinetics from neutron-irradiated lithium oxide

International Nuclear Information System (INIS)

Quanci, J.F.

1989-01-01

The research encompasses the measurement of the tritium breeding and release-rate kinetics from lithium oxide, a ceramic tritium-breeding material. A thermal extraction apparatus which allows the accurate measurement of the total tritium inventory and release rate from lithium oxide samples under different temperatures, pressures and carrier-gas compositions with an uncertainty not exceeding 3% was developed. The goal of the Lithium Blanket Module program was to determine if advanced computer codes could accurately predict the tritium production in the lithium oxide blanket of a fusion power plant. A fusion blanket module prototype was built and irradiated with a deuterium-tritium fusion-neutron source. The tritium production throughout the module was modeled with the MCNP three dimensional Monte Carlo code and was compared to the assay of the tritium bred in the module. The MCNP code accurately predicted tritium-breeding trends but underestimated the overall tritium breeding by 30%. The release rate of tritium from small grain polycrystalline sintered lithium oxides with a helium carrier gas from 300 to 450 C was found to be controlled by the first order surface desorption of monotritiated water. When small amounts of hydrogen were added to the helium carrier gas, the first order rate constant increased from the isotopic exchange of hydrogen for tritium at the lithium oxide surface occurring in parallel with the first order desorption process. The isotopic-exchange first order rate constant temperature dependence and hydrogen partial pressure dependence were evaluated

Effect of reacting surface density on the overall graphite oxidation rate

International Nuclear Information System (INIS)

Oh, Chang; Kim, Eung; Lim, Jong; Schultz, Richard; Petti, David

2009-01-01

Graphite oxidation in an air-ingress accident is presently a very important issue for the reactor safety of the very high temperature gas cooled-reactor (VHTR), the concept of the next generation nuclear plant (NGNP) because of its potential problems such as mechanical degradation of the supporting graphite in the lower plenum of the VHTR might lead to core collapse if the countermeasure is taken carefully. The oxidation process of graphite has known to be affected by various factors, including temperature, pressure, oxygen concentration, types of graphite, graphite shape and size, flow distribution, etc. However, our recent study reveals that the internal pore characteristics play very important roles in the overall graphite oxidation rate. One of the main issues regarding graphite oxidation is the potential core collapse problem that may occur following the degradation of graphite mechanical strength. In analyzing this phenomenon, it is very important to understand the relationship between the degree of oxidization and strength degradation. In addition, the change of oxidation rate by graphite oxidation degree characterization by burn-off (ratio of the oxidized graphite density to the original density) should be quantified because graphite strength degradation is followed by graphite density decrease, which highly affects oxidation rates and patterns. Because the density change is proportional to the internal pore surface area, they should be quantified in advance. In order to understand the above issues, the following experiments were performed: (1) Experiment on the fracture of the oxidized graphite and validation of the previous correlations, (2) Experiment on the change of oxidation rate using graphite density and data collection, (3) Measure the BET surface area of the graphite. The experiments were performed using H451 (Great Lakes Carbon Corporation) and IG-110 (Toyo Tanso Co., Ltd) graphite. The reason for the use of those graphite materials is because

Isotopic exchange rate of sodium ions between hydrous metal oxides and aqueous solutions

International Nuclear Information System (INIS)

Inoue, Yasushi; Yamazaki, Hiromichi

1991-01-01

To elucidate the kinetics of ion-exchange reaction on hydrous metal oxide, the isotopic exchange rates of sodium ions between hydrous metal oxides such as hydrous tin (IV), niobium (V), zirconium (IV) and titanium (IV) oxides, and aqueous solutions were measured radiochemically and compared with each other. The rate of reaction cannot be understood by an unified view since the rate controlling step differs with the kind of exchangers. The rate constants relevant to each exchanger such as diffusion constants and their activation energies were also determined. (author)

Measurement of sulfur dioxide oxidation rates in wintertime orographic clouds

International Nuclear Information System (INIS)

Snider, J.R.

1990-01-01

SO2-reaction studies in the clouds are examined and summarized to experimentally confirm model predictions and previous field studies regarding dominant SO2-reaction pathways. Controlled amounts of SO2 were released into nonprecipitating orographic clouds, and sulfate yields are compared to oxidant depletions. The sulfate yields were taken from cloud-water samples and liquid-water-concentration measurements, and oxidant-depletion data were generated from continuous gas-phase measurements. Comparisons of Y sub SO4 and D sub H2O2 suggest that H2O2 is the dominant oxidant, and the in-cloud reaction between H2O2 and the bisulfite ion can be expressed by a simple rate that agrees with predictions and laboratory results. The rate measurements are found to be inconsistent with the rate law proposed by Hegg and Hobbs (1982) and with some observational data. The present conclusions are of interest to evaluating the effects of sulfur dioxide emissions on sulfuric acid deposition. 30 refs

The effects of trichloroethane HCl and ion-implantation on the oxidation rate of silicon

International Nuclear Information System (INIS)

Ahmed, W.; Ahmed, E.

1994-01-01

The thermal oxidation of silicon was studied using a large-scale industrial oxidation system. The characteristics of the oxides resulting from pure hydrogen/oxygen (Hsub(2)/Osub(2)), trichloroethane/oxygen (TCA/Osub(2) and hydrogen chloride/oxygen (HCI/Osub(2)) mixtures are compared. Both HCI and TCA addition to oxygen produced an enhanced oxidation rate. The oxidation rate for TCA/Osub(2) was approximately 30-40% higher than for HCI/Osub(2) mixtures. A molar ratio of TCA/Osub(2) of 1% gives an optimum process for very-large-scale industrial (VLSI) applications. However, 3% HCI/Osub(2) gives comparable results to 1% TCA. In addition, boron and phosphorus implantation are observed to increase the oxidation rate. Phosphorus doping of the silicon yields a higher rate than boron-doped wafers. This behaviour is explained in terms of surface damage and chemistry. It appears that the overall mechanisms governing all these processes are similar. (8 figures, 22 references) (Author)

Modeling low-dose-rate effects in irradiated bipolar-base oxides

International Nuclear Information System (INIS)

Graves, R.J.; Cirba, C.R.; Schrimpf, R.D.; Milanowski, R.J.; Saigne, F.; Michez, A.; Fleetwood, D.M.; Witczak, S.C.

1997-02-01

A physical model is developed to quantify the contribution of oxide-trapped charge to enhanced low-dose-rate gain degradation in BJTs. Simulations show that space charge limited transport is partially responsible for the low-dose-rate enhancement

Zircaloy-oxidation and hydrogen-generation rates in degraded-core accident situations

International Nuclear Information System (INIS)

Chung, H.M.; Thomas, G.R.

1983-02-01

Oxidation of Zircaloy cladding is the primary source of hydrogen generated during a degraded-core accident. In this paper, reported Zircaloy oxidation rates, either measured at 1500 to 1850 0 C or extrapolated from the low-temperature data obtained at 0 C, are critically reviewed with respect to their applicability to a degraded-core accident situation in which the high-temperature fuel cladding is likely to be exposed to and oxidized in mixtures of hydrogen and depleted steam, rather than in an unlimited flux of pure steam. New results of Zircaloy oxidation measurements in various mixtures of hydrogen and steam are reported for >1500 0 C. The results show significantly smaller oxidation and, hence, hydrogen-generation rates in the mixture, compared with those obtained in pure steam. It is also shown that a significant fraction of hydrogen, generated as a result of Zircaloy oxidation, is dissolved in the cladding material itself, which prevents that portion of hydrogen from reaching the containment building space. Implications of these findings are discussed in relation to a more realistic method of quantifying the hydrogen source term for a degraded-core accident analysis

Oxygen transfer rate estimation in oxidation ditches from clean water measurements.

Science.gov (United States)

Abusam, A; Keesman, K J; Meinema, K; Van Straten, G

2001-06-01

Standard methods for the determination of oxygen transfer rate are based on assumptions that are not valid for oxidation ditches. This paper presents a realistic and simple new method to be used in the estimation of oxygen transfer rate in oxidation ditches from clean water measurements. The new method uses a loop-of-CSTRs model, which can be easily incorporated within control algorithms, for modelling oxidation ditches. Further, this method assumes zero oxygen transfer rates (KLa) in the unaerated CSTRs. Application of a formal estimation procedure to real data revealed that the aeration constant (k = KLaVA, where VA is the volume of the aerated CSTR) can be determined significantly more accurately than KLa and VA. Therefore, the new method estimates k instead of KLa. From application to real data, this method proved to be more accurate than the commonly used Dutch standard method (STORA, 1980).

Parabola-like shaped pH-rate profile for phenols oxidation by aqueous permanganate.

Science.gov (United States)

Du, Juanshan; Sun, Bo; Zhang, Jing; Guan, Xiaohong

2012-08-21

Oxidation of phenols by permanganate in the pH range of 5.0-9.0 generally exhibits a parabola-like shape with the maximum reaction rate obtained at pH close to phenols' pK(a). However, a monotonic increase or decrease is observed if phenols' pK(a) is beyond the pH range of 5.0-9.0. A proton transfer mechanism is proposed in which the undissociated phenol is directly oxidized by permanganate to generate products while a phenolate-permanganate adduct, intermediate, is formed between dissociated phenol and permanganate ion and this is the rate-limiting step for phenolates oxidation by permanganate. The intermediate combines with H(+) and then decomposes to products. Rate equations derived based on the steady-state approximation can well simulate the experimentally derived pH-rate profiles. Linear free energy relationships (LFERs) were established among the parameters obtained from the modeling, Hammett constants, and oxygen natural charges in phenols and phenolates. LFERs reveal that chlorine substituents have opposite influence on the susceptibility of phenols and phenolates to permanganate oxidation and phenolates are not necessarily more easily oxidized than their neutral counterparts. The chlorine substituents regulate the reaction rate of chlorophenolates with permanganate mainly by influencing the natural charges of the oxygen atoms of dissociated phenols while they influence the oxidation of undissociated chlorophenols by permanganate primarily by forming intramolecular hydrogen bonding with the phenolic group.

Contribution to the study of the influence of porosity on carbon oxidation rate

International Nuclear Information System (INIS)

Serpinet, Joseph

1956-01-01

In its first part, this research thesis presents and described experiments of carbon oxidation which comprised the measurement of combustion rate in function of the BET surface of new types of graphite samples, and measurements of other kinetic quantities (reaction rate, Arrhenius activation energy, concentration of various gaseous oxides in reaction products). The second part reports a theoretical and experimental study of the possibility of limitation of the reaction rate, by using the slowness of oxygen diffusion within graphite pores. Results are related to the Thiele-Wheeler theory on chemical reactions in catalyst pores. The third part presents and discusses suggested solutions to replace this 'porosity hypothesis', and to explain why oxidation rate is almost never proportional to the BET surface all along the combustion process of a same graphite sample [fr

Anodic oxidation of oxytetracycline: Influence of the experimental conditions on the degradation rate and mechanism

Directory of Open Access Journals (Sweden)

Annabel Fernandes

2014-12-01

Full Text Available The anodic oxidation of oxytetracycline was performed with success using as anode a boron-doped diamond electrode. The experiments were conducted in batch mode, using two different electrochemical cells: an up-flow cell, with recirculation, that was used to evaluate the influence of recirculation flow rate; and a stirred cell, used to determine the influence of the applied current density. Besides oxytetracyclin electrodegradation rate and mineralization extent, oxidation by-products were also assessed. Both the flow rate and the applied current density have shown positive influence on the oxytetracycline oxidation rate. On the other hand, the mineralization degree presented the highest values at the lowest flow rate and the lowest current density tested. The main oxidation by-products detected were oxalic, oxamic and maleic acids.

Low nitrous oxide production through nitrifier-denitrification in intermittent-feed high-rate nitritation reactors

DEFF Research Database (Denmark)

Su, Qingxian; Ma, Chun; Domingo-Felez, Carlos

2017-01-01

Nitrous oxide (N2O) production from autotrophic nitrogen conversion processes, especially nitritation systems, can be significant, requires understanding and calls for mitigation. In this study, the rates and pathways of N2O production were quantified in two lab-scale sequencing batch reactors...... to maintain high nitritation efficiency and high nitritation rates at 20-26 °C over a period of ∼300 days. Even at the high nitritation efficiencies, net N2O production was low (∼2% of the oxidized ammonium). Net N2O production rates transiently increased with a rise in pH after each feeding, suggesting...... operated with intermittent feeding and demonstrating long-term and high-rate nitritation. The resulting reactor biomass was highly enriched in ammonia-oxidizing bacteria, and converted ∼93 ± 14% of the oxidized ammonium to nitrite. The low DO set-point combined with intermittent feeding was sufficient...

Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

Science.gov (United States)

Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

2015-12-01

Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide.

Science.gov (United States)

Salter-Blanc, Alexandra J; Bylaska, Eric J; Lyon, Molly A; Ness, Stuart C; Tratnyek, Paul G

2016-05-17

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. In this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ(-)), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa, EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).

Mixed function oxidase induction in Carcinus aestuarii. Field and experimental studies for the evaluation of toxicological risk due to Mediterranean contaminants

International Nuclear Information System (INIS)

Fossi, M.C.; Savelli, C.; Casini, S.

1998-01-01

The aim of this study was to test and validate the use of mixed function oxidase (MFO) induction, in the crab Carcinus aestuarii, under experimental and field studies, for the evaluation of toxicological risk due to the main contaminants in the Mediterranean. Two different experiments were performed in the laboratory in order to identify the most suitable tissues for MFO studies in this species and the most suitable and sensitive MFO responses for evaluating chemical stress due to lipophilic contaminants. In order to validate this methodology in the field, two studies were carried out in two polluted Mediterranean lagoons: a transplant experiment in Orbetello Lagoon and an in situ experiment in Venice Lagoon. The following MFO responses were investigated in hepatopancres and gills of the crabs: ethoxyresorufin-O-deethylase (EROD) and benzo(a)pyrene hydroxylase (BPH) activities and reductase enzyme activities. The main results can be summarised as follows: midgut-gland and gills were confirmed to be useful for MFO tests; BPH activity in hepatopancreas was the most suitable and sensitive MFO response for evaluating chemical stress due to Mediterranean contaminants in laboratory and field studies; in the Orbetello Lagoon experiment, a statistically significant difference was found between sites subject to different human impact. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

International Nuclear Information System (INIS)

Salter-Blanc, Alexandra J.; Lyon, Molly A.; Science University, Portland, OR; Ness, Stuart C.; Science University, Portland, OR; Tratnyek, Paul G.; Science University, Portland, OR

2016-01-01

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO 2 ) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ − ), pK a s of the amines, and energies of the highest occupied molecular orbital (E HOMO )] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox )]. The selection of calculated descriptors (pK a ), E HOMO , and E ox ) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO 2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to E HOMO (calculated with a modest level of theory).

Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

Science.gov (United States)

Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

2005-01-01

A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

Examination of dialysis patients with the aminophenazone breath test

International Nuclear Information System (INIS)

Heinrich, H.G.; Adler, D.; Hornak, H.; Wuenschmann, H.J.; Mayer, W.K.

1989-01-01

In 12 endstage kidney disease patients (8 without and 4 with liver diseases) the activities of cytochrome P 450 -dependent mixed functional oxidases system (MFO) of the liver were studied by using the 14 C-aminophenazone breath test before and after dialysis. The results showed that uremia seems to have a pressing influence on MFO activity. The activity was only significantly increased after dialysis in the group of patients without liver diseases. The MFO activity was reduced in patients with liver diseases. This is a restriction of the hepatic metabolic demethylation capacity. It is unclear if the 14 C-aminophenazone breath test in dialysis patients is qualified to estimate metabolic capacity of the liver. Differentiation between the influence of uremia and of the liver disease on the alteration of MFO activity cannot be made. (author)

Investigations into the effect of spinel oxide composition on rate of carbon deposition

International Nuclear Information System (INIS)

Allen, G.C.; Jutson, J.A.

1987-11-01

The deposition of carbon on fuel cladding and other steels results in a reduction in heat transfer efficiency. Methane and carbon monoxide are added to the gaseous coolant in the Advanced Gas Cooled Reactor (AGR) to reduce the radiolytic oxidation of the graphite moderator and this is known to increase the rate of carbon deposition. However, the composition of oxides formed on steel surfaces within the reactor may also influence deposition. In this investigation carefully characterised spinel type oxides of varying composition have been subjected to γ radiation under conditions of temperature, pressure and atmosphere similar to those experienced in the reactor. The rate of carbon deposition has been studied using Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Analysis (EDX). (U.K.)

Rate for energy transfer from excited cyclohexane to nitrous oxide in the liquid phase

International Nuclear Information System (INIS)

Wada, T.; Hatano, Y.

1975-01-01

Pure liquid cyclohexane and cyclohexane solutions of nitrous oxide have been photolyzed at 163 nm. The quantum yield of the product hydrogen in the photolysis of pure cyclohexane is found to be 1.0. The addition of nitrous oxide results in the reduction in the yield of hydrogen and in the formation of nitrogen. The decrement of the hydrogen yield is approximately equal to the increment of the nitrogen yield. About 40 percent of the hydrogen yield in pure cyclohexane is found to be produced through a path which is not affected by the addition of nitrous oxide. The effect of the addition of nitrous oxide is attributed to energy transfer from excited cyclohexane to nitrous oxide with the rate constant of k = 1.0 x 10 11 M -1 sec -1 (at 15 0 C). This value is about a factor of 10 larger than that expected as for diffusion-controlled rate. A contribution of the energy transfer process to the formation of nitrogen in the radiolysis of cyclohexane solutions of nitrous oxide has also been discussed. (auth)

Low nitrous oxide production through nitrifier-denitrification in intermittent-feed high-rate nitritation reactors.

Science.gov (United States)

Su, Qingxian; Ma, Chun; Domingo-Félez, Carlos; Kiil, Anne Sofie; Thamdrup, Bo; Jensen, Marlene Mark; Smets, Barth F

2017-10-15

Nitrous oxide (N 2 O) production from autotrophic nitrogen conversion processes, especially nitritation systems, can be significant, requires understanding and calls for mitigation. In this study, the rates and pathways of N 2 O production were quantified in two lab-scale sequencing batch reactors operated with intermittent feeding and demonstrating long-term and high-rate nitritation. The resulting reactor biomass was highly enriched in ammonia-oxidizing bacteria, and converted ∼93 ± 14% of the oxidized ammonium to nitrite. The low DO set-point combined with intermittent feeding was sufficient to maintain high nitritation efficiency and high nitritation rates at 20-26 °C over a period of ∼300 days. Even at the high nitritation efficiencies, net N 2 O production was low (∼2% of the oxidized ammonium). Net N 2 O production rates transiently increased with a rise in pH after each feeding, suggesting a potential effect of pH on N 2 O production. In situ application of 15 N labeled substrates revealed nitrifier denitrification as the dominant pathway of N 2 O production. Our study highlights operational conditions that minimize N 2 O emission from two-stage autotrophic nitrogen removal systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of the oxidation rate and degree of graphitization of selected IG and NBG nuclear graphite grades

Science.gov (United States)

Chi, Se-Hwan; Kim, Gen-Chan

2008-10-01

The oxidation rate and degree of graphitization (DOG) were determined for some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) and compared in view of their filler coke type (i.e., pitch or petroleum coke) and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 and 960 °C in air by using a three-zone vertical tube furnace at a 10 l/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. The DOG was determined based on the lattice parameter c determined from an X-ray diffraction (XRD). Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600-950 °C, the differences between the grades were not significant. The oxidation rates determined for a 5-10% weight loss at the six temperatures were nearly the same except for 702 and 808 °C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608-808 °C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control. A relationship between the oxidation rate and DOG was not observed.

Comparison of the oxidation rate and degree of graphitization of selected IG and NBG nuclear graphite grades

International Nuclear Information System (INIS)

Chi, Se-Hwan; Kim, Gen-Chan

2008-01-01

The oxidation rate and degree of graphitization (DOG) were determined for some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) and compared in view of their filler coke type (i.e., pitch or petroleum coke) and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 and 960 deg. C in air by using a three-zone vertical tube furnace at a 10 l/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. The DOG was determined based on the lattice parameter c determined from an X-ray diffraction (XRD). Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600-950 deg. C, the differences between the grades were not significant. The oxidation rates determined for a 5-10% weight loss at the six temperatures were nearly the same except for 702 and 808 deg. C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608-808 deg. C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control. A relationship between the oxidation rate and DOG was not observed

Oxidative stress does not influence local sweat rate during high-intensity exercise.

Science.gov (United States)

Meade, Robert D; Fujii, Naoto; Poirier, Martin P; Boulay, Pierre; Sigal, Ronald J; Kenny, Glen P

2018-02-01

What is the central question of this study? We evaluated whether oxidative stress attenuates the contribution of nitric oxide to sweating during high-intensity exercise. What is the main finding and its importance? In contrast to our previous report of an oxidative stress-mediated reduction in nitric oxide-dependent cutaneous vasodilatation in this cohort during intense exercise, we demonstrated no influence of local ascorbate administration on the sweating response during moderate- (∼51% peak oxygen uptake) or high-intensity exercise (∼72% peak oxygen uptake). These new findings provide important mechanistic insight into how exercise-induced oxidative stress impacts sudomotor activity. Nitric oxide (NO)-dependent sweating is diminished during high- but not moderate-intensity exercise. We evaluated whether this impairment stems from increased oxidative stress during high-intensity exercise. On two separate days, 11 young (24 ± 4 years) men cycled in the heat (35°C) at a moderate [500 W; 52 ± 6% peak oxygen uptake (V̇O2 peak )] or high (700 W; 71 ± 5% V̇O2 peak ) rate of metabolic heat production. Each session included two 30 min exercise bouts separated by a 20 min recovery period. Local sweat rate was monitored at four forearm skin sites continuously perfused via intradermal microdialysis with the following: (i) lactated Ringer solution (Control); (ii) 10 mm ascorbate (Ascorbate; non-selective antioxidant); (iii) 10 mm N G -nitro-l-arginine methyl ester (l-NAME; NO synthase inhibitor); or (iv) 10 mm ascorbate plus 10 mm l-NAME (Ascorbate + l-NAME). During moderate exercise, sweat rate was attenuated at the l-NAME and Ascorbate + l-NAME sites (both ∼1.0 mg min -1  cm -2 ; all P < 0.05) but not at the Ascorbate site (∼1.1 mg min -1  cm -2 ; both P ≥ 0.28) in comparison to the Control site (∼1.1 mg min -1  cm -2 ). However, no differences were observed between treatment sites (∼1.4 mg min -1  cm -2 ; P = 0

Effect of cooling rate on achieving thermodynamic equilibrium in uranium-plutonium mixed oxides

Science.gov (United States)

Vauchy, Romain; Belin, Renaud C.; Robisson, Anne-Charlotte; Hodaj, Fiqiri

2016-02-01

In situ X-ray diffraction was used to study the structural changes occurring in uranium-plutonium mixed oxides U1-yPuyO2-x with y = 0.15; 0.28 and 0.45 during cooling from 1773 K to room-temperature under He + 5% H2 atmosphere. We compare the fastest and slowest cooling rates allowed by our apparatus i.e. 2 K s-1 and 0.005 K s-1, respectively. The promptly cooled samples evidenced a phase separation whereas samples cooled slowly did not due to their complete oxidation in contact with the atmosphere during cooling. Besides the composition of the annealing gas mixture, the cooling rate plays a major role on the control of the Oxygen/Metal ratio (O/M) and then on the crystallographic properties of the U1-yPuyO2-x uranium-plutonium mixed oxides.

Electro-oxidation of methanol diffused through proton exchange membrane on Pt surface: crossover rate of methanol

International Nuclear Information System (INIS)

Jung, Inhwa; Kim, Doyeon; Yun, Yongsik; Chung, Suengyoung; Lee, Jaeyoung; Tak, Yongsug

2004-01-01

Methanol crossover rate through proton exchange membrane (Nafion 117) was investigated with a newly designed electrochemical stripping cell. Nanosize Pt electrode was prepared by the electroless deposition. Distinct electrocatalytic oxidation behaviors of methanol inside membrane were similar to the methanol oxidation in aqueous electrolyte, except adsorption/desorption of hydrogen. The amount of methanol diffused through membrane was calculated from the charge of methanol oxidation during repetitive cyclic voltammetry (CV) and methanol crossover rate was estimated to be 0.69 nmol/s

Influence of maximal fat oxidation on long-term weight loss maintenance in humans

DEFF Research Database (Denmark)

Dandanell, Sune; Husted, Karina; Amdisen, Signe

2017-01-01

differences between CWL, MWL, and WR were observed in MFO (mean [95% confidence interval], in g/min, respectively: 0.46 [0.41–0.52]; 0.32 [0.27–0.38]; 0.45 [0.38–0.51]; P = 0.002), maximal oxygen uptake (V̇o2max, in ml·min−1·FFM−1, respectively; 49 [46–51]; 43 [40–47]; 41 [39–44]; P = 0.007), HAD-activity (in...

Evaluation of exhaled nitric oxide in schoolchildren at different exhalation flow rates.

Science.gov (United States)

Pedroletti, Christophe; Zetterquist, Wilhelm; Nordvall, Lennart; Alving, Kjell

2002-09-01

Nitric oxide (NO) in exhaled air is believed to reflect allergic inflammation in the airways. Measured levels of exhaled NO vary with the exhaled flow rate, which therefore must be standardized. The aim of this study was to estimate the optimal exhalation flow rate when measuring NO in exhaled air. We studied 15 asthmatic children (8-18 y) with elevated NO levels and 15 age-matched controls and focused on how the quality of the NO curve profile, the discriminatory power, and the reproducibility were influenced by the exhalation flow rate. We used an on-line system for NO measurements at six different exhalation flow rates in the interval of 11-382 mL/s. The fraction of exhaled nitric oxide (FENO) was highly flow-dependent as was expected. Intermediate flow rates yielded a flat and stable NO plateau and were considerably easier to interpret than those obtained at the highest and lowest flow rates. The ratio of FENO between asthmatics and controls was lower at higher flow rates and a considerable overlap in NO values was demonstrated at all flow rates except 50 mL/s. The reproducibility was much lower at more extreme flow rates and was best at 50 mL/s. We conclude that a target exhalation flow rate of approximately 50 mL/s is to be preferred using the single-breath method for on-line NO measurements in schoolchildren.

Oxidation rate in ferritic superheater materials

International Nuclear Information System (INIS)

Falk, I.

1992-05-01

On the steam side of superheater tubes, compact oxide layers are formed which have a tendency to crack and flake off (exfoliate). Oxide particles then travel with the steam and can give rise to erosion damage in valves and on turbine blades. In an evaluation of conditions in superheater tubes from Swedish power boilers, it was found that the exfoliation frequency for one material quality (SS 2218) was greater than for other qualities. Against this background, a literature study has been carried out in order to determine which mechanisms govern the build-up of oxide and the exfoliation phenomenon. The study reveals that the oxide morphology is similar on all ferritic steels with Cr contents up to 5%. and that the oxide properties can therefore be expected to be similar. The reason why the exfoliation frequency is greater for tubes of SS 2218 is probably that the tubes have been exposed to higher temperatures. SS 2218 (2.25 Cr) is normally used in a higher temperature range which is accompanied by improved strength data as compared with SS 2216 (1 Cr). The principal cause of the exfoliation is said to be stresses which arise in the oxide during the cooling-down process associated with shutdowns. The stresses give rise to longitudinal cracks in the oxide, and are formed as a result of differences in thermal expansion between the oxide and the tube material. In addition, accounts are presented of oxidation constants and growth velocities, and thickness and running time. These data constitute a valuable basis for practical estimates of the operating temperature in routine checks and investigations into damage in superheater tubes. (au)

Oxidation rates of carbon and nitrogen in char residues from solid fuels

Energy Technology Data Exchange (ETDEWEB)

Karlstroem, O.

2013-06-01

Computational fluid dynamics (CFD) modeling is an important tool in designing new combustion systems. By using CFD modeling, entire combustion systems can be modeled and the emissions and the performance can be predicted. CFD modeling can also be used to develop new and better combustion systems from an economical and environmental point of view. In CFD modeling of solid fuel combustion, the combustible fuel is generally treated as single fuel particles. One of the limitations with the CFD modeling concerns the sub-models describing the combustion of single fuel particles. Available models in the scientific literature are in many cases not suitable as submodels for CFD modeling since they depend on a large number of input parameters and are computationally heavy. In this thesis CFD-applicable models are developed for the combustion of single fuel particles. The single particle models can be used to improve the combustion performance in various combustion devices or develop completely new technologies. The investigated fields are oxidation of carbon (C) and nitrogen (N) in char residues from solid fuels. Modeled char-C oxidation rates are compared to experimental oxidation rates for a large number of pulverized solid fuel chars under relevant combustion conditions. The experiments have been performed in an isothermal plug flow reactor operating at 1123-1673 K and 3-15 vol.% O{sub 2}. In the single particle model, the char oxidation is based on apparent kinetics and depends on three fuel specific parameters: apparent pre-exponential factor, apparent activation energy, and apparent reaction order. The single particle model can be incorporated as a sub-model into a CFD code. The results show that the modeled char oxidation rates are in good agreement with experimental char oxidation rates up to around 70% of burnout. Moreover, the results show that the activation energy and the reaction order can be assumed to be constant for a large number of bituminous coal chars

Reduction Rates for Higher Americium Oxidation States in Nitric Acid

Energy Technology Data Exchange (ETDEWEB)

Grimes, Travis Shane [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mincher, Bruce Jay [Idaho National Lab. (INL), Idaho Falls, ID (United States); Schmitt, Nicholas C [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-09-30

The stability of hexavalent americium was measured using multiple americium concentrations and nitric acid concentrations after contact with the strong oxidant sodium bismuthate. Contrary to our hypotheses Am(VI) was not reduced faster at higher americium concentrations, and the reduction was only zero-order at short time scales. Attempts to model the reduction kinetics using zero order kinetic models showed Am(VI) reduction in nitric acid is more complex than the autoreduction processes reported by others in perchloric acid. The classical zero-order reduction of Am(VI) was found here only for short times on the order of a few hours. We did show that the rate of Am(V) production was less than the rate of Am(VI) reduction, indicating that some Am(VI) undergoes two electron-reduction to Am(IV). We also monitored the Am(VI) reduction in contact with the organic diluent dodecane. A direct comparison of these results with those in the absence of the organic diluent showed the reduction rates for Am(VI) were not statistically different for both systems. Additional americium oxidations conducted in the presence of Ce(IV)/Ce(III) ions showed that Am(VI) is reduced without the typical growth of Am(V) observed in the systems sans Ce ion. This was an interesting result which suggests a potential new reduction/oxidation pathway for Am in the presence of Ce; however, these results were very preliminary, and will require additional experiments to understand the mechanism by which this occurs. Overall, these studies have shown that hexavalent americium is fundamentally stable enough in nitric acid to run a separations process. However, the complicated nature of the reduction pathways based on the system components is far from being rigorously understood.

Semipermeable membrane devices concentrate mixed function oxygenase inducers from oil sands and refinery wastewaters

International Nuclear Information System (INIS)

Parrott, J.L.; Hewitt, L.M.

2002-01-01

The health of fish in the Athabasca River was examined to determine the effects of both natural and anthropogenic oil sands exposure on liver mixed function oxygenase (MFO) enzymes. Semipermeable membrane devices (SPMD) were used to concentrate bioavailable compounds that may result in MFO induction. The SPMDs were used for a period of 2 weeks in the Steepbank River as well as in oil refinery wastewater and intake ponds. They were then tested to see if they induced ethoxyresorufin-O-deethylase (EROD) activity in hepatoma cells, a cell line derived from a liver cancer of a small fish. SPMDs from the wastewater pond contained potent EROD inducers in fish liver cells. SPMDs from the Athabasca River exhibited some EROD inducers, but they were 1/100 as potent as those of the refinery wastewater. The characteristics of MFO inducers from refinery wastewater were different from natural inducers from the oil sands in the Athabasca and Steepbank Rivers. For instance, log Kow was less than 5 for refinery wastewater, but it was greater than 5 for Athabasca River wastewater and from natural oil sands exposure. In the case of the Steepbank River, the pattern of MFO induction was similar to the MFO induction seen in wild fish.The highest MFO inducers were found to be in the area of the mine, suggesting and anthropogenic pollution source. The less potent inducers were in the area of the natural and undisturbed oil sands. Very few inducers were found outside of the oil sands formation

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.

Effect of cooling rate on achieving thermodynamic equilibrium in uranium–plutonium mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Vauchy, Romain, E-mail: romain.vauchy@cea.fr [CEA, DEN, DTEC, Marcoule, 30207, Bagnols-sur-Cèze (France); CEA, DEN, DEC, Cadarache, 13108, Saint-Paul-lez-Durance (France); Belin, Renaud C.; Robisson, Anne-Charlotte [CEA, DEN, DEC, Cadarache, 13108, Saint-Paul-lez-Durance (France); Hodaj, Fiqiri [Univ. Grenoble Alpes, SIMAP, F-38000, Grenoble (France); CNRS, Grenoble INP, SIMAP, F-38000, Grenoble (France)

2016-02-15

In situ X-ray diffraction was used to study the structural changes occurring in uranium–plutonium mixed oxides U{sub 1−y}Pu{sub y}O{sub 2−x} with y = 0.15; 0.28 and 0.45 during cooling from 1773 K to room-temperature under He + 5% H{sub 2} atmosphere. We compare the fastest and slowest cooling rates allowed by our apparatus i.e. 2 K s{sup −1} and 0.005 K s{sup −1}, respectively. The promptly cooled samples evidenced a phase separation whereas samples cooled slowly did not due to their complete oxidation in contact with the atmosphere during cooling. Besides the composition of the annealing gas mixture, the cooling rate plays a major role on the control of the Oxygen/Metal ratio (O/M) and then on the crystallographic properties of the U{sub 1−y}Pu{sub y}O{sub 2−x} uranium–plutonium mixed oxides.

Parameters extraction of the three diode model for the multi-crystalline solar cell/module using Moth-Flame Optimization Algorithm

International Nuclear Information System (INIS)

Allam, Dalia; Yousri, D.A.; Eteiba, M.B.

2016-01-01

Highlights: • More detailed models are proposed to emulate the multi-crystalline solar cell/module. • Moth-Flame Optimizer (MFO) is proposed for the parameter extraction process. • The performance of MFO technique is compared with the recent optimization algorithms. • MFO algorithm converges to the optimal solution more rapidly and more accurately. • MFO algorithm accomplished with three diode model achieves the most accurate model. - Abstract: As a result of the wide prevalence of using the multi-crystalline silicon solar cells, an accurate mathematical model for these cells has become an important issue. Therefore, a three diode model is proposed as a more precise model to meet the relatively complicated physical behavior of the multi-crystalline silicon solar cells. The performance of this model is compared to the performance of both the double diode and the modified double diode models of the same cell/module. Therefore, there is a persistent need to keep searching for a more accurate optimization algorithm to estimate the more complicated models’ parameters. Hence, a proper optimization algorithm which is called Moth-Flame Optimizer (MFO), is proposed as a new optimization algorithm for the parameter extraction process of the three tested models based on data measured at laboratory and other data reported at previous literature. To verify the performance of the suggested technique, its results are compared with the results of the most recent and powerful techniques in the literature such as Hybrid Evolutionary (DEIM) and Flower Pollination (FPA) algorithms. Furthermore, evaluation analysis is performed for the three algorithms of the selected models at different environmental conditions. The results show that, MFO algorithm achieves the least Root Mean Square Error (RMSE), Mean Bias Error (MBE), Absolute Error at the Maximum Power Point (AEMPP) and best Coefficient of Determination. In addition, MFO is reaching to the optimal solution with the

Fiber optical dose rate measurement based on the luminescence of beryllium oxide

Directory of Open Access Journals (Sweden)

Teichmann Tobias

2018-01-01

Full Text Available This work presents a fiber optical dose rate measurement system based on the radioluminescence and optically stimulated luminescence of beryllium oxide. The system consists of a small, radiation sensitive probe which is coupled to a light detection unit with a long and flexible light guide. Exposing the beryllium oxide probe to ionizing radiation results in the emission of light with an intensity which is proportional to the dose rate. Additionally, optically stimulated luminescence can be used to obtain dose and dose rate information during irradiation or retrospectively. The system is capable of real time dose rate measurements in fields of high dose rates and dose rate gradients and in complex, narrow geometries. This enables the application for radiation protection measurements as well as for quality control in radiotherapy. One inherent drawback of fiber optical dosimetry systems is the generation of Cherenkov radiation and luminescence in the light guide itself when it is exposed to ionizing radiation. This so called “stem” effect leads to an additional signal which introduces a deviation in the dose rate measurement and reduces the spatial resolution of the system, hence it has to be removed. The current system uses temporal discrimination of the effect for radioluminescence measurements in pulsed radiation fields and modulated optically stimulated luminescence for continuous irradiation conditions. This work gives an overview of the major results and discusses new-found obstacles of the applied methods of stem discrimination.

Effect of Time Lenght Fermentation to Katsuobushi Oxidation Rate As Fish Flavor Based

Science.gov (United States)

Amalia, U.; Rianingsih, L.; Wijayanti, I.

2018-02-01

Katsuobushi or dried smoked skipjack had a distinctive flavor and widely used in traditional Japanese cuisine. This study aimed to evaluate the oxidation rate of Katsuobushi with different lenght fermentation. The processing treatment of the product were the differences of fish boiling time (30 min and 60 min) and the lenght of fermentation: 1 week, 2 weeks and 3 weeks. The glutamic acid content, the oxidation rate (thiobarbituric acid and peroxide value) and Total Plate Count of katsuobushi were analyzed statistically using analysis of varians. Significant differences were found among 3 weeks of fermentation compare to 1 weeks fermentation (P fermentation was potential to be developed become basic ingredients for the fish flavor.

The Influences of Water Vapor/Hydrogen Ratio, Gas-Flow Rate and Antimony on the Surface Oxidation of Trip Steels

International Nuclear Information System (INIS)

Kwon, You Jong; Zhu, Jing Xi; Sridhar, Seetharaman; Sohn, Il Ryong

2011-01-01

In the current paper, we are reporting the results from an investigation of the surface and sub-surface oxidation of a TRIP steel containing 2 wt.% Mn and 0.5 wt.% Al with and without 0.03 wt.% Sb. The oxidizing conditions in the gas were successively varied in terms of the linear gas flow-rate and dew-point, from conditions were gas-phase mass transport limited conditions prevailed, to those were solid state processes became the rate determining conditions. It was found, that at sufficient low oxidizing conditions (defined as flow-rate/dew-point), the metal surfaces were clear of any external oxides, and as the oxidizing conditions were increased, Mn- and Si- oxide nodules formed along with magnetite. As the oxidizing conditions were increased further, a dense magnetite layer was present. The limits of the various regions were experimentally quantified and a proposed hypothesis for their occurrences is presented. No obvious effect of Sb was noted in this micro-structural research of the oxides that results from the various conditions investigated in this study

Oxidative removal of quinclorac by permanganate through a rate-limiting [3 + 2] cycloaddition reaction.

Science.gov (United States)

Song, Dean; Cheng, Hanyang; Jiang, Xiaohua; Sun, Huiqing; Kong, Fanyu; Liang, Rongning; Qiang, Zhimin; Liu, Huijuan; Qu, Jiuhui

2018-04-05

Quinclorac, a widely used herbicide in agriculture, has been recognized as an emerging environmental pollutant owing to its long persistence and potential risk to humans. However, no related information is available on the degradation of quinclorac by employing oxidants. Herein, the reactivity of quinclorac with permanganate was systematically investigated in water by combining experimental and computational approaches. The reaction followed overall second-order kinetics pointing to a bimolecular rate-limiting step. The second-order rate constant was found to be 3.47 × 10-3 M-1 s-1 at 25 °C, which was independent of pH over the range from 5 to 9 and was dependent on temperature over the range from 19 to 35 °C. The initial product was identified by UPLC-Q-TOF-MS to be mono-hydroxylated quinclorac, which was more susceptible to further oxidation. The result could be supported by the complete simulation of the reaction process in DFT calculations, indicating the [3 + 2] cycloaddition oxidation of the benzene ring in the rate-limiting step. The plausible mechanism was then proposed, accompanied by the analysis of the HOMO indicating the hydroxylation position and of the ESP suggesting a more electron-rich moiety. Considering the high effectiveness and low toxicity, permanganate oxidation was considered to be a very promising technique for removing quinclorac from aquatic environments.

Are high rates of sulphate reduction associated with anaerobic oxidation of methane

Energy Technology Data Exchange (ETDEWEB)

Devol, A H; Ahmed, S I

1981-01-01

Classical models of sulphur diagenesis in marine sediments are based on the assumption that the rate of sulphate reduction is first order with respect to oxidizable particulate organic carbon (POC). This assumption requires that oxidizable POC, sulphate concentration and the sulphate reduction rate be highest at the top of the sulphate reduction zone and decrease exponentially with increasing sediment depth. However, to explain recent observations of concave upwards methane distributions, the anaerobic consumption of methane has been proposed. Furthermore, it has been proposed that this consumption takes place near the bottom of the sulphate reducing zone where sulphate concentrations are low. Thus, if sulphate reducing bacteria are associated with the anaerobic oxidation of methane, a peak in sulphate reduction rate might be expected in this deep consumption zone. The importance of the process in sedimentary sulphur diagenesis is indicated by calculations estimating that 30 to 75% of the downward sulphate flux at depth may be consumed by methane oxidation within this zone. We present here profiles of sulphate reduction rate in anoxic sediments that show distinct local maxima at the depth where the anaerobic oxidation of methane would be expected. Our measurements were made during July and August 1978 in Saanich Inlet, an anoxic fjord located on the south-east of Vancouver Island, British Columbia. The inlet has a shallow sill (approx 70 m) which restricts circulation of the deeper water (maximum depth 225 m) inside the basin to the extent that for about 8 months of the year the bottom waters contain hydrogen sulphide, the inlet is an ideal location for studying sedimentary sulphate reduction because reactions with oxygen and the effects of burrowing organisms can be neglected.

Relationship between turnover rate and oxidation rate of alanine in the post-absorptive state and during parenteral nutrition before and after surgery

NARCIS (Netherlands)

Sauerwein, H. P.; Michels, R. P.; Cejka, V.

1985-01-01

The influence of total parenteral nutrition and stomach resection on alanine turnover rate and alanine oxidation rate was measured in ten patients after single injection of U-14 C-alanine. Sequential studies were done in three patients. During parenteral nutrition alanine turnover was significantly

Effect of ion exchange on the rate of aerobic microbial oxidation of ammonium in hyporheic zone sediments.

Science.gov (United States)

Yan, Ailan; Liu, Chongxuan; Liu, Yuanyuan; Xu, Fen

2018-03-01

Microbially mediated ammonium oxidation is a major process affecting nitrogen transformation and cycling in natural environments. This study investigated whether ion exchange process can affect microbially mediated aerobic oxidation of ammonium in a hyporheic zone (HZ) sediments from the Columbia River at US Department of Energy's Hanford site, Washington State. Experiments were conducted using synthetic groundwater and river water to investigate their effect on ammonium oxidation. Results indicated that ammonium sorption through ion exchange reactions decreased the rate of ammonium oxidation, apparently resulting from the influence of the ion exchange on dissolved ammonium concentration, thus decreasing the bioavailability of ammonium for microbial oxidation. However, with the decrease in dissolved ammonium concentration, the sorbed ammonium released back to aqueous phase, and became bioavailable so that all the ammonium in the suspensions were oxidized. Our results implied a dynamic change in ammonium oxidation rates in an environment such as at HZ where river water and groundwater with different chemical compositions exchange frequently that can affect ammonium sorption and desorption through ion exchange reactions.

High basal metabolic rate does not elevate oxidative stress during reproduction in laboratory mice.

Science.gov (United States)

Brzęk, Paweł; Książek, Aneta; Ołdakowski, Łukasz; Konarzewski, Marek

2014-05-01

Increased oxidative stress (OS) has been suggested as a physiological cost of reproduction. However, previous studies reported ambiguous results, with some even showing a reduction of oxidative damage during reproduction. We tested whether the link between reproduction and OS is mediated by basal metabolic rate (BMR), which has been hypothesized to affect both the rate of radical oxygen species production and antioxidative capacity. We studied the effect of reproduction on OS in females of laboratory mice divergently selected for high (H-BMR) and low (L-BMR) BMR, previously shown to differ with respect to parental investment. Non-reproducing L-BMR females showed higher oxidative damage to lipids (quantified as the level of malondialdehyde in internal organ tissues) and DNA (quantified as the level of 8-oxodG in blood serum) than H-BMR females. Reproduction did not affect oxidative damage to lipids in either line; however, it reduced damage to DNA in L-BMR females. Reproduction increased catalase activity in liver (significantly stronger in L-BMR females) and decreased it in kidneys. We conclude that the effect of reproduction on OS depends on the initial variation in BMR and varies between studied internal organs and markers of OS.

High rate deposition of transparent conducting oxide thin films by vacuum arc plasma evaporation

International Nuclear Information System (INIS)

Minami, Tadatsugu; Ida, Satoshi; Miyata, Toshihiro

2002-01-01

Transparent conducting oxide (TCO) thin films have been deposited at a high rate above 370 nm/min by vacuum arc plasma evaporation (VAPE) using sintered oxide fragments as the source material. It was found that the deposition rate of TCO films was strongly dependent on the deposition pressure, whereas the obtained electrical properties were relatively independent of the pressure. Resistivities of 5.6x10 -4 and 2.3x10 -4 Ω·cm and an average transmittance above 80% (with substrate included) in the visible range were obtained in Ga-doped ZnO (GZO) thin films deposited at 100 and 350 deg. C, respectively. In addition, a resistivity as low as 1.4x10 -4 Ω·cm and an average transmittance above 80% were also obtained in indium-tin-oxide (ITO) films deposited at 300 deg. C. The deposited TCO films exhibited uniform distributions of resistivity and thickness on large area substrates

High rate deposition of transparent conducting oxide thin films by vacuum arc plasma evaporation

Energy Technology Data Exchange (ETDEWEB)

Minami, Tadatsugu; Ida, Satoshi; Miyata, Toshihiro

2002-09-02

Transparent conducting oxide (TCO) thin films have been deposited at a high rate above 370 nm/min by vacuum arc plasma evaporation (VAPE) using sintered oxide fragments as the source material. It was found that the deposition rate of TCO films was strongly dependent on the deposition pressure, whereas the obtained electrical properties were relatively independent of the pressure. Resistivities of 5.6x10{sup -4} and 2.3x10{sup -4} {omega}{center_dot}cm and an average transmittance above 80% (with substrate included) in the visible range were obtained in Ga-doped ZnO (GZO) thin films deposited at 100 and 350 deg. C, respectively. In addition, a resistivity as low as 1.4x10{sup -4} {omega}{center_dot}cm and an average transmittance above 80% were also obtained in indium-tin-oxide (ITO) films deposited at 300 deg. C. The deposited TCO films exhibited uniform distributions of resistivity and thickness on large area substrates.

Lowering temperature to increase chemical oxidation efficiency: the effect of temperature on permanganate oxidation rates of five types of well defined organic matter, two natural soils, and three pure phase products.

Science.gov (United States)

de Weert, J P A; Keijzer, T J S; van Gaans, P F M

2014-12-01

In situ chemical oxidation (ISCO) is a soil remediation technique to remove organic pollutants from soil and groundwater with oxidants, like KMnO4. However, also natural organic compounds in soils are being oxidized, which makes the technique less efficient. Laboratory experiments were performed to investigate the influence of temperature on this efficiency, through its effect on the relative oxidation rates - by permanganate - of natural organic compounds and organic pollutants at 16 and 15°C. Specific types of organic matter used were cellulose, oak wood, anthracite, reed - and forest peat, in addition to two natural soils. Dense Non-Aqueous Phase Liquid-tetrachloroethene (DNAPL-PCE), DNAPL trichloroethene (DNAPL-TCE) and a mixture of DNAPL-PCE, -TCE and -hexachlorobutadiene were tested as pollutants. Compared to 16°C, oxidation was slower at 5°C for the specific types of organic matter and the natural soils, with exception of anthracite, which was unreactive. The oxidation rate of DNAPL TCE was lower at 5°C too. However, at this temperature oxidation was fast, implying that no competitive loss to natural organic compounds will be expected in field applications by lowering temperature. Oxidation of DNAPL-PCE and PCE in the mixture proceeded at equal rates at both temperatures, due to the dissolution rate as limiting factor. These results show that applying permanganate ISCO to DNAPL contamination at lower temperatures will limit the oxidation of natural organic matter, without substantially affecting the oxidation rate of the contaminant. This will make such remediation more effective and sustainable in view of protecting natural soil quality. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of the Air Flow Rate on The Oxidation of NBG-18 and 25 Nuclear Graphite Grades

International Nuclear Information System (INIS)

Chi, Se-Hwan; Kim, Gen-Chan; Jang, Joon-Hee

2007-01-01

For a VHTR, graphite oxidation is regarded as a critical phenomenon for degrading the integrity of graphite components under normal or abnormal conditions. The oxidation of a graphite core component can occur by air which may permeate into the primary coolant operation and/or by impurities contained in the He coolant, or by air ingress during a severe accident. It is well known that the oxidation properties of a graphite are highly dependent on the source of raw materials, impurities, microstructures (crystallites, pore structure), and on the processing and environmental parameters, such as the forming methods, the coolant type, moisture and impurity content, temperature, flow rate and the oxygen potential of the coolants. A lot of work has been performed on the oxidation of graphite since the 1960s, and, for example, in the case of the temperature, a widely accepted oxidation model on the effects of a temperature has already been developed. However, in the case of the flow rate, even for its expected effects in a VHTR, for example, as to the expected changes in the bypass flow (10-20 %) during an operation, no systematic works have been performed. In this respect, as a preliminary study, the effects of an air flow rate on the oxidation of NBG-18 and 25 nuclear graphite were investigated

Anaerobic methane oxidation rates at the sulfate-methane transition in marine sediments from Kattegat and Skagerrak (Denmark)

International Nuclear Information System (INIS)

Iversen, N.; Jorgensen, B.B.

1985-01-01

Concomitant radiotracer measurements were made of in situ rates of sulfate reduction and anaerobic methane oxidation in 2-3-m-long sediment cores. Methane accumulated to high concentrations (> 1 mM CH 4 ) only below the sulfate zone, at 1 m or deeper in the sediment. Sulfate reduction showed a broad maximum below the sediment surface and a smaller, narrow maximum at the sulfate-methane transition. Methane oxidation was low (0.002-0.1 nmol CH 4 cm -3 d -1 ) throughout the sulfate zone and showed a sharp maximum at the sulfate-methane transition, coinciding with the sulfate reduction maximum. Total anaerobic methane oxidation at two stations was 0.83 and 1.16 mmol CH 4 m -2 d -1 , of which 96% was confined to the sulfate-methane transition. All the methane that was calculated to diffuse up into the sulfate-methane transition was oxidized in this zone. The methane oxidation was equivalent to 10% of the electron donor requirement for the total measured sulfate reduction. A third station showed high sulfate concentrations at all depths sampled and the total methane oxidation was only 0.013 mmol m -2 d -1 . From direct measurements of rates, concentration gradients, and diffusion coefficients, simple calculations were made of sulfate and methane fluxes and of methane production rates

Thermal analysis of thermo-gravimetric measurements of spent nuclear fuel oxidation rates

International Nuclear Information System (INIS)

Cramer, E.R.

1997-01-01

A detailed thermal analysis was completed of the sample temperatures in the Thermo-Gravimetric Analysis (TGA) system used to measure irradiated N Reactor fuel oxidation rates. Sample temperatures during the oxidation process did not show the increase which was postulated as a result of the exothermic reactions. The analysis shows the axial conduction of heat in the sample holder effectively removes the added heat and only a very small, i.e., <10 C, increase in temperature is calculated. A room temperature evaporation test with water showed the sample thermocouple sensitivity to be more than adequate to account for a temperature change of approximately 5 C. Therefore, measured temperatures in the TGA are within approximately 10 C of the actual sample temperatures and no adjustments to reported data to account for the heat input from the oxidation process are necessary

Microsomal detoxication enzyme responses of the marine snail, Thais haemastoma, to laboratory oil exposure

International Nuclear Information System (INIS)

Livingstone, D.R.; Stickle, W.B.; Kapper, M.; Wang, S.

1986-01-01

The cytochrome P-450 monooxygenase or mixed function oxidase (MFO) system is a widely distributed enzyme system involved in the detoxication of foreign organic compounds (xenobiotics) taken up by organisms. Increases in the activities of the MFO system, occur with exposure of the organism to organic xenobiotics and such responses in the field have been proposed as a means of identifying biological impact by organic pollution. The carnivorous marine gastropod Thais haemastoma, or southern oyster drill, rapidly accumulated polynuclear aromatic and other hydrocarbons from the environment, through both the food source and the water-column. In laboratory experiments T. haemastoma were exposed to the water soluble fraction (WSF) of South Louisiana crude oil and the responses of the MFO system examined. Preliminary characterization of the snail MFO system was carried out using methodology developed from studies on the common mussel Mytilus edulis. Microsomal benz[a]pyrene hydroxylase (BPH), NADH- and NADPH- dependent cytochrome c reductase (NAD(P)H-CYTCRED) and NADH-dependent ferricyanide reductase (NADH-FERRIRED) activities were measured but it was not possible to determine cytochrome P-450 or b 5

Effects of dissolved oxygen and pH on nitrous oxide production rates in autotrophic partial nitrification granules.

Science.gov (United States)

Rathnayake, Rathnayake M L D; Oshiki, Mamoru; Ishii, Satoshi; Segawa, Takahiro; Satoh, Hisashi; Okabe, Satoshi

2015-12-01

The effects of dissolved oxygen (DO) and pH on nitrous oxide (N2O) production rates and pathways in autotrophic partial nitrification (PN) granules were investigated at the granular level. N2O was primarily produced by betaproteobacterial ammonia-oxidizing bacteria, mainly Nitrosomonas europaea, in the oxic surface layer (production increased with increasing bulk DO concentration owing to activation of the ammonia (i.e., hydroxylamine) oxidation in this layer. The highest N2O emissions were observed at pH 7.5, although the ammonia oxidation rate was unchanged between pH 6.5 and 8.5. Overall, the results of this study suggest that in situ analyses of PN granules are essential to gaining insight into N2O emission mechanisms in a granule. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influences of Organic Carbon Supply Rate on Uranium Bioreduction in Initially Oxidizing, Contaminated Sediment

Energy Technology Data Exchange (ETDEWEB)

Tokunaga, Tetsu K.; Wan, Jiamin; Kim, Yongman; Daly, Rebecca A.; Brodie, Eoin L.; Hazen, Terry C.; Herman, Don; Firestone, Mary K.

2008-06-10

Remediation of uranium (U) contaminated sediments through in-situ stimulation of bioreduction to insoluble UO{sub 2} is a potential treatment strategy under active investigation. Previously, we found that newly reduced U(IV) can be reoxidized under reducing conditions sustained by a continuous supply of organic carbon (OC) because of residual reactive Fe(III) and enhanced U(VI) solubility through complexation with carbonate generated through OC oxidation. That finding motivated this investigation directed at identifying a range of OC supply rates that is optimal for establishing U bioreduction and immobilization in initially oxidizing sediments. The effects of OC supply rate, from 0 to 580 mmol OC (kg sediment){sup -1} year{sup -1}, and OC form (lactate and acetate) on U bioreduction were tested in flow-through columns containing U-contaminated sediments. An intermediate supply rate on the order of 150 mmol OC (kg sediment){sup -1} year{sup -1} was determined to be most effective at immobilizing U. At lower OC supply rates, U bioreduction was not achieved, and U(VI) solubility was enhanced by complexation with carbonate (from OC oxidation). At the highest OC supply rate, resulting highly carbonate-enriched solutions also supported elevated levels of U(VI), even though strongly reducing conditions were established. Lactate and acetate were found to have very similar geochemical impacts on effluent U concentrations (and other measured chemical species), when compared at equivalent OC supply rates. While the catalysts of U(VI) reduction to U(IV) are presumably bacteria, the composition of the bacterial community, the Fe reducing community, and the sulfate reducing community had no direct relationship with effluent U concentrations. The OC supply rate has competing effects of driving reduction of U(VI) to low solubility U(IV) solids, as well as causing formation of highly soluble U(VI)-carbonato complexes. These offsetting influences will require careful control of OC

Extreme nitrogen deposition can change methane oxidation rate in moist acidic tundra soil in Arctic regions

Science.gov (United States)

Lee, J.; Kim, J.; Kang, H.

2017-12-01

Recently, extreme nitrogen(N) deposition events are observed in Arctic regions where over 90% of the annual N deposition occurred in just a few days. Since Arctic ecosystems are typically N-limited, input of extremely high amount of N could substantially affect ecosystem processes. CH4 is a potent greenhouse gas that has 25 times greater global warming potential than CO2 over a 100-year time frame. Ammonium is known as an inhibitor of methane oxidation and nitrate also shows inhibitory effect on it in temperate ecosystems. However, effects of N addition on Arctic ecosystems are still elusive. We conducted a lab-scale incubation experiment with moist acidic tundra (MAT) soil from Council, Alaska to investigate the effect of extreme N deposition events on methane oxidation. Zero point five % methane was added to the head space to determine the potential methane oxidation rate of MAT soil. Three treatments (NH4NO3-AN, (NH4)2SO4-AS, KNO3-PN) were used to compare effects of ammonium, nitrate and salts. All treatments were added in 3 levels: 10μg N gd.w-1(10), 50μg N gd.w-1(50) and 100μg N gd.w-1(100). AN10 and AN50 increased methane oxidation rate 1.7, 6% respectively. However, AN100 shows -8.5% of inhibitory effect. In AS added samples, all 3 concentrations (AN10, AN50, AN100) stimulated methane oxidation rate with 4.7, 8.9, 4%, respectively. On the contrary, PN50 (-9%) and PN100 (-59.5%) exhibited a significant inhibitory effect. We also analyzed the microbial gene abundance and community structures of methane oxidizing bacteria using a DNA-based fingerprinting method (T-RFLP) Our study results suggest that NH4+ can stimulate methane oxidation in Arctic MAT soil, while NO3- can inhibit methane oxidation significantly.

The Effect of Vitamin E on the Survival Rate of unc-13 Caenorhabditis elegans mutants under Oxidative Stress

Directory of Open Access Journals (Sweden)

Jessica Porcelan

2012-01-01

Full Text Available Caenorhabditis elegans unc-13 mutants express decreased neuronal activity and thus are a good model strain for examining defective nervous systems. These unc-13 mutants as well as wild type N2 strains, show rapid mortality when under oxidative stress. However, the antioxidant vitamin E may prolong survival in unc-13 mutant and N2 strains under oxidative stress. The addition of vitamin E to organisms under oxidative stress has a protective effect in both N2 and unc-13 C. elegans strains. Interestingly, vitamin E resulted in a greater increase in survival rate in N2 worms than with unc-13 mutant worms. While both strains displayed lower mortality rates with the addition of vitamin E, this finding suggests that vitamin E more efficiently increases survival rates of C. elegans with typical nervous system function. The efficacy of vitamin E implies that use of antioxidants may lessen the damage caused by oxidative stress in both N2 and mutant worms.

Investigation of effect of air flow rate on Zircaloy-4 oxidation kinetics and breakaway phenomenon in air at 850 .deg. C

International Nuclear Information System (INIS)

Maeng, Yunhwan; Lee, Jaeyoung; Park, Sanggil

2016-01-01

This paper analyzed an effect of flow rate on oxidation kinetics of Zircaloy-4 in air at 850 .deg. C. In case of the oxidation of Zircaloy-4 in air at 850 .deg. C, acceleration of oxidation kinetics from parabolic to linear (breakaway phenomenon) occurs. Oxidation and breakaway kinetics of the Zircaloy-4 in air was experimentally studied by changing a flow rate of argon/air mixture. Tests were conducted at 850 .deg. C under constant ratio of argon and air. The effects of flow rate on the oxidation and breakaway kinetics was observed. This paper is based on a revised and considerably extended presentation given at the 21 st International Quench Workshop. The effects of flow conditions on the oxidation kinetics of Zircaloy-4 samples were explained with residence time and percent flow efficiency. In addition, several issues were observed from this study, interdiffusion at breakaway and deformation of oxide structure by breakaway phenomenon

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

International Nuclear Information System (INIS)

Tajima, Satomi; Tsuchiya, Shouichi; Matsumori, Masashi; Nakatsuka, Shigeki; Ichiki, Takanori

2011-01-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu 2 O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu 2 O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

High-rate reduction of copper oxide using atmospheric-pressure inductively coupled plasma microjets

Energy Technology Data Exchange (ETDEWEB)

Tajima, Satomi; Tsuchiya, Shouichi [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Matsumori, Masashi; Nakatsuka, Shigeki [Panasonic Factory Solutions Co., Ltd., 2-7 Matsuba-cho, Kadoma-city, Osaka, 571-8502 (Japan); Ichiki, Takanori, E-mail: ichiki@sogo.t.u-tokyo.ac.jp [Department of Bioengineering, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, 113-8656 (Japan); Institute of Engineering Innovation, Graduate School of Engineering, University of Tokyo, 2-11-16 Yayoi, Bunkyo-ku, Tokyo, 113-8656 (Japan)

2011-08-01

Reduction of copper oxide was performed using an atmospheric-pressure inductively coupled plasma (AP-ICP) microjet while varying the input power P between 15 and 50 W. Cuprous oxide (Cu{sub 2}O) and cupric oxide (CuO) were formed on the sputtered Cu surface by thermal annealing. Dynamic behavior of the microplasma jet, optical emission from H atoms, the substrate temperature, chemical bonding states of the treated surface, and the thickness of the reduced Cu layer were measured to study the fundamental reduction process. Surface composition and the thickness of the reduced Cu layer changed significantly with P. Rapid reduction of CuO and Cu{sub 2}O was achieved at a rate of 493 nm/min at P = 50 W since high-density H atoms were produced by the AP-ICP microjet.

High rates of anaerobic oxidation of methane, ethane and propane coupled to thiosulphate reduction.

Science.gov (United States)

Suarez-Zuluaga, Diego A; Weijma, Jan; Timmers, Peer H A; Buisman, Cees J N

2015-03-01

Anaerobic methane oxidation coupled to sulphate reduction and the use of ethane and propane as electron donors by sulphate-reducing bacteria represent new opportunities for the treatment of streams contaminated with sulphur oxyanions. However, growth of microbial sulphate-reducing populations with methane, propane or butane is extremely slow, which hampers research and development of bioprocesses based on these conversions. Thermodynamic calculations indicate that the growth rate with possible alternative terminal electron acceptors such as thiosulphate and elemental sulphur may be higher, which would facilitate future research. Here, we investigate the use of these electron acceptors for oxidation of methane, ethane and propane, with marine sediment as inoculum. Mixed marine sediments originating from Aarhus Bay (Denmark) and Eckernförde Bay (Germany) were cultivated anaerobically at a pH between 7.2 and 7.8 and a temperature of 15 °C in the presence of methane, ethane and propane and various sulphur electron acceptors. The sulphide production rates in the conditions with methane, ethane and propane with sulphate were respectively 2.3, 2.2 and 1.8 μmol S L(-1) day(-1). For sulphur, no reduction was demonstrated. For thiosulphate, the sulphide production rates were up to 50 times higher compared to those of sulphate, with 86.2, 90.7 and 108.1 μmol S L(-1) day(-1) for methane, ethane and propane respectively. This sulphide production was partly due to disproportionation, 50 % for ethane but only 7 and 14 % for methane and propane respectively. The oxidation of the alkanes in the presence of thiosulphate was confirmed by carbon dioxide production. This is, to our knowledge, the first report of thiosulphate use as electron acceptor with ethane and propane as electron donors. Additionally, these results indicate that thiosulphate is a promising electron acceptor to increase start-up rates for sulphate-reducing bioprocesses coupled to short-chain alkane oxidation.

Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

Energy Technology Data Exchange (ETDEWEB)

Crist, K.C.

1984-10-01

An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables.

Comparison of two lung clearance models based on the dissolution rates of oxidized depleted uranium

International Nuclear Information System (INIS)

Crist, K.C.

1984-10-01

An in-vitro dissolution study was conducted on two respirable oxidized depleted uranium samples. The dissolution rates generated from this study were then utilized in the International Commission on Radiological Protection Task Group lung clearance model and a lung clearance model proposed by Cuddihy. Predictions from both models based on the dissolution rates of the amount of oxidized depleted uranium that would be cleared to blood from the pulmonary region following an inhalation exposure were compared. It was found that the predictions made by both models differed considerably. The difference between the predictions was attributed to the differences in the way each model perceives the clearance from the pulmonary region. 33 references, 11 figures, 9 tables

Towards refactoring the Molecular Function Ontology with a UML profile for function modeling.

Science.gov (United States)

Burek, Patryk; Loebe, Frank; Herre, Heinrich

2017-10-04

Gene Ontology (GO) is the largest resource for cataloging gene products. This resource grows steadily and, naturally, this growth raises issues regarding the structure of the ontology. Moreover, modeling and refactoring large ontologies such as GO is generally far from being simple, as a whole as well as when focusing on certain aspects or fragments. It seems that human-friendly graphical modeling languages such as the Unified Modeling Language (UML) could be helpful in connection with these tasks. We investigate the use of UML for making the structural organization of the Molecular Function Ontology (MFO), a sub-ontology of GO, more explicit. More precisely, we present a UML dialect, called the Function Modeling Language (FueL), which is suited for capturing functions in an ontologically founded way. FueL is equipped, among other features, with language elements that arise from studying patterns of subsumption between functions. We show how to use this UML dialect for capturing the structure of molecular functions. Furthermore, we propose and discuss some refactoring options concerning fragments of MFO. FueL enables the systematic, graphical representation of functions and their interrelations, including making information explicit that is currently either implicit in MFO or is mainly captured in textual descriptions. Moreover, the considered subsumption patterns lend themselves to the methodical analysis of refactoring options with respect to MFO. On this basis we argue that the approach can increase the comprehensibility of the structure of MFO for humans and can support communication, for example, during revision and further development.

Changes in heart rate variability during anaesthesia induction using sevoflurane or isoflurane with nitrous oxide.

Science.gov (United States)

Nishiyama, Tomoki

2016-01-01

The purpose of this study was to compare cardiac sympathetic and parasympathetic balance using heart rate variability (HRV) during induction of anaesthesia between sevoflurane and isoflurane in combination with nitrous oxide. 40 individuals aged from 30 to 60 years, scheduled for general anaesthesia were equally divided into sevoflurane or isoflurane groups. After 100% oxygen inhalation for a few minutes, anaesthesia was induced with nitrous oxide 3 L min-1, oxygen 3 L min-1 and sevoflurane or isoflurane. Sevoflurane or isoflurane concentration was increased by 0.5% every 2 to 3 breaths until 5% was attained for sevoflurane, or 3% for isoflurane. Vecuronium was administered to facilitate tracheal intubation. After intubation, sevoflurane was set to 2% while isoflurane was set to 1% with nitrous oxide with oxygen (1:1) for 5 min. Both sevoflurane and isoflurane provoked a decrease in blood pressure, total power, the low frequency component (LF), and high frequency component (HF) of HRV. Although the heart rate increased during isoflurane anaesthesia, it decreased under sevoflurane. The power of LF and HF also decreased in both groups. LF was higher in the isoflurane group while HF was higher in the sevoflurane group. The LF/HF ratio increased transiently in the isoflurane group, but decreased in the sevoflurane group. Anaesthesia induction with isoflurane-nitrous oxide transiently increased cardiac sympathetic activity, while sevoflurane-nitrous oxide decreased both cardiac sympathetic and parasympathetic activities. The balance of cardiac parasympathetic/sympathetic activity was higher in sevoflurane anaesthesia.

Egypt: Background and U.S. Relations

Science.gov (United States)

2009-05-12

contributions from Germany , Japan, and Switzerland. For more information on the MFO, see http://www.mfo.org/Default.asp?bhcp=1. Egypt: Background and...2008 Report, Egypt’s pace of business reforms and deregulation between 2006 and 2007 ranked first worldwide. In recent years, the state has...reinvigorated its privatization program by divesting shares in the state-dominated banking and insurance sectors. Additionally, the government removed import

An electrochemical study of the flow rate effect on the oxide film of SA106 Gr.C piping

International Nuclear Information System (INIS)

Hong, S. M.; Kim, J. H.; Kim, I. S.

2002-01-01

Effect of water flow rate on the oxide film of SA106 Gr.C piping was evaluated quantitatively through electrochemical method. It was carried out with weight change experiments, polarization tests, and EIS tests with rig that simulates water flow. Without water flow, the oxide film is so stable that it effectively blocks current exchange. With water flow, the oxide film was damaged and electrochemical current density and oxide film properties, C dl and R p were significantly changed

Carotenoids, birdsong and oxidative status: administration of dietary lutein is associated with an increase in song rate and circulating antioxidants (albumin and cholesterol and a decrease in oxidative damage.

Directory of Open Access Journals (Sweden)

Stefania Casagrande

Full Text Available Despite the appealing hypothesis that carotenoid-based colouration signals oxidative status, evidence supporting the antioxidant function of these pigments is scarce. Recent studies have shown that lutein, the most common carotenoid used by birds, can enhance the expression of non-visual traits, such as birdsong. Nevertheless, the underlying physiological mechanisms remain unclear. In this study we hypothesized that male European starlings (Sturnus vulgaris fed extra lutein increase their song rate as a consequence of an improved oxidative status. Although birdsong may be especially sensitive to the redox status, this has, to the best of our knowledge, never been tested. Together with the determination of circulating oxidative damage (ROMs, reactive oxygen metabolites, we quantified uric acid, albumin, total proteins, cholesterol, and testosterone, which are physiological parameters potentially sensitive to oxidation and/or related to both carotenoid functions and birdsong expression. We found that the birds fed extra lutein sang more frequently than control birds and showed an increase of albumin and cholesterol together with a decrease of oxidative damage. Moreover, we could show that song rate was associated with high levels of albumin and cholesterol and low levels of oxidative damage, independently from testosterone levels. Our study shows for the first time that song rate honestly signals the oxidative status of males and that dietary lutein is associated with the circulation of albumin and cholesterol in birds, providing a novel insight to the theoretical framework related to the honest signalling of carotenoid-based traits.

Oxygen transfer rates and requirements in oxidative biocatalysis

DEFF Research Database (Denmark)

Pedersen, Asbjørn Toftgaard; Rehn, Gustav; Woodley, John

2015-01-01

Biocatalytic oxidation reactions offer several important benefits such as regio- and stereoselectivity, avoiding the use of toxic metal based catalysts and replacing oxidizing reagents by allowing the use of oxygen. However, the development of biocatalytic oxidation processes is a complex task......-up is relatively straight forward (Gabelman and Hwang, 1999), and membrane contactors are implemented for various industrial applications (Klaassen et al., 2005)....

Heat and mass transfer analysis for paraffin/nitrous oxide burning rate in hybrid propulsion

Science.gov (United States)

Ben-Basat (Sisi), Shani; Gany, Alon

2016-03-01

This research presents a physical-mathematical model for the combustion of liquefying fuels in hybrid combustors, accounting for blowing effect on the heat transfer. A particular attention is given to a paraffin/nitrous oxide hybrid system. The use of a paraffin fuel in hybrid propulsion has been considered because of its much higher regression rate enabling significantly higher thrust compared to that of common polymeric fuels. The model predicts the overall regression rate (melting rate) of the fuel and the different mechanisms involved, including evaporation, entrainment of droplets of molten material, and mass loss due to melt flow on the condensed fuel surface. Prediction of the thickness and velocity of the liquid (melt) layer formed at the surface during combustion was done as well. Applying the model for an oxidizer mass flux of 45 kg/(s m2) as an example representing experimental range, it was found that 21% of the molten liquid undergoes evaporation, 30% enters the gas flow by the entrainment mechanism, and 49% reaches the end of the combustion chamber as a flowing liquid layer. When increasing the oxidizer mass flux in the port, the effect of entrainment increases while that of the flowing liquid layer along the surface shows a relatively lower contribution. Yet, the latter is predicted to have a significant contribution to the overall mass loss. In practical applications it may cause reduced combustion efficiency and should be taken into account in the motor design, e.g., by reinforcing the paraffin fuel with different additives. The model predictions have been compared to experimental results revealing good agreement.

Multifield Optimization Intensity Modulated Proton Therapy for Head and Neck Tumors: A Translation to Practice

Energy Technology Data Exchange (ETDEWEB)

Frank, Steven J., E-mail: sjfrank@mdanderson.org [Department of Radiation Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Cox, James D. [Department of Radiation Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Gillin, Michael; Mohan, Radhe [Department of Radiation Physics, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Garden, Adam S.; Rosenthal, David I.; Gunn, G. Brandon [Department of Radiation Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Weber, Randal S. [Department of Head and Neck Surgery, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Kies, Merrill S. [Department of Head and Neck Medical Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Lewin, Jan S. [Department of Head and Neck Surgery, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Munsell, Mark F. [Department of Biostatistics, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Palmer, Matthew B. [Department of Radiation Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States); Sahoo, Narayan; Zhang, Xiaodong; Liu, Wei; Zhu, X. Ronald [Department of Radiation Physics, The University of Texas MD Anderson Cancer Center, Houston, Texas (United States)

2014-07-15

Background: We report the first clinical experience and toxicity of multifield optimization (MFO) intensity modulated proton therapy (IMPT) for patients with head and neck tumors. Methods and Materials: Fifteen consecutive patients with head and neck cancer underwent MFO-IMPT with active scanning beam proton therapy. Patients with squamous cell carcinoma (SCC) had comprehensive treatment extending from the base of the skull to the clavicle. The doses for chemoradiation therapy and radiation therapy alone were 70 Gy and 66 Gy, respectively. The robustness of each treatment plan was also analyzed to evaluate sensitivity to uncertainties associated with variations in patient setup and the effect of uncertainties with proton beam range in patients. Proton beam energies during treatment ranged from 72.5 to 221.8 MeV. Spot sizes varied depending on the beam energy and depth of the target, and the scanning nozzle delivered the spot scanning treatment “spot by spot” and “layer by layer.” Results: Ten patients presented with SCC and 5 with adenoid cystic carcinoma. All 15 patients were able to complete treatment with MFO-IMPT, with no need for treatment breaks and no hospitalizations. There were no treatment-related deaths, and with a median follow-up time of 28 months (range, 20-35 months), the overall clinical complete response rate was 93.3% (95% confidence interval, 68.1%-99.8%). Xerostomia occurred in all 15 patients as follows: grade 1 in 10 patients, grade 2 in 4 patients, and grade 3 in 1 patient. Mucositis within the planning target volumes was seen during the treatment of all patients: grade 1 in 1 patient, grade 2 in 8 patients, and grade 3 in 6 patients. No patient experienced grade 2 or higher anterior oral mucositis. Conclusions: To our knowledge, this is the first clinical report of MFO-IMPT for head and neck tumors. Early clinical outcomes are encouraging and warrant further investigation of proton therapy in prospective clinical trials.

Effect of pressure on the transient swelling rate of oxide fuel

International Nuclear Information System (INIS)

Gruber, E.E.

1982-04-01

An analysis of the transient swelling rate of oxide fuel, based on fission-gas bubble conditions calculated with the FRAS3 code, has been developed and implemented in the code. The need for this capability arises in the coupling of the FRAS3 fission-gas analysis code to the FPIN fuel-pin mechanics code. An efficient means of closely coupling the calculations of swelling strains and stresses between the modules is required. The present analysis provides parameters that allow the FPIN calculation to proceed through a fairly large time step, using estimated swelling rates, to calculate the stresses. These stress values can then be applied in the FRAS3 detailed calculation to refine the swelling calculation, and to provide new values for the parameters to estimate the swelling in the next time step. The swelling rates were calculated for two representative transients and used to estimate swelling over a short time period for various stress levels

Developmental toxicity in flounder embryos exposed to crude oils derived from different geographical regions.

Science.gov (United States)

Jung, Jee-Hyun; Lee, Eun-Hee; Choi, Kwang-Min; Yim, Un Hyuk; Ha, Sung Yong; An, Joon Geon; Kim, Moonkoo

2017-06-01

Crude oils from distinct geographical regions have distinct chemical compositions, and, as a result, their toxicity may be different. However, developmental toxicity of crude oils derived from different geographical regions has not been extensively characterized. In this study, flounder embryos were separately exposed to effluents contaminated by three crude oils including: Basrah Light (BLO), Pyrenees (PCO), and Sakhalin Vityaz (SVO), in addition to a processed fuel oil (MFO-380), to measure developmental toxicity and for gene expressions. Each oil possessed a distinct chemical composition. Edema defect was highest in embryos exposed to PCO and MFO-380 that both have a greater fraction of three-ring PAHs (33% and 22%, respectively) compared to BLO and SVO. Observed caudal fin defects were higher in embryos exposed to SVO and MFO-380, which are both dominated by naphthalenes (81% and 52%, respectively). CYP1A gene expressions were also highest in embryos exposed to SVO and MFO-380. Higher incidence of cardiotoxicity and lower nkx 2.5 expression were detected in embryos exposed to PCO. Unique gene expression profiles were observed in embryos exposed to crude oils with distinct compositions. This study demonstrates that crude oils of different geographical origins with different compositional characteristics induce developmental toxicity to different degrees. Copyright © 2017 Elsevier Inc. All rights reserved.

Characterization of Enzymatic profiles of Aedes aegypti strains from the State of Rio Grande do Norte, Brazil

Directory of Open Access Journals (Sweden)

Renan Flávio de França Nunes

2016-01-01

Full Text Available Abstract This study was conducted in four strains of Aedes aegypti mosquitoes to evaluate the enzymatic activity profiles in the city of Mossoró, Rio Grande do Norte, and correlate them with biochemical mechanisms of resistance to insecticides. Mosquitos were used to quantify the following detoxification enzymes: Mixed-Function Oxidase (MFO, PNPA-esterase (PNPA-EST, and Acetylcholinesterase (AChE. The profiles were compared statistically with profiles from the Rockefeller strain, through the Kruskal-Wallis test and Dunn's multiple comparisons (p 15% and 50%. The statistical analysis revealed significant differences in the MFO and AChE profiles, which are fundamental in the determination of profiles of resistance to insecticides. Three populations were classified as “Substantially changed” for MFO. The altered enzymatic activity showed that the changes could have an important role in exposing resistance to insecticides.

Recombination rates of hydrogen and oxygen over pure and impure plutonium oxides

International Nuclear Information System (INIS)

Morales, L.

1999-01-01

Long-term, safe storage of excess plutonium-bearing materials is required until stabilization and disposal methods are implemented or defined. The US Department of Energy (DOE) has established a plan to address the stabilization, packing, and storage of plutonium-bearing materials from around the complex. The DOE's standard method, DOE-STD-3013-96 and its proposed revision, for stabilizing pure and impure actinide materials is by calcination in air followed by sealing the material in welded stainless steel containers. The 3013 standard contains and equation that predicts the total pressure buildup in the can over the anticipated storage time of 50 yr. This equation was meant to model a worst-case scenario to ensure that pressures would not exceed the strength of the container at the end of 50 yr. As a result, concerns about pressure generation in the storage cans, both absolute values and rates, have been raised with regard to rupture and dispersal of nuclear materials. Similar issues have been raised about the transportation of these materials around the complex. The purpose of this work is to provide a stronger technical basis for the 3013 standard by measuring the recombination rates of hydrogen/oxygen mixtures in contact with pure and impure plutonium oxides. The goal of these experiments was to determine whether the rate of recombination is faster than the rate of water radiolysis under controlled conditions. This was accomplished by using a calibrated pressure-volume-temperature apparatus to measure the recombination rates in a fixed volume as the gas mixture was brought into contact with oxide powders whose temperatures ranged from 50 to 300 C. These conditions were selected in order to bracket the temperature conditions expected in a typical storage can. In addition, a 2% H 2 /air mixture encompasses scenarios in which the cans are sealed in air, and over time various amounts of hydrogen are formed

Studies of the kinetics and mechanism of the oxidation of uranium by dry and moist air A model for determining the oxidation rate over a wide range of temperatures and water vapour pressures

Science.gov (United States)

McGillivray, G. W.; Geeson, D. A.; Greenwood, R. C.

1994-01-01

The rate of oxidation of uranium metal by moist air has been measured at temperatures from 115 to 350°C and water vapour pressures from 0 to 47 kPa (350 Torr). From this and from previously reported data, a model has been developed which allows the rate of uranium oxidation to be calculated at any particular combination of temperature and water vapour pressure of interest, in the range 0-350°C and 0-101.3 kPa (760 Torr). The model is based on the assumption that the surface concentration of water determines the rate of reaction and that the adsorption of water onto the oxide follows a Langmuir type isotherm. Theoretical plots of rate as a function of water vapour pressure and Arrhenius plots derived from the model have been shown to be in good agreement with experimental data. The model assumes separate contributions to the overall observed rate from oxygen and water vapour. Surface studies have been carried out using SIMS (secondary ion mass spectrometry). Depth profiling of the oxide produced by isotopically labelled reagents ( 18O 2 and H 218O), has shown that oxygen from both reactants is incorporated into the oxide layer in the ratio predicted by the kinetic model. This supports a mechanism in which oxygen and water vapour produce separate diffusing species (possibly O 2- and OH -).

Mixed function oxidase dependent biotransformation of polychlorinated biphenyls by different species of fish from the North Sea

DEFF Research Database (Denmark)

Mehrtens, G.; Laturnus, F.

1999-01-01

Mixed function oxidase (MFO) dependent biotransformation of polychlorinated biphenyls (PCBs) was measured in three different fish species from the North Sea. Liver microsomes of plaice (Pleuronectes platessa), dab (Limanda limanda) and cod (Gadus morhua) were isolated and incubated with different....... Biotransformations were also species dependent. The flatfish dab and plaice exhibited higher metabolic rates than cod (C) 1999 Elsevier Science Ltd. All rights reserved....

Effects of high-intensity interval training on physical capacities and substrate oxidation rate in obese adolescents.

Science.gov (United States)

Lazzer, S; Tringali, G; Caccavale, M; De Micheli, R; Abbruzzese, L; Sartorio, A

2017-02-01

To investigate the effects of a 3-week weight-management program entailing moderate energy restriction, nutritional education, psychological counseling and three different exercise training (a: low intensity, LI: 40 % V'O 2 max; b: high intensity, HI: 70 % V'O 2 max; c: high-intensity interval training, HIIT), on body composition, energy expenditure and fat oxidation rate in obese adolescents. Thirty obese adolescents (age: 15-17 years, BMI: 37.5 kg m -2 ) participated in this study. Before starting (week 0, W0) and at the end of the weight-management program (week 3, W3), body composition was assessed by an impedancemeter; basal metabolic rate (BMR), energy expenditure and substrate oxidation rate were measured during exercise and post-exercise recovery by indirect calorimetry. At W3, body mass (BM) and fat mass (FM) decreased significantly in all groups, the decreases being significantly greater in the LI than in the HI and HIIT subgroups (BM: -8.4 ± 1.5 vs -6.3 ± 1.9 vs -4.9 ± 1.3 kg and FM: -4.2 ± 1.9 vs -2.8 ± 1.2 vs -2.3 ± 1.4 kg, p < 0.05, respectively). V'O 2 peak, expressed in relative values, changed significantly only in the HI and HIIT groups by 0.009 ± 0.005 and 0.007 ± 0.004 L kg FFM -1  min -1 (p < 0.05). Furthermore, the HI and HIIT subgroups exhibited a greater absolute rate of fat oxidation between 50 and 70 % V'O 2 peak at W3. No significant changes were observed at W3 in BMR, energy expenditure during exercise and post-exercise recovery. A 3-week weight-management program induced a greater decrease in BM and FM in the LI than in the HI and HIIT subgroups, and greater increase in V'O 2 peak and fat oxidation rate in the HI and HIIT than in the LI subgroup.

The effect of anti-depressant and narcoleptic drugs on isopropyl iodoamphetamine biodistribution

International Nuclear Information System (INIS)

Moretti, J.L.; Holman, B.L.; Delmon, L.; Carmel, A.; Johnson, D.; Moingeon, P.; Blau, M.; Chu, H.

1985-01-01

I-123 Nisopropyl p-iodoamphetamine (IMP) is a useful radiotracer for imaging regional cerebral perfursion in a wide variety of neurological and cerebrovascular diseases. The major route of amine metabolism in the lung is the mixed function oxidase (MFO) system. A number of antidepressants and narcoleptic agents have been shown to displace amphetamine from the lung. If these drugs release IMP before it is metabolized to lipophobic products, brain concentration will be affected. The authors investigated the effects of these drugs on IMP distribution in animals with high and low pulmonary concentrations of MFO. When 1 mg/kg imipramine (IM) was injected iv into Wistar rats 30 min before IMP and 50 min before sacrifice, lung activity was depressed (4 + 1% ID vs 12 + 4% ID). Brain activity was depressed only with 4 mg/kg IM (l.5 + .3% ID vs 2.7 + .7% ID). There was no significant difference in IMP brain activity without IM and when IM was given simultaneously with, 5 or 15 min after IMP. In New Zealand rabbits which have a low pulmonary MFO concentration, IM altered lung and brain uptake during simultaneous injection and as late as 15 min after IMP. Lung uptake was reduced 51% and brain uptake was increased 25%, 20%, and 19% when IM was injected 0, 5 and 15 min after IMP. The MAO inhibitors, phenelzine and L deprenyl, did not alter the brain, lung or liver IMP activity in rats at a dose of 5 mg/kg. These data are consistent with a model in which IMP is trapped and metabolized in the lung by the MFO system. Assuming an active MFO system in the human (unlike the rabbit), brain activity of IMP will not be altered by either IM or MAO inhibitors

International Conference CoMFoS15

CERN Document Server

Kimura, Masato; Chalupecký, Vladimír; Ohtsuka, Kohji; Tagami, Daisuke; Takada, Akira

2017-01-01

This book focuses on mathematical theory and numerical simulation related to various aspects of continuum mechanics, such as fracture mechanics, elasticity, plasticity, pattern dynamics, inverse problems, optimal shape design, material design, and disaster estimation related to earthquakes. Because these problems have become more important in engineering and industry, further development of mathematical study of them is required for future applications. Leading researchers with profound knowledge of mathematical analysis from the fields of applied mathematics, physics, seismology, engineering, and industry provide the contents of this book. They help readers to understand that mathematical theory can be applied not only to different types of industry, but also to a broad range of industrial problems including materials, processes, and products.

Studies of the kinetics and mechanism of the oxidation of uranium by dry and moist air. A model for determining the oxidation rate over a wide range of temperatures and water vapour pressures

Energy Technology Data Exchange (ETDEWEB)

McGillivray, G.W. (Atomic Weapons Establishment, Aldermaston, Reading (United Kingdom)); Geeson, D.A. (Atomic Weapons Establishment, Aldermaston, Reading (United Kingdom)); Greenwood, R.C. (Atomic Weapons Establishment, Aldermaston, Reading (United Kingdom))

1994-01-01

The rate of oxidation of uranium metal by moist air has been measured at temperatures from 115 to 350 C and water vapour pressures from 0 to 47 kPa (350 Torr). From this and from previously reported data, a model has been developed which allows the rate of uranium oxidation to be calculated at any particular combination of temperature and water vapour pressure of interest, in the range 0-350 C and 0-101.3 kPa (760 Torr). The model is based on the assumption that the surface concentration of water determines the rate of reaction and that the adsorption of water onto the oxide follows a Langmuir type isotherm. Theoretical plots of rate as a function of water vapour pressure and Arrhenius plots derived from the model have been shown to be in good agreement with experimental data. The model assumes separate contributions to the overall observed rate from oxygen and water vapour. Surface studies have been carried out using SIMS (secondary ion mass spectrometry). Depth profiling of the oxide produced by isotopically labelled reagents ([sup 18]O[sub 2] and H[sup 18][sub 2]O), has shown that oxygen from both reactants is incorporated into the oxide layer in the ratio predicted by the kinetic model. This supports a mechanism in which oxygen and water vapour produce separate diffusing species (possibly O[sup 2-] and OH[sup -]). (orig.)

A simple route to improve rate performance of LiFePO4/reduced graphene oxide composite cathode by adding Mg2+ via mechanical mixing

Science.gov (United States)

Huang, Yuan; Liu, Hao; Gong, Li; Hou, Yanglong; Li, Quan

2017-04-01

Introducing Mg2+ to LiFePO4 and reduced graphene oxide composite via mechanical mixing and annealing leads to largely improved rate performance of the cathode (e.g. ∼78 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite with Mg2+ introduction vs. ∼37 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite). X-ray photoelectron spectroscopy unravels that the enhanced reduction of Fe2+ to Fe0 occurs in the simultaneous presence of Mg2+ and reduced graphene oxide, which is beneficial for the rate capability of cathode. The simple fabrication process provides a simple and effective means to improve the rate performance of the LiFePO4 and reduced graphene oxide composite cathode.

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.

High rate capability of lithium/silver vanadium oxide cells

International Nuclear Information System (INIS)

Takeuchi, E.S.; Zelinsky, M.A.; Keister, P.

1986-01-01

High rate characteristics of the lithium/silver vanadium oxide system were investigated in test cells providing four different limiting surface areas. The cells were tested by constant current and constant resistance discharge with current densities ranging from 0.04 to 6.4 mA/cm/sup 2/. The maximum current density under constant resistance and constant current discharges which would deliver 50% of theoretical capacity was determined. The ability of the cells to deliver high current pulses was evaluated by application of 10 second pulses with current densities ranging from 3 to 30 mA/cm/sup 2/. The voltage delay characteristics of the cells were determined after 1 to 3 months of storage at open circuit voltage or under low level background currents. The volumetric and gravimetric energy density of the SVO system is compared to other cathode materials

The competing oxide and sub-oxide formation in metal-oxide molecular beam epitaxy

International Nuclear Information System (INIS)

Vogt, Patrick; Bierwagen, Oliver

2015-01-01

The hetero-epitaxial growth of the n-type semiconducting oxides β-Ga 2 O 3 , In 2 O 3 , and SnO 2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga 2 O, In 2 O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO 2 , somewhat lower for In 2 O 3 , and the lowest for Ga 2 O 3 . Our findings can be generalized to further oxides that possess related sub-oxides

THE ROLES OF DETOXIFYING ENZYMES AND AChE INSENSITIVITY IN METHAMIDOPHOS RESISTANCE DEVELOPMENT AND DECLINE IN NILAPARVATA LUGENS

Institute of Scientific and Technical Information of China (English)

Ze-wenLiu; Zhao-junHan; Ling-chunZhang

2003-01-01

Methamidophos resistance of brown planthopper (Nilaparvata lugens Stal, BPH) was selected in laboratory. After successive selection for 9 generations, the selection was ceased by rearing BPH without contact with any insecticide for 9 generations. In the full course, the successive changes of esterase activity, MFO activity, GSTs activity and AChE insensitivity were analyzed. The results showed that the change of esterase activity was high correlated with that of methamidophos in the full course, which indicated that esterase played very important role both in the resistance development and in the resistance decline. However, the change of AChE insensitivity only significantly correlated with that of resistance in the development stage, and the change of MFO activity or GSTs activity only significantly correlated with that of the resistance in the decline stage, which indicated the changes of AChE insensitivity, MFO activity or GSTs activity only played some roles in different stages of the resistance change.

Oxidation Resistant Graphite Studies

Energy Technology Data Exchange (ETDEWEB)

W. Windes; R. Smith

2014-07-01

The Very High Temperature Reactor (VHTR) Graphite Research and Development Program is investigating doped nuclear graphite grades exhibiting oxidation resistance. During a oxygen ingress accident the oxidation rates of the high temperature graphite core region would be extremely high resulting in significant structural damage to the core. Reducing the oxidation rate of the graphite core material would reduce the structural effects and keep the core integrity intact during any air-ingress accident. Oxidation testing of graphite doped with oxidation resistant material is being conducted to determine the extent of oxidation rate reduction. Nuclear grade graphite doped with varying levels of Boron-Carbide (B4C) was oxidized in air at nominal 740°C at 10/90% (air/He) and 100% air. The oxidation rates of the boronated and unboronated graphite grade were compared. With increasing boron-carbide content (up to 6 vol%) the oxidation rate was observed to have a 20 fold reduction from unboronated graphite. Visual inspection and uniformity of oxidation across the surface of the specimens were conducted. Future work to determine the remaining mechanical strength as well as graphite grades with SiC doped material are discussed.

Patterning crystalline indium tin oxide by high repetition rate femtosecond laser-induced crystallization

International Nuclear Information System (INIS)

Cheng, Chung-Wei; Lin, Cen-Ying; Shen, Wei-Chih; Lee, Yi-Ju; Chen, Jenq-Shyong

2010-01-01

A method is proposed for patterning crystalline indium tin oxide (c-ITO) patterns on amorphous ITO (a-ITO) thin films by femtosecond laser irradiation at 80 MHz repetition rate followed by chemical etching. In the proposed approach, the a-ITO film is transformed into a c-ITO film over a predetermined area via the heat accumulation energy supplied by the high repetition rate laser beam, and the unirradiated a-ITO film is then removed using an acidic etchant solution. The fabricated c-ITO patterns are observed using scanning electron microscopy and cross-sectional transmission electron microscopy. The crystalline, optical, electrical properties were measured by X-ray diffraction, spectrophotometer, and four point probe station, respectively. The experimental results show that a high repetition rate reduces thermal shock and yields a corresponding improvement in the surface properties of the c-ITO patterns.

Real time dose rate measurements with fiber optic probes based on the RL and OSL of beryllium oxide

International Nuclear Information System (INIS)

Teichmann, T.; Sponner, J.; Jakobi, Ch.; Henniger, J.

2016-01-01

This work covers the examination of fiber optical probes based on the radioluminescence and real time optically stimulated luminescence of beryllium oxide. Experiments are carried out to determine the fundamental dosimetric and temporal properties of the system and evaluate its suitability for dose rate measurements in brachytherapy and other applications using non-pulsed radiation fields. For this purpose the responses of the radioluminescence and optically stimulated luminescence signal have been investigated in the dose rate range of 20 mGy/h to 3.6 Gy/h and for doses of 1 mGy up to 6 Gy. Furthermore, a new, efficient analysis procedure, the double phase reference summing, is introduced, leading to a real time optically stimulated luminescence signal. This method allows a complete compensation of the stem effect during the measurement. In contrast to previous works, the stimulation of the 1 mm cylindrical beryllium oxide detectors is performed with a symmetric function during irradiation. The investigated dose rates range from 0.3 to 3.6 Gy/h. The real time optically stimulated luminescence signal of beryllium oxide shows a dependency on both the dose rate and the applied dose. To overcome the problem of dose dependency, further experiments using higher stimulation intensities have to follow. - Highlights: • RL and OSL measurements with BeO extended to low dose (rate) range. • A new method to obtain the real time OSL: Dual Phase Reference Summing. • Real time OSL signal shows both dose and dose rate dependency. • Real time OSL enables a complete discrimination of the stem effect.

QSAR models for oxidation of organic micropollutants in water based on ozone and hydroxyl radical rate constants and their chemical classification

KAUST Repository

Sudhakaran, Sairam

2013-03-01

Ozonation is an oxidation process for the removal of organic micropollutants (OMPs) from water and the chemical reaction is governed by second-order kinetics. An advanced oxidation process (AOP), wherein the hydroxyl radicals (OH radicals) are generated, is more effective in removing a wider range of OMPs from water than direct ozonation. Second-order rate constants (kOH and kO3) are good indices to estimate the oxidation efficiency, where higher rate constants indicate more rapid oxidation. In this study, quantitative structure activity relationships (QSAR) models for O3 and AOP processes were developed, and rate constants, kOH and kO3, were predicted based on target compound properties. The kO3 and kOH values ranged from 5 * 10-4 to 105 M-1s-1 and 0.04 to 18 * (109) M-1 s-1, respectively. Several molecular descriptors which potentially influence O3 and OH radical oxidation were identified and studied. The QSAR-defining descriptors were double bond equivalence (DBE), ionisation potential (IP), electron-affinity (EA) and weakly-polar component of solvent accessible surface area (WPSA), and the chemical and statistical significance of these descriptors was discussed. Multiple linear regression was used to build the QSAR models, resulting in high goodness-of-fit, r2 (>0.75). The models were validated by internal and external validation along with residual plots. © 2012 Elsevier Ltd.

Inhibition of acetaminophen oxidation by cimetidine and the effects on glutathione and activated sulphate synthesis rates

DEFF Research Database (Denmark)

Dalhoff, K; Poulsen, H E

1993-01-01

inhibition of cytochrome P-450 drug oxidation by cimetidine in isolated rat hepatocytes. The synthesis rates of glutathione and PAPS were determined simultaneously by an established method based on trapping of radioactivity (35S) in the prelabelled glutathione and PAPS pools. Preincubation of the hepatocytes...

Enhanced Rate Capability of Oxide Coated Lithium Titanate within Extended Voltage Ranges

Energy Technology Data Exchange (ETDEWEB)

Ahn, Dongjoon [College of Engineering, University of Kentucky, Lexington, KY (United States); Xiao, Xingcheng, E-mail: xingcheng.xiao@gm.com [Chemical and Materials Systems Laboratory, General Motors R& D Center, Warren, MI (United States)

2015-06-30

Lithium titanate (Li{sub 4}Ti{sub 5}O{sub 12} or LTO) is a promising negative electrode material of high-power lithium-ion batteries, due to its superior rate capability and excellent capacity retention. However, the specific capacity of LTO is less than one half of that of graphite electrode. In this work, we applied ultrathin oxide coating on LTO by the atomic layer deposition technique, aiming for increasing the energy density by extending the cell voltage window and specific capacity of LTO. We demonstrated that a few nanometer thick Al{sub 2}O{sub 3} coating can suppress the mechanical distortion of LTO cycled at low potential, which enable the higher specific capacity and excellent capacity retention. Furthermore, the surface coating can facilitate the charge transfer, leading to significantly improved rate capabilities, comparing with the uncoated LTO.

Ectopic expression of a horseradish peroxidase enhances growth rate and increases oxidative stress resistance in hybrid aspen.

Science.gov (United States)

Kawaoka, Akiyoshi; Matsunaga, Etsuko; Endo, Saori; Kondo, Shinkichi; Yoshida, Kazuya; Shinmyo, Atsuhiko; Ebinuma, Hiroyasu

2003-07-01

We previously demonstrated that overexpression of the horseradish (Armoracia rusticana) peroxidase prxC1a gene stimulated the growth rate of tobacco (Nicotiana tabacum) plants. Here, the cauliflower mosaic virus 35S::prxC1a construct was introduced into hybrid aspen (Populus sieboldii x Populus grandidentata). The growth rate of these transformed hybrid aspen plants was substantially increased under greenhouse conditions. The average stem length of transformed plants was 25% greater than that of control plants. There was no other obvious phenotypic difference between the transformed and control plants. Fast-growing transformed hybrid aspen showed high levels of expression of prxC1a and had elevated peroxidase activities toward guaiacol and ascorbate. However, there was no increase of the endogenous class I ascorbate peroxidase activities in the transformed plants by separate assay and activity staining of native polyacrylamide gel electrophoresis. Furthermore, calli derived from the transformed hybrid aspen grew faster than those from control plants and were resistant to the oxidative stress imposed by hydrogen peroxide. Therefore, enhanced peroxidase activity affects plant growth rate and oxidative stress resistance.

Methodological aspects of crossover and maximum fat-oxidation rate point determination.

Science.gov (United States)

Michallet, A-S; Tonini, J; Regnier, J; Guinot, M; Favre-Juvin, A; Bricout, V; Halimi, S; Wuyam, B; Flore, P

2008-11-01

Indirect calorimetry during exercise provides two metabolic indices of substrate oxidation balance: the crossover point (COP) and maximum fat oxidation rate (LIPOXmax). We aimed to study the effects of the analytical device, protocol type and ventilatory response on variability of these indices, and the relationship with lactate and ventilation thresholds. After maximum exercise testing, 14 relatively fit subjects (aged 32+/-10 years; nine men, five women) performed three submaximum graded tests: one was based on a theoretical maximum power (tMAP) reference; and two were based on the true maximum aerobic power (MAP). Gas exchange was measured concomitantly using a Douglas bag (D) and an ergospirometer (E). All metabolic indices were interpretable only when obtained by the D reference method and MAP protocol. Bland and Altman analysis showed overestimation of both indices with E versus D. Despite no mean differences between COP and LIPOXmax whether tMAP or MAP was used, the individual data clearly showed disagreement between the two protocols. Ventilation explained 10-16% of the metabolic index variations. COP was correlated with ventilation (r=0.96, P<0.01) and the rate of increase in blood lactate (r=0.79, P<0.01), and LIPOXmax correlated with the ventilation threshold (r=0.95, P<0.01). This study shows that, in fit healthy subjects, the analytical device, reference used to build the protocol and ventilation responses affect metabolic indices. In this population, and particularly to obtain interpretable metabolic indices, we recommend a protocol based on the true MAP or one adapted to include the transition from fat to carbohydrate. The correlation between metabolic indices and lactate/ventilation thresholds suggests that shorter, classical maximum progressive exercise testing may be an alternative means of estimating these indices in relatively fit subjects. However, this needs to be confirmed in patients who have metabolic defects.

Evaluation of flow accelerated corrosion by coupled analysis of corrosion and flow dynamics. Relationship of oxide film thickness, hematite/magnetite ratio, ECP and wall thinning rate

International Nuclear Information System (INIS)

Uchida, Shunsuke; Naitoh, Masanori; Okada, Hidetoshi; Uehara, Yasushi; Koshizuka, Seiichi

2011-01-01

Systematic approaches to evaluate flow accelerated corrosion (FAC) are desired before discussing application of countermeasures for FAC. First, future FAC occurrence should be evaluated to identify locations where a higher possibility of FAC occurrence exists, and then, wall thinning rate at the identified FAC occurrence zone is evaluated to obtain the preparation time for applying countermeasures. Wall thinning rates were calculated with two coupled models: 1.static electrochemical analysis and 2.dynamic oxide layer growth analysis. The anodic current density and the electrochemical corrosion potential (ECP) were calculated with the static electrochemistry model based on an Evans diagram. The ferrous ion release rate, determined by the anodic current density, was applied as input for the dynamic double oxide layer model. Some of the dissolved ferrous ion was removed to the bulk water and others precipitated on the surface as magnetite particles. The thickness of oxide layer was calculated with the dynamic oxide layer growth model and then its value was used as input in the electrochemistry model. It was confirmed that the calculated results (corrosion rate and ECP) based on the coupled models were in good agreement with the measured ones. Higher ECP was essential for preventing FAC rate. Moderated conditions due to lower mass transfer coefficients resulted in thicker oxide layer thickness and then higher ECP, while moderated corrosion conditions due to higher oxidant concentrations resulted in larger hematite/magnetite rate and then higher ECP.

Oxidation of zirconium-aluminum alloys

International Nuclear Information System (INIS)

Cox, B.

1967-10-01

Examination of the processes occurring during the oxidation of Zr-1% A1, Zr-3% A1, and Zr-1.5% A1-0.5% Mo alloys has shown that in steam rapid oxidation occurs predominantly around the Zr 3 A1 particles, which at low temperatures appear to be relatively unattacked. The unoxidised particles become incorporated in the oxide, and become fully oxidised as the film thickens. This rapid localised oxidation is preceded by a short period of uniform film growth, during which the oxide film thickness does not exceed ∼200A-o. Thus the high oxidation rates can probably be ascribed to aluminum in solution in the zirconium matrix, although its precise mode of operation has not been determined. Once the solubility limit of aluminum is exceeded, the size, distribution and number of intermetallic particles affects the oxidation rate merely by altering the distribution of regions of metal giving high oxidation rates. The controlling process during the early stages of oxidation is electron transport and not ionic transport. Thus, the aluminum in the oxide film is presumably increasing the ionic conductivity more than the electronic. The oxidation rates in atmospheric pressure steam are very high and their irregular temperature dependence suggests that the oxidation rate will be pressure dependent. This was confirmed, in part, by a comparison with oxidation in moist air. It was found that the rate of development of white oxide around intermetallic particles was considerably reduced by the decrease in the partial pressure of H 2 O; the incubation period was not much different, however. (author)

Ammonium supply rate influences archaeal and bacterial ammonia oxidizers in a wetland soil vertical profile.

Science.gov (United States)

Höfferle, Špela; Nicol, Graeme W; Pal, Levin; Hacin, Janez; Prosser, James I; Mandić-Mulec, Ines

2010-11-01

Oxidation of ammonia, the first step in nitrification, is carried out in soil by bacterial and archaeal ammonia oxidizers and recent studies suggest possible selection for the latter in low-ammonium environments. In this study, we investigated the selection of ammonia-oxidizing archaea and bacteria in wetland soil vertical profiles at two sites differing in terms of the ammonium supply rate, but not significantly in terms of the groundwater level. One site received ammonium through decomposition of organic matter, while the second, polluted site received a greater supply, through constant leakage of an underground septic tank. Soil nitrification potential was significantly greater at the polluted site. Quantification of amoA genes demonstrated greater abundance of bacterial than archaeal amoA genes throughout the soil profile at the polluted site, whereas bacterial amoA genes at the unpolluted site were below the detection limit. At both sites, archaeal, but not the bacterial community structure was clearly stratified with depth, with regard to the soil redox potential imposed by groundwater level. However, depth-related changes in the archaeal community structure may also be associated with physiological functions other than ammonia oxidation. © 2010 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Simulation of the induction of oxidation of low-density lipoprotein by high copper concentrations: evidence for a nonconstant rate of initiation.

Science.gov (United States)

Abuja, P M; Albertini, R; Esterbauer, H

1997-06-01

Kinetic simulation can help obtain deeper insight into the molecular mechanisms of complex processes, such as lipid peroxidation (LPO) in low-density lipoprotein (LDL). We have previously set up a single-compartment model of this process, initiating with radicals generated externally at a constant rate to show the interplay of radical scavenging and chain propagation. Here we focus on the initiating events, substituting constant rate of initiation (Ri) by redox cycling of Cu2+ and Cu+. Our simulation reveals that early events in copper-mediated LDL oxidation include (1) the reduction of Cu2+ by tocopherol (TocOH) which generates tocopheroxyl radical (TocO.), (2) the fate of TocO. which either is recycled or recombines with lipid peroxyl radical (LOO.), and (3) the reoxidation of Cu+ by lipid hydroperoxide which results in alkoxyl radical (LO.) formation. So TocO., LOO., and LO. can be regarded as primordial radicals, and the sum of their formation rates is the total rate of initiation, Ri. As experimental information of these initiating events cannot be obtained experimentally, the whole model was validated experimentally by comparison of LDL oxidation in the presence and absence of bathocuproine as predicted by simulation. Simulation predicts that Ri decreases by 2 orders of magnitude during lag time. This has important consequences for the estimation of oxidation resistance in copper-mediated LDL oxidation: after consumption of tocopherol, even small amounts of antioxidants may prolong the lag phase for a considerable time.

Changes in Fe Oxidation Rate in Hydrothermal Plumes as a Potential Driver of Enhanced Hydrothermal Input to Near-Ridge Sediments During Glacial Terminations

Science.gov (United States)

Cullen, J. T.; Coogan, L. A.

2017-12-01

Recent studies have hypothesized that changes in sea level due to glacial-interglacial cycles lead to changes in the rate of melt addition to the crust at mid-ocean ridges with globally significant consequences. Arguably the most compelling evidence for this comes from increases in the hydrothermal component in near-ridge sediments during glacial-interglacial transitions. Here we explore the hypothesis that changes in ocean bottom water [O2] and pH across glacial-interglacial transitions would lead to changes in the rate of Fe oxidation in hydrothermal plumes. A simple model shows that a several fold increase in the rate of Fe oxidation is expected at glacial-interglacial transitions. Uncertainty in bottom water chemistry and the relationship between oxidation and sedimentation rates prevent direct comparison of the model and data. However, it appears that the null hypothesis of invariant hydrothermal vent fluxes into ocean bottom water that changed in O2 content and pH across these transitions cannot currently be discounted.

Hydrogen permeation rate reduction by post-oxidation of aluminide coatings on DIN 1.4914 martensitic steel (MANET)

International Nuclear Information System (INIS)

Perujo, A.; Sample, T.

1996-01-01

In a previous work, it has been shown that lower aluminium content aluminide, having the same permeation rate reduction as the higher aluminium content, exhibited a lower hardness and greater ductility and therefore greater crack resistance than the higher aluminium content. In this work we combine this characteristic with a post-oxidation to obtain a further deuterium permeation reduction. The post-oxidation was performed in air at 1023 K for 15 h and at 1223 K for 10 h and 1 h. The maximum deuterium permeation rate reduction obtained is very moderate (maximum of a factor 500 for 1 h at 1223 K) as compared to that of the non-oxidised aluminide specimen (two orders of magnitude) and is constant in the temperature range studied (573-800 K). This method has the technological appeal of using air rather than the controlled environment used by other authors. (orig.)

Influence of air flow rate on structural and electrical properties of undoped indium oxide thin films

International Nuclear Information System (INIS)

Mirzapour, S.; Rozati, S.M.; Takwale, M.G.; Marathe, B.R.; Bhide, V.G.

1993-01-01

Using the spray pyrolysis technique thin films of indium oxide were prepared on Corning glass (7059) at a substrate temperature of 425 C at different flow rates. The electrical and structural properties of these films were studied. The Hall measurements at room temperature showed that the films prepared in an air flow rate of 7 litre min -1 have the highest mobility of 47 cm 2 V -1 s -1 and a minimum resistivity of 1.125 x 10 -3 Ω cm. The X-ray diffraction patterns showed that the films have a preferred orientation of [400] which peaks at the air flow rate of 7 litre min -1 . (orig.)

Palm oil based biofuel using blended crude palm oil/medium fuel oil: physical and thermal properties studies. Paper no. IGEC-1-015

International Nuclear Information System (INIS)

Chuah, T.G.; Zakiah, M.; Wan Hasamuddin, W.H.; Hj. Ahmad, H.; Fakhru'l-Razi, A.; Robiah, Y.; Choong, T.S.Y.; Yip, Y.F.

2005-01-01

Crude Palm Oil (CPO) is renewable bio-based resource. It is an attractive alternative fuel which provides the potential to reduce emission problems. CPO is an example of biofuels that can be blended with petroleum distillates as a fuel in mobile engines and industrial processes to help offset the increasing energy demand. This paper highlights the results of blended Crude Palm Oil (CPO)/Medium Fuel Oil (MFO) as an alternative environmentally friendly boiler's fuel. Heating values of the blend fuels have been measured using an oxygen bomb calorimeter. Combustion performance of a blend containing 50% CPO in MFO fuel was examined using a commercial boiler. The blend burned satisfactorily without major modification to the appliance and fuel delivery system. SO 2 emissions were 51.67% lower than MFO, H 2 S decreased about 55.61% while NO x were 18.67% reduced. Results indicate potential reductions of SO 2 , H 2 S and NO x , and greenhouse gas emissions for the petroleum distillates can be replaced with this blend. (author)

Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

Science.gov (United States)

Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

2016-06-01

Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

Effect of oxide ion concentration on the electrochemical oxidation of carbon in molten LiCl

International Nuclear Information System (INIS)

Yun, J. W.; Choi, I. K.; Park, Y. S.; Kim, W. H.

2001-01-01

The continuous measurement of lithium oxide concentration was required in DOR (Direct Oxide Reduction) process, which converts spent nuclear fuel to metal form, for the reactivity monitor and effective control of the process. The concentration of lithium oxide was measured by the electrochemical method, which was based on the phenomenon that carbon atoms of glassy carbon electrode electrochemically react with oxygen ions of lithium oxide in molten LiCl medium. From the results of electrode polarization experiments, the trend of oxidation rate of carbon atoms was classified into two different regions, which were proportional and non-proportional ones, dependent on the amount of lithium oxide. Below about 2.5 wt % Li 2 O, as the carbon atom ionization rate was fast enough for reacting with diffusing lithium oxide to the surface of carbon electrode. In this concentration range, the oxidation rate of carbon atoms was controlled by the diffusion of lithium oxide, and the concentration of lithium oxide could be measured by electrochemical method. But, above 2.5 wt % Li 2 O, the oxidation rate of carbon atoms was controlled by the applied electrochemical potential, because the carbon atom ionization rate was suppressed by the huge amounts of diffusing Li 2 O. Above this concentration, the electrochemical method was not applicable to determine the concentration of lithium oxide

High rates of denitrification and nitrous oxide emission in arid biological soil crusts from the Sultanate of Oman

DEFF Research Database (Denmark)

Abed, Raeid M M; Lam, Phyllis; De Beer, Dirk

2013-01-01

Using a combination of process rate determination, microsensor profiling and molecular techniques, we demonstrated that denitrification, and not anaerobic ammonium oxidation (anammox), is the major nitrogen loss process in biological soil crusts from Oman. Potential denitrification rates were 584...... that nitrogen loss via denitrification is a dominant process in crusts from Oman, which leads to N 2 O gas emission and potentially reduces desert soil fertility....

Effect of trichloroethylene enhancement on deposition rate of low-temperature silicon oxide films by silicone oil and ozone

Science.gov (United States)

Horita, Susumu; Jain, Puneet

2017-08-01

A low-temperature silcon oxide film was deposited at 160 to 220 °C using an atmospheric pressure CVD system with silicone oil vapor and ozone gases. It was found that the deposition rate is markedly increased by adding trichloroethylene (TCE) vapor, which is generated by bubbling TCE solution with N2 gas flow. The increase is more than 3 times that observed without TCE, and any contamination due to TCE is hardly observed in the deposited Si oxide films from Fourier transform infrared spectra.

Nickel-regulated heart rate variability: The roles of oxidative stress and inflammation

International Nuclear Information System (INIS)

Chuang, Hsiao-Chi; Hsueh, Tzu-Wei; Chang, Chuen-Chau; Hwang, Jing-Shiang; Chuang, Kai-Jen; Yan, Yuan-Horng; Cheng, Tsun-Jen

2013-01-01

Heart rate variability (HRV) has been reported to be a putative marker of cardiac autonomic imbalance caused by exposure to ambient particulate matter (PM). Our objective in this study was to determine the effects on HRV from exposure to nickel, an important chemical component of ambient PM that results in oxidative stress and inflammation. HRV data were collected for 72 h before lung exposure (baseline) and 72 h after intratracheal exposure (response) to nickel sulphate (NiSO 4 ; 526 μg) in Wistar Kyoto (WKY) and spontaneously hypertensive (SH) rats. The antioxidant N-acetyl-L-cysteine (NAC) and the anti-inflammatory celecoxib were intraperitoneally injected to examine post-exposure oxidative and inflammatory responses. Self-controlled experiments examined the effects of NiSO 4 exposure on average normal-to-normal intervals (ANN), natural logarithm-transformed standard deviation of the normal-to-normal intervals (LnSDNN) and root mean square of successive differences of adjacent normal-to-normal intervals (LnRMSSD); the resulting data were sequentially analysed using the generalised estimating equation model. HRV effects on NiSO 4 -exposed SH rats were greater than those on NiSO 4 -exposed WKY rats. After adjusted the HRV responses in the WKY rats as control, ANN and LnRMSSD were found to be quadratically increased over 72 h after exposure to NiSO 4 . Both NAC and celecoxib mitigated the NiSO 4 -induced alterations in HRV during the exposure period. The results suggest that concurrent Ni-induced oxidative stress and inflammatory responses play important roles in regulating HRV. These findings help bridge the gap between epidemiological and clinical studies on the plausible mechanisms of the cardiovascular consequences induced by chemical components in ambient PM. -- Highlights: ► To determine the effects on HRV from exposure to nickel. ► ANN and LnRMSSD were found to be quadratically increased after exposure to Ni. ► NAC and celecoxib mitigated the Ni

Nickel-regulated heart rate variability: The roles of oxidative stress and inflammation

Energy Technology Data Exchange (ETDEWEB)

Chuang, Hsiao-Chi, E-mail: r92841005@ntu.edu.tw [School of Respiratory Therapy, College of Medicine, Taipei Medical University, Taipei, Taiwan (China); Division of Pulmonary Medicine, Department of Internal Medicine, Shuang Ho Hospital, Taipei Medical University, Taipei, Taiwan (China); Hsueh, Tzu-Wei, E-mail: r95841015@ntu.edu.tw [Institute of Occupational Medicine and Industrial Hygiene, Department of Public Health, National Taiwan University, Taipei, Taiwan (China); Chang, Chuen-Chau, E-mail: nekota@tmu.edu.tw [Department of Anaesthesiology, Taipei Medical University Hospital, Taipei Medical University, Taipei, Taiwan (China); Hwang, Jing-Shiang, E-mail: jshwang@stat.sinica.edu.tw [Institute of Statistical Science, Academia Sinica, Taipei, Taiwan (China); Chuang, Kai-Jen, E-mail: kjc@tmu.edu.tw [Department of Public Health, School of Medicine, College of Medicine, Taipei Medical University, Taipei, Taiwan (China); School of Public Health, College of Public Health and Nutrition, Taipei Medical University, Taipei, Taiwan (China); Yan, Yuan-Horng, E-mail: d97841006@ntu.edu.tw [Institute of Occupational Medicine and Industrial Hygiene, Department of Public Health, National Taiwan University, Taipei, Taiwan (China); Department of Medical Research, Ditmanson Medical Foundation Chia-Yi Christian Hospital, Chiayi City, Taiwan (China); Cheng, Tsun-Jen, E-mail: tcheng@ntu.edu.tw [Institute of Occupational Medicine and Industrial Hygiene, Department of Public Health, National Taiwan University, Taipei, Taiwan (China); Department of Public Health, College of Public Health, National Taiwan University, Taipei, Taiwan (China)

2013-01-15

Heart rate variability (HRV) has been reported to be a putative marker of cardiac autonomic imbalance caused by exposure to ambient particulate matter (PM). Our objective in this study was to determine the effects on HRV from exposure to nickel, an important chemical component of ambient PM that results in oxidative stress and inflammation. HRV data were collected for 72 h before lung exposure (baseline) and 72 h after intratracheal exposure (response) to nickel sulphate (NiSO{sub 4}; 526 μg) in Wistar Kyoto (WKY) and spontaneously hypertensive (SH) rats. The antioxidant N-acetyl-L-cysteine (NAC) and the anti-inflammatory celecoxib were intraperitoneally injected to examine post-exposure oxidative and inflammatory responses. Self-controlled experiments examined the effects of NiSO{sub 4} exposure on average normal-to-normal intervals (ANN), natural logarithm-transformed standard deviation of the normal-to-normal intervals (LnSDNN) and root mean square of successive differences of adjacent normal-to-normal intervals (LnRMSSD); the resulting data were sequentially analysed using the generalised estimating equation model. HRV effects on NiSO{sub 4}-exposed SH rats were greater than those on NiSO{sub 4}-exposed WKY rats. After adjusted the HRV responses in the WKY rats as control, ANN and LnRMSSD were found to be quadratically increased over 72 h after exposure to NiSO{sub 4}. Both NAC and celecoxib mitigated the NiSO{sub 4}-induced alterations in HRV during the exposure period. The results suggest that concurrent Ni-induced oxidative stress and inflammatory responses play important roles in regulating HRV. These findings help bridge the gap between epidemiological and clinical studies on the plausible mechanisms of the cardiovascular consequences induced by chemical components in ambient PM. -- Highlights: ► To determine the effects on HRV from exposure to nickel. ► ANN and LnRMSSD were found to be quadratically increased after exposure to Ni. ► NAC and

Corium Oxidation at Temperatures Above 2000 K

International Nuclear Information System (INIS)

Hagrman, Donald L.; Rempe, Joy L.

2001-01-01

A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ∼4% of the zirconium oxidation heating rate.The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows:(unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T 2 /1.986T)]} 1/2 .As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O 2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation

Corium Oxidation at Temperatures Above 2000 K

Energy Technology Data Exchange (ETDEWEB)

Hagrman, Donald Lee; Rempe, Joy Lynn

2001-02-01

A mechanistic model, based on a quasi-equilibrium analysis of oxidation reactions, is proposed for predicting high-temperature corium oxidation. The analysis suggests that oxide forming on the surface of corium containing uranium, zirconium, and iron is similar to the oxides formed on zirconium and uranium as long as there is a small percentage of unoxidized zirconium or uranium in the metallic phase. This is because of the higher affinity of zirconium and uranium for oxygen. Hence, oxidation rates and heat production rates are similar to (U,Zr) compounds until nearly all the uranium and zirconium in the corium oxidizes. Oxidation rates after this point are predicted to be similar to those implied by the oxide thickness present when the forming oxide ceases to be protective, and heat generation rates should be similar to those implied by iron oxidation, i.e., ~4% of the zirconium oxidation heating rate. The maximum atomic ratio of unoxidized iron to unoxidized liquid zirconium plus uranium for the formation of a solid protective oxide below 2800 K is estimated for a temperature, T (in Kelvin), as follows: (unoxidized iron)/(unoxidized zirconium + turanium) = (1/28){5.7/exp[-(147 061 + 12.08T log(T) - 61.03T - 0.000555T2/1.986T)]}1/2. As long as this limit is not exceeded, either zirconium or uranium metal oxidation rates and heating describe the corium oxidation rate. If this limit is exceeded, diffusion of steam to the corium surface will limit the oxidation rate, and linear time-dependent growth of a nonprotective, mostly FeO, layer will occur below the protective (Zr,U) O2 scale. When this happens, the oxidation should be at the constant rate given by the thickness of the protective layer. Heat generation should be similar to that of iron oxidation.

Evaluation of flow accelerated corrosion by coupled analysis of corrosion and flow dynamics (3), relationship of oxide film thickness, hematite/magnetite ratio, ECP and wall thinning rate

International Nuclear Information System (INIS)

Uchida, Shunsuke; Naitoh, Masanori; Okada, Hidetoshi; Uehara, Yasushi; Koshizuka, Seiichi

2009-01-01

Systematic approaches for evaluating flow accelerated corrosion (FAC) are desired before discussing application of countermeasures for FAC. Firstly, future FAC occurrence should be evaluated to identify locations where a higher possibility of FAC occurrence exists, and then, wall thinning rate at the identified FAC occurrence zone is evaluated to obtain the preparation time for applying countermeasures. Wall thinning rates were calculated with the coupled models of static electrochemical analysis and dynamic double oxide layer analysis. Anodic current density and electrochemical corrosion potential (ECP) were calculated with the static electrochemistry model based on an Evans diagram and ferrous ion release rate determined by the anodic current density was applied as input for the dynamic double oxide layer model. Some of the dissolved ferrous ion was removed to the bulk water and others precipitated on the surface as magnetite particles. The thickness of oxide layer was calculated with the dynamic double oxide layer model and then was applied as input for the electrochemistry model. It was confirmed that the calculated results based on the coupled models resulted good agreement with the measured ones. Higher ECP was essential for preventing FAC rate. Moderated conditions due to lower mass transfer coefficients resulted in thicker oxide layer thickness and then higher ECP, while moderated corrosion conditions due to higher oxidant concentrations resulted in larger hematite/magnetite rate and then higher ECP. (author)

Assessment of the colorimetric and fluorometric assays for alkaline phosphatase activity in cow's, goat's, and sheep's milk.

Science.gov (United States)

Klotz, V; Hill, Art; Warriner, K; Griffiths, M; Odumeru, J

2008-09-01

Raw milk is a well-established vehicle for the carriage of human pathogens, and many regulatory bodies have consequently mandated compulsory pasteurization as a food safety intervention. The residual activity of alkaline phosphatase (ALP) has historically been used to verify the adequacy of pasteurization of cow's milk. However, there is uncertainty on how the current ALP standards and methods of analysis can be applied to sheep's and goat's milk, which naturally contain different levels of the enzyme than that found in cow's milk. The official ALP methods applied in Canada (colorimetric assay; MFO-3) and in the United States (Fluorophos) were assessed for their ability to detect enzyme activity in raw and pasteurized milk derived from cows, sheep, and goats. The detection limit and the limit of quantitation were 0.8 and 2.02 microg/ml phenol, respectively, for the MFO-3 method and 43 and 85 mU/liter, respectively, for the Fluorophos method. The average ALP levels in raw goat's, cow's, and sheep's milk were 165, 1,562, and 3,512 microg/ml phenol, respectively. Raw milk detection limits, which correspond to raw milk phosphatase levels, were 0.051, 0.485, and 0.023% in cow's, goat's, and sheep's milk, respectively, for the MFO-3 method and 0.007, 0.070, and 0.004%, respectively, for the Fluorophos method. Although both methods can be used for ALP determination in cow's, goat's, and sheep's milk, the Fluorophos assay was superior to the colorimetric MFO-3 method based on sensitivity and time required to complete the analysis.

Estimating Origin-Destination Matrices Using AN Efficient Moth Flame-Based Spatial Clustering Approach

Science.gov (United States)

Heidari, A. A.; Moayedi, A.; Abbaspour, R. Ali

2017-09-01

Automated fare collection (AFC) systems are regarded as valuable resources for public transport planners. In this paper, the AFC data are utilized to analysis and extract mobility patterns in a public transportation system. For this purpose, the smart card data are inserted into a proposed metaheuristic-based aggregation model and then converted to O-D matrix between stops, since the size of O-D matrices makes it difficult to reproduce the measured passenger flows precisely. The proposed strategy is applied to a case study from Haaglanden, Netherlands. In this research, moth-flame optimizer (MFO) is utilized and evaluated for the first time as a new metaheuristic algorithm (MA) in estimating transit origin-destination matrices. The MFO is a novel, efficient swarm-based MA inspired from the celestial navigation of moth insects in nature. To investigate the capabilities of the proposed MFO-based approach, it is compared to methods that utilize the K-means algorithm, gray wolf optimization algorithm (GWO) and genetic algorithm (GA). The sum of the intra-cluster distances and computational time of operations are considered as the evaluation criteria to assess the efficacy of the optimizers. The optimality of solutions of different algorithms is measured in detail. The traveler's behavior is analyzed to achieve to a smooth and optimized transport system. The results reveal that the proposed MFO-based aggregation strategy can outperform other evaluated approaches in terms of convergence tendency and optimality of the results. The results show that it can be utilized as an efficient approach to estimating the transit O-D matrices.

ESTIMATING ORIGIN-DESTINATION MATRICES USING AN EFFICIENT MOTH FLAME-BASED SPATIAL CLUSTERING APPROACH

Directory of Open Access Journals (Sweden)

A. A. Heidari

2017-09-01

Full Text Available Automated fare collection (AFC systems are regarded as valuable resources for public transport planners. In this paper, the AFC data are utilized to analysis and extract mobility patterns in a public transportation system. For this purpose, the smart card data are inserted into a proposed metaheuristic-based aggregation model and then converted to O-D matrix between stops, since the size of O-D matrices makes it difficult to reproduce the measured passenger flows precisely. The proposed strategy is applied to a case study from Haaglanden, Netherlands. In this research, moth-flame optimizer (MFO is utilized and evaluated for the first time as a new metaheuristic algorithm (MA in estimating transit origin-destination matrices. The MFO is a novel, efficient swarm-based MA inspired from the celestial navigation of moth insects in nature. To investigate the capabilities of the proposed MFO-based approach, it is compared to methods that utilize the K-means algorithm, gray wolf optimization algorithm (GWO and genetic algorithm (GA. The sum of the intra-cluster distances and computational time of operations are considered as the evaluation criteria to assess the efficacy of the optimizers. The optimality of solutions of different algorithms is measured in detail. The traveler's behavior is analyzed to achieve to a smooth and optimized transport system. The results reveal that the proposed MFO-based aggregation strategy can outperform other evaluated approaches in terms of convergence tendency and optimality of the results. The results show that it can be utilized as an efficient approach to estimating the transit O-D matrices.

Insulin and GH secretion in adolescent girls with irregular cycles: polycystic vs multifollicular ovaries.

Science.gov (United States)

Villa, P; Rossodivita, A; Fulghesu, A M; Cucinelli, F; Barini, A; Apa, R; Belosi, C; Lanzone, A

2003-04-01

In the present study insulin (I) and GH secretion was studied in a group of twenty-five young adolescent girls (mean age: 15 +/- 0.23 yr) with cycle irregularity associated to clinical signs of hyperandrogenism in comparison with that observed in eleven normal matched subjects with regular menses. All patients underwent basal hormone measurements and, on two consecutive days, an oral glucose tolerance test (OGTT) and a GHRH iv test. Therefore, all subjects had a transabdominal US scan for the measurement of ovarian volume and the characterization of ovarian morphology. On the basis of the US examination we found patients with polycystic ovaries (PCO-like group) and subjects with multifollicular ovaries (MFO group). PCO-like group exhibited T (pirregular menses showed plasma concentrations of AUC for I (AUC-I) significantly higher in respect to control group (7359.4 +/- 709 vs 5447 +/- 431 microIU/ml x 180 min, p<0.01) as well as both PCO-like group and MFO group did (p<0.001 and p<0.01) respectively. MFO group showed higher values of the AUC for GH (AUC-GH) (2809 +/- 432 ng/ml x 120 min) in respect to controls (1708 +/- 208 ng/ml x 120 min, p<0.05) and PCO-like subjects (p<0.001), who on the contrary showed the lowest AUC-GH values (618 +/- 119 ng/ml x 120 min). In conclusion, PCO-like patients associated hyperinsulinemia with a blunted GH secretion while MFO patients had higher GH secretion associated with higher AUC-I values in a way suggesting an immature and still developing reproductive system.

Optical measurements of atomic oxygen concentration, temperature and nitric oxide production rate in flames

Science.gov (United States)

Myhr, Franklin Henry

An optical method for measuring nitric oxide (NO) production rates in flames was developed and characterized in a series of steady, one-dimensional, atmospheric-pressure laminar flames of 0.700 Hsb2/0.199 Nsb2/0.101 COsb2 or 0.700 CHsb4/0.300 Nsb2 (by moles) with dry air, with equivalence ratios from 0.79 to 1.27. Oxygen atom concentration, (O), was measured by two-photon laser-induced fluorescence (LIF), temperature was measured by ultraviolet Rayleigh scattering, and nitrogen concentration was calculated from supplied reactant flows; together this information was used to calculate the NO production rate through the thermal (Zel'dovich) mechanism. Measurements by two other techniques were compared with results from the above method. In the first comparison, gas sampling was used to measure axial NO concentration profiles, the slopes of which were multiplied by velocity to obtain total NO production rates. In the second comparison, LIF measurements of hydroxyl radical (OH) were used with equilibrium water concentrations and a partial equilibrium assumption to find (O). Nitric oxide production rates from all three methods agreed reasonably well. Photolytic interference was observed during (O) LIF measurements in all of the flames; this is the major difficulty in applying the optical technique. Photolysis of molecular oxygen in lean flames has been well documented before, but the degree of interference observed in the rich flames suggests that some other molecule is also dissociating; the candidates are OH, CO, COsb2 and Hsb2O. An extrapolative technique for removing the effects of photolysis from (O) LIF measurements worked well in all flames where NO production was significant. Using the optical method to measure NO production rates in turbulent flames will involve a tradeoff among spatial resolution, systematic photolysis error, and random shot noise. With the conventional laser system used in this work, a single pulse with a resolution of 700 mum measured NO

Oxidation kinetics of Si and SiGe by dry rapid thermal oxidation, in-situ steam generation oxidation and dry furnace oxidation

Science.gov (United States)

Rozé, Fabien; Gourhant, Olivier; Blanquet, Elisabeth; Bertin, François; Juhel, Marc; Abbate, Francesco; Pribat, Clément; Duru, Romain

2017-06-01

The fabrication of ultrathin compressively strained SiGe-On-Insulator layers by the condensation technique is likely a key milestone towards low-power and high performances FD-SOI logic devices. However, the SiGe condensation technique still requires challenges to be solved for an optimized use in an industrial environment. SiGe oxidation kinetics, upon which the condensation technique is founded, has still not reached a consensus in spite of various studies which gave insights into the matter. This paper aims to bridge the gaps between these studies by covering various oxidation processes relevant to today's technological needs with a new and quantitative analysis methodology. We thus address oxidation kinetics of SiGe with three Ge concentrations (0%, 10%, and 30%) by means of dry rapid thermal oxidation, in-situ steam generation oxidation, and dry furnace oxidation. Oxide thicknesses in the 50 Å to 150 Å range grown with oxidation temperatures between 850 and 1100 °C were targeted. The present work shows first that for all investigated processes, oxidation follows a parabolic regime even for thin oxides, which indicates a diffusion-limited oxidation regime. We also observe that, for all investigated processes, the SiGe oxidation rate is systematically higher than that of Si. The amplitude of the variation of oxidation kinetics of SiGe with respect to Si is found to be strongly dependent on the process type. Second, a new quantitative analysis methodology of oxidation kinetics is introduced. This methodology allows us to highlight the dependence of oxidation kinetics on the Ge concentration at the oxidation interface, which is modulated by the pile-up mechanism. Our results show that the oxidation rate increases with the Ge concentration at the oxidation interface.

Fe2+ oxidation rate drastically affect the formation and phase of secondary iron hydroxysulfate mineral occurred in acid mine drainage

International Nuclear Information System (INIS)

Huang Shan; Zhou Lixiang

2012-01-01

During the processes of secondary iron hydroxysulfate mineral formation, Fe 2+ ion was oxidized by the following three methods: (1) biooxidation treatment by Acidithiobacillus ferrooxidans (A. ferrooxidans); (2) rapid abiotic oxidation of Fe 2+ with H 2 O 2 (rapid oxidation treatment); (3) slow abiotic oxidation of Fe 2+ with H 2 O 2 (slow oxidation treatment). X-ray diffraction (XRD) patterns, element composition, precipitate weight and total Fe removal efficiency were analyzed. The XRD patterns and element composition of precipitates synthesized through the biooxidation and the slow oxidation treatments well coincide with those of potassium jarosite, while precipitates formed at the initial stage of incubation in the rapid oxidation treatment showed a similar XRD pattern to schwertmannite. With the ongoing incubation, XRD patterns and element composition of the precipitates that occurred in the rapid oxidation treatment were gradually close to those in the biooxidation and the slow oxidation treatments. Due to the inhibition of A. ferrooxidans itself and its extracellular polymeric substances (EPS) in aggregation of precipitates, the amount of precipitates and soluble Fe removal efficiency were lower in the biooxidation treatment than in the slow oxidation treatment. Therefore, it is concluded that Fe 2+ oxidation rate can greatly affect the mineral phase of precipitates, and slow oxidation of Fe 2+ is helpful in improving jarosite formation. - Highlights: ► Slow oxidation of Fe 2+ is helpful in jarosite formation. ► The already-formed schwertmannite can be gradually transformed to jarosite. ► Precipitates formation can be inhibited probably by EPS from A. ferrooxidans.

Effect of Organic Fe-Ligands, Released by Emiliania huxleyi, on Fe(II Oxidation Rate in Seawater Under Simulated Ocean Acidification Conditions: A Modeling Approach

Directory of Open Access Journals (Sweden)

Guillermo Samperio-Ramos

2018-06-01

Full Text Available The potential effect of ocean acidification on the exudation of organic matter by phytoplankton and, consequently, on the iron redox chemistry is largely unknown. In this study, the coccolithophorid Emiliania huxleyi was exposed to different pCO2 conditions (225–900 μatm, in order to determine the role of natural organic ligands on the Fe(II oxidation rate. Oxidation kinetics of Fe(II were studied as a function of pH (7.75–8.25 and dissolved organic carbon levels produced (0–141.11 μmol C L−1 during the different growth stages. The Fe(II oxidation rate always decreased in the presence of exudates as compared to that in the exudates-free seawater. The organic ligands present in the coccolithophorid exudates were responsible for this decrease. The oxidation of Fe(II in artificial seawater was also investigated at nanomolar levels over a range of pH (7.75–8.25 at 25°C in the presence of different glucuronic acid concentrations. Dissolved uronic acids (DUA slightly increased the experimental rate compared to control artificial seawater (ASW which can be ascribed to the stabilization of the oxidized form by chelation. This behavior was a function of the Fe(II:DUA ratio and was a pH dependent process. A kinetic model in ASW, with a single organic ligand, was applied for computing the equilibrium constant (log KFeCHO+ = 3.68 ± 0.81 M−1 and the oxidation rate (log kFeCHO+ = 3.28 ± 0.41 M−1 min−1 for the Fe(II-DUA complex (FeCHO+, providing an excellent description of data obtained over a wide range of DUA concentrations and pH conditions. Considering the Marcus theory the Fe(III complexing constant with DUA was limited to between 1013 and 1016. For the seawater enriched with exudates of E. huxleyi a second kinetic modeling approach was carried out for fitting the Fe(II speciation, and the contribution of each Fe(II species to the overall oxidation rate as a function of the pH/pCO2 conditions. The influence of organic ligands in the

Effects of adipose tissue distribution on maximum lipid oxidation rate during exercise in normal-weight women.

Science.gov (United States)

Isacco, L; Thivel, D; Duclos, M; Aucouturier, J; Boisseau, N

2014-06-01

Fat mass localization affects lipid metabolism differently at rest and during exercise in overweight and normal-weight subjects. The aim of this study was to investigate the impact of a low vs high ratio of abdominal to lower-body fat mass (index of adipose tissue distribution) on the exercise intensity (Lipox(max)) that elicits the maximum lipid oxidation rate in normal-weight women. Twenty-one normal-weight women (22.0 ± 0.6 years, 22.3 ± 0.1 kg.m(-2)) were separated into two groups of either a low or high abdominal to lower-body fat mass ratio [L-A/LB (n = 11) or H-A/LB (n = 10), respectively]. Lipox(max) and maximum lipid oxidation rate (MLOR) were determined during a submaximum incremental exercise test. Abdominal and lower-body fat mass were determined from DXA scans. The two groups did not differ in aerobic fitness, total fat mass, or total and localized fat-free mass. Lipox(max) and MLOR were significantly lower in H-A/LB vs L-A/LB women (43 ± 3% VO(2max) vs 54 ± 4% VO(2max), and 4.8 ± 0.6 mg min(-1)kg FFM(-1)vs 8.4 ± 0.9 mg min(-1)kg FFM(-1), respectively; P normal-weight women, a predominantly abdominal fat mass distribution compared with a predominantly peripheral fat mass distribution is associated with a lower capacity to maximize lipid oxidation during exercise, as evidenced by their lower Lipox(max) and MLOR. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

RATES OF IRON OXIDATION AND ARSENIC SORPTION DURING GROUND WATER-SURFACE WATER MIXING AT A HAZARDOUS WASTE SITE

Science.gov (United States)

The fate of arsenic discharged from contaminated ground water to a pond at a hazardous waste site is controlled, in part, by the rate of ferrous iron oxidation-precipitation and arsenic sorption. Laboratory experiments were conducted using site-derived water to assess the impact...

New Measurements of Methyl Ethyl Ketone (MEK) Photolysis Rates and Their Relevance to Global Oxidative Capacity

Science.gov (United States)

Brewer, J.; Ravishankara, A. R.; Mellouki, A.; Fischer, E. V.; Kukui, A.; Véronique, D.; Ait-helal, W.; Leglise, J.; Ren, Y.

2017-12-01

Methyl ethyl ketone (MEK) is one of the most abundant ketones in the atmosphere. MEK can be emitted directly into the atmosphere from both anthropogenic and natural sources, and it is also formed during the gas-phase oxidation of volatile organic compounds (VOCs). MEK is lost via reaction with OH, photolysis and deposition to the surface. Similar to the other atmospheric ketones, the photolysis of MEK may represent a source of HOx (OH + HO2) radicals in the upper troposphere. The degradation of MEK also leads to the atmospheric formation of acetaldehyde and formaldehyde. This work presents a new analysis of the temperature dependence of MEK photolysis cross-sections and a quantification of MEK photolysis rates under surface pressures using the CNRS HELIOS outdoor atmospheric chamber (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans; http://www.era-orleans.org/ERA-TOOLS/helios-project.html). Additionally, we use the GEOS-Chem 3-D CTM (version 10-01, www.geos-chem.org) to investigate the impact of these newly measured rates and cross-sections on the global distribution and seasonality of MEK, as well as its importance to the tropospheric oxidative capacity.

In vitro covalent binding of 3-[14C]methylindole metabolites in goat tissues

International Nuclear Information System (INIS)

Bray, T.M.; Carlson, J.R.; Nocerini, M.R.

1984-01-01

Covalent binding of 3-[ 14 C]methylindole (3[ 14 C]MI) in crude microsomal preparations of goat lung, liver, and kidney was measured to determine if a reactive intermediate was formed during the in vitro metabolism of 3-methylindole (3MI). The bound radioactivity was highest in lung compared to liver and kidney. The amount of bound radioactivity per nanomole of cytochrome P-450 was approximately 10 times higher in the lung compared to the liver. No detectable bound radioactivity was found when 3-[ 3 H]methyloxindole was used as the substrate. Cofactor requirements and the effects of inhibitors indicate that a mixed function oxidase (MFO) system is involved in formation of a reactive intermediate. Inhibitors and conjugating agents that are known to reduce the severity of 3MI-induced lung injury such as piperonyl butoxide (MFO inhibitor) and glutathione (conjugating agent) significantly decreased the in vitro binding of 3[ 14 C]MI. The results indicate that a reactive intermediate is produced during the metabolism of 3MI by the MFO system. The organ specificity in binding suggests that covalent binding by lung microsomes may be related to the mechanism of 3MI-induced lung injury

Optimalisasi Of Efficiency Terms And Test The Value Kalor Of Perfomansi Boiler Use The Energi Biomassa Upon Which Burn Alternative

Directory of Open Access Journals (Sweden)

Imam Kholiq

2015-08-01

Full Text Available ABSTRACTION Especial Fuel used by Boiler PG MODJO PANGGUNG TULUNGAGUNG PTPN X is bagasse and oil burn the residu MFO. A lot of PG in Indonesia which exactly use the very costly fossil fuel so that generate the inefisiensi. Research by enhancing fiber cangkang fiber chaff to efficiency termis perfomansi and performance of boiler PG MODJO PODIUM. Assess the kalor of every-every fuel calculated given the composition of every fuel by using existing equation from literature calculation consume the fuel space volume burn the efficiency from every fuel to boiler and expense efficiency from every fuel used. From calculation of every fuel is hence got by result that Fuel efficiency use the smaller dregs fuel compared to from fuel of fiber and oil burn the residu MFO. LaterThen from facetof material cost burn the bagasse more efficient from at fuel of fiber and oil burn the residu MFO. To reply the the problem hence researcher use the indirect method. This method own the advantage that is can know the balance of complete and energi substance to eachevery stream which can facilitate in identifying opdon to increase is optimal of efficiency of termis boiler.

Potential rates of ammonium oxidation, nitrite oxidation, nitrate reduction and denitrification in the young barley rhizosphere

DEFF Research Database (Denmark)

Højberg, Ole; Binnerup, S. J.; Sørensen, Jan

1996-01-01

Potential activities (enzyme contents) of ammonium (NH4+) oxidizing, nitrite (NO2-) oxidizing, nitrate (NO3-) reducing and denitrifying bacteria were measured in bulk and rhizosphere soil obtained from young barley plants in the field. The activities as well as pools of inorganic N (NH4+, NO2...

Aeration to degas CO2, increase pH, and increase iron oxidation rates for efficient treatment of net alkaline mine drainage

International Nuclear Information System (INIS)

Kirby, C.S.; Dennis, A.; Kahler, A.

2009-01-01

Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering 'hybrid' systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m -2 day -1 and Fe loading from field data, 3.6 x 10 3 and 3.0 x 10 4 m 2 oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO 2 , increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Both net-alkaline discharges were suboxic with a pH of ∼5.7, Fe(II) concentration of ∼16 mg L -1 , and low Mn and Al concentrations. Flow rates were ∼4000 L min -1 at Site 21 and 15,000 L min -1 at Packer 5. Three-h aeration experiments with flow rates scaled to a 14-L reactor resulted in pH increases from 5.7 to greater than 7, temperature increases from 12 to 22 deg. C, dissolved O 2 increases to saturation with respect to the atmosphere, and Fe(II) concentration decreases from 16 to -1 . A 17,000-L pilot-scale reactor at Site 21 produced similar results although aeration was not as complete as in the smaller reactor. Two non-aerated experiments at Site 21 with 13 and 25-h run times resulted in pH changes of ≤0.2 and Fe(II) concentration decreases of less than 3 mg L -1 . An Fe(II) oxidation model written in a differential equation solver matched the field experiments very well using field-measured pH, temperature, dissolved O 2

Effects of gas flow rate on the structure and elemental composition of tin oxide thin films deposited by RF sputtering

Science.gov (United States)

Al-Mansoori, Muntaser; Al-Shaibani, Sahar; Al-Jaeedi, Ahlam; Lee, Jisung; Choi, Daniel; Hasoon, Falah S.

2017-12-01

Photovoltaic technology is one of the key answers for a better sustainable future. An important layer in the structure of common photovoltaic cells is the transparent conductive oxide. A widely applied transparent conductive oxide is tin oxide (SnO2). The advantage of using tin oxide comes from its high stability and low cost in processing. In our study, we investigate effects of working gas flow rate and oxygen content in radio frequency (RF)-sputtering system on the growth of intrinsic SnO2 (i-SnO2) layers. X-ray diffraction results showed that amorphous-like with nano-crystallite structure, and the surface roughness varied from 1.715 to 3.936 nm. X-Ray photoelectron spectroscopy analysis showed different types of point defects, such as tin interstitials and oxygen vacancies, in deposited i-SnO2 films.

Effects of gas flow rate on the structure and elemental composition of tin oxide thin films deposited by RF sputtering

Directory of Open Access Journals (Sweden)

Muntaser Al-Mansoori

2017-12-01

Full Text Available Photovoltaic technology is one of the key answers for a better sustainable future. An important layer in the structure of common photovoltaic cells is the transparent conductive oxide. A widely applied transparent conductive oxide is tin oxide (SnO2. The advantage of using tin oxide comes from its high stability and low cost in processing. In our study, we investigate effects of working gas flow rate and oxygen content in radio frequency (RF-sputtering system on the growth of intrinsic SnO2 (i-SnO2 layers. X-ray diffraction results showed that amorphous-like with nano-crystallite structure, and the surface roughness varied from 1.715 to 3.936 nm. X-Ray photoelectron spectroscopy analysis showed different types of point defects, such as tin interstitials and oxygen vacancies, in deposited i-SnO2 films.

Load Frequency Control of AC Microgrid Interconnected Thermal Power System

Science.gov (United States)

Lal, Deepak Kumar; Barisal, Ajit Kumar

2017-08-01

In this paper, a microgrid (MG) power generation system is interconnected with a single area reheat thermal power system for load frequency control study. A new meta-heuristic optimization algorithm i.e. Moth-Flame Optimization (MFO) algorithm is applied to evaluate optimal gains of the fuzzy based proportional, integral and derivative (PID) controllers. The system dynamic performance is studied by comparing the results with MFO optimized classical PI/PID controllers. Also the system performance is investigated with fuzzy PID controller optimized by recently developed grey wolf optimizer (GWO) algorithm, which has proven its superiority over other previously developed algorithm in many interconnected power systems.

Effects of Oxidation on Oxidation-Resistant Graphite

Energy Technology Data Exchange (ETDEWEB)

Windes, William [Idaho National Lab. (INL), Idaho Falls, ID (United States); Smith, Rebecca [Idaho National Lab. (INL), Idaho Falls, ID (United States); Carroll, Mark [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2015-05-01

The Advanced Reactor Technology (ART) Graphite Research and Development Program is investigating doped nuclear graphite grades that exhibit oxidation resistance through the formation of protective oxides on the surface of the graphite material. In the unlikely event of an oxygen ingress accident, graphite components within the VHTR core region are anticipated to oxidize so long as the oxygen continues to enter the hot core region and the core temperatures remain above 400°C. For the most serious air-ingress accident which persists over several hours or days the continued oxidation can result in significant structural damage to the core. Reducing the oxidation rate of the graphite core material during any air-ingress accident would mitigate the structural effects and keep the core intact. Previous air oxidation testing of nuclear-grade graphite doped with varying levels of boron-carbide (B4C) at a nominal 739°C was conducted for a limited number of doped specimens demonstrating a dramatic reduction in oxidation rate for the boronated graphite grade. This report summarizes the conclusions from this small scoping study by determining the effects of oxidation on the mechanical strength resulting from oxidation of boronated and unboronated graphite to a 10% mass loss level. While the B4C additive did reduce mechanical strength loss during oxidation, adding B4C dopants to a level of 3.5% or more reduced the as-fabricated compressive strength nearly 50%. This effectively minimized any benefits realized from the protective film formed on the boronated grades. Future work to infuse different graphite grades with silicon- and boron-doped material as a post-machining conditioning step for nuclear components is discussed as a potential solution for these challenges in this report.

Isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide and aqueous solutions

International Nuclear Information System (INIS)

Inoue, Yasushi; Yamazaki, Hiromichi; Itami, Akira

1989-01-01

The isotopic exchange rate of cobalt ions between hydrous tin(IV) oxide ion exchanger and aqueous solutions was radiochemically measured to obtain fundamental data which are useful for elucidating the ion-exchange kinetics of the material for the transition metal elements. The rate can be understood by considering that the cobalt ions were present in the exchanger as three kinds of species: (A 1 ) Free ions which can diffuse in the exchanger particles, (A 2 ) Weakly bound ions to the exchange sites which exchange rapidly with A 1 , and (B) Covalently fixed ions to the exchange sites which exchange very slowly with A 1 . At low fraction of B, the rate is controlled by the diffusion of A 1 with the effective diffusion coefficient, D eff , the values of which depend on the concentration ratios of A 2 to A 1 . When B predominates over the A species, the concentration ratios of B to A 1 affect greatly D eff . The values of D eff and their activation energy(20 kJ/mol) were also estimated

Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

Science.gov (United States)

Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

2017-07-06

The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

Imbalance of heterologous protein folding and disulfide bond formation rates yields runaway oxidative stress

Directory of Open Access Journals (Sweden)

Tyo Keith EJ

2012-03-01

Full Text Available Abstract Background The protein secretory pathway must process a wide assortment of native proteins for eukaryotic cells to function. As well, recombinant protein secretion is used extensively to produce many biologics and industrial enzymes. Therefore, secretory pathway dysfunction can be highly detrimental to the cell and can drastically inhibit product titers in biochemical production. Because the secretory pathway is a highly-integrated, multi-organelle system, dysfunction can happen at many levels and dissecting the root cause can be challenging. In this study, we apply a systems biology approach to analyze secretory pathway dysfunctions resulting from heterologous production of a small protein (insulin precursor or a larger protein (α-amylase. Results HAC1-dependent and independent dysfunctions and cellular responses were apparent across multiple datasets. In particular, processes involving (a degradation of protein/recycling amino acids, (b overall transcription/translation repression, and (c oxidative stress were broadly associated with secretory stress. Conclusions Apparent runaway oxidative stress due to radical production observed here and elsewhere can be explained by a futile cycle of disulfide formation and breaking that consumes reduced glutathione and produces reactive oxygen species. The futile cycle is dominating when protein folding rates are low relative to disulfide bond formation rates. While not strictly conclusive with the present data, this insight does provide a molecular interpretation to an, until now, largely empirical understanding of optimizing heterologous protein secretion. This molecular insight has direct implications on engineering a broad range of recombinant proteins for secretion and provides potential hypotheses for the root causes of several secretory-associated diseases.

High rate flame synthesis of highly crystalline iron oxide nanorods

International Nuclear Information System (INIS)

Merchan-Merchan, W; Taylor, A M; Saveliev, A V

2008-01-01

Single-step flame synthesis of iron oxide nanorods is performed using iron probes inserted into an opposed-flow methane oxy-flame. The high temperature reacting environment of the flame tends to convert elemental iron into a high density layer of iron oxide nanorods. The diameters of the iron oxide nanorods vary from 10 to 100 nm with a typical length of a few microns. The structural characterization performed shows that nanorods possess a highly ordered crystalline structure with parameters corresponding to cubic magnetite (Fe 3 O 4 ) with the [100] direction oriented along the nanorod axis. Structural variations of straight nanorods such as bends, and T-branched and Y-branched shapes are frequently observed within the nanomaterials formed, opening pathways for synthesis of multidimensional, interconnected networks

Comparison of nitrogen removal rates and nitrous oxide production from enriched anaerobic ammonium oxidizing bacteria in suspended and attached growth reactors.

Science.gov (United States)

Panwivia, Supaporn; Sirvithayapakorn, Sanya; Wantawin, Chalermraj; Noophan, Pongsak Lek; Munakata-Marr, Junko

2014-01-01

Attached growth-systems for the anaerobic ammonium oxidation (anammox) process have been postulated for implementation in the field. However, information about the anammox process in attached growth-systems is limited. This study compared nitrogen removal rates and nitrous oxide (N2O) production of enriched anammox cultures in both suspended and attached growth sequencing batch reactors (SBRs). Suspended growth reactors (SBR-S) and attached growth reactors using polystyrene sponge as a medium (SBR-A) were used in these experiments. After inoculation with an enriched anammox culture, significant nitrogen removals of ammonium (NH4 (+)) and nitrite (NO2 (-)) were observed under NH4 (+):NO2 (-) ratios ranging from 1:1 to 1:2 in both types of SBRs. The specific rates of total nitrogen removal in SBR-S and SBR-A were 0.52 mg N/mg VSS-d and 0.44 mg N/mg VSS-d, respectively, at an NH4 (+):NO2 (-) ratio of 1:2. N2O production by the enriched anammox culture in both SBR-S and SBR-A was significantly higher at NH4 (+):NO2 (-) ratio of 1:2 than at NH4 (+):NO2 (-) ratios of 1:1 and 1:1.32. In addition, N2O production was higher at a pH of 6.8 than at pH 7.3, 7.8, and 8.3 in both SBR-S and SBR-A. The results of this investigation demonstrate that the anammox process may avoid N2O emission by maintaining an NH4 (+):NO2 (-) ratio of less than 1:2 and pH higher than 6.8.

Measurement of the rates of oxindole-3-acetic acid turnover, and indole-3-acetic acid oxidation in Zea mays seedlings

Science.gov (United States)

Nonhebel, H. M.; Bandurski, R. S. (Principal Investigator)

1986-01-01

Oxindole-3-acetic acid is the principal catabolite of indole-3-acetic acid in Zea mays seedlings. In this paper measurements of the turnover of oxindole-3-acetic acid are presented and used to calculate the rate of indole-3-acetic acid oxidation. [3H]Oxindole-3-acetic acid was applied to the endosperm of Zea mays seedlings and allowed to equilibrate for 24 h before the start of the experiment. The subsequent decrease in its specific activity was used to calculate the turnover rate. The average half-life of oxindole-3-acetic acid in the shoots was found to be 30 h while that in the kernels had an average half-life of 35h. Using previously published values of the pool sizes of oxindole-3-acetic acid in shoots and kernels from seedlings of the same age and variety, and grown under the same conditions, the rate of indole-3-acetic acid oxidation was calculated to be 1.1 pmol plant-1 h-1 in the shoots and 7.1 pmol plant-1 h-1 in the kernels.

On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. V. Comparison and Properties of Electrochemical and Chemical Rate Constants

Science.gov (United States)

Marcus, R. A.

1962-01-01

Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism. (auth)

Nitrous oxide emissions and denitrification rates: A blueprint for smart management and remediation of agricultural landscapes.

Science.gov (United States)

Tomasek, A.; Hondzo, M.; Kozarek, J. L.

2015-12-01

resulting in the release of nitrous oxide, a greenhouse gas with 300 times the warming potential of carbon dioxide. The investigation of nitrous oxide emissions and correlation to denitrification rates will facilitate smart management and remediation efforts of agricultural landscapes.

Developing a computationally efficient dynamic multilevel hybrid optimization scheme using multifidelity model interactions.

Energy Technology Data Exchange (ETDEWEB)

Hough, Patricia Diane (Sandia National Laboratories, Livermore, CA); Gray, Genetha Anne (Sandia National Laboratories, Livermore, CA); Castro, Joseph Pete Jr. (; .); Giunta, Anthony Andrew

2006-01-01

Many engineering application problems use optimization algorithms in conjunction with numerical simulators to search for solutions. The formulation of relevant objective functions and constraints dictate possible optimization algorithms. Often, a gradient based approach is not possible since objective functions and constraints can be nonlinear, nonconvex, non-differentiable, or even discontinuous and the simulations involved can be computationally expensive. Moreover, computational efficiency and accuracy are desirable and also influence the choice of solution method. With the advent and increasing availability of massively parallel computers, computational speed has increased tremendously. Unfortunately, the numerical and model complexities of many problems still demand significant computational resources. Moreover, in optimization, these expenses can be a limiting factor since obtaining solutions often requires the completion of numerous computationally intensive simulations. Therefore, we propose a multifidelity optimization algorithm (MFO) designed to improve the computational efficiency of an optimization method for a wide range of applications. In developing the MFO algorithm, we take advantage of the interactions between multi fidelity models to develop a dynamic and computational time saving optimization algorithm. First, a direct search method is applied to the high fidelity model over a reduced design space. In conjunction with this search, a specialized oracle is employed to map the design space of this high fidelity model to that of a computationally cheaper low fidelity model using space mapping techniques. Then, in the low fidelity space, an optimum is obtained using gradient or non-gradient based optimization, and it is mapped back to the high fidelity space. In this paper, we describe the theory and implementation details of our MFO algorithm. We also demonstrate our MFO method on some example problems and on two applications: earth penetrators and

A Year in the Life: Annual Patterns of CO2 and CH4 from a Northern Finland Peatland, Including Anaerobic Methane Oxidation and Summer Ebullition Rates

Science.gov (United States)

Miller, K.; Lipson, D.; Biasi, C.; Dorodnikov, M.; Männistö, M.; Lai, C. T.

2014-12-01

The major ecological controls on methane (CH4) and carbon dioxide (CO2) fluxes in northern wetland systems are well known, yet estimates of source/sink magnitudes are often incongruous with measured rates. This mismatch persists because holistic flux datasets are rare, preventing 'whole picture' determinations of flux controls. To combat this, we measured net CO2 and CH4 fluxes from September 2012-2013 within a peatland in northern Lapland, Finland. In addition, we performed in situ manipulations and in vitro soil incubations to quantify anaerobic methane oxidation and methanogenic rates as they related to alternative electron acceptor availability. Average annual fluxes varied substantially between different depressions within the wetland, a pattern that persisted through all seasons. Season was a strong predictor of both CO2 and CH4 flux rates, yet CH4 rates were not related to melt-season 10cm or 30cm soil temperatures, and only poorly predicted with air temperatures. We found evidence for both autumnal and spring thaw CH4 bursts, collectively accounting for 26% of annual CH4 flux, although the autumnal burst was more than 5 fold larger than the spring burst. CH4 ebullition measured throughout the growing season augmented the CH4 source load by a factor of 1.5, and was linked with fine-scale spatial heterogeneity within the wetland. Surprisingly, CH4 flux rates were insensitive to Fe(III) and humic acid soil amendments, both of which amplified CO2 fluxes. Using in vitro incubations, we determined anaerobic methane oxidation and methanogenesis rates. Measured anaerobic oxidation rates showed potential consumption of between 6-39% of the methane produced, contributing approximately 1% of total carbon dioxide flux. Treatments of nitrate, sulfate and ferric iron showed that nitrate suppressed methanogenesis, but were not associated with anaerobic oxidation rates.

Oxygen permeation flux through La1-ySryFeO3 limited by the carbon monoxide oxidation rate

NARCIS (Netherlands)

van Hassel, B.A.; van Hassel, B.A.; ten Elshof, Johan E.; Bouwmeester, Henricus J.M.

1995-01-01

The oxygen permeation flux through La1-ySryFeO3-δ (y = 0.1, 0.2) in a large oxygen partial pressure gradient (air/CO, CO2 mixture) was found to be limited by the carbon monoxide oxidation rate at the low oxygen partial pressure side of the membrane. The oxygen permeation flux through the membrane

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Shan, Xiaoqiang [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Charles, Daniel S. [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Xu, Wenqian [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division; Feygenson, Mikhail [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH; Su, Dong [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Teng, Xiaowei [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering

2017-11-22

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO₂.H₂O birnessite phase and a (Co_0.83Mn_0.13Va_0.04)tetra(Co_0.38Mn_1.62)_octaO_3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g^-1 at a scan rate of 1 mV s^-1 in the half-cell and 81 mA h g^-1 at a current density of 2 A g^-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g^-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.

Vernonia cinerea Less. supplementation and strenuous exercise reduce smoking rate: relation to oxidative stress status and beta-endorphin release in active smokers.

Science.gov (United States)

Leelarungrayub, Donrawee; Pratanaphon, Sainatee; Pothongsunun, Prapas; Sriboonreung, Thanyaluck; Yankai, Araya; Bloomer, Richard J

2010-05-26

The aim of this study was to evaluate the effects of Vernonia cinerea Less. (VC) supplementation and exercise on oxidative stress biomarkers, beta-endorphin release, and the rate of cigarette smoking. Volunteer smokers were randomly divided into four groups: group 1: VC supplement; group 2: exercise with VC supplement; group 3: exercise; and group 4: control. VC was prepared by wash and dry techniques and taken orally before smoking, matching the frequency of strenuous exercise (three times weekly). Before and after a two month period, exhaled carbon monoxide (CO), blood oxidative stress (malondialdehyde [MDA], nitric oxide [NOx], protein hydroperoxide [PrOOH] and total antioxidant capacity [TAC]), beta-endorphin and smoking rate were measured, and statistically analyzed. In Group 1, MDA, PrOOH, and NOx significantly decreased, whereas TAC increased (p 0.05). In Group 3, MDA, PrOOH, NOx, TAC, and beta-endorphin levels increased significantly (p stress variables or beta-endorphine levels (p > 0.05). All groups had lower levels of CO after the intervention. The smoking rate for light cigarette decreased in group 2(62.7%), 1(59.52%), 3 (53.57%) and 4(14.04%), whereas in self-rolled cigarettes it decreased in group 1 (54.47%), 3 (42.30%), 2 (40%) and 4 (9.2%). Supplementation with Vernonia cinerea Less and exercise provided benefit related to reduced smoking rate, which may be related to oxidaive stress and beta-endorphine levels.

Vernonia cinerea Less. supplementation and strenuous exercise reduce smoking rate: relation to oxidative stress status and beta-endorphin release in active smokers

Directory of Open Access Journals (Sweden)

Yankai Araya

2010-05-01

Full Text Available Abstract Purpose The aim of this study was to evaluate the effects of Vernonia cinerea Less. (VC supplementation and exercise on oxidative stress biomarkers, beta-endorphin release, and the rate of cigarette smoking. Methods Volunteer smokers were randomly divided into four groups: group 1: VC supplement; group 2: exercise with VC supplement; group 3: exercise; and group 4: control. VC was prepared by wash and dry techniques and taken orally before smoking, matching the frequency of strenuous exercise (three times weekly. Before and after a two month period, exhaled carbon monoxide (CO, blood oxidative stress (malondialdehyde [MDA], nitric oxide [NOx], protein hydroperoxide [PrOOH] and total antioxidant capacity [TAC], beta-endorphin and smoking rate were measured, and statistically analyzed. Results In Group 1, MDA, PrOOH, and NOx significantly decreased, whereas TAC increased (p 0.05. In Group 3, MDA, PrOOH, NOx, TAC, and beta-endorphin levels increased significantly (p 0.05. All groups had lower levels of CO after the intervention. The smoking rate for light cigarette decreased in group 2(62.7%, 1(59.52%, 3 (53.57% and 4(14.04%, whereas in self-rolled cigarettes it decreased in group 1 (54.47%, 3 (42.30%, 2 (40% and 4 (9.2%. Conclusion Supplementation with Vernonia cinerea Less and exercise provided benefit related to reduced smoking rate, which may be related to oxidaive stress and beta-endorphine levels.

Radiolytic oxidation of iodine in the containment at high temperature and dose rate

International Nuclear Information System (INIS)

Guilbert, S.; Bosland, L.; Jacquemain, D.; Clement, B.; Andreo, F.; Ducros, G.; Dickinson, S.; Herranz, L.; Ball, J.

2007-01-01

Iodine Chemistry is one of the areas of top interest in the field of nuclear power plants (NPP) severe accidents studies. The strong radiological impact of iodine on man health and environment, mostly through its isotope I-131, has made it a key point to get an accurate prediction of the potential iodine release from the NPP containment to the environment in the low probable event of an accident leading to core melt. Released from the fuel as a gaseous form, iodine enters the containment in gaseous or particulate form and undergoes deposition processes that eventually take it to the containment surfaces and sump. Once in the sump, iodine, when present as soluble compounds, gets dissolved as non volatile iodide (I-). Nonetheless, in the presence of radiation and particularly in acidic sumps, iodine can be oxidized to volatile forms such as molecular iodine (I 2 ) and can escape from the sump to the containment atmosphere (sump radiolysis process), thus increasing its potential contribution to the iodine source term. Iodine sump radiolysis has been extensively studied experimentally in the past decades. Experiments have revealed that parameters such as pH, temperature and total iodine concentration have a large impact on iodine volatility. However, experimental data at elevated temperatures (> 80 O C) and elevated dose rates (> 1 kGy.h -1 ) anticipated in containment during a postulated severe accident are too scarce to provide for these relevant conditions an accurate determination of the volatile iodine fractions. Furthermore, some data were obtained from post-irradiation analysis and iodine concentration may be underestimated at the time of measurements compared with that during irradiation, due to post-irradiation reactions. To complete the existing database, the EPICUR program was launched by IRSN (Institut de Radioprotection et de Surete Nucleaire) and experiments have been performed in the frame of the International Source Term Program (ISTP) to provide on

Dose-rate effects of ethylene oxide exposure on developmental toxicity.

Science.gov (United States)

Weller, E; Long, N; Smith, A; Williams, P; Ravi, S; Gill, J; Henessey, R; Skornik, W; Brain, J; Kimmel, C; Kimmel, G; Holmes, L; Ryan, L

1999-08-01

In risk assessment, evaluating a health effect at a duration of exposure that is untested involves assuming that equivalent multiples of concentration (C) and duration (T) of exposure have the same effect. The limitations of this approach (attributed to F. Haber, Zur Geschichte des Gaskrieges [On the history of gas warfare], in Funf Vortrage aus den Jahren 1920-1923 [Five lectures from the years 1920-1923], 1924, Springer, Berlin, pp. 76-92), have been noted in several studies. The study presented in this paper was designed to specifically look at dose-rate (C x T) effects, and it forms an ideal case study to implement statistical models and to examine the statistical issues in risk assessment. Pregnant female C57BL/6J mice were exposed, on gestational day 7, to ethylene oxide (EtO) via inhalation for 1.5, 3, or 6 h at exposures that result in C x T multiples of 2100 or 2700 ppm-h. EtO was selected because of its short half-life, documented developmental toxicity, and relevance to exposures that occur in occupational settings. Concurrent experiments were run with animals exposed to air for similar periods. Statistical analysis using models developed to assess dose-rate effects revealed significant effects with respect to fetal death and resorptions, malformations, crown-to-rump length, and fetal weight. Animals exposed to short, high exposures of EtO on day 7 of gestation were found to have more adverse effects than animals exposed to the same C x T multiple but at longer, lower exposures. The implication for risk assessment is that applying Haber's Law could potentially lead to an underestimation of risk at a shorter duration of exposure and an overestimation of risk at a longer duration of exposure. Further research, toxicological and statistical, are required to understand the mechanism of the dose-rate effects, and how to incorporate the mechanistic information into the risk assessment decision process.

Uranium oxidation: characterization of oxides formed by reaction with water

International Nuclear Information System (INIS)

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

1983-01-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

Radiation-induced cationic polymerization of limonene oxide, α-pinene oxide, and β-pinene oxide

International Nuclear Information System (INIS)

Aikins, J.A.; Williams, F.

1984-01-01

After suitable drying, the subject monomers in the form of neat liquids undergo radiation-induced polymerization with no apparent side reactions and high conversions to precipitatable polymers of low molecular weight. A cationic mechanism is evidenced by the strongly retarding effect of tri-n-propylamine on the polymerization rate. At 25 0 C, limonene oxide gives the highest polymerization rates, an average conversion of 36% per Mrad being obtained in comparison with values of 5.7 and 7.3% per Mrad for the α-pinene and β-pinene oxides, respectively. Similarly, the average anti DP/sub n/ decreases from 11.8 for the limonene oxide polymer to 5.6 and 4.0 for the α-pinene oxide and β-pinene oxide polymers, respectively. A high frequency of chain transfer to monomer is indicated in each case by the fact that the kinetic chain lengths are estimated to be on the order of a hundred times larger than the anti DP/sub n/ values. Structural characterization of the limonene oxide polymer by 1 H and 13 C NMR spectroscopy provides conclusive evidence that the polymerization proceeds by the opening of the epoxide ring to yield a 1,2-trans polyether. Similar NMR studies on the polymers formed from the α-pinene and β-pinene oxides show that in the polymerization of these monomers, the opening of the epoxide ring is generally accompanied by the concomitant ring opening of the cyclobutane ring structure to yield a gem-dimethyl group in the main chain. The detection of isopropenyl end groups in the pinene oxide polymers is also consistent with this mode of propagation being followed by chain (proton) transfer to monomer

Review Of Plutonium Oxidation Literature

International Nuclear Information System (INIS)

Korinko, P.

2009-01-01

A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles ( 250 (micro)m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

Zircaloy oxidation studies

International Nuclear Information System (INIS)

Prater, J.T.; Beauchamp, R.H.; Saenz, N.T.

1985-06-01

The oxidation kinetics of Zircaloy-4 in steam have been determined at 1300-2400 0 C. Growth of the ZrO 2 and α-Zr layers display parabolic behavior over the entire temperature range studied. A discontinuity in the oxidation kinetics at 1510 0 C causes rates to increase above those previously established by the Baker-Just relationship. This increase coincides with the tetragonal-to-cubic phase transformation in ZrO/sub 2-x/. No discontinuity in the oxide growth rate is observed upon melting of Zr(0). The effects of temperature gradients have been taken into account and corrected values representative of near-isothermal conditions have been computed

Effects of keV electron irradiation on the avalanche-electron generation rates of three donors on oxidized silicon

International Nuclear Information System (INIS)

Sah, C.; Sun, J.Y.; Tzou, J.J.

1983-01-01

After keV electron beam irradiation of oxidized silicon, the avalanche-electron-injection generation rates and densities of the bulk compensating donor, the interface states, and the turnaround trap all increase. Heating at 200 0 C can anneal out these three donor-like traps, however, it cannot restore the generation rates back to their original and lower pre-keV electron irradiation values. The experimental results also indicate that all three traps may be related to the same mobile impurity species whose bonds are loosened by the keV electrons and then broken or released by the avalanche injected electrons

Novel texturing method for sputtered zinc oxide films prepared at high deposition rate from ceramic tube targets

Directory of Open Access Journals (Sweden)

Hüpkes J.

2011-10-01

Full Text Available Sputtered and wet-chemically texture etched zinc oxide (ZnO films on glass substrates are regularly applied as transparent front contact in silicon based thin film solar cells. In this study, chemical wet etching in diluted hydrofluoric acid (HF and subsequently in diluted hydrochloric acid (HCl on aluminum doped zinc oxide (ZnO:Al films deposited by magnetron sputtering from ceramic tube targets at high discharge power (~10 kW/m target length is investigated. Films with thickness of around 800 nm were etched in diluted HCl acid and HF acid to achieve rough surface textures. It is found that the etching of the films in both etchants leads to different surface textures. A two steps etching process, which is especially favorable for films prepared at high deposition rate, was systematically studied. By etching first in diluted hydrofluoric acid (HF and subsequently in diluted hydrochloric acid (HCl these films are furnished with a surface texture which is characterized by craters with typical diameter of around 500 − 1000 nm. The resulting surface structure is comparable to etched films sputtered at low deposition rate, which had been demonstrated to be able to achieve high efficiencies in silicon thin film solar cells.

High-temperature oxidation of Zircaloy in hydrogen-steam mixtures

International Nuclear Information System (INIS)

Chung, H.M.; Thomas, G.R.

1982-09-01

Oxidation rates of Zircaloy-4 cladding tubes have been measured in hydrogen-steam mixtures at 1200 to 1700 0 C. For a given isothermal oxidation temperature, the oxide layer thicknesses have been measured as a function of time, steam supply rate, and hydrogen overpressure. The oxidation rates in the mixtures were compared with similar data obtained in pure steam and helium-steam environments under otherwise identical conditions. The rates in pure steam and helium-steam mixtures were equivalent and comparable to the parabolic rates obtained under steam-saturated conditions and reported in the literature. However, when the helium was replaced with hydrogen of equivalent partial pressure, a significantly smaller oxidation rate was observed. For high steam-supply rates, the oxidation kinetics in a hydrogen-steam mixture were parabolic, but the rate was smaller than for pure steam or helium-steam mixtures. Under otherwise identical conditions, the ratio of the parabolic rate for hydrogen-steam to that for pure steam decreased with increasing temperature and decreasing steam-supply rate

Treatment rate improvement of the ozone oxidation method for laundry waste water

International Nuclear Information System (INIS)

Matsuo, Toshiaki; Nishi, Takashi

2001-01-01

Radioactive laundry waste water generated in nuclear power plants includes organic compounds to be removed, for which ozone oxidation treatment is a possibility. To verify the applicability, its total organic carbon concentration (TOC) lowering rate improvement was examined in 0.5x10 -3 m 3 batch and 3x10 -2 m 3 pilot equipment experiments. In the batch experiments, ozone at a concentration of 200 g/Nm 3 was dispersed into 0.5x10 -3 m 3 of Simulated Laundry Waste Water (SLWW) with TOC of 11 mM. Total organic carbon concentration was measured every hour to see the effects of the temperature, and the initial concentrations of both H 2 O 2 and NaOH which were added to urge OH radical generation from ozone. In the pilot equipment experiments, 1x10 -2 to 3x10 -2 m 3 of the SLWW were circulated using an ejector to disperse the ozone. The influences of the flow rate and the SLWW volume on lowering TOC were examined, because they were related to the ejector dispersion performance and the appropriate ozone addition per SLWW volume. Appropriate initial H 2 O 2 and NaOH concentrations in the batch experiments were 14.7 mM and 1 mM, respectively. Lowering of TOC became faster at higher temperatures, because ozone self-decomposition and OH radial diffusion to the organic compound molecules were promoted. Lowering of TOC also became faster at higher flow rates, while the influence of the volume became saturated. (author)

Radiation dose rate affects the radiosensitization of MCF-7 and HeLa cell lines to X-rays induced by dextran-coated iron oxide nanoparticles.

Science.gov (United States)

Khoshgard, Karim; Kiani, Parvaneh; Haghparast, Abbas; Hosseinzadeh, Leila; Eivazi, Mohammad Taghi

2017-08-01

The aim of radiotherapy is to deliver lethal damage to cancerous tissue while preserving adjacent normal tissues. Radiation absorbed dose of the tumoral cells can increase when high atomic nanoparticles are present in them during irradiation. Also, the dose rate is an important aspect in radiation effects that determines the biological results of a given dose. This in vitro study investigated the dose-rate effect on the induced radiosensitivity by dextran-coated iron oxide in cancer cells. HeLa and MCF-7 cells were cultured in vitro and incubated with different concentrations of dextran-coated iron oxide nanoparticles. They were then irradiated with 6 MV photons at dose rates of 43, 185 and 370 cGy/min. The MTT test was used to obtain the cells' survival after 48 h of irradiations. Incubating the cells with the nanoparticles at concentrations of 10, 40 and 80 μg/ml showed no significant cytotoxicity effect. Dextran-coated iron oxide nanoparticles showed more radiosensitivity effect by increasing the dose rate and nanoparticles concentration. Radiosensitization enhancement factors of MCF-7 and HeLa cells at a dose-rate of 370 cGy/min and nanoparticles' concentration of 80 μg/ml were 1.21 ± 0.06 and 1.19 ± 0.04, respectively. Increasing the dose rate of 6 MV photons irradiation in MCF-7 and HeLa cells increases the radiosensitization induced by the dextran-coated iron nanoparticles in these cells.

Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

Science.gov (United States)

Stearns, C. A.; Kohl, F. J.; Fryburg, G. C.

1974-01-01

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory.

Gas phase deposition of oxide and metal-oxide coatings on fuel particles

International Nuclear Information System (INIS)

Patokin, A.P.; Khrebtov, V.L.; Shirokov, B.M.

2008-01-01

Production processes and properties of oxide (Al 2 O 3 , ZrO 2 ) and metal-oxide (Mo-Al 2 O 3 , Mo-ZrO 2 , W-Al 2 O 3 , W-ZrO 2 ) coatings on molybdenum substrates and uranium dioxide fuel particles were investigated. It is shown that the main factors that have an effect on the deposition rate, density, microstructure and other properties of coatings are the deposition temperature, the ratio of H 2 and CO 2 flow rates, the total reactor pressure and the ratio of partial pressures of corresponding metal chlorides during formation of metal-oxide coatings

Two-Step Oxidation of Refractory Gold Concentrates with Different Microbial Communities.

Science.gov (United States)

Wang, Guo-Hua; Xie, Jian-Ping; Li, Shou-Peng; Guo, Yu-Jie; Pan, Ying; Wu, Haiyan; Liu, Xin-Xing

2016-11-28

Bio-oxidation is an effective technology for treatment of refractory gold concentrates. However, the unsatisfactory oxidation rate and long residence time, which cause a lower cyanide leaching rate and gold recovery, are key factors that restrict the application of traditional bio-oxidation technology. In this study, the oxidation rate of refractory gold concentrates and the adaption of microorganisms were analyzed to evaluate a newly developed two-step pretreatment process, which includes a high temperature chemical oxidation step and a subsequent bio-oxidation step. The oxidation rate and recovery rate of gold were improved significantly after the two-step process. The results showed that the highest oxidation rate of sulfide sulfur could reach to 99.01 % with an extreme thermophile microbial community when the pulp density was 5%. Accordingly, the recovery rate of gold was elevated to 92.51%. Meanwhile, the results revealed that moderate thermophiles performed better than acidophilic mesophiles and extreme thermophiles, whose oxidation rates declined drastically when the pulp density was increased to 10% and 15%. The oxidation rates of sulfide sulfur with moderate thermophiles were 93.94% and 65.73% when the pulp density was increased to 10% and 15%, respectively. All these results indicated that the two-step pretreatment increased the oxidation rate of refractory gold concentrates and is a potential technology to pretreat the refractory sample. Meanwhile, owing to the sensitivity of the microbial community under different pulp density levels, the optimization of microbial community in bio-oxidation is necessary in industry.

Kinetics of plasma oxidation of germanium-tin (GeSn)

Science.gov (United States)

Wang, Wei; Lei, Dian; Dong, Yuan; Zhang, Zheng; Pan, Jisheng; Gong, Xiao; Tok, Eng-Soon; Yeo, Yee-Chia

2017-12-01

The kinetics of plasma oxidation of GeSn at low temperature is investigated. The oxidation process is described by a power-law model where the oxidation rate decreases rapidly from the initial oxidation rate with increasing time. The oxidation rate of GeSn is higher than that of pure Ge, which can be explained by the higher chemical reaction rate at the GeSn-oxide/GeSn interface. In addition, the Sn atoms at the interface region exchange positions with the underlying Ge atoms during oxidation, leading to a SnO2-rich oxide near the interface. The bandgap of GeSn oxide is extracted to be 5.1 ± 0.2 eV by XPS, and the valence band offset at the GeSn-oxide/GeSn heterojunction is found to be 3.7 ± 0.2 eV. Controlled annealing experiments demonstrate that the GeSn oxide is stable with respect to annealing temperatures up to 400 °C. However, after annealing at 450 °C, the GeO2 is converted to GeO, and desorbs from the GeSn-oxide/GeSn, leaving behind Sn oxide.

On hydrazine oxidation in nitric acid media

International Nuclear Information System (INIS)

Zil'berman, B.Ya.; Lelyuk, G.A.; Mashkin, A.N.; Yasnovitskaya, A.L.

1988-01-01

Yield of products of radiolytic ( 60 Co gamma radiation) and chemical hydrazine (HZ) oxidation in nitric acid media is studied. Under radiolyte HZ oxidation by nitric acid hydrazoic acid, ammonia and nitrogen appear to be the reaction products. HN 3 yield maximum under HZN oxidation makes up ∼ 0.35 mol per a mol of oxiduzed HZN. Under chemical oxidation HZN is oxidized by HNO 3 according to reaction catalysed by technetium HN 3 yield makes up ∼ 0.35 mol per a mol of oxidized HZN. Radiation-chemical oxidation of HN 3 proceeds up to its complete decomposition, decomposition rate is comparable with HZ oxidation rate. Under the chemical oxidation HN 3 is more stable, it is slowly decomposed after complete HZ decomposition

Characteristics of oxide scale formed on Cu-bearing austenitic stainless steel during early stages of high temperature oxidation

Energy Technology Data Exchange (ETDEWEB)

Swaminathan, Srinivasan, E-mail: swaminathan@kist.re.kr [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of); Krishna, Nanda Gopala [Metallurgy & Materials Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603 102 (India); Kim, Dong-Ik, E-mail: dongikkim@kist.re.kr [High Temperature Energy Materials Research Center, Korea Institute of Science and Technology, Seongbuk-gu, Seoul 136 791 (Korea, Republic of)

2015-10-30

Highlights: • Initial oxidation characteristics of Cu-bearing austenitic stainless steel at 650 °C were studied. • Strong segregation and oxidation of Mn and Nb were found in the entire oxide scale. • Surface coverage by metallic Cu-rich precipitates increases with exposure time. • Chemical heterogeneity of oxide scale revealed initial oxidation to be non-selective. • Fe-Cr and Mn-Cr mixed oxides were realized along with binary oxides of Fe, Cr and Mn. - Abstract: Oxide scale evolution on Cu-bearing austenitic stainless steel 304H at 650 °C, in ambient air, for exposure times 100, 300, 500 and 1000 h, has been investigated. Surface morphology and chemistry of the oxide scale grown were examined using SEM/EDX and XPS. The oxidation kinetics was determined by measuring the weight change using an electronic balance. At the initial stage, up to 500 h of exposure time, the oxidation rate was rapid due to surface reactions governed primarily by oxygen ingress, and then, dropped to a low rate after prolonged oxidation for 1000 h. The diffusion of reactants through the initially formed oxide scale limits the oxidation rate at longer times, thus, the progress of reaction followed the parabolic kinetics. The formed oxide scale was enriched significantly with segregation and subsequent oxidation of Nb, and finely dispersed metallic Cu particles. Within the time frame of oxidation, the oxide scale was mainly composed of mixed oxides such as FeCr{sub 2}O{sub 4} and MnCr{sub 2}O{sub 4} along with the binary oxides of Fe, Cr and Mn. Moreover, the precipitation fraction of Cu-rich particles on the oxide scale increased markedly with increase of exposure times. The chemical heterogeneity of oxide scale suggests that the oxidation occurred in a non-selective manner.

Flow rate effect on the structure and morphology of molybdenum oxide nanoparticles deposited by atmospheric-pressure microplasma processing

International Nuclear Information System (INIS)

Bose, Arumugam Chandra; Shimizu, Yoshiki; Mariotti, Davide; Sasaki, Takeshi; Terashima, Kazuo; Koshizaki, Naoto

2006-01-01

Nanoparticles of crystalline molybdenum oxide were prepared by changing the flow rate of plasma gas (2% oxygen balanced by Ar) using an atmospheric-pressure microplasma technique. The morphology and crystalline structure of the nanoparticles were characterized by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The FESEM results revealed that the shape of the deposited nanoparticles depended on the plasma gas flow rate. The TEM results supported the FESEM observations. The transmission electron diffraction (TED) pattern revealed that the obtained nanoparticles changed from MoO 2 to MoO 3 with the flow-rate increase, and correspondingly the nanoparticle size drastically decreased. A process mechanism is proposed from the observations of optical emission spectroscopy (OES) during the process and consumed wire surface analysis from x-ray photoelectron spectroscopy (XPS) and FESEM studies

Aeration to degas CO{sub 2}, increase pH, and increase iron oxidation rates for efficient treatment of net alkaline mine drainage

Energy Technology Data Exchange (ETDEWEB)

Kirby, C.S.; Dennis, A.; Kahler, A. [Bucknell University, Lewisburg, PA (United States). Dept. of Geology

2009-07-15

Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering 'hybrid' systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m{sup -2} day{sup -1} and Fe loading from field data, 3.6 x 10{sup 3} and 3.0 x 10{sup 4} m{sup 2} oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO{sub 2}, increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Iron(II) oxidation modeling of actively aerated systems predicted that a 1-m deep pond with 10 times less area than estimated for passive treatment would lower Fe(II) concentrations to less than 1 mg L-1 at summer and winter temperatures for both sites. The use of active aeration for treatment Of CO{sub 2}-rich, net-alkaline discharges (including partially treated effluent from anoxic limestone drains) can result in considerably reduced treatment area for oxidation and may lower treatment costs, but settling of Fe hydroxides was not considered in this study. The reduced capital cost for earthmoving will need to be compared to energy and maintenance costs for aeration.

A study on the oxidation behavior of uranium

International Nuclear Information System (INIS)

Kim, Tae Kook; Kang, Kweon Ho; Kim, Kil Jeang; Kang, Il Sik; Jung, Kyung Whan

1998-03-01

When storing depleted uranium wastes, careful handling is required due to their very high oxidation rates. To determine the oxidation mechanism and oxidation rate of depleted uranium wastes, the most important factors to be considered in their treatment, an experiment was carried out by varying the heating rates of the Air-Controlled Oxidizer. The experiment, showed that depleted uranium wastes are pulverized after complete oxidation because of the density difference and then converted to UO 2 , U 3 O 7 , U 3 O 8 . The grain size of pulverized powder decrease with increased temperature. (author). 30 refs., 5 tabs., 28 figs

Efficient synthesis of graphene oxide and the mechanisms of oxidation and exfoliation

Science.gov (United States)

Yuan, Rui; Yuan, Jing; Wu, Yanping; Chen, Lei; Zhou, Huidi; Chen, Jianmin

2017-09-01

An efficient method for the preparation of graphene oxide (GO) was descried through inducing the ultrasonic in the rate-determining step of oxidation processes. Both the transformation procedures and the detailed molecular behavior of parent graphene (PG), partially oxidized graphene (PGO) and GO in H2SO4 and aqueous solution were investigated by molecular dynamic simulation (MD) combining with experiments. The results obtained from MD simulation show that the addition of KMnO4 truly marked the beginning of the reaction which carried out from the border of PG flakes to the centre. This oxidation procedure was the rate-determining step and mainly contained three steps: the boundary carbon atoms oxidized, the distance of the corresponding interlayer enlarged and the oxidizing agent diffused into the unoxidized region, the processes was repeated until oxidized completely. So, the introducing ultrasonic in this section can accelerate not only the exfoliation of layers but also the diffusion of oxidizer and finally raises the oxidation efficiency dramatically. To further clarify these simulation results, the GO was prepared by the method mentioned above. The analyses results for the X-ray diffraction (XRD), Raman spectra and X-ray photoelectron spectroscopy (XPS) of the resulting GO show that the ultrasonic method could perfectly shortens the oxidation time from 12 h to 3 h and forms the higher degree of oxidation products with more carboxylic acid groups on its edges. Thus, this study provides a better understanding of the transformation procedures of graphite and proposes an efficient way to produce GOs suitable for various chemical modifications.

Oxidation effects during corium melt in-vessel retention

Energy Technology Data Exchange (ETDEWEB)

Almyashev, V.I.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Sulatsky, A.A.; Vitol, S.A. [Alexandrov Scientific-Research Institute of Technology (NITI), Sosnovy Bor (Russian Federation); Gusarov, V.V. [Ioffe Institute, St. Petersburg (Russian Federation); Bechta, S. [Royal Institute of Technology (KHT), Stockholm (Sweden); Barrachin, M.; Fichot, F. [Institut de Radioprotection et de Sûreté Nucléaire (IRSN), St Paul lez Durance (France); Bottomley, P.D., E-mail: paul.bottomley@ec.europa.eu [Joint Research Centre, Institut für Transurane (ITU), Karlsruhe (Germany); Fischer, M. [AREVA GmbH, Erlangen (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI (France)

2016-08-15

Highlights: • Corium–steel interaction tests were re-examined particularly for transient processes. • Oxidation of corium melt was sensitive to oxidant supply and surface characteristics. • Consequences for vessel steel corrosion rates in severe accidents were discussed. - Abstract: In the in-vessel corium retention studies conducted on the Rasplav-3 test facility within the ISTC METCOR-P project and OECD MASCA program, experiments were made to investigate transient processes taking place during the oxidation of prototypic molten corium. Qualitative and quantitative data have been produced on the sensitivity of melt oxidation rate to the type of oxidant, melt composition, molten pool surface characteristics. The oxidation rate is a governing factor for additional heat generation and hydrogen release; also for the time of secondary inversion of oxidic and metallic layers of corium molten pool.

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes

Science.gov (United States)

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-01

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

Accelerated evaporation of water on graphene oxide.

Science.gov (United States)

Wan, Rongzheng; Shi, Guosheng

2017-03-29

Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

Science.gov (United States)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation

Pyrite oxidation at circumneutral pH

Science.gov (United States)

Moses, Carl O.; Herman, Janet S.

1991-02-01

Previous studies of pyrite oxidation kinetics have concentrated primarily on the reaction at low pH, where Fe(III) has been assumed to be the dominant oxidant. Studies at circumneutral pH, necessitated by effective pH buffering in some pyrite oxidation systems, have often implicitly assumed that the dominant oxidant must be dissolved oxygen (DO), owing to the diminished solubility of Fe(III). In fact, Fe(III)(aq) is an effective pyrite oxidant at circumneutral pH, but the reaction cannot be sustained in the absence of DO. The purpose of this experimental study was to ascertain the relative roles of Fe(III) and DO in pyrite oxidation at circumneutral pH. The rate of pyrite oxidation was first-order with respect to the ratio of surface area to solution volume. Direct determinations of both Fe(II) (aq)> and Fe(III) (aq) demonstrated a dramatic loss of Fe(II) from the solution phase in excess of the loss for which oxidation alone could account. Based on rate data, we have concluded that Fe(II) is adsorbed onto the pyrite surface. Furthermore, Fe(II) is preferred as an adsorbate to Fe(III), which we attribute to both electrostatic and acid-base selectivity. We also found that the rate of pyrite oxidation by either Fe(III) (aq) or DO is reduced in the presence of aqueous Fe(II), which leads us to conclude that, under most natural conditions, neither Fe(III) (aq) nor DO directly attacks the pyrite surface. The present evidence suggests a mechanism for pyrite oxidation that involves adsorbed Fe( II ) giving up electrons to DO and the resulting Fe(III) rapidly accepting electrons from the pyrite. The adsorbed Fe is, thus, cyclically oxidized and reduced, while it acts as a conduit for electrons traveling from pyrite to DO. Oxygen is transferred from the hydration sphere of the adsorbed Fe to pyrite S. The cycle of adsorbed Fe oxidation and reduction and the successive addition of oxygen to pyrite S continues until a stable sulfoxy species dissociates from the surface. Prior

High Temperature Oxidation of Ferritic Steels for Solid Oxide Electrolysis Stacks

DEFF Research Database (Denmark)

Molin, Sebastian; Chen, Ming; Bentzen, Janet Jonna

2013-01-01

atmospheres at 800°C. Four commercially available alloys: Crofer 22 APU, Crofer 22 H, AL29-4, E-Brite were characterized in humidified hydrogen. One alloy, Crofer 22 APU was also characterized in pure oxygen both in the as-prepared state and after application of a protective coating. Best corrosion resistance......Oxidation rates of ferritic steels used as interconnector plates in Solid Oxide Electrolysis Stacks are of concern as they may be determining for the life time of the technology. In this study oxidation experiments were carried out for up to 1000 hours in hydrogen-side and oxygen-side simulated...... in humidified hydrogen atmosphere was observed for Crofer 22 APU and Crofer 22 H alloys. Corrosion rates for Crofer 22 APU measured in humidified hydrogen are similar to the corrosion rates measured in air. Both coatings of plasma sprayed LSM and dual layer coatings (Co3O4/LSM-Co3O4) applied by wet spraying...

THE EFFECT OF GROUP IIIA TO VIA ELEMENTS AND THEIR OXIDES ON GRAPHITE OXIDATION

Energy Technology Data Exchange (ETDEWEB)

Rakszawski, J F; Parker, W E

1963-06-15

The effect of group IIIA to VIA elements and oxides on graphite oxidation was determined. Additives were molded with spectroscopically pure graphite powder. The concentration was maintained constant at 0.1 mole percent based on the element. The rate of reaction with 1 atm of air was measured at 700 and 800 deg C. Air flow rate from 2000 to 3000 cc/min had no effect on the oxidation rate of the pure graphite at 700, 750, and 800 deg C indicating that reaction was not occurring in Zone III. The calculated Ea of 54 kcal/mole suggested reaction in Zone I. Visual inspection of the rods after reaction substantiated this conclusion. The reaction was first order with respect to oxygen partial pressure at 700 and 800 deg C. B, B/sub 2/O/sub 5/, P, and P/sub 2/ O/sub 6/ inhibited the oxid ation of graphite at 700 and 800 deg C while the other elements and oxides catalyzed the reaction to various degrees. The reaction remained kinetically of the first order when inhibited. A systematic variation in reaction rates appears to follow the diagonals of the periodic relationship of the element from the upper left to the lower right. These variations can be correlated with average ionization energy or electron affinity. (auth)

Hydrogen-water deuterium exchange over metal oxide promoted nickel catalysts

Energy Technology Data Exchange (ETDEWEB)

Sagert, N H; Shaw-Wood, P E; Pouteau, R M.L. [Atomic Energy of Canada Ltd., Pinawa, Manitoba. Whiteshell Nuclear Research Establishment

1975-11-01

Specific rates have been measured for hydrogen-water deuterium isotope exchange over unsupported nickel promoted with about 20% of various metal oxides. The oxides used were Cr/sub 2/O/sub 3/, MoO/sub 2/, MnO, WO/sub 2/-WO/sub 3/, and UO/sub 2/. Nickel surface areas, which are required to measure the specific rates, were determined by hydrogen chemisorption. Specific rates were measured as a function of temperature in the range 353 to 573 K and as a function of the partial pressure of hydrogen and water over a 10-fold range of partial pressure. The molybdenum and tungsten oxides gave the highest specific rates, and manganese and uranium oxides the lowest. Chromium oxide was intermediate, although it gave the highest rate per gram of catalyst. The orders with respect to hydrogen and water over molybdenum oxide and tungsten oxide promoted nickel were consistent with a mechanism in which nickel oxide is formed from the reaction of water with the catalyst, and then is reduced by hydrogen. Over manganese and uranium oxide promoted catalysts, these orders are consistent with a mechanism in which adsorbed water exchanges with chemisorbed hydrogen atoms on the nickel surface. Chromium oxide is intermediate. It was noted that those oxides which favored the nickel oxide route had electronic work functions closest to those of metallic nickel and nickel oxide.

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate

Energy Technology Data Exchange (ETDEWEB)

Forsey, S.P.; Thomson, N.R.; Barker, J.F. [University of Waterloo, Waterloo, ON (Canada). Dept. of Civil & Environmental Engineering

2010-04-15

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalene < phenanthrene < pyrene. The rate of side chain reactivity is controlled by the C-H bond strength. For the alkyl substituted benzenes an excellent correlation was observed between the reaction rate coefficients and bond dissociation energies, but for the substituted PAHs the relationship was poor. A trend was found between the reaction rate coefficients and the calculated heats of complexation indicating that significant ring oxidation occurred in addition to side chain oxidation. Clar's aromatic sextet theory was used to predict the relative stability of arenes towards ring oxidation by permanganate.

Increased electrochemical properties of ruthenium oxide and graphene/ruthenium oxide hybrid dispersed by polyvinylpyrrolidone

International Nuclear Information System (INIS)

Chen, Yao; Zhang, Xiong; Zhang, Dacheng; Ma, Yanwei

2012-01-01

Highlights: ► A good dispersion of RuO 2 and graphene/RuO 2 is obtained by polyvinylpyrrolidone. ► PVP as a dispersant also can prevent the formation of metal Ru in graphene/RuO 2 . ► The max capacitances of the hybrid and RuO 2 reach 435 and 597 F g −1 at 0.2 A g −1 . ► The hybrid shows the best rate capability of 39% at 50 A g −1 . - Abstract: Ruthenium oxide has been prepared by a sol–gel method. Polyvinylpyrrolidone (PVP) as an excellent polymeric dispersant is adopted to prevent aggregation of ruthenium oxide. In order to enhance the rate capability of ruthenium oxide, graphene with residual oxygen functional groups as a 2D support has been merged into ruthenium oxide. These oxygen functional groups not only favor to form stable few layers of graphene colloids, but also offer the sites to anchor ruthenium oxide nanoparticles. X-ray diffraction infers that PVP can also hinder the partial formation of Ru by blocking the direct contact between the Ru 3+ and the graphene in the sol–gel synthesis of the hybrids. The ruthenium oxide and the graphene/ruthenium oxide hybrids dispersed by PVP have superior electrochemical properties due to good dispersing and protecting ability of PVP. Especially, the hybrids using PVP exhibit the best rate capability, indicating that the composites possess an advanced structure of combining sheets and particles in nano-scale.

Accelerated oxidation processes is biodiesel

Energy Technology Data Exchange (ETDEWEB)

Canakci, M.; Monyem, A.; Van Gerpen, J.

1999-12-01

Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feedstocks such as vegetable oil and animal fats. These feedstocks are reacted with an alcohol to produce alkyl monoesters that can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This article reports the results of experiments to track the chemical and physical changes that occur in biodiesel as it oxidizes. These results show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are explored also. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq/kg ester, the acid value and viscosity increase monotonically as oxidation proceeds.

Kinetics of oxidic phase dissolution in acids

International Nuclear Information System (INIS)

Gorichev, I.G.; Kipriyanov, N.A.

1981-01-01

The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

Thick-film effects in the oxidation and hydriding of zirconium alloys

International Nuclear Information System (INIS)

Johnson, A.B. Jr.

1989-08-01

One of the fundamental discoveries involving radiation effects on the oxidation of Zircaloy in low-oxygen aqueous environments is the influence of thick oxide films. Zircaloy oxidation rates in low-oxygen (hydrogen-rich) coolants initially proceed at relatively low rates, often almost uninfluenced by radiation. Marked upturns in oxidation rate have signaled the onset of radiation effects. The radiation effects appear to correlate with a threshold oxide thickness. Results of the test reactor experiments lead to formulation of the Thick-Film Hypothesis: beyond a threshold oxide thickness, radiolysis of water that infiltrates oxide cracks and pores controls the oxidation rate; radiation creates microenvironments inside the oxide film, producing highly oxidizing conditions, that are no longer suppressed by the coolant-borne hydrogen. Upturns in oxidation rate on high-exposure Zircaloy pressure tubes add confirmatory evidence for the thick-film effect. This paper summarizes the early evidence for thick-film behavior, including oxidation and hydriding trends, updates confirmatory evidence from Zircaloy reactor and fuel assembly components, and highlights other observations from the test reactor series that have potential fundamental significance to explanations of radiation effects on Zircaloy. 23 refs., 10 figs

Antioxidant N-acetylcysteine restores systemic nitric oxide availability and corrects depressions in arterial blood pressure and heart rate in diabetic rats.

Science.gov (United States)

Xia, Zhengyuan; Nagareddy, Prabhakara R; Guo, Zhixin; Zhang, Wei; McNeill, John H

2006-02-01

Increased oxidative stress and reduced nitric oxide (NO) bioactivity are key features of diabetes mellitus that eventually result in cardiovascular abnormalities. We assessed whether N-acetylcysteine (NAC), an antioxidant and glutathione precursor, could prevent the hyperglycaemia induced increase in oxidative stress, restore NO availability and prevent depression of arterial blood pressure and heart rate in vivo in experimental diabetes. Control (C) and streptozotocin-induced diabetic (D) rats were treated or not treated with NAC in drinking water for 8 weeks, initiated 1 week after induction of diabetes. At termination, plasma levels of free 15-F2t-isoprostane, a specific marker of oxygen free radical induced lipid peroxidation, was increased while the plasma total antioxidant concentration was decreased in untreated diabetic rats as compared to control rats (P<0.05). This was accompanied by a significant reduction of plasma levels of nitrate and nitrite, stable metabolites of NO, (P<0.05, D vs. C) and a reduced endothelial NO synthase protein expression in the heart and in aortic and mesenteric artery tissues. Systolic, diastolic and mean arterial blood pressures (SBP, DBP and MAP) and heart rate (HR) were reduced in diabetic rats (P<0.05 vs. C) and NAC normalised the changes that occurred in the diabetic rats. The protective effects may be attributable to restoration of NO bioavailability in the circulation.

The GC/AED studies on the reactions of sulfur mustard with oxidants

International Nuclear Information System (INIS)

Popiel, StanisIaw; Witkiewicz, Zygfryd; Szewczuk, Aleksander

2005-01-01

A gas chromatograph coupled with an atomic emission detector was used to identify and to determine the products formed on oxidation of sulfur mustard. The oxidation rate and the resulting oxidates were studied in relation to oxidant type and reaction medium parameters. Hydrogen peroxide, sodium hypochlorite, sodium perborate, potassium monopercarbonate, ammonium peroxydisulfate, potassium peroxymonosulfate (oxone), and tert-butyl peroxide were used as oxidants. Oxidations were run in aqueous media or in solvents of varying polarities. The oxidation rate was found to be strongly related to oxidant type: potassium peroxymonosulfate (oxone) and sodium hypochlorite were fast-acting oxidants; sodium perborate, hydrogen peroxide, ammonium peroxydisulfate, and sodium monopercarbonate were moderate oxidants; tert-butyl peroxide was the slowest-acting oxidant. In non-aqueous solvents, the oxidation rate was strongly related to solvent polarity. The higher the solvent polarity, the faster the oxidation rate. In the acid and neutral media, the mustard oxidation rates were comparable. In the alkaline medium, oxidation was evidently slower. A suitable choice of the initial oxidant-to-mustard concentration ratio allowed to control the type of the resulting mustard oxidates. As the pH of the reaction medium was increased, the reaction of elimination of hydrogen chloride from mustard oxidates becomes more and more intensive

High-temperature oxidation of ion-implanted tantalum

International Nuclear Information System (INIS)

Kaufmann, E.N.; Musket, R.G.; Truhan, J.J.; Grabowski, K.S.; Singer, I.L.; Gossett, C.R.

1982-01-01

The oxidation of ion-implanted Ta in two different high temperature regimes has been studied. Oxidations were carried out at 500 0 C in Ar/O 2 mixtures, where oxide growth is known to follow a parabolic rate law in initial stages, and at 1000 0 C in pure O 2 , where a linear-rate behavior obtains. Implanted species include Al, Ce, Cr, Li, Si and Zr at fluences of the order of 10 17 /cm 2 . Oxidized samples were studied using Rutherford backscattering, nuclear reaction analysis, Auger spectroscopy, secondary-ion mass spectroscopy, x-ray diffraction and optical microscopy. Significant differences among the specimens were noted after the milder 500 0 C treatment, specifically, in the amount of oxide formed, the degree of oxygen dissolution in the metal beneath the oxide, and in the redistribution behavior of the implanted solutes. Under the severe 1000 0 C treatment, indications of different solute distributions and of different optical features were found, whereas overall oxidation rate appeared to be unaffected by the presence of the solute. 7 figures

Kinetics of Photoelectrochemical Oxidation of Methanol on Hematite Photoanodes

Science.gov (United States)

2017-01-01

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-Fe2O3 is retarded ∼20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution. PMID:28735533

Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

Science.gov (United States)

Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2015-12-01

The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our results provide new empirical data that should allow for more precise quantitative constraints on atmospheric pO2 based on the sedimentary rock record. 1Anbar, A.D. et al., 2007. Science, 317, i. 5846: 1903-1906. 2Williamson & Rimstidt, 1994. Geochim. et Cosmochim

Supporting information for the estimation of plutonium oxide leak rates through very small apertures

International Nuclear Information System (INIS)

Schwendiman, L.C.

1977-01-01

Information is presented from which an estimate can be made of the release of plutonium oxide from shipping containers. The leak diameter is estimated from gas leak tests of the container and an estimate is made of gas leak rate as a function of pressure over the time of interest in the accident. These calculations are limited in accuracy because of assumptions regarding leak geometry and the basic formulations of hydrodynamic flow for the assumed conditions. Sonic flow is assumed to be the limiting gas flow rate. Particles leaking from the air space above the powder will be limited by the low availability of particles due to rapid settling, the very limited driving force (pressure buildup) during the first minute, and the deposition in the leak channel. Equations are given to estimate deposition losses. Leaks of particles occurring below the level of the bulk powder will be limited by mechanical interference when leaks are of dimension smaller than particle sizes present. Some limiting cases can be calculated. When the leak dimension is large compared to the particle sizes present, maximum particle releases can be estimated, but will be very conservative

UO2 dissolution rates: A review

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-09-01

This report reviews literature data on UO 2 dissolution kinetics and provides a framework for guiding future experimental studies as well as theoretical modeling studies. Under oxidizing conditions, UO 2 dissolution involves formation of an oxidized surface layer which is then dissolved by formation of aqueous complexes. Higher oxygen pressures or other oxidants are required at higher temperatures to have dissolution rates independent of oxygen pressure. At high oxygen pressures (1-5 atm, 25-70 C), the dissolution rate has a one-half order dependence on oxygen pressure, whereas at oxygen pressures below 0.2 atm, Grandstaff (1976), but nobody else, observed a first-order dependence on dissolution rate. Most people found a first-order dependence on carbonate concentration; Posey-Dowty (1987) found independence of carbonate at pH 7 to 8.2. Dissolution rates increase with temperature except in experiments involving granitic groundwater. Dissolution rates were generally greater under acid or basic conditions than near neutral pH

Nitrous oxide-based techniques versus nitrous oxide-free techniques for general anaesthesia.

Science.gov (United States)

Sun, Rao; Jia, Wen Qin; Zhang, Peng; Yang, KeHu; Tian, Jin Hui; Ma, Bin; Liu, Yali; Jia, Run H; Luo, Xiao F; Kuriyama, Akira

2015-11-06

Nitrous oxide has been used for over 160 years for the induction and maintenance of general anaesthesia. It has been used as a sole agent but is most often employed as part of a technique using other anaesthetic gases, intravenous agents, or both. Its low tissue solubility (and therefore rapid kinetics), low cost, and low rate of cardiorespiratory complications have made nitrous oxide by far the most commonly used general anaesthetic. The accumulating evidence regarding adverse effects of nitrous oxide administration has led many anaesthetists to question its continued routine use in a variety of operating room settings. Adverse events may result from both the biological actions of nitrous oxide and the fact that to deliver an effective dose, nitrous oxide, which is a relatively weak anaesthetic agent, needs to be given in high concentrations that restrict oxygen delivery (for example, a common mixture is 30% oxygen with 70% nitrous oxide). As well as the risk of low blood oxygen levels, concerns have also been raised regarding the risk of compromising the immune system, impaired cognition, postoperative cardiovascular complications, bowel obstruction from distention, and possible respiratory compromise. To determine if nitrous oxide-based anaesthesia results in similar outcomes to nitrous oxide-free anaesthesia in adults undergoing surgery. We searched the Cochrane Central Register of Controlled Trials (CENTRAL; 2014 Issue 10); MEDLINE (1966 to 17 October 2014); EMBASE (1974 to 17 October 2014); and ISI Web of Science (1974 to 17 October 2014). We also searched the reference lists of relevant articles, conference proceedings, and ongoing trials up to 17 October 2014 on specific websites (http://clinicaltrials.gov/, http://controlled-trials.com/, and http://www.centerwatch.com). We included randomized controlled trials (RCTs) comparing general anaesthesia where nitrous oxide was part of the anaesthetic technique used for the induction or maintenance of general

Tritium oxidation and exchange: preliminary studies

International Nuclear Information System (INIS)

Phillips, J.E.; Easterly, C.E.

1978-05-01

The radiological hazard resulting from an exposure to either tritium oxide or tritium gas is discussed and the factors contributing to the hazard are presented. From the discussion it appears that an exposure to tritium oxide vapor is 10 4 to 10 5 times more hazardous than exposure to tritium gas. Present and future sources of tritium are briefly considered and indicate that most of the tritium has been and is being released as tritium oxide. The likelihood of gaseous releases, however, is expected to increase in the future, calling to task the present general release assumption that 100% of all tritium released is as oxide. Accurate evaluation of the hazards from a gaseous release will require a knowledge of the conversion rate of tritium gas to tritium oxide. An experiment for determining the conversion rate of tritium gas to tritium oxide is presented along with some preliminary data. The conversion rates obtained for low initial concentrations (10 -4 to 10 -1 mCi/ml) indicate the conversion may proceed more rapidly than would be expected from an extrapolation of previous data taken at higher concentrations

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

Science.gov (United States)

Suarez-Bertoa, R; Picquet-Varrault, B; Tamas, W; Pangui, E; Doussin, J-F

2012-11-20

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

Contribution to the identification of the processes kinetically limiting of the zirconium alloys oxidation; characterization of the oxide films formed at high temperature by solids electrochemistry

International Nuclear Information System (INIS)

Vermoyal, J.J.

2000-06-01

The corrosion behavior of zirconium alloys used for cladding tubes has been extensively studied under several oxidation conditions (temperature, steam, dry air, oxygen...) in order to clarify the mechanism(s) of oxide growth and breakdown. Oxidation rate is generally assumed to be controlled by oxygen diffusion inwards the oxide layer. Nevertheless, several experimental facts, such as acceleration or inhibition of corrosion rate in coupling conditions, suggest that electrochemical processes are involved as a rate determining step. This work is an attempt to shed light about the rate-limiting-mechanism of two zirconium alloys oxidation: Zircaloy-4 (Zy-4) and Zr-Nb(1%)O(0,13%). Impedance spectroscopy characterizations of oxide films formed in high temperature water and studied in gaseous atmosphere clearly show the difference of electrical properties between the two alloys. The in situ electrochemical and thermogravimetric investigations in gaseous medium, and the polarization effects on oxidation and hydridation of Zr alloys in PWRs conditions indicate that oxygen diffusion can be considered as the limiting kinetic step for Zy-4 oxidation. On the contrary, the acceleration of oxide growth on Zr-Nb(1%)O(0,13%) under anodic polarization in PWRs conditions (360 deg C) suggests that either the electronic conductivity in the oxide or an interfacial process at least partially control the oxidation rate. Catalytic effects observed in gaseous medium when noble metals increase the oxygen reduction rate would tend to corroborate the oxidation control of this alloy by an interfacial mechanism. An electrochemical description and a heterogeneous kinetics approach based on a diffusion-interfacial process as rate determining step are then proposed. (author)

High-temperature oxidation behavior of dense SiBCN monoliths: Carbon-content dependent oxidation structure, kinetics and mechanisms

International Nuclear Information System (INIS)

Li, Daxin; Yang, Zhihua; Jia, Dechang; Wang, Shengjin; Duan, Xiaoming; Zhu, Qishuai; Miao, Yang; Rao, Jiancun; Zhou, Yu

2017-01-01

Highlights: •The scale growth for all investigated monoliths at 1500 °C cannot be depicted by a linear or parabolic rate law. •The carbon-rich monoliths oxidize at 1500 °C according to a approximately linear weight loss equation. •The excessive carbon in SiBCN monoliths deteriorates the oxidation resistance. •The oxidation resistance stems from the characteristic oxide structures and increased oxidation resistance of BN(C). -- Abstract: The high temperature oxidation behavior of three SiBCN monoliths: carbon-lean SiBCN with substantial Si metal, carbon-moderate SiBCN and carbon-rich SiBCN with excessive carbon, was investigated at 1500 °C for times up to15 h. Scale growth for carbon-lean and −moderate monoliths at 1500 °C cannot be described by a linear or parabolic rate law, while the carbon-rich monoliths oxidize according to a approximately linear weight loss equation. The microstructures of the oxide scale compose of three distinct layers. The passivating layer of carbon and boron containing amorphous SiO 2 and increased oxidation resistance of BN(C) both benefit the oxidation resistance.

Uranium Metal to Oxide Conversion by Air Oxidation –Process Development

Energy Technology Data Exchange (ETDEWEB)

Duncan, A

2001-12-31

Published technical information for the process of metal-to-oxide conversion of uranium components has been reviewed and summarized for the purpose of supporting critical decisions for new processes and facilities for the Y-12 National Security Complex. The science of uranium oxidation under low, intermediate, and high temperature conditions is reviewed. A process and system concept is outlined and process parameters identified for uranium oxide production rates. Recommendations for additional investigations to support a conceptual design of a new facility are outlined.

Dietary-Induced Chronic Hypothyroidism Negatively Affects Rat Follicular Development and Ovulation Rate and Is Associated with Oxidative Stress.

Science.gov (United States)

Meng, Li; Rijntjes, Eddy; Swarts, Hans; Bunschoten, Annelies; van der Stelt, Inge; Keijer, Jaap; Teerds, Katja

2016-04-01

The long-term effects of chronic hypothyroidism on ovarian follicular development in adulthood are not well known. Using a rat model of chronic diet-induced hypothyroidism initiated in the fetal period, we investigated the effects of prolonged reduced plasma thyroid hormone concentrations on the ovarian follicular reserve and ovulation rate in prepubertal (12-day-old) and adult (64-day-old and 120-day-old) rats. Besides, antioxidant gene expression, mitochondrial density and the occurrence of oxidative stress were analyzed. Our results show that continuous hypothyroidism results in lower preantral and antral follicle numbers in adulthood, accompanied by a higher percentage of atretic follicles, when compared to euthyroid age-matched controls. Not surprisingly, ovulation rate was lower in the hypothyroid rats. At the age of 120 days, the mRNA and protein content of superoxide dismutase 1 (SOD1) were significantly increased while catalase (CAT) mRNA and protein content was significantly decreased, suggesting a disturbed antioxidant defense capacity of ovarian cells in the hypothyroid animals. This was supported by a significant reduction in the expression of peroxiredoxin 3 ( ITALIC! Prdx3), thioredoxin reductase 1 ( ITALIC! Txnrd1), and uncoupling protein 2 ( ITALIC! Ucp2) and a downward trend in glutathione peroxidase 3 ( ITALIC! Gpx3) and glutathione S-transferase mu 2 ( ITALIC! Gstm2) expression. These changes in gene expression were likely responsible for the increased immunostaining of the oxidative stress marker 4-hydroxynonenal. Together these results suggest that chronic hypothyroidism initiated in the fetal/neonatal period results in a decreased ovulation rate associated with a disturbance of the antioxidant defense system in the ovary. © 2016 by the Society for the Study of Reproduction, Inc.

Oxidation of boron carbide at high temperatures

International Nuclear Information System (INIS)

Steinbrueck, Martin

2005-01-01

The oxidation kinetics of various types of boron carbides (pellets, powder) were investigated in the temperature range between 1073 and 1873 K. Oxidation rates were measured in transient and isothermal tests by means of mass spectrometric gas analysis. Oxidation of boron carbide is controlled by the formation of superficial liquid boron oxide and its loss due to the reaction with surplus steam to volatile boric acids and/or direct evaporation at temperatures above 1770 K. The overall reaction kinetics is paralinear. Linear oxidation kinetics established soon after the initiation of oxidation under the test conditions described in this report. Oxidation is strongly influenced by the thermohydraulic boundary conditions and in particular by the steam partial pressure and flow rate. On the other hand, the microstructure of the B 4 C samples has a limited influence on oxidation. Very low amounts of methane were produced in these tests

The fate of arsenic adsorbed on iron oxides in the presence of arsenite-oxidizing bacteria.

Science.gov (United States)

Zhang, Zhennan; Yin, Naiyi; Du, Huili; Cai, Xiaolin; Cui, Yanshan

2016-05-01

Arsenic (As) is a redox-active metalloid whose toxicity and mobility in soil depend on its oxidation state. Arsenite [As(III)] can be oxidized by microbes and adsorbed by minerals in the soil. However, the combined effects of these abiotic and biotic processes are not well understood. In this study, the fate of arsenic in the presence of an isolated As(III)-oxidizing bacterium (Pseudomonas sp. HN-1, 10(9) colony-forming units (CFUs)·ml(-1)) and three iron oxides (goethite, hematite, and magnetite at 1.6 g L(-1)) was determined using batch experiments. The total As adsorption by iron oxides was lower with bacteria present and was higher with iron oxides alone. The total As adsorption decreased by 78.6%, 36.0% and 79.7% for goethite, hematite and magnetite, respectively, due to the presence of bacteria. As(III) adsorbed on iron oxides could also be oxidized by Pseudomonas sp. HN-1, but the oxidation rate (1.3 μmol h(-1)) was much slower than the rate in the aqueous phase (96.2 μmol h(-1)). Therefore, the results of other studies with minerals only might overestimate the adsorptive capacity of solids in natural systems; the presence of minerals might hinder As(III) oxidation by microbes. Under aerobic conditions, in the presence of iron oxides and As(III)-oxidizing bacteria, arsenic is adsorbed onto iron oxides within the adsorption capacity, and As(V) is the primary form in the solid and aqueous phases. Copyright © 2016 Elsevier Ltd. All rights reserved.

High temperature steam oxidation of Al3Ti-based alloys for the oxidation-resistant surface layer on Zr fuel claddings

International Nuclear Information System (INIS)

Park, Jeong-Yong; Kim, Il-Hyun; Jung, Yang-Il; Kim, Hyun-Gil; Park, Dong-Jun; Choi, Byung-Kwon

2013-01-01

We investigated the feasibility to apply Al 3 Ti-based alloys as the surface layer for improving the oxidation resistance of Zr fuel claddings under accident conditions. Two types of Al 3 Ti-based alloys with the compositions of Al–25Ti–10Cr and Al–21Ti–23Cr in atomic percent were prepared by arc-melting followed by homogenization annealing at 1423 K for 48 h. Al–25Ti–10Cr alloy showed an L1 2 quasi-single phase microstructure with a lot of needle-shaped minor phase and pores. Al–21Ti–23Cr alloy consisted of an L1 2 matrix and Cr 2 Al as the second phase. Al 3 Ti-based alloys showed an extremely low oxidation rate in a 1473 K steam for up to 7200 s when compared to Zircaloy-4. Both alloys exhibited almost the same oxidation rate in the early stage of oxidation, but Al–25Ti–10Cr showed a little lower oxidation rate after 4000 s than Al–21Ti–23Cr. The difference in the oxidation rate between two types of Al 3 Ti-based alloys was too marginal to distinguish the oxidation behavior of each alloy. The resultant oxide exhibited almost the same characteristics in both alloys even though the microstructure was explicitly distinguished from each other. The crystal structure of the oxide formed up to 2000 s was identified as Al 2 O 3 in both alloys. The oxide morphology consisted of columnar grains whose length was almost identical to the average oxide thickness. On the basis of the results obtained, it is considered that Al 3 Ti-based alloy is one of the promising candidates for the oxidation-resistant surface layer on Zr fuel claddings

Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

Science.gov (United States)

Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

2015-11-17

Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

Radiolytic graphite oxidation revisited

International Nuclear Information System (INIS)

Minshall, P.C.; Sadler, I.A.; Wickham, A.J.

1996-01-01

The importance of radiolytic oxidation in graphite-moderated CO 2 -cooled reactors has long been recognised, especially in the Advanced Gas-Cooled Reactors where potential rates are higher because of the higher gas pressure and ratings than the earlier Magnox designs. In all such reactors, the rate of oxidation is partly inhibited by the CO produced in the reaction and, in the AGR, further reduced by the deliberate addition of CH 4 . Significant roles are also played by H 2 and H 2 O. This paper reviews briefly the mechanisms of these processes and the data on which they are based. However, operational experience has demonstrated that these basic principles are unsatisfactory in a number of respects. Gilsocarbon graphites produced by different manufacturers have demonstrated a significant difference in oxidation rate despite a similar specification and apparent equivalence in their pore size and distribution, considered to be the dominant influence on oxidation rate for a given coolant-gas composition. Separately, the inhibiting influence of CH 4 , which for many years had been considered to arise from the formation of a sacrificial deposit on the pore walls, cannot adequately be explained by the actual quantities of such deposits found in monitoring samples which frequently contain far less deposited carbon than do samples from Magnox reactors where the only source of such deposits is the CO. The paper also describes the current status of moderator weight-loss predictions for Magnox and AGR Moderators and the validation of the POGO and DIFFUSE6 codes respectively. 2 refs, 5 figs

Determination of glucose exchange rates and permeability of erythrocyte membrane in preeclampsia and subsequent oxidative stress-related protein damage using dynamic-{sup 19}F-NMR

Energy Technology Data Exchange (ETDEWEB)

Dickinson, Elizabeth, E-mail: elizabeth.dickinson@york.ac.uk [University of York, Department of Chemistry (United Kingdom); Arnold, John R. P. [Selby College (United Kingdom); Fisher, Julie [University of Leeds, School of Chemistry (United Kingdom)

2017-02-15

The cause of the pregnancy condition preeclampsia (PE) is thought to be endothelial dysfunction caused by oxidative stress. As abnormal glucose tolerance has also been associated with PE, we use a fluorinated-mimic of this metabolite to establish whether any oxidative damage to lipids and proteins in the erythrocyte membrane has increased cell membrane permeability. Data were acquired using {sup 19}F Dynamic-NMR (DNMR) to measure exchange of 3-fluoro-3-deoxyglucose (3-FDG) across the membrane of erythrocytes from 10 pregnant women (5 healthy control women, and 5 from women suffering from PE). Magnetisation transfer was measured using the 1D selective inversion and 2D EXSY pulse sequences, over a range of time delays. Integrated intensities from these experiments were used in matrix diagonalisation to estimate the values of the rate constants of exchange and membrane permeability. No significant differences were observed for the rate of exchange of 3-FDG and membrane permeability between healthy pregnant women and those suffering from PE, leading us to conclude that no oxidative damage had occurred at this carrier-protein site in the membrane.

Determination of glucose exchange rates and permeability of erythrocyte membrane in preeclampsia and subsequent oxidative stress-related protein damage using dynamic-"1"9F-NMR

International Nuclear Information System (INIS)

Dickinson, Elizabeth; Arnold, John R. P.; Fisher, Julie

2017-01-01

The cause of the pregnancy condition preeclampsia (PE) is thought to be endothelial dysfunction caused by oxidative stress. As abnormal glucose tolerance has also been associated with PE, we use a fluorinated-mimic of this metabolite to establish whether any oxidative damage to lipids and proteins in the erythrocyte membrane has increased cell membrane permeability. Data were acquired using "1"9F Dynamic-NMR (DNMR) to measure exchange of 3-fluoro-3-deoxyglucose (3-FDG) across the membrane of erythrocytes from 10 pregnant women (5 healthy control women, and 5 from women suffering from PE). Magnetisation transfer was measured using the 1D selective inversion and 2D EXSY pulse sequences, over a range of time delays. Integrated intensities from these experiments were used in matrix diagonalisation to estimate the values of the rate constants of exchange and membrane permeability. No significant differences were observed for the rate of exchange of 3-FDG and membrane permeability between healthy pregnant women and those suffering from PE, leading us to conclude that no oxidative damage had occurred at this carrier-protein site in the membrane.

Oxidation Kinetics of Cast TiAl3

Science.gov (United States)

Smialek, J. L.; Humphrey, D. L.

1992-01-01

The isothermal oxidation kinetics of the TiAl3 compound over a wide temperature range is documented, and these rates are related to exclusive alpha-Al2O3 scale growth. The specific weight change vs time curves are shown. Two abnormalities are immediately apparent. One is that a rapid initial uptake of oxygen occurs at times less than 5 h, followed by a lower oxidation rate at longer times, for tests at 900 C and below. The other is that the final weight changes for the 700, 800, and 900 C tests are not in the sequence expected with respect to temperature. Isothermal oxidation of drop cast TiAl above 1000 C was found to exhibit parabolic oxidation controlled by protective alpha-Al2O3 scale formation. TiAl is the only phase in the binary Ti-Al system that forms exclusive scales of alpha-Al2O3 in isothermal oxidation. High anomalous rates at short times and at temperatures below 1000 C resulted from the internal oxidation of a second phase of aluminum.

The effect of poly-β-hydroxyalkanoates degradation rate on nitrous oxide production in a denitrifying phosphorus removal system.

Science.gov (United States)

Wei, Yan; Wang, Shuying; Ma, Bin; Li, Xiyao; Yuan, Zhiguo; He, Yuelan; Peng, Yongzhen

2014-10-01

Poly-β-hydroxyalkanoates (PHAs) and free nitrous acid (FNA) have been revealed as significant factors causing nitrous oxide (N2O) production in denitrifying phosphorus removal systems. In this study, the effect of PHA degradation rate on N2O production was studied at low FNA levels. N2O production always maintained at approximately 40% of the amount of nitrite reduced independent of the PHA degradation rate. The electrons distributed to nitrite reduction were 1.6 times that to N2O reduction. This indicated that electron competition between these two steps was not affected by the PHA degradation rate. Continuous feed of nitrate was proposed, and demonstrated to reduce N2O accumulation by 75%. While being kept low, a possible compounding effect of a low-level FNA could not be ruled out. The sludge used likely contained both polyphosphate- and glycogen-accumulating organisms, and the results could not be simply attributed to either group of organisms. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Effect of A Course of Pilates Exercise on Hypertension, Nitric Oxide, and Resting Heart Rate in the Eldrly Men with Hypertension

Directory of Open Access Journals (Sweden)

Farid Eghbali

2017-02-01

Full Text Available Abstract Background: High blood pressure increases various cardiovascular events about 2 to 3 times in a person. The purpose of this study is to recognize the effect of a course of pilates exercise on hypertension, nitric oxide, and resting heart rate in the eldrlymen with hypertension. Materials and Methods: Subjects of this quasi-experimental research included 30 elderly men with hypertension grade one(in the range of systolic-diastolic 140/90 to 159/99mm Hg who participated voluntarily and accessibly in the study and were divided randomly into two experimental peer (15 people and control (15 people groups. Weight, height and BMI of subjects were 75±80, 170±175 and 25-26, respectively. The experimental group did selected exercise of Pilates for eight weeks (three one-hour sessions per week. Desired variables of the subjects of both groups were evaluated 24 hours before the start of exercise and 24 hours after the last session. Data analysis was conducted using dependent and independent t-test by SPSS16 statistical software at the significant level of p≥0.05. Results: The research results showed that the eight-week pilates exercise gave rise to reduction in blood pressure(p≤0.05 as well as resting heart rate (p≤0.05 and to increase in nitric oxide of elderly men with hypertension (p≤0.05. Conclusion: The eight-week pilates exercise reduced blood pressure and resting heart rate and increased the production of nitric oxide in elderly men. So, it seems that the regular physical exercise can be effective as a preventive factor in the outbreak of cardiovascular diseases of the elderly men.

Impact of Chaos Functions on Modern Swarm Optimizers.

Directory of Open Access Journals (Sweden)

E Emary

Full Text Available Exploration and exploitation are two essential components for any optimization algorithm. Much exploration leads to oscillation and premature convergence while too much exploitation slows down the optimization algorithm and the optimizer may be stuck in local minima. Therefore, balancing the rates of exploration and exploitation at the optimization lifetime is a challenge. This study evaluates the impact of using chaos-based control of exploration/exploitation rates against using the systematic native control. Three modern algorithms were used in the study namely grey wolf optimizer (GWO, antlion optimizer (ALO and moth-flame optimizer (MFO in the domain of machine learning for feature selection. Results on a set of standard machine learning data using a set of assessment indicators prove advance in optimization algorithm performance when using variational repeated periods of declined exploration rates over using systematically decreased exploration rates.

Highly n-Type Titanium Oxide as an Electronically Active Support for Platinum in the Catalytic Oxidation of Carbon Monoxide

KAUST Repository

Baker, L. Robert

2011-08-18

The role of the oxide-metal interface in determining the activity and selectivity of chemical reactions catalyzed by metal particles on an oxide support is an important topic in science and industry. A proposed mechanism for this strong metal-support interaction is electronic activation of surface adsorbates by charge carriers. Motivated by the goal of using electronic activation to drive nonthermal chemistry, we investigated the ability of the oxide support to mediate charge transfer. We report an approximately 2-fold increase in the turnover rate of catalytic carbon monoxide oxidation on platinum nanoparticles supported on stoichiometric titanium dioxide (TiO2) when the TiO2 is made highly n-type by fluorine (F) doping. However, for nonstoichiometric titanium oxide (TiOX<2) the effect of F on the turnover rate is negligible. Studies of the titanium oxide electronic structure show that the energy of free electrons in the oxide determines the rate of reaction. These results suggest that highly n-type TiO2 electronically activates adsorbed oxygen (O) by electron spillover to form an active O- intermediate. © 2011 American Chemical Society.

In-situ synthesis of reduced graphene oxide modified lithium vanadium phosphate for high-rate lithium-ion batteries via microwave irradiation

International Nuclear Information System (INIS)

Wang, Zhaozhi; Guo, Haifu; Yan, Peng

2015-01-01

Highlights: • Graphene-decorated Li 3 V 2 (PO 4 ) 3 is synthesized via microwave irradiation. • Both Li 3 V 2 (PO 4 ) 3 and RGO can be simultaneously achieved through this route. • The GO is reduced by microwave irradiation not the carbon. • Li 3 V 2 (PO 4 ) 3 /RGO displays excellent high-rate ability and cyclic stability. - Abstract: We report a simple and rapid method to synthesize graphene-modified Li 3 V 2 (PO 4 ) 3 as cathode material for lithium-ion batteries via microwave irradiation. By treating graphene oxide and the precursor of Li 3 V 2 (PO 4 ) 3 in a commercial microwave oven, both reduced graphene oxide and Li 3 V 2 (PO 4 ) 3 could be simultaneously synthesized within 5 min. The structure, morphology and electrochemical performances of as-synthesized graphene-modified Li 3 V 2 (PO 4 ) 3 are investigated systematically by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, charge/discharge tests, electrochemical impedance spectra (EIS) and cyclic voltammetry (CV). The XRD result indicates that single-phase graphene-modified Li 3 V 2 (PO 4 ) 3 with monoclinic structure can be obtained. Both SEM and TEM images show that Li 3 V 2 (PO 4 ) 3 nanocrystals are embedded in the reduced graphene oxide sheets which could provide an easy path for the electrons and Li-ions during the cycling process. Compared with the pristine Li 3 V 2 (PO 4 ) 3 electrode, graphene-modified Li 3 V 2 (PO 4 ) 3 exhibits a better high-rate ability and cyclic stability. These superior electrochemical performances are attributed to the good conductivity of reduced graphene oxide which enhances the electrons and Li-ions transport on the surface of Li 3 V 2 (PO 4 ) 3 . Thus, this simple and rapid method could be promising to synthesize graphene-modified electrode materials

Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

International Nuclear Information System (INIS)

Fossing, H.

1992-01-01

Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

Protein and lipid oxidative damage and complex I content are lower in the brain of budgerigar and canaries than in mice. Relation to aging rate.

Science.gov (United States)

Pamplona, Reinald; Portero-Otín, Manuel; Sanz, Alberto; Ayala, Victoria; Vasileva, Ekaterina; Barja, Gustavo

2005-12-01

What are the mechanisms determining the rate of animal aging? Of the two major classes of endothermic animals, bird species are strikingly long-lived compared to mammals of similar body size and metabolic rate. Thus, they are ideal models to identify longevity-related characteristics not linked to body size or low metabolic rates. Since oxidative stress seems to be related to the basic aging process, we measured specific markers of different kinds of oxidative damage to proteins, like glutamic and aminoadipic semialdehydes (GSA and AASA, specific protein carbonyls), Nɛ-(carboxyethyl)lysine (CEL), Nɛ-(carboxymethyl)lysine (CML), and Nɛ-(malondialdehyde)lysine (MDAL), as well as mitochondrial Complex I content and amino acid and membrane fatty acyl composition, in the brain of short-lived mice (maximum life span [MLSP] 3.5 years) compared with those of long-lived budgerigar 'parakeets' (MLSP, 21 years) and canaries (MLSP, 24 years). The brains of both bird species had significantly lower levels of compounds formed as a result of oxidative (GSA and AASA), glycoxidative (CEL and CML), and lipoxidative (CML and MDAL) protein modifications, as well as a lower levels of mitochondrial complex I protein. Although it is known that fatty acid unsaturation is lower in many tissues of long-lived compared to short-lived mammals, this is not true in the particular case of brain. In agreement with this, we also found that the brain tissue of bugerigars and canaries contains no fewer double bonds than that of mice. Amino acid composition analyses revealed that bird proteins have a significantly lower content of His, Leu and Phe, as well as, interestingly, of methionine, whereas Asp, Glu, Ala, Val, and Lys contents were higher than in the mammals. These results, together with those previously described in other tissues of pigeons (MLSP, 35 years) compared to rats (MLSP, 4 years), indicate that oxidative damage to proteins, lipids and mitochondrial DNA are lower in birds (very

The effect of puberty on fat oxidation rates during exercise in overweight and normal-weight girls.

Science.gov (United States)

Chu, L; Riddell, M C; Schneiderman, J E; McCrindle, B W; Hamilton, J K

2014-01-01

Excess weight is often associated with insulin resistance (IR) and may disrupt fat oxidation during exercise. This effect is further modified by puberty. While studies have shown that maximal fat oxidation rates (FOR) during exercise decrease with puberty in normal-weight (NW) and overweight (OW) boys, the effect of puberty in NW and OW girls is unclear. Thirty-three NW and OW girls ages 8-18 yr old completed a peak aerobic capacity test on a cycle ergometer. FOR were calculated during progressive submaximal exercise. Body composition and Tanner stage were determined. For each participant, a best-fit polynomial curve was constructed using fat oxidation vs. exercise intensity to estimate max FOR. In a subset of the girls, IR derived from an oral glucose tolerance test (n = 20), and leptin and adiponectin levels (n = 11) were assessed in relation to FOR. NW pre-early pubertal girls had higher max FOR [6.9 ± 1.4 mg·kg fat free mass (FFM)(-1)·min(-1)] than NW mid-late pubertal girls (2.2 ± 0.9 mg·kg FFM(-1)·min(-1)) (P = 0.002), OW pre-early pubertal girls (3.8 ± 2.1 mg·kg FFM(-1)·min(-1)), and OW mid-late pubertal girls (3.3 ± 0.9 mg·kg FFM(-1)·min(-1)) (P puberty; however, this decrease associated with puberty was blunted in OW girls due to lower FOR in pre-early puberty. The presence of IR due to obesity potentially masks the effect of puberty on FOR during exercise in girls.

Water-oxidation catalysis by synthetic manganese oxides--systematic variations of the calcium birnessite theme.

Science.gov (United States)

Frey, Carolin E; Wiechen, Mathias; Kurz, Philipp

2014-03-21

Layered manganese oxides from the birnessite mineral family have been identified as promising heterogeneous compounds for water-oxidation catalysis (WOC), a key reaction for the conversion of renewable energy into storable fuels. High catalytic rates were especially observed for birnessites which contain calcium as part of their structures. With the aim to systematically improve the catalytic performance of such oxide materials, we used a flexible synthetic route to prepare three series of calcium birnessites, where we varied the calcium concentrations, the ripening times of the original precipitates and the temperature of the heat treatment following the initial synthetic steps (tempering) during the preparation process. The products were carefully analysed by a number of analytical techniques and then probed for WOC activity using the Ce(4+)-system. We find that our set of twenty closely related manganese oxides shows large, but somewhat systematic alterations in catalytic rates, indicating the importance of synthesis parameters for maximum catalytic performance. The catalyst of the series for which the highest water-oxidation rate was found is a birnessite of medium calcium content (Ca : Mn ratio 0.2 : 1) that had been subjected to a tempering temperature of 400 °C. On the basis of the detailed analysis of the results, a WOC reaction scheme for birnessites is proposed to explain the observed trends in reactivity.

The oxidation and corrosion of ODS alloys

Science.gov (United States)

Lowell, Carl E.; Barrett, Charles A.

1990-01-01

The oxidation and hot corrosion of high temperature oxide dispersion strengthened (ODS) alloys are reviewed. The environmental resistance of such alloys are classified by oxide growth rate, oxide volatility, oxide spalling, and hot corrosion limitations. Also discussed are environmentally resistant coatings for ODS materials. It is concluded that ODS NiCrAl and FeCrAl alloys are highly oxidation and corrosion resistant and can probably be used uncoated.

Oxidation And Hot Corrosion Of ODS Alloy

Science.gov (United States)

Lowell, Carl E.; Barrett, Charles A.

1993-01-01

Report reviews oxidation and hot corrosion of oxide-dispersion-strengthened (ODS) alloys, intended for use at high temperatures. Classifies environmental resistances of such alloys by rates of growth of oxides, volatilities of oxides, spalling of oxides, and limitations imposed by hot corrosion. Also discusses environmentally resistant coatings for ODS materials. Concludes ODS NICrAl and FeCrAl alloys highly resistant to oxidation and corrosion and can be used uncoated.

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17%Cr and Cu-17%Cr-5%Al. Part 1; Oxidation Kinetics

Science.gov (United States)

Raj. Sai V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu- 17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9 9.5 kJ mol-1. In contrast, the oxidation kinetics for the Cu-17%Cr- 5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR- 5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Assessment of fish health around the Terra Nova oil development site on the Grand Banks

Energy Technology Data Exchange (ETDEWEB)

Mathieu, A.; Hanlon, J.; Melvin, W.; French, B. [Oceans Ltd., St. John' s, NL (Canada); Myers, M. [Northwest Fisheries Science Center, Seattle, WA (United States); Williams, U.; Janes, G. [Petro-Canada, East Coast Operations, St. John' s, NL (Canada); Wight, F. [Husky Oil Operations Ltd., St. John' s, NL (Canada)

2010-07-01

American plaice are used as an indicator species for environmental effects monitoring (EEM) programs in the Grand Banks area of Newfoundland. This study reported on fish health studies conducted between 2000 to 2006 at the Terra Nova oil development site before and after the release of produced waters. A total of 500 fishes were studied for a 5-year period in order to evaluate health effect indicators including fish condition; visible skin and organ lesions; levels of mixed-function-oxygenase (MFO) enzymes; haematology; and various histopathological indices in the liver and gills. The study demonstrated slight elevations of MFO enzyme activity in fish from the development site in 2002, before the release of produced water. On the basis of the various studied indicators, results suggest that the project is not having a significant impact on the health of American plaice.

Assessment of fish health around the Terra Nova oil development site on the Grand Banks

International Nuclear Information System (INIS)

Mathieu, A.; Hanlon, J.; Melvin, W.; French, B.; Myers, M.; Williams, U.; Janes, G.; Wight, F.

2010-01-01

American plaice are used as an indicator species for environmental effects monitoring (EEM) programs in the Grand Banks area of Newfoundland. This study reported on fish health studies conducted between 2000 to 2006 at the Terra Nova oil development site before and after the release of produced waters. A total of 500 fishes were studied for a 5-year period in order to evaluate health effect indicators including fish condition; visible skin and organ lesions; levels of mixed-function-oxygenase (MFO) enzymes; haematology; and various histopathological indices in the liver and gills. The study demonstrated slight elevations of MFO enzyme activity in fish from the development site in 2002, before the release of produced water. On the basis of the various studied indicators, results suggest that the project is not having a significant impact on the health of American plaice.

Radiolytic oxidation

International Nuclear Information System (INIS)

Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

1991-01-01

Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

Tuning inner-layer oxygen functional groups of reduced graphene oxide by potentiostatic oxidation for high performance electrochemical energy storage devices

International Nuclear Information System (INIS)

Wang, Huixin; Feng, Bingmei; Ye, Yifan; Guo, Jinghua; Fang, Hai-Tao

2017-01-01

Graphical abstract: Tuning inner-layer oxygen functional groups of reduced graphene oxide by potentiostatic oxidation in carbonate-based electrolyte improves the electrochemical performance. - Abstract: The electrochemical lithiation/delithiation of oxygen-containing functional groups (OCFGs) of nanocarbon materials, particularly graphene, have attracted intensive interest in recent years. Here, we propose a controllable potentiostatic oxidation approach to tune the OCFGs of as-prepared reduced graphene oxide (rGO) in a carbonate-based electrolyte to improve the specific capacity and rate capability. By X-Ray absorption spectroscopy in total fluorescence yield mode and X-Ray diffraction, we confirm that potentiostatic oxidations generate new OCFGs in the inner-layer of rGO. The content of OCFGs increases as oxidation potential being elevated. Such increasing of OCFGs in quantity significantly enhances the capacity. For instance, the specific capacity of 170.4 mAh g −1 for pristine rGO electrode is increased to 290.5 mAh g −1 after the oxidation at 5.0 V. We demonstrate that oxidations at moderate potentials can reduce the electrochemical and ohmic polarizations of rGO electrodes without deteriorating diffusion dynamic, thereby improving rate capability. After the optimal oxidation at 4.7 V, rGO electrode exhibits an excellent rate capability, delivering 58.4 mAh g −1 at 20 A g −1 .

The oxidation kinetics and the structure of the oxide film on Zircaloy before and after the kinetic transition

International Nuclear Information System (INIS)

Arima, T.; Masuzumi, T.; Furuya, H.; Idemitsu, K.; Inagaki, Y.

2001-01-01

Oxidation kinetics of Zircaloy-4 have been measured using a micro-balance technique in CO-CO 2 gas mixtures between 450 deg. C and 600 deg. C. Oxidation kinetics of Zircaloy-4 obeyed a cubic rate law with time at 450-600 deg. C up to 24 h. At 600 deg. C, the kinetic transition occurred after about 36 h. After the transition, oxidation kinetics obeyed a linear rate law. X-ray diffraction patterns for the samples oxidized at 600 deg. C showed that the volume fraction of tetragonal phase of zirconia decreased with time until the kinetic transition occurred and was almost constant after that. In addition, stresses in the oxide films were found to be larger for the pre-transition samples than for the post-transition ones. (authors)

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

Science.gov (United States)

Fox, P.M.; Davis, J.A.; Luther, G. W.

2009-01-01

The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Atmospheric cycles of nitrogen oxides and ammonia. [source strengths and destruction rates

Science.gov (United States)

Bottger, A.; Ehhalt, D. H.; Gravenhorst, G.

1981-01-01

The atmospheric cycles of nitrogenous trace compounds for the Northern and Southern Hemispheres are discussed. Source strengths and destruction rates for the nitrogen oxides: NO, NO2 and HNO3 -(NOX) and ammonia (NH3) are given as a function of latitude over continents and oceans. The global amounts of NOX-N and NH3-N produced annually in the period 1950 to 1975 (34 + 5 x one trillion g NOx-N/yr and 29 + or - 6 x one trillion g NH3-N/yr) are much less than previously assumed. Globally, natural and anthropogenic emissions are of similar magnitude. The NOx emission from anthropogenic sources is 1.5 times that from natural processes in the Northern Hemisphere, whereas in the Southern Hemisphere, it is a factor of 3 or 4 less. More than 80% of atmospheric ammonia seems to be derived from excrements of domestic animals, mostly by bulk deposition: 24 + or - 9 x one trillion g NO3 -N/yr and 21 + or - 9 x one trillion g NH4+-N/yr. Another fraction may be removed by absorption on vegetation and soils.

Oxidation behavior of fuel cladding tube in spent fuel pool accident condition

International Nuclear Information System (INIS)

Nemoto, Yoshiyuki; Kaji, Yoshiyuki; Ogawa, Chihiro; Nakashima, Kazuo; Tojo, Masayuki

2017-01-01

In spent fuel pool (SFP) under loss-of-cooling or loss-of-coolant severe accident condition, the spent fuels will be exposed to air and heated by their own residual decay heat. Integrity of fuel cladding is crucial for SFP safety therefore study on cladding oxidation in air at high temperature is important. Zircaloy-2 (Zry2) and zircaloy-4 (Zry4) were applied for thermogravimetric analyses (TGA) in different temperatures in air at different flow rates to evaluate oxidation behavior. Oxidation rate increased with testing temperature. In a range of flow rate of air which is predictable in spent fuel lack during a hypothetical SFP accident, influence of flow rate was not clearly observed below 950degC for the Zry2, or below 1050degC for Zry4. In higher temperature, oxidation rate was higher in high rate condition, and this trend was seen clearer when temperature increased. Oxide layers were carefully examined after the TGA analyses and compared with mass gain data to investigate detail of oxidation process in air. It was revealed that the mass gain data in pre-breakaway regime reflects growth of dense oxide film on specimen surface, meanwhile in post-breakaway regime, it reflects growth of porous oxide layer beneath fracture of the dense oxide film. (author)

Hydrogen oxidation in Azospirillum brasilense

Energy Technology Data Exchange (ETDEWEB)

Tibelius, K.

1984-01-01

Hydrogen oxidation by Azospirillum brasilense Sp7 was studied in N/sub 2/-fixing and NH/sub 4//sup +/-grown batch cultures. The K/sub m/ for H/sub 2/ of O/sub 2/-dependent H/sup 3/H oxidation in whole cells was 9 uM. The rates of H/sup 3/H and H/sub 2/ oxidation were very similar, indicating that the initial H/sub 2/ activation step in the overall H/sub 2/ oxidation reaction was not rate-limiting and that H/sup 3/H oxidation was a valid measure of H/sub 2/-oxidation activity. Hydrogen-oxidation activity was inhibited irreversibly by air. In N-free cultures the O/sub 2/ optima for O/sub 2/-dependent H/sub 2/ oxidation, ranging from 0.5-1.25% O/sub 2/ depending on the phase of growth, were significantly higher than those of C/sub 2/H/sub 2/ reduction, 0.15-0.35%, suggesting that the H/sub 2/-oxidation system may have a limited ability to aid in the protection of nitrogenase against inactivation by O/sub 2/. Oxygen-dependent H/sub 2/ oxidation was inhibited by NO/sub 2//sup +/, NO, CO, and C/sub 2/H/sub 2/ with apparent K/sub 1/ values of 20, 0.4, 28, and 88 uM, respectively. Hydrogen-oxidation activity was 50 to 100 times higher in denitrifying cultures when the terminal electron acceptor for growth was N/sub 2/O rather than NO/sub 3//sup -/, possibly due to the irreversible inhibition of hydrogenase by NO/sub 2//sup -/ and NO in NO/sub 3//sup -/-grown cultures.

Capacitive behavior of highly-oxidized graphite

Science.gov (United States)

Ciszewski, Mateusz; Mianowski, Andrzej

2014-09-01

Capacitive behavior of a highly-oxidized graphite is presented in this paper. The graphite oxide was synthesized using an oxidizing mixture of potassium chlorate and concentrated fuming nitric acid. As-oxidized graphite was quantitatively and qualitatively analyzed with respect to the oxygen content and the species of oxygen-containing groups. Electrochemical measurements were performed in a two-electrode symmetric cell using KOH electrolyte. It was shown that prolonged oxidation causes an increase in the oxygen content while the interlayer distance remains constant. Specific capacitance increased with oxygen content in the electrode as a result of pseudo-capacitive effects, from 0.47 to 0.54 F/g for a scan rate of 20 mV/s and 0.67 to 1.15 F/g for a scan rate of 5 mV/s. Better cyclability was observed for the electrode with a higher oxygen amount.

An analysis of the effects of Mn2+ on oxidative phosphorylation in liver, brain, and heart mitochondria using state 3 oxidation rate assays

International Nuclear Information System (INIS)

Gunter, Thomas E.; Gerstner, Brent; Lester, Tobias; Wojtovich, Andrew P.; Malecki, Jon; Swarts, Steven G.; Brookes, Paul S.; Gavin, Claire E.; Gunter, Karlene K.

2010-01-01

Manganese (Mn) toxicity is partially mediated by reduced ATP production. We have used oxidation rate assays-a measure of ATP production-under rapid phosphorylation conditions to explore sites of Mn 2+ inhibition of ATP production in isolated liver, brain, and heart mitochondria. This approach has several advantages. First, the target tissue for Mn toxicity in the basal ganglia is energetically active and should be studied under rapid phosphorylation conditions. Second, Mn may inhibit metabolic steps which do not affect ATP production rate. This approach allows identification of inhibitions that decrease this rate. Third, mitochondria from different tissues contain different amounts of the components of the metabolic pathways potentially resulting in different patterns of ATP inhibition. Our results indicate that Mn 2+ inhibits ATP production with very different patterns in liver, brain, and heart mitochondria. The primary Mn 2+ inhibition site in liver and heart mitochondria, but not in brain mitochondria, is the F 1 F 0 ATP synthase. In mitochondria fueled by either succinate or glutamate + malate, ATP production is much more strongly inhibited in brain than in liver or heart mitochondria; moreover, Mn 2+ inhibits two independent sites in brain mitochondria. The primary site of Mn-induced inhibition of ATP production in brain mitochondria when succinate is substrate is either fumarase or complex II, while the likely site of the primary inhibition when glutamate plus malate are the substrates is either the glutamate/aspartate exchanger or aspartate aminotransferase.

Pathways of carbon oxidation in continental margin sediments off central Chile

DEFF Research Database (Denmark)

Thamdrup, B; Canfield, Donald Eugene

1996-01-01

Rates and oxidative pathways of organic carbon mineralization were determined in sediments at six stations on the shelf and slope off Concepcion Bay at 36.5 degrees S. The depth distribution of C oxidation rates was determined to 10 cm from accumulation of dissolved inorganic C in 1-5-d incubations...... the shelf was rich in NO3- and depleted of O2. Sediments at the four shelf stations were covered by mats of filamentous bacteria of the genera Thioploca and Beggiatoa. Carbon oxidation rates at these sites were extremely high near the sediment surface (>3 micromol cm-3 d-1) and decreased exponentially...... C oxidation between 0 and 10 cm. Carbon oxidation through Fe reduction contributed a further 12-29% of the depth-integrated rate, while the remainder of C oxidation was through SO4(2-) reduction. The depth distribution of Fe reduction agreed well with the distribution of poorly crystalline Fe oxides...

Tantalum high-temperature oxidation kinetics

International Nuclear Information System (INIS)

Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

1981-01-01

Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

Graphite Oxidation Thermodynamics/Reactions

International Nuclear Information System (INIS)

Propp, W.A.

1998-01-01

The vulnerability of graphite-matrix spent nuclear fuel to oxidation by the ambient atmosphere if the fuel canister is breached was evaluated. Thermochemical and kinetic data over the anticipated range of storage temperatures (200 to 400 C) were used to calculate the times required for a total carbon mass loss of 1 mgcm-2 from a fuel specimen. At 200 C, the time required to produce even this small loss is large, 900,000 yr. However, at 400 C the time required is only 1.9 yr. The rate of oxidation at 200 C is negligible, and the rate even at 400 C is so small as to be of no practical consequence. Therefore, oxidation of the spent nuclear fuel upon a loss of canister integrity is not anticipated to be a concern based upon the results of this study

Ammonia and nitrite oxidation in the Eastern Tropical North Pacific

Science.gov (United States)

Peng, Xuefeng; Fuchsman, Clara A.; Jayakumar, Amal; Oleynik, Sergey; Martens-Habbena, Willm; Devol, Allan H.; Ward, Bess B.

2015-12-01

Nitrification plays a key role in the marine nitrogen (N) cycle, including in oceanic oxygen minimum zones (OMZs), which are hot spots for denitrification and anaerobic ammonia oxidation (anammox). Recent evidence suggests that nitrification links the source (remineralized organic matter) and sink (denitrification and anammox) of fixed N directly in the steep oxycline in the OMZs. We performed shipboard incubations with 15N tracers to characterize the depth distribution of nitrification in the Eastern Tropical North Pacific (ETNP). Additional experiments were conducted to investigate photoinhibition. Allylthiourea (ATU) was used to distinguish the contribution of archaeal and bacterial ammonia oxidation. The abundance of archaeal and β-proteobacterial ammonia monooxygenase gene subunit A (amoA) was determined by quantitative polymerase chain reaction. The rates of ammonia and nitrite oxidation showed distinct subsurface maxima, with the latter slightly deeper than the former. The ammonia oxidation maximum coincided with the primary nitrite concentration maximum, archaeal amoA gene maximum, and the subsurface nitrous oxide maximum. Negligible rates of ammonia oxidation were found at anoxic depths, where high rates of nitrite oxidation were measured. Archaeal amoA gene abundance was generally 1 to 2 orders of magnitude higher than bacterial amoA gene abundance, and inhibition of ammonia-oxidizing bacteria with 10 μM ATU did not affect ammonia oxidation rates, indicating the dominance of archaea in ammonia oxidation. These results depict highly dynamic activities of ammonia and nitrite oxidation in the oxycline of the ETNP OMZ.

Study of the oxidation behavior of zirconoium and its alloys

International Nuclear Information System (INIS)

Costa, I.

1985-01-01

The oxidation behavior of zirconium, zircaloy-4 and Zr-2,5% Nb alloy, as well as the influence of temperature, oxidising atmosphere, metal composition, heat treatment, surface treatment and specimen size on the oxidation of these materials in the temperature range 350 - 900 0 C and at atmospheric pressure have been studied with the aid of thermogravimetry. The results indicate that oxidation rate increases with temperature and the rate of oxidation of the zirconium alloys was appreciable beyond 600 0 C. At temperature higher than 500 0 C, the oxidation curves of the zirconium alloys revealed a rate transition, the kinetics after transition being either mixed parabolic and linear or linear. The transition produced an alteration in oxide characteristics, from being dark and adherent and protective, to white or grey and revealing at times cracks and scaling. The oxidation atmospheres were oxygen and air, and the results showed that the extent of oxidation in air was higher than that in oxygen. Among the metals, zirconium showed a low degree of oxidation, and the alloy Zr-2,5% Nb the lowest resistance to oxidation. Specimens heat treated in the α-phase showed the highest resistance to oxidation, and those heat treated in the β-phase the lowest. Surface treatments in aqueous solutions containing a high concentration of the fluoride ion, left behind fluorates on the surface and increased the oxidation rates of zirconium and zircaloy-4. Specimens with a high proportion of corners in relation to the total area, showed a high extent of oxidation giving rise to cracks in the oxide at the corners. (Author) [pt

Constraints on mechanisms and rates of anaerobic oxidation of methane by microbial consortia: process-based modeling of ANME-2 archaea and sulfate reducing bacteria interactions

Directory of Open Access Journals (Sweden)

B. Orcutt

2008-11-01

Full Text Available Anaerobic oxidation of methane (AOM is the main process responsible for the removal of methane generated in Earth's marine subsurface environments. However, the biochemical mechanism of AOM remains elusive. By explicitly resolving the observed spatial arrangement of methanotrophic archaea and sulfate reducing bacteria found in consortia mediating AOM, potential intermediates involved in the electron transfer between the methane oxidizing and sulfate reducing partners were investigated via a consortium-scale reaction transport model that integrates the effect of diffusional transport with thermodynamic and kinetic controls on microbial activity. Model simulations were used to assess the impact of poorly constrained microbial characteristics such as minimum energy requirements to sustain metabolism and cell specific rates. The role of environmental conditions such as the influence of methane levels on the feasibility of H₂, formate and acetate as intermediate species, and the impact of the abundance of intermediate species on pathway reversal were examined. The results show that higher production rates of intermediates via AOM lead to increased diffusive fluxes from the methane oxidizing archaea to sulfate reducing bacteria, but the build-up of the exchangeable species can cause the energy yield of AOM to drop below that required for ATP production. Comparison to data from laboratory experiments shows that under the experimental conditions of Nauhaus et al. (2007, none of the potential intermediates considered here is able to support metabolic activity matching the measured rates.

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.

Biodegradation of dispersed marine fuel oil in sediment under engineered pre-spill application strategy

International Nuclear Information System (INIS)

Hua, J.

2006-01-01

Biodegradation of marine fuel oil was studied by monitoring changes in residual oil and populations of microorganisms in marine sediments. Biodegradation rates for dispersant and soap water were 2.09 and 2.27 g/kg per day, respectively, under pre-application strategy, suggesting that the strategy may promote MFO dispersion and provide with sufficient source of food. The effect of temperature on the effectiveness of pre-application strategy is particularly obvious for the growth of fungi and Pseudomonas maltophilia. The effect of pre-application of soap water on the tolerance of aerobic bacteria, Escherichia coli, and P. maltophilia, was gradually diminished within 25-33 days. (author)

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

Science.gov (United States)

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

2015-11-05

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

Ferrous Iron Oxidation under Varying pO2 Levels: The Effect of Fe(III)/Al(III) Oxide Minerals and Organic Matter.

Science.gov (United States)

Chen, Chunmei; Thompson, Aaron

2018-01-16

Abiotic Fe(II) oxidation by O 2 commonly occurs in the presence of mineral sorbents and organic matter (OM) in soils and sediments; however, this tertiary system has rarely been studied. Therefore, we examined the impacts of mineral surfaces (goethite and γ-Al 2 O 3 ) and organic matter [Suwannee River fulvic acid (SRFA)] on Fe(II) oxidation rates and the resulting Fe(III) (oxyhydr)oxides under 21 and 1% pO 2 at pH 6. We tracked Fe dynamics by adding 57 Fe(II) to 56 Fe-labeled goethite and γ-Al 2 O 3 and characterized the resulting solids using 57 Fe Mössbauer spectroscopy. We found Fe(II) oxidation was slower at low pO 2 and resulted in higher-crystallinity Fe(III) phases. Relative to oxidation of Fe(II) (aq) alone, both goethite and γ-Al 2 O 3 surfaces increased Fe(II) oxidation rates regardless of pO 2 levels, with goethite being the stronger catalyst. Goethite surfaces promoted the formation of crystalline goethite, while γ-Al 2 O 3 favored nano/small particle or disordered goethite and some lepidocrocite; oxidation of Fe(II) aq alone favored lepidocrocite. SRFA reduced oxidation rates in all treatments except the mineral-free systems at 21% pO 2 , and SRFA decreased Fe(III) phase crystallinity, facilitating low-crystalline ferrihydrite in the absence of mineral sorbents, low-crystalline lepidocrocite in the presence of γ-Al 2 O 3 , but either crystalline goethite or ferrihydrite when goethite was present. This work highlights that the oxidation rate, the types of mineral surfaces, and OM control Fe(III) precipitate composition.

Reaction path of the oxidative coupling of methane over a lithium-doped magnesium oxide catalyst : Factors affecting the Rate of Total Oxidation of Ethane and Ethylene

NARCIS (Netherlands)

Roos, J.A.; Korf, S.J.; Veehof, R.H.J.; van Ommen, J.G.; Ross, J.R.H.

1989-01-01

Experiments using gas mixtures of O2, C2H6 or C2H4 and CH4 or He have been carried out with a Li/MgO catalyst using a well-mixed reaction system which show that the total oxidation products, CO and CO2, are formed predominantly from ethylene, formed in the oxidative coupling of methane. It is

Rate and Selectivity Control in Thioether and Alkene Oxidation with H ₂ O ₂ over Phosphonate-Modified Niobium(V)-Silica Catalysts

Energy Technology Data Exchange (ETDEWEB)

Thornburg, Nicholas E.; Notestein, Justin M. (NWU)

2017-09-05

Supported metal oxide catalysts are versatile materials for liquid-phase oxidations, including alkene epoxidation and thioether sulfoxidation with H2O2. Periodic trends in H2O2 activation was recently demonstrated for alkene epoxidation, highlighting Nb-SiO2 as a more active and selective catalyst than Ti-SiO2. Three representative catalysts are studied consisting of NbV, TiIV, and ZrIV on silica, each made through a molecular precursor approach that yields highly dispersed oxide sites, for thioanisole oxidation by H2O2. Initial rates trend Nb>Ti>>Zr, as for epoxidation, and Nb outperforms Ti for a number of other thioethers. In contrast, selectivity to sulfoxide vs. sulfone trends Ti>Nb>>Zr at all conversions. Modifying the Nb-SiO2 catalyst with phenylphosphonic acid does not completely remove sulfoxidation reactivity, as it did for photooxidation and epoxidation, and results in an unusual material active for sulfoxidation but neither epoxidation nor overoxidation to the sulfone.

Kinetics of the reduction of uranium oxide catalysts

International Nuclear Information System (INIS)

Heynen, H.W.G.; Camp-van Berkel, M.M.; Bann, H.S. van der

1977-01-01

The reduction of uranium oxide and uranium oxide on alumina catalysts by ethylbenzene and by hydrogen has been studied in a thermobalance. Ethylbenzene mole fractions between 0.0026 and 0.052 and hydrogen mole fractions between 0.1 and 0.6 were applied at temperatures of 425--530 0 C. During the reduction the uranium oxides are converted into UO 2 . The rate of reduction of pure uranium oxide appears to be constant in the composition region UO/sub 2.6/-UO/sub 2.25/. The extent of this region is independent of the concentration of the reducing agents and of the reaction temperature. The constant rate is explained in terms of a constant oxygen pressure which is in equilibrium with the two solid phases, U 3 O/sub 8-x/ and U 4 O 9 . The reduction rate is first order in hydrogen and zero order in ethylbenzene with activation energies of 120 and 190 kJ mol -1 , respectively. Oxygen diffusion through the lattice is probably not rate limiting. The reduction behavior of uranium oxide on alumina is different from that of pure uranium oxide; the rate of reduction continuously decreases with increasing degree of reduction. An explanation for this behavior has been given by visualizing this catalyst as a set of isolated uranium oxide crystallites with a relative wide variation of diameters, in an alumina matrix. At the beginning of the reduction, carbon dioxide and water are the only reaction products. Thereafter, benzene is found as well and, finally, at U/O ratios below 2.25, styrene also appears in the reactor outlet

Zirconium metal-water oxidation kinetics. V. Oxidation of Zircaloy in high pressure steam

International Nuclear Information System (INIS)

Pawel, R.E.; Cathcart, J.V.; Campbell, J.J.; Jury, S.H.

1977-12-01

A series of scoping tests to determine the influence of steam pressure on the isothermal oxidation kinetics of Zircaloy-4 PWR tubing was undertaken. The oxidation experiments were conducted in flowing steam at 3.45, 6.90, and 10.34 MPa (500, 1000, and 1500 psi) at 905 0 C (1661 0 F), and at 3.45 and 6.90 MPa at 1101 0 C (2014 0 F). A comparison of the results of these experiments with those obtained for oxidation in steam at atmospheric pressure under similar conditions indicated that measurable enhancement of the oxidation rate occurred with increasing pressure at 905 0 C, but not at 1100 0 C

Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

Science.gov (United States)

Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

1984-04-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

Results of the post-irradiation examination of a highly-rated mixed oxide fuel rod from the Mol 7B experiment

International Nuclear Information System (INIS)

Coquerelle, M.; Walker, C.T.; Whitlow, W.H.

1980-01-01

The experiment MOL 7B was carried out in a epithermal flux in the Belgian reactor BR2. The pin examined contained fuel of initial composition (Usub(0.7)Pusub(0.3))Osub(1.98). It had been irradiated to a maximum burn-up of 13.2 at% at a maximum linear power of 568Wcm -1 . The fuel was clad with coldworked stainless steel. Electron microprobe analysis indicated that a Cr 2 O 3 type oxide was the main constituent of the grey phases in the gap. A metallic phase on the fuel surface had apparently resulted from the mechanical compaction of fragments of cladding that had been depleted in chromium by oxidation. Thus the main components of the phase were iron and nickel. Chromium loss from the inner cladding surface was significant only in the upper regions of the pin. In pin sections that were metallographically examined sigma phase and carbides of the type M 23 C 6 were present at the grain boundaries of the cladding. Cladding corrosion was not an Arrhenius function of the cladding temperature: the amount of metal lost from the inner cladding surface decreased with rise in cladding temperature above 910 K. A contributor to metal loss was the mechanical detachment of fragments of cladding which reformed as a metallic layer on the surface of the fuel. Chromium depletion and sigma phase formation at grain boundaries lowered the cohesive forces between grains which were then mechanically detached. Chromium loss from grain boundaries is mainly the results of oxidation of the cladding by the mixed oxide fuel. Data are presented to support the view that the local average O/M of the fuel determined the rate of oxidation and consequently the extent of chromium depletion. Fuel-cladding mechanical interactions were weak in the upper regions of the pin where metal loss was small

The effect of natural antioxidants on the rate of accumulation of oxidation products in the fat phase of butter cream

Directory of Open Access Journals (Sweden)

M. S. Voronina

2016-01-01

Full Text Available Describes the main finishing prefabricated pastries and cakes-cream. Researched range of cream depending on the fruit components and method of production. Aim: to study the degree of oxidation cream with natural antioxidants from fruits and berries processing products, namely in the form of concentrated juice of fruits and berries. Outlines the process of oxidation of lipids, one of the fundamental processes of loss of quality food products. Describes the action of antioxidants as antioxidants on accumulation intensity concentrations of primary and secondary oxidation products, making the final product unsuitable for the consumer and the bounding its shelf life. Presents the results of a study of the contents of primary and secondary oxidation products in butter cream immediately after cooking, as well as samples, stored for five days with the addition of antioxidants in the form of concentrated juice of fruits and berries in the amount of 2–7% by weight of cream. As a control sample has been used cream with no additives. Quality indicators to characterize the degree of oxidation of the product: acid, peroxide, anizidin and tioburbit number. The study found that adding a concentrated juice of fruits and berries as antioxidant in recipe cream reduces the growth rate of the concentration of free fatty acids on the fifth day, as compared with the reference sample. Adding concentrated juice of fruits and berries slows down the process of dissolution of the fat molecules in fat fraction of cream with the formation of free fatty acids; intensity decay reaction of peroxides and hydroxides slows down and, consequently, decreases the formation of aldehydes, deteriorating the taste and smell of the cream; quantitatively reduced the growth of education malondial′degida.

Insecticide resistance may enhance the response to a host-plant volatile kairomone for the codling moth, Cydia pomonella (L.)

Science.gov (United States)

Sauphanor, Benoît; Franck, Pierre; Lasnier, Thérèse; Toubon, Jean-François; Beslay, Dominique; Boivin, Thomas; Bouvier, Jean-Charles; Renou, Michel

2007-06-01

The behavioral and electroantennographic responses of Cydia pomonella (L.) to the ripe pear volatile ethyl (2 E,4 Z)-2,4-decadienoate (Et- E, Z-DD), were compared in insecticide-susceptible and -resistant populations originating from southern France. A dose-response relationship to this kairomonal attractant was established for antennal activity and did not reveal differences between susceptible and resistant strains. Conversely, males of the laboratory strains expressing metabolic [cytochrome P450-dependent mixed-function oxidases (mfo)] or physiological (kdr-type mutation of the sodium-channel gene) resistance mechanisms exhibited a significantly higher response to Et- E, Z-DD than those of the susceptible strain in a wind tunnel experiment. No response of the females to this kairomone could be obtained in our wind-tunnel conditions. In apple orchards, mfo-resistant male moths were captured at significantly higher rates in kairomone-baited traps than in traps baited with the sex pheromone of C. pomonella. Such a differential phenomenon was not verified for the kdr-resistant insects, which exhibited a similar response to both the sex pheromone and the kairomonal attractant in apple orchards. Considering the widespread distribution of metabolic resistance in European populations of C. pomonella and the enhanced behavioral response to Et- E, Z-DD in resistant moths, the development of control measures based on this kairomonal compound would be of great interest for the management of insecticide resistance in this species.

Modeling and sensitivity analysis on the transport of aluminum oxide nanoparticles in saturated sand: effects of ionic strength, flow rate, and nanoparticle concentration.

Science.gov (United States)

Rahman, Tanzina; Millwater, Harry; Shipley, Heather J

2014-11-15

Aluminum oxide nanoparticles have been widely used in various consumer products and there are growing concerns regarding their exposure in the environment. This study deals with the modeling, sensitivity analysis and uncertainty quantification of one-dimensional transport of nano-sized (~82 nm) aluminum oxide particles in saturated sand. The transport of aluminum oxide nanoparticles was modeled using a two-kinetic-site model with a blocking function. The modeling was done at different ionic strengths, flow rates, and nanoparticle concentrations. The two sites representing fast and slow attachments along with a blocking term yielded good agreement with the experimental results from the column studies of aluminum oxide nanoparticles. The same model was used to simulate breakthrough curves under different conditions using experimental data and calculated 95% confidence bounds of the generated breakthroughs. The sensitivity analysis results showed that slow attachment was the most sensitive parameter for high influent concentrations (e.g. 150 mg/L Al2O3) and the maximum solid phase retention capacity (related to blocking function) was the most sensitive parameter for low concentrations (e.g. 50 mg/L Al2O3). Copyright © 2014 Elsevier B.V. All rights reserved.

Oxidation behaviour of ribbon shape carbon fibers and their composites

International Nuclear Information System (INIS)

Manocha, L.M.; Warrier, Ashish; Manocha, S.; Edie, D.D.; Ogale, A.A.

2006-01-01

Carbon fibers, though important constituent as reinforcements for high performance carbon/carbon composites, are shadowed by their oxidation in air at temperatures beginning 450 deg. C. Owing to tailorable properties of carbon fibers, efforts are underway to explore structural modification possibilities to improve the oxidation resistance of the fibers and their composites. The pitch based ribbon shape carbon fibers are found to have highly preferential oriented graphitic structure resulting in high mechanical properties and thermal conductivity. In the present work oxidation behaviour of ribbon shape carbon fibers and their composites heat treated to 1000-2700 deg. C has been studied. SEM examination of these composites exhibits development of graphitic texture and ordering within the fibers with increase in heat treatment temperature. Oxidation studies made by thermogravimetric analysis in air show that matrix has faster rate of oxidation and in the initial stages the matrix gets oxidized at faster rate with slower rate of oxidation of the fibers depending on processing conditions of fibers and composites

Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

KAUST Repository

Hervier, Antoine

2011-11-24

Platinum films of 1 nm thickness were deposited by electron beam evaporation onto 100 nm thick titanium oxide films (TiOx) with variable oxygen vacancy concentrations and fluorine (F) doping. Methanol oxidation on the platinum films produced formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiOx was stoichiometric (TiO 2), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO1.9). These results correlate with the chemical behavior of the same types of catalysts in CO oxidation. Fluorine doping of stoichiometric TiO2 also increased selectivity toward partial oxidation of methanol to formaldehyde and methyl formate, but had an opposite effect in the case of nonstoichiometric TiOx. Introduction of oxygen vacancies and fluorine doping both increased the conductivity of the TiO x film. For oxygen vacancies, this occurred by the formation of a conduction channel in the band gap, whereas in the case of fluorine doping, F acted as an n-type donor, forming a conduction channel at the bottom of the conduction band, about 0.5-1.0 eV higher in energy. The higher energy electrons in F-doped stoichiometric TiOx led to higher turnover rates and increased selectivity toward partial oxidation of methanol. This correlation between electronic structure and turnover rate and selectivity indicates that the ability of the support to transfer charges to surface species controls in part the activity and selectivity of the reaction. © 2011 American Chemical Society.

Oxidative Ce"3"+ sequestration by fungal manganese oxides with an associated Mn(II) oxidase activity

International Nuclear Information System (INIS)

Zheng, Haisu; Tani, Yukinori; Naitou, Hirotaka; Miyata, Naoyuki; Tojo, Fuyumi

2016-01-01

Sequestration of Ce"3"+ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce"3"+ solution, newly formed BMOs exhibited stoichiometric Ce"3"+ oxidation, where the molar ratio of Ce"3"+ sequestered (Ce_s_e_q) relative to Mn"2"+ released (Mn_r_e_l) was maintained at approximately two throughout the reaction. A similar Ce"3"+ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN_3. Aerobic Ce"3"+ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce"3"+ sequestration over Mn"2"+ release, yielding Ce_s_e_q/Mn_r_e_l > 200, whereas heated or poisoned BMOs released a significant amount of Mn"2"+ with lower Ce"3"+ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn"2"+ release and enhanced oxidative Ce"3"+ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce"3"+ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce"3"+ oxidation at the solid phase produced through primary Ce"3"+ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce"3"+ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO_2 (CeO_2_,_B_M_O) showed faster auto-catalytic Ce"3"+ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce"3"+ oxidation on CeO_2_,_B_M_O was two orders of magnitude higher. Consequently, we concluded that Ce"3"+ contact with BMOs sequesters Ce"3"+ through two oxidation paths: primary Ce"3

On the deposition parameters of indium oxide (IO) and tin oxide (TO) by reactive evaporation technique

International Nuclear Information System (INIS)

Hassan, F.; Abdullah, A.H.; Salam, R.

1990-01-01

Thin films of tin oxide (TO) and indium oxide (IO) are prepared by the reactive evaporation technique, where indium or tin sources are evaporated and made to react with oxygen gas injected close to the substrate. In both depositions a substrate temperature of 380 0 C and a chamber pressure of 2x10 -5 mbar are utilized, but however different oxygen flow rates has been maintained. For TO, the deposition rate is found to be constant up to about 55 minutes of deposition time with a deposition rate of about 0.10 A/s, but for longer deposition time the deposition rate increases rapidly up to about 0.30 A/s. The IO displays a higher deposition rate of about 0.80 A/s over a deposition time 30 minutes, beyond which the deposition rate increases gradually

High temperature oxidation of β-NbTi alloys

International Nuclear Information System (INIS)

Parida, S.C.; Gupta, N.K.; Rama Rao, G.A.; Sen, B.K.; Krishnan, K.

2008-01-01

The isothermal oxidation kinetics of pure Ti metal and two different β-NbTi alloys with compositions of 85 and 75 at.% Ti were studied using thermogravimetric technique in the temperature range of 1073-1323 K at an interval of 50 K. The value of the power exponent n of the rate equation was found to be close to one suggesting that each reaction follows first order kinetic rate law. X-ray diffraction analysis of oxidation products at each temperature revealed the simultaneous formation of TiO 2 and TiNb 2 O 7 . The rate constants and the activation energies of oxidation reactions for each alloy compositions were evaluated. (author)

Oxidation stability of rapeseed biodiesel/petroleum diesel blends

DEFF Research Database (Denmark)

Østerstrøm, Freja From; Anderson, James E.; Mueller, Sherry A.

2016-01-01

of the oxidation of a biodiesel fuel blend consisting of 30% (v/v) rapeseed methyl ester in petroleum diesel (B30) was conducted at 70 and 90 °C with three aeration rates. Oxidation rates increased with increasing temperature as indicated by decreases in induction period (Rancimat), concentrations of unsaturated...

Iron-oxidation processes in an electroflocculation (electrocoagulation) cell

Energy Technology Data Exchange (ETDEWEB)

Sasson, Moshe Ben, E-mail: mosheinspain@hotmail.com [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, Hebrew University of Jerusalem, Rehovot 76100 (Israel); Calmano, Wolfgang [Institute of Environmental Technology and Energy Economics, Technical University of Hamburg-Harburg, 21073 Hamburg (Germany); Adin, Avner [Department of Soil and Water Sciences, Robert H. Smith Faculty of Agriculture, Food and Environment, Hebrew University of Jerusalem, Rehovot 76100 (Israel)

2009-11-15

The processes of iron oxidation in an electroflocculation cell were investigated for a pH range of 5-9 and electric currents of 0.05-0.4 A (equivalent current densities of 8.6-69 A/m{sup 2}). At all pH values and electric currents investigated, it was demonstrated and proven that for all practical purposes, the form of iron that dissolves from the anode is Fe{sup 2+} (ferrous). The difference between the amount of theoretical dissolution as calculated by Faraday's law and the amount of observed dissolved iron ions may indicate two phenomena in electrochemical cells. The first is possible dissolution of the anode even without the operation of an electric current; this led to higher theoretical dissolution rates at lower pH. The second is the participation of some of the electrons of the electric current in reactions other than anode dissolution which led to lower theoretical dissolution rates at higher pH. Those other reactions did not lead to an increase in the local oxidation saturation level near the anode and did not affect iron-oxidation rates in the electroflocculation processes. The oxidation rates of the dissolved Fe{sup 2+} (ferrous) to Fe{sup 3+} (ferric) ions in electroflocculation processes were strongly dependent on the pH and were similar to the known oxidation rates of iron in non-electrochemical cells.

Iron-oxidation processes in an electroflocculation (electrocoagulation) cell

International Nuclear Information System (INIS)

Sasson, Moshe Ben; Calmano, Wolfgang; Adin, Avner

2009-01-01

The processes of iron oxidation in an electroflocculation cell were investigated for a pH range of 5-9 and electric currents of 0.05-0.4 A (equivalent current densities of 8.6-69 A/m 2 ). At all pH values and electric currents investigated, it was demonstrated and proven that for all practical purposes, the form of iron that dissolves from the anode is Fe 2+ (ferrous). The difference between the amount of theoretical dissolution as calculated by Faraday's law and the amount of observed dissolved iron ions may indicate two phenomena in electrochemical cells. The first is possible dissolution of the anode even without the operation of an electric current; this led to higher theoretical dissolution rates at lower pH. The second is the participation of some of the electrons of the electric current in reactions other than anode dissolution which led to lower theoretical dissolution rates at higher pH. Those other reactions did not lead to an increase in the local oxidation saturation level near the anode and did not affect iron-oxidation rates in the electroflocculation processes. The oxidation rates of the dissolved Fe 2+ (ferrous) to Fe 3+ (ferric) ions in electroflocculation processes were strongly dependent on the pH and were similar to the known oxidation rates of iron in non-electrochemical cells.

Activity incorporation into zinc doped PWR oxides

International Nuclear Information System (INIS)

Maekelae, Kari

1998-01-01

Activity incorporation into the oxide layers of PWR primary circuit constructional materials has been studied in Halden since 1993. The first zinc injection tests showed that zinc addition resulted in thinner oxide layers on new metal surfaces and reduced further incorporation of activity into already existing oxides. These tests were continued to find out the effects of previous zinc additions on the pickup of activity onto the surface oxides which were subsequently exposed to zinc-free coolant. The results showed that previous zinc addition will continue to reduce the rate of Co-60 build-up on out-of-core surfaces in subsequent exposure to zinc-free coolants. However, the previous Zn free test was performed for a relatively short period of time and the water chemistry programme was continued to find out the long term effects for extended periods without zinc. The activity incorporation into the stainless steel oxides started to increase as soon as zinc dosing to the coolant was stopped. The Co-60 concentration was lowest on all of the coupons which were first oxidised in Zn containing primary coolant. After the zinc injection period the thickness of the oxides increased, but activity in the oxide films did not increase at the same rate. This could indicate that zinc in the oxide blocks the adsorption sites for Co-60 incorporation. The Co-60 incorporation rate into the oxides on Inconel 600 seemed to be linear whether the oxide was pre-oxidised with or without Zn. The results indicate that zinc can either replace or prevent cobalt transport in the oxides. The results show that for zinc injection to be effective it should be carried out continuously. Furthermore the actual mechanism by which Zn inhibits the activity incorporation into the oxides is still not clear. Therefore, additional work has to follow with specified materials to verify the conclusions drawn in this work. (author)

Reduced water vapor transmission rates of low-temperature solution-processed metal oxide barrier films via ultraviolet annealing

Energy Technology Data Exchange (ETDEWEB)

Park, Seonuk; Jeong, Yong Jin; Baek, Yonghwa; Kim, Lae Ho; Jang, Jin Hyuk; Kim, Yebyeol [POSTECH Organic Electronics Laboratory, Polymer Research Institute, Department of Chemical Engineering, Pohang University of Science and Technology, Pohang, 790-784 (Korea, Republic of); An, Tae Kyu [Department of Polymer Science & Engineering, Korea National University of Transportation, 50 Daehak-Ro, Chungju (Korea, Republic of); Nam, Sooji, E-mail: sjnam15@etri.re.kr [Information Control Device Section, Electronics and Telecommunications Research Institute, Daejeon, 305-700 (Korea, Republic of); Kim, Se Hyun, E-mail: shkim97@yu.ac.kr [School of Chemical Engineering, Yeungnam University, Gyeongsan, North Gyeongsang 712-749 (Korea, Republic of); Jang, Jaeyoung, E-mail: jyjang15@hanyang.ac.kr [Department of Energy Engineering, Hanyang University, Seoul, 133-791 (Korea, Republic of); Park, Chan Eon, E-mail: cep@postech.ac.kr [POSTECH Organic Electronics Laboratory, Polymer Research Institute, Department of Chemical Engineering, Pohang University of Science and Technology, Pohang, 790-784 (Korea, Republic of)

2017-08-31

Highlights: • Sol-gel-derived aluminum oxide thin films were prepared using ultraviolet (UV) annealing. • UV irradiation dramatically promoted the densification of AlO{sub x} during the annealing stage, thereby forming a close-packed AlO{sub x} film. • The resulting AlO{sub x} films deposited on polymer substrates exhibited good water vapor blocking properties with low water vapor transmission rates (WVTRs). - Abstract: Here, we report the fabrication of low-temperature sol-gel-derived aluminum oxide (AlO{sub x}) films via ultraviolet (UV) annealing and the investigation of their water vapor blocking properties by measuring the water vapor transmission rates (WVTRs). The UV annealing process induced the formation of a dense metal-oxygen-metal bond (Al-O-Al structure) at low temperatures (<200 °C) that are compatible with commercial plastic substrates. The density of the UV-annealed AlO{sub x} thin film at 180 °C was comparable to that of AlO{sub x} thin films that have been thermally annealed at 350 °C. Furthermore, the UV-annealed AlO{sub x} thin films exhibited a high optical transparency in the visible region (>99%) and good electrical insulating properties (∼10{sup −7} A/cm{sup 2} at 2 MV/cm). Finally, we confirmed that a dense AlO{sub x} thin film was successfully deposited onto the plastic substrate via UV annealing at low temperatures, leading to a substantial reduction in the WVTRs. The Ca corrosion test was used to measure the WVTRs of AlO{sub x} thin films deposited onto polyethylene naphthalate or polyimide substrates, determined to be 0.0095 g m{sup −2} day{sup −1} (25 °C, 50% relative humidity) and 0.26 g m{sup −2} day{sup −1}, respectively.

Effect of interval training intensity on fat oxidation, blood lactate and the rate of perceived exertion in obese men

OpenAIRE

Alkahtani, Shaea A; King, Neil A; Hills, Andrew P; Byrne, Nuala M

2013-01-01

Purpose The objectives of this study were to examine the effect of 4-week moderate- and high-intensity interval training (MIIT and HIIT) on fat oxidation and the responses of blood lactate (BLa) and rating of perceived exertion (RPE). Methods Ten overweight/obese men (age?=?29 ?3.7?years, BMI?=?30.7 ?3.4?kg/m2) participated in a cross-over study of 4-week MIIT and HIIT training. The MIIT training sessions consisted of 5-min cycling stages at mechanical workloads 20% above and 20% below 45%VO2...

Comparison of the Isothermal Oxidation Behavior of As-Cast Cu-17 Percent Cr and Cu-17 Percent Cr-5 Percent Al. Part 1; Oxidation Kinetics

Science.gov (United States)

Raj, S. V.

2008-01-01

The isothermal oxidation kinetics of as-cast Cu-17%Cr and Cu-17%Cr-5%Al in air were studied between 773 and 1173 K under atmospheric pressure. These observations reveal that Cu-17%Cr-5%Al oxidizes at significantly slower rates than Cu-17%Cr. The rate constants for the alloys were determined from generalized analyses of the data without an a priori assumption of the nature of the oxidation kinetics. Detailed analyses of the isothermal thermogravimetric weight change data revealed that Cu-17%Cr exhibited parabolic oxidation kinetics with an activation energy of 165.9+/-9.5 kJ/mol. In contrast, the oxidation kinetics for the Cu-17%Cr-5%Al alloy exhibited a parabolic oxidation kinetics during the initial stages followed by a quartic relationship in the later stages of oxidation. Alternatively, the oxidation behavior of Cu-17%CR-5%Al could be better represented by a logarithmic relationship. The parabolic rate constants and activation energy data for the two alloys are compared with literature data to gain insights on the nature of the oxidation mechanisms dominant in these alloys.

Oxidation behaviour of titanium in high temperature steam

International Nuclear Information System (INIS)

Moroishi, Taishi; Shida, Yoshiaki

1978-01-01

The oxidation of pure titanium was studied in superheated steam at 400 -- 550 0 C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500 0 C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550 0 C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450 0 C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO 2 . Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO 2 scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal. (auth.)

Influence of irradiation and radiolysis on the corrosion rates and mechanisms of zirconium alloys

International Nuclear Information System (INIS)

Verlet, Romain

2015-01-01

The nuclear fuel of pressurized water reactors (PWR) in the form of uranium oxide UO 2 pellets (or MOX) is confined in a zirconium alloy cladding. This cladding is very important because it represents the first containment barrier against the release of fission products generated by the nuclear reaction to the external environment. Corrosion by the primary medium of zirconium alloys, particularly the Zircaloy-4, is one of the factors limiting the reactor residence time of the fuel rods (UO 2 pellets + cladding). To optimize core management and to extend the lifetime of the fuel rods in reactor, new alloys based on zirconium-niobium (M5) have been developed. However, the corrosion mechanisms of these are not completely understood because of the complexity of these materials, corrosion environment and the presence of radiation from the nuclear fuel. Therefore, this thesis specifically addresses the effects of radiolysis and defects induced by irradiation with ions in the matrix metal and the oxide layer on the corrosion rate of Zircaloy-4 and M5. The goal is to separate the influence of radiation damage to the metal, that relating to defects created in the oxide and that linked to radiolysis of the primary medium on the oxidation rate of zirconium alloys in reactor. 1) Regarding effect of irradiation of the metal on the oxidation rate: type dislocation loops appear and increase the oxidation rate of the two alloys. For M5, in addition to the first effect, a precipitation of fines needles of niobium reduced the solid solution of niobium concentration in the metal and ultimately in the oxide, which strongly reduces the oxidation rate of the alloy. 2) Regarding the effect of irradiation of the oxide layer on the oxidation rate: defects generated by the nuclear cascades in the oxide increase the oxidation rate of the two materials. For M5, germination of niobium enriched zones in irradiated oxide also causes a decrease of the niobium concentration in solid solution

Viscous properties of aluminum oxide nanotubes and aluminium oxide nanoparticles - silicone oil suspensions

Science.gov (United States)

Thapa, Ram; French, Steven; Delgado, Adrian; Ramos, Carlos; Gutierrez, Jose; Chipara, Mircea; Lozano, Karen

2010-03-01

Electrorheological (ER) fluids consisting of γ-aluminum oxide nanotubes and γ-aluminum oxide nanoparticles dispersed within silicone oil were prepared. The relationship between shear stress and shear rate was measured and theoretically simulated by using an extended Bingham model for both the rheological and electrorheological features of these systems. Shear stress and viscosity showed a sharp increase for the aluminum oxide nanotubes suspensions subjected to applied electric fields whereas aluminum oxide nanoparticles suspensions showed a moderate change. It was found that the transition from liquid to solid state (mediated by the applied electric field) can be described by a power law and that for low applied voltages the relationship is almost linear.

Comparison of Oxidation Characteristics of Selected Nuclear Graphite Grades

International Nuclear Information System (INIS)

Chi, Se Hwan; Kim, Gen Chan

2010-02-01

The oxidation behavior of some selected nuclear graphite grades (i.e., IG-110, IG-430, NBG-18, NBG-25) were compared in view of their filler coke type and the physical property of the grades. Oxidation rates were determined at six temperatures between 600 ∼ 960 .deg. C in air by using a three-zone vertical tube furnace at a 10 L/min air flow rate. The specimens were a cylinder with a 25.4 mm diameter and a 25.4 mm length. Results showed that, even though the four examined nuclear graphite grades showed a highly temperature-sensitive oxidation behavior through out the test temperature range of 600 ∼ 950 .deg. C, the differences between the grades were not significant. The oxidation rates determined for a 5∼10 % weight loss at the six temperatures were nearly the same except for 702 and 808 .deg. C, where the pitch coke graphites showed an apparent decrease in their oxidation rate, more so than the petroleum coke graphites. These effects of the coke type reduced or nearly disappeared with an increasing temperature. The average activation energy determined for 608 ∼ 808 .deg. C was 161.5 ± 7.3 kJ/mol, showing that the dominant oxidation reaction occurred by a chemical control

Ammonia removal in electrochemical oxidation: Mechanism and pseudo-kinetics

International Nuclear Information System (INIS)

Li Liang; Liu Yan

2009-01-01

This paper investigated the mechanism and pseudo-kinetics for removal of ammonia by electrochemical oxidation with RuO 2 /Ti anode using batch tests. The results show that the ammonia oxidation rates resulted from direct oxidation at electrode-liquid interfaces of the anode by stepwise dehydrogenation, and from indirect oxidation by hydroxyl radicals were so slow that their contribution to ammonia removal was negligible under the condition with Cl - . The oxidation rates of ammonia ranged from 1.0 to 12.3 mg N L -1 h -1 and efficiency reached nearly 100%, primarily due to the indirect oxidation of HOCl, and followed pseudo zero-order kinetics in electrochemical oxidation with Cl - . About 88% ammonia was removed from the solution. The removed one was subsequently found in the form of N 2 in the produced gas. The rate at which Cl - lost electrons at the anode was a major factor in the overall ammonia oxidation. Current density and Cl - concentration affected the constant of the pseudo zero-order kinetics, expressed by k = 0.0024[Cl - ] x j. The ammonia was reduced to less than 0.5 mg N L -1 after 2 h of electrochemical oxidation for the effluent from aerobic or anaerobic reactors which treated municipal wastewater. This result was in line with the strict discharge requirements

Nitrous oxide emissions from estuarine intertidal sediments

NARCIS (Netherlands)

Middelburg, J.J.; Klaver, G.; Nieuwenhuize, J.; Markusse, R.M.; Vlug, T.; Nat, F.J.W.A. van der

1995-01-01

From September 1990 through December 1991 nitrous oxide flux measurements were made at 9 intertidal mud flat sites in the Scheldt Estuary. Nitrous oxide release rates were highly variable both between sites and over time at any one site. Annual nitrous oxide fluxes vary from about 10 mmol N m-2 at

Macrokinetics of magnesium sulfite oxidation inhibited by ascorbic acid

International Nuclear Information System (INIS)

Lidong, Wang; Yongliang, Ma; Wendi, Zhang; Qiangwei, Li; Yi, Zhao; Zhanchao, Zhang

2013-01-01

Graphical abstract: Ascorbic acid is used as an inhibitor to retard the oxidation rate of magnesium sulfite. It shows that the oxidation rate would decrease greatly with the rise of initial ascorbic acid concentration, which provides a useful reference for sulfite recovery in magnesia desulfurization. -- Highlights: • We studied the kinetics of magnesium sulfite oxidation inhibited by ascorbic acid. • The oxidation process was simulated by a three-phase model and proved by HPLC–MS. • We calculated the kinetic parameters of intrinsic oxidation of magnesium sulfite. -- Abstract: Magnesia flue gas desulfurization is a promising process for small to medium scale industrial coal-fired boilers in order to reduce sulfur dioxide emissions, in which oxidation control of magnesium sulfite is of great importance for the recycling of products. Effects of four inhibitors were compared by kinetic experiments indicating that ascorbic acid is the best additive, which retards the oxidation process of magnesium sulfite in trace presence. The macrokinetics of magnesium sulfite oxidation inhibited by ascorbic acid were studied. Effects of the factors, including ascorbic acid concentration, magnesium sulfite concentration, oxygen partial pressure, pH, and temperature, were investigated in a stirred reactor with bubbling. The results show that the reaction rate is −0.55 order in ascorbic acid, 0.77 in oxygen partial pressure, and zero in magnesium sulfite concentration, respectively. The apparent activation energy is 88.0 kJ mol −1 . Integrated with the kinetic model, it is concluded that the oxidation rate of magnesium sulfite inhibited by ascorbic acid is controlled by the intrinsic chemical reaction. The result provides a useful reference for sulfite recovery in magnesia desulfurization

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

Effects of stress on the oxide layer thickness and post-oxidation creep strain of zircaloy-4

International Nuclear Information System (INIS)

Lim, Sang Ho; Yoon, Young Ku

1986-01-01

Effects of compressive stress generated in the oxide layer and its subsequent relief on oxidation rate and post-oxidation creep characteristics of zircaloy-4 were investigated by oxidation studies in steam with and without applied tensile stress and by creep testing at 700 deg C in high purity argon. The thickness of oxide layer increased with the magnitude of tensile stress applied during oxidation at 650 deg C in steam whereas similar phenomenon was not observed during oxidation at 800 deg C. Zircaloy-4 specimens oxidized at 600 deg C in steam without applied stress exhibited higher creep strain than that shown by unoxidized specimens when creep-tested in argon. Zircaloy-4 specimens oxidized at 600 deg C steam under the applied stress of 8.53MPa and oxidized at 800 deg C under the applied stress of 0 and 8.53MPa exhibited lower strain than that shown by unoxidized specimen. The above experimental results were accounted for on the basis of interactions among applied stress during oxidation, compressive stress generated in the oxide layer and elasticity of zircaloy-4 matrix. (Author)

Practical considerations of pyrite oxidation control in uranium tailings

International Nuclear Information System (INIS)

1984-05-01

The problems posed by the oxidation of pyrite in uranium tailings include the generation of sulfuric acid and acid sulfate metal salts. These have substantial negative impacts on watercourse biota by themselves, and the lowered pH levels tend to mobilize heavy metals present in the tailings the rate of oxidation of pyrite at lower pH levels is catalyzed by sulfur and iron oxidizing bacteria present in soils. No single clear solution to the problems came from this study. Exclusion of air is a most important preventative of bacterial catalysis of oxidation. Bactericides, chemically breaking the chain of integrated oxidation reactions, maintaining anaerobic conditions, or maintaining a neutral or alkaline pH all reduce the oxidation rate. Removal of pyrite by flotation will reduce but not eliminate the impact of pyrite oxidation. Controlled oxidation of the remaining sulfide in the flotation tails would provide an innocuous tailing so far as acidity generation is concerned

The high temperature oxidation behaviour of austenitic stainless steels

International Nuclear Information System (INIS)

Hales, R.

1977-04-01

High temperature annealing in a dynamic vacuum has been utilised to induce the growth of duplex oxide over the whole surface of stainless steel specimens. It is found that duplex oxide grows at a rate which does not obey a simple power law. The oxidation kinetics and oxide morphology have also been studied for a series of ternary austenitic alloys which cover a range of composition between 5 and 20% chromium. A model has been developed to describe the formation of duplex oxide and the subsequent formation of a 'healing layer' which virtually causes the oxidation process to stop. This phase tends to form at grain boundaries and a relationship has been derived for the reaction kinetics which relates the reaction rate with grain size of the substrate. (author)

Oxidative deterioration of pork during superchilling storage.

Science.gov (United States)

Pomponio, Luigi; Ruiz-Carrascal, Jorge

2017-12-01

In superchilling (SC), meat is kept at temperatures around 1 °C below its initial freezing point, leading to a significant increase in shelf life. This study aimed to address the oxidative changes taking place in pork loins during prolonged storage at SC temperature. Loins were stored either at chilling (CH) conditions (2-4 °C) for 4 weeks or at SC temperature (around -1 °C) for 12 weeks. Storage at SC temperature diminished the rate of lipid and protein oxidation and discoloration in pork loins, so that final levels of most oxidation products and instrumental color values after 12 weeks of SC storage were similar to those after 4 weeks at CH conditions. However, hexanal content peaked by the end of SC storage, pointing to a potential accumulation of compounds from lipid oxidation during SC storage. SC storage of pork slows down the rate of lipid and protein oxidation. However, accumulation of volatile compounds from lipid oxidation could be a limiting factor for shelf life. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Dissolution of Fe(III) (hydr) oxides by metal-EDTA complexes

Science.gov (United States)

Ngwack, Bernd; Sigg, Laura

1997-03-01

The dissolution of Fe(III)(hydr)oxides (goethite and hydrous ferric oxide) by metal-EDTA complexes occurs by ligand-promoted dissolution. The process is initiated by the adsorption of metal-EDTA complexes to the surface and is followed by the dissociation of the complex at the surface and the release of Fe(III)EDTA into solution. The dissolution rate is decreased to a great extent if EDTA is complexed by metals in comparison to the uncomplexed EDTA. The rate decreases in the order EDTA CaEDTA ≫ PbEDTA > ZnEDTA > CuEDTA > Co(II)EDTA > NiEDTA. Two different rate-limiting steps determine the dissolution process: (1) detachment of Fe(III) from the oxide-structure and (2) dissociation of the metal-EDTA complexes. In the case of goethite, step 1 is slower than step 2 and the dissolution rates by various metals are similar. In the case of hydrous ferric oxide, step 2 is rate-limiting and the effect of the complexed metal is very pronounced.

Isothermal oxidation behavior of ternary Zr-Nb-Y alloys at high temperature

Energy Technology Data Exchange (ETDEWEB)

Prajitno, Djoko Hadi, E-mail: djokohp@batan.go.id [Research Center for Nuclear Materials and Radiometry, Jl. Tamansari 71, Bandung 40132 (Indonesia); Soepriyanto, Syoni; Basuki, Eddy Agus [Metallurgy Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia); Wiryolukito, Slameto [Materials Engineering, Institute Technology Bandung, Jl. Ganesha 10, Bandung 40132 (Indonesia)

2014-03-24

The effect of yttrium content on isothermal oxidation behavior of Zr-2,5%Nb-0,5%Y, Zr-2,5%Nb-1%Y Zr-2,5%Nb-1,5%Y alloy at high temperature has been studied. High temperature oxidation carried out at tube furnace in air at 600,700 and 800°C for 1 hour. Optical microscope is used for microstructure characterization of the alloy. Oxidized and un oxidized specimen was characterized by x-ray diffraction. In this study, kinetic oxidation of Zr-2,5%Nb with different Y content at high temperature has also been studied. Characterization by optical microscope showed that microstructure of Zr-Nb-Y alloys relatively unchanged and showed equiaxed microstructure. X-ray diffraction of the alloys depicted that the oxide scale formed during oxidation of zirconium alloys is monoclinic ZrO2 while unoxidised alloy showed two phase α and β phase. SEM-EDS examination shows that depletion of Zr composition took place under the oxide layer. Kinetic rate of oxidation of zirconium alloy showed that increasing oxidation temperature will increase oxidation rate but increasing yttrium content in the alloys will decrease oxidation rate.

Economic analysis of ultrasound-assisted oxidative desulfurization

OpenAIRE

Anderson, K.; Atkins, M.P.; Borges, P; Chan, Z.P.; Rafeen, M.S.; Sebran, N.H.; van der Pool, E; Vleeming, J.H.

2017-01-01

Oxidative desulfurization is a method of removing sulfur from diesel fuel that has the potential to compete with conventional hydrodesulfurization processes in refineries. Ultrasound has been shown to greatly increase peroxide oxidation rates of sulfur compounds and can thereby enhance the technology. Through the use of conceptual design modeling, this article critically assesses a range of novel process options. Calculations show that the rate enhancement achieved by ultrasound can translate...

Oxidation and dissolution of UO{sub 2} in bicarbonate media: Implications for the spent nuclear fuel oxidative dissolution mechanism

Energy Technology Data Exchange (ETDEWEB)

Gimenez, J. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain)]. E-mail: francisco.javier.gimenez@upc.edu; Clarens, F. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Casas, I. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Rovira, M. [CTM Centre Tecnologic, Avda. Bases de Manresa 1. 08240 Manresa (Spain); Pablo, J. de [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Bruno, J. [Enresa-Enviros Environmental Science and Waste Management Chair, UPC, Jordi Girona 1-3 B2, 08034 Barcelona (Spain)

2005-10-15

The objective of this work is to study the UO{sub 2} oxidation by O{sub 2} and dissolution in bicarbonate media and to extrapolate the results obtained to improve the knowledge of the oxidative dissolution of spent nuclear fuel. The results obtained show that in the studied range the oxygen consumption rate is independent on the bicarbonate concentration while the UO{sub 2} dissolution rate does depend on. Besides, at 10{sup -4} mol dm{sup -3} bicarbonate concentration, the oxygen consumption rate is almost two orders of magnitude higher than the UO{sub 2} dissolution rate. These results suggest that at low bicarbonate concentration (<10{sup -2} mol dm{sup -3}) the alteration of the spent nuclear fuel cannot be directly derived from the measured uranium concentrations in solution. On the other hand, the study at low bicarbonate concentrations of the evolution of the UO{sub 2} surface at nanometric scale by means of the SFM technique shows that the difference between oxidation and dissolution rates is not due to the precipitation of a secondary solid phase on UO{sub 2}.

Biphasic oxidation of oxy-hemoglobin in bloodstains.

Directory of Open Access Journals (Sweden)

Rolf H Bremmer

Full Text Available BACKGROUND: In forensic science, age determination of bloodstains can be crucial in reconstructing crimes. Upon exiting the body, bloodstains transit from bright red to dark brown, which is attributed to oxidation of oxy-hemoglobin (HbO(2 to met-hemoglobin (met-Hb and hemichrome (HC. The fractions of HbO(2, met-Hb and HC in a bloodstain can be used for age determination of bloodstains. In this study, we further analyze the conversion of HbO(2 to met-Hb and HC, and determine the effect of temperature and humidity on the conversion rates. METHODOLOGY: The fractions of HbO(2, met-Hb and HC in a bloodstain, as determined by quantitative analysis of optical reflectance spectra (450-800 nm, were measured as function of age, temperature and humidity. Additionally, Optical Coherence Tomography around 1300 nm was used to confirm quantitative spectral analysis approach. CONCLUSIONS: The oxidation rate of HbO(2 in bloodstains is biphasic. At first, the oxidation of HbO(2 is rapid, but slows down after a few hours. These oxidation rates are strongly temperature dependent. However, the oxidation of HbO(2 seems to be independent of humidity, whereas the transition of met-Hb into HC strongly depends on humidity. Knowledge of these decay rates is indispensable for translating laboratory results into forensic practice, and to enable bloodstain age determination on the crime scene.

The upper and lower limits of the mechanistic stoichiometry of mitochondrial oxidative phosphorylation. Stoichiometry of oxidative phosphorylation.

Science.gov (United States)

Beavis, A D; Lehninger, A L

1986-07-15

Determination of the intrinsic or mechanistic P/O ratio of oxidative phosphorylation is difficult because of the unknown magnitude of leak fluxes. Applying a new approach developed to overcome this problem (see our preceding paper in this journal), the relationships between the rate of O2 uptake [( Jo)3], the net rate of phosphorylation (Jp), the P/O ratio, and the respiratory control ratio (RCR) have been determined in rat liver mitochondria when the rate of phosphorylation was systematically varied by three specific means. (a) When phosphorylation is titrated with carboxyatractyloside, linear relationships are observed between Jp and (Jo)3. These data indicate that the upper limit of the mechanistic P/O ratio is 1.80 for succinate and 2.90 for 3-hydroxybutyrate oxidation. (b) Titration with malonate or antimycin yields linear relationships between Jp and (Jo)3. These data give the lower limit of the mechanistic P/O ratio of 1.63 for succinate and 2.66 for 3-hydroxybutyrate oxidation. (c) Titration with a protonophore yields linear relationships between Jp, (Jo)3, and (Jo)4 and between P/O and 1/RCR. Extrapolation of the P/O ratio to 1/RCR = 0 yields P/O ratios of 1.75 for succinate and 2.73 for 3-hydroxybutyrate oxidation which must be equal to or greater than the mechanistic stoichiometry. When published values for the H+/O and H+/ATP ejection ratios are taken into consideration, these measurements suggest that the mechanistic P/O ratio is 1.75 for succinate oxidation and 2.75 for NADH oxidation.

Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation

International Nuclear Information System (INIS)

Moradmand Jalali, Hamed; Bashiri, Hadis; Rasa, Hossein

2015-01-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO 2 , ZnO and ZrO 2 ) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO 2 (rutile and anatase), ZnO and ZrO 2 . • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained

Low temperature ozone oxidation of solid waste surrogates

Science.gov (United States)

Nabity, James A.; Lee, Jeffrey M.

2015-09-01

Solid waste management presents a significant challenge to human spaceflight and especially, long-term missions beyond Earth orbit. A six-month mission will generate over 300 kg of solid wastes per crewmember that must be dealt with to eliminate the need for storage and prevent it from becoming a biological hazard to the crew. There are several methods for the treatment of wastes that include oxidation via ozone, incineration, microbial oxidation or pyrolysis and physical methods such as microwave drying and compaction. In recent years, a low temperature oxidation process using ozonated water has been developed for the chemical conversion of organic wastes to CO2 and H2O. Experiments were conducted to evaluate the rate and effectiveness with which ozone oxidized several different waste materials. Increasing the surface area by chopping or shredding the solids into small pieces more than doubled the rate of oxidation. A greater flow of ozone and agitation of the ozonated water system also increased processing rates. Of the materials investigated, plastics have proven the most difficult to oxidize. The processing of plastics above the glass transition temperatures caused the plastics to clump together which reduced the exposed surface area, while processing at lower temperatures reduced surface reaction kinetics.

Catalytic activity of oxide cerium-molybdenum-tellurium catalysts in oxidation ammonolysis

International Nuclear Information System (INIS)

Dzhordano, N.; Bart, D.; Madzhori, R.

1984-01-01

A commercial catalyst containing a mixture of Ce-, Mo-, Te oxides deposited on SiO 2 is shown to manifest a high efficiency in oxidative ammonolysis of propylene (C 3 - ) to acrylonitrile (AN). The dependence of the catalytic properties on the catalyst composition and reaction conditions is studied. It is established that three-component mixtures are more active and selective than the systems with a lesser number of components. Using the catalyst with the optimum ratio of constituent oxides in a microreactor at 440 deg enabled one to achieve initial selectivity in terms of AN equal to 82.5% at 97% conversion of C 3 - . Acrolein, acetonitrile, HCN and nitrogen oxides are the reaction by-products. A supposition is made that the reaction proceeds via the formation of π-compleXes on the centres of Te(4). Setective oxidation occurs on oxygen atoms bonded with the Mo(6) ions. Tellurium enhances the molybdenum reducibleness due to delocalization of electrons, whereas the cerium addition to the mixture of tellurium- and molybdenum oxides increases the rate of molybdenum reoxidation and thus enhances the catalytic system stability

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.

High pressure oxidation of sponge-Zr in steam/hydrogen mixtures

International Nuclear Information System (INIS)

Kim, Y.S.

1997-01-01

A thermogravimetric apparatus for operation in 1 and 70 atm steam-hydrogen or steam-helium mixtures was used to investigate the oxidation kinetics of sponge-Zr containing 215 ppm Fe. Weight-gain rates, reflecting both oxygen and hydrogen uptake, were measured in the temperature range 350-400 C. The specimens consisted of thin sponge-Zr layers metallurgically bonded to a Zircaloy disk. The edges of the disk specimens were coated with a thin layer of pure gold to avoid the deleterious effect of corners. Following each experiment, the specimens were examined metallographically to reveal the morphology of the oxide and/or hydride formed. Two types of oxide, one black and uniform and the other white and nodular, were observed on sponge-Zr surfaces oxidized in steam environments at 70 atm. The oxidation rate when white-nodular oxide formed was a factor of two higher than that of black-uniform oxide at 400 C for steam contents above 1 mol%. The oxidation rate was independent of total pressure, the carrier gas (H 2 or He) and steam content above ∝1 mol%. The oxidation kinetics of sponge-Zr follows a linear law for maximum reaction times up to ∝6 days. The oxidation rate in steam-hydrogen mixtures at 70 atm total pressure decreases when the steam content approaches the steam-starved region (∝0.5 mol% steam at 400 C and ∝0.02 mol% steam at 350 C). Lower steam concentrations cause massive hydriding of the specimens. Even at steam concentrations above the critical value, direct hydrogen absorption from the gas was manifest by hydrogen pickup fractions greater than unity. (orig.)

AN EXPERIMENTAL INVESTIGATION ON OXIDATIVE STABILITY OF BIODIESEL

Directory of Open Access Journals (Sweden)

Mustafa ÇANAKÇI

2004-02-01

Full Text Available Biodiesel is an alternative fuel for diesel engines that can be produced from renewable feed stocks such as vegetable oil and animal fats. These feed stocks are reacted with an alcohol to produce alkyl monoesters. The obtained ester can be used in conventional diesel engines with little or no modification. Biodiesel, especially if produced from highly unsaturated oils, oxidizes more rapidly than diesel fuel. This paper reports the results of accelerated oxidation tests on biodiesel. These tests show the impact of time, oxygen flow rate, temperature, metals, and feedstock type on the rate of oxidation. Blending with diesel fuel and the addition of antioxidants are also explored. The data indicate that without antioxidants, biodiesel will oxidize very quickly at temperatures typical of diesel engines. This oxidation results in increases in peroxide value, acid value, and viscosity. While the peroxide value generally reaches a plateau of about 350 meq O2/kg, the acid value and viscosity increase monotonically as oxidation proceeds.

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

Science.gov (United States)

Forsey, Steven P; Thomson, Neil R; Barker, James F

2010-04-01

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalenepermanganate. 2010 Elsevier Ltd. All rights reserved.

Development of evaluation method on flow-induced vibration and corrosion of components in two-phase flow by coupled analysis. 5. Evaluation of wall thinning rate with the coupled model of static electrochemical analysis and dynamic double oxide layer analysis

International Nuclear Information System (INIS)

Uchida, Shunsuke; Naitoh, Masanori; Okada, Hidetoshi; Uehara, Yasushi

2008-01-01

Wall thinning rates due to FAC were calculated with the coupled model of static electrochemical analysis and dynamic double oxide layer analysis at the identified danger zone. Anodic and cathodic current densities and ECPs were calculated with the static electrochemistry model and ferrous ion release rate determined by the anodic current density was used as input for the dynamic double oxide layer model. Thickness of oxide film and its characteristics determined by the dynamic double oxide layer model were used for the electrochemistry model to determine the resistances of cathodic current from the bulk to the surface and anodic current from the surface to the bulk. Two models were coupled to determine local corrosion rate and ECP for various corrosive conditions. The calculated results of the coupled models had good agreement with the measured ones. (author)

Supported versus colloidal zinc oxide for advanced oxidation processes

Science.gov (United States)

Laxman, Karthik; Al Rashdi, Manal; Al Sabahi, Jamal; Al Abri, Mohammed; Dutta, Joydeep

2017-07-01

Photocatalysis is a green technology which typically utilizes either supported or colloidal catalysts for the mineralization of aqueous organic contaminants. Catalyst surface area and surface energy are the primary factors determining its efficiency, but correlation between the two is still unclear. This work explores their relation and hierarchy in a photocatalytic process involving both supported and colloidal catalysts. In order to do this the active surface areas of supported zinc oxide nanorods (ZnO NR's) and colloidal zinc oxide nanoparticles (having different surface energies) were equalized and their phenol oxidation mechanism and capacity was analyzed. It was observed that while surface energy had subtle effects on the oxidation rate of the catalysts, the degradation efficiency was primarily a function of the surface area; which makes it a better parameter for comparison when studying different catalyst forms of the same material. Thus we build a case for the use of supported catalysts, wherein their catalytic efficiency was tested to be unaltered over several days under both natural and artificial light, suggesting their viability for practical applications.

Oxidation of coals in the course of mechanical treatment

Energy Technology Data Exchange (ETDEWEB)

A.G. Proidakov; G.A. Kalabin [Irkutsk State University, Irkutsk (Russian Federation)

2009-04-15

The results of a study of coal oxidation under stationary conditions and during mechanical treatment are presented. A considerable increase in the reaction rate constants of coal oxidation during mechanical treatment because of oxidative mechanical degradation was found.

Transmission Congestion Management using a Wind Integrated Compressed Air Energy Storage System

Directory of Open Access Journals (Sweden)

S. Gope

2017-08-01

Full Text Available Transmission congestion is a vital problem in the power system security and reliability sector. To ensure the stable operation of the system, a congestion free power network is desirable. In this paper, a new Congestion Management (CM technique, the Wind integrated Compressed Air Energy Storage (WCAES system is used to alleviate transmission congestion and to minimize congestion mitigation cost. The CM problem has been solved by using the Generator Sensitivity Factor (GSF and the Bus Sensitivity Factor (BSF. BSF is used for finding the optimal location of WCAES in the system. GSF with a Moth Flame Optimization (MFO algorithm is used for rescheduling the generators to alleviate congestion and to minimize congestion cost by improving security margin. The impact of the WCAES system is tested with a 39 bus system. To validate this approach, the same problem has been solved with a Particle Swarm Optimization (PSO algorithm and the obtained results are compared with the ones from the MFO algorithm.

Kinetic Studies of Catalytic Oxidation of Cyclohexene Using ...

African Journals Online (AJOL)

Cyclohexene was oxidized using chromium (VI) oxide (CrO3) in pure acetic acid medium. The products of oxidation were analysed using simple qualitative analysis, IR spectroscopy and Gas chromatography-Mass spectrometry (GC/MS). Kinetics studies were carried out to determine the order of reaction, rate constant and ...

Kinetics and mechanisms of the oxidation of cobalt at 600-8000C

International Nuclear Information System (INIS)

Hsu, H.S.; Yurek, G.J.

1982-01-01

Two-phase layered scales comprising CoO and Co 3 O 4 formed on cobalt during oxidation at 600 0 , 700 0 , and 800 0 C and at oxygen partial pressures in the range 0.001-1 atm. The kinetics, which were obtained by thermogravimetric analysis, obeyed a parabolic rate law after an initial, nonparabolic stage of oxidation. The monoxide consisted of relatively large grains (10μ) and the spinel comprised small grains (3μ) for all conditions of oxidation. Grain boundary diffusion of cations played a significant role in the growth of the spinal layer. Thermogravimetric data and the steady-state ratio of the oxide layer thicknesses were employed to calculate the rates of thickening of the individual oxide layers and the rate of oxidation of CoO to Co 3 O 4

Oxidation behaviour of U2Ti alloy in dry air

International Nuclear Information System (INIS)

Roy, S.P.; Gupta, N.K.; Jat, Ram Avtar; Parida, S.C.; Mukerjee, S.K.

2016-01-01

U 2 Ti alloy is being considered as promising storage material for storage of hydrogen isotopes. However, the absorption capacity of this reactive alloy can be affected due to presence of oxygen in the process gas. Hence, it is necessary to know the kinetic of this alloy in presence of oxygen. In this study, U 2 Ti alloy was prepared by arc melting method followed by vacuum annealing. The alloy was characterized by XRD, SEM and EDX methods. The isothermal oxidation behaviour of U 2 Ti alloy was investigated in the temperature range of 548-623 K in dry air for 24 hours by using thermo gravimetric technique. The oxidation curves are shown. The oxidation curves were analysed using the rate equation: (Δm/a) n = kt, where, (Δm/a) is the mass gain per unit area, n is the power exponent, k is the rate constant and t is time in (seconds). Analysis of the results shows that the oxidation reaction follows linear rate law (n ~ 1). Using the linear rate law, the rate constant (k) of oxidation reaction was evaluated at each temperature in the range 548-623 K. The variation of (ln k) with reciprocal temperature is shown. The activation energy of this oxidation reaction in the temperature range 548-623 K was calculated using the Arrhenius equation and found to be 76 kJ/mol. The XRD analysis of the oxidation products was found to be U 3 O 8 and TiO 2 . (author)

Oxidation and corrosion of silicon-based ceramics and composites

International Nuclear Information System (INIS)

Jacobson, N.S.; Fox, D.S.; Smialek, J.L.

1997-01-01

Silica scales exhibit slow growth rates and a low activation energy. Thus silica-protected materials are attractive high temperature structural materials for their potentially excellent oxidation resistance and well-documented high temperature strength. This review focuses on silicon carbide, silicon nitride, and composites of these materials. It is divided into four parts: (i) Fundamental oxidation mechanisms, (ii) Special properties of silica scales, (iii) Protective coatings, and (iv) Internal oxidation behavior of composites. While the fundamental oxidation mechanism of SiC is understood, there are still many questions regarding the oxidation mechanism of Si 3 N 4 . Silica scales exhibit many unique properties as compared to chromia and alumina. These include slower growth rates, SiO(g) formation, sensitivity to water vapor and impurities, and dissolution by basic molten salts. Protective coatings can limit the deleterious effects. The fourth area-internal oxidation of fibers and fiber coatings in composites-has limited the application of these novel materials. Strategies for understanding and limiting this internal oxidation are discussed. (orig.)

Status of Chronic Oxidation Studies of Graphite

Energy Technology Data Exchange (ETDEWEB)

Contescu, Cristian I. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert W. [Univ. of Tennessee, Knoxville, TN (United States)

2016-05-01

Graphite will undergo extremely slow, but continuous oxidation by traces of moisture that will be present, albeit at very low levels, in the helium coolant of HTGR. This chronic oxidation may cause degradation of mechanical strength and thermal properties of graphite components if a porous oxidation layer penetrates deep enough in the bulk of graphite components during the lifetime of the reactor. The current research on graphite chronic oxidation is motivated by the acute need to understand the behavior of each graphite grade during prolonged exposure to high temperature chemical attack by moisture. The goal is to provide the elements needed to develop predictive models for long-time oxidation behavior of graphite components in the cooling helium of HTGR. The tasks derived from this goal are: (1) Oxidation rate measurements in order to determine and validate a comprehensive kinetic model suitable for prediction of intrinsic oxidation rates as a function of temperature and oxidant gas composition; (2) Characterization of effective diffusivity of water vapor in the graphite pore system in order to account for the in-pore transport of moisture; and (3) Development and validation of a predictive model for the penetration depth of the oxidized layer, in order to assess the risk of oxidation caused damage of particular graphite grades after prolonged exposure to the environment of helium coolant in HTGR. The most important and most time consuming of these tasks is the measurement of oxidation rates in accelerated oxidation tests (but still under kinetic control) and the development of a reliable kinetic model. This report summarizes the status of chronic oxidation studies on graphite, and then focuses on model development activities, progress of kinetic measurements, validation of results, and improvement of the kinetic models. Analysis of current and past results obtained with three grades of showed that the classical Langmuir-Hinshelwood model cannot reproduce all

Activity of molybdenum-containing oxide catalysts in the reaction of ethane oxidation

International Nuclear Information System (INIS)

Konovalov, V.I.; Ehpova, T.I.; Shchukin, V.P.; Averbukh, A.Ya.

1977-01-01

Investigation results concerning the catalytic activity of molybdenum-containing catalysts in ethane oxidation reaction are presented. It has been found that the greatest activity in the temperature range from 450 to 600 deg C is exhibited by cobalt-molybdenum catalyst; at 600 deg C bismuth-molybdenum catalyst is the most active. Nickel-molybdenum catalyst is selective and active with respect to ethylene. Iron- and manganese-molybdenum catalysts do not show high ethane oxidation rates and their selectivity is insignificant

Microbial Fe(II) oxidation at circumneutral pH: Reaction kinetics, mineral products, and distribution of neutrophilic iron oxidizers in wetland soils

NARCIS (Netherlands)

Vollrath, S.

2012-01-01

Multiple studies have shown that neutrophilic Fe(II) oxidizers can conserve energy from Fe(II) oxidation, however, it is still unclear how they can compete against the fast abiotic reaction at neutral pH, or to which extent these bacteria increase the overall Fe(II) oxidation rate. Similar to

Oxidation behaviour of titanium in high temperature steam

Energy Technology Data Exchange (ETDEWEB)

Moroishi, T; Shida, Y [Sumitomo Metal Industries Ltd., Amagasaki, Hyogo (Japan). Central Research Labs.

1978-03-01

The oxidation of pure titanium was studied in superheated steam at 400 -- 550/sup 0/C. The effects of prior cold working and several heat treatment conditions on the oxidation were examined and also the effects of the addition of small amounts of iron and oxygen were investigated. The oxidation mechanism of pure titanium is discussed in relation to the scale structure and the oxidation kinetics. Hydrogen absorption rate was also measured. As a result, the following conclusions were drawn: (1) The oxidation of pure titanium in steam was faster than in air and breakaway oxidation was observed above 500/sup 0/C after the specimen had gained a certain weight. Prior cold working and heat treatment conditions scarcely affected the oxidation rate, whereas the specimen containing small amounts of iron and oxygen showed a little more rapid oxidation. (2) At 500 and 550/sup 0/C a dark grey inner scale and a yellow-brown outer scale were formed. The outer scale was apt to exfoliate after the occurrence of breakaway oxidation. At 400 and 450/sup 0/C only a dark grey scale was observed. All of these oxides were identified as the rutile type, TiO/sub 2/. Furthermore, the presence of a thin and uniform oxygen rich layer beneath the external scale was confirmed at all test temperatures. (3) The measured weight gain approximately followed the cubic rate law; this would be expected for the following reason; one component of the weight gain is due to the dissolved oxygen, the amount of which remains constant after the early stages of oxidation. The second component is due to the parabolic growth of the external TiO/sub 2/ scale. When these contributions are added a pseudo-cubic weight gain curve results. (4) It was shown that 50 percent of the hydrogen generated during the oxidation was absorbed into the metal.

Investigation of Zirconium Oxide Films in Different Dissolved Hydrogen Concentration

International Nuclear Information System (INIS)

Kim, Taeho; Choi, Kyoung Joon; Yoo, Seung Chang; Kim, Ji Hyun

2016-01-01

It has been reported that in pre-transition zirconium oxide, the volume fraction of tetragonal zirconium oxide increased near the oxide/metal (O/M) interface, and the sub-stoichiometric zirconium oxide layer was observed. The diffusion of oxygen ion through the oxide layer is the rate-limiting process during the pre-transition oxidation process, and this diffusion mainly occurs in the grain boundaries. The two layered oxide structure is formed in pre-transition oxide for the zirconium alloy in high-temperature water environment. It is known that the corrosion rate is related to the volume fraction of zirconium oxide and the pores in the oxides; therefore, the aim of this paper is to investigate the oxidation behavior in the pre-transition zirconium oxide in high-temperature water chemistry. In this study, in situ Raman and TEM analysis were conducted for investigating the phase transformation of zirconium alloy in primary water. From this study, the following conclusions are drawn: 1. The zirconium alloy was oxidized in primary water chemistry for 100 d, and Raman and TEM were measured after 30, 50, 80, and 100 d from start-up. 2. TEM and FFT analysis showed that the zirconium oxide mostly consisted of the monoclinic phase. The tetragonal zirconium oxide was just found near the O/M interface

A Decade of Improvements for Solid Oxide Electrolysis Cells. Long-Term Degradation Rate from 40%/Kh to 0.4 % Kh

DEFF Research Database (Denmark)

Hauch, Anne; Brodersen, Karen; Chen, Ming

2016-01-01

Solid oxide electrolysis cells (SOEC) have the potential for efficient large-scale conversion from electrical energy to chemical energy stored in fuels, such as hydrogen or synthetic hydrocarbon fuels by use of well-known catalysis processes. Key issues for the break-through of this technology...... are to provide inexpensive, reliable, high performing and long-term stable SOEC for stack and system applications. At DTU Energy (formerly Department of Fuel Cells and Solid State Chemistry, Risø National Laboratory), research within SOEC for more than a decade has led to long-term degradation rates on cell...

A catalytic wet oxidation process for mixed waste volume reduction/recycling

International Nuclear Information System (INIS)

Dhooge, Patrick M.

1992-01-01

Mixed wastes have presented a challenge to treatment and destruction technologies. A recently developed catalytic wet oxidation method has promising characteristics for volume reduction and recycling of mixed wastes. The process utilizes iron (III) as an oxidant in the presence of homogeneous cocatalysts which increase organics' oxidation rates and the rate of oxidation of iron (II) by oxygen. The reaction is conducted in an aqueous mineral acid solution at temperatures of 373 - 573 deg K. The mineral acid should solvate a number of heavy metals, including U and Pu. Studies of reaction rates show that the process can oxidize a wide range of organic compounds including aromatics and chlorinated hydrocarbons. Rate constants in the range of 10 -7 to 10 -4 sec -1 , depending on the cocatalyst, acidity, type of anions, type of organic, temperature, and time. Activation energies ranged from 25. to 32. KJ/mole. Preliminary measurements of the extent of oxidation which could be obtained ranged from 80% for trichloroethylene to 99.8% for 1,2,4-trimethylbenzene; evidence was obtained that absorption by the fluorocarbon liners of the reaction bombs allowed some of the organics to escape exposure to the catalyst solution. The results indicate that complete oxidation of the organics used here, and presumably many others, can be achieved. (author)

High-temperature oxidation kinetics of sponge-based E110 cladding alloy

Science.gov (United States)

Yan, Yong; Garrison, Benton E.; Howell, Mike; Bell, Gary L.

2018-02-01

Two-sided oxidation experiments were recently conducted at 900°C-1200 °C in flowing steam with samples of sponge-based Zr-1Nb alloy E110. Although the old electrolytic E110 tubing exhibited a high degree of susceptibility to nodular corrosion and experienced breakaway oxidation rates in a relatively short time, the new sponge-based E110 demonstrated steam oxidation behavior comparable to Zircaloy-4. Sample weight gain and oxide layer thickness measurements were performed on oxidized E110 specimens and compared to oxygen pickup and oxide layer thickness calculations using the Cathcart-Pawel correlation. Our study shows that the sponge-based E110 follows the parabolic law at temperatures above 1015 °C. At or below 1015 °C, the oxidation rate was very low when compared to Zircaloy-4 and can be represented by a cubic expression. No breakaway oxidation was observed at 1000 °C for oxidation times up to 10,000 s. Arrhenius expressions are given to describe the parabolic rate constants at temperatures above 1015 °C and cubic rate constants are provided for temperatures below 1015 °C. The weight gains calculated by our equations are in excellent agreement with the measured sample weight gains at all test temperatures. In addition to the as-fabricated E110 cladding sample, prehydrided E110 cladding with hydrogen concentrations in the 100-150 wppm range was also investigated. The effect of hydrogen content on sponge-based E110 oxidation kinetics was minimal. No significant difference was found between as-fabricated and hydrided samples with regard to oxygen pickup and oxide layer thickness for hydrogen contents below 150 wppm.

[Solidification of volatile oil with graphene oxide].

Science.gov (United States)

Yan, Hong-Mei; Jia, Xiao-Bin; Zhang, Zhen-Hai; Sun, E; Xu, Yi-Hao

2015-02-01

To evaluate the properties of solidifying volatile oil with graphene oxide, clove oil and zedoary turmeric oil were solidified by graphene oxide. The amount of graphene oxide was optimized with the eugenol yield and curcumol yield as criteria. Curing powder was characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The effects of graphene oxide on dissolution in vitro and thermal stability of active components were studied. The optimum solidification ratio of graphene oxide to volatile oil was 1:1. Dissolution rate of active components had rare influence while their thermal stability improved after volatile oil was solidified. Solidifying herbal volatile oil with graphene oxide deserves further study.

Oxidation catalyst

Science.gov (United States)

Ceyer, Sylvia T.; Lahr, David L.

2010-11-09

The present invention generally relates to catalyst systems and methods for oxidation of carbon monoxide. The invention involves catalyst compositions which may be advantageously altered by, for example, modification of the catalyst surface to enhance catalyst performance. Catalyst systems of the present invention may be capable of performing the oxidation of carbon monoxide at relatively lower temperatures (e.g., 200 K and below) and at relatively higher reaction rates than known catalysts. Additionally, catalyst systems disclosed herein may be substantially lower in cost than current commercial catalysts. Such catalyst systems may be useful in, for example, catalytic converters, fuel cells, sensors, and the like.

Zirconium metal-water oxidation kinetics. III. Oxygen diffusion in oxide and alpha Zircaloy phases

International Nuclear Information System (INIS)

Pawel, R.E.

1976-10-01

The reaction of Zircaloy in steam at elevated temperature involves the growth of discrete layers of oxide and oxygen-rich alpha Zircaloy from the parent beta phase. The multiphase, moving boundary diffusion problem involved is encountered in a number of important reaction schemes in addition to that of Zircaloy-oxygen and can be completely (albeitly ideally) characterized through an appropriate model in terms of oxygen diffusion coefficients and equilibrium concentrations for the various phases. Conversely, kinetic data for phase growth and total oxygen consumption rates can be used to compute diffusion coefficients. Equations are developed that express the oxygen diffusion coefficients in the oxide and alpha phases in terms of the reaction rate constants and equilibrium solubility values. These equations were applied to recent experimental kinetic data on the steam oxidation of Zircaloy-4 to determine the effective oxygen diffusion coefficients in these phases over the temperature range 1000--1500 0 C

Spent fuel. Dissolution and oxidation

International Nuclear Information System (INIS)

Grambow, B.

1989-03-01

Data from studies of the low temperature air oxidation of spent fuel were retrieved in order to provide a basis for comparison between the mechanism of oxidation in air and corrosion in water. U 3 O 7 is formed by diffusion of oxygen into the UO 2 lattice. A diffusion coefficient of oxygen in the fuel matric was calculated for 25 degree C to be in the range of 10 -23 to 10 -25 m 2 /s. The initial rates of U release from spent fuel and from UO 2 appear to be similar. The lowest rates (at 25 degree c >10 -4 g/(m 2 d)) were observed under reducing conditions. Under oxidizing conditions the rates depend mainly of the nature and concentraion of the oxidant and/or on corbonate. In contact with air, typical initial rates at room temperature were in the range between 0.001 and 0.1 g/(m 2 d). A study of apparent U solubility under oxidizing conditions was performed and it was suggested that the controlling factor is the redox potential at the UO 2 surface rather than the E h of the bulk solution. Electrochemical arguments were used to predict that at saturation, the surface potential will eventually reach a value given by the boundaries at either the U 3 O 7 /U 3 O 8 or the U 3 O 7 /schoepite stability field, and a comparison with spent fuel leach data showed that the solution concentration of uranium is close to the calculated U solubility at the U 3 O 7 /U 3 O 8 boundary. The difference in the cumulative Sr and U release was calculated from data from Studsvik laboratory. The results reveal that the rate of Sr release decreases with the square root of time under U-saturated conditions. This time dependence may be rationalized either by grain boundary diffusion or by diffusion into the fuel matrix. Hence, there seems to be a possibility of an agreement between the Sr release data, structural information and data for oxygen diffusion in UO 2 . (G.B.)

High temperature oxidation test of oxide dispersion strengthened (ODS) steel claddings

International Nuclear Information System (INIS)

Narita, Takeshi; Ukai, Shigeharu; Kaito, Takeji; Ohtsuka, Satoshi; Matsuda, Yasushi

2006-07-01

In a feasibility study of ODS steel cladding, its high temperature oxidation resistance was evaluated. Although addition of Cr is effective for preventing high temperature oxidation, excessively higher amount of Cr leads to embrittlement due to the Cr-rich α' precipitate formation. In the ODS steel developed by the Japan Atomic Energy Agency (JAEA), the Cr content is controlled in 9Cr-ODS martensite and 12Cr-ODS ferrite. In this study, high temperature oxidation test was conducted for ODS steels, and their results were compared with that of conventional austenitic stainless steel and ferritic-martensitic stainless steel. Following results were obtained in this study. (1) 9Cr-ODS martensitic and 12Cr-ODS ferritic steel have superior high temperature oxidation resistance compared to 11mass%Cr PNC-FMS and even 17mass% SUS430 and equivalent to austenitic PNC316. (2) The superior oxidation resistance of ODS steel was attributed to earlier formation of the protective alpha-Cr 2 O 3 layer at the matrix and inner oxide scale interface. The grain size of ODS steel is finer than that of PNC-FMS, so the superior oxidation resistance of ODS steel can be attributed to the enhanced Cr-supplying rate throughout the accelerated grain boundary diffusion. Finely dispersed Y 2 O 3 oxide particles in the ODS steel matrix may also stabilized the adherence between the protective alpha-Cr 2 O 3 layer and the matrix. (author)

"A New Class of Creep Resistant Oxide/Oxide Ceramic Matrix Composites"

Energy Technology Data Exchange (ETDEWEB)

Dr. Mohit Jain, Dr. Ganesh Skandan, Prof. Roger Cannon, Rutgers University

2007-03-30

Despite recent progress in the development of SiC-SiC ceramic matrix composites (CMCs), their application in industrial gas turbines for distributed energy (DE) systems has been limited. The poor oxidation resistance of the non-oxide ceramics warrants the use of envrionmental barrier coatings (EBCs), which in turn lead to issues pertaining to life expectancy of the coatings. On the other hand, oxide/oxide CMCs are potential replacements, but their use has been limited until now due to the poor creep resistance at high temperatures, particularly above 1200 oC: the lack of a creep resistant matrix has been a major limiting factor. Using yttrium aluminum garnet (YAG) as the matrix material system, we have advanced the state-of-the-art in oxide/oxide CMCs by introducing innovations in both the structure and composition of the matrix material, thereby leading to high temperature matrix creep properties not achieved until now. An array of YAG-based powders with a unique set of particle characteristics were produced in-house and sintered to full density and compressive creep data was obtained. Aided in part by the composition and the microstructure, the creep rates were found to be two orders of magnitude smaller than the most creep resistant oxide fiber available commercially. Even after accounting for porosity and a smaller matrix grain size in a practical CMC component, the YAG-based matrix material was found to creep slower than the most creep resistant oxide fiber available commercially.

High Current Oxide Cathodes

National Research Council Canada - National Science Library

Luhmann, N

2000-01-01

.... The vacuum are plasma deposition gun developed at Lawrence Berkeley National Laboratory (LBNL) has been used to deposit oxides and nitrides with very precise control over deposition rate and composition.

Metal oxide nanorod arrays on monolithic substrates

Energy Technology Data Exchange (ETDEWEB)

Gao, Pu-Xian; Guo, Yanbing; Ren, Zheng

2018-01-02

A metal oxide nanorod array structure according to embodiments disclosed herein includes a monolithic substrate having a surface and multiple channels, an interface layer bonded to the surface of the substrate, and a metal oxide nanorod array coupled to the substrate surface via the interface layer. The metal oxide can include ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide. The substrate can include a glass substrate, a plastic substrate, a silicon substrate, a ceramic monolith, and a stainless steel monolith. The ceramic can include cordierite, alumina, tin oxide, and titania. The nanorod array structure can include a perovskite shell, such as a lanthanum-based transition metal oxide, or a metal oxide shell, such as ceria, zinc oxide, tin oxide, alumina, zirconia, cobalt oxide, and gallium oxide, or a coating of metal particles, such as platinum, gold, palladium, rhodium, and ruthenium, over each metal oxide nanorod. Structures can be bonded to the surface of a substrate and resist erosion if exposed to high velocity flow rates.

Three Rate-Constant Kinetic Model for Permanganate Reactions Autocatalyzed by Colloidal Manganese Dioxide: The Oxidation of L-Phenylalanine.

Science.gov (United States)

Perez-Benito, Joaquin F; Ferrando, Jordi

2014-12-26

The reduction of permanganate ion to MnO(2)-Mn(2)O(3) soluble colloidal mixed oxide by l-phenylalanine in aqueous phosphate-buffered neutral solutions has been followed by a spectrophotometric method, monitoring the decay of permanganate ion at 525 nm and the formation of the colloidal oxide at 420 nm. The reaction is autocatalyzed by the manganese product, and three rate constants have been required to fit the experimental absorbance-time kinetic data. The reaction shows base catalysis, and the values of the activation parameters at different pHs have been determined. A mechanism including both the nonautocatalytic and the autocatalytic reaction pathways, and in agreement with the available experimental data, has been proposed. Some key features of this mechanism are the following: (i) of the two predominant forms of the amino acid, the anionic form exhibits a stronger reducing power than the zwitterionic form; (ii) the nonautocatalytic reaction pathway starts with the transfer of the hydrogen atom in the α position of the amino acid to permanganate ion; and (iii) the autocatalytic reaction pathway involves the reduction of Mn(IV) to Mn(II) by the amino acid and the posterior reoxidation of Mn(II) to Mn(IV) by permanganate ion.

The rate of aucubin, a secondary metabolite in Plantago lanceolata and potential nitrification inhibitor, needed to reduce ruminant urine patch nitrous oxide emissions

Science.gov (United States)

Gardiner, C. A.; Clough, T.; Cameron, K.; Di, H.; Edwards, G. R.

2017-12-01

Nitrous oxide (N2O) losses derived from grazing ruminant livestock urine patches account for 40% of global N2O emissions. It has been shown that Plantago lanceolata, an herb species used in grazed pastures, contains an active secondary metabolite (aucubin) that has the potential to be excreted by grazing ruminants and inhibit nitrification in the urine patch, a key step in soil N2O production. However, the urinary excretion rate of aucubin needed to significantly reduce urine patch N2O emissions remains unknown. Aucubin was dissolved in bovine urine at three rates (47, 243, and 486 kg ha-1), based on rates used in Dietz et al. (2013) and the calculated highest potential aucubin application rate, from Gardiner et al. (2017). A control, along with a urine treatment and the three aucubin treatments (all urine applied at 700 kg N ha-1), was applied to 20 g soil and incubated in the laboratory for 35 d. Soils were monitored for surface pH, inorganic N concentration (NH4+/NO3-), and gas (N2O and CO2) fluxes. This experiment is currently underway and the results will be presented at the conference. Dietz M, Machill S, Hoffmann H, Schmidtke K 2013. Inhibitory effects of Plantago lanceolata L. on soil N mineralization. Plant and Soil 368: 445-458. Gardiner CA, Clough TJ, Cameron KC, Di HJ, Edwards GR, de Klein CAM 2017. The potential inhibitory effects of Plantago lanceolata and its active secondary metabolite aucubin on soil nitrification and nitrous oxide emissions under ruminant urine patch conditions. Manuscript submitted for publication.

DETERMINATION OF THE RATES AND PRODUCTS OF FERROUS IRON OXIDATION IN ARSENIC-CONTAMINATED POND WATER.

Science.gov (United States)

Dissolved ferrous iron and arsenic in the presence of insufficient oxygenated ground water is released into a pond. When the mixing of ferrous iron and oxygenated water within the pond occurs, the ferrous iron is oxidized and precipitated as an iron oxide. Groups of experiments...

The burnup dependence of light water reactor spent fuel oxidation

International Nuclear Information System (INIS)

Hanson, B.D.

1998-07-01

Over the temperature range of interest for dry storage or for placement of spent fuel in a permanent repository under the conditions now being considered, UO 2 is thermodynamically unstable with respect to oxidation to higher oxides. The multiple valence states of uranium allow for the accommodation of interstitial oxygen atoms in the fuel matrix. A variety of stoichiometric and nonstoichiometric phases is therefore possible as the fuel oxidizers from UO 2 to higher oxides. The oxidation of UO 2 has been studied extensively for over 40 years. It has been shown that spent fuel and unirradiated UO 2 oxidize via different mechanisms and at different rates. The oxidation of LWR spent fuel from UO 2 to UO 2.4 was studied previously and is reasonably well understood. The study presented here was initiated to determine the mechanism and rate of oxidation from UO 2.4 to higher oxides. During the early stages of this work, a large variability in the oxidation behavior of samples oxidized under nearly identical conditions was found. Based on previous work on the effect of dopants on UO 2 oxidation and this initial variability, it was hypothesized that the substitution of fission product and actinide impurities for uranium atoms in the spent fuel matrix was the cause of the variable oxidation behavior. Since the impurity concentration is roughly proportional to the burnup of a specimen, the oxidation behavior of spent fuel was expected to be a function of both temperature and burnup. This report (1) summarizes the previous oxidation work for both unirradiated UO 2 and spent fuel (Section 2.2) and presents the theoretical basis for the burnup (i.e., impurity concentration) dependence of the rate of oxidation (Sections 2.3, 2.4, and 2.5), (2) describes the experimental approach (Section 3) and results (Section 4) for the current oxidation tests on spent fuel, and (3) establishes a simple model to determine the activation energies associated with spent fuel oxidation (Section 5)

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

International Nuclear Information System (INIS)

Ono, Y.; Rachi, T.; Yokouchi, M.; Kamimoto, Y.; Nakajima, A.; Okada, K.

2013-01-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO 2 /apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO 2 )/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acid concentration, the TiO 2 /HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO 2 particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO 2 powder, Degussa P25. The highest rate was obtained in the TiO 2 /HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO 2 photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO 2 /HAp composites compared with the TiO 2 powders

Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate.

Science.gov (United States)

Rodríguez, Eva; Onstad, Gretchen D; Kull, Tomas P J; Metcalf, James S; Acero, Juan L; von Gunten, Urs

2007-08-01

As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.

Anodic oxidation of benzoquinone using diamond anode.

Science.gov (United States)

Panizza, Marco

2014-01-01

The anodic degradation of 1,4-benzoquinone (BQ), one of the most toxic xenobiotic, was investigated by electrochemical oxidation at boron-doped diamond anode. The electrolyses have been performed in a single-compartment flow cell in galvanostatic conditions. The influence of applied current (0.5-2 A), BQ concentration (1-2 g dm(-3)), temperature (20-45 °C) and flow rate (100-300 dm(3) h(-1)) has been studied. BQ decay kinetic, the evolution of its oxidation intermediates and the mineralization of the aqueous solutions were monitored during the electrolysis by high-performance liquid chromatograph (HPLC) and chemical oxygen demand (COD) measurements. The results obtained show that the use of diamond anode leads to total mineralization of BQ in any experimental conditions due to the production of oxidant hydroxyl radicals electrogenerated from water discharge. The decay kinetics of BQ removal follows a pseudo-first-order reaction, and the rate constant increases with rising current density. The COD removal rate was favoured by increasing of applied current, recirculating flow rate and it is almost unaffected by solution temperature.

Oxidation of carbon monoxide by perferrylmyoglobin

DEFF Research Database (Denmark)

Libardi, Silvia H; Skibsted, Leif Horsfelt; Cardoso, Daniel R

2014-01-01

Perferrylmyoglobin is found to oxidize CO in aerobic aqueous solution to CO2. Tryptophan hydroperoxide in the presence of tetra(4-sulfonatophenyl)-porphyrinate-iron(III) or simple iron(II)/(III) salts shows similar reactivity against CO. The oxidation of CO is for tryptophan hydroperoxide concluded...... to depend on the formation of alkoxyl radicals by reductive cleavage by iron(II) or on the formation of peroxyl radicals by oxidative cleavage by iron(III). During oxidation of CO, the tryptophan peroxyl radical was depleted with a rate constant of 0.26 ± 0.01 s(-1) for CO-saturated aqueous solution of pH 7...

High-temperature oxidation of Zircaloy-2 and Zircaloy-4 in steam

International Nuclear Information System (INIS)

Urbanic, V.F.; Heidrick, T.R.

1978-01-01

At temperatures above the (α + β)/β transformation temperature for zirconium alloys, steam reacts with β-Zr to form a superficial layer of zirconium oxide (ZrO 2 ) and an intermediate layer of oxygen-stabilized α-Zr. Reaction kinetics and the rate of growth of the combined (ZrO 2 + α-Zr) layer for Zircaloy-2 and Zircaloy-4 oxidation in steam were measured over the temperature range 1050-1850 o C. The reaction rates for both alloys were similar, obeyed parabolic kinetics and were not limited by gas phase diffusion. The parabolic rate constants were consistently less than those given by the Baker and Just correlation for zirconium oxidation in steam. A discontinuity was found in the temperature dependence of both the reaction rate and the rate of growth of the combined (ZrO 2 + α-Zr) layer. The discontinuity is attributed to a change in the oxide microstructure at the discontinuity temperature, an observation which is consistent with the zirconium-oxygen phase diagram. (author)

New investigations in the USA into formation of nitrogen oxides

Energy Technology Data Exchange (ETDEWEB)

Kotler, V.R.

1983-06-01

This paper discusses laboratory investigations in the USA on air pollution by nitrogen oxides during coal combustion. Laboratory combustors used for combustion of black coal, anthracite and brown coal are described. Measuring systems and measuring instruments used for flue gas analyses and determining nitrogen oxide, hydrocyanic acid and ammonia content in flue gas are evaluated. Effects of excess air on nitrogen oxide formation are analyzed. Analyses show that excess air influences relation between nitrogen oxides, hydrocyanic acid and ammonia. Recommendations on the optimum excess air rate are made. In the case of all coal typs, with the exception of anthracite, the optimum excess air rate is 0.7 which guarantees the highest transformation rate of nitrogen in fuel into molecular nitrogen. Effects of excess air on oxidation of hydrocyanic acid and ammonia are described. The analyses consider effects of excess air on chemical reactions during coal combustion under laboratory conditions. (4 refs.) (In Russian)

Study of photo-oxidative reactivity of sunscreening agents based on photo-oxidation of uric acid by kinetic Monte Carlo simulation

Energy Technology Data Exchange (ETDEWEB)

Moradmand Jalali, Hamed; Bashiri, Hadis, E-mail: hbashiri@kashanu.ac.ir; Rasa, Hossein

2015-05-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO{sub 2}, ZnO and ZrO{sub 2}) was obtained by applying kinetic Monte Carlo simulation. The values of the rate constants for each step of the suggested mechanism have been obtained by simulation. The effect of the initial concentration of mineral oxides and uric acid on the rate of uric acid photo-oxidation by irradiation of some sun care agents has been studied. The kinetic Monte Carlo simulation results agree qualitatively with the existing experimental data for the production of free radicals by sun care agents. - Highlights: • The mechanism and kinetics of uric acid photo-oxidation by irradiation of sun care agents has been obtained by simulation. • The mechanism has been used for free radical production of TiO{sub 2} (rutile and anatase), ZnO and ZrO{sub 2}. • The ratios of photo-activity of ZnO to anastase, rutile and ZrO have been obtained. • By doubling the initial concentrations of mineral oxide, the rate of reaction was doubled. • The optimum ratio of initial concentration of mineral oxides to uric acid has been obtained.

Investigation of surface oxide morphology in SG feedwater pipes and study of its influence on flow accelerated corrosion rate

International Nuclear Information System (INIS)

Qiu, G.; Alos-Ramos, O.; Monchecourt, D.; Mansour, C.; Delaunay, S.; Trevin, S.

2015-01-01

Flow accelerated corrosion (FAC) affects carbon steel components in the secondary circuits of PWR plants. The mandatory use of the prediction tool BRT-CICERO in all its PWR plants enables EDF to perform efficient inspections programs and minimize the number of leaks in the secondary circuits. Due to the operating conditions, SG feedwater flow regulation (ARE) circuits can be affected by FAC phenomenon. Thickness loss has been reported by several plants during the last 10 years, although significant damage by FAC remains very rare. This paper describes the surface features observed on an ARE straight tube that has orange peel pattern with thickness loss on the one half of its inner surface and a thick fouling layer without much thickness loss on the other. An analysis of the oxide porosity and structure by SEM investigation has been carried out. The origin of fouling layer and its behavior in the ARE circuits environment (oxide solubility, flow stability/turbulence) have been discussed. Finally by comparing with the classic FAC models, an attempt of correlation between the presence of the fouling layer and the lower corrosion rate is proposed. (authors)

Nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst

Energy Technology Data Exchange (ETDEWEB)

Osipova, Z.G.; Sokolovskii, V.D.

1979-03-01

The nature of hydrocarbon activation in oxidative ammonolysis of propane to acrylonitrile over a gallium-antimony oxide catalyst GaSbNiPOx (1:3:1.5:1 atomic ratios of the elements) was studied by comparing the rate of this reaction at 550/sup 0/C and 5Vertical Bar3< by vol propane/6Vertical Bar3< ammonia/18.6Vertical Bar3< oxygen/70.4Vertical Bar3< helium reactant mixture with that of isobutane ammoxidation to methacrylonitrile under the same conditions, at low (Vertical Bar3; 20Vertical Bar3<) conversions that prevent secondary oxidation of the products. Both the over-all hydrocarbon conversion rate and that of nitrile formation were higher for propane, suggesting that the reactions proceed via the respective carbanions (probably primary carbanions), rather than carbocations or uncharged radicals.

Nanocomposite of graphene and metal oxide materials

Science.gov (United States)

Liu, Jun; Aksay, Ilhan A.; Choi, Daiwon; Wang, Donghai; Yang, Zhenguo

2012-09-04

Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10C.

Nanocomposite of graphene and metal oxide materials

Science.gov (United States)

Liu, Jun; Aksay, Ilhan A.; Choi, Daiwon; Wang, Donghai; Yang, Zhenguo

2013-10-15

Nanocomposite materials comprising a metal oxide bonded to at least one graphene material. The nanocomposite materials exhibit a specific capacity of at least twice that of the metal oxide material without the graphene at a charge/discharge rate greater than about 10 C.

Effect of coating density on oxidation resistance and Cr vaporization from solid oxide fuel cell interconnects

DEFF Research Database (Denmark)

Talic, Belma; Falk-Windisch, Hannes; Venkatachalam, Vinothini

2017-01-01

•Protective action of dense and porous spinel coatings on Crofer 22 APU was compared. •Reduction and re-oxidation produces denser coatings than heat treating in air only. •Coating density has minor influence on oxidation resistance at 800 °C in air. •Dense coating resulted in three times lower Cr...... evaporation rate than porous coating....

Role of Free Radicals, Oxidative Stress and Xenobiotics in Carcinogenesis by Environmental Pollutants

Directory of Open Access Journals (Sweden)

Dibyajyoti Saha

2014-09-01

Full Text Available Carcinogenesis by many small molecular weight chemicals involves either a direct action of the chemical on cellular DNA or metabolism of the parent chemical to an active or ultimate form, which can than react with cellular DNA to produce a permanent chemical change in a DNA structure. A free radical is an atom or molecule that has one or more unpaired electron(s. These are highly reactive species capable of wide spread, indiscriminate oxidation and per oxidation of proteins, lipids and DNA which can lead to significant cellular damage and even tissue and/or organ failure. . Oxidative stress is a leading cause to damage cells by oxidation. The rate at which oxidative damage is induced (input and the rate at which it is efficiently repaired and removed (output. Xenobiotics are a compound that is foreign to the body. Xenobiotics can produce a variety of biological effects, including pharmacologic responses, toxicity, genes, immunologic reactions and cancer. Oxidative stress is a leading cause to damage cells by oxidation. The rate at which oxidative damage is induced (input and the rate at which it is efficiently repaired and removed (output. This communication highlights the role of carcinogens as environmental pollutants with the possible mechanism of free radicals, oxidative stress and xenobiotics.

[Effects of nitrogen application rate on nitrate reductase activity, nitric oxide content and gas exchange in winter wheat leaves].

Science.gov (United States)

Shangguan, Zhou-Ping

2007-07-01

In this paper, the effects of different nitrogen application rates on the nitrate reductase (NR) activity, nitric oxide (NO) content and gas exchange parameters in winter wheat (Triticum aestivum L.) leaves from tillering stage to heading stage and on grain yield were studied. The results showed that the photosynthetic rate (P(n)), transpiration rate (T(r)) and instantaneous water use efficiency (IWUE) of leaves as well as the grain yield were increased with increasing nitrogen application rate first but decreased then, with the values of all these parameters reached the highest in treatment N180. The NR activity increased with increasing nitrogen application rate, and there was a significant linear correlation between NR activity and NO content at tillering and jointing stages (R2 > or = 0.68, n = 15). NO content had a quadratic positive correlation with stomatal conductance (G(s)) (R2 > or = 0.43, n = 15). The lower NO content produced by lower NR activity under lower nitrogen application rate promoted the stoma opened, while the higher NO content produced by higher NR activity under higher nitrogen application rate induced the stoma closed. Although the leaf NO content had a quadratic positive correlation with stomatal conductance (R2 > or = 0.36, n = 15), no remarkable correlation was observed between NR activity and NO content at heading stage, suggesting that nitrogen fertilization could not affect leaf NO content through promoting NR activity, and further more, regulate the stomatal action. Under appropriate nitrogen application the leaf NR activity and NO content were lower, G(s), T(r) and IWUE were higher, and thus, the crop had a better drought-resistant ability, higher P(n), and higher grain yield.

Oxidation of tritium in packed bed of noble metal catalyst for detritiation from system gases

International Nuclear Information System (INIS)

Nishikawa, Masabumi; Takeishi, Toshiharu; Munakata, Kenzo; Kotoh, Kenji; Enoeda, Mikio

1985-01-01

Catalytic oxidation rates of tritium in the bed of the noble metal catalysts are obtained and compared with the oxidation rates observed for the packed bed of spongy copper oxide or hopcalites. Use of Pt- or Pd-aluminia catalysts is recommended in this study because they give effective oxidation rates of tritium in the ambient temperature range. The adsorption performance of tritiated water in the catalyst bed is also discussed. (orig.)

A study on the corrosion rate for metal nuclear fuel by the soxhlet

International Nuclear Information System (INIS)

Oh, S. J.; Lee, Y. R.; Lee, D. B.; Park, J. M.; Kim, K. H.; Lee, Y. S.; Park, H. D.; Kim, C. K.

2002-01-01

In order to compare in-pile performance of nuclear fuel candidates for HANARO, corrosion test with the Soxhlet apparatus for rare-earth-oxide added U-Mo alloy fuels has been carried out by measuring a leaching rate. It appeared from the result that the leaching rate of the U-Mo fuel specimen became decreased as a rare-earth-oxide added, and there was a little difference in the leaching rate depending on the kind of the rare-earth-oxide

Rheology and microstructure of dilute graphene oxide suspension

International Nuclear Information System (INIS)

Tesfai, Waka; Singh, Pawan; Shatilla, Youssef; Iqbal, Muhammad Z.; Abdala, Ahmed A.

2013-01-01

Graphene and graphene oxide are potential candidates as nanofluids for thermal management applications. Here, we investigate the rheological properties and intrinsic viscosity of aqueous suspension of graphene and use the measured intrinsic viscosity to determine the aspect ratio of graphene oxide. Dilute suspension of graphene oxide (0.05 to 0.5 mg/mL) exhibits a shear thinning behavior at low shear rates followed by a shear-independent region that starts at shear rate between 5 and 100/s depending on the concentration. This shear thinning behavior becomes more pronounced with the increase of particle loading. Moreover, AFM imaging of the dried graphene oxide indicates the evolution of irregular and thin low fractal aggregates of 0.3–1.8 nm thickness at lower concentrations to oblate compact structures of 1–18 nm thickness of nanosheets at higher concentration. These observations elucidate the microstructure growth mechanisms of graphene oxide in multiphase systems, which are important for nanofluids applications and for dispersing graphene and graphene oxide in composite materials. The suspension has a very high intrinsic viscosity of 1661 due to the high graphene oxide aspect ratio. Based on this intrinsic viscosity, we predict graphene oxide aspect ratio of 2445. While the classical Einstein and Batchelor models underestimate the relative viscosity of graphene oxide suspension, Krieger–Dougherty prediction is in a good agreement with the experimental measurement

Oxidation kinetics of hydride-bearing uranium metal corrosion products

International Nuclear Information System (INIS)

Totemeier, T.C.; Pahl, R.G.; Frank, S.M.

1998-01-01

The oxidation behavior of hydride-bearing uranium metal corrosion products from zero power physics reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2 , Ar-9%O 2 , and Ar-20%O 2 . Ignition of corrosion product samples from two moderately corroded plates was observed between 125 C and 150 C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride. (orig.)

Fructose and Sucrose Intake Increase Exogenous Carbohydrate Oxidation during Exercise

Science.gov (United States)

Trommelen, Jorn; Fuchs, Cas J.; Beelen, Milou; Lenaerts, Kaatje; Jeukendrup, Asker E.; Cermak, Naomi M.; van Loon, Luc J. C.

2017-01-01

Peak exogenous carbohydrate oxidation rates typically reach ~1 g·min−1 during exercise when ample glucose or glucose polymers are ingested. Fructose co-ingestion has been shown to further increase exogenous carbohydrate oxidation rates. The purpose of this study was to assess the impact of fructose co-ingestion provided either as a monosaccharide or as part of the disaccharide sucrose on exogenous carbohydrate oxidation rates during prolonged exercise in trained cyclists. Ten trained male cyclists (VO2peak: 65 ± 2 mL·kg−1·min−1) cycled on four different occasions for 180 min at 50% Wmax during which they consumed a carbohydrate solution providing 1.8 g·min−1 of glucose (GLU), 1.2 g·min−1 glucose + 0.6 g·min−1 fructose (GLU + FRU), 0.6 g·min−1 glucose + 1.2 g·min−1 sucrose (GLU + SUC), or water (WAT). Peak exogenous carbohydrate oxidation rates did not differ between GLU + FRU and GLU + SUC (1.40 ± 0.06 vs. 1.29 ± 0.07 g·min−1, respectively, p = 0.999), but were 46% ± 8% higher when compared to GLU (0.96 ± 0.06 g·min−1: p exogenous carbohydrate oxidation rates during the latter 120 min of exercise were 46% ± 8% higher in GLU + FRU or GLU + SUC compared with GLU (1.19 ± 0.12, 1.13 ± 0.21, and 0.82 ± 0.16 g·min−1, respectively, p exogenous carbohydrate oxidation rates during prolonged exercise in trained cyclists. PMID:28230742

Evidence of contamination by oil and oil products in the Santos-São Vicente estuary, São Paulo, Brazil

Directory of Open Access Journals (Sweden)

Juliana Souza Azevedo

2012-06-01

Full Text Available Different components of the mixed function oxidase (MFO system and the levels of fluorescent aromatic compounds in bile (FACs were measured in Cathorops spixii in order to assess the impact of polycyclic aromatic hydrocarbons (PAHs. Fish were sampled in an estuary (Santos/São Vicente with a history of contamination by PAHs, mainly due to the presence of the industrial complex of Cubatão city and of another of low anthropogenic influence (Cananéia on the Brazilian coast. FACs were higher in fish from the polluted site, and the PAH 5 and 6-ring metabolites were the most frequent - with 14% and 15%, respectively. Levels of the different components of the MFO system showed the same variation profile as the FACs for both estuaries. Therefore, the values found for somatic indexes and biomarkers with data of bile PAH metabolites indicate the presence of organic contaminants, especially in the area subject to the influence of the industrial complex on the Santos/São Vicente estuary.Diferentes componentes do sistema oxidase de função mista (MFO e os níveis de compostos aromáticos fluorescentes em bile (FACS foram determinados em Cathorops spixii a fim de avaliar o impacto de hidrocarbonetos policíclicos aromáticos (PAHs. Os peixes foram coletados em um estuário com histórico de contaminação por PAHs (Santos/São Vicente, devido principalmente a presença do complexo industrial na cidade de Cubatão e em outro com baixa influência antropogênica (Cananéia na costa brasileira. FACs foram maiores nos peixes oriundos da área contaminada, sendo os metabolitos de HPAs com 5 e 6 anéis, os mais representativos com 14% e 15%, respectivamente. Os níveis dos diferentes componentes do sistema MFO mostraram o mesmo perfil de variação que os FACs em ambos os estuários. Portanto, os valores encontrados para os índices somáticos e os biomarcadores considerados, em associação com os dados de metabólitos biliares de PAHs, indicam a presença de

High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 - O2 environment

Science.gov (United States)

Farrokhzad, M. A.; Khan, T. I.

2014-06-01

Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al2O3 and TiO2) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO2, 10% O2 and 75% N2. This research investigates the effects of CO2 and O2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings.

Bioturbation determines the response of benthic ammonia-oxidizing microorganisms to ocean acidification

Science.gov (United States)

Laverock, B.; Kitidis, V.; Tait, K.; Gilbert, J. A.; Osborn, A. M.; Widdicombe, S.

2013-01-01

Ocean acidification (OA), caused by the dissolution of increasing concentrations of atmospheric carbon dioxide (CO2) in seawater, is projected to cause significant changes to marine ecology and biogeochemistry. Potential impacts on the microbially driven cycling of nitrogen are of particular concern. Specifically, under seawater pH levels approximating future OA scenarios, rates of ammonia oxidation (the rate-limiting first step of the nitrification pathway) have been shown to dramatically decrease in seawater, but not in underlying sediments. However, no prior study has considered the interactive effects of microbial ammonia oxidation and macrofaunal bioturbation activity, which can enhance nitrogen transformation rates. Using experimental mesocosms, we investigated the responses to OA of ammonia oxidizing microorganisms inhabiting surface sediments and sediments within burrow walls of the mud shrimp Upogebia deltaura. Seawater was acidified to one of four target pH values (pHT 7.90, 7.70, 7.35 and 6.80) in comparison with a control (pHT 8.10). At pHT 8.10, ammonia oxidation rates in burrow wall sediments were, on average, fivefold greater than in surface sediments. However, at all acidified pH values (pH ≤ 7.90), ammonia oxidation rates in burrow sediments were significantly inhibited (by 79–97%; p < 0.01), whereas rates in surface sediments were unaffected. Both bacterial and archaeal abundances increased significantly as pHT declined; by contrast, relative abundances of bacterial and archaeal ammonia oxidation (amoA) genes did not vary. This research suggests that OA could cause substantial reductions in total benthic ammonia oxidation rates in coastal bioturbated sediments, leading to corresponding changes in coupled nitrogen cycling between the benthic and pelagic realms. PMID:23980243

Methane oxidation and degradation of organic compounds in landfill soil covers

DEFF Research Database (Denmark)

Scheutz, Charlotte; Kjeldsen, Peter

2002-01-01

High rates of methane oxidation and degradation of the lowed halogenated methanes (TCM and DCM) and HCFCs (HCFC-21 and HCFC-22) were found in an investigation of the oxidation of methane and halogenated organic compunds (HOCs) in landfill gas affected soil. The degradation followed zero-order kin......High rates of methane oxidation and degradation of the lowed halogenated methanes (TCM and DCM) and HCFCs (HCFC-21 and HCFC-22) were found in an investigation of the oxidation of methane and halogenated organic compunds (HOCs) in landfill gas affected soil. The degradation followed zero...

Dense CdS thin films on fluorine-doped tin oxide coated glass by high-rate microreactor-assisted solution deposition

Energy Technology Data Exchange (ETDEWEB)

Su, Yu-Wei, E-mail: suyuweiwayne@gmail.com [School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, OR 97330 (United States); Microproducts Breakthrough Institute and Oregon Process Innovation Center, Corvallis, Oregon 97330 (United States); Ramprasad, Sudhir [Energy Processes and Materials Division, Pacific Northwest National Laboratory, Corvallis, OR 9730 (United States); Microproducts Breakthrough Institute and Oregon Process Innovation Center, Corvallis, Oregon 97330 (United States); Han, Seung-Yeol; Wang, Wei [School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, OR 97330 (United States); Microproducts Breakthrough Institute and Oregon Process Innovation Center, Corvallis, Oregon 97330 (United States); Ryu, Si-Ok [School of Display and Chemical Engineering, Yeungnam University, 214-1 Dae-dong, Gyeonsan, Gyeongbuk 712-749 (Korea, Republic of); Palo, Daniel R. [Barr Engineering Co., Hibbing, MN 55747 (United States); Paul, Brian K. [School of Mechanical, Industrial and Manufacturing Engineering, Oregon State University, Corvallis, OR 97330 (United States); Microproducts Breakthrough Institute and Oregon Process Innovation Center, Corvallis, Oregon 97330 (United States); Chang, Chih-hung [School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, OR 97330 (United States); Microproducts Breakthrough Institute and Oregon Process Innovation Center, Corvallis, Oregon 97330 (United States)

2013-04-01

Continuous microreactor-assisted solution deposition is demonstrated for the deposition of CdS thin films on fluorine-doped tin oxide (FTO) coated glass. The continuous flow system consists of a microscale T-junction micromixer with the co-axial water circulation heat exchanger to control the reacting chemical flux and optimize the heterogeneous surface reaction. Dense, high quality nanocrystallite CdS thin films were deposited at an average rate of 25.2 nm/min, which is significantly higher than the reported growth rate from typical batch chemical bath deposition process. Focused-ion-beam was used for transmission electron microscopy specimen preparation to characterize the interfacial microstructure of CdS and FTO layers. The band gap was determined at 2.44 eV by UV–vis absorption spectroscopy. X-ray photon spectroscopy shows the binding energies of Cd 3d{sub 3/2}, Cd 3d{sub 5/2}, S 2P{sub 3/2} and S 2P{sub 1/2} at 411.7 eV, 404.8 eV, 162.1 eV and 163.4 eV, respectively. - Highlights: ► CdS films deposited using continuous microreactor-assisted solution deposition (MASD) ► Dense nanocrystallite CdS films can be reached at a rate of 25.2 [nm/min]. ► MASD can approach higher film growth rate than conventional chemical bath deposition.

Properties of protective oxide scales containing cerium on Incoloy 800H in oxidizing and sulfidizing environments. I. Constant-extension-rate study of mechanical properties

NARCIS (Netherlands)

Haanappel, V.A.C.; Fransen, T.; Geerdink, Bert; Gellings, P.J.

1988-01-01

The mechanical properties of ceramic coatings containing cerium oxide, prepared by the sol-gel method and used to protect Incoloy 800H against aggressive environments, are reported. Deformation and cracking behavior in oxidizing and sulfidizing environments has been investigated by

Sulfide Oxidation in the Anoxic Black-Sea Chemocline

DEFF Research Database (Denmark)

JØRGENSEN, BB; FOSSING, H.; WIRSEN, CO

1991-01-01

per day, occurred in anoxic water at the top of the sulfide zone concurrent with the highest rates of dark CO2 assimilation. The main soluble oxidized products of sulfide were thiosulfate (68-82%) and sulfate. Indirect evidence was presented for the formation of elemental sulfur which accumulated...... that the measured H2S oxidation rates were 4-fold higher than could be explained by the downward flux of organic carbon and too high to balance the availability of electron acceptors such as oxidized iron or manganese. A nitrate maximum at the lower boundary of the O2 zone did not extend down to the sulfide zone....

Porous Co3O4 nanofibers surface-modified by reduced graphene oxide as a durable, high-rate anode for lithium ion battery

International Nuclear Information System (INIS)

Hu, Renzong; Zhang, Houpo; Bu, Yunfei; Zhang, Hanyin; Zhao, Bote; Yang, Chenghao

2017-01-01

Here we report our findings in synthesis and characterization of porous Co 3 O 4 nanofibers coated with a surface-modification layer, reduced graphene oxide. The unique porous Co 3 O 4 @rGO architecture enables efficient stress relaxation and fast Li + ions and electron transport during discharge/charge cycling. When tested in a half cell, the Co 3 O 4 @rGO electrodes display high Coulombic efficiency, enhanced cyclic stability, and high rate capability (∼900 mAh/g at 1A/g, and ∼600 mAh/g at 5 A/g). The high capacity is contributed by a stable capacity yielded from reversible conversion reactions above 0.8 V vs. Li/Li + , and a increasing capacity induced by the electrolyte decomposition and interfacial storage between 0.8 0.01 V during discahrge. A full cell constructed from a Co 3 O 4 @rGO anode and a LiMn 2 O 4 cathode delivers good capacity retention with operation voltage of ∼2.0 V. These performances are better than those of other full cells using alloy or metal oxide anodes. Our work is a preliminary attempt for practicality of high capacity metal oxide anodes in Li-ion batteries used for the electronic devices.

A field study on chemistry, S(IV) oxidation rates and vertical transport during fog conditions

Science.gov (United States)

Joos, F.; Baltensperger, U.

An extensive fog study was carried out in the central plateu of Switzerland. Ninety-seven fog samples were collected along with aerosol filter and cascade impactor samples, and measurements of O 3, SO 2, NO, NO x, PAN, temperature, and wind speed and direction. Maximum levels in fogwater were 4.3, 4.4., 0.033, 1.7, 0.5, 0.024 and 9.2 mmol ℓ -1 for Cl -, NO 3-, NO 2-, SO 42-, S(IV), oxalate and NH 4+, respectively. pH varied between 2.9 and 7.1. Sixteen additional elements were determined in the fog samples by ICP. The sum of the concentrations of SO 42- and S(IV) agreed very with the total sulfur concentration as determined by ICP. A substantial excess of S(IV) (up to 0.2 mmol ℓ -1) compared to Henry and acid-base equilibrium calculations was found, which can probably be attributed to complex formations with aldehydes. S(IV) oxidation rates of up to 650 nmol ℓ -1 s -1 with ozone and of up to 100 nmol ℓ -1 s -1 with NO 2 were calculated. S(IV) oxidation due to PAN, NO 2- and Fe(III) was of minor importance. A substantial fraction of the major ions was present in the intersitial aerosol (aerosol particles < 4 μm) even during fog conditions. High correlations were found for NH 4+, NO 32-. From their ratios in the fog water and the aerosol (< 4 μm) it could be concluded that at least 40% of NO 3- and 20% of NH 4+ in fog water was due to gas phase scavenging. Increasing concentrations in fog water were found during fog dissipation. Concentrations decreased with increasing height. A vertical transport model including turbulent diffusion and droplet sedimentation is introduced, which matches the experimental data of this vertical profile.

Oxidation of ammonium sulfite by a multi-needle-to-plate gas phase pulsed corona discharge reactor

Science.gov (United States)

Ren, Hua; Lu, Na; Shang, Kefeng; Li, Jie; Wu, Yan

2013-03-01

The oxidation of ammonium sulfite in the ammonia-based flue gas desulfurization (FGD) process was investigated in a multi-needle-to-plate gas phase pulsed corona discharge reactor in this paper. The effect of several parameters, including capacitance and peak pulse voltage of discharge system, electrode gap and bubbling gas flow rate on the oxidation rate of ammonium sulfite was reviewed. The oxidation rate of ammonium sulfite could reach 47.2% at the capacitance, the peak pulse voltage, electrode gap and bubbling gas flow rate equal to 2 nF, -24.6 k V, 35 mm and 4 L min-1 within treatment time of 40 min The experimental results indicate that the gas phase pulsed discharge system with a multi-needle-to-plate electrode can oxide the ammonium sulfite. The oxidation rate increased with the applied capacitance and peak pulse voltage and decreased with the electrode gap. As the bubbling gas flow rate increased, the oxidation rate increased first and then tended to reach a stationary value. These results would be important for the process optimization of the (NH4)2SO3 to (NH4)2SO4 oxidation.

The oxidation of acid azo dye AY 36 by a manganese oxide containing mine waste

International Nuclear Information System (INIS)

Clarke, Catherine E.; Kielar, Filip; Johnson, Karen L.

2013-01-01

Highlights: ► This study looks at the oxidative breakdown of the amine containing dye acid yellow 36 by a Mn oxide containing mine waste. ► The oxidation proceeds by successive one electron transfers between the dye molecule and the Mn oxide minerals. ► The initial decolorization of the dye is rapid, but does not involve the cleavage of the azo bond. -- Abstract: The oxidative breakdown of acid azo dye acid yellow 36 (AY 36) by a Mn oxide containing mine tailings is demonstrated. The oxidation reaction is pH dependent with the rate of decolorization increasing with decreasing pH. The oxidation reaction mechanism is initiated at the amino moiety and proceeds via successive, one electron transfers from the dye to the Mn oxide minerals. The reaction pathway involves the formation of a number of colorless intermediate products, some of which hydrolyze in a Mn oxide-independent step. Decolorization of the dye is rapid and is observed before the cleavage of the azo-bond, which is a slower process. The terminal oxidation products were observed to be p-benzoquinone and 3-hydroxybenzenesulfonate. The reaction order of the initial decolorization was determined to be pseudo fractional order with respect to pH and pseudo first order with respect to dye concentration and Mn tailings’ surface area

Nitrous Oxide/Paraffin Hybrid Rocket Engines

Science.gov (United States)

Zubrin, Robert; Snyder, Gary

2010-01-01

Nitrous oxide/paraffin (N2OP) hybrid rocket engines have been invented as alternatives to other rocket engines especially those that burn granular, rubbery solid fuels consisting largely of hydroxyl- terminated polybutadiene (HTPB). Originally intended for use in launching spacecraft, these engines would also be suitable for terrestrial use in rocket-assisted takeoff of small airplanes. The main novel features of these engines are (1) the use of reinforced paraffin as the fuel and (2) the use of nitrous oxide as the oxidizer. Hybrid (solid-fuel/fluid-oxidizer) rocket engines offer advantages of safety and simplicity over fluid-bipropellant (fluid-fuel/fluid-oxidizer) rocket en - gines, but the thrusts of HTPB-based hybrid rocket engines are limited by the low regression rates of the fuel grains. Paraffin used as a solid fuel has a regression rate about 4 times that of HTPB, but pure paraffin fuel grains soften when heated; hence, paraffin fuel grains can, potentially, slump during firing. In a hybrid engine of the present type, the paraffin is molded into a 3-volume-percent graphite sponge or similar carbon matrix, which supports the paraffin against slumping during firing. In addition, because the carbon matrix material burns along with the paraffin, engine performance is not appreciably degraded by use of the matrix.

Iron Oxide Nanoparticle Agglomeration Influences Dose-Rates and Modulates Oxidative Stress Mediated Dose-Response Profiles In Vitro

Energy Technology Data Exchange (ETDEWEB)

Sharma, Gaurav; Kodali, Vamsi K.; Gaffrey, Matthew J.; Wang, Wei; Minard, Kevin R.; Karin, Norman J.; Teeguarden, Justin G.; Thrall, Brian D.

2013-07-31

Spontaneous agglomeration of engineered nanoparticles (ENPs) is a common problem in cell culture media which can confound interpretation of in vitro nanotoxicity studies. The authors created stable agglomerates of iron oxide nanoparticles (IONPs) in conventional culture medium, which varied in hydrodynamic size (276 nm-1.5 μm) but were composed of identical primary particles with similar surface potentials and protein coatings. Studies using C10 lung epithelial cells show that the dose rate effects of agglomeration can be substantial, varying by over an order of magnitude difference in cellular dose in some cases. Quantification by magnetic particle detection showed that small agglomerates of carboxylated IONPs induced greater cytotoxicity and redox-regulated gene expression when compared with large agglomerates on an equivalent total cellular IONP mass dose basis, whereas agglomerates of amine-modified IONPs failed to induce cytotoxicity or redox-regulated gene expression despite delivery of similar cellular doses. Dosimetry modelling and experimental measurements reveal that on a delivered surface area basis, large and small agglomerates of carboxylated IONPs have similar inherent potency for the generation of ROS, induction of stress-related genes and eventual cytotoxicity. The results suggest that reactive moieties on the agglomerate surface are more efficient in catalysing cellular ROS production than molecules buried within the agglomerate core. Because of the dynamic, size and density-dependent nature of ENP delivery to cells in vitro, the biological consequences of agglomeration are not discernible from static measures of exposure concentration (μg/ml) alone, highlighting the central importance of integrated physical characterisation and quantitative dosimetry for in vitro studies. The combined experimental and computational approach provides a quantitative framework for evaluating relationships between the biocompatibility of nanoparticles and their

Iron oxide nanoparticle agglomeration influences dose rates and modulates oxidative stress-mediated dose–response profiles in vitro

Science.gov (United States)

Sharma, Gaurav; Kodali, Vamsi; Gaffrey, Matthew; Wang, Wei; Minard, Kevin R.; Karin, Norman J.; Teeguarden, Justin G.; Thrall, Brian D.

2014-01-01

Spontaneous agglomeration of engineered nanoparticles (ENPs) is a common problem in cell culture media which can confound interpretation of in vitro nanotoxicity studies. The authors created stable agglomerates of iron oxide nanoparticles (IONPs) in conventional culture medium, which varied in hydrodynamic size (276 nm–1.5 μm) but were composed of identical primary particles with similar surface potentials and protein coatings. Studies using C10 lung epithelial cells show that the dose rate effects of agglomeration can be substantial, varying by over an order of magnitude difference in cellular dose in some cases. Quantification by magnetic particle detection showed that small agglomerates of carboxylated IONPs induced greater cytotoxicity and redox-regulated gene expression when compared with large agglomerates on an equivalent total cellular IONP mass dose basis, whereas agglomerates of amine-modified IONPs failed to induce cytotoxicity or redox-regulated gene expression despite delivery of similar cellular doses. Dosimetry modelling and experimental measurements reveal that on a delivered surface area basis, large and small agglomerates of carboxylated IONPs have similar inherent potency for the generation of ROS, induction of stress-related genes and eventual cytotoxicity. The results suggest that reactive moieties on the agglomerate surface are more efficient in catalysing cellular ROS production than molecules buried within the agglomerate core. Because of the dynamic, size and density-dependent nature of ENP delivery to cells in vitro, the biological consequences of agglomeration are not discernible from static measures of exposure concentration (μg/ml) alone, highlighting the central importance of integrated physical characterisation and quantitative dosimetry for in vitro studies. The combined experimental and computational approach provides a quantitative framework for evaluating relationships between the biocompatibility of nanoparticles and their

Photo-oxidation of gaseous ethanol on photocatalyst prepared by acid leaching of titanium oxide/hydroxyapatite composite

Energy Technology Data Exchange (ETDEWEB)

Ono, Y., E-mail: ono-y@kanagawa-iri.go.jp [Mechanical and Material Engineering Division, Kanagawa Industrial Technology Center, Ebina, Kanagawa 243-0435 (Japan); Rachi, T.; Yokouchi, M.; Kamimoto, Y. [Mechanical and Material Engineering Division, Kanagawa Industrial Technology Center, Ebina, Kanagawa 243-0435 (Japan); Nakajima, A. [Department of Metallurgy and Ceramics Science, Tokyo Institute of Technology, Meguro, Tokyo 152-8552 (Japan); Okada, K. [Materials and Structures Laboratory, Tokyo Institute of Technology, Midori, Yokohama, Kanagawa 226-8503 (Japan)

2013-06-01

Highlights: ► Photocatalyst powder was prepared by acid leaching of TiO{sub 2}/apatite composite. ► The photocatalytic activity was evaluated from in situ FT-IR study using ethanol. ► Apatite in the composite had positive effect for the photo-oxidation of ethanol. ► The enhanced oxidation rate was explained by the difference in deactivation rate. - Abstract: Highly active photocatalysts were synthesized by leaching of heat-treated titanium dioxide (TiO{sub 2})/hydroxyapatite (HAp) powder with hydrochloric acid at 0.25, 0.50, 0.75 mol/l, and their photocatalytic activities were evaluated from in situ Fourier transform infrared (FT-IR) study of photo-oxidation of gaseous ethanol. By changing the acid concentration, the TiO{sub 2}/HAp composite had different atomic ratios of Ca/Ti (0.0–2.8) and P/Ti (0.3–2.1). It was found that phosphate group remained on the surface of TiO{sub 2} particle even in the sample treated with concentrated acid (0.75 mol/l). These acid-treated samples showed higher rates for ethanol photo-oxidation than the commercial TiO{sub 2} powder, Degussa P25. The highest rate was obtained in the TiO{sub 2}/HAp composite treated with the dilute (0.25 mol/l) acid in spite of its low content of TiO{sub 2} photocatalyst. This enhanced photocatalytic activity was attributed to the result that the deactivation with repeated injections of ethanol gas was suppressed in the TiO{sub 2}/HAp composites compared with the TiO{sub 2} powders.

Growth kinetics of hydrogen sulfide oxidizing bacteria in corroded concrete from sewers

International Nuclear Information System (INIS)

Jensen, Henriette Stokbro; Lens, Piet N.L.; Nielsen, Jeppe L.; Bester, Kai; Nielsen, Asbjorn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes

2011-01-01

Hydrogen sulfide oxidation by microbes present on concrete surfaces of sewer pipes is a key process in sewer corrosion. The growth of aerobic sulfur oxidizing bacteria from corroded concrete surfaces was studied in a batch reactor. Samples of corrosion products, containing sulfur oxidizing bacteria, were suspended in aqueous solution at pH similar to that of corroded concrete. Hydrogen sulfide was supplied to the reactor to provide the source of reduced sulfur. The removal of hydrogen sulfide and oxygen was monitored. The utilization rates of both hydrogen sulfide and oxygen suggested exponential bacterial growth with median growth rates of 1.25 d -1 and 1.33 d -1 as determined from the utilization rates of hydrogen sulfide and oxygen, respectively. Elemental sulfur was found to be the immediate product of the hydrogen sulfide oxidation. When exponential growth had been achieved, the addition of hydrogen sulfide was terminated leading to elemental sulfur oxidation. The ratio of consumed sulfur to consumed oxygen suggested that sulfuric acid was the ultimate oxidation product. To the knowledge of the authors, this is the first study to determine the growth rate of bacteria involved in concrete corrosion with hydrogen sulfide as source of reduced sulfur.

Iron sulfide oxidation as influenced by calcium carbonate application

Energy Technology Data Exchange (ETDEWEB)

Hossner, L.R.; Doolittle, J.J. [Texas A& M University, College Station, TX (USA). Dept. of Soil & Crop Science

2003-06-01

Two overburden materials, with different FeS{sub 2} contents (1.9 and 4.1%) and low acid neutralization potential, were limed with CaCO{sub 3} at rates of 0, 25,50,75, 100, and 125% based on the amount of CaCO{sub 3} needed to provide an acid-base account deficit (A/B-a) of zero (A/B-a = neutratization potential - potential acidity - exchangeable acidity). The limed overburden materials were inoculated with Thiobacillus ferrooxidans and leached weekly with deionized water. Residual FeS{sub 2} and CaCO{sub 3} were determined in samples over a 378-d period. Oxidation followed zero-order kinetics with respect to FeS{sub 2} concentration at pH values greater than 4 and first-order kinetics at pH values less than 4. Zero-order oxidation rates ranged from 0.01 to 0.46 {mu}mol g{sup -1} d{sup -1} in the overburden with 1.9% FeS{sub 2} and from 0.01 to 0.22 {mu}mol g{sup -1} d{sup -1} in the overburden with 4.1% FeS{sub 2}. Oxidation following the first-order rate law had a first-order rate constant of 0.03 d{sup -1} in the 1.9% FeS{sub 2} overburden and 0.01 d{sup -1} in the 4.1% FeS{sub 2} overburden. The calculated half-life was 23 d for the 1.9% FeS{sub 2} overburden and 69 d for the 4.1% FeS{sub 2} overburden. Additions of CaCO{sub 3} affected FeS{sub 2} oxidation by controlling the pH of the system. Liming to greater than 50% of the acid-base account deficit did not significantly affect the zero-order oxidation rate. Dissolution of the applied CaCO{sub 3} was found to be faster than the oxidation of FeS{sub 2} at pH values greater than 4. It was projected that at lime rates up to 125%, the CaCO{sub 3} would dissolve and leach out of the system before all the FeS{sub 2} oxidized, leaving the potential for acid minesoil formation.

Thulium oxide fuel characterization study: Part 3, Procedures

International Nuclear Information System (INIS)

Nelson, C.A.; Anderson, R.W.; Talbot, M.; Bierds, W.

1970-06-01

Procedures are presented for the following: Tm 2 O 3 -Yb 2 O 3 pseudo - binary phase diagram tests; compatibility tests; thulium-170 oxide dose rate measurements; preparation of Tm 2 O 3 wafers; SRL thulium and/or ytterbium oxide powder reprocessing for sintering; cold pressing and sintering thulium oxide wafers; preparation of thulium and/or ytterbium oxide powder via precipitation with oxalic acid, ammonium oxalate, urea and methyl oxalate; determination of the total surface area of rare earth oxide powders; determining oxygen in thulia - thulia/ytterbia for the purpose of determining metal-to-oxygen ratios; and determination of the impact resistance to fines generation of sintered rare earth oxide

Uranium oxidation kinetics monitored by in-situ X-ray diffraction

Energy Technology Data Exchange (ETDEWEB)

Zalkind, S., E-mail: shimonzl@nrcn.org.il; Rafailov, G.; Halevy, I.; Livneh, T.; Rubin, A.; Maimon, H.; Schweke, D.

2017-03-15

The oxidation kinetics of U-0.1 wt%Cr at oxygen pressures of 150 Torr and the temperature range of 90–150 °C was studied by means of in-situ X-ray diffraction (XRD). A “breakaway” in the oxidation kinetics is found at ∼0.25 μm, turning from a parabolic to a linear rate law. At the initial stage of oxidation the growth plane of UO{sub 2}(111) is the prominent one. As the oxide thickens, the growth rate of UO{sub 2}(220) plane increases and both planes grow concurrently. The activation energies obtained for the oxide growth are Q{sub parabolic} = 17.5 kcal/mol and Q{sub linear} = 19 kcal/mol. Enhanced oxidation around uranium carbide (UC) inclusions is clearly observed by scanning electron microscopy (SEM).

Oxidation of oily sludge in supercritical water

International Nuclear Information System (INIS)

Cui Baochen; Cui Fuyi; Jing Guolin; Xu Shengli; Huo Weijing; Liu Shuzhi

2009-01-01

The oxidation of oily sludge in supercritical water is performed in a batch reactor at reaction temperatures between 663 and 723 K, the reaction times between 1 and 10 min and pressure between 23 and 27 MPa. Effect of reaction parameters such as reaction time, temperature, pressure, O 2 excess and initial COD on oxidation of oily sludge is investigated. The results indicate that chemical oxygen demand (COD) removal rate of 92% can be reached in 10 min. COD removal rate increases as the reaction time, temperature and initial COD increase. Pressure and O 2 excess have no remarkable affect on reaction. By taking into account the dependence of reaction rate on COD concentration, a global power-law rate expression was regressed from experimental data. The resulting pre-exponential factor was 8.99 x 10 14 (mol L -1 ) -0.405 s -1 ; the activation energy was 213.13 ± 1.33 kJ/mol; and the reaction order for oily sludge (based on COD) is 1.405. It was concluded that supercritical water oxidation (SCWO) is a rapidly emerging oily sludge processing technology.

Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

Science.gov (United States)

Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

2016-02-12

The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane. Copyright © 2016, American Association for the Advancement of Science.

Formation of iron oxides from acid mine drainage and magnetic separation of the heavy metals adsorbed iron oxides

Energy Technology Data Exchange (ETDEWEB)

Kwon, Hee Won; Kim, Jeong Jin; Kim, Young Hun [Andong National University, Andong (Korea, Republic of); Ha, Dong Woo [Korea Electrotechnology Research Institute, Changwon (Korea, Republic of)

2016-03-15

There are a few thousand abandoned metal mines in South Korea. The abandoned mines cause several environmental problems including releasing acid mine drainage (AMD), which contain a very high acidity and heavy metal ions such as Fe, Cu, Cd, Pb, and As. Iron oxides can be formed from the AMD by increasing the solution pH and inducing precipitation. Current study focused on the formation of iron oxide in an AMD and used the oxide for adsorption of heavy metals. The heavy metal adsorbed iron oxide was separated with a superconducting magnet. The duration of iron oxide formation affected on the type of mineral and the degree of magnetization. The removal rate of heavy metal by the adsorption process with the formed iron oxide was highly dependent on the type of iron oxide and the solution pH. A high gradient magnetic separation (HGMS) system successfully separated the iron oxide and harmful heavy metals.

Riboflavin photosensitized oxidation of myoglobin.

Science.gov (United States)

Grippa, Juliana M; de Zawadzki, Andressa; Grossi, Alberto B; Skibsted, Leif H; Cardoso, Daniel R

2014-02-05

The reaction of the fresh meat pigment oxymyoglobin, MbFe(II)O₂, and its oxidized form metmyoglobin, MbFe(III), with triplet-state riboflavin involves the pigment protein, which is oxidatively cleaved or dimerized as shown by SDS-PAGE and Western blotting. The overall rate constant for oxidation of MbFe(II)O₂ by ³Rib is (3.0 ± 0.5) × 10⁹ L·mol⁻¹·s⁻¹ and (3.1 ± 0.4) × 10⁹ L·mol⁻¹·s⁻¹ for MbFe(III) in phosphate buffer of pH 7.4 at 25 °C as determined by laser flash photolysis. The high rates are rationalized by ground state hydrophobic interactions as detected as static quenching of fluorescence from singlet-excited state riboflavin by myoglobins using time-resolved fluorescence spectroscopy and a Stern-Volmer approach. Binding of riboflavin to MbFe(III) has K(a) = (1.2 ± 0.2) × 10⁴ mol·L⁻¹ with ΔH° = -112 ± 22 kJ·mol⁻¹ and ΔS° = -296 ± 75 J·mol⁻¹·K⁻¹. For meat, riboflavin is concluded to be a photosensitizer for protein oxidation but not for discoloration.

Oxidation of zircaloy-2 in high temperature steam

International Nuclear Information System (INIS)

Ikeda, Seiichi; Ito, Goro; Ohashi, Shigeo

1975-01-01

Oxidation tests were conducted for zircaloy-2 in steam at temperature ranging from 900 to 1300 0 C to clarify its oxidation kinetics as a nuclear fuel cladding materials in case of a loss-of-coolant accident. The influence of maximum temperature and heating rate of the specimen on its oxidation rate in steam was investigated. The changes in mechanical properties of the specimens after oxidation tests are also studied. The results obtained were summarized as follows: (1) The weight of the specimen after oxidation in steam increased two times as the time required to reach the maximum temperature increased from 1 to 10 mins. (2) The kinetics of oxidation of zircaloy-2 in steam were not affected by the difference in the surface condition before test such as chemical polishing or pre-oxidation in steam. (3) The dominant growth of oxide film on the surface of zircaloy-2 was observed at the initial stage of oxidation in steam. However, the thickness of oxygen-rich solid solution layer under the film increased gradually with the progress of oxidation and the ratio of oxygen in oxide to that in solid solution has a constant value of 8:2. (4) The breakaway took place only in the specimen subjected to 900 0 C repeated heating. This penomenon was caused by the local growth of the oxide below a crack of the oxide film resulting from the reheating of the specimen. (5) The results of bending tests showed that the deflection until fracture of the specimen was smaller for the one heated at a higher temperature even if the weight increase was of the same order of magnitude for both specimens. (6) It was concluded that the ductility of zircaloy-2 decreased remarkably at a heating temperature in excess of 1100 0 C for more than 5 min. (auth.)

Oxidation kinetics of a continuous carbon phase in a nonreactive matrix

Science.gov (United States)

Eckel, Andrew J.; Cawley, James D.; Parthasarathy, Triplicane A.

1995-01-01

Analytical solutions of and experimental results on the oxidation kinetics of carbon in a pore are presented. Reaction rate, reaction sequence, oxidant partial pressure, total system pressure, pore/crack dimensions, and temperature are analyzed with respect to the influence of each on an overall linear-parabolic rate relationship. Direct measurement of carbon recession is performed using two microcomposite model systems oxidized in the temperature range of 700 to 1200 C, and for times to 35 h. Experimental results are evaluated using the derived analytical solutions. Implications on the oxidation resistance of continuous-fiber-reinforced ceramic-matrix composites containing a carbon constituent are discussed.

Influence of inlet concentration and light intensity on the photocatalytic oxidation of nitrogen(II) oxide at the surface of Aeroxide® TiO2 P25

International Nuclear Information System (INIS)

Dillert, Ralf; Stötzner, Julia; Engel, Astrid; Bahnemann, Detlef W.

2012-01-01

Highlights: ► The photocatalytic oxidation of nitrogen(II) oxide at the TiO 2 surface was studied. ► The effect of the UV(A) light intensity on the reaction rate was evaluated. ► The effect of the NO concentration on the reaction rate was evaluated. ► A mechanistic model for the heterogeneous NO oxidation is presented. ► A rate law describing the influence of NO concentration and light intensity is given. - Abstract: Air pollution by nitrogen oxides represents a serious environmental problem in urban areas where numerous sources of these pollutants are concentrated. One approach to reduce the concentration of these air pollutants is the light-induced oxidation in the presence of molecular oxygen and a photocatalytically active building material, e.g., paints, roof tiles, or pavement stones. Herein, results of an investigation concerning the photocatalytic oxidation of nitrogen(II) oxide (NO) in the presence of molecular oxygen and UV(A) irradiated TiO 2 powder are presented. The standard operating procedure described in ISO 22197-1 which was developed to characterize the photocatalytic activity of air-cleaning products was successfully applied to determine the photocatalytic activity of a bare TiO 2 powder. The experimental data reveal that at the light intensity stipulated by the operation procedure the amount of NO removed from the gas phase by photocatalytic oxidation is strongly affected by small changes of this light intensity as well as of the NO concentration in the gas stream in the photoreactor. Therefore, these parameters have to be controlled very carefully. Based upon the experimental data obtained in this study a rate law for the photocatalytic NO oxidation inside the photoreactor is derived.

High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 – O2 environment

International Nuclear Information System (INIS)

Farrokhzad, M A; Khan, T I

2014-01-01

Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al 2 O3 and TiO 2 ) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO 2 , 10% O 2 and 75% N 2 . This research investigates the effects of CO 2 and O 2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO 2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO 2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO 2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings

Behavior of shut-down dose rate of recirculation piping of BWR under noble metal application

International Nuclear Information System (INIS)

Fuse, Motomasa; Nagase, Makoto; Aizawa, Motohiro; Wada, Yoichi; Ishida, Kazushige; Hosokawa, Hideyuki; Hettiarachchi, Samson; Weber, Christoph

2014-01-01

The cause of shut-down dose rate change of the recirculation piping observed in KKM (Kern Kraftwerk Mühleberg) after application of noble metal injection method is analyzed. The plant experienced the sharp decrease of piping dose rate in the cycle just after the application of noble metal(classic NobleChem TM ) and re-buildup of radioactivity in the subsequent several cycles. After the application of online noble metal injection (online NobleChem TM ), gradual decrease of dose rate has been observed. The presence of a certain amount of noble metal on the iron rich oxide film promotes the dissolution of the oxide under hydrogen addition, resulting in a decrease of deposited noble metal on the oxide film surface as well as of radioactive species in the film. Under the condition of lower amount of noble metal on the surface oxides, the oxidant species, especially hydrogen peroxide, slightly increases facilitating the re-growth of iron rich oxides along with re-buildup of radioactivity. After the application of online noble metal injection during each cycle, gradual dissolution of iron rich oxides and gradual decrease of radioactivity in the oxides proceed to decrease the piping dose rate. In the radioactivity decreasing phase, the presence of zinc is considered to assist the suppression of radioactivity buildup in the oxide film. From the analysis, treating piping surface with platinum after chemical decontamination process is expected to work well for suppression of the piping dose rate. (author)

The influence of ion implantation on the oxidation of nickel

International Nuclear Information System (INIS)

Goode, P.D.

1975-11-01

The effects of ion implantation on the oxidation of polycrystalline nickel have been studied for a range of implanted species: viz. He, Li, Ne, Ca, Ti, Ni, Co, Xe, Ce and Bi. The oxides were grown in dry oxygen at 630 0 C and the 16 O(d,p) 17 O nuclear reaction technique used to determine the amount of oxygen taken up. The influence of atomic and ionic size, valency and electronegativity of the implanted impurities was studied as also were the effects of ion bombardment damage and the influence of sputtering during implantation. Atomic size and the annealing of disorder were found to have a marked influence on oxide growth rate. The dependence of oxidation on annealing was further studied by implanting polycrystalline specimens with self ions and observing the oxide growth rate as a function of annealing temperature. A peak in the curve was found at 400 0 C and a similar peak observed at a somewhat higher temperature for oxidised single crystals. It is concluded that the oxidation rate will be influenced by those factors which alter the epitaxial relationship between metal and growing oxide. Such factors include atomic size of the implanted species, surface strain induced by implantation and changes in surface topography as a result of sputtering. In addition a model based on vacancy assisted cation migration is proposed to explain enhanced oxidation observed over a limited temperature range. (author)

Optimization of a model of red blood cells for the study of anti-oxidant drugs, in terms of concentration of oxidant and phosphate buffer.

Science.gov (United States)

Bureau, A; Lahet, J-J; Lenfant, F; Bouyer, F; Petitjean, M; Chaillot, B; Freysz, M

2005-08-01

The aggression of erythrocytes by an oxidative stress induces hemolysis. This paper aims to valid a model of erythrocytes in terms of composition of the phosphate buffer solution and of concentration of a well-known oxidant, AAPH. Three compositions of phosphate buffer solution are mixed with three concentrations of oxidant. The influence of these two parameters on hemolysis is independently studied by a variance analysis and a Kruskal-Wallis test when ANOVA is not available. The hemolysis rate increases with time at fixed oxidant concentration, but is not influenced by the composition of the buffer solution. The highest hemolysis rate, 90%, was only measured within 2 h with the highest oxidant concentration. If we retain this concentration of oxidant, the lower concentration of the buffer can by eliminated by a significant less hemolysis and the highest concentration of the buffer can by chosen in regard of the better precision for a similar hemolysis compared to the mean buffer. We hope to study the effect of anti-oxidant agent with such a model of erythrocytes.

Improvement of uptake of chrome tan on hide protein by basic oxides

International Nuclear Information System (INIS)

Nashya, E.H.A.; Aggiagh, A.E.; Khedra, M.H.; El-Sayeda, N.H.E.

2005-01-01

Three basic oxides were used to improve uptake of chrome tan as well as shrinkage temperature of the tanned leather. In addition, the skin quality is one of the most important factors taking into consideration. Three basic oxides, named magnesium oxide, manganese oxide and sodium bicarbonate. The process was optimized taking into the account the shaking rate, chrome concentration (%), initial ph, basic oxides concentration, temperature and contact time. The optimum conditions for exhaustion, fixation, shrinkage temperature as well as skin quality showed that agitation rate of 150 rpm, chrome concentration of 16%, initial ph of 2.5, basic oxide concentration of 4% magnesium oxide, temperature of 35 degree C and contact time of 24 hr. The best results obtained are 88% exhaustion, 90.03% fixation and 109 degree C shrinkage temperature in aqueous medium

MHz-rate nitric oxide planar laser-induced fluorescence imaging in a Mach 10 hypersonic wind tunnel.

Science.gov (United States)

Jiang, Naibo; Webster, Matthew; Lempert, Walter R; Miller, Joseph D; Meyer, Terrence R; Ivey, Christopher B; Danehy, Paul M

2011-02-01

Nitric oxide planar laser-induced fluorescence (NO PLIF) imaging at repetition rates as high as 1 MHz is demonstrated in the NASA Langley 31 in. Mach 10 hypersonic wind tunnel. Approximately 200 time-correlated image sequences of between 10 and 20 individual frames were obtained over eight days of wind tunnel testing spanning two entries in March and September of 2009. The image sequences presented were obtained from the boundary layer of a 20° flat plate model, in which transition was induced using a variety of different shaped protuberances, including a cylinder and a triangle. The high-speed image sequences captured a variety of laminar and transitional flow phenomena, ranging from mostly laminar flow, typically at a lower Reynolds number and/or in the near wall region of the model, to highly transitional flow in which the temporal evolution and progression of characteristic streak instabilities and/or corkscrew-shaped vortices could be clearly identified.

Formation of Oxides in the Interior of Friction Stir Welds

Science.gov (United States)

Schneider, Judy; Chen, Po; Nunes, Arthur C., Jr.

2016-01-01

In friction stir welding (FSWing) the actual solid state joining takes place between the faying surfaces which form the weld seam. Thus the seam trace is often investigated for clues when the strength of the weld is reduced. Aluminum and its alloys are known to form a native, protective oxide on the surface. If these native surface oxides are not sufficiently broken up during the FSW process, they are reported to remain in the FSW interior and weaken the bond strength. This type of weld defect has been referred to as a lazy "S", lazy "Z", joint line defect, kissing bond, or residual oxide defect. Usually these defects are mitigated by modification of the process parameters, such as increased tool rotation rate, which causes a finer breakup of the native oxide particles. This study proposes that there may be an alternative mechanism for formation of oxides found within the weld nugget. As the oxidation rate increases at elevated temperatures above 400ºC, it may be possible for enhanced oxidation to occur on the interior surfaces during the FSW process from entrained air entering the seam gap. Normally, FSWs of aluminum alloys are made without a purge gas and it is unknown how process parameters and initial fit up could affect a potential air path into the interior during the processing. In addition, variations in FSW parameters, such as the tool rotation, are known to have a strong influence on the FSW temperature which may affect the oxidation rate if internal surfaces are exposed to entrained air. A series of FSWs were made in 3 different thickness panels of AA2219 (0.95, 1.27 and 1.56 cm) at 2 different weld pitches. As the thickness of the panels increased, there was an increased tendency for a gap to form in advance of the weld tool. If sufficient air is able to enter the workpiece gap prior to consolidation, the weld temperature can increase the oxidation rate on the interior surfaces. These oxidation rates would also be accelerated in areas of localized

Oxidation of Zircaloy-4 under limited steam supply at 1000 and 13000C

International Nuclear Information System (INIS)

Uetsuka, H.

1984-12-01

With the view of examining the oxidation behavior of Zircaloy-4 under limited steam supply occurring in severe accidents of LWRs, Zircaloy-4 cladding specimens were examined at the isothermal oxidation temperatures of 1000 and 1300 0 C under a steam atmosphere, flowing at a reduced and constant rate in the range of 3proportional170 mg/cm 2 xmin. The effect of steam starvation, which was restricted to very low levels of steam supply rate, was observed at the two examined temperatures. And the critical supply rate of steam starvation was evaluated to be 13 and 20 mg/cm 2 xmin for the oxidation at 1000 and 1300 0 C, respectively. Variation of the oxidation duration between 2 and 60 min at 1000 0 C allowed to compare the reaction kinetics for three different rates of steam supply. The short-term results confirmed the reduced reaction rates for the lower steam supplies. At the longer times, however, a clear trend towards linear kinetics was observed for the lower supplies. This can be interpreted as the result of earlier breakaway transition under limited steam supply. In the test at 1300 0 C, an acceleration of the oxidation rate was measured for the specified steam supply rate between 20 and 60 mg/cm 2 xmin. This related strongly with high hydrogen concentration in the atmosphere. Hydrogen blanketing - the retarding effect of hydrogen on Zircaloy oxidation - was not identified in the examined temperature range. (orig./HP) [de

Aromatics oxidation and soot formation in flames

Energy Technology Data Exchange (ETDEWEB)

Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T. [Massachusetts Institute of Technology, Cambridge (United States)

1993-12-01

This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify and to determine or confirm rate constants for the main benzene oxidation reactions in flames, and to characterize fullerenes and their formation mechanisms and kinetics.

Formation and dissolution of the anodic oxide film on zirconium in alcoholic aqueous solutions

International Nuclear Information System (INIS)

Mogoda, A.S.

1995-01-01

The dissolution behavior of the anodic oxide film formed in alcoholic aqueous solutions was studied. Results indicated the dissolution mechanism of the duplex oxide film followed a zero-order rate equation. The increase in methanol concentration in the formation medium (phosphoric acid [H 3 PO 4 ]) resulted in formation of an oxide film that incorporated little phosphate ion and that dissolved at a low rate. The dissolution rate of the oxide film decreased with increasing methanol concentration in the dissolution medium. This was attributed to the increase in the viscosity of the medium, which led to a decrease in the diffusion coefficient of the dissolution product of the zirconium oxide film. Dissolution of the anodic oxide film also was investigated as a function of the chain length of alcohols

Copper-mediated oxidative degradation of catecholamines and oxidative damage of protein

Energy Technology Data Exchange (ETDEWEB)

Goncalves, P.R.; Harria, M.I.N.; Felix, J.M.; Hoffmann, M.E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Biologia

1997-12-31

Full text. Degradative oxidation of catecholamines has been a matter of large interest in recent years due to the evidences associating their autoxidation with the etiology of neurotoxic and cardiotoxic processes. In this work we present data on the degradative oxidation of catecholamines of physiological importance: isoproterenol (IP), epinephrine (EP), norepinephrine (NEP), deoxyepinephrine (DEP) and dopamine (DA). The degradative oxidation of the catecholamines was followed by measurement of spectral changes and oxygen consumption by neutral aqueous solutions. The data show that Cu{sup 2+} strongly accelerated the rate of catecholamine oxidation, following the decreasing order; EP>DEP>IP>NEP>DA. The production of superoxide anion radical during catecholamine oxidation was very slow, even in the presence of Cu{sup 2+}. The ability of IP to induce damages on bovine serum albumin (BSA) was determined by measuring the formation of carbonyl-groups in the protein, detected by reduction with tritiated Na BH{sub 4}. The incubation of BSA with IP (50-500{mu}M), in the presence of 100{mu}M Cu{sup 2+} leaded to an increased and dose dependent {sup 3} H-incorporation by the oxidized protein. The production of oxidative damage by IP/Cu{sup 2+} was accompanied by marked BSA fragmentation, detected by SDS-polyacrylamide gel dependent (25-400{mu}M IP) des appearance of the original BSA band and appearance of smaller fragments spread in the gel, when incubation has been done in the presence of 100{mu}M Cu{sup 2+}. These results suggest that copper-catalysed oxidative degradation of proteins induced by catecholamines might be critically involved in the toxic action of these molecules

Comparison of iron and copper doped manganese cobalt spinel oxides as protective coatings for solid oxide fuel cell interconnects

DEFF Research Database (Denmark)

Talic, Belma; Molin, Sebastian; Wiik, Kjell

2017-01-01

MnCo2O4, MnCo1.7Cu0.3O4 and MnCo1.7Fe0.3O4 are investigated as coatings for corrosion protection of metallic interconnects in solid oxide fuel cell stacks. Electrophoretic deposition is used to deposit the coatings on Crofer 22 APU alloy. All three coating materials reduce the parabolic oxidation...... rate in air at 900 °C and 800 °C. At 700 °C there is no significant difference in oxidation rate between coated samples and uncoated pre-oxidized Crofer 22 APU. The cross-scale area specific resistance (ASR) is measured in air at 800 °C using La0.85Sr0.1Mn1.1O3 (LSM) contact plates to simulate...... contain significant amounts of Cr after aging, while all three coatings effectively prevent Cr diffusion into the LSM. A complex Cr-rich reaction layer develops at the coating-alloy interface during oxidation. Cu and Fe doping reduce the extent of this reaction layer at 900 °C, while at 800 °C the effect...

Relationship between hyposalivation and oxidative stress in aging mice.

Science.gov (United States)

Yamauchi, Yoshitaka; Matsuno, Tomonori; Omata, Kazuhiko; Satoh, Tazuko

2017-07-01

The increase in oxidative stress that accompanies aging has been implicated in the abnormal advance of aging and in the onset of various systemic diseases. However, the details of what effects the increase in oxidative stress that accompanies aging has on saliva secretion are not known. In this study, naturally aging mice were used to examine the stimulated whole saliva flow rate, saliva and serum oxidative stress, antioxidant level, submandibular gland H-E staining, and immunofluorescence staining to investigate the effect of aging on the volume of saliva secretion and the relationship with oxidative stress, as well as the effect of aging on the structure of salivary gland tissue. The stimulated whole saliva flow rate decreased significantly with age. Also, oxidative stress increased significantly with age. Antioxidant levels, however, decreased significantly with age. Structural changes of the submandibular gland accompanying aging included atrophy of parenchyma cells and fatty degeneration and fibrosis of stroma, and the submandibular gland weight ratio decreased. These results suggest that oxidative stress increases with age, not just systemically but also locally in the submandibular gland, and that oxidative stress causes changes in the structure of the salivary gland and is involved in hyposalivation.

Oxidation kinetics of hydride-bearing uranium metal corrosion products

Science.gov (United States)

Totemeier, Terry C.; Pahl, Robert G.; Frank, Steven M.

The oxidation behavior of hydride-bearing uranium metal corrosion products from Zero Power Physics Reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2, Ar-9%O 2, and Ar-20%O 2. Ignition of corrosion product samples from two moderately corroded plates was observed between 125°C and 150°C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride.

Platinized titanium dioxide electrodes for methanol oxidation and photo-oxidation

Directory of Open Access Journals (Sweden)

IOANNIS POULIOS

2012-11-01

Full Text Available Platinized deposits have been formed on TiO2 particulate films supported on Ti substrates, by means of galvanic replacement of pre-deposited metallic Cu and subsequent immersion of the Cu/TiO2 coatings into a chloroplatinic acid solution. The spontaneous replacement of Cu by Pt results in Pt(Cu/TiO2/Ti electrodes. Both the platinized and the precursor TiO2/Ti electrodes have been characterized by SEM micro­scopy/EDS spectroscopy, their surface electrochemistry has been assessed by cyclic voltammetry in the dark and their photoelectrochemical properties by photovolta­m­metry under UV illumination. It has been found that, although platinized rutile-rich electrodes exhibit typical Pt surface electrochemistry, the anatase-rich electrodes show only traces of oxide formation and stripping. The latter has been translated to a suppression of methanol oxidation at anatase-rich electrodes. On the contrary, methanol oxidation at platinized rutile-rich electrodes occurs at significant rates and can be further enhanced upon UV illumination, as a result of Pt and TiO2 synergism in the photoelectrochemical oxidation of methanol.