Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Explosive decomposition of ethylene oxide at elevated condition: effect of ignition energy, nitrogen dilution, and turbulence.

PubMed

Pekalski, A A; Zevenbergen, J F; Braithwaite, M; Lemkowitz, S M; Pasman, H J

2005-02-14

Experimental and theoretical investigation of explosive decomposition of ethylene oxide (EO) at fixed initial experimental parameters (T=100 degrees C, P=4 bar) in a 20-l sphere was conducted. Safety-related parameters, namely the maximum explosion pressure, the maximum rate of pressure rise, and the Kd values, were experimentally determined for pure ethylene oxide and ethylene oxide diluted with nitrogen. The influence of the ignition energy on the explosion parameters was also studied. All these dependencies are quantified in empirical formulas. Additionally, the effect of turbulence on explosive decomposition of ethylene oxide was investigated. In contrast to previous studies, it is found that turbulence significantly influences the explosion severity parameters, mostly the rate of pressure rise. Thermodynamic models are used to calculate the maximum explosion pressure of pure and of nitrogen-diluted ethylene oxide, at different initial temperatures. Soot formation was experimentally observed. Relation between the amounts of soot formed and the explosion pressure was experimentally observed and was calculated.

High-resolution experiments on chemical oxidation of DNAPL in variable-aperture fractures

NASA Astrophysics Data System (ADS)

Arshadi, Masoud; Rajaram, Harihar; Detwiler, Russell L.; Jones, Trevor

2015-04-01

Chemical oxidation of dense nonaqueous-phase liquids (DNAPLs) by permanganate has emerged as an effective remediation strategy in fractured rock. We present high-resolution experimental investigations in transparent analog variable-aperture fractures to improve understanding of chemical oxidation of residual entrapped trichloroethylene (TCE) in fractures. Four experiments were performed with different permanganate concentrations, flow rates, and initial TCE phase geometry. The initial aperture field and evolving entrapped-phase geometry were quantified for each experiment. The integrated mass transfer rate from the TCE phase for all experiments exhibited three time regimes: an early-time regime with slower mass transfer rates limited by low specific interfacial area; an intermediate-time regime with higher mass transfer rates resulting from breakup of large TCE blobs, which greatly increases specific interfacial area; and a late-time regime with low mass transfer rates due to the deposition of MnO2 precipitates. In two experiments, mass balance analyses suggested that TCE mass removal rates exceeded the maximum upper bound mass removal rates derived by assuming that oxidation and dissolution are the only mechanisms for TCE mass removal. We propose incomplete oxidation by permanganate and TCE solubility enhancement by intermediate reaction products as potential mechanisms to explain this behavior. We also speculate that some intermediate reaction products with surfactant-like properties may play a role in lowering the TCE-water interfacial tension, thus causing breakup of large TCE blobs. Our quantitative experimental measurements will be useful in the context of developing accurate computational models for chemical oxidation of TCE in fractures.

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

NASA Astrophysics Data System (ADS)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral-water interface.

Acetobacter pasteurianus metabolic change induced by initial acetic acid to adapt to acetic acid fermentation conditions.

PubMed

Zheng, Yu; Zhang, Renkuan; Yin, Haisong; Bai, Xiaolei; Chang, Yangang; Xia, Menglei; Wang, Min

2017-09-01

Initial acetic acid can improve the ethanol oxidation rate of acetic acid bacteria for acetic acid fermentation. In this work, Acetobacter pasteurianus was cultured in ethanol-free medium, and energy production was found to increase by 150% through glucose consumption induced by initial acetic acid. However, oxidation of ethanol, instead of glucose, became the main energy production pathway when upon culturing ethanol containing medium. Proteome assay was used to analyze the metabolism change induced by initial acetic acid, which provided insight into carbon metabolic and energy regulation of A. pasteurianus to adapt to acetic acid fermentation conditions. Results were further confirmed by quantitative real-time PCR. In summary, decreased intracellular ATP as a result of initial acetic acid inhibition improved the energy metabolism to produce more energy and thus adapt to the acetic acid fermentation conditions. A. pasteurianus upregulated the expression of enzymes related to TCA and ethanol oxidation to improve the energy metabolism pathway upon the addition of initial acetic acid. However, enzymes involved in the pentose phosphate pathway, the main pathway of glucose metabolism, were downregulated to induce a change in carbon metabolism. Additionally, the enhancement of alcohol dehydrogenase expression promoted ethanol oxidation and strengthened the acetification rate, thereby producing a strong proton motive force that was necessary for energy production and cell tolerance to acetic acid.

Surface spectroscopy studies of the oxidation behavior of uranium

NASA Astrophysics Data System (ADS)

Bloch, J.; Atzmony, U.; Dariel, M. P.; Mintz, M. H.; Shamir, N.

1982-02-01

Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) techniques were utilized to study the oxidation behavior of clean uranium surfaces, at very low pressures of various atmospheres (UHV, H 2, O 2, and CO 2), at room temperature. Both for O 2 and CO 2, a precursor chemisorbed oxygen species has been identified at the very initial stage of the oxidation reaction. This chemisorbed oxygen transforms to the oxide form at a rate which depends on the pressure of the oxidizing atmosphere. Residual gaseous carbon compounds which are present even under UHV conditions result in the simultaneous formation of surface carbide which accompanies the initial stage of oxidation. This carbide however decomposes later as oxidation proceeds. Adventitious hydrocarbon adsorption occurs on the formed oxide layer.

Factors Affecting Oxidation of Thiosalts by Thiobacilli

PubMed Central

Silver, M.; Dinardo, O.

1981-01-01

The effects of temperature, initial pH, and the concentrations of ammonium, phosphate, and heavy metals on the oxidation of thiosalts by an authentic strain of Thiobacillus thiooxidans (ATCC 8085) and by a mixed culture isolated from a base metal-processing mill effluent pond were studied. The optimum temperature was 30°C and the optimum initial pH was 3.75 for both cultures using thiosulfate and for the mixed culture using tetrathionate. T. thiooxidans ATCC 8085 did not oxidize tetrathionate. For a thiosalt concentration of 2,000 ppm (2,000 mg/liter), maximal rates of destruction occurred at concentrations of ammonium ion above 2 mg/liter and in the presence of 1 mg of phosphate per liter. Under optimal conditions, the rate of thiosulfate oxidation by the pure culture was 55 ± 3 mg/liter per h; the mixed culture oxidized thiosulfate at the rate of 40 ± 1 mg/liter per h and tetrathionate at the rate of 50 ± 2 mg/liter per h. Metal ions caused normal inhibition kinetics in the oxidation of thiosulfate by T. thiooxidans ATCC 8085. Ki values were calculated for cadmium (16 mg/liter), copper (0.46 mg/liter), lead (2 mg/liter), silver (3.1 mg/liter), and zinc (33 mg/liter). Only a slight additive effect was apparent in the presence of all of these metal ions. The mixed culture of thiosalt-oxidizing bacteria was less sensitive to heavy metal inhibition; the order of inhibition of thiosulfate oxidation was Cd < Zn < Pb < Ag < Cu, and that of tetrathionate oxidation was Zn < Cd < Pb < Ag < Cu. PMID:16345785

Theoretical perspectives on the mechanism and kinetics of the OH radical-initiated gas-phase oxidation of PCB126 in the atmosphere.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Wang, Wenxing

2015-06-01

Polychlorinated biphenyls (PCBs) primarily exist in the gas phase in air and may undergo atmospheric oxidation degradations, particularly the oxidation reaction initiated by OH radicals. In this work, the mechanism of the OH radical-initiated atmospheric oxidation of the most toxic PCB congener 3,3',4,4',5-pentachlorobiphenyl (PCB126) was investigated by using quantum chemistry methods. The rate constants of the crucial elementary reactions were estimated by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The oxidation products of the reaction of PCB126 with OH radicals include 3,3',4,4',5-pentachlorobiphenyl-ols, chlorophenols, 2,3,4,7,8-pentachlorodibenzofuran, 2,3,4,6,7-pentachlorodibenzofuran, dialdehydes, 3,3',4,4',5-pentachloro-5'-nitro-biphenyl, and 4,5-dichloro-2-nitrophenol. Particularly, the formation of polychlorinated dibenzofurans (PCDFs) from the atmospheric oxidation of PCBs is revealed for the first time. The overall rate constant of the OH addition reaction is 2.52×10(-13)cm(3)molecule(-1)s(-1) at 298K and 1atm. The atmospheric lifetime of PCB126 determined by OH radicals is about 47.08days which indicates that PCB126 can be transported long distances from local to global scales. Copyright © 2015 Elsevier B.V. All rights reserved.

Literature survey on oxidations and fatigue lives at elevated temperatures

NASA Technical Reports Server (NTRS)

Liu, H. W.; Oshida, Y.

1984-01-01

Nickel-base superalloys are the most complex and the most widely used for high temperature applications such as aircraft engine components. The desirable properties of nickel-base superalloys at high temperatures are tensile strength, thermomechanical fatigue resistance, low thermal expansion, as well as oxidation resistance. At elevated temperature, fatigue cracks are often initiated by grain boundary oxidation, and fatigue cracks often propagate along grain boundaries, where the oxidation rate is higher. Oxidation takes place at the interface between metal and gas. Properties of the metal substrate, the gaseous environment, as well as the oxides formed all interact to make the oxidation behavior of nickel-base superalloys extremely complicated. The important topics include general oxidation, selective oxidation, internal oxidation, grain boundary oxidation, multilayer oxide structure, accelerated oxidation under stress, stress-generation during oxidation, composition and substrate microstructural changes due to prolonged oxidation, fatigue crack initiation at oxidized grain boundaries and the oxidation accelerated fatigue crack propagation along grain boundaries.

Neutral fat hydrolysis and long-chain fatty acid oxidation during anaerobic digestion of slaughterhouse wastewater.

PubMed

Masse, L; Massé, D I; Kennedy, K J; Chou, S P

2002-07-05

Neutral fat hydrolysis and long-chain fatty acid (LCFA) oxidation rates were determined during the digestion of slaughterhouse wastewater in anaerobic sequencing batch reactors operated at 25 degrees C. The experimental substrate consisted of filtered slaughterhouse wastewater supplemented with pork fat particles at various average initial sizes (D(in)) ranging from 60 to 450 microm. At the D(in) tested, there was no significant particle size effect on the first-order hydrolysis rate. The neutral fat hydrolysis rate averaged 0.63 +/- 0.07 d(-1). LCFA oxidation rate was modelled using a Monod-type equation. The maximum substrate utilization rate (kmax) and the half-saturation concentration (Ks) averaged 164 +/- 37 mg LCFA/L/d and 35 +/- 31 mg LCFA/L, respectively. Pork fat particle degradation was mainly controlled by LCFA oxidation rate and, to a lesser extent, by neutral fat hydrolysis rate. Hydrolysis pretreatment of fat-containing wastewaters and sludges should not substantially accelerate their anaerobic treatment. At a D(in) of 450 microm, fat particles were found to inhibit methane production during the initial 20 h of digestion. Inhibition of methane production in the early phase of digestion was the only significant effect of fat particle size on anaerobic digestion of pork slaughterhouse wastewater. Soluble COD could not be used to determine the rate of lipid hydrolysis due to LCFA adsorption on the biomass.

The effect of oxide film properties on the corrosion behavior of SiC/Al metal-matrix composites

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

Golledge, S.L.

1991-01-01

Oxide growth on pure aluminum, aluminum alloy 6061, and the aluminum-based metal matrix composite SiC/AA6061 was studied, and the properties of the oxides related to the pit-initiation behavior of the materials. The objectives of the work were to identify the effect of alloying elements and SiC reinforcement on the oxide film, and to better understand how the oxide properties control pit initiation behavior. To this end, electrochemical and optical studies of the materials were carried out in a buffered sodium/boric acid solution at pH values of 8.4 and 7.2. The alloy and metal-matrix composite showed a slightly lesser tendency tomore » pit than pure aluminum, as measured by the pitting potential. The oxide on the composite was less resistant to pit initiation, and was found to exhibit slower repassivation rates than the other materials. The repassivation behavior and resistance to pit initiation were quite similar in the case of the alloy and the pure aluminum. Induction times for pit initiation were consistent with the predictions of Heusler's model for the breakdown of passivity.« less

A long-term bench-scale investigation of permanganate consumption by aquifer materials.

PubMed

Xu, Xiuyuan; Thomson, Neil R

2009-11-20

In situ chemical oxidation (ISCO) applications using permanganate involve the injection or release of permanganate into the subsurface to destroy various target contaminants. Naturally occurring reduced components associated with aquifer materials can exert a significant oxidant demand thereby reducing the amount of permanganate available for the destruction of contaminants as well as reducing the overall rate of oxidation. Quantification of this natural oxidant demand (NOD) is a requirement for site-specific assessment and the design of cost-effective oxidant delivery systems. To further our understanding of the interaction between permanganate and aquifer materials, aerobic and anaerobic aquifer materials from eight representative sites throughout North America were tested in a series of systematic bench-scale experiments. Various permanganate to aquifer solids mass loading ratios at different initial permanganate concentrations in well-mixed batch reactors were monitored for >300 days. All NOD temporal profiles demonstrated an initial fast consumption rate followed by a persistent slower consumption rate. The data generated show that the mass loading ratio, the initial permanganate concentration, and the nature and quantity of reduced aquifer material species are the main factors controlling permanganate consumption rates. A higher initial permanganate concentration or a larger mass loading ratio produced a larger fast NOD consumption rate and generated a corresponding higher maximum NOD value. Hence, both the NOD temporal profile and the maximum NOD are not single-valued but are heavily dependent on the experimental conditions. Predictive relationships were developed to estimate the maximum NOD and the NOD at 7 days based on aquifer material properties. The concentration of manganese oxides deposited on the aquifer solids was highly correlated with the mass of permanganate consumed suggesting that passivation of NOD reaction sites occurred due to the formation of manganese oxide coating on the grains. A long-term NOD kinetic model was developed assuming a single fast and slow reacting oxidizable aquifer material species, passivation of NOD reaction sites, and the presence of an autocatalytic reaction. The developed model was able to successfully capture the observed NOD temporal profiles, and can be used to estimate in situ NOD behavior using batch reactor experimental data. The use of batch tests to provide data representative of in situ conditions should be used with caution.

Transport with Bimolecular Reactions: Applications to In-Situ Chemical Oxidation of DNAPLs by Permanganate in Fractured Rock

NASA Astrophysics Data System (ADS)

Arshadi, Masoud

Chemical oxidation of dense nonaqueous-phase liquids (DNAPLs) by permanganate has emerged as an effective remediation strategy in fractured rock. Our objectives in this research were to carry out a sequence of experimental, computational and theoretical tasks aimed at improving current understanding of permanganate oxidation in fractured rock systems, and also develop modeling tools that can be used for preliminary design of oxidation schemes at field sites. Our research focused on both free-phase entrapped DNAPL in variable-aperture fractures and dissolved DNAPL in the rock matrix. In the first section of our research, we present high-resolution experimental investigations in transparent analog variable-aperture fractures to improve understanding of chemical oxidation of residual entrapped trichloroethylene (TCE) in fractures. Four experiments were performed with different permanganate concentrations, flow rates, and initial TCE phase geometry. The initial aperture field and evolving entrapped-phase geometry were measured quantitatively. We present results on the time-evolution of fracture-scale TCE consumption and DNAPL removal rates for all the experiments. In the next part of this work, we developed theoretical understanding of the reaction front dynamics in the case of chemical oxidation of aqueous-phase DNAPL within fracture-matrix system, backed up by numerical simulations. We also consider the influence of NOD consumption and contaminant sorption to solid aquifer materials in our models. Based on the results from this task we are able to propose simple strategies for remediation design (e.g. the time needed to degrade DNAPL inside the fracture-matrix system and the permanganate injection pattern) for a given set of conditions. Our numerical simulations of diffusion with bimolecular reaction in the rock matrix demonstrated a transition in the spatially integrated reaction rate - increasing with time initially, and transitioning to a decrease with time. We developed a general non-dimensionalization of the problem and a perturbation analysis to show that there is always an early time regime where the spatially integrated reaction rate scales as √t rather than 1/√t. The duration of this early time regime (where the total reaction rate is kinetically rather than diffusion controlled) is shown to depend on the kinetic rate parameters, diffusion coefficients and initial concentrations of the two species.

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

Mihaela Grigore; Richard Sakurovs; David French

Gasification of coke contributes to its degradation in the blast furnace. In this study, the effect of gasification on the inherent catalytic minerals in cokes and their reciprocal influence on gasification are investigated. The catalytic mineral phases identified in the cokes used in this study were metallic iron, iron sulfides, and iron oxides. Metallic iron and pyrrhotite were rapidly oxidized during gasification to iron oxide. The catalysts had a strong influence on the apparent rates at the initial stages of reaction. As gasification proceeds, their effect on the reaction rate diminishes as a result of reducing the surface contact betweenmore » catalyst and carbon matrix because of carbon consumption around the catalyst particles; with extended burnout the reactivity of the coke becomes increasingly dependent on surface area. The reaction rate in the initial stages was also influenced by the particle size of the catalytic minerals; for a given catalytic iron level, the cokes whose catalytic minerals were more finely dispersed had a higher apparent reaction rate than cokes containing larger catalytic particles. Iron, sodium, and potassium in the amorphous phase did not appear to affect the reaction rate. 40 refs., 16 figs., 6 tabs.« less

Modification of molybdenum surface by low-energy oxygen implantation at room temperature

NASA Astrophysics Data System (ADS)

Kavre Piltaver, Ivna; Jelovica Badovinac, Ivana; Peter, Robert; Saric, Iva; Petravic, Mladen

2017-12-01

We have studied the initial stages of oxide formation on molybdenum surfaces under 1 keV O2+ ion bombardment at room temperature (RT), using x-ray photoelectron spectroscopy around Mo 3d or O 1s core-levels and the valence band photoemission. The results are compared with the oxidation mechanism of thermally oxidized Mo at RT. The thermal oxidation reveals the formation of a very thin MoO2 layer that prevents any further adsorption of oxygen at higher oxygen doses. Oxygen implantation is more efficient in creating thicker oxide films with the simultaneous formation of several oxide compounds. The oxidation rates of MoO2 and Mo2O5 follow the parabolic growth rate consistent with the mass transport driven by diffusion of either neutral or singly and doubly charged oxygen interstitials. The oxidation of MoO3, which occurs at a later oxidation stage, follows the logarithmic rate driven by the diffusion of cations in an electric field.

A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene

NASA Astrophysics Data System (ADS)

Cui, Yang; Ding, Zhezheng; Sun, Yanhui; Yi, Yayi; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

2018-05-01

OH-initiated atmospheric oxidation mechanism of 1-chloronaphthalene (1-CN) was investigated using density functional theory (DFT) calculations. The oxidation is predicted to be initiated by OH addition to the α-positions, and the additions to C4 and C5 are more favorable. 1-CN-OH adducts tend to react with ambient O2 to produce peroxy intermediates, followed by intramolecular H-shifts producing C10H7OCl and diketone or unimolecular ring closure forming methyl glyoxal and Cl-substituted phthalaldialdehyde. Despite that the rate constants are influenced by the tunneling factors, intramolecular H-shift reactions are suggested to be more favorable. The OH-determined lifetime of 1-CN is 0.62 days.

High-temperature oxidation behavior of reaction-formed silicon carbide ceramics

NASA Technical Reports Server (NTRS)

Ogbuji, Linus U. J. T.; Singh, M.

1995-01-01

The oxidation behavior of reaction-formed silicon carbide (RFSC) ceramics was investigated in the temperature range of 1100 to 1400 C. The oxidation weight change was recorded by TGA; the oxidized materials were examined by light and electron microscopy, and the oxidation product by x-ray diffraction analysis (XRD). The materials exhibited initial weight loss, followed by passive weight gain (with enhanced parabolic rates, k(sub p)), and ending with a negative (logarithmic) deviation from the parabolic law. The weight loss arose from the oxidation of residual carbon, and the enhanced k(sub p) values from internal oxidation and the oxidation of residual silicon, while the logarithmic kinetics is thought to have resulted from crystallization of the oxide. The presence of a small amount of MoSi, in the RFSC material caused a further increase in the oxidation rate. The only solid oxidation product for all temperatures studied was silica.

Oxidation Behavior of GRCop-84 (Cu-8Cr-4Nb) at Intermediate and High Temperatures

NASA Technical Reports Server (NTRS)

Thomas-Ogbuji, Linus U.; Humphrey, Donald L.; Greenbauer-Seng, Leslie (Technical Monitor)

2000-01-01

The oxidation behavior of GRCop-84 (Cu-8 at %Cr-4 at %Nb) has been investigated in air and in oxygen, for durations of 0.5 to 50 hours and temperatures ranging from 500 to 900 C. For comparison, data was also obtained for the oxidation of Cu and NARloy-Z (Cu-3 wt% Ag-0.5 wt% Zr) under the same conditions. Arrhenius plots of those data showed that all three materials had similar oxidation rates at high temperatures (> 750 C). However, at intermediate temperatures (500 to 750 C) GRCop exhibited significantly higher oxidation resistance than Cu and NARloy-Z. The oxidation kinetics of GRCop-84 exhibited a sharp and discontinuous jump between the two regimes. Also, in the high temperature regime GRCop-84 oxidation rate was found to change from a high initial value to a significantly smaller terminal value at each temperature, with progress of oxidation; the two different oxidation rates were found to correlate with a porous intial oxide and a dense final oxide, respectively.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

Zalkind, S.; Rafailov, G.; Halevy, I.; Livneh, T.; Rubin, A.; Maimon, H.; Schweke, D.

2017-03-01

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 UO2(111) is the prominent one. As the oxide thickens, the growth rate of UO2(220) plane increases and both planes grow concurrently. The activation energies obtained for the oxide growth are Qparabolic = 17.5 kcal/mol and Qlinear = 19 kcal/mol. Enhanced oxidation around uranium carbide (UC) inclusions is clearly observed by scanning electron microscopy (SEM).

Fabrication of a Biologically-Implantable, Multiplexed, Multielectrode Array of JFETS for Cortical Implantation.

DTIC Science & Technology

1984-12-01

which could be implanted at the surface of the brain. Electrodes of microfine dimensions I-1 . ..6...to check the operation of the diffusion furnace oxidation tube by comparing measured thicknesses of the oxide against calculated values. Oxide Growth...faster rate than that of Eq ), (11-2). Initial adjustments made prior to using the diffusion furnace included: (1) profiling the oxidation tube to

A Comparative Study of Cyclic Oxidation and Sulfates-Induced Hot Corrosion Behavior of Arc-Sprayed Ni-Cr-Ti Coatings at Moderate Temperatures

NASA Astrophysics Data System (ADS)

Guo, Wenmin; Wu, Yuping; Zhang, Jianfeng; Hong, Sheng; Chen, Liyan; Qin, Yujiao

2015-06-01

The cyclic oxidation and sulfates-induced hot corrosion behaviors of a Ni-43Cr-0.3Ti arc-sprayed coating at 550-750 °C were characterized and compared in this study. In general, all the oxidation and hot corrosion kinetic curves of the coating followed a parabolic law, i.e., the weight of the specimens showed a rapid growth initially and then reached the gradual state. However, the initial stage of the hot corrosion process was approximately two times longer than that of the oxidation process, indicating a longer preparation time required for the formation of a protective scale in the former process. At 650 °C, the parabolic rate constant for the hot corrosion was 7.2 × 10-12 g2/(cm4·s), approximately 1.7 times higher than that for the oxidation at the same temperature. The lower parabolic rate constant for the oxidation was mainly attributed to the formation of a protective oxide scale on the surface of corroded specimens, which was composed of a mixture of NiO, Cr2O3, and NiCr2O4. However, as the liquid molten salts emerged during the hot corrosion, these protective oxides would be dissolved and the coating was corrupted acceleratedly.

Halogens and the Chemistry of the Free Troposphere

NASA Technical Reports Server (NTRS)

Lary, David John

2004-01-01

The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of BrONO2 alone can contribute more than 35% of the HNO3 production rate in the free-troposphere.

[Effect of SO2 volume fraction in flue gas on the adsorption behaviors adsorbed by ZL50 activated carbon and kinetic analysis].

PubMed

Gao, Ji-xian; Wang, Tie-feng; Wang, Jin-fu

2010-05-01

The influence of SO2 dynamic adsorption behaviors using ZL50 activated carbon for flue gas desulphurization and denitrification under different SO2 volume fraction was investigated experimentally, and the kinetic analysis was conducted by kinetic models. With the increase of SO2 volume fraction in flue gas, the SO2 removal ratio and the activity ratio of ZL50 activated carbon decreased, respectively, and SO2 adsorption rate and capacity increased correspondingly. The calculated results indicate that Bangham model has the best prediction effect, the chemisorption processes of SO2 was significantly affected by catalytic oxidative reaction. The adsorption rate constant of Lagergren's pseudo first order model increased with the increase of inlet SO, volume fraction, which indicated that catalytic oxidative reaction of SO2 adsorbed by ZL50 activated carbon may be the rate controlling step in earlier adsorption stage. The Lagergren's and Bangham's initial adsorption rate were deduced and defined, respectively. The Ho's and Elovich's initial adsorption rate were also deduced in this paper. The Bangham's initial adsorption rate values were defined in good agreement with those of experiments. The defined Bangham's adsorptive reaction kinetic model can describe the SO2 dynamic adsorption rate well. The studied results indicated that the SO2 partial order of initial reaction rate was one or adjacent to one, while the O2 and water vapor partial order of initial reaction rate were constants ranging from 0.15-0.20 and 0.45-0.50, respectively.

Mechanism and kinetic properties for the OH-initiated atmospheric oxidation degradation of 9,10-Dichlorophenanthrene.

PubMed

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu; Hu, Jingtian; Wang, Wenxing

2015-02-01

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl₂Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl₂Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35 × 10(-12)cm(3) molecule(-1)s(-1) at 298 K and 1 atm. The atmospheric lifetime of 9,10-Cl₂Phe determined by OH radicals is about 5.05 days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl₂Phe and should contribute to clarifying its atmospheric fate. Copyright © 2014 Elsevier B.V. All rights reserved.

THE BREAKDOWN OF THE PROTECTIVE OXIDE FILM ON TRANSITION METAL ALLOYS

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

Smeltzer, W.W.

1960-04-01

Initial breaks in oxidation curves of iron-chromium alloys were found to be associated with the ferriteaustenitic phase transformation. This transformation was caused by preferential oxidation of chromium at a rate much larger than its replenishment by diffusion the metal-oxide interface. The stress resulting from this transformation caused breakdown of the protective oxide film. Results indicated that continuous oxidation curves for iron-chromium alloys could be obtained under conditions where preferential oxidation of in alloy constituent did not cause the ferritic-austentic phase transformation. (M.C.G.)

Formation of Manganese Oxide Coatings onto Sand for Adsorption of Trace Metals from Groundwater.

PubMed

Tilak, A S; Ojewole, S; Williford, C W; Fox, G A; Sobecki, T M; Larson, S L

2013-11-01

Manganese oxide (MnO) occurs naturally in soil and has a high affinity for trace metals adsorption. In this work, we quantified the factors (pH; flow rate; use of oxidants such as bleach, HO, and O; initial Mn(II) concentrations; and two types of geologic media) affecting MnO coatings onto Ottawa and aquifer sand using batch and column experiments. The batch experiments consisted of manual and automated titration, and the column experiments mimicked natural MnO adsorption and oxidation cycles as a strategy for in situ adsorption. A Pb solution of 50 mg L was passed through MnO-coated sand at a flow rate of 4 mL min to determine its adsorption capacity. Batch experimental results showed that MnO coatings increased from pH 6 to 8, with maximum MnO coating occurring at pH 8. Regarding MnO coatings, bleach and O were highly effective compared with HO. The Ottawa sand had approximately twice the MnO coating of aquifer sand. The sequential increase in initial Mn(II) concentrations on both sands resulted in incremental buildup of MnO. The automated procedure enhanced MnO coatings by 3.5 times compared with manual batch experiments. Column results showed that MnO coatings were highly dependent on initial Mn(II) and oxidant concentrations, pH, flow rate, number of cycles (h), and the type of geologic media used. Manganese oxide coating exceeded 1700 mg kg for Ottawa sand and 130 mg kg for aquifer sand. The Pb adsorption exceeded 2200 mg kg for the Ottawa sand and 300 mg kg for the aquifer sand. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Effect of temperature and initial dibutyl sulfide concentration in chloroform on its oxidation rate by ozone.

PubMed

Popiel, Stanisław; Nalepa, Tomasz; Dzierzak, Dorota; Stankiewicz, Romuald; Witkiewicz, Zygfryd

2008-09-15

A scheme of dibutyl sulfide (DBS) oxidation with ozone and generation of transitional products was determined in this study. The main identified intermediate product was dibutyl sulfoxide (DBSO), and the main end product of DBS oxidation was dibutyl sulfone (DBSO2). It was determined that for three temperatures: 0, 10 and 20 degrees C there was certain initial DBS concentration for which half-times observed in experimental conditions were equal and independent from temperature. Generation of phosgene and water as by-products was confirmed for the reaction of DBS with ozone in chloroform. Results of the described study allowed to present generalized mechanism of sulfide oxidation with ozone.

The effect of surface tension, superheat and surface films on the rate of heat transfer from an iron droplet to a water cooled copper mold

NASA Astrophysics Data System (ADS)

Phinichka, Natthapong

In strip casting the cast surface forms during the initial stage of solidification and the phenomenon that occurs during the first 50 milliseconds of contact time between the liquid steel and the mold define the cast surface and its quality. However the exact mechanism of the initial solidification and the process variables that affect initial solidification phenomena during that time are not well understood. The primary goal of this work is to develop a fundamental understanding of factors controlling strip casting. The purpose of the experimental study is to better understand the role of processing parameters on initial solidification phenomena, heat transfer rate and the formation of the cast steel surface. An investigation was made to evaluate the heat transfer rate of different kinds of steels. The experimental apparatus was designed for millisecond resolution of heat transfer behavior. A novel approach of simultaneous in-situ observation and measurement of rapid heat transfer was developed and enabled a coupling between the interfacial heat transfer rate and droplet solidification rate. The solidification rate was estimated from the varying position of the solidification front as captured by a CCD camera. The effects of experimental parameters such as melt superheat, sulfur content and oxide accumulation at the interface on measured heat flux were studied. It was found that the heat flux increased slightly when the percent of sulfur and increased significantly when superheat increased. The oxide accumulation at the interface was found to be manganese and silicon based oxide. When the liquid steel droplets were ejected onto the copper substrate repeatedly, without cleaning the substrate surface between the ejections, a large increase in the interfacial heat flux was observed. The results of the film study indicated that a liquid oxide film existed at the interface. The surface roughness measurement of the solidified specimen decreased with repeated experimentation and better contact between the droplet and the mold was found to be the cause of the improved heat transfer rate.

The Effect of Temperature and Ionic Strength on the Oxidation of Iodide by Iron(III): A Clock Reaction Kinetic Study

ERIC Educational Resources Information Center

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2012-01-01

A laboratory exercise has recently been reported in which the students use the initial rates method based on the clock reaction approach to deduce the rate law and propose a reaction mechanism for the oxidation of iodide by iron(III) ions. The same approach is used in the exercise proposed herein; the students determine the dependence of the…

Oxygen and SO2 Consumption Rates in White and Rosé Wines: Relationship with and Effects on Wine Chemical Composition.

PubMed

Carrascón, Vanesa; Bueno, Mónica; Fernandez-Zurbano, Purificación; Ferreira, Vicente

2017-11-01

This Article addresses the study of O 2 and SO 2 consumption rates of white and rosé wines, their relationship to the initial chemical composition, and their effects on the chemical changes experienced by wine during oxidation. Eight wines were subjected to five consecutive air-saturation cycles. O 2 was monitored periodically; SO 2 , color, and antioxidant indexes were determined after each cycle, and the initial and final compositions of the wines were thoroughly determined. Wines consumed oxygen at progressively decreasing rates. In the last cycles, after a strong decrease, consistent increases of oxygen levels were seen. Oxygen consumption rates were satisfactorily modeled, being proportional to wine copper, quercetin, and kaempherol contents and negatively proportional to cinnamic acids. SO 2 consumption rates were highly diverse between wines and were positively related to free SO 2 , Mn, and pH, among others. In the last saturations, SO 2 consumption took place regardless of O 2 consumption, implying that SO 2 should reduce chemical species oxidized in previous saturations. Some volatile phenols seem to be the end point of radical-mediated oxidation of polyphenols taking place preferably in the first saturation.

Electro-Fenton oxidation of reverse osmosis concentrate from sanitary landfill leachate: Evaluation of operational parameters.

PubMed

Fernandes, Annabel; Labiadh, Lazhar; Ciríaco, Lurdes; Pacheco, Maria José; Gadri, Abdellatif; Ammar, Salah; Lopes, Ana

2017-10-01

The electro-Fenton oxidation of a concentrate from reverse osmosis of a sanitary landfill leachate, with an initial chemical oxygen demand (COD) of 42 g L -1 , was carried out using a carbon-felt cathode and a boron doped diamond anode. The influence of the applied current intensity, initial pH and dissolved iron initial concentration on the electro-Fenton process was assessed. For the experimental conditions used, results showed that the initial pH is the parameter that more strongly influences the current efficiency of the electro-Fenton process, being this influence more pronounced on the oxidation rate than on the mineralization rate of the organic matter. The increase in iron initial concentration was found to be detrimental, since the natural amount of iron present in the effluent, 73 mg L -1 of total iron and 61 mg L -1 of dissolved iron, was sufficient to ensure the electro-Fenton process at the applied intensities - 0.2-1.4 A. For the more favourable conditions studied, initial pH of 3 and natural iron concentration, it was found an increase in the organic load and nitrogen removals with the applied current intensity. For the highest current intensity applied, a COD removal of 16.7 g L -1 was achieved after 8-h experiments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Gum and deposit formation from jet-turbine and diesel fuels at 100 C

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

Mayo, F.R.; Lan, B.Y.

1987-01-01

Rates of oxidation and gum formation for six hydrocarbons, three jet-turbine fuels and three diesel fuels have been measured at 100 C in the presence of t-Bu2O2 tert-butyl-peroxide as initiator. Four of six fuels oxidize faster at 100 C than in previous work at 130 C with initiator. Four any single substrate, the amount of gum produced for the oxygen absorbed is similar at 100 and 130 C even with large changes in rates and t-Bu2O2 concentrations. Thus, one mechanism of gum formation is intimately associated with oxidation. The effects of t-Bu2O2 concentration on the rates of oxygen absorption andmore » gum formation show that gum formation is associated with chain termination by two peroxy radicals. In general, the pure hydrocarbons have long kinetic chains and give good yields of hydroperoxides. The fuels give short kinetic chains and produce little hydroperoxide but but much more gum formation is the coupling of substrates by peroxides in the absence of oxygen. The mechanism, condensation of oxidation products from alkylnaphthalenes, is also proposed.« less

ARIES Oxide Production Program Assessment of Risk to Long-term Sustainable Production Rate

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

Whitworth, Julia; Lloyd, Jane Alexandria; Majors, Harry W.

2017-05-04

This report describes an assessment of risks and the development of a risk watch list for the ARIES Oxide Production Program conducted in the Plutonium Facility at LANL. The watch list is an active list of potential risks and opportunities that the management team periodically considers to maximize the likelihood of program success. The initial assessments were made in FY 16. The initial watch list was reviewed in September 2016. The initial report was not issued. Revision 1 has been developed based on management review of the original watch list and includes changes that occurred during FY-16.

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

NASA Technical Reports Server (NTRS)

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. 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.

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

NASA Technical Reports Server (NTRS)

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.

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

NASA Technical Reports Server (NTRS)

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.

Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS)

PubMed Central

Ginder-Vogel, Matthew; Landrot, Gautier; Fischel, Jason S.; Sparks, Donald L.

2009-01-01

Quantification of the initial rates of environmental reactions at the mineral/water interface is a fundamental prerequisite to determining reaction mechanisms and contaminant transport modeling and predicting environmental risk. Until recently, experimental techniques with adequate time resolution and elemental sensitivity to measure initial rates of the wide variety of environmental reactions were quite limited. Techniques such as electron paramagnetic resonance and Fourier transform infrared spectroscopies suffer from limited elemental specificity and poor sensitivity to inorganic elements, respectively. Ex situ analysis of batch and stirred-flow systems provides high elemental sensitivity; however, their time resolution is inadequate to characterize rapid environmental reactions. Here we apply quick-scanning x-ray absorption spectroscopy (Q-XAS), at sub-second time-scales, to measure the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide. Using Q-XAS, As(III) and As(V) concentrations were determined every 0.98 s in batch reactions. The initial apparent As(III) depletion rate constants (t < 30 s) measured with Q-XAS are nearly twice as large as rate constants measured with traditional analytical techniques. Our results demonstrate the importance of developing analytical techniques capable of analyzing environmental reactions on the same time scale as they occur. Given the high sensitivity, elemental specificity, and time resolution of Q-XAS, it has many potential applications. They could include measuring not only redox reactions but also dissolution/precipitation reactions, such as the formation and/or reductive dissolution of Fe(III) (hydr)oxides, solid-phase transformations (i.e., formation of layered-double hydroxide minerals), or almost any other reaction occurring in aqueous media that can be measured using x-ray absorption spectroscopy. PMID:19805269

The oxidation of aluminum at high temperature studied by Thermogravimetric Analysis and Differential Scanning Calorimetry.

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

Coker, Eric Nicholas

2013-10-01

The oxidation in air of high-purity Al foil was studied as a function of temperature using Thermogravimetric Analysis with Differential Scanning Calorimetry (TGA/DSC). The rate and/or extent of oxidation was found to be a non-linear function of the temperature. Between 650 and 750 ÀC very little oxidation took place; at 850 ÀC oxidation occurred after an induction period, while at 950 ÀC oxidation occurred without an induction period. At oxidation temperatures between 1050 and 1150 ÀC rapid passivation of the surface of the aluminum foil occurred, while at 1250 ÀC and above, an initial rapid mass increase was observed, followedmore » by a more gradual increase in mass. The initial rapid increase was accompanied by a significant exotherm. Cross-sections of oxidized specimens were characterized by scanning electron microscopy (SEM); the observed alumina skin thicknesses correlated qualitatively with the observed mass increases.« less

Enhanced hydrophilicity of chlorided aluminum oxide particulates

NASA Technical Reports Server (NTRS)

Cofer, W. R., III

1978-01-01

An enhancement of hydrophilicity for chlorided aluminas was demonstrated by the results obtained from gaseous H2O sorptions at 70-, 80-, and 86-percent relative humidity on alpha and gamma aluminum oxide particulates and on alpha and gamma aluminum oxide particulates with a chemisorbed surface chloride phase (produced by reactions of gaseous HCl + H2O on alumina). Continuous sorption histories for H2O on chlorided aluminas having specific surface areas that range from 7 to 227 sq m/g before chloriding indicated that initial sorption rates were directly linked to the extent of chemisorbed chlorided coverage and implied the same relationship for sorption capacities. The initial sorption rate on chlorided aluminas was found to be slower for the first exposure to H2O than for subsequent exposures (which reached equilibrated H2O coverages much faster), suggesting that slow chemical reactions between H2O and chlorided alumina may have been operative during initial exposures. Chlorided alumina particles were found to remain very hydrophilic (relative to nonchlorided analogs) for several H2O sorption/desorption cycles.

Effects of biochar and wood pellets amendments added to landfill cover soil on microbial methane oxidation: A laboratory column study.

PubMed

Yargicoglu, Erin N; Reddy, Krishna R

2017-05-15

Alternate landfill covers designed to enhance microbial methane (CH 4 ) oxidation and reduce the negative impacts of landfill gas emissions on global climate have recently been proposed and investigated. In this study, the use of biochar as a soil amendment is examined in order to assess the feasibility and effectiveness for enhanced CH 4 removal in landfill covers when incorporated under high compaction conditions and relatively low soil moisture. Four different cover configurations were tested in large soil columns for ∼510 days and potential CH 4 oxidation rates were determined following long-term incubation in small batch assays. Cover designs tested include: a thin biochar layer at 15-18 cm; 2% mixed soil-biochar layer at 20-40 cm; 2% mixed soil-uncharred wood pellets at 20-40 cm; and soil obtained from intermediate cover at an active landfill site. The placement of a thin biochar layer in the cover significantly impacted moisture distribution and infiltration, which in turn affected CH 4 oxidation potential with depth. An increase in CH 4 removal rates was observed among all columns over the 500 day incubation period, with steady-state CH 4 removal efficiencies ranging from ∼60 to 90% in the final stages of incubation (inlet load ∼80 g CH 4  m -2  d -1 ). The thin biochar layer had the lowest average removal efficiency as a result of reduced moisture availability below the biochar layer. The addition of 2% biochar to soil yielded similar CH 4 oxidation rates in terminal assays as the 2% uncharred wood pellet amendment. CH 4 oxidation rates in terminal assays were positively correlated with soil moisture, which was affected by the materials' water holding capacity. The high water holding capacity of biochar led to higher oxidation rates within the thin biochar layer, supporting the initial hypothesis that biochar may confer more favorable physical conditions for methanotrophy. Ultimate performance was apparently affected by soil type and CH 4 exposure history, with the highest oxidation rates observed in the unamended field soil with higher initial methanotrophic activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

Quantitative Analysis of Major Phytochemicals in Orthodox tea (Camellia sinensis), Oxidized under Compressed Air Environment.

PubMed

Panda, Brajesh Kumar; Datta, Ashis Kumar

2016-04-01

This study describes major changes in phytochemical composition of orthodox tea (Camellia sinensis var. Assamica) oxidized under compressed air (CA). The experiments for oxidation were conducted under air pressure (101, 202, and 303 kPa) for 150 min. Relative change in the concentrations of caffeine, catechins, theaflavins (TF), and thearubigins (TR) were analyzed. Effect of CA pressure was found to be nonsignificant in regulating caffeine concentration during oxidation. But degradation in different catechins as well as formation of different TF was significantly affected by CA pressure. At high CA pressure, TF showed highest peak value. TR was found to have slower rate of formation during initial phase of oxidation than TF. Even though the rate of TR formation was significantly influenced by CA, a portion of catechins remained unoxidized at end of oxidation. Except caffeine, the percent change in rate of formation or degradation were more prominent at 202 kPa. © 2016 Institute of Food Technologists®

Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

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

Smith, Steven C.; Peper, Shane M.; Douglas, Matthew

2009-11-01

Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

Autoignition of hydrogen in shear flows

NASA Astrophysics Data System (ADS)

Kalbhor, Abhijit; Chaudhuri, Swetaprovo; Chitilappilly, Lazar

2018-05-01

In this paper, we compare the autoignition characteristics of laminar, nitrogen-diluted hydrogen jets in two different oxidizer flow configurations: (a) co-flowing heated air and (b) wake of heated air, using two-dimensional numerical simulations coupled with detailed chemical kinetics. In both cases, autoignition is observed to initiate at locations with low scalar dissipation rates and high HO2 depletion rates. It is found that the induction stage prior to autoignition is primarily dominated by chemical kinetics and diffusion while the improved scalar mixing imparted by the large-scale flow structures controls the ignition progress in later stages. We further investigate the ignition transience and its connection with mixing by varying the initial wake conditions and fuel jet to oxidizer velocity ratios. These studies reveal that the autoignition delay times are independent of initial wake flow conditions. However, with increased jet velocity ratios, the later stages of ignition are accelerated, mainly due to enhanced mixing facilitated by the higher scalar dissipation rates. Furthermore, the sensitivity studies for the jet in wake configuration show a significant reduction in ignition delay even for about 0.14% (by volume) hydrogen dilution in the oxidizer. In addition, the detailed autoignition chemistry and the relative roles of certain radical species in the initiation of the autoignition process in these non-premixed jets are investigated by tracking the evolution of important chain reactions using a Lagrangian particle tracking approach. The reaction H2 + O2 ↔ HO2 + H is recognized to be the dominant chain initiation reaction that provides H radicals essential for the progress of subsequent elementary reactions during the pre-ignition stage.

Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

USGS Publications Warehouse

Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

2006-01-01

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as r As(V) = k???ox [Mn(IV) OH3][AsO3] with apparent second-order rate constants of koxf??? = 6.28 ?? 10-1 and koxs??? = 1.25 ?? 10-2 M-1 s-1 for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid-base behavior of the surface oxidative sites by considering a surface pKa = 6.2 (I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems. ?? 2005 Elsevier Inc. All rights reserved.

Ruthenium nanoparticles supported on CeO2 for catalytic permanganate oxidation of butylparaben.

PubMed

Zhang, Jing; Sun, Bo; Guan, Xiaohong; Wang, Hui; Bao, Hongliang; Huang, Yuying; Qiao, Junlian; Zhou, Gongming

2013-11-19

This study developed a heterogeneous catalytic permanganate oxidation system with ceria supported ruthenium, Ru/CeO2 (0.8‰ as Ru), as catalyst for the first time. The catalytic performance of Ru/CeO2 toward butylparaben (BP) oxidation by permanganate was strongly dependent on its dosage, pH, permanganate concentration and temperature. The presence of 1.0 g L(-1) Ru/CeO2 increased the oxidation rate of BP by permanganate at pH 4.0-8.0 by 3-96 times. The increase in Ru/CeO2 dosage led to a progressive enhancement in the oxidation rate of BP by permanganate at neutral pH. The XANES analysis revealed that (1) Ru was deposited on the surface of CeO2 as Ru(III); (2) Ru(III) was oxidized by permanganate to its higher oxidation state Ru(VI) and Ru(VII), which acted as the co-oxidants in BP oxidation; (3) Ru(VI) and Ru(VII) were reduced by BP to its initial state of Ru(III). Therefore, Ru/CeO2 acted as an electron shuttle in catalytic permanganate oxidation process. LC-MS/MS analysis implied that BP was initially attacked by permanganate or Ru(VI) and Ru(VII) at the aromatic ring, leading to the formation of various hydroxyl-substituted and ring-opening products. Ru/CeO2 could maintain its catalytic activity during the six successive runs. In conclusion, catalyzing permanganate oxidation with Ru/CeO2 is a promising technology for degrading phenolic pollutants in water treatment.

Effect of reactive element oxide coating on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; El Messki, S.

2004-05-01

The influence of yttrium oxide coating (processed by the sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373 K. The scale growth kinetics of the uncoated alloy obey a parabolic rate law during the whole oxidation test, whereas the kinetic curves of the Y-coated specimen exhibit an initial transient stage for the first few hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not provide the beneficial effect usually ascribed to reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constant values are strictly identical for both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen comprised, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO 3, Y 3Al 5O 12) located in the outermost part of the layer.

Oxidation Kinetics of Cast TiAl3

NASA Technical Reports Server (NTRS)

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.

Tailoring nanostructured MnO2 as anodes for lithium ion batteries with high reversible capacity and initial Coulombic efficiency

NASA Astrophysics Data System (ADS)

Zhang, Lifeng; Song, Jiajia; Liu, Yi; Yuan, Xiaoyan; Guo, Shouwu

2018-03-01

Developing high energy storage lithium ion batteries (LIBs) using manganese oxides as anodes is an attractive challenge due to their high theoretical capacity and abundant resources. However, the manganese oxides anodes still suffer from the low initial Coulombic efficiency and poor rate performance. Herein, we demonstrate that nano-sized morphological engineering is a facile and effective strategy to improve the electrochemical performance of the manganese dioxide (MnO2) for LIBs. The tailored MnO2 nanoparticles (NPs) exhibit high reversible capacity (1095 mAh g-1 at 100 mA g-1), high initial Coulombic efficiency (94.5%) and good rate capability (464 mAh g-1 at 2000 mA g-1). The enhanced electrochemical performance of MnO2 NPs can be attributed to the presences of numerous electrochemically active sites and interspaces among the NPs.

Kinetics and Near-Infrared Spectroscopy of Organic Peroxy Radicals

NASA Astrophysics Data System (ADS)

Smarte, M. D.; Okumura, M.

2016-12-01

Organic peroxy radicals are important intermediates in atmospheric chemistry with fates that control the rate of radical propagation in an oxidation mechanism. Laboratory methods for detecting peroxy radicals are essential to measuring precise rate constants that constrain these fates. In this work, we discuss the use of near-infrared cavity ringdown spectroscopy to detect organic peroxy radicals for the purpose of laboratory kinetics measurements. We focus on chlorine-substituted peroxy radicals generated in the oxidation of alkenes by chlorine, a minor tropospheric oxidant found in marine and coastal regions. Previous kinetics experiments on peroxy radicals have largely used UV absorption spectroscopy via the dissociative B-X transition. However, the spectra produced are featureless and exhibit substantial overlap; determining the concentration profile of an individual peroxy radical can be an arduous task. In our work, we probe the forbidden peroxy radical A-X transition in the near-infrared. While this approach requires overcoming small cross sections ( 10-21 cm2), the A state is bound and leads to structured absorption spectra that may be useful in constraining the kinetics of mixtures of organic peroxy radicals formed in the oxidation of complex hydrocarbons. Only a few kinetics studies utilizing the A-X transition exist in the literature and they are focused on small, unsubstituted species. This presentation explores the ability of the A-X transition to unravel the kinetics of more complex peroxy radicals in laboratory experiments using several example systems: (1) Determining rate constants for the self and cross reactions of β-chloroethylperoxy and HO2. (2) Detecting the second generation of peroxy radicals formed from alkoxy radical decomposition in the chlorine-initiated oxidation of 2-butene. (3) Observing different rates of reactivity with NO across the pool of peroxy radical isomers formed in the chlorine-initiated oxidation of isoprene.

Gum and deposit formation from jet turbine and diesel fuels at 100/sup 0/C

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

Mayo, F.R.; Lan, B.Y.

1987-02-01

Rates of oxidation and gum formation for six hydrocarbons, three jet turbine fuels and three diesel fuels have been measured at 100/sup 0/C in the presence of t-Bu/sub 2/O/sub 2/ as initiator. Four of the six fuels oxidize faster at 100/sup 0/C than in previous work at 130/sup 0/C without initiator. For any single substrate, the amount of gum produced for the oxygen absorbed is similar at 100 and 130/sup 0/C, even with large changes in rates and t-Bu/sub 2/O/sub 2/ concentrations. In general, the pure hydrocarbons have long kinetic chains and give good yields of hydroperoxides.

Growth Kinetics of the S Sub H Center on Magnesium Oxide Using Electron Paramagnetic Resonance

NASA Technical Reports Server (NTRS)

Jayne, J. P.

1971-01-01

Electron paramagnetic resonance spectroscopy was used to study the growth of S sub H centers on magnesium oxide powder which had hydrogen adsorbed on its surface. The centers were produced by ultraviolet radiation. The effects of both radiation intensity and hydrogen pressure were also studied. At constant hydrogen pressure and radiation dose, the initial S sub H center growth rate was found to be zero order. Beyond the initial region the growth rate deviated from zero order and finally approached saturation. The results are interpreted in terms of a model which assumes that the S sub H center is a hydrogen atom associated with a surface vacancy. Saturation appears to result from a limited supply of surface vacancies.

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

PubMed

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 naphthalene

Kinetics and mechanism for the sonochemical degradation of a nonionic surfactant.

PubMed

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

The sonolytic degradation of the nonionic surfactant, octaethylene glycol monododecyl ether (C(12)E(8)), has been studied at various initial concentrations below and above its critical micelle concentration (CMC). It has been observed that the degradation rate increases with an increase in the initial concentration of the surfactant until the CMC is reached. Above the CMC an almost constant degradation rate is observed, suggesting that the surfactant in its monomer form is involved in the degradation process. The degradation process of C(12)E(8) involves two distinct primary processes occurring at the bubble/solution interface: (a) hydroxylation/oxidation of the surfactant and (b) pyrolytic fragmentation of the surfactant. The oxidative cleavage of ethylene oxide units provides evidence for OH radical attack. Hydroxylation of the ethoxy chain gives rise to various short-chain carboxyalkyl-polyethylene glycol intermediates. The polyethylene glycol chain formed, due to the scission of the C(12)E(8) molecule, undergoes rapid hydroxylation/oxidation to yield simple compounds that have the potential to undergo further degradation. The detection of multiple intermediates indicates that several processes affect the complete degradation pathways of the surfactant molecule. TOC analysis, however, indicates that the sonolytic mineralization of the surfactant is difficult to achieve at reasonable rates due to the relatively low surface activity of the degradation products formed during sonolysis.

Evaluation of the Effects of Iron Oxides on Soil Reducing Conditions and Methane Generation in Cambodian Wetland Rice Fields

NASA Astrophysics Data System (ADS)

Weaver, M.; Benner, S.; Fendorf, S.; Sampson, M.; Leng, M.

2007-12-01

Atmospheric concentrations of methane have been steadily increasing over the last 100 years, which has given rise to research of wetland rice fields, recently identified as a major anthropomorphic source of methane. Establishment of experimental soil pots, cultivating an aromatic early variety rice strain in the Kean Svay District of Cambodia, have recently been carried out to evaluate methods to minimize methane release by promoting redox buffering by iron oxides. In the first series of experiments, iron oxides were added to the soils and the rate of change in reducing conditions and methanogenesis onset was monitored. In the second series of experiments, plots are subject to periodic drying cycles to promote rejuvenation of buffering iron oxides. Initial results indicate a delay in the onset of methanogenesis, and overall methane generation, in plots where initial iron oxides concentrations are elevated.

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

PubMed

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

2015-05-01

In the present study, the mechanism of free radical production by light-reflective agents in sunscreens (TiO2, ZnO and ZrO2) 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. Copyright © 2015 Elsevier B.V. All rights reserved.

Reductive reactivity of iron(III) oxides in the east china sea sediments: characterization by selective extraction and kinetic dissolution.

PubMed

Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

2013-01-01

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k' (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k' and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases.

Reductive Reactivity of Iron(III) Oxides in the East China Sea Sediments: Characterization by Selective Extraction and Kinetic Dissolution

PubMed Central

Chen, Liang-Jin; Zhu, Mao-Xu; Yang, Gui-Peng; Huang, Xiang-Li

2013-01-01

Reactive Fe(III) oxides in gravity-core sediments collected from the East China Sea inner shelf were quantified by using three selective extractions (acidic hydroxylamine, acidic oxalate, bicarbonate-citrate buffered sodium dithionite). Also the reactivity of Fe(III) oxides in the sediments was characterized by kinetic dissolution using ascorbic acid as reductant at pH 3.0 and 7.5 in combination with the reactive continuum model. Three parameters derived from the kinetic method: m 0 (theoretical initial amount of ascorbate-reducible Fe(III) oxides), k′ (rate constant) and γ (heterogeneity of reactivity), enable a quantitative characterization of Fe(III) oxide reactivity in a standardized way. Amorphous Fe(III) oxides quantified by acidic hydroxylamine extraction were quickly consumed in the uppermost layer during early diagenesis but were not depleted over the upper 100 cm depth. The total amounts of amorphous and poorly crystalline Fe(III) oxides are highly available for efficient buffering of dissolved sulfide. As indicated by the m 0, k′ and γ, the surface sediments always have the maximum content, reactivity and heterogeneity of reactive Fe(III) oxides, while the three parameters simultaneously downcore decrease, much more quickly in the upper layer than at depth. Albeit being within a small range (within one order of magnitude) of the initial rates among sediments at different depths, incongruent dissolution could result in huge discrepancies of the later dissolution rates due to differentiating heterogeneity, which cannot be revealed by selective extraction. A strong linear correlation of the m 0 at pH 3.0 with the dithionite-extractable Fe(III) suggests that the m 0 may represent Fe(III) oxide assemblages spanning amorphous and crystalline Fe(III) oxides. Maximum microbially available Fe(III) predicted by the m 0 at pH 7.5 may include both amorphous and a fraction of other less reactive Fe(III) phases. PMID:24260377

Quantitative confirmation of diffusion-limited oxidation theories

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

Gillen, K.T.; Clough, R.L.

1990-01-01

Diffusion-limited (heterogeneous) oxidation effects are often important for studies of polymer degradation. Such effects are common in polymers subjected to ionizing radiation at relatively high dose rate. To better understand the underlying oxidation processes and to aid in the planning of accelerated aging studies, it would be desirable to be able to monitor and quantitatively understand these effects. In this paper, we briefly review a theoretical diffusion approach which derives model profiles for oxygen surrounded sheets of material by combining oxygen permeation rates with kinetically based oxygen consumption expressions. The theory leads to a simple governing expression involving the oxygenmore » consumption and permeation rates together with two model parameters {alpha} and {beta}. To test the theory, gamma-initiated oxidation of a sheet of commercially formulated EPDM rubber was performed under conditions which led to diffusion-limited oxidation. Profile shapes from the theoretical treatments are shown to accurately fit experimentally derived oxidation profiles. In addition, direct measurements on the same EPDM material of the oxygen consumption and permeation rates, together with values of {alpha} and {beta} derived from the fitting procedure, allow us to quantitatively confirm for the first time the governing theoretical relationship. 17 refs., 3 figs.« less

Biological treatment of toxic petroleum spent caustic in fluidized bed bioreactor using immobilized cells of Thiobacillus RAI01.

PubMed

Potumarthi, Ravichandra; Mugeraya, Gopal; Jetty, Annapurna

2008-12-01

In the present studies, newly isolated Thiobacillus sp was used for the treatment of synthetic spent sulfide caustic in a laboratory-scale fluidized bed bioreactor. The sulfide oxidation was tested using Ca-alginate immobilized Thiobacillus sp. Initially, response surface methodology was applied for the optimization of four parameters to check the sulfide oxidation efficiency in batch mode. Further, reactor was operated in continuous mode for 51 days at different sulfide loading rates and retention times to test the sulfide oxidation and sulfate and thiosulfate formation. Sulfide conversions in the range of 90-98% were obtained at almost all sulfide loading rates and hydraulic retention times. However, increased loading rates resulted in lower sulfide oxidation capacity. All the experiments were conducted at constant pH of around 6 and temperature of 30 +/- 5 degrees C.

Degradation of sodium dodecyl sulphate in water using solar driven Fenton-like advanced oxidation processes.

PubMed

Bandala, Erick R; Peláez, Miguel A; Salgado, Maria J; Torres, Luis

2008-03-01

Synthetic wastewater samples containing a model surfactant were treated using two different Fenton-like advanced oxidation processes promoted by solar radiation; the photo-Fenton reaction and Co/PMS/UV processes. Comparison between the different experimental conditions was performed by means of the overall surfactant degradation achieved and by obtaining the initial rate in the first 15 min of reaction (IR15). It was found that, for dark Fenton reaction, the maximum surfactant degradation achieved was 14% under low iron and oxidant concentration. Increasing Fenton reagents by one magnitude order, surfactant degradation achieved 63% in 60 min. The use of solar radiation improved the reaction rate by 17% under same conditions and an additional increase of 12.5% was obtained by adjusting initial pH to 2. IR15 values for dark and irradiated Fenton reactions were 0.143 and 0.154 mmol/min, respectively, for similar reaction conditions and this value increased to 0.189 mmol/min when initial pH was adjusted. The use of the Co/PMS system allow us to determine an increase in the degradation rate, for low reaction conditions (1 mM of transition metal; 4 mM oxidant) similar to those used in dark Fenton reaction. Surfactant degradation increased from 3%, for Fenton reaction, to 44.5% in the case of Co/PMS. When solar irradiation was included in the experiments, under same reaction conditions described earlier, surfactant degradation up to 64% was achieved. By increasing Co/PMS reagent concentration by almost 9 times under irradiated conditions, almost complete (>99%) surfactant degradation was reached in 5 min. Comparing IR15 values for Co/PMS and Co/PMS/UV, it allow us to observe that the use of solar radiation increased the degradation rate in one magnitude order when compared with dark experiments and further increase of reagent concentration increased reaction rate twice.

Determination of kinetic data for soot oxidation: Modeling of competition between oxygen diffusion and reaction during thermogravimetric analysis

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

Gilot, P.; Bonnefoy, F.; Marcuccilli, F.

1993-10-01

Kinetic data concerning carbon black oxidation in the temperature range between 600 and 900 C have been obtained using thermogravimetric analysis. Modeling of diffusion in a boundary layer above the pan and inside the porous medium coupled to oxygen reaction with carbon black is necessary to obtain kinetic constants as a function of temperature. These calculations require the knowledge of the oxidation rate at a given constant temperature as a function of the initial mass loading m[sub o]. This oxidation rate, expressed in milligrams of soot consumed per second and per milligram of initial soot loading, decreases when m[sub o]more » increases, in agreement with a reaction in an intermediary regime where the kinetics and the oxygen diffusion operate. The equivalent diffusivity of oxygen inside the porous medium is evaluated assuming two degrees of porosity: between soot aggregates and inside each aggregate. Below 700 C an activation energy of about 103 kJ/mol can be related to a combustion reaction probably kinetically controlled. Beyond 700 C the activation energy of about 20 kJ/ mol corresponds to a reaction essentially controlled by oxygen diffusion leading to a constant density oxidation with oxygen consumption at or near the particle surface. To validate these data, they are used in the modeling of a Diesel particulate trap regeneration. In this particular case, the oxidizing flux is forced across the carbon black deposit, oxygen diffusion being insignificant. A good agreement between experimental results and model predictions is obtained, proving the rate constants validity.« less

Increased work in cardiac trabeculae causes decreased mitochondrial NADH fluorescence followed by slow recovery.

PubMed Central

Brandes, R; Bers, D M

1996-01-01

The oxidative phosphorylation rate in isolated mitochondria is stimulated by increased [ADP], resulting in decreased [NADH]. In intact hearts, however, increased mechanical work has generally not been shown to cause an increase in [ADP]. Therefore, increased [NADH] has been suggested as an alternative for stimulating the phosphorylation rate. Such a rise in [NADH] could result from stimulation of various substrate dehydrogenases by increased intracellular [Ca2+] (e.g., during increased pacing frequency). We have monitored mitochondrial [NADH] in isolated rat ventricular trabeculae, using a novel fluorescence spectroscopy method where a native fluorescence signal was used to correct for motion artifacts. Work was controlled by increased pacing frequency and assessed using time-averaged force. At low-pacing rates (approximately 0.1 Hz), [NADH] immediately decreased during contraction and then slowly recovered (approximately 5 s) before the next contraction. At higher rates, [NADH] initially decreased by an amount related to pacing rate (i.e., work). However, during prolonged stimulation, [NADH] slowly (approximately 60 s) recovered to a new steady-state level below the initial level. We conclude that 1) during increased work, oxidative phosphorylation is not initially stimulated by increased mitochondrial [NADH]; and 2) increased pacing frequency slowly causes stimulation of NADH production. Images FIGURE 2 FIGURE 4 PMID:8842239

Dissolution kinetics of iron-, manganese-, and copper-containing synthetic hydroxyapatites

NASA Technical Reports Server (NTRS)

Sutter, B.; Hossner, L. R.; Ming, D. W.

2005-01-01

Micronutrient-substituted synthetic hydroxyapatite (SHA) is being evaluated by the National Aeronautics and Space Administration's (NASA) Advanced Life Support (ALS) Program for crop production on long-duration human missions to the International Space Station or for future Lunar or Martian outposts. The stirred-flow technique was utilized to characterize Ca, P, Fe, Mn, and Cu release characteristics from Fe-, Mn-, and Cu-containing SHA in deionized (DI) water, citric acid, and diethylene-triamine-pentaacetic acid (DTPA). Initially, Ca and P release rates decreased rapidly with time and were controlled by a non-SHA calcium phosphate phase(s) with low Ca/P solution molar ratios (0.91-1.51) relative to solid SHA ratios (1.56-1.64). At later times, Ca/P solution molar ratios (1.47-1.79) were near solid SHA ratios and release rates decreased slowly indicating that SHA controlled Ca and P release. Substituted SHA materials had faster dissolution rates relative to unsubstituted SHA. The initial metal release rate order was Mn >> Cu > Fe which followed metal-oxide/phosphate solubility suggesting that poorly crystalline metal-oxides/phosphates were dominating metal release. Similar metal release rates for all substituted SHA (approximately 0.01 cmol kg-1 min-1) at the end of the DTPA experiment indicated that SHA dissolution was supplying the metals into solution and that poorly crystalline metal-oxide/phosphates were not controlling metal release. Results indicate that non-SHA Ca-phosphate phases and poorly crystalline metal-oxide/phosphates will contribute Ca, P, and metals. After these phases have dissolved, substituted SHA will be the source of Ca, P, and metals for plants.

Detailed mechanism of benzene oxidation

NASA Technical Reports Server (NTRS)

Bittker, David A.

1987-01-01

A detailed quantitative mechanism for the oxidation of benzene in both argon and nitrogen diluted systems is presented. Computed ignition delay time for argon diluted mixtures are in satisfactory agreement with experimental results for a wide range of initial conditions. An experimental temperature versus time profile for a nitrogen diluted oxidation was accurately matched and several concentration profiles were matched qualitatively. Application of sensitivity analysis has given approximate rate constant expressions for the two dominant heat release reactions, the oxidation of C6H5 and C5H5 radicals by molecular oxygen.

In situ X-ray diffraction contribution to the study of reactive element oxide coating effect on the high temperature oxidation behaviour of FeCrAl alloys

NASA Astrophysics Data System (ADS)

Cueff, R.; Buscail, H.; Caudron, E.; Riffard, F.; Issartel, C.; Perrier, S.; El Messki, S.

2004-11-01

The influence of yttrium oxide coating (processed by sol-gel method) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373K. The scale growth kinetic of the uncoated alloy obeys a parabolic rate law during the whole oxidation test whereas the kinetic curve of the Y-coated specimen exhibits an initial transient stage during the first hours, followed by a parabolic regime. The yttrium sol-gel coating deposited on the bare alloy does not conduct to the beneficial effect usually ascribed to the reactive elements. No oxidation rate improvement of the coated alloy is observed, the parabolic rate constants values are strictly identical for the both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-coated specimen revealed, in addition to α-alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO{3}, Y{3}Al{5}O{12}) located in the outermost part of the layer.

[Kinetics of catalytic wet air oxidation of phenol in trickle bed reactor].

PubMed

Li, Guang-ming; Zhao, Jian-fu; Wang, Hua; Zhao, Xiu-hua; Zhou, Yang-yuan

2004-05-01

By using a trickle bed reactor which was designed by the authors, the catalytic wet air oxidation reaction of phenol on CuO/gamma-Al2O3 catalyst was studied. The results showed that in mild operation conditions (at temperature of 180 degrees C, pressure of 3 MPa, liquid feed rate of 1.668 L x h(-1) and oxygen feed rate of 160 L x h(-1)), the removal of phenol can be over 90%. The curve of phenol conversion is similar to "S" like autocatalytic reaction, and is accordance with chain reaction of free radical. The kinetic model of pseudo homogenous reactor fits the catalytic wet air oxidation reaction of phenol. The effects of initial concentration of phenol, liquid feed rate and temperature for reaction also were investigated.

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature.

PubMed

Yang, Yang; Kushima, Akihiro; Han, Weizhong; Xin, Huolin; Li, Ju

2018-04-11

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. Here, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can match the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass-glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.

Air oxidation of Zircaloy-4 in the 600-1000 °C temperature range: Modeling for ASTEC code application

NASA Astrophysics Data System (ADS)

Coindreau, O.; Duriez, C.; Ederli, S.

2010-10-01

Progress in the treatment of air oxidation of zirconium in severe accident (SA) codes are required for a reliable analysis of severe accidents involving air ingress. Air oxidation of zirconium can actually lead to accelerated core degradation and increased fission product release, especially for the highly-radiotoxic ruthenium. This paper presents a model to simulate air oxidation kinetics of Zircaloy-4 in the 600-1000 °C temperature range. It is based on available experimental data, including separate-effect experiments performed at IRSN and at Forschungszentrum Karlsruhe. The kinetic transition, named "breakaway", from a diffusion-controlled regime to an accelerated oxidation is taken into account in the modeling via a critical mass gain parameter. The progressive propagation of the locally initiated breakaway is modeled by a linear increase in oxidation rate with time. Finally, when breakaway propagation is completed, the oxidation rate stabilizes and the kinetics is modeled by a linear law. This new modeling is integrated in the severe accident code ASTEC, jointly developed by IRSN and GRS. Model predictions and experimental data from thermogravimetric results show good agreement for different air flow rates and for slow temperature transient conditions.

Direct Method for Continuous Determination of Iron Oxidation by Autotrophic Bacteria

PubMed Central

Steiner, Michael; Lazaroff, Norman

1974-01-01

A method for direct, continuous determination of ferric ions produced in autotrophic iron oxidation, which depends upon the measurement of ferric ion absorbance at 304 nm, is described. The use of initial rates is shown to compensate for such changes in extinction during oxidation, which are due to dependence of the extinction coefficient on the ratio of complexing anions to ferric ions. A graphical method and a computer method are given for determination of absolute ferric ion concentration, at any time interval, in reaction mixtures containing Thiobacillus ferrooxidans and ferrous ions at known levels of SO42+ and hydrogen ion concentrations. Some examples are discussed of the applicability of these methods to study of the rates of ferrous ion oxidation related to sulfate concentration. PMID:4441066

Ceruloplasmin enhances smooth muscle cell- and endothelial cell-mediated low density lipoprotein oxidation by a superoxide-dependent mechanism

NASA Technical Reports Server (NTRS)

Mukhopadhyay, C. K.; Ehrenwald, E.; Fox, P. L.

1996-01-01

Cultured vascular smooth muscle cells (SMC) and endothelial cells (EC) stimulate low density lipoprotein (LDL) oxidation by free radical-mediated, transition metal-dependent mechanisms. The physiological source(s) of metal ions is not known; however, purified ceruloplasmin, a plasma protein containing 7 coppers, oxidizes LDL in vitro. We now show that ceruloplasmin also increases LDL oxidation by vascular cells. In metal ion-free medium, human ceruloplasmin increased bovine aortic SMC- and EC-mediated LDL oxidation by up to 30- and 15-fold, respectively. The maximal response was at 100-300 microg ceruloplasmin/ml, a level at or below the unevoked physiological plasma concentration. Oxidant activity was dependent on protein structure as a specific proteolytic cleavage or removal of one of the seven ceruloplasmin copper atoms inhibited activity. Three lines of evidence indicated a critical role for cellular superoxide (O2.) in ceruloplasmin-stimulated oxidation. First, the rate of production of O2. by cells correlated with their rates of LDL oxidation. Second, superoxide dismutase effectively blocked ceruloplasmin-stimulated oxidation by both cell types. Finally, O2. production by SMC quantitatively accounted for the observed rate of LDL oxidation. To show this, the course of O2. production by SMC was simulated by repeated addition of xanthine and xanthine oxidase to culture medium under cell-free conditions. Neither ceruloplasmin nor O2. alone increased LDL oxidation, but together they completely reconstituted the oxidation rate of ceruloplasmin-stimulated SMC. These results are the first to show that ceruloplasmin stimulates EC- and SMC-mediated oxidation of LDL and that cell-derived O2. accounts quantitatively for metal-dependent, free radical-initiated oxidation of LDL by these cells.

Oxidation and the Effects of High Temperature Exposures on Notched Fatigue Life of an Advanced Powder Metallurgy Disk Superalloy

NASA Technical Reports Server (NTRS)

Sudbrack, Chantal K.; Draper, Susan L.; Gorman, Timothy T.; Telesman, Jack; Gab, Timothy P.; Hull, David R.

2012-01-01

Oxidation and the effects of high temperature exposures on notched fatigue life were considered for a powder metallurgy processed supersolvus heat-treated ME3 disk superalloy. The isothermal static oxidation response at 704 C, 760 C, and 815 C was consistent with other chromia forming nickel-based superalloys: a TiO2-Cr2O3 external oxide formed with a branched Al2O3 internal subscale that extended into a recrystallized - dissolution layer. These surface changes can potentially impact disk durability, making layer growth rates important. Growth of the external scales and dissolution layers followed a cubic rate law, while Al2O3 subscales followed a parabolic rate law. Cr- rich M23C6 carbides at the grain boundaries dissolved to help sustain Cr2O3 growth to depths about 12 times thicker than the scale. The effect of prior exposures was examined through notched low cycle fatigue tests performed to failure in air at 704 C. Prior exposures led to pronounced debits of up to 99 % in fatigue life, where fatigue life decreased inversely with exposure time. Exposures that produced roughly equivalent 1 m thick external scales at the various isotherms showed statistically equivalent fatigue lives, establishing that surface damage drives fatigue debit, not exposure temperature. Fractographic evaluation indicated the failure mode for the pre-exposed specimens involved surface crack initiations that shifted with exposure from predominately single intergranular initiations with transgranular propagation to multi-initiations from the cracked external oxide with intergranular propagation. Weakened grain boundaries at the surface resulting from the M23C6 carbide dissolution are partially responsible for the intergranular cracking. Removing the scale and subscale while leaving a layer where M23C6 carbides were dissolved did not lead to a significant fatigue life improvement, however, also removing the M23C6 carbide dissolution layer led to nearly full recovery of life, with a transgranular initiation typical to that observed in unexposed specimens.

Microbial oxidation of lithospheric organic carbon in rapidly eroding tropical mountain soils

NASA Astrophysics Data System (ADS)

Hemingway, Jordon D.; Hilton, Robert G.; Hovius, Niels; Eglinton, Timothy I.; Haghipour, Negar; Wacker, Lukas; Chen, Meng-Chiang; Galy, Valier V.

2018-04-01

Lithospheric organic carbon (“petrogenic”; OCpetro) is oxidized during exhumation and subsequent erosion of mountain ranges. This process is a considerable source of carbon dioxide (CO2) to the atmosphere over geologic time scales, but the mechanisms that govern oxidation rates in mountain landscapes are poorly constrained. We demonstrate that, on average, 67 ± 11% of the OCpetro initially present in bedrock exhumed from the tropical, rapidly eroding Central Range of Taiwan is oxidized in soils, leading to CO2 emissions of 6.1 to 18.6 metric tons of carbon per square kilometer per year. The molecular and isotopic evolution of bulk OC and lipid biomarkers during soil formation reveals that OCpetro remineralization is microbially mediated. Rapid oxidation in mountain soils drives CO2 emission fluxes that increase with erosion rate, thereby counteracting CO2 drawdown by silicate weathering and biospheric OC burial.

Photoproduction of One-Electron Reducing Intermediates by Chromophoric Dissolved Organic Matter (CDOM): Relation to O2- and H2O2 Photoproduction and CDOM Photooxidation.

PubMed

Zhang, Yi; Blough, Neil V

2016-10-06

A molecular probe, 3-amino-2,2,5,5,-tetramethy-1-pyrrolydinyloxy (3ap), was employed to determine the formation rates of one-electron reducing intermediates generated photochemically from both untreated and borohydride-reduced Suwanee River fulvic and humic acids (SRFA and SRHA, respectively). This stable nitroxyl radical reacts rapidly with reducing radicals and other one-electron reductants to produce a relatively stable product, the hydroxylamine, which can be derivatized with fluorescamine, separated by HPLC and quantified fluorimetrically. We provide evidence that O 2 and 3ap compete for the same pool(s) of photoproduced reducing intermediates, and that under appropriate experimental conditions, the initial rate of hydroxylamine formation (R H ) can provide an estimate of the initial rate of superoxide (O 2 - ) formation. However, comparison of the initial rates of H 2 O 2 formation (R H2O2 ) to that of R H show far larger ratios of R H /R H2O2 (∼6-13) than be accounted for by simple O 2 - dismutation (R H /R H2O2 = 2), implying a significant oxidative sink of O 2 - (∼67-85%). Because of their high reactivity with O 2 - and their likely importance in the photochemistry of CDOM, we suggest that coproduced phenoxy radicals could represent a viable oxidative sink. Because O 2 - /phenoxy radical reactions can lead to more highly oxidized products, O 2 - could be playing a far more significant role in the photooxidation of CDOM than has been previously recognized.

Kinetics and Mechanism of Iodide Oxidation by Iron(III): A Clock Reaction Approach

ERIC Educational Resources Information Center

Bauer, Jurica; Tomisic, Vladislav; Vrkljan, Petar B. A.

2008-01-01

A simple method for studying the kinetics of a chemical reaction is described and the significance of reaction orders in deducing reaction mechanisms is demonstrated. In this student laboratory experiment, oxidation of iodide by iron(III) ions in an acidic medium is transformed into a clock reaction. By means of the initial rates method, it is…

Hydrogen peroxide-enhanced iron-mediated aeration for the treatment of mature landfill leachate.

PubMed

Deng, Yang; Englehardt, James D

2008-05-01

Municipal landfill leachate is being disallowed for biological treatment by some sewer authorities due to its recalcitrance and corrosiveness, and therefore physicochemical treatment may be needed. In this paper, hydrogen peroxide-enhanced iron (Fe(0))-mediated aeration (IMA) was studied as an alternative for the treatment of mature landfill leachate. Bench-scale Taguchi array screening tests and full factorial tests were conducted. Iron grade, initial pH, H(2)O(2) addition rate, and aeration rate significantly influenced both overall chemical oxygen demand (COD) removal and iron consumption. In the enhanced IMA-treated leachate at an initial pH of 8.2, COD was reduced by 50% due to oxidation and coagulation, a level almost equivalent to those obtained by Fenton treatment. Meanwhile, the 5-day biochemical oxygen demand (BOD(5))/COD ratio was increased from 0.02 to 0.17. In particular, the effect of initial pH became minor at H(2)O(2) addition rate greater than the theoretical demand for complete oxidation of organics by H(2)O(2). In addition, 83% of 300 mg/L ammonia nitrogen and 38% of 8.30 mS/cm electrical conductivity were removed when the initial pH was not adjusted. Based on these results, the process appears suitable for treatment of mature leachate.

Life on the energetic edge: Iron oxidation by circumneutral lithotrophic bacteria in the wetland plant rhizosphere

NASA Astrophysics Data System (ADS)

Neubauer, S. C.; Emerson, D.; Megonigal, J. P.; Weiss, J. V.

2002-05-01

We have discovered a phylogenetically and genotypically coherent group of obligately lithotrophic Fe-oxidizing bacteria that grow at neutral pH and are globally distributed in a range of habitats, from the rhizosphere of freshwater wetlands to deep-sea hydrothermal vents. We have initiated bioreactor studies using pure cultures of these organisms to determine the significance of microbial Fe(II) oxidation at circumneutral pH and identify the biotic and abiotic variables that affect the partitioning between microbial and chemical oxidation. These studies have focused on strain BrT, which was isolated from an iron oxide precipitate in rhizosphere of a wetland plant. In one set of experiments, Fe(II) oxidation rates were measured before and after cultures of strain BrT were poisoned with sodium azide. These experiments indicated that 18 to 53 % of total iron oxidation was due to microbial metabolism. In a second set of experiments, Fe(II) was constantly added to bioreactors inoculated with live cells, killed cells, or no cells. A statistical model fit to the experimental data demonstrated that metabolic Fe(II) oxidation accounted for up to 62 % of total oxidation. Total Fe(II) oxidation rates in these experiments were strongly limited by the rate of Fe(II) delivery to the system, and were also influenced by O2 and total iron concentrations. Additionally, the model suggested that the microbes inhibited rates of abiotic Fe(II) oxidation, perhaps by binding Fe(II) to bacterial exopolymers. The net effect of strain BrT was to accelerate total oxidation rates by up to 18 % versus cell-free treatments. Using two independent techniques, we demonstrated that strain BrT actively metabolizes Fe(II) and can account for up to 50 to 60 % of total Fe(II) oxidation in laboratory cultures. These results suggest that neutrophilic Fe(II)-oxidizing bacteria may compete for limited O2 in the rhizosphere and influence the biogeochemistry of other elements including carbon, phosphorus, and sulfur.

Comparision of photocatalysis and photolysis processes for arsenic oxidation in water.

PubMed

Fontana, Klaiani B; Lenzi, Giane G; Seára, Eriton C R; Chaves, Eduardo S

2018-04-30

The oxidation of As(III) to As(V) in aqueous solution was evaluated using heterogeneous photocatalysis and photolysis. The influence of TiO 2 as catalyst in different crystalline (rutile, anatase) and commercial forms was evaluated in a batch reactor and an insignificant difference was observed between them. The process by photocatalysis reached up to 97% As(III) oxidation and no significant difference was observed comparing to results obtained by photolysis. The photolysis experiments (UV radiation only), also carried out in a batch system, showed a high oxidation rate of As(III) (90% in 20min). The influence of different matrices (well water, river water and public water supply) were evaluated. Additionally, the effect of As(V) concentration, generated during the oxidation process, was studied. Continuous photolysis experiments using only UV radiation were performed, resulting in a high As(III) oxidation rate. Using a flow rate of 5mLmin -1 and an initial concentration of As(III) 200µgL -1 , gave an oxidation percentage of As(III) of up to 72%, showing a simple and economical alternative to the oxidation step of As(III) to As(V) in the treatment of water contaminated with arsenic. Copyright © 2018 Elsevier Inc. All rights reserved.

Mechanistic Study of Nickel-Catalyzed Ynal Reductive Cyclizations Through Kinetic Analysis

PubMed Central

Baxter, Ryan D.; Montgomery, John

2011-01-01

The mechanism of nickel-catalyzed, silane-mediated reductive cyclization of ynals has been evaluated. The cyclizations are first-order in [Ni] and [ynal] and zeroth-order in [silane]. These results, in combination with the lack of rapid silane consumption upon reaction initiation are inconsistent with mechanisms involving reaction initiation by oxidative addition of Ni(0) to the silane. Silane consumption occurs only when both the alkyne and aldehyde and are present. Mechanisms involving rate-determining oxidative cyclization to a metallacycle followed by rapid reaction with the silane are consistent with the data obtained. PMID:21438642

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

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

Wang, Zheming; Shi, Zhi; Shi, Liang

2015-08-25

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, some evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin that are proposed to mediate electron transfer (Marsili et al., 2008). In this work, we used methyl viologen (MV•+)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of secreted flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 µM) by MELs ([MV•+] ~ 42 µM and MtrABC ≤ 1 nM)more » were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MV•+ and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 seconds. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (≤ 1 µM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. However, at higher FMN concentrations (> 1 µM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction. The implications of the observed kinetic behaviors to flavin-mediated Fe(III) oxide reduction in natural environments are discussed.« less

Physiological responses to acid stress by Saccharomyces cerevisiae when applying high initial cell density

PubMed Central

2016-01-01

High initial cell density is used to increase volumetric productivity and shorten production time in lignocellulosic hydrolysate fermentation. Comparison of physiological parameters in high initial cell density cultivation of Saccharomyces cerevisiae in the presence of acetic, formic, levulinic and cinnamic acids demonstrated general and acid-specific responses of cells. All the acids studied impaired growth and inhibited glycolytic flux, and caused oxidative stress and accumulation of trehalose. However, trehalose may play a role other than protecting yeast cells from acid-induced oxidative stress. Unlike the other acids, cinnamic acid did not cause depletion of cellular ATP, but abolished the growth of yeast on ethanol. Compared with low initial cell density, increasing initial cell density reduced the lag phase and improved the bioconversion yield of cinnamic acid during acid adaptation. In addition, yeast cells were able to grow at elevated concentrations of acid, probable due to the increase in phenotypic cell-to-cell heterogeneity in large inoculum size. Furthermore, the specific growth rate and the specific rates of glucose consumption and metabolite production were significantly lower than at low initial cell density, which was a result of the accumulation of a large fraction of cells that persisted in a viable but non-proliferating state. PMID:27620460

Effect of oxidized leachate on degradation of lignin by sulfate-reducing bacteria.

PubMed

Kim, Jong-Ho; Kim, Moonil; Bae, Wooken

2009-08-01

Municipal solid waste materials (MSWs) in landfills need a long period of stabilization because lignin compounds in MSWs and leachate are not readily biodegraded, but inhibit methanogenic metabolism. Recirculation of leachate into the landfill offers the potential advantage of increasing the rate of decomposition of organic matter. However, the degradation of lignin by leachate recirculation alone is quite difficult. Several recent studies have demonstrated that sulfate-reducing bacteria (SRB) were able to degrade lignin compounds. In this study, batch tests were conducted to investigate the impacts of SRB enrichment on lignin decomposition rates as well as the decomposition of other biodegradable organics. Further, the effects of nitrite and nitrate on lignin degradation rates were also studied. A 16S rRNA assay showed that the SRB used herein, which were obtained by enriching solid waste collected from a closed MSW landfill, were Thaurea sp. and Desulfovibrio sp. Lignin was found to be biodegraded by the SRB and the rate of lignin removal per unit of waste volatile suspended solid was 2.9 mg lignin g(-1) VSS day(- 1). It was found that the initial degradation rate increased under higher initial lignin concentrations. However, the degradation rate during days 6-19 became slower than that during the initial 9 days because lignin consisted of complexly bonded aromatic compounds that were not readily biodegradable. Adding other organics such as lactate seemed to improve the rate and amount of lignin degradation, probably due to the increase in SRB associated with consumption of the additional organics. The lignin removal percentage decreased with increases in oxidized nitrogen (nitrite or nitrate) concentrations, indicating that oxidized nitrogen could inhibit SRB activity. Conclusively, the study verified the existence of SRB in the landfill and showed that the SRB could be activated for the degradation of lignin by the recirculation of the leachate, which is consistent with other studies showing that leachate recirculation could shorten the stabilization period of the landfill.

Biotransformation of acyclovir by an enriched nitrifying culture.

PubMed

Xu, Yifeng; Yuan, Zhiguo; Ni, Bing-Jie

2017-03-01

This work evaluates the biodegradation of the antiviral drug acyclovir by an enriched nitrifying culture during ammonia oxidation and without the addition of ammonium. The study on kinetics was accompanied with the structural elucidation of biotransformation products through batch biodegradation experiments at two different initial levels of acyclovir (15 mg L -1 and 15 μg L -1 ). The pseudo first order kinetic studies of acyclovir in the presence of ammonium indicated the higher degradation rates under higher ammonia oxidation rates than those constant degradation rates in the absence of ammonium. The positive correlation was found between acyclovir degradation rate and ammonia oxidation rate, confirming the cometabolism of acyclovir by the enriched nitrifying culture in the presence of ammonium. Formation of the product carboxy-acyclovir (P239) indicated the main biotransformation pathway was aerobic oxidation of the terminal hydroxyl group, which was independent on the metabolic type (i.e. cometabolism or metabolism). This enzyme-linked reaction might be catalyzed by monooxygenase from ammonia oxidizing bacteria or heterotrophs. The formation of carboxy-acyclovir was demonstrated to be irrelevant to the acyclovir concentrations applied, indicating the revealed biotransformation pathway might be the dominant removal pathway of acyclovir in wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Photoinduced Cross-Linking of Dynamic Poly(disulfide) Films via Thiol Oxidative Coupling.

PubMed

Feillée, Noémi; Chemtob, Abraham; Ley, Christian; Croutxé-Barghorn, Céline; Allonas, Xavier; Ponche, Arnaud; Le Nouen, Didier; Majjad, Hicham; Jacomine, Léandro

2016-01-01

Initially developed as an elastomer with an excellent record of barrier and chemical resistance properties, poly(disulfide) has experienced a revival linked to the dynamic nature of the S-S covalent bond. A novel photobase-catalyzed oxidative polymerization of multifunctional thiols to poly(disulfide) network is reported. Based solely on air oxidation, the single-step process is triggered by the photodecarboxylation of a xanthone acetic acid liberating a strong bicyclic guanidine base. Starting with a 1 μm thick film based on trithiol poly(ethylene oxide) oligomer, the UV-mediated oxidation of thiols to disulfides occurs in a matter of minutes both selectively, i.e., without overoxidation, and quantitatively as assessed by a range of spectroscopic techniques. Thiolate formation and film thickness determine the reaction rates and yield. Spatial control of the photopolymerization serves to generate robust micropatterns, while the reductive cleavage of S-S bridges allows the recycling of 40% of the initial thiol groups. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of Layered-Spinel Microsphere/Reduced Graphene Oxide Cathode Materials for Ultrafast Charge-Discharge Lithium-Ion Batteries.

PubMed

Luo, Dong; Fang, Shaohua; Yang, Li; Hirano, Shin-Ichi

2017-12-22

Although Li-rich layered oxides (LLOs) have the highest capacity of any cathodes used, the rate capability of LLOs falls short of meeting the requirements of electric vehicles and smart grids. Herein, a layered-spinel microsphere/reduced graphene oxide heterostructured cathode (LS@rGO) is prepared in situ. This cathode is composed of a spinel phase, two layered structures, and a small amount of reduced graphene oxide (1.08 wt % of carbon). The assembly delivers a considerable charge capacity (145 mA h g -1 ) at an ultrahigh charge- discharge rate of 60 C (12 A g -1 ). The rate capability of LS@rGO is influenced by the introduced spinel phase and rGO. X-ray absorption and X-ray photoelectron spectroscopy data indicate that Cr ions move from octahedral lattice sites to tetrahedral lattice sites, and that Mn ions do not participate in the oxidation reaction during the initial charge process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation chamber studies of the atmospheric degradation of xylene oxidation products

NASA Astrophysics Data System (ADS)

Clifford, G.; Rea, G.; Thuener, L.; Wenger, J.

2003-04-01

Aromatic compounds are emitted to the atmosphere from their use in automobile fuels and solvents. In addition to being important primary pollutants, many aromatics, including the xylenes, possess high photochemical reactivity and make a major contribution to the formation of oxidants, such as ozone and nitrates, in the troposphere. The atmospheric oxidation of aromatics produces a wide variety of products and the atmospheric reactivity of many of these species is unknown. The aim of this work was to study the atmospheric degradation processes for dimethylphenols, tolualdehydes and dicarbonyl compounds which are produced from the hydroxyl radical initiated oxidation of the xylenes. Experiments on the hydroxyl (OH) and nitrate radical initiated oxidation of dimethylphenols and tolualdehydes have been performed in a large atmospheric simulation chamber in our laboratory. The chamber is made of FEP foil and has a volume of about 4750 litres. It is equipped with gas chromatography, GC-MS, and in situ FTIR spectroscopy for chemical analysis and a scanning mobility particle sizer for aerosol measurements. Rate coefficients have been determined for the reactions of hydroxyl and nitrate radicals with dimethylphenols and tolualdehydes. Gas-phase products and the yield of secondary organic aerosol have also been determined for the OH-initiated oxidation of these compounds. Mechanisms for the formation of the products are proposed. The photolysis of the unsaturated dicarbonyls, butenedial and 4-oxo-pent-2-enal, has been studied using real sunlight at the European Photoreactor (EUPHORE) in Valencia, Spain. Photolysis rates were measured and indicate that photolysis by sunlight is the major atmospheric degradation process for these compounds. Product studies show the formation of a ketene intermediate that decays to form five membered ring compounds such as furanones and maleic anhydride. Mechanisms for the formation of the products are proposed. Finally, the data obtained in this work is used to access the atmospheric impact of xylene oxidation products and to provide valuable information on their pollution forming potential.

Kinetics of ozone-initiated oxidation of textile dye, Amaranth in aqueous systems.

PubMed

Dachipally, Purnachandar; Jonnalagadda, Sreekanth B

2011-01-01

The ozone facilitated oxidation mechanism of water soluble azo anionic dye, amaranth (Am) was investigated monitoring the depletion kinetics of the dye spectrometrically at 521 nm. The oxidation kinetics of the dye by ozone was studied under semi-batch conditions, by bubbling ozone enriched oxygen through the aqueous reaction mixture of dye, as function of flow rate, ionic strength, [O(3)] and pH variations. With excess concentration of ozone and other reagents and low [amaranth], reaction followed pseudo-first-order kinetics with respect to the dye. Added neutral salts had marginal effect on the reaction rate and the variation of pH from 7 to 2 and 7 to 12 exerted only small increases in the reaction rate suggesting molecular ozone possibly is the principle reactive species in oxidation of dye. The reaction order with respect ozone was near unity and it varied slightly with pH and flow rate variations. The overall second-order rate constant for the reaction was (105 ± 4) M(-1) min(-1). The main oxidation products immediately after amaranth decolorization were identified. The reaction mechanism and overall rate law were proposed. After spiking the seawater, river water and wastewaters with Amaranth dye, the reaction rates and trends in BOD and COD under control and natural conditions were investigated. The rate of depletion of the dye in natural waters was relatively lower, but the ozonation process significantly decreased both the BOD and COD levels.

Prediction of scuffing failure based on competitive kinetics of oxide formation and removal: Application to lubricated sliding of AISI 52100 steel on steel

NASA Astrophysics Data System (ADS)

Cutiongco, Eric C.; Chung, Yip-Wah

1994-07-01

A method for predicting scuffing failure based on the competitive kinetics of oxide formation and removal has been developed and applied to the sliding of AISI 52100 steel on steel with poly-alpha-olefin as the lubricant. Oxide formation rates were determining using static oxidation tests on coupons of 52100 steel covered with poly-alpha-olefin at temperatures of 140 C to 250 C. Oxide removal rates were determined at different combinations of initial average nominal contact pressures (950 MPa to 1578 MPa) and sliding velocities (0.4 m/s to 1.8 m/s) using a ball-on-disk vacuum tribotester. The nominal asperity flash temperatures generated during the wear tests were calculated and the temperatures corresponding to the intersection of the the Arrhenius plots of oxide formation and removal rates were determined and taken as the critical failure temperatures. The pressure-velocity failure transition diagram was constructed by plotting the critical failure temperatures along isotherms of average nominal asperity flash temperatures calculated at different combinations of contact stress and sliding speed. The predicted failure transition curve agreed well with experimental scuffing data.

Advanced oxidation of acridine orange by aqueous alkaline iodine.

PubMed

Azmat, Rafia; Qamar, Noshab; Naz, Raheela; Khursheed, Anum

2016-11-01

The advanced oxidation process is certainly used for the dye waste water treatment. In this continuation a new advanced oxidation via aqueous alkaline iodine was developed for the oxidation of acridine orange (AO) {3, 6 -bis (dimethylamino) acridine zinc chloride double salt}. Oxidation Kinetics of AO by alkaline solution of iodine was investigated spectrophotometrically at λ max 491 nm. The reaction was monitored at various operational parameters like several concentrations of dye and iodine, pH, salt electrolyte and temperature. The initial steps of oxidation kinetics followed fractional order reaction with respect to the dye while depend upon the incremental amount of iodine to certain extent whereas maximum oxidation of AO was achieved at high pH. Decline in the reaction rate in the presence of salt electrolyte suggested the presence of oppositely charged species in the rate determining step. Kinetic data revealed that the de-colorization mechanism involves triodate (I 3 - ) species, instead of hypoidate (OI - ) and hypiodous acid (HOI), in alkaline medium during the photo-excitation of hydrolyzed AO. Alleviated concentration of alkali result in decreasing of rate of reaction, clearly indicate that the iodine species are active oxidizing species instead of OH radical. Activation parameters at elevated temperatures were determined which revealed that highly solvated state of dye complex existed into solution. Reaction mixture was subjected to UV/Visible and GC mass spectrum analysis that proves the secondary consecutive reaction was operative in rate determining step and finally dye complex end into smaller fragments.

Oxidation behavior of a thermal barrier coating

NASA Technical Reports Server (NTRS)

Miller, R. A.

1984-01-01

Thermal barrier coatings, consisting of a plasma sprayed calcium silicate ceramic layer and a CoCrAlY or NiCrAlY bond coat, were applied on B-1900 coupons and cycled hourly in air in a rapid-response furnace to maximum temperatures of 1030, 1100, or 1160 C. Eight specimens were tested for each of the six conditions of bond-coat composition and temperature. Specimens were removed from test at the onset of failure, which was taken to be the formation of a fine surface crack visible at 10X magnification. Specimens were weighed periodically, and plots of weight gain vs time indicate that weight is gained at a parabolic rate after an initial period where weight was gained at a much greater rate. The high initial oxidation rate is thought to arise from the initially high surface area in the porous bond coat. Specimen life (time to first crack) was found to be a strong function of temperature. However, while test lives varied greatly with time, the weight gain at the time of specimen failure was quite insensitive to temperature. This indicates that there is a critical weight gain at which the coating fails when subjected to this test.

The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

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

Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.

A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. Themore » reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.« less

Thermal-mechanical coupling effect on initial stage oxidation of Si(100) surface

NASA Astrophysics Data System (ADS)

Sun, Yu; Liu, Yilun; Chen, Xuefeng; Zhai, Zhi; Izumi, Satoshi

2018-04-01

The initial stage oxidation of biaxially strained Si(100) at temperatures ranging from 300 K to 1200 K has been investigated by Reactive Force Field Molecular Dynamics simulations. We reported that the oxidation process involving the reaction rate and the amount of absorbed O atoms could be enhanced by the coupling effect of higher temperatures and larger external tension. By fitting the simulation results, the relationship between absorbed oxygen and the coupling of temperature and strain was obtained. In probing the mechanism, we observed that there was a ballistic transport of O atoms, displaying an enhancement of inward penetration by external tension. Since such an inward transport was favored by thermal actuation, more O atoms penetrated into deeper layers when the 9% strained Si oxidized at 1200 K. Moreover, the evolution of stress in the surface region during the oxidation process was discussed, as well as the related oxide structure and the film quality. These present results may provide a way to understand the thermally-mechanically coupled chemical reactions and propose an effective approach to optimize microscale component processing in the electronic field.

Co-culture microorganisms with different initial proportions reveal the mechanism of chalcopyrite bioleaching coupling with microbial community succession.

PubMed

Ma, Liyuan; Wang, Xingjie; Feng, Xue; Liang, Yili; Xiao, Yunhua; Hao, Xiaodong; Yin, Huaqun; Liu, Hongwei; Liu, Xueduan

2017-01-01

The effect of co-culture microorganisms with different initial proportions on chalcopyrite bioleaching was investigated. Communities were rebuilt by six typical strains isolated from the same habitat. The results indicated, by community with more sulfur oxidizers at both 30 and 40°C, the final copper extraction rate was 19.8% and 6.5% higher, respectively, than that with more ferrous oxidizers. The variations of pH, redox potential, ferrous and copper ions in leachate also provided evidences that community with more sulfur oxidizers was more efficient. Community succession of free and attached cells revealed that initial proportions played decisive roles on community dynamics at 30°C, while communities shared similar structures, not relevant to initial proportions at 40°C. X-ray diffraction analysis confirmed different microbial functions on mineral surface. A mechanism model for chalcopyrite bioleaching was established coupling with community succession. This will provide theoretical basis for reconstructing an efficient community in industrial application. Copyright © 2016 Elsevier Ltd. All rights reserved.

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

USGS Publications Warehouse

Power, L.E.; Arai, Y.; Sparks, D.L.

2005-01-01

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Population of Nitrifying Bacteria and Nitrification in Ammonium Saturated Clinoptilolite

NASA Technical Reports Server (NTRS)

McGilloway, R. L.; Weaver, R. W.; Ming, Douglas W.; Gruener, J.

1999-01-01

As humans begin to spend longer periods of time in space, plants will be incorporated into life support systems. Ammonium saturated clinoptilolite is one plant growth substrate but a balance between ammonium and nitrate is needed. A laboratory study was conducted to determine effects of nitrifying bacteria on ammonium concentrations and kinetics of nitrification. Columns containing clinoptilolite substrate amended with nitrifying bacteria obtained from soil enrichment were analyzed weekly for a 90 day period. The enrichment culture initially contained 1 x 10(exp 5) ammonium oxidizing bacteria and 1 x 10(exp 2) nitrite oxidizing bacteria per gram of substrate. Populations of ammonium oxidizing bacteria increased to 1 x 10(exp 6) and nitrite oxidizing bacteria increased to 1 x 10(exp 3) per gram of substrate. The nitrification rate was approximately 0.25mg NO3(-)-N/kg.hr. Experiments were also conducted to enumerate nitrifying bacteria in a clinoptilolite substrate used to grow wheat (Triticum aestivum L.). Seventy days following the initial inoculation with an unknown number of commercial nitrifying bacteria, 1 x 10(exp 5) ammonium oxidizing bacteria per gram of substrate were present. The number of nitrite oxidizing bacteria was between 1 x 10(exp 3) to 10(exp 4) per gram of substrate as measured by the most probable number method. Nitrification rates were approximately 0.20mg NO3(-)-N/kg.hr. Clinoptilolite readily exchanged sufficient concentrations of ammonium to support nitrifying bacteria and they survived well in this medium.

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

NASA Technical Reports Server (NTRS)

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

2003-01-01

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

Oxidative deterioration of pork during superchilling storage.

PubMed

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.

Elucidating the oxide growth mechanism on platinum at the cathode in PEM fuel cells.

PubMed

Redmond, Erin L; Setzler, Brian P; Alamgir, Faisal M; Fuller, Thomas F

2014-03-21

Simulations of platinum oxidation in literature have yet to fully replicate an experimental cyclic voltammogram. In this manuscript a mechanism for platinum oxidation is proposed based upon the results of in operando X-ray absorption spectroscopy, where it was found that PtO2 is present at longer hold times. A new method to quantify extended X-ray absorption fine structure data is presented, and the extent of oxidation is directly compared to electrochemical data. This comparison indicated that PtO2 was formed at the expense of an initial oxide species. From previous literature studies it can be concluded that the rate of platinum oxidation is not a function of only potential and coverage. To that end, the concept of a heterogeneous oxide layer was introduced into the model, whereby place-exchanged PtO2 structures of varying energy states are formed through a single transition state. This treatment allowed, for the first time, the simulation of the correct current-potential behavior at varying scan rates and upper potential limits.

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature

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

Yang, Yang; Kushima, Akihiro; Han, Weizhong

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. In this letter, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can matchmore » the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass–glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.« less

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature

DOE PAGES

Yang, Yang; Kushima, Akihiro; Han, Weizhong; ...

2018-02-28

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. In this letter, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can matchmore » the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass–glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.« less

Simplified Two-Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydorgen/Oxygen

NASA Technical Reports Server (NTRS)

Molnar, Melissa; Marek, C. John

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two-time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (> 1 x 10(exp -20) moles/cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T4). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/air fuel and for the H2/O2. A similar correlation is also developed using data from NASA s Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T4) as a function of overall fuel/air ratio, pressure and initial temperature (T3). High values of the regression coefficient R2 are obtained.

Summary of Simplified Two Time Step Method for Calculating Combustion Rates and Nitrogen Oxide Emissions for Hydrogen/Air and Hydrogen/Oxygen

NASA Technical Reports Server (NTRS)

Marek, C. John; Molnar, Melissa

2005-01-01

A simplified single rate expression for hydrogen combustion and nitrogen oxide production was developed. Detailed kinetics are predicted for the chemical kinetic times using the complete chemical mechanism over the entire operating space. These times are then correlated to the reactor conditions using an exponential fit. Simple first order reaction expressions are then used to find the conversion in the reactor. The method uses a two time step kinetic scheme. The first time averaged step is used at the initial times with smaller water concentrations. This gives the average chemical kinetic time as a function of initial overall fuel air ratio, temperature, and pressure. The second instantaneous step is used at higher water concentrations (greater than l x 10(exp -20)) moles per cc) in the mixture which gives the chemical kinetic time as a function of the instantaneous fuel and water mole concentrations, pressure and temperature (T(sub 4)). The simple correlations are then compared to the turbulent mixing times to determine the limiting properties of the reaction. The NASA Glenn GLSENS kinetics code calculates the reaction rates and rate constants for each species in a kinetic scheme for finite kinetic rates. These reaction rates are used to calculate the necessary chemical kinetic times. This time is regressed over the complete initial conditions using the Excel regression routine. Chemical kinetic time equations for H2 and NOx are obtained for H2/Air fuel and for H2/O2. A similar correlation is also developed using data from NASA's Chemical Equilibrium Applications (CEA) code to determine the equilibrium temperature (T(sub 4)) as a function of overall fuel/air ratio, pressure and initial temperature (T(sub 3)). High values of the regression coefficient R squared are obtained.

Complete and simultaneous removal of ammonium and m-cresol in a nitrifying sequencing batch reactor.

PubMed

Zepeda, Alejandro; Ben-Youssef, Chérif; Rincón, Susana; Cuervo-López, Flor; Gómez, Jorge

2013-06-01

The kinetic behavior, oxidizing ability and tolerance to m-cresol of a nitrifying sludge exposed to different initial concentrations of m-cresol (0-150 mg C L(-1)) were evaluated in a sequencing batch reactor fed with 50 mg NH4 (+)-N L(-1) and operated during 4 months. Complete removal of ammonium and m-cresol was achieved independently of the initial concentration of aromatic compound in all the assays. Up to 25 mg m-cresol-C L(-1) (C/N ratio of 0.5), the nitrifying yield (Y-NO3 (-)) was 0.86 ± 0.05, indicating that the nitrate was the main product of the process; no biomass growth was detected. From 50 to 150 mg m-cresol-C L(-1) (1.0 ≤ C/N ≤ 3.0), simultaneous microbial growth and partial ammonium-to-nitrate conversion were obtained, reaching a maximum microbial total protein concentration of 0.763 g L(-1) (247 % of its initial value) and the lowest Y-NO3 (-) 0.53 ± 0.01 at 150 mg m-cresol-C L(-1). m-Cresol induced a significant decrease in the values of both specific rates of ammonium and nitrite oxidation, being the ammonium oxidation pathway the mainly inhibited. The nitrifying sludge was able to completely oxidize up to 150 mg m-cresol-C L(-1) by SBR cycle, reaching a maximum specific removal rate of 6.45 g m-cresol g(-1) microbial protein-N h(-1). The number of SBR cycles allowed a metabolic adaptation of the nitrifying consortium since nitrification inhibition decreased and faster oxidation of m-cresol took place throughout the cycles.

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

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

Peyton, Brent M.; Timothy, Ginn R.; Sani, Rajesh K.

2013-08-14

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2. We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phasemore » when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2. The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.« less

Oxidation characteristics of porous-nickel prepared by powder metallurgy and cast-nickel at 1273 K in air for total oxidation time of 100 h.

PubMed

Mohamed, Lamiaa Z; Ghanem, Wafaa A; El Kady, Omayma A; Lotfy, Mohamed M; Ahmed, Hafiz A; Elrefaie, Fawzi A

2017-11-01

The oxidation behavior of two types of inhomogeneous nickel was investigated in air at 1273 K for a total oxidation time of 100 h. The two types were porous sintered-nickel and microstructurally inhomogeneous cast-nickel. The porous-nickel samples were fabricated by compacting Ni powder followed by sintering in vacuum at 1473 K for 2 h. The oxidation kinetics of the samples was determined gravimetrically. The topography and the cross-section microstructure of each oxidized sample were observed using optical and scanning electron microscopy. X-ray diffractometry and X-ray energy dispersive analysis were used to determine the nature of the formed oxide phases. The kinetic results revealed that the porous-nickel samples had higher trend for irreproducibility. The average oxidation rate for porous- and cast-nickel samples was initially rapid, and then decreased gradually to become linear. Linear rate constants were 5.5 × 10 -8  g/cm 2  s and 3.4 × 10 -8  g/cm 2  s for the porous- and cast-nickel samples, respectively. Initially a single-porous non-adherent NiO layer was noticed on the porous- and cast-nickel samples. After a longer time of oxidation, a non-adherent duplex NiO scale was formed. The two layers of the duplex scales were different in color. NiO particles were observed in most of the pores of the porous-nickel samples. Finally, the linear oxidation kinetics and the formation of porous non-adherent duplex oxide scales on the inhomogeneous nickel substrates demonstrated that the addition of new layers of NiO occurred at the scale/metal interface due to the thermodynamically possible reaction between Ni and the molecular oxygen migrating inwardly.

Effect of applied voltage, initial concentration and natural organic matter on sequential reduction/oxidation of nitrobenzene by graphite electrodes

PubMed Central

Sun, Mei; Reible, Danny D.; Lowry, Gregory V.; Gregory, Kelvin B.

2012-01-01

Carbon electrodes are proposed in reactive sediment caps for in situ treatment of contaminants. The electrodes produce reducing conditions and H2 at the cathode and oxidizing conditions and O2 at the anode. Emplaced perpendicular to seepage flow, the electrodes provide the opportunity for sequential reduction and oxidation of contaminants. The objectives of this study are to demonstrate degradation of nitrobenzene (NB) as a probe compound for sequential electrochemical reduction and oxidation, and to determine the effect of applied voltage, initial concentration and natural organic matter on the degradation rate. In H-cell reactors with graphite electrodes and buffer solution, NB was reduced stoichiometrically to aniline (AN) at the cathode with nitrosobenzene (NSB) as the intermediate. AN was then removed at the anode, faster than the reduction step. No common AN oxidation intermediate was detected in the system. Both the first order reduction rate constants of NB (kNB) and NSB (kNSB) increased with applied voltage between 2V and 3.5 V (when the initial NB concentration was 100 µM, kNB=0.3 d−1 and kNSB=0.04 d−1at 2V; kNB=1.6 d−1 and kNSB=0.64 d−1at 3.5 V) but stopped increasing beyond the threshold of 3.5V. When initial NB concentration decreased from 100 to 5 µM, kNB and kNSB became 9 and 5 times faster, respectively, suggesting that competition for active sites on the electrode surface is an important factor in NB degradation. Presence of natural organic matter (in forms of either humic acid or Anacostia River sediment porewater) decreased kNB while slightly increased kNSB, but only to a limited extent (~factor of 3) for dissolved organic carbon content up to 100 mg/l. These findings suggest that electrode-based reactive sediment capping via sequential reduction/oxidation is a potentially robust and tunable technology for in situ contaminants degradation. PMID:22571797

Process for light-driven hydrocarbon oxidation at ambient temperatures

DOEpatents

Shelnutt, John A.

1990-01-01

A photochemical reaction for the oxidation of hydrocarbons uses molecular oxygen as the oxidant. A reductive photoredox cycle that uses a tin(IV)- or antimony(V)-porphyrin photosensitizer generates the reducing equivalents required to activate oxygen. This artificial photosynthesis system drives a catalytic cycle, which mimics the cytochrome P.sub.450 reaction, to oxidize hydrocarbons. An iron(III)- or manganese(III)-porphyrin is used as the hydrocarbon-oxidation catalyst. Methylviologen can be used as a redox relay molecule to provide for electron-transfer from the reduced photosensitizer to the Fe or Mn porphyrin. The system is long-lived and may be used in photo-initiated spectroscopic studies of the reaction to determine reaction rates and intermediates.

Fenton Oxidation Kinetics and Intermediates of Nonylphenol Ethoxylates

PubMed Central

Cui, Kai; Yi, Hao; Zhou, Zi-jian; Zhuo, Qiong-fang; Bing, Yong-xin; Guo, Qing-wei; Xu, Zhen-cheng

2014-01-01

Abstract Removal of nonylphenol ethoxylates (NPEOs) in aqueous solution by Fenton oxidation process was studied in a laboratory-scale batch reactor. Operating parameters, including initial pH temperature, hydrogen peroxide, and ferrous ion dosage, were thoroughly investigated. Maximum NPEOs reduction of 84% was achieved within 6 min, under an initial pH of 3.0, 25°C, an H2O2 dosage of 9.74×10−3 M, and a molar ratio of [H2O2]/[Fe2+] of 3. A modified pseudo-first-order kinetic model was found to well represent experimental results. Correlations of reaction rate constants and operational parameters were established based on experimental data. Results indicated that the Fenton oxidation rate and removal efficiency were more dependent on the dosage of H2O2 than Fe2+, and the apparent activation energy (ΔE) was 17.5 kJ/mol. High-performance liquid chromatography and gas chromatograph mass spectrometer analytical results indicated degradation of NPEOs obtained within the first 2 min stepwise occurred by ethoxyl (EO) unit shortening. Long-chain NPEOs mixture demonstrated a higher degradation rate than shorter-chain ones. Nonylphenol (NP), short-chain NPEOs, and NP carboxyethoxylates were identified as the primary intermediates, which were mostly further degraded. PMID:24868141

Geochemical controls on microbial nitrate-dependent U(IV) oxidation

USGS Publications Warehouse

Senko, John M.; Suflita, Joseph M.; Krumholz, Lee R.

2005-01-01

After reductive immobilization of uranium, the element may be oxidized and remobilized in the presence of nitrate by the activity of dissimilatory nitrate-reducing bacteria. We examined controls on microbially mediated nitrate-dependent U(IV) oxidation in landfill leachate-impacted subsurface sediments. Nitrate-dependent U(IV)-oxidizing bacteria were at least two orders of magnitude less numerous in these sediments than glucose- or Fe(II)-oxidizing nitrate-reducing bacteria and grew more slowly than the latter organisms, suggesting that U(IV) is ultimately oxidized by Fe(III) produced by nitrate-dependent Fe(II)-oxidizing bacteria or by oxidation of Fe(II) by nitrite that accumulates during organotrophic dissimilatory nitrate reduction. We examined the effect of nitrate and reductant concentration on nitrate-dependent U(IV) oxidation in sediment incubations and used the initial reductive capacity (RDC = [reducing equivalents] - [oxidizing equivalents]) of the incubations as a unified measurement of the nitrate or reductant concentration. When we lowered the RDC with progressively higher nitrate concentrations, we observed a corresponding increase in the extent of U(IV) oxidation, but did not observe this relationship between RDC and U(IV) oxidation rate, especially when RDC > 0, suggesting that nitrate concentration strongly controls the extent, but not the rate of nitrate-dependent U(IV) oxidation. On the other hand, when we raised the RDC in sediment incubations with progressively higher reductant (acetate, sulfide, soluble Fe(II), or FeS) concentrations, we observed progressively lower extents and rates of nitrate-dependent U(IV) oxidation. Acetate was a relatively poor inhibitor of nitrate-dependent U(IV) oxidation, while Fe(II) was the most effective inhibitor. Based on these results, we propose that it may be possible to predict the stability of U(IV) in a bioremediated aquifer based on the geochemical characteristics of that aquifer.

The effect of metal (hydr)oxide nano-enabling on intraparticle mass transport of organic contaminants in hybrid granular activated carbon.

PubMed

Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D

2017-05-15

The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Photochemical oxidation of persistent cyanide-related compounds

NASA Astrophysics Data System (ADS)

Budaev, S. L.; Batoeva, A. A.; Khandarkhaeva, M. S.; Aseev, D. G.

2017-03-01

Kinetic regularities of the photolysis of thiocyanate solutions using of mono- and polychromatic UV radiation sources with different spectral ranges are studied. Comparative experiments aimed at investigating the role of photochemical action during the oxidation of thiocyanates with persulfates and additional catalytic activation with iron(III) ions are performed. The rate of conversion and the initial rate of thiocyanate oxidation are found to change in the order UV < UV/S2O 8 2- < S2O 8 2- /Fe3+ < UV/S2O 8 2- /Fe3+. A synergistic effect is detected when using the combined catalytic method for the destruction of thiocyanates by the UV/S2O 8 2- /Fe3+ oxidation system. This effect is due to the formation of reactive oxygen species, as a result of both the decomposition of persulfate and the reduction of inactive Fe3+ intermediates into Fe3+.

Microbial oxidation of lithospheric organic carbon in rapidly eroding tropical mountain soils.

PubMed

Hemingway, Jordon D; Hilton, Robert G; Hovius, Niels; Eglinton, Timothy I; Haghipour, Negar; Wacker, Lukas; Chen, Meng-Chiang; Galy, Valier V

2018-04-13

Lithospheric organic carbon ("petrogenic"; OC petro ) is oxidized during exhumation and subsequent erosion of mountain ranges. This process is a considerable source of carbon dioxide (CO 2 ) to the atmosphere over geologic time scales, but the mechanisms that govern oxidation rates in mountain landscapes are poorly constrained. We demonstrate that, on average, 67 ± 11% of the OC petro initially present in bedrock exhumed from the tropical, rapidly eroding Central Range of Taiwan is oxidized in soils, leading to CO 2 emissions of 6.1 to 18.6 metric tons of carbon per square kilometer per year. The molecular and isotopic evolution of bulk OC and lipid biomarkers during soil formation reveals that OC petro remineralization is microbially mediated. Rapid oxidation in mountain soils drives CO 2 emission fluxes that increase with erosion rate, thereby counteracting CO 2 drawdown by silicate weathering and biospheric OC burial. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Thermoactivated persulfate oxidation of pesticide chlorpyrifos in aquatic system: kinetic and mechanistic investigations.

PubMed

Zhou, Lei; Zhang, Ya; Ying, Rongrong; Wang, Guoqing; Long, Tao; Li, Jianhua; Lin, Yusuo

2017-04-01

The widespread occurrence of organophosphorus pesticides (OPPs) in the environment poses risks to both ecologic system as well as human health. This study investigated the oxidation kinetics of chlorpyrifos (CP), one of the typical OPPs, by thermoactivated persulfate (PS) oxidation process, and evaluated the influence of key kinetic factors, such as PS concentrations, pH, temperature, bicarbonate, and chloride ions. The reaction pathways and mechanisms were also proposed based on products identification by LC-MS techniques. Our results revealed that increasing initial PS concentration and temperature favored the decomposition of CP, whereas the oxidation efficiency was not affected by pH change ranging from 3 to 11. Bicarbonate was found to play a detrimental role on CP removal rates, while chloride showed no effect. The oxidation pathways including initial oxidation of P=S bond to P=O, dechlorination, dealkylation, and the dechlorination-hydroxylation were proposed, and the detailed underlying mechanisms were also discussed. Molecular orbital (MO) calculations indicated that P=S bond was the most favored oxidation site of the molecule. The toxicity of reaction solution was believed to increase due to the formation of products with P=O structures. This work demonstrates that OPPs can readily react with SO 4 ·- and provides important information for further research on the oxidation of these contaminants.

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

PubMed

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

2014-12-15

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

Mouse Betaine-Homocysteine S-Methyltransferase Deficiency Reduces Body Fat via Increasing Energy Expenditure and Impairing Lipid Synthesis and Enhancing Glucose Oxidation in White Adipose Tissue*

PubMed Central

Teng, Ya-Wen; Ellis, Jessica M.; Coleman, Rosalind A.; Zeisel, Steven H.

2012-01-01

Betaine-homocysteine S-methyltransferase (BHMT) catalyzes the synthesis of methionine from homocysteine. In our initial report, we observed a reduced body weight in Bhmt−/− mice. We initiated this study to investigate the potential role of BHMT in energy metabolism. Compared with the controls (Bhmt+/+), Bhmt−/− mice had less fat mass, smaller adipocytes, and better glucose and insulin sensitivities. Compared with the controls, Bhmt−/− mice had increased energy expenditure, with no changes in food intake, fat uptake or absorption, or in locomotor activity. The reduced adiposity in Bhmt−/− mice was not due to hyperthermogenesis. Bhmt−/− mice failed to maintain a normal body temperature upon cold exposure because of limited fuel supplies. In vivo and ex vivo tests showed that Bhmt−/− mice had normal lipolytic function. The rate of 14C-labeled fatty acid incorporated into [14C]triacylglycerol was the same in Bhmt+/+ and Bhmt−/− gonadal fat depots (GWAT), but it was 62% lower in Bhmt−/− inguinal fat depots (IWAT) compared with that of Bhmt+/+ mice. The rate of 14C-labeled fatty acid oxidation was the same in both GWAT and IWAT from Bhmt+/+ and Bhmt−/− mice. At basal level, Bhmt−/− GWAT had the same [14C]glucose oxidation as did the controls. When stimulated with insulin, Bhmt−/− GWAT oxidized 2.4-fold more glucose than did the controls. Compared with the controls, the rate of [14C]glucose oxidation was 2.4- and 1.8-fold higher, respectively, in Bhmt−/− IWAT without or with insulin stimulus. Our results show for the first time a role for BHMT in energy homeostasis. PMID:22362777

In situ characterization of Zircaloy-4 oxidation at 500 °C in dry air

NASA Astrophysics Data System (ADS)

Vermoyal, J. J.; Dessemond, L.; Hammou, A.; Frichet, A.

2001-10-01

The in situ oxidation of Zircaloy-4 at 500 °C in dry air was investigated by thermogravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The coating of the alloy by a platinum film as electrode material was observed as not to modify the oxidation kinetic properties. After an initial cubic rate law, a transition to a quasi-linear curve occurs. The independence of the oxidation behavior to the Pt coupling is compatible with oxygen diffusion as the rate-determining step. During the pre-transition step, the rest potential of the cell Pt/oxide/Zy-4, the color of the oxide and the modulus of the single EIS signature indicate the high non-stoichiometry of the oxide. The kinetic transition was proposed to be correlated to the degradation of the film into a partially porous layer. This alteration of the oxide is associated to the appearance of a 1.2 V constant rest potential and the modification of the impedance diagrams in two high modulus contributions. The Cole-Cole representation has been used to demonstrate that the time variation of impedance spectra is related to the oxide growth. An equivalent circuit including two RC loops in series, whose capacitances are frequency dispersed, was proposed to be related to the film structure. Fitted data show that the thickness of the assumed protective layer of the film, close to the metal-oxide interface, is time independent in agreement with a constant oxidation rate. Finally, electrical properties of this inner layer were found to be quite different in pre- and post-transition stage.

Enzymatic hydrolysis of cellulose dissolved in N-methyl morpholine oxide/water solutions.

PubMed

Ramakrishnan, S; Collier, J; Oyetunji, R; Stutts, B; Burnett, R

2010-07-01

In situ hydrolysis of cellulose (dissolving pulp) in N-methyl morpholine oxide (NMMO) solutions by commercially available Accellerase1000 is carried out. The yield of reducing sugars is followed as a function of time at three different temperatures and four different enzyme loadings to study the effect of system parameters on enzymatic hydrolysis. Initial results show that rates of hydrolysis of cellulose and yields of reducing sugars in the presence of NMMO-water is superior initially (ratio of initial reaction rates approximately 4) and comparable to that of regenerated cellulose (for times greater than 5h) when suspended in aqueous solutions. The usage of Accellerase1000 results predominantly in the formation of glucose with minimal amounts of cellobiose. This study proves the ability of cellulases to remain active in NMMO to carry out an in situ saccharification of cellulose thus eliminating the need to recover regenerated cellulose. Thus this work will form the basis for developing a continuous process for conversion of biomass to hydrogen, ethanol and other hydrocarbons. Copyright 2009 Elsevier Ltd. All rights reserved.

Salt Marsh sediment 15N/13C "Push-Pull" assays reveal coupled sulfur, nitrogen, and carbon cycling

NASA Astrophysics Data System (ADS)

Thomas, S. M.; Tucker, J.; Thomas, F.; Sievert, S. M.; Cardon, Z. G.; Giblin, A. E.

2016-12-01

Salt marshes are extraordinarily productive ecosystems found in estuaries worldwide, hosting intensive sulfur, nitrogen, and carbon cycling. Although it has been hypothesized that in this environment sulfur oxidation may be important for energy flow, there is little direct data. At the heart of these hypothesized interactions are sulfur oxidizing microbes. Sulfur oxidizers can catalyze sulfide (re-)oxidation with nitrate as the electron acceptor under anaerobic conditions, producing ammonium (via DNRA) or dinitrogen gas (via denitrification). The form of sulfur present in marsh systems influences whether autotrophic or heterotrophic processes transform nitrate either to dinitrogen gas or ammonium through DNRA. To examine the fate of nitrate and interactions with sulfur, we conducted a series of "push-pull" experiments in marsh sediment at the Plum Island Ecosystems Long-Term Ecological Research site in Massachusetts. Porewater was extracted anoxically and amended with isotopically labeled nitrate (15N) and bicarbonate (13C). Porewater was pumped back into the sediment and then withdrawn at intervals of several hours. Dissolved inorganic nitrogen, sulfur, and carbon were measured as well as isotopes of nitrogen gas and ammonium. These push-pull experiments were conducted at several times during the growing season, to coincide with salt marsh grass initial growth (May), maximum growth (July), flowering (August), and senescence (October). Porewater sulfides were very low to non-detectable in May (time of initial plant growth) and increased to a maximum of 3 mM in October (time of plant senescence). Combined rates of denitrification and DNRA also varied seasonally: rates were higher in May (0.16 - 17.5 nmoles N/cm3/hr) and much lower in October (0 - 0.03 nmoles N/cm3/hr). Interestingly, DNRA rates were always higher than denitrification rates, often by an order of magnitude or more.

The preparation of Fe2O3-ZSM-5 catalysts by metal-organic chemical vapour deposition method for catalytic wet peroxide oxidation of m-cresol.

PubMed

Yang, Yi; Zhang, Huiping; Yan, Ying

2018-03-01

Fe 2 O 3 -ZSM-5 catalysts (0.6 wt% Fe load) prepared by metal-organic chemical vapour deposition (MOCVD) method were evaluated in the catalytic wet peroxide oxidation (CWPO) of m -cresol in a batch reactor. The catalysts have a good iron dispersion and small iron crystalline size, and exhibit high stability during reaction. In addition, the kinetics of the reaction were studied and the initial oxidation rate equation was given. Catalysts were first characterized by N 2 adsorption-desorption isotherms, scanning electronic microscopy, energy-dispersive spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. Results show that extra-framework Fe 3+ species (presenting in the form of Fe 2 O 3 ) are successfully loaded on ZSM-5 supports by MOCVD method. Performances of catalysts were tested and effects of different temperature, stirring rate, catalyst amount on hydrogen peroxide, m -cresol, total organic carbon (TOC) conversion and Fe leaching concentration were studied. Results reveal that catalytic activity increased with higher temperature, faster stirring rate and larger catalyst amount. In all circumstances, m -cresol conversion could reach 99% in 0.5-2.5 h, and the highest TOC removal (80.5%) is obtained after 3 h under conditions of 60°C, 400 r.p.m. and catalyst amount of 2.5 g l -1 . The iron-leaching concentrations are less than 1.1 mg l -1 under all conditions. The initial oxidation rate equation [Formula: see text] is obtained for m -cresol degradation with Fe 2 O 3 -ZSM-5 catalysts.

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

PubMed

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.

Evidence for a Terpene-Based Food Chain in the Gulf of Alaska

PubMed Central

Button, D. K.

1984-01-01

A mixture of 14C-terpenes was prepared from conifer seedlings and introduced into fresh seawater samples taken near Seward, Alaska. Initial rates of oxidation by the indigenous bacteria were linear and faster than the rates of toluene oxidation. Turnover times were 4 to 19 days. Autoradiographic measurements with 3H-terpenes indicated that at least 10% of the 0.6 × 109 to 2.7 × 109 bacteria per liter present could catabolize terpenes. The rate of terpene oxidation, 24 μg of terpenes per g of cells per h with 3 μg of terpenes added per liter, was a constant function of bacterial biomass. The specific affinity of the process was estimated to be between 8.1 and 81 liters/g of cells per h, indicating a high state of induction and the probable presence of terpenes. Terpene-oxidizing bacteria were grown on [14C]alanine and added to fresh seawater samples. Transfer of the bacterial radioactivity into larger particles at a rate of 146 pg/liter per h from the 2.3 × 109 organisms added indicated that any terpenes present would participate in the food chain. PMID:16346658

Epitaxial thinning process

NASA Technical Reports Server (NTRS)

Siegel, C. M. (Inventor)

1984-01-01

A method is described for thinning an epitaxial layer of a wafer that is to be used in producing diodes having a specified breakdown voltage and which also facilitates the thinning process. Current is passed through the epitaxial layer, by connecting a current source between the substrate of the wafer and an electrolyte in which the wafer is immersed. When the wafer is initially immersed, the voltage across the wafer initially drops and then rises at a steep rate. When light is applied to the wafer the voltage drops, and when the light is interrupted the voltage rises again. These changes in voltage, each indicate the breakdown voltage of a Schottky diode that could be prepared from the wafer at that time. The epitaxial layer is thinned by continuing to apply current through the wafer while it is immersed and light is applied, to form an oxide film and when the oxide film is thick the wafer can then be cleaned of oxide and the testing and thinning continued. Uninterrupted thinning can be achieved by first forming an oxide film, and then using an electrolyte that dissolves the oxide about as fast as it is being formed, to limit the thickness of the oxide layer.

Solid State Research, 1980:4

DTIC Science & Technology

1980-10-31

and is initiated at the periphery of the de- vice at opening in the SijNj layer. Rate measurement* of thi* prove** made on the GKOUSS imager using...dimensions, single-mode opera- tion can be obtained. There is a stripe opening in the oxide film running parallel to the etched rib, which can be...seen in cross section in Fig. I-l(a). This stripe opening is the nucleation region for the epitaxial growth. Other oxide-confined waveguide

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

PubMed

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.

Tyrosinase kinetics: failure of acceleration in oxidation of ring-blocked monohydric phenol substrate.

PubMed

Naish-Byfield, S; Riley, P A

1998-04-01

When 2,5,6-trimethyl-4-hydroxyanisole is used as substrate for mushroom tyrosinase the oxidation rate is slow and the kinetics do not exhibit an initial acceleration (lag period), in contrast to the kinetics of oxidation of the parent compound, 4-hydroxyanisole. This finding is interpreted as evidence that the acceleration of oxidation of 4-hydroxyanisole is indirectly contingent on a reductive nucleophile addition to the orthoquinone product of the monohydric phenol, which is prevented by ring methylation. Such a view is consistent with the proposal that the lag-phase characteristic of the kinetics of monohydric phenol oxidation by tyrosinase is due to the activation of previously inactive enzyme by electron donation from an orthodiphenol substrate formed from the orthoquinone oxidation product.

Silicon dioxide space coatings studied ellipsometrically

NASA Technical Reports Server (NTRS)

De, Bhola N.; Zhao, Yong; Hruska, Jane; Peterkin, Jane; Woollam, John A.

1990-01-01

Mechanisms of initial oxidation of silicon for the formation of silicon dioxide have been investigated. The oxidation of silicon in an atomic oxigen plasma environment is found to exhibit two distinct and linear oxide growth curves for each of the plasma powers used in ashing (25, 50, and 100 watts). Data obtained indicate that the exponent to the pressure in the oxide growth rate formula changes from 1.4 + or - 0.1 to 0.7 + or - 0.1 as one crosses the critical thickness. These data contradict the theory predicting that this exponent should be 1 for both regimes. The activation energy for oxidation in the zone reaction regime is found to be 0.17 eV, in contrast to the published value of 1-2 eV for thermally grown oxides.

High-rate sulphidogenic fluidised-bed treatment of metal-containing wastewater at high temperature.

PubMed

Sahinkaya, E; Ozkaya, B; Kaksonen, A H; Puhakka, J A

2007-01-01

The applicability of fluidised-bed reactor (FBR) based sulphate reducing bioprocess was investigated for the treatment of iron containing (40-90 mg/L) acidic wastewater at 65 degrees C. The FBR was inoculated with sulphate-reducing bacteria (SRB) originally enriched from a hot mining environment. Ethanol or acetate was supplemented as carbon and electron source for the SRB. A rapid startup with 99.9, 46 and 29% ethanol, sulphate and acetate removals, in respective order, was observed even after 6 days. Iron was almost completely removed with a rate of 90 mg/L.d. The feed pH was decreased gradually from its initial value of 6 to around 3.7 during 100 days of operation. The wastewater pH of 4.3-4.4 was neutralised by the alkalinity produced in acetate oxidation and the average effluent pH was 7.8 +/- 0.8. Although ethanol removal was complete, acetate accumulated. Later the FBR was fed with acetate only. Although acetate was present in the reactor for 295 days, its oxidation rates did not improve, which may be due to low growth rate and poor attachment ability of acetate oxidising SRB. Hence, the oxidation of acetate is the rate limiting step in the sulphidogenic ethanol oxidation by the thermophilic SRB.

Kinetic modeling of low density lipoprotein oxidation in arterial wall and its application in atherosclerotic lesions prediction.

PubMed

Karimi, Safoora; Dadvar, Mitra; Modarress, Hamid; Dabir, Bahram

2013-01-01

Oxidation of low-density lipoprotein (LDL) is one of the major factors in atherogenic process. Trapped oxidized LDL (Ox-LDL) in the subendothelial matrix is taken up by macrophage and leads to foam cell generation creating the first step in atherosclerosis development. Many researchers have studied LDL oxidation using in vitro cell-induced LDL oxidation model. The present study provides a kinetic model for LDL oxidation in intima layer that can be used in modeling of atherosclerotic lesions development. This is accomplished by considering lipid peroxidation kinetic in LDL through a system of elementary reactions. In comparison, characteristics of our proposed kinetic model are consistent with the results of previous experimental models from other researches. Furthermore, our proposed LDL oxidation model is added to the mass transfer equation in order to predict the LDL concentration distribution in intima layer which is usually difficult to measure experimentally. According to the results, LDL oxidation kinetic constant is an important parameter that affects LDL concentration in intima layer so that existence of antioxidants that is responsible for the reduction of initiating rates and prevention of radical formations, have increased the concentration of LDL in intima by reducing the LDL oxidation rate. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

The initial stage of uranium oxidation: mechanism of UO(2) scale formation in the presence of a native lateral stress field.

PubMed

Chernia, Z; Ben-Eliyahu, Y; Kimmel, G; Braun, G; Sariel, J

2006-11-23

In this work, an oxidation model for alpha-uranium is presented. It describes the internally lateral stress field built in the oxide scale during the reaction. The thickness of the elastic, stress-preserving oxide (UO(2+x)) scale is less than 0.5 microm. A lateral, 6.5 GPa stress field has been calculated from strains derived from line shifts (delta(2theta)) as measured by the X-ray diffraction of UO(2). It is shown that in the elastic growth domain, (110) is the main UO(2) growth plane for gas-solid oxidation. The diffusion-limited oxidation mechanism discussed here is based on the known "2:2:2" cluster theory which describes the mechanism of fluorite-based hyperstoichiometric oxides. In this study, it is adapted to describe oxygen-anion hopping. Anion hopping toward the oxide-metal interface proceeds at high rates in the [110] direction, hence making this pipeline route the principal growth direction in UO(2) formation. It is further argued that growth in the pure elastic domain of the oxide scale should be attributed entirely to anion hopping in 110. Anions, diffusing isotropically via grain boundaries and cracks, are shown to have a significant impact on the overall oxidation rate in relatively thick (>0.35 microm) oxide scales if followed by an avalanche break off in the postelastic regime. Stress affects oxidation in the elastic domain by controlling the hopping rate directly. In the postelastic regime, stress weakens hopping, indirectly, by enhancing isotropic diffusion. Surface roughness presents an additional hindering factor for the anion hopping. In comparison to anisotropic hopping, diffusion of isotropic hopping has a lower activation energy barrier. Therefore, a relatively stronger impact at lower temperatures due to isotropic diffusion is displayed.

Reverse Stability Kinetics of Meat Pigment Oxidation in Aqueous Extract from Fresh Beef.

PubMed

Frelka, John C; Phinney, David M; Wick, Macdonald P; Heldman, Dennis R

2017-12-01

The use of kinetic models is an evolving approach to describing quality changes in foods during processes, including storage. Previous studies indicate that the oxidation rate of myoglobin is accelerated under frozen storage conditions, a phenomenon termed reverse stability. The goal of this study was to develop a model for meat pigment oxidation to incorporate the phenomenon of reverse stability. In this investigation, the model system was an aqueous extract from beef which was stored under a range of temperatures, both unfrozen and frozen. The kinetic analysis showed that in unfrozen solutions, the temperature dependence of oxidation rate followed Arrhenius kinetics. However, under in frozen solutions the rate of oxidation increased with decreasing temperature until reaching a local maximum around -20 °C. The addition of NaCl to the model system increased oxidation rates at all temperatures, even above the initial freezing temperature. This observation suggests that this reaction is dependent on the ionic strength of the solution as well as temperature. The mechanism of this deviant kinetic behavior is not fully understood, but this study shows that the interplay of temperature and composition on the rate of oxidation of meat pigments is complicated and may involve multiple mechanisms. A better understanding of the kinetics of quality loss in a meat system allows for a re-examination of the current recommendations for frozen storage. The deviant kinetic behavior observed in this study indicates that the relationship between quality loss and temperature in a frozen food is not as simple as once thought. Product-specific recommendations could be implemented in the future that would allow for a decrease in energy consumption without a significant loss of quality. © 2017 Institute of Food Technologists®.

Oxidation feature and diffusion mechanism of Zr-based metallic glasses near the glass transition point

NASA Astrophysics Data System (ADS)

Hu, Zheng; Lei, Xianqi; Wang, Yang; Zhang, Kun

2018-03-01

The oxidation behaviors of as-cast, pre-deformed, and crystallized Zr47.9Ti0.3Ni3.1Cu39.3Al9.4 metallic glasses (MGs) were studied near the glass transition point. The oxidation kinetics of the crystallized MGs followed a parabolic-rate law, and the as-cast and pre-deformed MGs exerted a typical two-stage behavior above the glass transition temperature (T g). Most interesting, pre-deformed treatment can significantly improve the oxidation rate of MGs, as the initial oxidation appeared earlier than for the as-cast MGs, and was accompanied by much thicker oxide scale. The EDS and XPS results showed that the metal Al acted as the preferred scavenger that absorbed intrinsic oxygen in the near-surface region of as-cast MGs. However, a homogeneous mixed layer without Al was observed in the pre-deformed MGs. We speculated the accelerated diffusion of other elements in the MGs was due to the local increase in the free volume and significant shear-induced dilation of the local structure. The results from this study demonstrate that MGs exhibit controllable atomic diffusion during the oxidation process, which can facilitate use in super-cooled liquid region applications.

Ferrate(VI): a green chemical for the oxidation of cyanide in aqueous/waste solutions.

PubMed

Tiwari, Diwakar; Kim, Hyoung-Uk; Choi, Bong-Jong; Lee, Seung-Mok; Kwon, Oh-Heung; Choi, Kyu-Man; Yang, Jae-Kyu

2007-05-01

The higher oxidation state of iron, i.e. Fe(VI), was employed for the oxidation of the important toxic ion cyanide in aqueous/waste waters. Cyanide was oxidized to cyanate, which is 1,000 times less toxic than cyanide, and can often be accepted for its ultimate disposal. It was noted that Fe(VI) is a very powerful oxidizing agent, and can oxidize most of the cyanide within a few minutes, ca 5 minutes, of contact. The extent of the reduction of Fe(VI) was obtained using the UV-Visible measurements. Further, the UV-Visible data was used to explain the reaction kinetics involved in the redox reaction between ferrate(VI) and cyanide. The pseudo-first-order rate constant was calculated by maintaining the cyanide concentration in excess, with the overall second order rate constant values obtained for initial Fe(VI) concentrations of 1.0 and 0.1 mmol/L. The oxidation of cyanide was again confirmed using a cyanide probe. Fe(VI) was further employed for its possible application in the treatment of industrial wastewaters containing cyanide, along with some heavy metals, such as those obtained from electroplating industries.

A spontaneous change in the oxidation states of Pd/WO3 toward an active phase during catalytic cycles of CO oxidation

NASA Astrophysics Data System (ADS)

Jeon, Byungwook; Kim, Ansoon; Lee, Young-Ahn; Seo, Hyungtak; Kim, Yu Kwon

2017-11-01

CO oxidation over Pd/WO3 films prepared on a glass substrate has been examined at the substrate temperature of 150 - 250 °C and pressures less than 1 Torr with a stoichiometric mixture of CO and O2. Under the given reaction condition, the chemical states of the Pd/WO3 film gradually change into the most catalytically active form with the highest saturation reaction rate regardless of the initial oxidation states. The measured CO oxidation rate over the Pd/WO3 is strongly dependent on the chemical states of Pd and W. Either metallic Pd or fully oxidized PdO phase is not as catalytically active as the active form with mixed metallic Pd and thin PdO layers supported on WO3 with partially reduced W5+ state which is spontaneously obtained during the catalytic reaction cycles. Our results indicate that the facile oxygen transfer between Pd and WO3 layers not only facilitate the spontaneous changes into the active form, but also act as a promotional role in CO oxidation over the Pd layer.

Local Anodic Oxidation of Thin GeO Films and Formation of Nanostructures Based on Them

NASA Astrophysics Data System (ADS)

Astankova, K. N.; Kozhukhov, A. S.; Azarov, I. A.; Gorokhov, E. B.; Sheglov, D. V.; Latyshev, A. V.

2018-04-01

The process of local anodic oxidation of thin GeO films has been studied using an atomic force microscope. The electron-probe microanalysis showed that oxidized areas of a GeO film were germanium dioxide. The effect of the voltage pulse duration applied to the probe-substrate system and the atmospheric humidity on the height of the oxide structures has been studied. The kinetics of the local anodic oxidation (LAO) in a semi-contact mode obeys the Cabrera-Mott model for large times. The initial growth rate of the oxide ( R 0) significantly increases and the time of starting the oxidation ( t 0) decreases as the atmospheric humidity increases by 20%, which is related to an increase in the concentration of oxygen-containing ions at the surface of the oxidized GeO film. It was shown that nanostructures in thin GeO layers can be formed by the LAO method.

Vapor deposition and condensate flow on combustion turbine blades - Theoretical model to predict/understand some corrosion rate consequences of molten alkali sulfate deposition in the field or laboratory

NASA Technical Reports Server (NTRS)

Rosner, Daniel E.; Nagarajan, R.

1987-01-01

An analysis is undertaken of aerodynamically- and centrifugally-driven liquid condensate layers on nonisothermal combustion turbines' stator vanes and rotor blades. Attention is given to the quantitative consequences of one possible mechanism for the initiation of 'hot corrosion' in the underlying blade material through a 'fluxing' of the protective oxide coating by the molten salt of the Newtonian condensate film. Illustrative calculations are presented for the condensate streamline pattern and the distributions of the steady-state condensate layer thickness, together with the corresponding oxide dissolution rate, for a test turbine blade.

Control of Alq3 wetting layer thickness via substrate surface functionalization.

PubMed

Tsoi, Shufen; Szeto, Bryan; Fleischauer, Michael D; Veinot, Jonathan G C; Brett, Michael J

2007-06-05

The effects of substrate surface energy and vapor deposition rate on the initial growth of porous columnar tris(8-hydroxyquinoline)aluminum (Alq3) nanostructures were investigated. Alq3 nanostructures thermally evaporated onto as-supplied Si substrates bearing an oxide were observed to form a solid wetting layer, likely caused by an interfacial energy mismatch between the substrate and Alq3. Wetting layer thickness control is important for potential optoelectronic applications. A dramatic decrease in wetting layer thickness was achieved by depositing Alq3 onto alkyltrichlorosilane-derivatized Si/oxide substrates. Similar effects were noted with increasing deposition rates. These two effects enable tailoring of the wetting layer thickness.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-06-01

The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

NASA Astrophysics Data System (ADS)

van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

2014-11-01

The retention of phosphorus in surface waters through co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater into surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and surface water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than a week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an important geochemical mechanism in the transformation of dissolved phosphate to structural phosphate and, therefore, a major control on the P retention in natural waters that drain anaerobic aquifers.

Thermodynamic Versus Surface Area Control of Microbial Fe(III) Oxide Reduction Kinetics

NASA Astrophysics Data System (ADS)

Roden, E. E.

2003-12-01

Recent experimental studies of synthetic and natural Fe(III) oxide reduction permit development of conceptual and quantitative models of enzymatic Fe(III) oxide reduction at circumneutral pH that can be compared to and contrasted with established models of abiotic mineral dissolution. The findings collectively support a model for controls on enzymatic reduction that differs fundamentally from those applied to abiotic reductive dissolution as a result of two basic phenomena: (1) the relatively minor influence of oxide mineralogical and thermodynamic properties on surface area-normalized rates of enzymatic reduction compared to abiotic reductive dissolution; and (2) the major limitation which sorption and/or surface precipitation of biogenic Fe(II) on residual oxide and Fe(III)-reducing bacterial cell surfaces poses to enzymatic electron transfer in the presence of excess electron donor. Parallel studies with two major Fe(III)-reducing bacteria genera (Shewanella and Geobacter) lead to common conclusions regarding the importance of these phenomena in regulating the rate and long-term extent of Fe(III) oxide reduction. Although the extent to which these phenomena can be traced to underlying kinetic vs. thermodynamic effects cannot be resolved with current information, models in which rates of enzymatic reduction are limited kinetically by the abundance of "available" oxide surface sites (as controlled by oxide surface area and the abundance of surface-bound Fe(II)) provide an adequate macroscopic description of controls on the initial rate and long-term extent of oxide reduction. In some instances, thermodynamic limitation posed by the accumulation of aqueous reaction end-products (i.e. Fe(II) and alkalinity) must also be invoked to explain observed long-term patterns of reduction. In addition, the abundance of Fe(III)-reducing microorganisms plays an important role in governing rates of reduction and needs to be considered in models of Fe(III) reduction in nonsteady-state systems, e.g. subsurface environments in which Fe(III) reduction is stimulated by contamination with organics or for the purposes of metal/radionuclide bioremediation.

Initiation of Anaerobic Degradation of p-Cresol by Formation of 4-Hydroxybenzylsuccinate in Desulfobacterium cetonicum

PubMed Central

Müller, Jochen A.; Galushko, Alexander S.; Kappler, Andreas; Schink, Bernhard

2001-01-01

The anaerobic bacterium Desulfobacterium cetonicum oxidized p-cresol completely to CO2 with sulfate as the electron acceptor. During growth, 4-hydroxybenzylsuccinate accumulated in the medium. This finding indicated that the methyl group of p-cresol is activated by addition to fumarate, analogous to anaerobic toluene, m-xylene, and m-cresol degradation. In cell extracts, the formation of 4-hydroxybenzylsuccinate from p-cresol and fumarate was detected at an initial rate of 0.57 nmol min−1 (mg of protein)−1. This activity was specific for extracts of p-cresol-grown cells. 4-Hydroxybenzylsuccinate was degraded further to 4-hydroxybenzoyl-coenzyme A (CoA), most likely via β-oxidation. 4-Hydroxybenzoyl-CoA was reductively dehydroxylated to benzoyl-CoA. There was no evidence of degradation of p-cresol via methyl group oxidation by p-cresol-methylhydroxylase in this bacterium. PMID:11133971

Oxidation of ammonium sulfite in aqueous solutions using ozone technology

NASA Astrophysics Data System (ADS)

Li, Yue; Shang, Kefeng; Lu, Na; Li, Jie; Wu, Yan

2013-03-01

How to deal with unstable ammonium sulfite, the byproduct of flue gas desulfuration by ammonia absorption methods, has been a difficult problem in recent years. Oxidation of ammonium sulfite in aqueous solutions using ozone produced by a surface discharge system was investigated in the paper. The oxidation efficiency of ammonium sulfite by ozone and traditional air aeration were compared, and the factors including ozone concentration, gas flow rate, initial concentration of ammonium sulfite solution and reaction temperature were discussed. The results show that the oxidation efficiency of ammonium sulfite by ozone technology reached nearly 100% under the optimum conditions, which had a significant increase compared with that by air aeration.

Effects of soluble flavin on heterogeneous electron transfer between surface-exposed bacterial cytochromes and iron oxides

NASA Astrophysics Data System (ADS)

Wang, Zheming; Shi, Zhi; Shi, Liang; White, Gaye F.; Richardson, David J.; Clarke, Thomas A.; Fredrickson, Jim K.; Zachara, John M.

2015-08-01

Dissimilatory iron-reducing bacteria can utilize insoluble Fe(Mn)-oxides as a terminal electron acceptor under anaerobic conditions. For Shewanella species specifically, evidence suggests that iron reduction is associated with the secretion of flavin mononucleotide (FMN) and riboflavin. However, the exact mechanism of flavin involvement is unclear; while some indicate that flavins mediate electron transfer (Marsili et al., 2008), others point to flavin serving as co-factors to outer membrane proteins (Okamoto et al., 2013). In this work, we used methyl viologen (MVrad +)-encapsulated, porin-cytochrome complex (MtrCAB) embedded liposomes (MELs) as a synthetic model of the Shewanella outer membrane to investigate the proposed mediating behavior of microbially produced flavins. The reduction kinetics of goethite, hematite and lepidocrocite (200 μM) by MELs ([MVrad +] ∼ 40 μM and MtrABC ⩽ 1 nM) were determined in the presence FMN at pH 7.0 in N2 atmosphere by monitoring the concentrations of MVrad + and FMN through their characteristic UV-visible absorption spectra. Experiments were performed where (i) FMN and Fe(III)-oxide were mixed and then reacted with the reduced MELs and (ii) FMN was reacted with the reduced MELs followed by addition of Fe(III)-oxide. The redox reactions proceeded in two steps: a fast step that was completed in a few seconds, and a slower one lasting over 400 s. For all three Fe(III)-oxides, the initial reaction rate in the presence of a low concentration of FMN (⩽1 μM) was at least a factor of five faster than those with MELs alone, and orders of magnitude faster than those by FMNH2, suggesting that FMN may serve as a co-factor that enhances electron transfer from outer-membrane c-cytochromes to Fe(III)-oxides. The rate and extent of the initial reaction followed the order of lepidocrocite > hematite > goethite, the same as their reduction potentials, implying thermodynamic control on reaction rate. For LEP, with the highest reduction potential among the three Fe(III)-oxides, its reduction by FMNH2 was completed in less than 10 min, suggesting that FMN was capable of mediating electron transfer to LEP. At higher FMN concentrations (>1 μM), the reaction rates for both steps decreased and varied inversely with FMN concentration, indicating that FMN inhibited the MEL to Fe(III)-oxide electron transfer reaction under these conditions. The implications of the observed kinetic behaviors to flavin-mediated Fe(III)-oxide reduction in natural environments are discussed.

Influence of growth conditions on subsequent submonolayer oxide decomposition on Si(111)

NASA Astrophysics Data System (ADS)

Shklyaev, A. A.; Aono, Masakazu; Suzuki, Takanori

1996-10-01

The decomposition kinetics of oxide with a coverage between 0.1 and 0.5 ML, grown by oxidation of the Si(111)-7×7 surface at temperatures between 550 and 800 °C for oxygen pressures (Pox) between 3×10-8 and 2×10-6 Torr, is investigated with optical second-harmonic generation. Through the analysis of the pressure dependence of the initial oxide-growth rate, we separate the conditions for a slow oxide growth at Pox near Ptr(T) and for a rapid oxide growth at Pox>3Ptr(T), where Ptr(T) is the transition pressure to Si-etching regime without oxide growth. For the rapidly grown oxide, the oxide decomposition rate decreases with increasing oxide coverage, whereas the activation energy of about 3 eV does not change significantly. While in the case when the oxide is desorbed at the same temperature as are used for oxide growth, the oxide decomposition is described by an apparent activation energy of 1.5 eV. For the slowly grown oxide of 0.1 ML coverage, the oxide desorption kinetics shows a rapid decomposition stage followed by a slow stage. For the slowly grown oxide of 0.3 ML coverage, the slow stage with a large activation energy of 4.1 eV becomes dominant in the latter part of decomposition. The dependence of the desorption kinetics on the oxide-growth conditions described here could be a reason for the scattering of the kinetic parameters in the literature for O2 interaction with silicon at elevated temperatures.

AIBA as Free Radical Initiator for Abrasive-Free Polishing of Hard Disk Substrate

NASA Astrophysics Data System (ADS)

Lei, Hong; Ren, Xiaoyan

2015-04-01

In order to optimize the existing slurry for abrasive-free polishing (AFP) of a hard disk substrate, a water-soluble free radical initiator, 2,2'-azobis (2-methylpropionamidine) dihydrochloride (AIBA) was introduced into H2O2-based slurry in the present work. Polishing experiment results with AIBA in the H2O2 slurry indicate that the material removal rate (MRR) increases and the polished surface has a lower surface roughness. The mechanism of AIBA in AFP was investigated using electron spin-resonance spectroscopy and UV-Visible analysis, which showed that the concentration of hydroxyl radical (a stronger oxidizer than H2O2) in the slurry was enhanced in the present of AIBA. The structure of the film formed on the substrate surface was investigated by scanning electron microscopy, auger electron spectroscopy and electrochemical impedance spectroscopy technology, showing that a looser and porous oxide film was found on the hard disk substrate surface when treated with the H2O2-AIBA slurry. Furthermore, potentiodynamic polarization tests show that the H2O2-AIBA slurry has a higher corrosion current density, implying that a fast dissolution reaction can occur on the substrate surface. Therefore, we can conclude that the stronger oxidation ability, loose oxide film on the substrate surface, and the higher corrosion-wear rate of the H2O2-AIBA slurry lead to the higher MRR.

Krebs cycle metabolites and preferential succinate oxidation following neonatal hypoxic-ischemic brain injury in mice

PubMed Central

Sahni, Prateek V.; Zhang, Jimmy; Sosunov, Sergey; Galkin, Alexander; Niatsetskaya, Zoya; Starkov, Anatoly; Brookes, Paul S.; Ten, Vadim S.

2017-01-01

Background Reverse electron transport (RET) driven by the oxidation of succinate has been proposed as the mechanism of accelerated production of reactive oxygen species (ROS) in post-ischemic mitochondria. However, it remains unclear whether upon reperfusion, mitochondria preferentially oxidase succinate. Methods Neonatal mice were subjected to Rice-Vannucci model of hypoxicischemic brain injury (HI) followed by assessment of Krebs cycle metabolites, mitochondrial substrate preference, and H2O2 generation rate in the ischemic brain. Results While brain mitochondria from control mice exhibited a rotenonesensitive complex-I-dependent respiration, HI-brain mitochondria, at the initiation of reperfusion, demonstrated complex-II-dependent respiration, as rotenone minimally affected, but inhibition of complex-II ceased respiration. This was associated with a 30-fold increase of cerebral succinate concentration and significantly elevated H2O2 emission rate in HI-mice compared to controls. At sixty minutes of reperfusion, cerebral succinate content and the mitochondrial response to rotenone did not differ from that in controls. Conclusion These data are the first ex-vivo evidence, that at the initiation of reperfusion, brain mitochondria transiently shift their metabolism from complex-I-dependent oxidation of NADH toward complex II-linked oxidation of succinate. Our study provides a critical piece of support for existence of the RET-dependent mechanism of elevated ROS production in reperfusion. PMID:29211056

Krebs cycle metabolites and preferential succinate oxidation following neonatal hypoxic-ischemic brain injury in mice.

PubMed

Sahni, Prateek V; Zhang, Jimmy; Sosunov, Sergey; Galkin, Alexander; Niatsetskaya, Zoya; Starkov, Anatoly; Brookes, Paul S; Ten, Vadim S

2018-02-01

BackgroundReverse electron transport (RET) driven by the oxidation of succinate has been proposed as the mechanism of accelerated production of reactive oxygen species (ROS) in post-ischemic mitochondria. However, it remains unclear whether upon reperfusion, mitochondria preferentially oxidase succinate.MethodsNeonatal mice were subjected to Rice-Vannucci model of hypoxic-ischemic brain injury (HI) followed by assessment of Krebs cycle metabolites, mitochondrial substrate preference, and H 2 O 2 generation rate in the ischemic brain.ResultsWhile brain mitochondria from control mice exhibited a rotenone-sensitive complex-I-dependent respiration, HI-brain mitochondria, at the initiation of reperfusion, demonstrated complex-II-dependent respiration, as rotenone minimally affected, but inhibition of complex-II ceased respiration. This was associated with a 30-fold increase of cerebral succinate concentration and significantly elevated H 2 O 2 emission rate in HI-mice compared to controls. At 60 min of reperfusion, cerebral succinate content and the mitochondrial response to rotenone did not differ from that in controls.ConclusionThese data are the first ex vivo evidence, that at the initiation of reperfusion, brain mitochondria transiently shift their metabolism from complex-I-dependent oxidation of NADH toward complex II-linked oxidation of succinate. Our study provides a critical piece of support for existence of the RET-dependent mechanism of elevated ROS production in reperfusion.

Partially Oxidized SnS2 Atomic Layers Achieving Efficient Visible-Light-Driven CO2 Reduction.

PubMed

Jiao, Xingchen; Li, Xiaodong; Jin, Xiuyu; Sun, Yongfu; Xu, Jiaqi; Liang, Liang; Ju, Huanxin; Zhu, Junfa; Pan, Yang; Yan, Wensheng; Lin, Yue; Xie, Yi

2017-12-13

Unraveling the role of surface oxide on affecting its native metal disulfide's CO 2 photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS 2 atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS 2 atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g -1 h -1 , roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS 2 atomic layers and the SnS 2 atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO 2 reduction property, paving a new way for obtaining high-efficiency CO 2 photoreduction performances.

Native oxide formation on pentagonal copper nanowires: A TEM study

NASA Astrophysics Data System (ADS)

Hajimammadov, Rashad; Mohl, Melinda; Kordas, Krisztian

2018-06-01

Hydrothermally synthesized copper nanowires were allowed to oxidize in air at room temperature and 30% constant humidity for the period of 22 days. The growth of native oxide layer was followed up by high-resolution transmission electron microscopy and diffraction to reveal and understand the kinetics of the oxidation process. Copper oxides appear in the form of differently oriented crystalline phases around the metallic core as a shell-like layer (Cu2O) and as nanoscopic islands (CuO) on the top of that. Time dependent oxide thickness data suggests that oxidation follows the field-assisted growth model at the beginning of the process, as practically immediately an oxide layer of ∼2.8 nm thickness develops on the surface. However, after this initial rapid growth, the local field attenuates and the classical parabolic diffusion limited growth plays the main role in the oxidation. Because of the single crystal facets on the side surface of penta-twinned Cu nanowires, the oxidation rate in the diffusion limited regime is lower than in polycrystalline films.

Incorporating Geochemical And Microbial Kinetics In Reactive Transport Models For Generation Of Acid Rock Drainage

NASA Astrophysics Data System (ADS)

Andre, B. J.; Rajaram, H.; Silverstein, J.

2010-12-01

Acid mine drainage, AMD, results from the oxidation of metal sulfide minerals (e.g. pyrite), producing ferrous iron and sulfuric acid. Acidophilic autotrophic bacteria such as Acidithiobacillus ferrooxidans and Leptospirillum ferrooxidans obtain energy by oxidizing ferrous iron back to ferric iron, using oxygen as the electron acceptor. Most existing models of AMD do not account for microbial kinetics or iron geochemistry rigorously. Instead they assume that oxygen limitation controls pyrite oxidation and thus focus on oxygen transport. These models have been successfully used for simulating conditions where oxygen availability is a limiting factor (e.g. source prevention by capping), but have not been shown to effectively model acid generation and effluent chemistry under a wider range of conditions. The key reactions, oxidation of pyrite and oxidation of ferrous iron, are both slow kinetic processes. Despite being extensively studied for the last thirty years, there is still not a consensus in the literature about the basic mechanisms, limiting factors or rate expressions for microbially enhanced oxidation of metal sulfides. An indirect leaching mechanism (chemical oxidation of pyrite by ferric iron to produce ferrous iron, with regeneration of ferric iron by microbial oxidation of ferrous iron) is used as the foundation of a conceptual model for microbially enhanced oxidation of pyrite. Using literature data, a rate expression for microbial consumption of ferrous iron is developed that accounts for oxygen, ferrous iron and pH limitation. Reaction rate expressions for oxidation of pyrite and chemical oxidation of ferrous iron are selected from the literature. A completely mixed stirred tank reactor (CSTR) model is implemented coupling the kinetic rate expressions, speciation calculations and flow. The model simulates generation of AMD and effluent chemistry that qualitatively agrees with column reactor and single rock experiments. A one dimensional reaction diffusion model at the scale of a single rock is developed incorporating the proposed kinetic rate expressions. Simulations of initiation, washout and AMD flows are discussed to gain a better understanding of the role of porosity, effective diffusivity and reactive surface area in generating AMD. Simulations indicate that flow boundary conditions control generation of acid rock drainage as porosity increases.

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

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

Thornburg, Nicholas E.; Notestein, Justin M.

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.more » 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.« less

Degradation of pentachlorophenol by hydroxyl radicals and sulfate radicals using electrochemical activation of peroxomonosulfate, peroxodisulfate and hydrogen peroxide.

PubMed

Govindan, Kadarkarai; Raja, Mohan; Noel, Michael; James, E J

2014-05-15

The present study is to investigate the reactivity of free radicals (SO4(-) and HO) generated from common oxidants (peroxomonosulfate (PMS), peroxodisulfate (PDS) and hydrogen peroxide (HP)) activated by electrochemically generated Fe(2+)/Fe(3+) ions which furthermore are evaluated to destroy pentachlorophenol (PCP) in aqueous solution. The effect of solution pH and amount of oxidants (PMS, PDS and HP) in electrocoagulation (EC) on PCP degradation is analyzed in detail. The experimental results reveal that, optimum initial solution pH is 4.5 and PMS is more efficient oxidant addition in EC. 75% PCP degradation is achieved at 60min electrolysis time from PMS assisted EC. According to the first order rate constant, faster PCP degradation rate is obtained by PMS assisted EC. The PCP degradation rate by oxidant assisted EC is observed in the following order: EC/PMS>EC/PDS>EC/HP>EC. Further to identify the influences of experimental factors involved in PCP degradation by oxidant assisted EC, an experimental design based on an orthogonal array (OA) L9 (3(3)) is proposed using Taguchi method. The factors that most significantly affect the process robustness are identified as A (oxidant) and B (pH) which together account for nearly 86% of the variance. Copyright © 2014 Elsevier B.V. All rights reserved.

Mass-Dependent and -Independent Fractionation of Mercury Isotope during Gas-Phase Oxidation of Elemental Mercury Vapor by Atomic Cl and Br.

PubMed

Sun, Guangyi; Sommar, Jonas; Feng, Xinbin; Lin, Che-Jen; Ge, Maofa; Wang, Weigang; Yin, Runsheng; Fu, Xuewu; Shang, Lihai

2016-09-06

This study presents the first measurement of Hg stable isotope fractionation during gas-phase oxidation of Hg(0) vapor by halogen atoms (Cl(•), Br(•)) in the laboratory at 750 ± 1 Torr and 298 ± 3 K. Using a relative rate technique, the rate coefficients for Hg(0)+Cl(•) and Hg(0)+Br(•) reactions are determined to be (1.8 ± 0.5) × 10(-11) and (1.6 ± 0.8) × 10(-12) cm(3) molecule(-1) s(-1), respectively. Results show that heavier isotopes are preferentially enriched in the remaining Hg(0) during Cl(•) initiated oxidation, whereas being enriched in the product during oxidation by Br(•). The fractionation factors for (202)Hg/(198)Hg during the Cl(•) and Br(•) initiated oxidations are α(202/198) = 0.99941 ± 0.00006 (2σ) and 1.00074 ± 0.00014 (2σ), respectively. A Δ(199)Hg/Δ(201)Hg ratio of 1.64 ± 0.30 (2σ) during oxidation of Hg(0) by Br atoms suggests that Hg-MIF is introduced by the nuclear volume effect (NVE). In contrast, the Hg(0) + Cl(•) reaction produces a Δ(199)Hg/Δ(201)Hg-slope of 1.89 ± 0.18 (2σ), which in addition to a high degree of odd-mass-number isotope MIF suggests impacts from MIF effects other than NVE. This reaction also exhibits significant MIF of (200)Hg (Δ(200)Hg, up to -0.17‰ in the reactant) and is the first physicochemical process identified to trigger (200)Hg anomalies that are frequently detected in atmospheric samples.

The Effect of the Concentration of Oxidant, Cr(VI), on the Iron Oxidation in Saline Water

NASA Astrophysics Data System (ADS)

Ahn, H.; Jo, H. Y.; Ryu, J. H.; Koh, Y. K.

2014-12-01

Deep geological disposal is currently considered as the most appropriate method to isolate high level radioactive wastes (HLRWs) from the ecosystem. If groundwater seeps into underground disposal facilities, water molecules can be dissociated to radicals or peroxides, which can oxidize metal canisters and HLRWs. The oxidized radionuclides with a high solubility can be dissolved in the groundwater. Some dissolved radionuclides can act as oxidants. The continuous radiolysis of water molecules, which results from continuous seepage of groundwater, can enable the continuous production of the radioactive oxidants, resulting in an increase in concentration of oxidants. In this study, the effect of oxidant concentration on iron oxidation in the presence of salt was evaluated. Zero valent iron (ZVI) particles were reacted with Cr(VI) solutions with initial Cr(VI) concentrations ranged from 50 to 300 mg/L in reactors. The initial pH and NaCl concentration were fixed at 3 and 0.5 M, respectively. An increase in the initial Cr(VI) concentration caused an increase in the rate and extend of H2 gas production. The decrement of Cr(VI) was increased as the initial Cr(VI) concentration was increased. The penetration of H+ ions in the presence Cl- ions through the passive film on the ZVI particles caused the reaction between H+ ions and ZVI particles, producing H2 gas and Fe2+ ions. The passive film was damaged during the reaction due to the eruption of H2 gas or peptization by Cl- ions. The Fe2+ ions were reacted with Cr(VI) ions in the solution, producing Fe(III)-Cr(III) (oxy)hydroxides on the passive film of ZVI particles or in the solution as colloidal particles. The Fe(III)-Cr(III) (oxy)hydroxides tends to be precipitated as colloidal particles at a high Cr(VI) concentration and precipitated on the passive film at a low Cr(VI) concentration. The passive film was repaired or thickened by additional formation of Fe(III)-Cr(III) (oxy)hydroxides at a lower Cr(VI) concentration.

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution.

PubMed

Monteagudo, J M; Carmona, M; Durán, A

2005-08-01

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.

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

NASA Technical Reports Server (NTRS)

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

2001-01-01

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

Impact of short-term acidification on nitrification and nitrifying bacterial community dynamics in soilless cultivation media.

PubMed

Cytryn, Eddie; Levkovitch, Irit; Negreanu, Yael; Dowd, Scot; Frenk, Sammy; Silber, Avner

2012-09-01

Soilless medium-based horticulture systems are highly prevalent due to their capacity to optimize growth of high-cash crops. However, these systems are highly dynamic and more sensitive to physiochemical and pH perturbations than traditional soil-based systems, especially during nitrification associated with ammonia-based fertilization. The objective of this study was to assess the impact of nitrification-generated acidification on ammonia oxidation rates and nitrifying bacterial community dynamics in soilless growth media. To achieve this goal, perlite soilless growth medium from a commercial bell pepper greenhouse was incubated with ammonium in bench-scale microcosm experiments. Initial quantitative real-time PCR analysis indicated that betaproteobacterial ammonia oxidizers were significantly more abundant than ammonia-oxidizing archaea, and therefore, research focused on this group. Ammonia oxidation rates were highest between 0 and 9 days, when pH values dropped from 7.4 to 4.9. Pyrosequencing of betaproteobacterial ammonia-oxidizing amoA gene fragments indicated that r-strategist-like Nitrosomonas was the dominant ammonia-oxidizing bacterial genus during this period, seemingly due to the high ammonium concentration and optimal growth conditions in the soilless media. Reduction of pH to levels below 4.8 resulted in a significant decrease in both ammonia oxidation rates and the diversity of ammonia-oxidizing bacteria, with increased relative abundance of the r-strategist-like Nitrosospira. Nitrite oxidizers (Nitrospira and Nitrobacter) were on the whole more abundant and less sensitive to acidification than ammonia oxidizers. This study demonstrates that nitrification and nitrifying bacterial community dynamics in high-N-load intensive soilless growth media may be significantly different from those in in-terra agricultural systems.

Impact of Short-Term Acidification on Nitrification and Nitrifying Bacterial Community Dynamics in Soilless Cultivation Media

PubMed Central

Levkovitch, Irit; Negreanu, Yael; Dowd, Scot; Frenk, Sammy; Silber, Avner

2012-01-01

Soilless medium-based horticulture systems are highly prevalent due to their capacity to optimize growth of high-cash crops. However, these systems are highly dynamic and more sensitive to physiochemical and pH perturbations than traditional soil-based systems, especially during nitrification associated with ammonia-based fertilization. The objective of this study was to assess the impact of nitrification-generated acidification on ammonia oxidation rates and nitrifying bacterial community dynamics in soilless growth media. To achieve this goal, perlite soilless growth medium from a commercial bell pepper greenhouse was incubated with ammonium in bench-scale microcosm experiments. Initial quantitative real-time PCR analysis indicated that betaproteobacterial ammonia oxidizers were significantly more abundant than ammonia-oxidizing archaea, and therefore, research focused on this group. Ammonia oxidation rates were highest between 0 and 9 days, when pH values dropped from 7.4 to 4.9. Pyrosequencing of betaproteobacterial ammonia-oxidizing amoA gene fragments indicated that r-strategist-like Nitrosomonas was the dominant ammonia-oxidizing bacterial genus during this period, seemingly due to the high ammonium concentration and optimal growth conditions in the soilless media. Reduction of pH to levels below 4.8 resulted in a significant decrease in both ammonia oxidation rates and the diversity of ammonia-oxidizing bacteria, with increased relative abundance of the r-strategist-like Nitrosospira. Nitrite oxidizers (Nitrospira and Nitrobacter) were on the whole more abundant and less sensitive to acidification than ammonia oxidizers. This study demonstrates that nitrification and nitrifying bacterial community dynamics in high-N-load intensive soilless growth media may be significantly different from those in in-terra agricultural systems. PMID:22773643

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

NASA Technical Reports Server (NTRS)

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

2000-01-01

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

Research on the Treatment of Aluminum Alloy Chemical Milling Wastewater with Fenton Process

NASA Astrophysics Data System (ADS)

Zong-liang, Huang; Ru, Li; Peng, Luo; Jun-li, Gu

2018-03-01

The aluminum alloy chemical milling wastewater was treated by Fenton method. The effect of pH value, reaction time, rotational speed, H2O2 dosage, Fe2+ dosage and the molar ratio between H2O2 and Fe2+ on the COD removal rate of aluminum alloy chemical milling wastewater were investigated by single factor experiment and orthogonal experiment. The results showed that the optimum operating conditions for Fenton oxidation were as follows: the initial pH value was 3, the rotational speed was 250r/min, the molar ratio of H2O2 and Fe2+ was 8, the reaction time was 90 min. Under the optimum conditions, the removal rate of the wastewater’s COD is about 72.36%. In the reaction kinetics that aluminum alloy chemical milling wastewater was oxidized and degraded by Fenton method under the optimum conditions, the reaction sequence of the initial COD was 0.8204.

Corrosion characteristics of Ni-base superalloys in high temperature steam with and without hydrogen

NASA Astrophysics Data System (ADS)

Kim, Donghoon; Kim, Daejong; Lee, Ho Jung; Jang, Changheui; Yoon, Duk Joo

2013-10-01

The hot steam corrosion behavior of Alloy 617 and Haynes 230 were evaluated in corrosion tests performed at 900 °C in steam and steam + 20 vol.% H2 environments. Corrosion rates of Alloy 617 was faster than that of Haynes 230 at 900 °C in steam and steam + 20 vol.% H2 environments. When hydrogen was added to steam, the corrosion rate was accelerated because added hydrogen increased the concentration of Cr interstitial defects in the oxide layer. Isolated nodular MnTiO3 oxides were formed on the MnCr2O4/Cr2O3 oxide layer and sub-layer Cr2O3 was formed in steam and steam + 20 vol.% H2 for Alloy 617. On the other hand, a MnCr2O4 layer was formed on top of the Cr2O3 oxide layer for Haynes 230. The extensive sub-layer Cr2O3 formation resulted from the oxygen or hydroxide inward diffusion in such environments. When hydrogen was added, the initial surface oxide morphology was changed from a convex shape to platelets because of the accelerated diffusion of cations under the oxide layer.

Laccase/Mediator Systems: Their Reactivity toward Phenolic Lignin Structures.

PubMed

Hilgers, Roelant; Vincken, Jean-Paul; Gruppen, Harry; Kabel, Mirjam A

2018-02-05

Laccase-mediator systems (LMS) have been widely studied for their capacity to oxidize the nonphenolic subunits of lignin (70-90% of the polymer). The phenolic subunits (10-30% of the polymer), which can also be oxidized without mediators, have received considerably less attention. Consequently, it remains unclear to what extent the presence of a mediator influences the reactions of the phenolic subunits of lignin. To get more insight in this, UHPLC-MS was used to study the reactions of a phenolic lignin dimer (GBG), initiated by a laccase from Trametes versicolor , alone or in combination with the mediators HBT and ABTS. The role of HBT was negligible, as its oxidation by laccase occurred slowly in comparison to that of GBG. Laccase and laccase/HBT oxidized GBG at a comparable rate, resulting in extensive polymerization of GBG. In contrast, laccase/ABTS converted GBG at a higher rate, as GBG was oxidized both directly by laccase but also by ABTS radical cations, which were rapidly formed by laccase. The laccase/ABTS system resulted in Cα oxidation of GBG and coupling of ABTS to GBG, rather than polymerization of GBG. Based on these results, we propose reaction pathways of phenolic lignin model compounds with laccase/HBT and laccase/ABTS.

SrCo1−xTixO3−δ perovskites as excellent catalysts for fast degradation of water contaminants in neutral and alkaline solutions

PubMed Central

Miao, Jie; Sunarso, Jaka; Su, Chao; Zhou, Wei; Wang, Shaobin; Shao, Zongping

2017-01-01

Perovskite-like oxides SrCo1−xTixO3−δ (SCTx, x = 0.1, 0.2, 0.4, 0.6) were used as heterogeneous catalysts to activate peroxymonosulfate (PMS) for phenol degradation under a wide pH range, exhibiting more rapid phenol oxidation than Co3O4 and TiO2. The SCT0.4/PMS system produced a high activity at increased initial pH, achieving optimized performance at pH ≥ 7 in terms of total organic carbon removal, the minimum Co leaching and good catalytic stability. Kinetic studies showed that the phenol oxidation kinetics on SCT0.4/PMS system followed the pseudo-zero order kinetics and the rate on SCT0.4/PMS system decreased with increasing initial phenol concentration, decreased PMS amount, catalyst loading and solution temperature. Quenching tests using ethanol and tert-butyl alcohol demonstrated sulfate and hydroxyl radicals for phenol oxidation. This investigation suggested promising heterogeneous catalysts for organic oxidation with PMS, showing a breakthrough in the barriers of metal leaching, acidic pH, and low efficiency of heterogeneous catalysis. PMID:28281656

Perform Tests and Document Results and Analysis of Oxide Layer Effects and Comparisons

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

Collins, E. D.; DelCul, G. D.; Spencer, B. B.

2014-08-30

During the initial feasibility test using actual used nuclear fuel (UNF) cladding in FY 2012, an incubation period of 30–45 minutes was observed in the initial dry chlorination. The cladding hull used in the test had been previously oxidized in a dry air oxidation pretreatment prior to removal of the fuel. The cause of this incubation period was attributed to the resistance to chlorination of an oxide layer imparted by the dry oxidation pretreatment on the cladding. Subsequently in 2013, researchers at the Korea Atomic Energy Institute (KAERI) reported on their chlorination study [R1] on ~9-gram samples of unirradiated ZirloTMmore » cladding tubes that had been previously oxidized in air at 500oC for various time periods to impart oxide layers of varying thickness. In early 2014, discussions with Indefinite Delivery, Indefinite Quantity (IDIQ) contracted technical consultants from Westinghouse described their previous development (and patents) [R2] on methods of chemical washing to remove some or all of the hydrous oxide layer imparted on UNF cladding during irradiation in light water reactors (LWRs) . Thus, the Oak Ridge National Laboratory (ORNL) study, described herein, was planned to extend the KAERI study on the effects of anhydrous oxide layers, but on larger ~100-gram samples of unirradiated zirconium alloy cladding tubes, and to investigate the effects of various methods of chemical pretreatment prior to chlorination with 100% chlorine on the average reaction rates and Cl2 usage efficiencies.« less

Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

NASA Astrophysics Data System (ADS)

van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

2016-08-01

Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with natural groundwater showed no principal differences in Fe(II) oxidation kinetics and in PO4 immobilisation dynamics compared with synthetic solutions with corresponding P/Fe ratio, pH and oxygen pressure. However, aeration of groundwater with relative high DOC concentrations and a low salinity lead to P-rich Fe colloids that were colloidally stable. The formation of a Fe hydroxyphosphate phase with a molar P/Fe ratio of 0.6 can be used for predictive modelling of PO4 immobilisation upon aeration of pH-neutral natural groundwater with an (P/Fe)ini ratio up to 1.5. These findings provide a solid basis for further studies on transport and bioavailability of phosphorus in streams, ditches and channels that receive anoxic Fe-rich groundwater.

Sulfidogenic fluidized-bed treatment of metal-containing wastewater at low and high temperatures.

PubMed

Sahinkaya, Erkan; Ozkaya, Bestamin; Kaksonen, Anna H; Puhakka, Jaakko A

2007-04-15

The applicability of a fluidized-bed reactor (FBR)-based sulfate reducing bioprocess was investigated for the treatment of iron-containing (40-90 mg/L) acidic wastewater at low (8 degrees C) and high (65 degrees C) temperatures. The FBRs operated at low and high temperatures were inoculated with cultures of sulfate-reducing bacteria (SRB) originally enriched from arctic and hot mining environments, respectively. Ethanol was supplemented as carbon and electron source for SRB. At 8 degrees C, ethanol oxidation and sulfate reduction rates increased steadily and reached 320 and 265 mg/L.day, respectively, after 1 month of operation. After this point, the rates did not change significantly during 130 days of operation. Despite the complete ethanol oxidation and iron precipitation, the average sulfate reduction efficiency was 35 +/- 4% between days 30 and 130 due to the accumulation of acetate. At 65 degrees C, a rapid startup was observed as 99.9, 46, and 29% ethanol, sulfate, acetate removals, in respective order, were observed after 6 days. The feed pH was decreased gradually from its initial value of 6 to around 3.7 during 100 days of operation. The wastewater pH of 4.3-4.4 was neutralized by the alkalinity produced in acetate oxidation and the average effluent pH was 7.8 +/- 0.8. As in the low temperature FBR, acetate accumulated. Hence, the oxidation of acetate is the rate-limiting step in the sulfidogenic ethanol oxidation by thermophilic and psychrotrophic SRB. The sulfate reduction rate is three times and acetate oxidation rate is four times higher at 65 degrees C than at 8 degrees C. (c) 2006 Wiley Periodicals, Inc.

Kinetics and oxidative mechanism for H2O2-enhanced iron-mediated aeration (IMA) treatment of recalcitrant organic compounds in mature landfill leachate.

PubMed

Deng, Yang; Englehardt, James D

2009-09-30

A hydrogen peroxide (H(2)O(2))-enhanced iron (Fe(0))-mediated aeration (IMA) process has been recently demonstrated to effectively remove organic wastes from mature landfill leachate. In this paper, the kinetics and oxidative mechanisms of the enhanced IMA treatment were studied. Bench-scale full factorial tests were conducted in an orbital shaker reactor for treatment of a mature leachate with an initial chemical oxygen demand (COD) of 900-1200 mg/L. At the maximum aeration rate (8.3 mL air/min mL sample), process variables significantly influencing the rates of H(2)O(2) decay and COD removal were pH (3.0-8.0), initial H(2)O(2) doses (0.21-0.84 M), and Fe(0) surface area concentrations (0.06-0.30 m(2)/L). Empirical kinetic models were developed and verified for the degradation of H(2)O(2) and COD. High DO maintained by a high aeration rate slowed the H(2)O(2) self-decomposition, accelerated Fe(0) consumption, and enhanced the COD removal. In hydroxyl radical (OH*) scavenging tests, the rate of removal of glyoxylic acid (target compound) was not inhibited by the addition of para-chlorobenzoic acid (OH* scavenger) at pH 7.0-7.5, ruling out hydroxyl radical as the principal oxidant in neutral-weakly basic solution. These experimental results show that this enhanced IMA technology is a potential alternative for the treatment of high strength recalcitrant organic wastewaters.

Cyclic Oxidation Modeling Program Rewritten for MS Windows

NASA Technical Reports Server (NTRS)

Smialek, James L.; Auping, Judith V.

2002-01-01

Turbine superalloy components are subject to high-temperature oxidation during operation. Protection is often conferred by coatings designed to form slow-growing, adherent oxide scales. Degradation by oxidation is exacerbated by the thermal cycling encountered during normal aircraft operations. Cooling has been identified as the major contributor to stresses in the oxidation scales, and it may often cause some oxide scale spallation with a proportional loss of protective behavior. Overall oxidation resistance is, thus, studied by the weight change behavior of alloy coupons during high-temperature cyclic oxidation in furnace or burner rig tests. The various characteristics of this behavior are crucial in understanding the performance of alloys at high temperatures. This new modeling effort helps in the understanding of the major factors involved in the cyclic oxidation process. Weight change behavior in cyclic oxidation is typified by an initial parabolic weight gain response curve that eventually exhibits a maximum, then transitions into a linear rate of weight loss due to spalling. The overall shape and magnitude of the curve are determined by the parabolic growth rate, kp, the cycle duration, the type of oxide scale, and the regular, repetitive spalling process. This entire process was modeled by a computer program called the Cyclic Oxidation Spalling Program (COSP) previously developed at the NASA Glenn Research Center. Thus, by supplying appropriate oxidation input parameters, one can determine the best fit to the actual data. These parameters describe real behavior and can be used to compare alloys and project cyclic oxidation behavior for longer times or under different cycle frequencies.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Synthesis and photocatalytic property of Zinc Oxide (ZnO) fine particle using flame spray pyrolysis method

NASA Astrophysics Data System (ADS)

Widiyandari, Hendri; Ayu Ketut Umiati, Ngurah; Dwi Herdianti, Rizki

2018-05-01

Advance oxidation process (AOP) using photocatalysis constitute a promising technology for the treatment of wastewaters containing non-easily removable organic compound. Zinc oxide (ZnO) is one of efficient photocatalyst materials. This research reported synthesis of ZnO fine particle from zinc nitrate hexahydrate using Flame Spray Pyrolysis (FSP) method. In this method, oxygen (O2) gas were used as oxidizer and LPG (liquid petroleum gas) were used as fuel. The effect of O2 gas flow rate during ZnO particle fabrication to the microstructure, optical and photocatalytic properties were systematically discussed. The photocatalytic activity of ZnO was tested for the degradation of amaranth dye with initial concentration of 10 ppm under irradiation of solar simulator. The rate of decrease in amaranth concentration was measured using UV-Visible spectrophotometer. The ZnO synthesized using FSP has a hexagonal crystalline structure. Scanning electron microscope images showed that ZnO has a spherical formed which was the mixture of solid and hollow particles. The optimum condition for amaranth degradation was shown by ZnO produced at a flow rate of 1.5 L/min which able to degrade amaranth dye up to 95,3 % at 75 minutes irradiation.

Mechanisms of deep benzene oxidation on the Pt(1 1 1) surface using temperature-programmed reaction methods

NASA Astrophysics Data System (ADS)

Marsh, Anderson L.; Gland, John L.

2003-06-01

The catalytic oxidation of benzene on the Pt(1 1 1) surface has been characterized using temperature-programmed reaction spectroscopy (TPRS) over a wide range of benzene and oxygen coverages. Coadsorbed atomic oxygen and benzene are the primary reactants on the surface during the initial oxidation step. Benzene is oxidized over the 300-500 K range to produce carbon dioxide and water. Carbon-hydrogen and carbon-carbon bond activation are clearly rate-limiting steps for these reactions. Preferential oxidation causes depletion of bridge-bonded benzene, suggesting enhanced reactivity in this bonding configuration. When oxygen is in excess on the surface, all of the surface carbon and hydrogen is oxidized. When benzene is in excess on the surface, hydrogen produced by dehydrogenation is desorbed after all of the surface oxygen has been consumed. Repulsive interactions between benzene and molecular oxygen dominate at low temperatures. Preadsorption of oxygen inhibits adsorption of less reactive benzene in threefold hollow sites. The desorption temperature of this non-reactive chemisorbed benzene decreases and overlaps with the multilayer desorption peak with increasing oxygen exposure. The results presented here provide a clear picture of rate-limiting steps during deep oxidation of benzene on the Pt(1 1 1) surface.

Kinetic Modeling of a Heterogeneous Fenton Oxidative Treatment of Petroleum Refining Wastewater

PubMed Central

Basheer Hasan, Diya'uddeen; Abdul Raman, Abdul Aziz; Wan Daud, Wan Mohd Ashri

2014-01-01

The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k 2′), their final oxidation step (k 1′), and the direct conversion to endproducts step (k 3′) were 10.12, 3.78, and 0.24 min−1 for GKM; 0.98, 0.98, and nil min−1 for GLKM; and nil, nil, and >0.005 min−1 for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics. PMID:24592152

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures.

PubMed

Zhao, Hai-Qian; Wang, Zhong-Hua; Gao, Xing-Cun; Liu, Cheng-Hao; Qi, Han-Bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100-500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300-500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption.

Optimization of NO oxidation by H2O2 thermal decomposition at moderate temperatures

PubMed Central

Wang, Zhong-hua; Gao, Xing-cun; Liu, Cheng-hao; Qi, Han-bing

2018-01-01

H2O2 was adopted to oxidize NO in simulated flue gas at 100–500°C. The effects of the H2O2 evaporation conditions, gas temperature, initial NO concentration, H2O2 concentration, and H2O2:NO molar ratio on the oxidation efficiency of NO were investigated. The reason for the narrow NO oxidation temperature range near 500°C was determined. The NO oxidation products were analyzed. The removal of NOx using NaOH solution at a moderate oxidation ratio was studied. It was proven that rapid evaporation of the H2O2 solution was critical to increase the NO oxidation efficiency and broaden the oxidation temperature range. the NO oxidation efficiency was above 50% at 300–500°C by contacting the outlet of the syringe needle and the stainless-steel gas pipe together to spread H2O2 solution into a thin film on the surface of the stainless-steel gas pipe, which greatly accelerated the evaporation of H2O2. The NO oxidation efficiency and the NO oxidation rate increased with increasing initial NO concentration. This method was more effective for the oxidation of NO at high concentrations. H2O2 solution with a concentration higher than 15% was more efficient in oxidizing NO. High temperatures decreased the influence of the H2O2 concentration on the NO oxidation efficiency. The oxidation efficiency of NO increased with an increase in the H2O2:NO molar ratio, but the ratio of H2O2 to oxidized NO decreased. Over 80% of the NO oxidation product was NO2, which indicated that the oxidation ratio of NO did not need to be very high. An 86.7% NO removal efficiency was obtained at an oxidation ratio of only 53.8% when combined with alkali absorption. PMID:29668672

Improve oxidation resistance at high temperature by nanocrystalline surface layer

NASA Astrophysics Data System (ADS)

Xia, Z. X.; Zhang, C.; Huang, X. F.; Liu, W. B.; Yang, Z. G.

2015-08-01

An interesting change of scale sequence occurred during oxidation of nanocrystalline surface layer by means of a surface mechanical attrition treatment. The three-layer oxide structure from the surface towards the matrix is Fe3O4, spinel FeCr2O4 and corundum (Fe,Cr)2O3, which is different from the typical two-layer scale consisted of an Fe3O4 outer layer and an FeCr2O4 inner layer in conventional P91 steel. The diffusivity of Cr, Fe and O is enhanced concurrently in the nanocrystalline surface layer, which causes the fast oxidation in the initial oxidation stage. The formation of (Fe,Cr)2O3 inner layer would inhabit fast diffusion of alloy elements in the nanocrystalline surface layer of P91 steel in the later oxidation stage, and it causes a decrease in the parabolic oxidation rate compared with conventional specimens. This study provides a novel approach to improve the oxidation resistance of heat resistant steel without changing its Cr content.

Investigation into the role of NaCL deposited on oxide and metal substrates in the initiation of hot corrosion

NASA Technical Reports Server (NTRS)

Birks, N.

1981-01-01

The conversion to Na2SO4 of NaCl deposited on oxide substrates was studied as a function of temperature, in air with various SO2 and H2O partial pressures. The substrate was either a pure oxide or an oxide scale growing on a metal specimen. The progress of the reaction was observed using the SEM-EDAX technique to monitor morphological effects and, as far as possible, establish the rate of the process. The physical characteristics of the interaction between salt and substrate were also examined with particular reference to physical damage to the underlying oxide, especially when this is a scale on a metal specimen. An effort was also made to establish the conditions under which liquid phases may form and the mechanisms by which they form.

Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

NASA Astrophysics Data System (ADS)

Powell, C. L.; Goltz, M. N.; Agrawal, A.

2014-12-01

Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots.

PubMed

Powell, C L; Goltz, M N; Agrawal, A

2014-12-01

Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

The Effect of Spray Initial Conditions on Heat Release and Emissions in LDI CFD Calculations

NASA Technical Reports Server (NTRS)

Iannetti, Anthony C.; Liu, Nan-Suey; Davoudzadeh, Farhad

2008-01-01

The mass and velocity distribution of liquid spray has a primary effect on the combustion heat release process. This heat release process then affects emissions like nitrogen oxides (NOx) and carbon monoxide (CO). Computational Fluid Dynamics gives the engineer insight into these processes, but various setup options exist (number of droplet groups, and initial droplet temperature) for spray initial conditions. This paper studies these spray initial condition options using the National Combustion Code (NCC) on a single swirler lean direct injection (LDI) flame tube. Using laminar finite rate chemistry, comparisons are made against experimental data for velocity measurements, temperature, and emissions (NOx, CO).

SINTERING OF NASCENT CALCIUM OXIDE

EPA Science Inventory

The paper discusses the measurement of the sintering rate of CaO in a nitrogen atmosphere at temperatures of 700-1100 C. CaO prepared from ultrapure CaCO3 was compared with an impure CaO derived from limestone. Both materials yielded an initial surface area of 104 sq m/g. The rat...

Applications of high pressure differential scanning calorimetry to aviation fuel thermal stability research

NASA Technical Reports Server (NTRS)

Neveu, M. C.; Stocker, D. P.

1985-01-01

High pressure differential scanning calorimetry (DSC) was studied as an alternate method for performing high temperature fuel thermal stability research. The DSC was used to measure the heat of reaction versus temperature of a fuel sample heated at a programmed rate in an oxygen pressurized cell. Pure hydrocarbons and model fuels were studied using typical DSC operating conditions of 600 psig of oxygen and a temperature range from ambient to 500 C. The DSC oxidation onset temperature was determined and was used to rate the fuels on thermal stability. Kinetic rate constants were determined for the global initial oxidation reaction. Fuel deposit formation is measured, and the high temperature volatility of some tetralin deposits is studied by thermogravimetric analysis. Gas chromatography and mass spectrometry are used to study the chemical composition of some DSC stressed fuels.

OXIDATION OF INCONEL 718 IN AIR AT TEMPERATURES FROM 973K TO 1620K.

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

GREENE,G.A.; FINFROCK,C.C.

2000-10-01

As part of the APT project, it was necessary to quantify the release of tungsten from the APT spallation target during postulated accident conditions in order to develop accident source terms for accident consequence characterization. Experiments with tungsten rods at high temperatures in a flowing steam environment characteristic of postulated accidents revealed that considerable vaporization of the tungsten occurred as a result of reactions with the steam and that the aerosols which formed were readily transported away from the tungsten surfaces, thus exposing fresh tungsten to react with more steam. The resulting tungsten release fractions and source terms were undesirablemore » and it was decided to clad the tungsten target with Inconel 718 in order to protect it from contact with steam during an accident and mitigate the accident source term and the consequences. As part of the material selection criteria, experiments were conducted with Inconel 718 at high temperatures to evaluate the rate of oxidation of the proposed clad material over as wide a temperature range as possible, as well as to determine the high-temperature failure limit of the material. Samples of Inconel 718 were inserted into a preheated furnace at temperatures ranging from 973 K to 1620 K and oxidized in air for varying periods of time. After oxidizing in air at a constant temperature for the prescribed time and then being allowed to cool, the samples would be reweighed to determine their weight gain due to the uptake of oxygen. From these weight gain measurements, it was possible to identify three regimes of oxidation for Inconel 718: a low-temperature regime in which the samples became passivated after the initial oxidation, an intermediate-temperature regime in which the rate of oxidation was limited by diffusion and exhibited a constant parabolic rate dependence, and a high-temperature regime in which material deformation and damage accompanied an accelerated oxidation rate above the parabolic regime. At temperatures below 1173 K, the rate of oxidation of the Inconel 718 surface was found to decrease markedly with time; the parabolic oxidation rate coefficient was not a constant but decreased with time. This was taken to indicate that the oxide film on the surface was having a passivating effect on oxygen transport through the oxide to the underlying metal. For temperatures in the range 1173 K to 1573 K, the time-dependent rate of oxidation as determined once again by weight-gain measurements was found to display the classical parabolic rate behavior, indicating that the rate of transport of reactants through the oxide was controlled by diffusion through the growing oxide layer. Parabolic rate coefficients were determined by least-squares analysis of time-dependent mass-gain data at 1173 K, 1273 K, 1373 K, 1473 K and 1573 K. At temperatures above 1540 K, post test examination of the oxidized samples revealed that the Inconel 718 began to lose strength and to deform. At 1540 K, samples which were suspended from their ends during testing began to demonstrate axial curvature as they lost strength and bowed under their own weight. As the temperatures of the tests were increased, rivulets were seen to appear on the surfaces of the test specimens; damage became severe at 1560 K. Although melting was never observed in any of these tests even up to. 1620 K, it was concluded from these data that the Inconel 718 clad should not be expected to protect the underlying tungsten at temperatures above 1540 K.« less

Nitric oxide production by cultured human aortic smooth muscle cells: stimulation by fluid flow

NASA Technical Reports Server (NTRS)

Papadaki, M.; Tilton, R. G.; Eskin, S. G.; McIntire, L. V.

1998-01-01

This study demonstrated that exposure of cultured human aortic smooth muscle cells (SMC) to fluid flow resulted in nitric oxide (NO) production, monitored by nitrite and guanosine 3',5'-cyclic monophosphate production. A rapid burst in nitrite production rate was followed by a more gradual increase throughout the period of flow exposure. Neither the initial burst nor the prolonged nitrite production was dependent on the level of shear stress in the range of 1.1-25 dyn/cm2. Repeated exposure to shear stress after a 30-min static period restimulated nitrite production similar to the initial burst. Ca(2+)-calmodulin antagonists blocked the initial burst in nitrite release. An inhibitor of nitric oxide synthase (NOS) blocked nitrite production, indicating that changes in nitrite reflect NO production. Treatment with dexamethasone or cycloheximide had no effect on nitrite production. Monoclonal antibodies directed against the inducible and endothelial NOS isoforms showed no immunoreactivity on Western blots, whereas monoclonal antibodies directed against the neuronal NOS gave specific products. These findings suggest that human aortic SMC express a constitutive neuronal NOS isoform, the enzymatic activity of which is modulated by flow.

Experimental Research on the Sterilization of Escherichia Coli and Bacillus Subtilis in Drinking Water by Dielectric Barrier Discharge

NASA Astrophysics Data System (ADS)

Li, Yang; Yi, Chengwu; Li, Jingjing; Yi, Rongjie; Wang, Huijuan

2016-02-01

The bactericidal effect on the representative type of Gram-negative Escherichia coli (E. coli) and Gram-positive Bacillus subtilis in drinking water was investigated in this paper by using dielectric barrier discharge (DBD) advanced oxidation technology. The sterilizing rates under different conditions of reaction time t, input voltage V, pH value, and initial concentration of bacteria C0 were investigated to figure out the optimum sterilization conditions. Our observations and comparisons of cell morphology alteration by scanning electron microscopy and transmission electron microscopy revealed the sterilization mechanisms. The results showed that the sterilizing rate increased obviously with the extension of reaction time t and the rise of input voltage V. The optimal sterilization effect was achieved when the pH value was 7.1. As the initial concentration of bacteria rose, the sterilizing rate decreased. When the input voltage was 2.2 kV and the initial concentration of bacteria was relatively low, the sterilizing rate almost reached 100% after a certain treatment time in neutral aqueous solution. The reasons for the great damage of cell structure and the killing of bacteria are the oxidation of O3, OH and the accumulation of active species produced by DBD. The article provides a certain theoretical and experimental basis for DBD application in water pollution treatment. supported by the Science and Technology Support Project Plan and Social Development of Jiangsu Province, China (No. BE2011732), the Science and Technology Support Project Plan and Social Development of Zhenjiang, Jiangsu Province, China (No. SH2012013)

Kinetics and mechanism of permanganate oxidation of iota- and lambda-carrageenan polysaccharides as sulfated carbohydrates in acid perchlorate solutions.

PubMed

Hassan, Refat M; Fawzy, Ahmed; Ahmed, Gamal A; Zaafarany, Ishaq A; Asghar, Basim H; Takagi, Hideo D; Ikeda, Yasuhisa

2011-10-18

The kinetics of oxidation of iota- and lambda-carrageenan as sulfated carbohydrates by permanganate ion in aqueous perchlorate solutions at a constant ionic strength of 2.0 mol dm(-3) have been investigated spectrophotometrically. The pseudo-first-order plots were found to be of inverted S-shape throughout the entire courses of reactions. The initial rates were found to be relatively slow in the early stages, followed by an increase in the oxidation rates over longer time periods. The experimental observations showed first-order dependences in permanganate and fractional first-order kinetics with respect to both carrageenans concentration for both the induction and autoacceleration periods. The results obtained at various hydrogen ion concentrations showed that the oxidation processes in these redox systems are acid-catalyzed throughout the two stages of oxidation reactions. The added salts lead to the prediction that Mn(III) is the reactive species throughout the autoacceleration periods. Kinetic evidence for the formation of 1:1 intermediate complexes was revealed. The kinetic parameters have been evaluated and tentative reaction mechanisms in good agreement with the kinetic results are discussed. Copyright © 2011 Elsevier Ltd. All rights reserved.

Efficient anti-corrosive coating of cold-rolled steel in a seawater environment using an oil-based graphene oxide ink.

PubMed

Singhbabu, Y N; Sivakumar, B; Singh, J K; Bapari, H; Pramanick, A K; Sahu, Ranjan K

2015-05-07

We report the production of an efficient anti-corrosive coating of cold-rolled (CR) steel in a seawater environment (∼3.5 wt% NaCl aqueous solution) using an oil-based graphene oxide ink. The graphene oxide was produced by heating Aeschynomene aspera plant as a carbon source at 1600 °C in an argon atmosphere. The ink was prepared by cup-milling the mixture of graphene oxide and sunflower oil for 10 min. The coating of ink on the CR steel was made using the dip-coating method, followed by curing at 350 °C for 10 min in air atmosphere. The results of the potentiodynamic polarization show that the corrosion rate of bare CR steel decreases nearly 10,000-fold by the ink coating. Furthermore, the salt spray test results show that the red rusting in the ink-coated CR steel is initiated after 100 h, in contrast to 24 h and 6 h in the case of oil-coated and bare CR steel, respectively. The significant decrease in the corrosion rate by the ink-coating is discussed based on the impermeability of graphene oxide to the corrosive ions.

Oxidation of U-20 at% Zr alloy in air at 423 1063 K

NASA Astrophysics Data System (ADS)

Matsui, Tsuneo; Yamada, Takanobu; Ikai, Yasushi; Naito, Keiji

1993-01-01

The oxidation behavior of U 0.80Zr 0.20 alloy (two-phase mixture of U and UZr 2 below 878 K and single solid solution above 1008 K) was studied by thermogravimetry in the temperature range from 423 to 1063 K in air. During oxidation in the low temperature region (423-503 K), the sample kept its initial shape (a rectangular rod) and the surface of the sample was covered by a black thin adherent UO2 + x oxide layer. On the other hand, by oxidation in the middle temperature region, the sample broke to several pieces of thin plates and blocks, and fine powder at 643-723 K and entirely to fine powder at 775-878 K, all of which were analyzed to be a mixture of U 3O 8 and ZrO 2. By oxidation in the high temperature region (1008-1063 K) the sample broke to very fine powder, which consisted of U 3O 8 and ZrO 2. Based on the sample shape, the oxide phase identified after oxidation and the slope value of the bilogarithmic plots of the weight gain against time, the oxidation kinetics was analyzed with a paralinear equation in the low temperature region below 503 K and a linear equation in the middle and high temperature regions above 643 K. Oxidation rates of U 0.80Zr 0.20 (two-phase mixture) in the low and middle temperature regions were smaller than those of uranium metal. A discontinuity in the plot of the linear oxidation rate constant versus reciprocal temperature was found to be present between 723 and 838 K, similarly to the case of uranium metal previously reported. The linear rate constants of single-phase solid solution in the high temperature region above 1008 K seemed to be a little smaller than those estimated by the extrapolation of the values in the middle temperature region.

Pulsed corona discharge oxidation of aqueous lignin: decomposition and aldehydes formation.

PubMed

Panorel, Iris; Kaijanen, Laura; Kornev, Iakov; Preis, Sergei; Louhi-Kultanen, Marjatta; Sirén, Heli

2014-01-01

Lignin is the mass waste product of pulp and paper industry mostly incinerated for energy recovery. Lignin is, however, a substantial source of raw material for derivatives currently produced in costly wet oxidation processes. The pulsed corona discharge (PCD) for the first time was applied to lignin oxidation aiming a cost-effective environmentally friendly lignin removal and transformation to aldehydes. The experimental research into treatment of coniferous kraft lignin aqueous solutions was undertaken to establish the dependence of lignin oxidation and aldehyde formation on the discharge parameters, initial concentration of lignin and gas phase composition. The rate and the energy efficiency of lignin oxidation increased with increasing oxygen concentration reaching up to 82 g kW-1 h-1 in 89% vol. oxygen. Oxidation energy efficiency in PCD treatment exceeds the one for conventional ozonation by the factor of two under the experimental conditions. Oxidation at low oxygen concentrations showed a tendency of the increasing aldehydes and glyoxylic acid formation yield.

Nitrous oxide for labor analgesia: Utilization and predictors of conversion to neuraxial analgesia.

PubMed

Sutton, Caitlin D; Butwick, Alexander J; Riley, Edward T; Carvalho, Brendan

2017-08-01

We examined the characteristics of women who choose nitrous oxide for labor analgesia and identified factors that predict conversion from nitrous oxide to labor neuraxial analgesia. Retrospective descriptive study. Labor and Delivery Ward. 146 pregnant women who used nitrous oxide for analgesia during labor and delivery between September 2014 and September 2015. Chart review only. Demographic, obstetric, and intrapartum characteristics of women using nitrous oxide were examined. Multivariable logistic regression was performed to identify factors associated with conversion from nitrous oxide to neuraxial analgesia. Data are presented as n (%), median [IQR], adjusted relative risk (aRR), and 95% confidence intervals (CI) as appropriate. During the study period, 146 women used nitrous oxide for labor analgesia (accounting for 3% of the total deliveries). The majority (71.9%) of women who used nitrous oxide were nulliparous, and over half (51.9%) had expressed an initial preference for "nonmedical birth." The conversion rate to neuraxial blockade was 63.2%, compared to a concurrent institutional rate of 85.1% in women who did not use nitrous oxide. Factors associated with conversion from nitrous oxide to neuraxial blockade were labor induction (aRR=2.0, CI 1.2-3.3) and labor augmentation (aRR=1.7, CI 1.0-2.9). Only a small number of women opted to use nitrous oxide during labor, analgesia was minimal, and most converted to neuraxial analgesia. Women with induced and augmented labors should be counseled about the increased likelihood that they will convert to neuraxial analgesia. Copyright © 2017 Elsevier Inc. All rights reserved.

Advanced water remediation from ofloxacin by ionizing radiation

NASA Astrophysics Data System (ADS)

Esposito, Biagio R.; Capobianco, Massimo L.; Martelli, Alessandro; Navacchia, Maria Luisa; Pretali, Luca; Saracino, Michela; Zanelli, Alberto; Emmi, Salvatore S.

2017-12-01

The performances of remediation processes initiated by ionizing radiation on ofloxacin are investigated in ambient conditions. The effectiveness of the decomposition of ofloxacin has been assessed both by γ-rays and electron beam in various aqueous solutions differentiated by the dissolved gases (Air or oxygen saturated) and H2O2. By HPLC it is shown that ofloxacin is removed according to a first order process vs. dose in any system. O2 accelerates the decomposition rate, while H2O2 does not seem to enhance any oxidation effect. The simultaneous oxidative-reductive treatment (no additive) demonstrated to have better mineralizing performances than the fully oxidative one (H2O2 present). Mineralization by γ results to be more efficient than by EB. The Total Organic Carbon decrease was investigated in dependence of dose and of the •OH production rate. The latter parameter was changed over 7 orders of magnitude by controlling dose rate and/or by adding H2O2. A steep increase of acidity remarks the phases of fluorine-carbon bond break.

Oxidation of white phosphorus by peroxides in water

NASA Astrophysics Data System (ADS)

Abdreimova, R. R.; Akbaeva, D. N.; Polimbetova, G. S.

2017-10-01

A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOH; R = H, 3-ClC6H4CO, (CH3)3C] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of HO• radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.

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

Guardia, A. de, E-mail: amaury.de-guardia@cemagref.f; Universite Europeenne de Bretagne, F-35000 Rennes; Mallard, P.

This paper aimed to compare household waste, separated pig solids, food waste, pig slaughterhouse sludge and green algae regarding processes ruling nitrogen dynamic during composting. For each waste, three composting simulations were performed in parallel in three similar reactors (300 L), each one under a constant aeration rate. The aeration flows applied were comprised between 100 and 1100 L/h. The initial waste and the compost were characterized through the measurements of their contents in dry matter, total carbon, Kjeldahl and total ammoniacal nitrogen, nitrite and nitrate. Kjeldahl and total ammoniacal nitrogen and nitrite and nitrate were measured in leachates andmore » in condensates too. Ammonia and nitrous oxide emissions were monitored in continue. The cumulated emissions in ammonia and in nitrous oxide were given for each waste and at each aeration rate. The paper focused on process of ammonification and on transformations and transfer of total ammoniacal nitrogen. The parameters of nitrous oxide emissions were not investigated. The removal rate of total Kjeldahl nitrogen was shown being closely tied to the ammonification rate. Ammonification was modelled thanks to the calculation of the ratio of biodegradable carbon to organic nitrogen content of the biodegradable fraction. The wastes were shown to differ significantly regarding their ammonification ability. Nitrogen balances were calculated by subtracting nitrogen losses from nitrogen removed from material. Defaults in nitrogen balances were assumed to correspond to conversion of nitrate even nitrite into molecular nitrogen and then to the previous conversion by nitrification of total ammoniacal nitrogen. The pool of total ammoniacal nitrogen, i.e. total ammoniacal nitrogen initially contained in waste plus total ammoniacal nitrogen released by ammonification, was calculated for each experiment. Then, this pool was used as the referring amount in the calculation of the rates of accumulation, stripping and nitrification of total ammoniacal nitrogen. Separated pig solids were characterised by a high ability to accumulate total ammoniacal nitrogen. Whatever the waste, the striping rate depended mostly on the aeration rate and on the pool concentration in biofilm. The nitrification rate was observed as all the higher as the concentration in total ammoniacal nitrogen in the initial waste was low. Thus, household waste and green algae exhibited the highest nitrification rates. This result could mean that in case of low concentrations in total ammoniacal nitrogen, a nitrifying biomass was already developed and that this biomass consumed it. In contrast, in case of high concentrations, this could traduce some difficulties for nitrifying microorganisms to develop.« less

Carbon Sequestration and Nitrous Oxide Emissions from Urban Turfgrass Ecosystems in Southern California

NASA Astrophysics Data System (ADS)

Ampleman, M. D.; Czimczik, C. I.; Townsend-Small, A.; Trumbore, S. E.

2008-12-01

Irrigated turfgrass ecosystems sequester carbon in soil organic matter, but they may also release nitrous oxide, due to fertilization associated with intensive management practices. Nitrous oxide is an important green house gas with a global warming potential (GWP) of 300 times that of carbon dioxide on a 100 yr time horizon. Although regular irrigation and fertilization of turfgrass create favorable conditions for both C storage and N2O release via nitrification and denitrification by soil microbes, emissions from these highly managed ecosystems are poorly constrained. We quantified N2O emissions and C storage rates for turf grass in four urban parks in the city of Irvine, CA. The turf grass systems we studied were managed by the City of Irvine. Parks were established between 1975 and 2006 on former range land with the same initial parent material; are exposed to the same climate; and form a time series (chronosequence) for investigating rates of C accumulation. We also investigated the effects of management (e.g. grass species, fertilization rate), soil moisture and temperature, and park age on N2O emission from these parks. We quantified N2O emissions using static soil chamber with four 7 min. sampling intervals, and analyzed the samples using an electron capture gas chromatograph. Soil carbon accumulation rates were determined from the slope of the organic C inventory (from 0-20 cm depth) plotted against park age. C storage rates for soils in "leisure" areas were close to 2 Mg C ha-1 yr-1, similar to rates associated with forest regrowth in northeastern US forests. However, as park age and C storage increased, N2O emissions increased as well, such that emissions from the older parks (~20 ngN m-2 s-1) were comparable to published temperate agricultural fluxes. Initial estimates suggest that the GWP associated with N2O emissions approximately offsets the effect of C storage in these ecosystems.

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

NASA Astrophysics Data System (ADS)

Roden, Eric E.

2004-08-01

Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.

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

PubMed

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.

Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

PubMed

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

A Review of In Situ Observations of Crystallization and Growth in High Temperature Oxide Melts

NASA Astrophysics Data System (ADS)

Wang, Zhanjun; Sohn, Il

2018-05-01

This review summarizes the significant results of high-temperature confocal laser scanning microscopy (CLSM) and single hot thermocouple technology (SHTT) and its application in observing the crystallization and growth in high-temperature oxide melts from iron- and steel-making slags to continuous casting mold fluxes. Using in situ observations of CLSM and SHTT images of high-temperature molten oxides with time, temperature, and composition, the crystallization behavior, including crystal morphology, crystallization temperature, initial nucleation and growth rate, could be obtained. The broad range of applications using in situ observations during crystallization have provided a wealth of opportunities in pyrometallurgy and is provided in this review.

Preparation of Diatomite Supported Nano Zinc Oxide Composite Photocatalytic Material and Study on its Formaldehyde Degradation

NASA Astrophysics Data System (ADS)

Xiao, Liguang; Pang, Bo

2017-09-01

This experiment used zinc nitrate as precursor, ethanol as solvent and polyethylene glycol as dispersant, diatomite as carrier, diatomite loaded nano Zinc Oxide was prepared by sol-gel method, in addition, the formaldehyde degradation was studied by two kinds of experimental methods: preparation and loading, preparation and post loading, The samples were characterized by SEM, XRD, BET and IR. Experimental results showed that: Diatomite based nano Zinc Oxide had a continuous adsorption and degradation of formaldehyde, formaldehyde gas with initial concentration was 0.7mg/m3, after 36h degradation, the concentration reached 0.238mg/m3, the degradation rate reached to 66%.

Combustion stability analysis of preburners in liquid propellant rocket engines during shutdown

NASA Technical Reports Server (NTRS)

Lim, Kair-Chuan; George, Paul E., II

1987-01-01

A linearized one-dimensional lumped-parameter model capable of predicting the occurrence of the low frequency combustion instability (chugging) experienced during preburner shutdown in the Space Shuttle Main Engines is discussed, and predictions are compared with NASA experimental results. Results from a parametric study of parameters including chamber pressure, fuel and oxygen temperatures, and the effective bulk modulus of the liquid oxidizer suggest that chugging is probably affected by conditions at shutdown through the fuel and oxidizer temperatures. It is suggested that chugging is initiated when the fuel, oxidizer, and helium temperature and flow rates pass into an unstable region, and that chugging may be terminated by decaying pressures.

Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

PubMed

Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

2016-02-01

The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

Laboratory Investigation of Organic Aerosol Formation from Aromatic Hydrocarbons

DOE R&D Accomplishments Database

Molina, Luisa T.; Molina, Mario J.; Zhang, Renyi

2006-08-23

Our work for this DOE funded project includes: (1) measurements of the kinetics and mechanism of the gas-phase oxidation reactions of the aromatic hydrocarbons initiated by OH; (2) measurements of aerosol formation from the aromatic hydrocarbons; and (3) theoretical studies to elucidate the OH-toluene reaction mechanism using quantum-chemical and rate theories.

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1996-01-01

The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic bacteria and thus on methane oxidation potential per se.

Enhanced chlorine dioxide decay in the presence of metal oxides: relevance to drinking water distribution systems.

PubMed

Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

2013-08-06

Chlorine dioxide (ClO2) decay in the presence of typical metal oxides occurring in distribution systems was investigated. Metal oxides generally enhanced ClO2 decay in a second-order process via three pathways: (1) catalytic disproportionation with equimolar formation of chlorite and chlorate, (2) reaction to chlorite and oxygen, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly stronger abilities than goethite (α-FeOOH) to catalyze the ClO2 disproportionation (pathway 1), which predominated at higher initial ClO2 concentrations (56-81 μM). At lower initial ClO2 concentrations (13-31 μM), pathway 2 also contributed. The CuO-enhanced ClO2 decay is a base-assisted reaction with a third-order rate constant of 1.5 × 10(6) M(-2) s(-1) in the presence of 0.1 g L(-1) CuO at 21 ± 1 °C, which is 4-5 orders of magnitude higher than in the absence of CuO. The presence of natural organic matter (NOM) significantly enhanced the formation of chlorite and decreased the ClO2 disproportionation in the CuO-ClO2 system, probably because of a higher reactivity of CuO-activated ClO2 with NOM. Furthermore, a kinetic model was developed to simulate CuO-enhanced ClO2 decay at various pH values. Model simulations that agree well with the experimental data include a pre-equilibrium step with the rapid formation of a complex, namely, CuO-activated Cl2O4. The reaction of this complex with OH(-) is the rate-limiting and pH-dependent step for the overall reaction, producing chlorite and an intermediate that further forms chlorate and oxygen in parallel. These novel findings suggest that the possible ClO2 loss and the formation of chlorite/chlorate should be carefully considered in drinking water distribution systems containing copper pipes.

Degradation of n-butylparaben and 4- tert-octylphenol in H 2O 2/UV system

NASA Astrophysics Data System (ADS)

BŁędzka, Dorota; Gryglik, Dorota; Olak, Magdalena; Gębicki, Jerzy L.; Miller, Jacek S.

2010-04-01

The degradation of two endocrine disrupting compounds: n-butylparaben (BP) and 4- tert-octylphenol (OP) in the H 2O 2/UV system was studied. The effect of operating variables: initial hydrogen peroxide concentration, initial substrate concentration, pH of the reaction solution and photon fluency rate of radiation at 254 nm on reaction rate was investigated. The influence of hydroxyl radical scavengers, humic acid and nitrate anion on reaction course was also studied. A very weak scavenging effect during BP degradation was observed indicating reactions different from hydroxyl radical oxidation. The second-order rate constants of BP and OP with OH radicals were estimated to be 4.8×10 9 and 4.2×10 9 M -1 s -1, respectively. For BP the rate constant equal to 2.0×10 10 M -1 s -1was also determined using water radiolysis as a source of hydroxyl radicals.

Reaction rate kinetics for in situ combustion retorting of Michigan Antrim oil shale

USGS Publications Warehouse

Rostam-Abadi, M.; Mickelson, R.W.

1984-01-01

The intrinsic reaction rate kinetics for the pyrolysis of Michigan Antrim oil shale and the oxidation of the carbonaceous residue of this shale have been determined using a thermogravimetric analysis method. The kinetics of the pyrolysis reaction were evaluated from both isothermal and nonisothermal rate data. The reaction was found to be second-order with an activation energy of 252.2 kJ/mole, and with a frequency factor of 9.25 ?? 1015 sec-1. Pyrolysis kinetics were not affected by heating rates between 0.01 to 0.67??K/s. No evidence of any reactions among the oil shale mineral constituents was observed at temperatures below 1173??K. However, it was found that the presence of pyrite in oil shale reduces the primary devolatilization rate of kerogen and increases the amount of residual char in the spent shale. Carbonaceous residues which were prepared by heating the oil shale at a rate of 0.166??K/s to temperatures between 923??K and 1073??K, had the highest reactivities when oxidized at 0.166??K/s in a gas having 21 volume percent oxygen. Oxygen chemisorption was found to be the initial precursor to the oxidation process. The kinetics governing oxygen chemisorption is (Equation Presented) where X is the fractional coverage. The oxidation of the carbonaceous residue was found also to be second-order. The activation energy and the frequency factor determined from isothermal experiments were 147 kJ/mole and 9.18??107 sec-1 respectively, while the values of these parameters obtained from a nonisothermal experiment were 212 kJ/mole and 1.5??1013 sec-1. The variation in the rate constants is attributed to the fact that isothermal and nonisothermal analyses represent two different aspects of the combustion process.

Synergistic effect of calcium stearate and photo treatment on the rate of biodegradation of low density polyethylene spent saline vials.

PubMed

Carol, D; Karpagam, S; Kingsley, S J; Vincent, S

2012-07-01

The biodegradation of spent saline bottles, a low density polyethylene product (LDPE) by two selected Arthrobacter sp. under in vitro conditions is reported. Chemical and UV pretreatment play a vital role in enhancing the rate of biodegradation. Treated LDPE film exhibits a higher weight loss and density when compared to untreated films. Arthrobacter oxydans and Arthrobacter globiformis grew better in medium containing pretreated film than in medium containing untreated film. The decrease in density and weight loss of LDPE was also more for pretreated film when compared to untreated film indicating the affect of abiotic treatment on mechanical properties of LDPE. The decrease in the absorbance corresponding to carbonyl groups and double bonds that were generated during pretreatment suggest that some of the double bonds were cut by Arthrobacter species. Since Arthrobacter sp. are capable of degrading urea, splitting of urea group were also seen in FTIR spectrum indicating the evidence of biodegradation after microbial incubation. The results indicated that biodegradation rate could be enhanced by exposing LDPE to calcium stearate (a pro-oxidant) which acts as an initiator for the oxidation of the polymers leading to a decrease of molecular weight and formation of hydrophilic group. Therefore, the initial step for biodegradation of many inert polymers depends on a photo-oxidation of those polymers. The application in sufficient details with improved procedures utilizing recombinant microorganism with polymer degradation capacity can lead to a better plastic waste management in biomedical field. The present plastic disposal trend of waste accumulation can be minimized with this promising eco-friendly technique.

Reactors as a Source of Antineutrinos: Effects of Fuel Loading and Burnup for Mixed-Oxide Fuels

NASA Astrophysics Data System (ADS)

Bernstein, Adam; Bowden, Nathaniel S.; Erickson, Anna S.

2018-01-01

In a conventional light-water reactor loaded with a range of uranium and plutonium-based fuel mixtures, the variation in antineutrino production over the cycle reflects both the initial core fissile inventory and its evolution. Under an assumption of constant thermal power, we calculate the rate at which antineutrinos are emitted from variously fueled cores, and the evolution of that rate as measured by a representative ton-scale antineutrino detector. We find that antineutrino flux decreases with burnup for low-enriched uranium cores, increases for full mixed-oxide (MOX) cores, and does not appreciably change for cores with a MOX fraction of approximately 75%. Accounting for uncertainties in the fission yields in the emitted antineutrino spectra and the detector response function, we show that the difference in corewide MOX fractions at least as small as 8% can be distinguished using a hypothesis test. The test compares the evolution of the antineutrino rate relative to an initial value over part or all of the cycle. The use of relative rates reduces the sensitivity of the test to an independent thermal power measurement, making the result more robust against possible countermeasures. This rate-only approach also offers the potential advantage of reducing the cost and complexity of the antineutrino detectors used to verify the diversion, compared to methods that depend on the use of the antineutrino spectrum. A possible application is the verification of the disposition of surplus plutonium in nuclear reactors.

HIgh Temperature Photocatalysis over Semiconductors

NASA Astrophysics Data System (ADS)

Westrich, Thomas A.

Due in large part to in prevalence of solar energy, increasing demand of energy production (from all sources), and the uncertain future of petroleum energy feedstocks, solar energy harvesting and other photochemical systems will play a major role in the developing energy market. This dissertation focuses on a novel photochemical reaction process: high temperature photocatalysis (i.e., photocatalysis conducted above ambient temperatures, T ≥ 100°C). The overarching hypothesis of this process is that photo-generated charge carriers are able to constructively participate in thermo-catalytic chemical reactions, thereby increasing catalytic rates at one temperature, or maintaining catalytic rates at lower temperatures. The photocatalytic oxidation of carbon deposits in an operational hydrocarbon reformer is one envisioned application of high temperature photocatalysis. Carbon build-up during hydrocarbon reforming results in catalyst deactivation, in the worst cases, this was shown to happen in a period of minutes with a liquid hydrocarbon. In the presence of steam, oxygen, and above-ambient temperatures, carbonaceous deposits were photocatalytically oxidized over very long periods (t ≥ 24 hours). This initial experiment exemplified the necessity of a fundamental assessment of high temperature photocatalytic activity. Fundamental understanding of the mechanisms that affect photocatalytic activity as a function of temperatures was achieved using an ethylene photocatalytic oxidation probe reaction. Maximum ethylene photocatalytic oxidation rates were observed between 100 °C and 200 °C; the maximum photocatalytic rates were approximately a factor of 2 larger than photocatalytic rates at ambient temperatures. The loss of photocatalytic activity at temperatures above 200 °C is due to a non-radiative multi-phonon recombination mechanism. Further, it was shown that the fundamental rate of recombination (as a function of temperature) can be effectively modeled as a temperature-dependent quantum efficiency term, and is directly driven by bulk photocatalyst crystal parameters: maximum phonon energy and the number of phonons allowed per unit cell. This analysis extends to multiple photocatalysts and can explain experimental observations of photocatalytic oxidation rates with varied reactant concentrations. Lastly, this dissertation applies this knowledge to a thermo-catalytic reaction (CO-oxidation) using a Au/TiO 2 catalyst. The combined photo/thereto-catalytic reaction showed a 10-25% increase in CO conversion during a temperature programmed reaction experiment.

Cultivation and characterization of thermophilic Nitrospira species from geothermal springs in the US Great Basin, China, and Armenia.

PubMed

Edwards, Tara A; Calica, Nicole A; Huang, Dolores A; Manoharan, Namritha; Hou, Weiguo; Huang, Liuqin; Panosyan, Hovik; Dong, Hailiang; Hedlund, Brian P

2013-08-01

Despite its importance in the nitrogen cycle, little is known about nitrite oxidation at high temperatures. To bridge this gap, enrichment cultures were inoculated with sediment slurries from a variety of geothermal springs. While nitrite-oxidizing bacteria (NOB) were successfully enriched from seven hot springs located in US Great Basin, south-western China, and Armenia at ≤ 57.9 °C, all attempts to enrich NOB from > 10 hot springs at ≥ 61 °C failed. The stoichiometric conversion of nitrite to nitrate, chlorate sensitivity, and sensitivity to autoclaving all confirmed biological nitrite oxidation. Regardless of origin, all successful enrichments contained organisms with high 16S rRNA gene sequence identity (≥ 97%) with Nitrospira calida. In addition, Armenian enrichments also contained close relatives of Nitrospira moscoviensis. Physiological properties of all enrichments were similar, with a temperature optimum of 45-50 °C, yielding nitrite oxidation rates of 7.53 ± 1.20 to 23.0 ± 2.73 fmoles cell(-1) h(-1), and an upper temperature limit between 60 and 65 °C. The highest rates of NOB activity occurred with initial NO2 - concentrations of 0.5-0.75 mM; however, lower initial nitrite concentrations resulted in shorter lag times. The results presented here suggest a possible upper temperature limit of 60-65 °C for Nitrospira and demonstrate the wide geographic range of Nitrospira species in geothermal environments. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Formation of Oxides in the Interior of Friction Stir Welds

NASA Technical Reports Server (NTRS)

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 liquation. Metallographs from the weld panels showed indications of liquation at the grain boundaries. In FSWs of thicker panels, these regions of liquation were found to be heavily oxidized. The quality of the FSWs was evaluated from tensile testing at room temperature. As the panel thickness increased, a slight decrease in tensile strength was observed which was attributed to the presence of oxides. No oxide formation was observed in the thinner workpieces, although there were indications of localized liquation at the grain boundaries. Results from this study will assist in a better understand of the mechanisms of oxide formation in FSW interiors and provide methodology for minimizing their occurrence.

Measurement of the initial phase of ozone decomposition in water and wastewater by means of a continuous quench-flow system: application to disinfection and pharmaceutical oxidation.

PubMed

Buffle, Marc-Olivier; Schumacher, Jochen; Salhi, Elisabeth; Jekel, Martin; von Gunten, Urs

2006-05-01

Due to a lack of adequate experimental techniques, the kinetics of the first 20s of ozone decomposition in natural water and wastewater is still poorly understood. Introducing a continuous quench-flow system (CQFS), measurements starting 350 ms after ozone addition are presented for the first time. Very high HO. to O3 exposures ratios (Rct=integralHO.dt/integralO3dt) reveal that the first 20s of ozonation present oxidation conditions that are similar to ozone-based advanced oxidation processes (AOP). The oxidation of carbamazepine could be accurately modeled using O3 and HO. exposures measured with CQFS during wastewater ozonation. These results demonstrate the applicability of bench scale determined second-order rate constants for wastewater ozonation. Important degrees of pharmaceutical oxidation and microbial inactivation are predicted, indicating that a significant oxidation potential is available during wastewater ozonation, even when ozone is entirely decomposed in the first 20s.

Oxidation of 304 stainless steel in high-temperature steam

NASA Astrophysics Data System (ADS)

Ishida, Toshihisa; Harayama, Yasuo; Yaguchi, Sinnosuke

1986-08-01

An experiment on oxidation of 304 stainless steel was performed in steam between 900°C and 1350°C, using the spare cladding of the reactor of the nuclear-powered ship Mutsu. The temperature range was appropriate for a postulated loss of coolant accident (LOCA) analysis of a LWR. The oxidation kinetics were found to obey the parabolic law during the first period of 8 min. After the first period, the parabolic reaction rate constant decreased in the case of heating temperatures between 1100°C and 1250°C. At 1250°C, especially, a marked decrease was observed in the oxide scale-forming kinetics when the surface treated initially by mechanical polishing and given a residual stress. This enhanced oxidation resistance was attributed to the presence of a chromium-enriched layer which was detected by use of an X-ray microanalyzer. The oxidation kinetics equation obtained for the first 8 min is applicable to the model calculation of a hypothetical LOCA in a LWR, employing 304 stainless steel cladding.

Inhibiting the photosensitized oxidation of anthracene and tryptophan by means of natural antioxidants

NASA Astrophysics Data System (ADS)

Aksenova, N. A.; Vyzhlova, E. N.; Malinovskaya, V. V.; Parfenov, V. V.; Solov'eva, A. B.; Timashev, P. S.

2013-08-01

It is shown that model reactions of photosensitized oxidation of anthracene and tryptophan can be used for evaluation and comparison of antioxidant activity of various classes of compounds. Inhibition of the oxidation of substrates in the presence of the familiar antioxidants tocopherol (vitamin E), ascorbic acid (vitamin C), and mixtures of these vitamins with methionine, and in the presence of reputed antioxidants dihydroquercetin and taurine, are considered. It is concluded that all of the above compounds except for taurine have antioxidant properties; i.e., they reduce the rate constants of the photosensitized oxidation of anthracene and tryptophan. It is found that the inhibition of oxidation is associated with the interaction between antioxidants and singlet oxygen. Analysis of the kinetic dependences of the photosensitized oxidation of substrates in the presence of antioxidants reveals that a mixture of vitamins inhibits the process most efficiently, and inhibition occurs at the initial stages due to more active interaction between singlet oxygen and vitamin C

Characteristics of two novel cold- and salt-tolerant ammonia-oxidizing bacteria from Liaohe Estuarine Wetland.

PubMed

Huang, Xiao; Bai, Jie; Li, Kui-Ran; Zhao, Yang-Guo; Tian, Wei-Jun; Dang, Jia-Jia

2017-01-15

To achieve a better contaminant removal efficiency in a low-temperature and high-salt environment, two novel strains of cold- and salt-tolerant ammonia-oxidizing bacteria (AOB), i.e., Ochrobactrum sp. (HXN-1) and Aquamicrobium sp. (HXN-2), were isolated from the surface sediment of Liaohe Estuarine Wetland (LEW), China. The optimization of initial ammonia nitrogen concentration, pH, carbon-nitrogen ratio, and petroleum hydrocarbons (PHCs) to improve the ammonia-oxidation capacity of the two bacterial strains was studied. Both bacterial strains showed a high ammonia nitrogen removal rate of over 80% under a high salinity of 10‰. Even at a temperature as low as 15°C, HXN-1 and HXN-2 could achieve an ammonia nitrogen removal rate of 53% and 62%, respectively. The cold- and salt-tolerant AOB in this study demonstrated a high potential for ammonia nitrogen removal from LEW. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cumene oxidation by cis-[RuIV(bpy)2(py)(O)]2+, revisited.

PubMed

Bryant, Jasmine R; Matsuo, Takashi; Mayer, James M

2004-02-23

cis-[RuIV(bpy)2(py)(O)]2+ oxidizes cumene (2-phenylpropane) in acetonitrile solution primarily to cumyl alcohol (2-phenyl-2-propanol), alpha-methylstyrene, and acetophenone. Contrary to a prior report, the rate of the reaction is not accelerated by added nucleophiles. There is thus no evidence for the hydride transfer mechanism originally proposed. Instead, the results are consistent with a mechanism of initial hydrogen atom transfer from cumene to the ruthenium oxo group. This is indicated by the correlation of rate with C-H bond strength and by the various products observed. The formation of acetophenone, with one carbon less than cumene, is suggested to occur via a multistep pathway involving decarbonylation of the acyl radical from 2-phenylpropanal. An alternative mechanism involving beta-scission of cumyloxyl radical is deemed unlikely because of the difficulty of generating alkoxyl radicals under anaerobic conditions and the lack of rearranged products in the oxidation of triphenylmethane by cis-[RuIV(bpy)2(py)(O)]2+.

Effects of ethylene oxide sterilization on 82: 18 PLLA/PGA copolymer craniofacial fixation plates.

PubMed

Pietrzak, William S

2010-01-01

Bioabsorbable devices are generally susceptible to some form of degradation or alteration of material properties in response to exposure to the terminal sterilization cycle. In addition to affecting the material strength, sterilization can also increase the rate of hydrolysis, both of which can impact clinical performance. The impact of sterilization on the material/device is unpredictable and must be empirically determined. This study examined the effects of ethylene oxide treatment on the material properties of LactoSorb 82:18 poly(L-lactic acid)-poly(glycolic acid) craniofacial plates. Compared with untreated control plates, there was no effect on the initial inherent viscosity (1.3 dL/g), the glass transition temperature (58 degrees C), or on the flexural mechanical properties. Furthermore, there was no effect on the in vitro rate of hydrolysis and mechanical strength loss profile. This provides evidence that the ethylene oxide sterilization cycle is compatible with these copolymer plates and that such treatment should not affect the clinical performance.

Effect of degrading yellow oxo-biodegradable low-density polyethylene films to water quality

NASA Astrophysics Data System (ADS)

Requejo, B. A.; Pajarito, B. B.

2017-05-01

Polyethylene (PE) contributes largely to plastic wastes that are disposed in aquatic environment as a consequence of its widespread use. In this study, yellow oxo-biodegradable low-density PE films were immersed in deionized water at 50°C for 49 days. Indicators of water quality: pH, oxidation-reduction potential, turbidity, and total dissolved solids (TDS), were monitored at regular intervals. It was observed that pH initially rises and then slowly decreases with time, oxidation-reduction potential decreases then slowly increases with time, turbidity rises above the control at varied rates, and TDS increases abruptly and rises at a hindered rate. Moreover, the films potentially leach out lead chromate. The results imply that degrading oxo-biodegradable LDPE films results to significant reduction of water quality.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

NASA Astrophysics Data System (ADS)

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; Crowhurst, Jonathan C.; Rose, Timothy P.; Koroglu, Batikan; Radousky, Harry B.; Armstrong, Michael R.

2017-12-01

In this work, we present a newly constructed U x O y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. The global model is used to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.

Compliance with dental treatment recommendations by rural paediatric patients after a live-video teledentistry consultation: A preliminary report.

PubMed

McLaren, Sean W; Kopycka-Kedzierawski, Dorota T

2016-04-01

The purpose of this research was to assess the compliance rate with recommended dental treatment by rural paediatric dental patients after a live-video teledentistry consultation. A retrospective dental chart review was completed for 251 rural paediatric patients from the Finger Lakes region of New York State who had an initial teledentistry appointment with a paediatric dentist located remotely at the Eastman Institute for Oral Health in Rochester, NY. The recommended treatment modalities were tabulated and comprehensive dental treatment completion rates were obtained. The recommended treatment modality options of: treatment in the paediatric dental clinic; treatment using nitrous oxide anxiolysis; treatment with oral sedation; treatment in the operating room with general anaesthesia; or teleconsultation were identified for the 251 patients. Compliance rates for completed dental treatment based on initial teleconsultation recommendations were: 100% for treatment in the paediatric dental clinic; 56% for nitrous oxide patients; 87% for oral sedation; 93% for operating room; and 90% for teleconsultations. The differences in the compliance rates for all treatment modalities were not statistically significant (Fisher's exact test, p > 0.05). Compliance rates for completed comprehensive dental treatment for this rural population of paediatric dental patients were quite high, ranging from 56% to 100%, and tended to be higher when treatment was completed in fewer visits. Live-video teledentistry consultations conducted among rural paediatric patients and a paediatric dentist in the specialty clinic were feasible options for increasing dental treatment compliance rates when treating complex paediatric dental cases. © The Author(s) 2015.

Transport rates of radiolytic substances into Europa's ocean: implications for the potential origin and maintenance of life.

PubMed

Greenberg, Richard

2010-04-01

Abstract Bombardment of the surface of Europa produces oxidants and other biologically useful substances, but they can only contribute to the habitability of the ocean if they are delivered down through the icy crust. Previous estimates of the thickness of the oxygenated layer of ice assumed that impact gardening is the dominant factor and concluded that the ocean may be habitable if the oxidant delivery time, via undefined mechanisms, is sufficiently short. Consideration of the types of processes that continually resurface Europa suggests that the oxygenated layer is thicker than approximately 300 m, far greater than the few meters indicated by impact gardening alone, and possibly includes the entire ice crust. The estimated delivery rate to the ocean is such that the oxygen levels could now be high enough to support macrofauna; and, at approximately 3 x 10(11) mol/yr of oxygen, it could maintain 3 million tons of macrofauna, assuming respiration rates similar to terrestrial marine organisms. These values are independent of any additional contributions due to possible photosynthesis. Initial formation of life would be difficult with so much oxygen, but the start of oxidant delivery into the ocean would have been delayed by 1-2 billion years while the crust became loaded with oxidants. In the ocean, this delay would have allowed time for prebiotic assemblages and anaerobic biological development prior to the increasing oxidant concentration to otherwise toxic levels.

The oxidative transformation of sodium arsenite at the interface of alpha-MnO2 and water.

PubMed

Li, Xiu-juan; Liu, Cheng-shuai; Li, Fang-bai; Li, Yong-tao; Zhang, Li-jia; Liu, Chuan-ping; Zhou, Yong-zhang

2010-01-15

Arsenite is acute contaminant to human health in soil and water environment. In this study, Pyrolusite (alpha-MnO(2)) was used to investigate the oxidative transformation of arsenite into arsenate with batch experiments under different reaction conditions. The results showed that arsenite transformation occurred and was accompanied by the adsorption and fixation of both As(III) and As(V) on alpha-MnO(2). About 90% of sodium arsenite (10mg/L) were transformed by alpha-MnO(2) under the conditions of 25 degrees C and pH 6.0, 36.6% of which was adsorbed and 28.9% fixed by alpha-MnO(2). Increased alpha-MnO(2) dosages promoted As (III) transformation rate and adsorption of arsenic species. The transformation rate and adsorption of arsenic species raised with increasing pH values of reaction solution from 4.7 to 8.0. The oxidation rate decreased and adsorbed As(III) and As(V) increased with increasing initial arsenite concentration. The enhancement on oxidative transformation of sodium arsenite may result from abundant active sites of alpha-MnO(2). Along with adsorption and fixation of arsenic species during the reaction, the crystal structure of alpha-MnO(2) did not change, but the surface turned petty and loosen. Our results demonstrated that alpha-MnO(2) has important potential in arsenic transformation and removal as the environmentally friendly natural oxidant in soil and surface water.

Kinetic analysis of Legionella inactivation using ozone in wastewater.

PubMed

Li, Jun; Li, Kunquan; Zhou, Yan; Li, Xuebin; Tao, Tao

2017-02-01

Legionella inactivation using ozone was studied in wastewater using kinetic analysis and modeling. The experimental results indicate that the relationship between the ozone concentration, germ concentration, and chemical oxygen demand (COD) can be used to predict variations in germ and COD concentrations. The ozone reaction with COD and inactivation of Legionella occurred simultaneously, but the reaction with COD likely occurred at a higher rate than the inactivation, as COD is more easily oxidized by ozone than Legionella. Higher initial COD concentrations resulted in a lower inactivation rate and higher lnN/N 0 . Higher temperature led to a higher inactivation efficiency. The relationship of the initial O 3 concentration and Legionella inactivation rate was not linear, and thus, the Ct value required for a 99.99% reduction was not constant. The initial O 3 concentration was more important than the contact time, and a reduction of the initial O 3 concentration could not be compensated by increasing the contact time. The Ct values were compared over a narrow range of initial concentrations; the Ct values could only be contrasted when the initial O 3 concentrations were very similar. A higher initial O 3 concentration led to a higher inflection point value for the lnN/N 0 vs C 0 t curve. Energy consumption using a plasma corona was lower than when using boron-doped diamond electrodes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Atmospheric chemistry of n-butanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NO(x).

PubMed

Hurley, M D; Wallington, T J; Laursen, L; Javadi, M S; Nielsen, O J; Yamanaka, T; Kawasaki, M

2009-06-25

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.

Molecular dynamics simulation study of nanoscale passive oxide growth on Ni-Al alloy surfaces at low temperatures

NASA Astrophysics Data System (ADS)

Sankaranarayanan, Subramanian K. R. S.; Ramanathan, Shriram

2008-08-01

Oxidation kinetics of Ni-Al (100) alloy surface is investigated at low temperatures (300-600 K) and at different gas pressures using molecular dynamics (MD) simulations with dynamic charge transfer between atoms. Monte Carlo simulations employing the bond order simulation model are used to generate the surface segregated minimum energy initial alloy configurations for use in the MD simulations. In the simulated temperature-pressure-composition regime for Ni-Al alloys, we find that the oxide growth curves follow a logarithmic law beyond an initial transient regime. The oxidation rates for Ni-Al alloys were found to decrease with increasing Ni composition. Structure and dynamical correlations in the metal/oxide/gas environments are used to gain insights into the evolution and morphology of the growing oxide film. Oxidation of Ni-Al alloys is characterized by the absence of Ni-O bond formation. Oxide films formed on the various simulated metal surfaces are amorphous in nature and have a limiting thickness ranging from ˜1.7nm for pure Al to 1.1 nm for 15% Ni-Al surfaces. Oxide scale analysis indicates significant charge transfer as well as variation in the morphology and structure of the oxide film formed on pure Al and 5% Ni-Al alloy. For oxide scales thicker than 1 nm, the oxide structure in case of pure Al exhibits a mixed tetrahedral (AlO4˜37%) and octahedral (AlO6˜19%) environment, whereas the oxide scale on Ni-Al alloy surface is almost entirely composed of tetrahedral environment (AlO4˜60%) with very little AlO6 (<1%) . The oxide growth kinetic curves are fitted to Arrhenius-type plots to get an estimate of the activation energy barriers for metal oxidation. The activation energy barrier for oxidation on pure Al was found to be 0.3 eV lower than that on 5% Ni-Al surface. Atomistic observations as well as calculated dynamical correlation functions indicate a layer by layer growth on pure Al, whereas a transition from an initial island growth mode (<75ps) to a layer by layer mode (>100ps) occurs in case of 5% Ni-Al alloy. The oxide growth on both pure Al and Ni-Al alloy surfaces occurs by inward anion and outward cation diffusions. The cation diffusion in both the cases is similar, whereas the anion diffusion in case of 5% Ni-Al is 25% lower than pure Al, thereby resulting in reduced self-limiting thickness of oxide scale on the alloy surface. The simulation findings agree well with previously reported experimental observations of oxidation on Ni-Al alloy surface.

ROS Initiated Oxidation of Dopamine under Oxidative Stress Conditions in Aqueous and Lipidic Environments

PubMed Central

2011-01-01

Dopamine is known to be an efficient antioxidant and to protect neurocytes from oxidative stress by scavenging free radicals. In this work, we have carried out a systematic quantum chemistry and computational kinetics study on the reactivity of dopamine toward hydroxyl (•OH) and hydroperoxyl (•OOH) free radicals in aqueous and lipidic simulated biological environments, within the density functional theory framework. Rate constants and branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the reactivity of dopamine toward hydroxyl radicals, in water at physiological pH, the main mechanism of the reaction is proposed to be the sequential electron proton transfer (SEPT), whereas in the lipidic environment, hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways contribute almost equally to the total reaction rate. In both environments, dopamine reacts with hydroxyl radicals at a rate that is diffusion-controlled. Reaction with the hydroperoxyl radical is much slower and occurs only by abstraction of any of the phenolic hydrogens. The overall rate coefficients are predicted to be 2.23 × 105 and 8.16 × 105 M–1 s–1, in aqueous and lipidic environment, respectively, which makes dopamine a very good •OOH, and presumably •OOR, radical scavenger. PMID:21919526

Oxidative Folding and N-terminal Cyclization of Onconase+

PubMed Central

Welker, Ervin; Hathaway, Laura; Xu, Guoqiang; Narayan, Mahesh; Pradeep, Lovy; Shin, Hang-Cheol; Scheraga, Harold A.

2008-01-01

Cyclization of the N-terminal glutamine residue to pyroglutamic acid in onconase, an anti-cancer chemotherapeutic agent, increases the activity and stability of the protein. Here, we examine the correlated effects of the folding/unfolding process and the formation of this N-terminal pyroglutamic acid. The results in this study indicate that cyclization of the N-terminal glutamine has no significant effect on the rate of either reductive unfolding or oxidative folding of the protein. Both the cyclized and uncyclized proteins seem to follow the same oxidative folding pathways; however, cyclization altered the relative flux of the protein in these two pathways by increasing the rate of formation of a kinetically trapped intermediate. Glutaminyl cyclase (QC) catalyzed the cyclization of the unfolded, reduced protein, but had no effect on the disulfide-intact, uncyclized, folded protein. The structured intermediates of uncyclized onconase were also resistant to QC-catalysis, consistent with their having a native-like fold. These observations suggest that, in vivo, cyclization takes place during the initial stages of oxidative folding, specifically, before the formation of structured intermediates. The competition between oxidative folding and QC-mediated cyclization suggests that QC-catalyzed cyclization of the N-terminal glutamine in onconase occurs in the endoplasmic reticulum, probably co-translationally. PMID:17439243

Electrical energy per order and current efficiency for electrochemical oxidation of p-chlorobenzoic acid with boron-doped diamond anode.

PubMed

Lanzarini-Lopes, Mariana; Garcia-Segura, Sergi; Hristovski, Kiril; Westerhoff, Paul

2017-12-01

Electrochemical oxidation (EO) is an advanced oxidation process for water treatment to mineralize organic contaminants. While proven to degrade a range of emerging pollutants in water, less attention has been given to quantify the effect of operational variables such applied current density and pollutant concentration on efficiency and energy requirements. Particular figures of merit were mineralization current efficiency (MCE) and electrical energy per order (E EO ). Linear increases of applied current exponentially decreased the MCE due to the enhancement of undesired parasitic reactions that consumed generated hydroxyl radical. E EO values ranged from 39.3 to 331.8 kW h m -3 order -1 . Increasing the applied current also enhanced the E EO due to the transition from kinetics limited by current to kinetics limited by mass transfer. Further increases in current did not influence the removal rate, but it raised the E EO requirement. The E EO requirement diminished when decreasing initial pollutant loading with the increase of the apparent kinetic rate because of the relative availability of oxidant per pollutant molecule in solution at a defined current. Oxidation by-products released were identified, and a plausible degradative pathway has been suggested. Copyright © 2017. Published by Elsevier Ltd.

Preparation and properties of polytetrafluoroethylene impregnated with rhenium oxides

NASA Technical Reports Server (NTRS)

Leibecki, H. F.; Easter, R. W.

1973-01-01

The results of tests carried out to determine the properties of polytetrafluorethylene (PTFE) impregnated with rhenium oxides are presented. The tests included measurement of physical properties of the impregnated material and investigation of the effects of preparation process variables. Based on the latter tests a mechanism to describe the permeation process is postulated which identifies the rate controlling step to be diffusion of ReF6 molecules into the solid during the initial ReF6 soak. Physical property tests indicated that the electronic conductance is increased by many orders of magnitude while the desirable properties of the PTFE remain virtually unchanged.

Kaolinite-catalyzed air oxidation of hydrazine: Consideration of several compositional, structural and energetic factors in surface activation

NASA Technical Reports Server (NTRS)

Coyne, L. M.; Mariner, R.; Rice, A.

1991-01-01

Clay minerals have been shown to have numerous, curious, energetic properties by virtue of ultra-violet light release which can be triggered by gentle environmental changes such as wetting and dewetting by a variety of liquids, unique among them water and hydrazine. Since both water and hydrazine play multiple key roles in the air-oxidation of hydrazine on kaolinite surfaces, this reaction would seem to have prime potential for studying interrelationships of energy storage, release and chemical reactivity of clay surfaces, capacities basic to either the Bernal or Cairns-Smith roles of minerals in the origin of life. Establishment of the capacity for stored electronic energy to significantly alter surface chemistry is important, regardless of the reaction chosen to demonstrate it. Hydrazine air oxidation is overawingly complex, given the possibilities for step-wise control and monitoring of parameters. In the light of recently extended characterization of the kaolinite and model sheet catalysts we used to study hydrazine oxidation and gamma-irradiated silica, previous studies of hydrazine air-oxidation on aluminosilicate surfaces have been reevaluated. Our former conclusion remains intact that, whereas trace structural and surface contaminants do play some role in the catalysis of oxidation, they are not the only, nor even the dominant, catalytic centers. Initial intermediates in the oxidation can now be proposed which are consistent with production via O(-)-centers as well as ferric iron centers. The greater than square dependence of the initial reaction rate on the weight of the clay is discussed in the light of these various mechanistic possibilities.

Enhanced adsorption of arsenic through the oxidative treatment of reduced aquifer solids.

PubMed

Huling, Jenna R; Huling, Scott G; Ludwig, Ralph

2017-10-15

Arsenic (As) contamination in drinking water is an epidemic in many areas of the world, especially Eastern Asian countries. Developing affordable and efficient procedures to remove arsenic from drinking water is critical to protect human health. In this study, the oxidation of aquifer solids through the use of sodium permanganate (NaMnO 4 ), hydrogen peroxide (H 2 O 2 ), and exposure to air, enhanced the adsorption of arsenic to the aquifer material resulting in treatment of the water. NaMnO 4 was more effective than H 2 O 2 . NaMnO 4 was tested at different loading rates (0.5, 1.5, 2.4, 3.4, and 4.9 g NaMnO 4 /kg aquifer material), and after 30 days contact time, arsenic removal ([As +3 ] INITIAL  = 610 μg/L) was 77%, 88%, 93%, 95%, 97%, respectively, relative to un-oxidized aquifer material. Arsenic removal increased with increasing contact time (30, 60, 90 days) suggesting removal was not reversible under the conditions of these experiments. Oxidative treatment by exposing the aquifer solids to air for 68 days resulted in >99% removal of Arsenic ([As +3 ] INITIAL  = 550 μg/L). Less arsenic removal (38.2%) was measured in the un-oxidized aquifer material. In-situ oxidation of aquifer materials using NaMnO 4 , or ex-situ oxidation of aquifer materials through exposure to air could be effective in the removal of arsenic in ground water and a potential treatment method to protect human health. Published by Elsevier Ltd.

Oxidative stress increases eukaryotic initiation factor 4E phosphorylation in vascular cells.

PubMed Central

Duncan, Roger F; Peterson, Hazel; Hagedorn, Curt H; Sevanian, Alex

2003-01-01

Dysregulated cell growth can be caused by increased activity of protein synthesis eukaryotic initiation factor (eIF) 4E. Dysregulated cell growth is also characteristic of atherosclerosis. It is postulated that exposure of vascular cells, such as endothelial cells, smooth muscle cells and monocytes/macrophages, to oxidants, such as oxidized low-density lipoprotein (oxLDL), leads to the elaboration of growth factors and cytokines, which in turn results in smooth muscle cell hyperproliferation. To investigate whether activation of eIF4E might play a role in this hyperproliferative response, vascular cells were treated with oxLDL, oxidized lipid components of oxLDL and several model oxidants, including H(2)O(2) and dimethyl naphthoquinone. Exposure to each of these compounds led to a dose- and time-dependent increase in eIF4E phosphorylation in all three types of vascular cells, correlated with a modest increase in overall translation rate. No changes in eIF4EBP, eIF2 or eIF4B modification state were observed. Increased eIF4E phosphorylation was paralleled by increased presence of eIF4E in high-molecular-mass protein complexes characteristic of its most active form. Anti-oxidants at concentrations typically employed to block oxidant-induced cell signalling likewise promoted eIF4E phosphorylation. The results of this study indicate that increased eIF4E activity may contribute to the pathophysiological events in early atherogenesis by increasing the expression of translationally inefficient mRNAs encoding growth-promoting proteins. PMID:12215171

Synthesis and property of novel MnO2@polypyrrole coaxial nanotubes as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Yao, Wei; Zhou, Hui; Lu, Yun

2013-11-01

Novel MnO2@polypyrrole (PPy) coaxial nanotubes have been prepared via a simple and green approach without any surfactant and additional oxidant. Under the acidic condition, MnO2 nanotubes act as both template and oxidant to initiate the polymerization of pyrrole monomers on its fresh-activated surface. Fourier transform infrared spectra (FT-IR), X-ray diffraction patterns (XRD), thermo-gravimetric analysis data (TG) and X-ray photoelectron spectra (XPS) suggest the formation of composite structure of MnO2@PPy. Also, FESEM and TEM images intuitively confirm that the PPy shell is coated uniformly on the surface of MnO2 nanotubes. Adjusting the concentrations of sulfuric acid or adding oxidant can modulate the morphology of the products accordingly. Due to the synergic effect between MnO2 core and PPy shell, the MnO2@PPy coaxial nanotubes possess better rate capability, larger specific capacitance of 380 F g-1, doubling the specific capacitance of MnO2 nanotubes, and good capacitance retention of 90% for its initial capacitance after 1000 cycles.

Dissolution kinetics of small amounts of oxygen in tantalum alloy T-111 and internal oxide displacement reactions during annealing

NASA Technical Reports Server (NTRS)

Stecura, S.

1976-01-01

Oxygen was added to T-111 (Ta-8W-2Hf, wt. %) at 820 and 990 C at an oxygen pressure of about 0.0003 torr. The technique employed permitted predetermined and reproducible doping of T-111 up to 3.0 at. % oxygen. Based on the temperature dependence of the doping reaction, it is concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the latter oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and of other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high-temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C. The vaporization of WO3 has no apparent affect on the doping reaction.

Addition of oxygen to and distribution of oxides in tantalum alloy T-111 at low concentrations

NASA Technical Reports Server (NTRS)

Stecura, S.

1975-01-01

Oxygen was added at 820 and 990 C at an oxygen pressure of about .0003 torr. The technique permitted predetermined and reproducible oxygen doping of the tantalum alloy (T-111). Based on the temperature dependency of the doping reaction, it was concluded that the initial rates of oxygen pickup are probably controlled by solution of oxygen into the T-111 lattice. Although hafnium oxides are more stable than those of tantalum or tungsten, analyses of extracted residues indicate that the tantalum and tungsten oxides predominate in the as-doped specimens, presumably because of the higher concentrations of tantalum and tungsten in the alloy. However, high-temperature annealing promotes gettering of dissolved oxygen and oxygen from other oxides to form hafnium oxides. Small amounts of tantalum and tungsten oxides were still present after high temperature annealing. Tungsten oxide (WO3) volatilizes slightly from the surface of T-111 at 990 C but not at 820 C. The vaporization of WO3 has no apparent effect on the doping reaction.

Sulfate formation catalyzed by coal fly ash, mineral dust and iron(iii) oxide: variable influence of temperature and light.

PubMed

Gankanda, Aruni; Coddens, Ellen M; Zhang, Yaping; Cwiertny, David M; Grassian, Vicki H

2016-12-08

Recent atmospheric field and modeling studies have highlighted a lack of understanding of the processes responsible for high levels of sulfate aerosol in the atmosphere, ultimately arising from a dearth of experimental data on such processes. Here we investigated the effect of temperature and simulated solar radiation on the catalytic oxidation of S(iv) to S(vi) (i.e., sulfite to sulfate) in aqueous suspensions of several metal-containing, atmospherically relevant particles including coal fly ash (FA), Arizona test dust (ATD) and an iron oxide (γ-Fe 2 O 3 ). The effect of temperature and light on S(iv) oxidation was found to be very different for these three samples. For example, in the presence of FA and γ-Fe 2 O 3 the temporal evolution of dissolved Fe(ii) (formed via reductive particle dissolution) correlated with S(iv) oxidation. Accordingly, we propose that S(iv) oxidation in most of these systems initially occurs primarily at the particle surface (i.e., a heterogeneous reaction pathway), although a solution-phase (i.e., homogeneous) catalytic pathway also contributes over later timescales due to the formation and accumulation of dissolved Fe(iii) (generated via oxidation of dissolved Fe(ii) by O 2 ). It is likely that the homogeneous reaction pathway is operative at initial times in the presence of γ-Fe 2 O 3 at 25 °C. In contrast, S(iv) oxidation in the presence of ATD appears to proceed entirely via a heterogeneous reaction, which notably does not lead to any iron dissolution. In fact, the greater overall rate of S(iv) loss in the presence of ATD compared to FA and γ-Fe 2 O 3 suggests that other factors, including greater adsorption of sulfite, transition metal ion (TMI) catalysis by other metal ions (e.g., Ti), or different species of iron in ATD, play a role. Overall these studies suggest that the rate, extent and products of atmospheric S(iv) oxidation can be highly variable and dependent upon the nature of aerosol sources and ambient conditions (e.g., temperature and irradiance). Ultimately, such complexity precludes simple, broadly generalized schemes for this reaction when modeling atmospheric processes involving diverse components of different mineral dust aerosol as well as other metal-containing aerosol.

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

DOE PAGES

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

2016-04-16

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

The low temperature oxidation of lithium thin films on HOPG by O 2 and H 2O

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

Wulfsberg, Steven M.; Koel, Bruce E.; Bernasek, Steven L.

Lithiated graphite and lithium thin films have been used in fusion devices. In this environment, lithiated graphite will undergo oxidation by background gases. In order to gain insight into this oxidation process, thin (< 15 monolayer (ML)) lithium films on highly ordered pyrolytic graphite (HOPG) were exposed in this paper to O 2(g) and H 2O (g) in an ultra-high vacuum chamber. High resolution electron energy loss spectroscopy (HREELS) was used to identify the surface species formed during O 2(g) and H 2O (g) exposure. Auger electron spectroscopy (AES) was used to obtain the relative oxidation rates during O 2(g)more » and H 2O (g) exposure. AES showed that as the lithium film thickness decreased from 15 to 5 to 1 ML, the oxidation rate decreased for both O 2(g) and H 2O (g). HREELS showed that a 15 ML lithium film was fully oxidized after 9.7 L (L) of O 2(g) exposure and Li 2O was formed. HREELS also showed that during initial exposure (< 0.5 L) H 2O (g), lithium hydride and lithium hydroxide were formed on the surface of a 15 ML lithium film. Finally, after 0.5 L of H 2O (g) exposure, the H 2O (g) began to physisorb, and after 15 L of H 2O (g) exposure, the 15 ML lithium film was not fully oxidized.« less

High-Resolution Experimental Investigation of mass transfer enhancement by chemical oxidation from DNAPL entrapped in variable-aperture fractures

NASA Astrophysics Data System (ADS)

Arshadi, M.; Rajaram, H.; Detwiler, R. L.; Jones, T.

2012-12-01

Permanganate oxidation of DNAPL- contaminated fractured rock is an effective remediation technology. Permanganate ion reacts with dissolved DNAPL in a bi-molecular oxidation-reduction reaction. The consumption of dissolved DNAPL in this reaction results in increased concentration gradients away from the free-phase DNAPL, resulting in reaction-enhanced mass transfer, which accelerates contaminant removal. The specific objective of our research was to perform high-resolution non-intrusive experimental studies of permanganate oxidation in a 15.24 × 15.24 cm, transparent, analog, variable-aperture fracture with complex initial TCE entrapped phase geometry. Our experimental system uses light-transmission techniques to accurately measure both fracture aperture and the evolution of individual entrapped DNAPL blobs during the remediation experiments at high resolution (pixel size : 6.2×10-3 cm). Three experiments were performed with different flow rates and permanganate inflow concentrations to observe DNAPL-permanganate interactions across a broader range of conditions. Prior to initiating each experiment, the aperture field within the fracture was measured. The oxidation experiment was initiated by TCE injection into the water saturated fracture till the TCE reached the outflow end, followed by water re-injection through the fracture. The flowing water mobilized some TCE. We continued injection of water till TCE mobilization ceased, leaving behind the residual TCE entrapped within the variable-aperture fracture. Subsequently, permanganate injection through the fracture resulted in propagation of a fingered reaction front into the fracture. We developed image processing algorithms to analyze the evolution of DNAPL phase geometry over the duration of the experiment. The permanganate consumption rate varied significantly within the fracture due to the complex flow and DNAPL concentration fields. Precipitated MnO2 was clearly evident on the downstream side of DNAPL blobs near the inflow boundary indicating high reaction rates in these regions. This behavior is explained by the diversion of permanganate around entrapped DNAPL blobs and downstream advection of dissolved DNAPL. Our results indicate that the total rate of mass transfer from the DNAPL blobs is higher at early times, when not much MnO2 has formed and precipitated. With time, MnO2 precipitation in the fracture leads to changes the aperture field and flow field. Precipitated MnO2 around TCE blobs also decreases the DNAPL accessible surface area. By comparing the results of three experiments, we conclude that low permanganate concentrations and high flow rates lead to more efficient DNAPL remediation, resulting from the fact that under these conditions there would be slower MnO2 formation and less precipitation within the fracture. We also present results on the time-evolution of fracture-scale permanganate consumption and DNAPL removal rates. The experimental observations are being used to develop improved high-resolution numerical models of reactive transport in variable-aperture fractures. The overall goal is to relate the coupled processes of DNAPL removal, permanganate consumption, MnO2 formation and associated changes in aperture and interface area; to derive fracture-scale effective representations of these processes.

Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

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

Cooper, J.F.; Krueger, R.; Farmer, J.C.

1995-10-11

Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100more » C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.« less

Radical Cation Salt-initiated Aerobic C-H Phosphorylation of N-Benzylanilines: Synthesis of a-Aminophosphonates.

PubMed

Jia, Xiao Dong; Liu, Xiaofei; Yuan, Yu; Li, Pengfei; Hou, Wentao; He, Kaixuan

2018-06-03

A radical cation salt-initiated phosphorylation of N-benzylanilines was realized through the aerobic oxidation of sp3 C-H bond, providing a series of α-aminophosphonates in high yields. The investigation of the reaction scope revealed that this mild catalyst system is superior in good functional group tolerance and high reaction efficiency. The mechanistic study implied that the cleavage of the sp3 C-H bond was involved in the rate-determining step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In-situ, time resolved monitoring of uranium in BFS:OPC grout. Part 1: Corrosion in water vapour.

PubMed

Stitt, C A; Paraskevoulakos, C; Banos, A; Harker, N J; Hallam, K R; Davenport, A; Street, S; Scott, T B

2017-08-11

Uranium encapsulated in grout was exposed to water vapour for extended periods of time. Through synchrotron x-ray powder diffraction and tomography measurements, uranium dioxide was determined the dominant corrosion product over a 50-week time period. The oxide growth rate initiated rapidly, with rates comparable to the U + H 2 O reaction. Over time, the reaction rate decreased and eventually plateaued to a rate similar to the U + H 2 O + O 2 reaction. This behaviour was not attributed to oxygen ingress, but instead the decreasing permeability of the grout, limiting oxidising species access to the metal surface.

Oxidation and Condensation of Zinc Fume From Zn-CO 2-CO-H 2O Streams Relevant to Steelmaking Off-Gas Systems

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

Bronson, Tyler Mark; Ma, Naiyang; Zhu, Liang Zhu

Here the objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO 2-CO-H 2O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H 2O or CO 2 does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO 2/CO = 40/7). Rate expressions that correlate CO 2 and H 2O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows: Ratemore » $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 406 exp $$ \\left(\\frac{-50.2 kJ/mol}{RT}\\right) $$ (pZnpCO 2 $-$ PCO/K eqCO 2) $$\\frac{mol}{m^2 x s}$$ Rate $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 32.9 exp $$ \\left(\\frac{-13.7 kJ/mol}{RT}\\right) $$ (pZnPH 2O $-$ PH 2/K eqH 2O) $$\\frac{mol}{m^2 x s}$$. It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO 2 and H 2O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO 2:CO ratios, and H 2O partial pressures.« less

Oxidation and Condensation of Zinc Fume From Zn-CO 2-CO-H 2O Streams Relevant to Steelmaking Off-Gas Systems

DOE PAGES

Bronson, Tyler Mark; Ma, Naiyang; Zhu, Liang Zhu; ...

2017-01-23

Here the objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO 2-CO-H 2O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H 2O or CO 2 does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO 2/CO = 40/7). Rate expressions that correlate CO 2 and H 2O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows: Ratemore » $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 406 exp $$ \\left(\\frac{-50.2 kJ/mol}{RT}\\right) $$ (pZnpCO 2 $-$ PCO/K eqCO 2) $$\\frac{mol}{m^2 x s}$$ Rate $$ \\left(\\frac{mol}{m^2s}\\right) $$ = 32.9 exp $$ \\left(\\frac{-13.7 kJ/mol}{RT}\\right) $$ (pZnPH 2O $-$ PH 2/K eqH 2O) $$\\frac{mol}{m^2 x s}$$. It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO 2 and H 2O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO 2:CO ratios, and H 2O partial pressures.« less

Improved vacuum-UV (VUV)-initiated photomineralization of organic compounds in water with a xenon excimer flow-through photoreactor (Xe2* lamp, 172 nm) containing an axially centered ceramic oxygenator.

PubMed

Oppenländer, Thomas; Walddörfer, Carsten; Burgbacher, Jens; Kiermeier, Martin; Lachner, Klaus; Weinschrott, Helga

2005-07-01

Xenon excimer (Xe2*) lamps can be used for the oxidation and mineralization of organic compounds in aqueous solution. This vacuum-ultraviolet (VUV) photochemical method is mainly based on the photochemically initiated homolysis of water that produces hydrogen atoms and hydroxyl radicals. The efficiency of substrate oxidation and mineralization is limited markedly due to the high absorbance of water at the emission maximum of the Xe2* lamp (lambda(max)=172 nm). This photochemical condition generates an extreme heterogeneity between the irradiated volume V(irr) and the non-irradiated ("dark") bulk solution. During VUV-initiated photomineralization of organic substrates, the fast scavenging of hydrogen atoms and of carbon-centered radicals by dissolved molecular oxygen produces a permanent oxygen deficit within V(irr) and adjacent compartments. Hence, at a constant photon flux the concentration of dissolved molecular oxygen within the zones of photo and thermal radical reactions limits the rate of mineralization, i.e. the rate of TOC diminution. Thus, a simple and convenient technique is presented that overcomes this limitation by injection of molecular oxygen (or air) into the irradiated volume by use of a ceramic oxygenator (aerator). The tube oxygenator was centered axially within the xenon excimer flow-through lamp. Consequently, the oxygen or air bubbles enhanced the transfer of dissolved molecular oxygen into the VUV-irradiated volume leading to an increased rate of mineralization of organic model compounds, e.g. 1-heptanol, benzoic acid and potassium hydrogen phthalate.

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

PubMed

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.

Liquid-Phase Heat-Release Rates of the Systems Hydrazine-Nitric Acid and Unsymmetrical Dimethylhydrazine-Nitric Acid

NASA Technical Reports Server (NTRS)

Somogyi, Dezso; Feiler, Charles E.

1960-01-01

The initial rates of heat release produced by the reactions of hydrazine and unsymmetrical dimethylhydrazine with nitric acid were determined in a bomb calorimeter under conditions of forced mixing. Fuel-oxidant weight ratio and injection velocity were varied. The rate of heat release apparently depended on the interfacial area between the propellants. Above a narrow range of injection velocities representing a critical amount of interfacial area, the rates reached a maximum and were almost constant with injection velocity. The maximum rate for hydrazine was about 70 percent greater than that for unsymmetrical dimethylhydrazine. The total heat released did not vary with mixture ratio over the range studied.

Effects of daily ingestion of chilli on serum lipoprotein oxidation in adult men and women.

PubMed

Ahuja, Kiran D K; Ball, Madeleine J

2006-08-01

Laboratory studies have shown that the resistance of isolated LDL-cholesterol or linoleic acid to oxidation is increased in incubations with chilli extracts or capsaicin--the active ingredient of chilli. It is unknown if these in vitro antioxidative effects also occur in the serum of individuals eating chilli regularly. The present study investigated the effects of regular consumption of chilli on in vitro serum lipoprotein oxidation and total antioxidant status (TAS) in healthy adult men and women. In a randomised cross-over study, twenty-seven participants (thirteen men and fourteen women) ate 'freshly chopped chilli' blend (30 g/d; 55% cayenne chilli) and no chilli (bland) diets, for 4 weeks each. Use of other spices, such as cinnamon, ginger, garlic and mustard, was restricted to minimum amounts. At the end of each dietary period serum samples were analysed for lipids, lipoproteins, TAS and Cu-induced lipoprotein oxidation. Lag time (before initiation of oxidation) and rate of oxidation (slope of propagation phase) were calculated. There was no difference in the serum lipid, lipoproteins and TAS at the end of the two dietary periods. In the whole group, the rate of oxidation was significantly lower (mean difference -0.23 absorbance x10(-3)/min; P=0.04) after the chilli diet, compared with the bland diet. In women, lag time was higher (mean difference 9.61 min; P<0.001) after the chilli diet, compared with the bland diet. In conclusion, regular consumption of chilli for 4 weeks increases the resistance of serum lipoproteins to oxidation.

Bacterial oxidation of ferrous iron at low temperatures.

PubMed

Kupka, Daniel; Rzhepishevska, Olena I; Dopson, Mark; Lindström, E Börje; Karnachuk, Olia V; Tuovinen, Olli H

2007-08-15

This study comprises the first report of ferrous iron oxidation by psychrotolerant, acidophilic iron-oxidizing bacteria capable of growing at 5 degrees C. Samples of mine drainage-impacted surface soils and sediments from the Norilsk mining region (Taimyr, Siberia) and Kristineberg (Skellefte district, Sweden) were inoculated into acidic ferrous sulfate media and incubated at 5 degrees C. Iron oxidation was preceded by an approximately 3-month lag period that was reduced in subsequent cultures. Three enrichment cultures were chosen for further work and one culture designated as isolate SS3 was purified by colony isolation from a Norilsk enrichment culture for determining the kinetics of iron oxidation. The 16S rRNA based phylogeny of SS3 and two other psychrotolerant cultures, SS5 from Norilsk and SK5 from Northern Sweden, was determined. Comparative analysis of amplified 16S rRNA gene sequences showed that the psychrotolerant cultures aligned within Acidithiobacillus ferrooxidans. The rate constant of iron oxidation by growing cultures of SS3 was in the range of 0.0162-0.0104 h(-1) depending on the initial pH. The oxidation kinetics followed an exponential pattern, consistent with a first order rate expression. Parallel iron oxidation by a mesophilic reference culture of Acidithiobacillus ferrooxidans was extremely slow and linear. Precipitates harvested from the 5 degrees C culture were identified by X-ray diffraction as mixtures of schwertmannite (ideal formula Fe(8)O(8)(OH)(6)SO(4)) and jarosite (KFe(3)(SO(4))(2)(OH)(6)). Jarosite was much more dominant in precipitates produced at 30 degrees C. (c) 2007 Wiley Periodicals, Inc.

Aerobic composting of distilled grain waste eluted from a Chinese spirit-making process: The effects of initial pH adjustment.

PubMed

Wang, Shi-Peng; Zhong, Xiao-Zhong; Wang, Ting-Ting; Sun, Zhao-Yong; Tang, Yue-Qin; Kida, Kenji

2017-12-01

Aerobic composting of distilled grain waste (DGW) at different initial pH values adjusted by CaO addition was investigated. Three pH-adjusted treatments with initial pH values of 4 (R1), 5 (R2) and 6 (R3) and a control treatment (R0) with a pH value of 3.5 were conducted simultaneously. The results showed that R0 had an unsuccessful start-up of composting. However, the pH-adjusted treatments produced remarkable results, with a relatively high initial pH being beneficial for the start-up. Within 65days of composting, the degradation of volatile solids (VS) and the physicochemical properties of R2 and R3 displayed similar tendencies, and both produced a mature end-product, while R1 exhibited a lower VS degradation rate, and some of its physicochemical properties indicated the end-product was immature. Quantitative PCR analysis of ammonia oxidizers indicated that the occurrence of nitrification during the composting of DGW could be attributed to the activity of ammonia-oxidizing bacteria. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Situ Investigation of Electrochemically Mediated Surface-Initiated Atom Transfer Radical Polymerization by Electrochemical Surface Plasmon Resonance.

PubMed

Chen, Daqun; Hu, Weihua

2017-04-18

Electrochemically mediated atom transfer radical polymerization (eATRP) initiates/controls the controlled/living ATRP chain propagation process by electrochemically generating (regenerating) the activator (lower-oxidation-state metal complex) from deactivator (higher-oxidation-state metal complex). Despite successful demonstrations in both of the homogeneous polymerization and heterogeneous systems (namely, surface-initiated ATRP, SI-ATRP), the eATRP process itself has never been in situ investigated, and important information regarding this process remains unrevealed. In this work, we report the first investigation of the electrochemically mediated SI-ATRP (eSI-ATRP) by rationally combining the electrochemical technique with real-time surface plasmon resonance (SPR). In the experiment, the potential of a SPR gold chip modified by the self-assembled monolayer of the ATRP initiator was controlled to electrochemically reduce the deactivator to activator to initiate the SI-ATRP, and the whole process was simultaneously monitored by SPR with a high time resolution of 0.1 s. It is found that it is feasible to electrochemically trigger/control the SI-ATRP and the polymerization rate is correlated to the potential applied to the gold chip. This work reveals important kinetic information for eSI-ATRP and offers a powerful platform for in situ investigation of such complicated processes.

The kinetics of the oxidation of ferrous iron in synthetic and natural waters

NASA Astrophysics Data System (ADS)

Davison, W.; Seed, G.

1983-01-01

The rate of oxidation of ferrous iron in a seasonally anoxic lake was measured on 39 occasions with respect to both depth and time. Sample disturbance was minimal as only oxygen had to be introduced to initiate the reaction. The data were consistent with the simple rate law for homogeneous chemical kinetics previously established for synthetic solutions. The rate constant for the oxidation reaction in lake water was indistinguishable from that measured in synthetic samples. It did not appear to be influenced by changes in the microbial populations or by changes in any particulate or soluble components in the water, including iron and manganese. Analysis of the errors inherent in the kinetic measurements showed that the estimation of pH was the major source of inaccuracy and that values of the rate constant determined by different workers could easily differ by a factor of six. The present data, together with a comprehensive survey of the literature, are used to suggest a 'universal' rate constant of ca. 2 × 10 13 M -2 atm -1 min -1 (range 1.5-3 × 10 13) in the rate law -d[Fe II]/dt = k[Fe II]pO 2 (OH-) 2 for natural freshwaters in the pH range 6.5-7.4. Discrepancies in the effects of ionic strength and interfering substances reported in the literature are highlighted. Generally substances have only been found to interfere at concentrations which far exceed those in most natural waters.

Pure rotational CARS thermometry studies of low-temperature oxidation kinetics in air and ethene-air nanosecond pulse discharge plasmas

NASA Astrophysics Data System (ADS)

Zuzeek, Yvette; Choi, Inchul; Uddi, Mruthunjaya; Adamovich, Igor V.; Lempert, Walter R.

2010-03-01

Pure rotational CARS thermometry is used to study low-temperature plasma assisted fuel oxidation kinetics in a repetitive nanosecond pulse discharge in ethene-air at stoichiometric and fuel lean conditions at 40 Torr pressure. Air and fuel-air mixtures are excited by a burst of high-voltage nanosecond pulses (peak voltage, 20 kV; pulse duration, ~ 25 ns) at a 40 kHz pulse repetition rate and a burst repetition rate of 10 Hz. The number of pulses in the burst is varied from a few pulses to a few hundred pulses. The results are compared with the previously developed hydrocarbon-air plasma chemistry model, modified to incorporate non-empirical scaling of the nanosecond discharge pulse energy coupled to the plasma with number density, as well as one-dimensional conduction heat transfer. Experimental time-resolved temperature, determined as a function of the number of pulses in the burst, is found to agree well with the model predictions. The results demonstrate that the heating rate in fuel-air plasmas is much faster compared with air plasmas, primarily due to energy release in exothermic reactions of fuel with O atoms generated by the plasma. It is found that the initial heating rate in fuel-air plasmas is controlled by the rate of radical (primarily O atoms) generation and is nearly independent of the equivalence ratio. At long burst durations, the heating rate in lean fuel air-mixtures is significantly reduced when all fuel is oxidized.

Creep Response and Deformation Processes in Nanocluster Strengthened Ferritic Steels

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

Hayashi, Taisuke; Sarosi, P. M.; Schneibel, Joachim H

2008-01-01

There is increasing demand for oxide-dispersion-strengthened ferritic alloys that possess both high-temperature strength and irradiation resistance. Improvement of the high-temperature properties requires an understanding of the operative deformation mechanisms. In this study, the microstructures and creep properties of the oxide-dispersion-strengthened alloy 14YWT have been evaluated as a function of annealing at 1000 C for 1 hour up to 32 days. The ultra-fine initial grain size (approx. 100nm) is stable after the shortest annealing time, and even after subsequent creep at 800 C. Longer annealing periods lead to anomalous grain growth that is further enhanced following creep. Remarkably, the minimum creepmore » rate is relatively insensitive to this dramatic grain-coarsening. The creep strength is attributed to highly stable, Ti-rich nanoclusters that appear to pin the initial primary grains, and present strong obstacles to dislocation motion in the large, anomalously grown grains.« less

Modification of graphene oxide films by radiofrequency N2 plasma

NASA Astrophysics Data System (ADS)

Neustroev, E. P.; Burtseva, E. K.; Soloviev, B. D.; Prokopiev, A. R.; Popov, V. I.; Timofeev, V. B.

2018-04-01

The effect of treatment in nitrogen plasma on the properties of partially reduced graphene oxide (rGO) was studied. A comparison is made between two different sample locations in the reaction chamber. It is shown that in the case when rGO films were turned towards the inductor of the plasma system, the etching rate is much higher. Effective nitrogen functionalization of rGO was established in the second position, when the rGO films were turned in the opposite direction. In this case, the nitrogen content increases to 5 at% of the initial value. The change in the current-voltage characteristics is observed under illumination, which is independent of the wavelength. On and off daylight changes the resistance to 30% of the initial value. The magnitude of the photocurrent increases depending on the applied voltage. The effect is most noticeable for thin rGO films 10-15 nm in thickness.

Oxidation/volatilization rates in air for candidate fusion reactor blanket materials, PCA and HT-9

NASA Astrophysics Data System (ADS)

Piet, S. J.; Kraus, H. G.; Neilson, R. M.; Jones, J. L.

1986-11-01

Large uncertainties exist in the quantity of neutron-induced activation products that can be mobilized in potential fusion accidents. The accidental combination of high temperatures and oxidizing conditions might lead to mobilization of a significant amount of activation products from structural materials. Here, the volatilization of constituents of PCA and HT-9 resulting form oxidation in air was investigated. Tests were conducted in flowing air at temperatures from 600 to 1300°C for 1, 5, or 20 h. Elemental volatility was calculated in terms of the weight fraction of the element volatilized from the initial alloy. Molybdenum and manganese were the radiologically significant primary constituents most volatilized, suggesting that molybdenum and manganese should be minimized in fusion steel compositions. Higher chromium content appears beneficial in reducing hazards from mobile activation products. Scanning electron microscopy and energy dispersive spectroscopy were used to study the oxide layer on samples.

The oxidation of phenol by ferrate(VI) and ferrate(V). A pulse radiolysis and stopped-flow study.

PubMed

Rush, J D; Cyr, J E; Zhao, Z; Bielski, B H

1995-04-01

Potassium ferrate, K2FeO4, is found to oxidize phenol in aqueous solution (5.5 < or = pH < or = 10) by a process which is second order in both reactants; -d[FeVI]/dt=k1[FeVI][phenol], k1 = 10(7)M-1s-1. Product analysis by HPLC showed a mixture of hydroxylated products, principally paraquinone, and biphenols that indicate that oxidation of phenol occurs by both one-electron and two-electron pathways. The two-electron oxidant, producing both para- and ortho-hydroxylated phenols is considered to be ferrate(V) which is itself produced by the initial one-electron reduction of ferrate(VI). The rate of ferrate(V) reaction with phenol was determined by pre-mix stopped flow pulse-radiolysis and found to be k7 = (3.8 +/- 0.4) x 10(5)M-1s-1.

Steam Oxidation Testing in the Severe Accident Test Station

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

Pint, Bruce A.

After the March 2011 accident at Fukushima Daiichi, Oak Ridge National Laboratory (ORNL) began conducting high temperature steam oxidation testing of candidate materials for accident tolerant fuel (ATF) cladding in August 2011 [1-11]. The ATF concept is to enhance safety margins in light water reactors (LWR) during severe accident scenarios by identifying materials with 100× slower steam oxidation rates compared to current Zr-based alloys. In 2012, the ORNL laboratory equipment was expanded and made available to the entire ATF community as the Severe Accident Test Station (SATS) [4,12]. Compared to the current UO2/Zr-based alloy fuel system, an ATF alternative wouldmore » significantly reduce the rate of heat and hydrogen generation in the core during a coolant-limited severe accident [13-14]. The steam oxidation behavior of candidate materials is a key metric in the evaluation of ATF concepts and also an important input into models [15-17]. However, initial modeling work of FeCrAl cladding has used incomplete information on the physical properties of FeCrAl. Also, the steam oxidation data being collected at 1200°-1700°C is unique as no prior work has considered steam oxidation of alloys at such high temperatures. Also, because many accident scenarios include steadily increasing temperatures, the required data are not traditional isothermal exposures but exposures with varying “ramp” rates. In some cases, the steam oxidation behavior has been surprising and difficult to interpret. Thus, more fundamental information continues to be collected. In addition, more work continues to focus on commercially-manufactured tube material. This report summarizes recent work to characterize the behavior of candidate alloys exposed to high temperature steam, evaluate steam oxidation behavior in various ramp scenarios and continue to collect integral data on FeCrAl compared to conventional Zr-based cladding.« less

Photo Degradation of Methyl Orange by Persulfate Activated with Zero Valent Iron

NASA Astrophysics Data System (ADS)

Munkoeva, V. A.; Sizykh, M. R.; Batoeva, A. A.

2017-11-01

The oxidative degradation of Methyl Orange (MO) subjected to direct photolysis (Solar) and various oxidative systems was studied. The comparative experiments have shown that MO conversion and mineralization increases in the following order: Solar ∼ Solar/Fe0 ∼ Solar/S2O82- < S2O82-/Fe0 < Solar/S2O82-/Fe0. The influence of the main factors (duration of exposure, the ratio of initial concentrations of MO:S2O82-:Fe0, pH and temperature of the reaction medium) on the degree of MO conversion and mineralization was studied. The optimal pH and temperature of the reaction medium were 5.8 and 25°C, respectively. The rate of MO decomposition and mineralization increased proportionally to the initial concentration of the oxidant at the molar ratios [S2O82-] :[MO] ≤ 12. Judging by the nature of the kinetic curves, a further increase of this ratio is impractical. However, an increase in the oxidant concentration had a positive effect on the degrees of conversion and mineralization of total organic carbon (TOC). Thus, at the ratios of 12:1 and 48:1, the conversion efficiency of TOC was 23 and 60 %, respectively. The optimal concentration of Fe0 was 100 mg/l.

Real-time sensing of epithelial cell-cell and cell-substrate interactions by impedance spectroscopy on porous substrates

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

Mondal, D.; RoyChaudhuri, C., E-mail: chirosreepram@yahoo.com; Pal, D.

2015-07-28

Oxidized porous silicon (PS) is a common topographical biocompatible substrate that potentially provides a distinct in vitro environment for better understanding of in vivo behavior. But in the reported studies on oxidized PS, cell-cell and cell-substrate interactions have been detected only by fluorescent labeling. This paper is the first attempt to investigate real-time sensing of these interactions on HaCaT cells by label-free impedance spectroscopy on oxidized PS of two pore diameters (50 and 500 nm). One of the major requirements for successful impedance spectroscopy measurement is to restrict the channeling of electric field lines through the pores. To satisfy this criterion,more » we have designed the pore depths after analyzing the penetration of the medium by using computational fluid dynamics simulation. A distributed electrical model was also developed for estimating the various cellular attributes by considering a pseudorandom distribution of pores. It is observed from the impedance measurements and from the model that the proliferation rate increases for 50 nm pores but decreases for 500 nm pores compared to that for planar substrates. The rate of decrease in cell substrate separation (h) in the initial stage is more than the rate of increase in cell-cell junction resistance (R{sub b}) corresponding to the initial adhesion phase of cells. It is observed that R{sub b} and h are higher for 50 nm pores than those for planar substrates, corresponding to the fact that substrates more conducive toward cell adhesion encourage cell-cell interactions than direct cell-substrate interactions. Thus, the impedance spectroscopy coupled with the proposed theoretical framework for PS substrates can sense and quantify the cellular interactions.« less

Mechanisms of High-Temperature Fatigue Failure in Alloy 800H

NASA Technical Reports Server (NTRS)

BhanuSankaraRao, K.; Schuster, H.; Halford, G. R.

1996-01-01

The damage mechanisms influencing the axial strain-controlled Low-Cycle Fatigue (LCF) behavior of alloy 800H at 850 C have been evaluated under conditions of equal tension/compression ramp rates (Fast-Fast (F-F): 4 X 10(sup -3)/s and Slow-Slow (S-S): 4 X 10(sup -5)/s) and asymmetrical ramp rates (Fast-Slow (F-S): 4 x 10(sup -3)/s / 4 X 10(sup -5/s and Slow-Fast (S-F): 4 X 10(sup -5) / 4 X 10(sup -3)/s) in tension and compression. The fatigue life, cyclic stress response, and fracture modes were significantly influenced by the waveform shape. The fatigue lives displayed by different loading conditions were in the following order: F-F greater than S-S greater than F-S greater than S-F. The fracture mode was dictated by the ramp rate adopted in the tensile direction. The fast ramp rate in the tensile direction led to the occurrence of transgranular crack initiation and propagation, whereas the slow ramp rate caused intergranular initiation and propagation. The time-dependent processes and their synergistic interactions, which were at the basis of observed changes in cyclic stress response and fatigue life, were identified. Oxidation, creep damage, dynamic strain aging, massive carbide precipitation, time-dependent creep deformation, and deformation ratcheting were among the several factors influencing cyclic life. Irrespective of the loading condition, the largest effect on life was exerted by oxidation processes. Deformation ratcheting had its greatest influence on life under asymmetrical loading conditions. Creep damage accumulated the greatest amount during the slow tensile ramp under S-F conditions.

Multiple laser pulse ignition method and apparatus

DOEpatents

Early, James W.

1998-01-01

Two or more laser light pulses with certain differing temporal lengths and peak pulse powers can be employed sequentially to regulate the rate and duration of laser energy delivery to fuel mixtures, thereby improving fuel ignition performance over a wide range of fuel parameters such as fuel/oxidizer ratios, fuel droplet size, number density and velocity within a fuel aerosol, and initial fuel temperatures.

A model of early formation of uranium molecular oxides in laser-ablated plasmas

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

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

A model of early formation of uranium molecular oxides in laser-ablated plasmas

DOE PAGES

Finko, Mikhail S.; Curreli, Davide; Weisz, David G.; ...

2017-10-12

Here, in this work, we present a newly constructed U xO y reaction mechanism that consists of 30 reaction channels (21 of which are reversible channels) for 11 uranium molecular species (including ions). Both the selection of reaction channels and calculation of corresponding rate coefficients is accomplished via a comprehensive literature review and application of basic reaction rate theory. The reaction mechanism is supplemented by a detailed description of oxygen plasma chemistry (19 species and 142 reaction channels) and is used to model an atmospheric laser ablated uranium plume via a 0D (global) model. Finally, the global model is usedmore » to analyze the evolution of key uranium molecular species predicted by the reaction mechanism, and the initial stage of formation of uranium oxide species.« less

Friction and oxidative wear of 440C ball bearing steels under high load and extreme bulk temperatures

NASA Technical Reports Server (NTRS)

Chaudhuri, Dilip K.; Slifka, Andrew J.; Siegwarth, James D.

1993-01-01

Unlubricated sliding friction and wear of 440C steels in an oxygen environment have been studied under a variety of load, speed, and temperature ranging from approximately -185 to 675 deg C. A specially designed test apparatus with a ball-on-flat geometry has been used for this purpose. The observed dependencies of the initial coefficient of friction, the average dynamic coefficient of friction, and the wear rate on load, speed, and test temperatures have been examined from the standpoint of existing theories of friction and wear. High contact temperatures are generated during the sliding friction, causing rapid oxidation and localized surface melting. A combination of fatigue, delamination, and loss of hardness due to tempering of the martensitic structure is responsible for the high wear rate observed and the coefficient of friction.

The oxidative debt of fasting: evidence for short- to medium-term costs of advanced fasting in adult king penguins.

PubMed

Schull, Quentin; Viblanc, Vincent A; Stier, Antoine; Saadaoui, Hédi; Lefol, Emilie; Criscuolo, François; Bize, Pierre; Robin, Jean-Patrice

2016-10-15

In response to prolonged periods of fasting, animals have evolved metabolic adaptations helping to mobilize body reserves and/or reduce metabolic rate to ensure a longer usage of reserves. However, those metabolic changes can be associated with higher exposure to oxidative stress, raising the question of how species that naturally fast during their life cycle avoid an accumulation of oxidative damage over time. King penguins repeatedly cope with fasting periods of up to several weeks. Here, we investigated how adult male penguins deal with oxidative stress after an experimentally induced moderate fasting period (PII) or an advanced fasting period (PIII). After fasting in captivity, birds were released to forage at sea. We measured plasmatic oxidative stress on the same individuals at the start and end of the fasting period and when they returned from foraging at sea. We found an increase in activity of the antioxidant enzyme superoxide dismutase along with fasting. However, PIII individuals showed higher oxidative damage at the end of the fast compared with PII individuals. When they returned from re-feeding at sea, all birds had recovered their initial body mass and exhibited low levels of oxidative damage. Notably, levels of oxidative damage after the foraging trip were correlated to the rate of mass gain at sea in PIII individuals but not in PII individuals. Altogether, our results suggest that fasting induces a transitory exposure to oxidative stress and that effort to recover in body mass after an advanced fasting period may be a neglected carryover cost of fasting. © 2016. Published by The Company of Biologists Ltd.

Characterization of shock-dependent reaction rates in an aluminum/perfluoropolyether pyrolant

NASA Astrophysics Data System (ADS)

Wilson, Dennis; Granier, John; Johnson, Richard; Littrell, Donald

2017-01-01

Energetic formulations of perfluoropolyether (PFPE) and aluminum are highly non-ideal. They release energy via a fast self-oxidized combustion wave rather than a true self-sustaining detonation. Unlike high explosives, the reactions are shock dependent and can be overdriven to control energy release rate. Reaction rate experiments show that the velocity can vary from 1.25 to 3 km/s. This paper examines the effect of the initial shock conditions upon the reaction rate of the explosive. The following conditions were varied in a series of reaction rate experiments: the high explosive booster mass and geometry; shock attenuation; confinement; and rate stick diameter and length. Several experiments designed to isolate and quantify these dependencies are described and summarized.

Mechanisms of ilmenite reduction and their impact on the design of effective reactor systems

NASA Technical Reports Server (NTRS)

Briggs, R. A.; Sacco, A.

1991-01-01

One of the first activities at a lunar base could be oxygen recovery from ilmenite (FeTiO3). Oxygen produced from lunar soils could be used to fuel transportation vehicles operating in near-earth space. The first step in developing a suitable reactor system for lunar operation is to determine the mechanisms and rates of oxygen removal from ilmenite. In-situ gravimetric measurements and microscopic examinations were used to determine the hydrogen reduction mechanisms of synthetic ilmenite discs between 823 to 1353 K. A shrinking core reaction model, modified to account for the growth of an iron film on the surface of discs, was capable of predicting experimentally observed conversion-time relationships. The observed reduction mechanism, kinetic rates, and associated activation energy established a base line from which comparisons could be made to improve oxygen yield and removal rates. One proposed technique to improve the rate and extent of oxygen removal was to preoxidize ilmenite. Preoxidation is commonly used during the reduction of ilmenite ores in the iron industry and has been employed for many years to lower operating temperatures and increase reduction rates. This technology could prove beneficial for oxygen production facilities on the Moon as less massive reactor vessels and/or less energy could be associated with a process including preoxidation. X ray diffraction and energy dispersive spectroscopy were utilized to follow the progression of ilmenite oxidation at 1123 and 1140 K and the reduction of pseudobrookite (Fe2TiO5) at 873 and 973 K. Structures formed during the progress of oxidation were related to the system's phase diagrams. Results indicated that after initially producing ilmenite-hematite solutions and rutile (TiO2), pseudobrookite was the end product of oxidation at all temperatures examined (1049 to 1273 K). Initial results from the reduction of pseudobrookite indicate a series of phases are produced including ferropseudobrookite (FeTi2O5), ulvospinel (Fe2TiO4), and ilmenite. Rates of pseudobrookite reduction were typically 50 to 200 times that of ilmenite.

A rapid and low energy consumption method to decolorize the high concentration triphenylmethane dye wastewater: operational parameters optimization for the ultrasonic-assisted ozone oxidation process.

PubMed

Zhou, Xian-Jiao; Guo, Wan-Qian; Yang, Shan-Shan; Ren, Nan-Qi

2012-02-01

This research set up an ultrasonic-assisted ozone oxidation process (UAOOP) to decolorize the triphenylmethane dyes wastewater. Five factors - temperature, initial pH, reaction time, ultrasonic power (low frequency 20 kHz), and ozone concentration - were investigated. Response surface methodology was used to find out the major factors influencing color removal rate and the interactions between these factors, and optimized the operating parameters as well. Under the experimental conditions: reaction temperature 39.81 °C, initial pH 5.29, ultrasonic power 60 W and ozone concentration 0.17 g/L, the highest color removals were achieved with 10 min reaction time and the initial concentration of the MG solution was 1000 mg/L. The optimal results indicated that the UAOOP was a rapid, efficient and low energy consumption technique to decolorize the high concentration MG wastewater. The predicted model was approximately in accordance with the experimental cases with correlation coefficients R(2) and R(adj)(2) of 0.9103 and 0.8386. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Tailoring Anisotropic Li-Ion Transport Tunnels on Orthogonally Arranged Li-Rich Layered Oxide Nanoplates Toward High-Performance Li-Ion Batteries.

PubMed

Xu, Ming; Fei, Linfeng; Zhang, Weibing; Li, Tao; Lu, Wei; Zhang, Nian; Lai, Yanqing; Zhang, Zhian; Fang, Jing; Zhang, Kai; Li, Jie; Huang, Haitao

2017-03-08

High-performance Li-rich layered oxide (LRLO) cathode material is appealing for next-generation Li-ion batteries owing to its high specific capacity (>300 mAh g -1 ). Despite intense studies in the past decade, the low initial Coulombic efficiency and unsatisfactory cycling stability of LRLO still remain as great challenges for its practical applications. Here, we report a rational design of the orthogonally arranged {010}-oriented LRLO nanoplates with built-in anisotropic Li + ion transport tunnels. Such a novel structure enables fast Li + ion intercalation and deintercalation kinetics and enhances structural stability of LRLO. Theoretical calculations and experimental characterizations demonstrate the successful synthesis of target cathode material that delivers an initial discharge capacity as high as 303 mAh g -1 with an initial Coulombic efficiency of 93%. After 200 cycles at 1.0 C rate, an excellent capacity retention of 92% can be attained. Our method reported here opens a door to the development of high-performance Ni-Co-Mn-based cathode materials for high-energy density Li-ion batteries.

Initial stage corrosion of nanocrystalline copper particles and thin films

NASA Astrophysics Data System (ADS)

Tao, Weimin

1997-12-01

Corrosion behavior is an important issue in nanocrystalline materials research and development. A very fine grain size is expected to have significant effects on the corrosion resistance of these novel materials. However, both the macroscopic corrosion properties and the corresponding structure evolution during corrosion have not been fully studied. Under such circumstances, conducting fundamental research in this area is important and necessary. In this study, high purity nanocrystalline and coarse-grained copper were selected as our sample material, sodium nitrite aqueous solution at room temperature and air at a high temperature were employed as corrosive environments. The weight loss testing and electrochemical methods were used to obtain the macroscopic corrosion properties, whereas the high resolution transmission electron microscope was employed for the structure analysis. The weight loss tests indicate that the corrosion rate of nanocrystalline copper is about 5 times higher than that of coarse-grained copper at the initial stage of corrosion. The electrochemical measurements show that the corrosion potential of the nanocrystalline copper has a 230 mV negative shift in comparison with that of the coarse-grained copper. The nanocrystalline copper also exhibits a significantly higher exchange current density than the coarse-grained copper. High resolution TEM revealed that the surface structure changes at the initial stage of corrosion. It was found that the first copper oxide layer formed on the surface of nanocrystalline copper thin film contains a large density of high angle grain boundaries, whereas that formed on the surface of coarse-grained copper shows highly oriented oxide nuclei and appears to show a strong tendency for forming low angle grain boundaries. A correlation between the macroscopic corrosion properties and the structure characteristics is proposed for the nanocrystalline copper based on the concept of the "apparent" exchange current density associated with mass transport of ions in the oxide layer. A hypothesis is developed that the high corrosion rate of the nanocrystalline copper is closely associated with the structure of the copper oxide layer. Therefore, a high "apparent" exchange current density for the nanocrystalline copper is associated with the high angle grain boundary structure in the initial oxide layer. Additional structure analysis was also carried out: (a) High resolution TEM imaging has provided a cross sectional view of the epitaxial interface between nanocrystalline copper and copper (I) oxide and explicitly discloses the presence of interface defects such as misfit dislocations. Based on this observation, a mechanism was proposed to explain the Cu/Cusb2O interface misfit accommodation. This appears to be the first time this interface has been directly examined. (b) A nanocrystalline analogue to a cross-section of Gwathmey's copper single crystal sphere was revealed by high resolution TEM imaging. A partially oxidized nanocrystalline copper particle is used to examine the variation of the Cu/Cusb2O orientation relationship with respect to changes in surface orientation. A new orientation relationship, Cu (011) //Cusb2O (11), ˜ Cu(011)//Cusb2O(111), was found for the oxidation of nanocrystalline copper.

Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility

PubMed Central

Fairbanks, Benjamin D.; Schwartz, Michael P.; Bowman, Christopher N.; Anseth, Kristi S.

2009-01-01

Due to mild reaction conditions and temporal and spatial control over material formation, photopolymerization has become a valuable technique for the encapsulation of living cells in three dimensional, hydrated, biomimetic materials. For such applications,2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) is the most commonly used photoinitiator (by virtue of its moderate water solubility), yet this initiator has an absorption spectrum that is poorly matched with wavelengths of light generally regarded as benign to living cells, limiting the rate at which it may initiate polymerization in their presence. In contrast, acylphosphine oxide photoinitiators, generally exhibit absorption spectra at wavelengths suitable for cell encapsulation, yet commercially available initiators of this class have low water solubility. Here, a water soluble lithium acylphosphinate salt is evaluated for its ability to polymerize diacrylated poly(ethylene glycol) (PEGDA) monomers rapidly into hydrogels, while maintaining high viability during direct encapsulation of cells. Through rheometric measurements, the time to reach gelation of a PEGDA solution with the phosphinate initiator is one tenth the time for that using I2959 at similar concentrations, when exposed to 365 nm light. Further, polymerization with the phosphinate initiator at 405 nm visible light exposure is achieved with low initiator concentrations and light intensities, precluded in polymerizations initiated with I2959 by its absorbance profile. When examined 24 hours after encapsulation, survival rates of human neonatal fibroblasts encapsulated in hydrogels polymerized with the phosphinate initiator exceed 95%, demonstrating the cytocompatibility of this initiating system. PMID:19783300

Extremely high-rate, uniform dissolution of alloy C-22 in anhydrous organic solutions at room temperature

DOE PAGES

Schindelholz, Eric J.; Christie, Michael A.; Allwein, Shawn P.; ...

2016-06-21

During routine pharmaceutical development and scale-up work, severe corrosion of a Hastelloy Alloy C-22 filter dryer was observed after single, short (several hours) contact with the product slurry at room temperature. Initial investigations showed that the presence of both 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and HCl was sufficient in an acetonitrile solution to cause rapid corrosion of C-22. More detailed mass loss studies showed initial corrosion rates exceeding25 mm/year that then decreased over several hours to steady state rates of 3-5 mm/year. The corrosion was highly uniform. Electrochemical measurements demonstrated that although C-22 is spontaneously passive in acetonitrile solution, the presence of HClmore » leads to the development of a transpassive region. Furthermore, DDQ is a sufficiently strong oxidizer, particularly in acidic solutions, to polarize the C-22 well into the transpassive region, leading to the observed high corrosion rates.« less

Efficient degradation of TCE in groundwater using Pd and electro-generated H2 and O2: a shift in pathway from hydrodechlorination to oxidation in the presence of ferrous ions.

PubMed

Yuan, Songhu; Mao, Xuhui; Alshawabkeh, Akram N

2012-03-20

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.

Efficient Degradation of TCE in Groundwater Using Pd and Electro-generated H2 and O2: A Shift in Pathway from Hydrodechlorination to Oxidation in the Presence of Ferrous Ions

PubMed Central

Yuan, Songhu; Mao, Xuhui; Alshawabkeh, Akram N.

2012-01-01

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H2 and O2 is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H2O2 up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radical are detected due to decomposition of H2O2, slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 μM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 μM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na2SO4, NaCl, NaNO3, NaHCO3, K2SO4, CaSO4 and MgSO4 does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppresses degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation. PMID:22315993

Formation of a cytochrome c-nitrous oxide reductase complex is obligatory for N2O reduction by Paracoccus pantotrophus.

PubMed

Rasmussen, Tim; Brittain, Thomas; Berks, Ben C; Watmough, Nicholas J; Thomson, Andrew J

2005-11-07

Nitrous oxide reductase (N2OR) catalyses the final step of bacterial denitrification, the two-electron reduction of nitrous oxide (N2O) to dinitrogen (N2). N2OR contains two metal centers; a binuclear copper center, CuA, that serves to receive electrons from soluble donors, and a tetranuclear copper-sulfide center, CuZ, at the active site. Stopped flow experiments at low ionic strengths reveal rapid electron transfer (kobs=150 s-1) between reduced horse heart (HH) cytochrome c and the CuA center in fully oxidized N2OR. When fully reduced N2OR was mixed with oxidized cytochrome c, a similar rate of electron transfer was recorded for the reverse reaction, followed by a much slower internal electron transfer from CuZ to CuA(kobs=0.1-0.4 s-1). The internal electron transfer process is likely to represent the rate-determining step in the catalytic cycle. Remarkably, in the absence of cytochrome c, fully reduced N2OR is inert towards its substrate, even though sufficient electrons are stored to initiate a single turnover. However, in the presence of reduced cytochrome c and N2O, a single turnover occurs after a lag-phase. We propose that a conformational change in N2OR is induced by its specific interaction with cytochrome c that in turn either permits electron transfer between CuA and CuZ or controls the rate of N2O decomposition at the active site.

Measurements of in situ chemical ozone (oxidant) production rates

NASA Astrophysics Data System (ADS)

Huang, Hao; Faloon, Kate; Najera, Juan; Bloss, William

2013-04-01

Tropospheric ozone is a major air pollutant, harmful to human health, agricultural crops and vegetation, the main precursor to the atmospheric oxidants which initiate the degradation of most reactive gases emitted to the atmosphere, and an important greenhouse gas in its own right. The capacity to understand and predict tropospheric ozone levels is a key goal for atmospheric science - but one which is challenging, as ozone is formed in the atmosphere from the complex oxidation of VOCs in the presence of NOx and sunlight, on a timescale such that in situ chemical processes, deposition and transport all affect ozone levels. Known uncertainties in emissions, chemistry, dynamics and deposition affect the accuracy of predictions of current and future ozone levels, and hinder development of optimal air quality policies to mitigate against ozone exposure. Recently new approaches to directly measure the local chemical ozone production rate, bypassing the many uncertainties in emissions and chemical schemes, have been developed (Cazorla & Brune, AMT 2010). Here, we describe the development of an analogous Ozone Production Rate (OPR) approach: Air is sampled into parallel reactors, within which ozone formation either occurs as in the ambient atmosphere, or is suppressed. Comparisons of ozone levels exiting a pair of such reactors determines the net chemical oxidant production rate, after correction for perturbation of the NOx-O3 photochemical steady state, and when operated under conditions such that wall effects are minimised. We report preliminary measurements of local chemical ozone production made during the UK NERC ClearfLo (Clean Air for London) campaign at an urban background location in London in January and July 2012. The OPR system was used to measure the local chemical oxidant formation rate, which is compared with observed trends in O3 and NOx and the prevailing meteorology, and with the predictions of a detailed zero-dimensional atmospheric chemistry model, constrained by observations of long-lived species.

Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

PubMed Central

Ma, Yingqun; Lin, Chuxia

2013-01-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria. PMID:23760258

Microbial Oxidation of Fe2+ and Pyrite Exposed to Flux of Micromolar H2O2 in Acidic Media

NASA Astrophysics Data System (ADS)

Ma, Yingqun; Lin, Chuxia

2013-06-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe2+ was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe2+ could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe2+ to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe2+-Fe3+ conversion rate in the solution (due to reduced microbial activity) weakened the Fe3+-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.

Microbial oxidation of Fe²⁺ and pyrite exposed to flux of micromolar H₂O₂ in acidic media.

PubMed

Ma, Yingqun; Lin, Chuxia

2013-01-01

At an initial pH of 2, while abiotic oxidation of aqueous Fe(2+) was enhanced by a flux of H2O2 at micromolar concentrations, bio-oxidation of aqueous Fe(2+) could be impeded due to oxidative stress/damage in Acidithiobacillus ferrooxidans caused by Fenton reaction-derived hydroxyl radical, particularly when the molar ratio of Fe(2+) to H2O2 was low. When pyrite cubes were intermittently exposed to fluxes of micromolar H2O2, the reduced Fe(2+)-Fe(3+) conversion rate in the solution (due to reduced microbial activity) weakened the Fe(3+)-catalyzed oxidation of cubic pyrite and added to relative importance of H2O2-driven oxidation in the corrosion of mineral surfaces for the treatments with high H2O2 doses. This had effects on reducing the build-up of a passivating coating layer on the mineral surfaces. Cell attachment to the mineral surfaces was only observed at the later stage of the experiment after the solutions became less favorable for the growth of planktonic bacteria.

Early Stage of Oxidation on Titanium Surface by Reactive Molecular Dynamics Simulation

DOE PAGES

Yang, Liang; Wang, C. Z.; Lin, Shiwei; ...

2018-01-01

Understanding of metal oxidation is very critical to corrosion control, catalysis synthesis, and advanced materials engineering. Metal oxidation is a very complex phenomenon, with many different processes which are coupled and involved from the onset of reaction. In this work, the initial stage of oxidation on titanium surface was investigated in atomic scale by molecular dynamics (MD) simulations using a reactive force field (ReaxFF). We show that oxygen transport is the dominant process during the initial oxidation. Our simulation also demonstrate that a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Titaniummore » (0001) surface and further prevented oxidation in the deeper layers. As a result, the mechanism of initial oxidation observed in this work can be also applicable to other self-limiting oxidation.« less

Computational method for analysis of polyethylene biodegradation

NASA Astrophysics Data System (ADS)

Watanabe, Masaji; Kawai, Fusako; Shibata, Masaru; Yokoyama, Shigeo; Sudate, Yasuhiro

2003-12-01

In a previous study concerning the biodegradation of polyethylene, we proposed a mathematical model based on two primary factors: the direct consumption or absorption of small molecules and the successive weight loss of large molecules due to β-oxidation. Our model is an initial value problem consisting of a differential equation whose independent variable is time. Its unknown variable represents the total weight of all the polyethylene molecules that belong to a molecular-weight class specified by a parameter. In this paper, we describe a numerical technique to introduce experimental results into analysis of our model. We first establish its mathematical foundation in order to guarantee its validity, by showing that the initial value problem associated with the differential equation has a unique solution. Our computational technique is based on a linear system of differential equations derived from the original problem. We introduce some numerical results to illustrate our technique as a practical application of the linear approximation. In particular, we show how to solve the inverse problem to determine the consumption rate and the β-oxidation rate numerically, and illustrate our numerical technique by analyzing the GPC patterns of polyethylene wax obtained before and after 5 weeks cultivation of a fungus, Aspergillus sp. AK-3. A numerical simulation based on these degradation rates confirms that the primary factors of the polyethylene biodegradation posed in modeling are indeed appropriate.

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

Yang, Liang; Wang, C. Z.; Lin, Shiwei

Understanding of metal oxidation is very critical to corrosion control, catalysis synthesis, and advanced materials engineering. Metal oxidation is a very complex phenomenon, with many different processes which are coupled and involved from the onset of reaction. In this work, the initial stage of oxidation on titanium surface was investigated in atomic scale by molecular dynamics (MD) simulations using a reactive force field (ReaxFF). We show that oxygen transport is the dominant process during the initial oxidation. Our simulation also demonstrate that a compressive stress was generated in the oxide layer which blocked the oxygen transport perpendicular to the Titaniummore » (0001) surface and further prevented oxidation in the deeper layers. As a result, the mechanism of initial oxidation observed in this work can be also applicable to other self-limiting oxidation.« less

Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4.

PubMed

Epolito, William J; Yang, Hanbae; Bottomley, Lawrence A; Pavlostathis, Spyros G

2008-12-30

The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100gL(-1) NaCl) and base (3gL(-1) Na2CO3 and 1gL(-1) NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000mgL(-1), the pseudo first-order rate constant (kobs) was 0.029+/-0.006h(-1), corresponding to a half-life of 24.2h and a ZVI surface area-normalized rate constant (kSA) of 2.9x10(-4)Lm(-2)h(-1). However, as the initial dye concentration increased, the kobs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (Vm) of 720+/-88mgL(-1)h(-1) and a half-saturation constant (K) of 1299+/-273mgL(-1). Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2-5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.

Contaminant degradation by irradiated semiconducting silver chloride particles: kinetics and modelling.

PubMed

Ma, Tian; Garg, Shikha; Miller, Christopher J; Waite, T David

2015-05-15

The kinetics and mechanism of light-mediated formic acid (HCOO(-)) degradation in the presence of semiconducting silver chloride particles are investigated in this study. Our experimental results show that visible-light irradiation of AgCl(s) results in generation of holes and electrons with the photo-generated holes and its initial oxidation product carbonate radical, oxidizing HCOO(-) to form CO2. The HCOO(-) degradation rate increases with increase in silver concentration due to increase in rate of photo-generation of holes while the increase in chloride concentration decreases the degradation rate of HCOO(-) as a result of the scavenging of holes by Cl(-), thereby resulting in decreased holes and carbonate radical concentration. The results obtained indicate that a variety of other solution conditions including dioxygen concentration, bicarbonate concentration and pH influence the availability of holes and hence the HCOO(-) degradation rate in a manner consistent with our understanding of key processes. Based on our experimental results, we have developed a kinetic model capable of predicting AgCl(s)-mediated HCOO(-) photo-degradation over a wide range of conditions. Copyright © 2014 Elsevier Inc. All rights reserved.

Removal of lindane wastes by advanced electrochemical oxidation.

PubMed

Dominguez, Carmen M; Oturan, Nihal; Romero, Arturo; Santos, Aurora; Oturan, Mehmet A

2018-07-01

The effective removal of recalcitrant organochlorine pesticides including hexachlorocyclohexane (HCH) present in a real groundwater coming from a landfill of an old lindane (γ-HCH) factory was performed by electrochemical oxidation using a BDD anode and a carbon felt cathode. Groundwater (ΣHCHs = 0.42 mg L -1 , TOC 0  = 9 mg L -1 , pH 0  = 7, conductivity = 3.7 mS cm -1 ) was treated as received, achieving the complete depletion of the HCH isomers and a mineralization degree of 90% at 4 h electrolysis at constant current of 400 mA. Initial groundwater contains high chloride concentration (Cl 0 -  = 630 mg L -1 ) that is progressively decreased due to its oxidation to different oxychlorine species: Cl 2 , HClO, ClO - , ClO 2 - ClO 3 - and ClO 4 - some of them (Cl 2 , HClO, ClO - ) playing an important role in the oxidation of organic pollutants. The oxidation rate of chloride (and its oxidized intermediates) depends on the applied current value. Although some of the species generated from them are active oxidants, the presence of inorganic salts is detrimental to the efficiency of the electrochemical process when working at current densities above 100 mA due to the high consumption of hydroxyl radicals in wasting reactions. The initial organic carbon content is not crucial for the extension of the process but high organic loads are more profitable for cost effectiveness. The addition of a supporting electrolyte to the solution could be interesting since it increases the conductivity, reducing the cell potential and therefore, decreasing the energy consumption. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electrochemical mineralization and detoxification of naphthenic acids on boron-doped diamond anodes.

PubMed

Diban, Nazely; Urtiaga, Ane

2018-01-05

Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m 2 and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m 2 of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC 50 towards Vibrio fischeri) after 2 h of treatment.

Marine microbes rapidly adapt to consume ethane, propane, and butane within the dissolved hydrocarbon plume of a natural seep

NASA Astrophysics Data System (ADS)

Mendes, Stephanie D.; Redmond, Molly C.; Voigritter, Karl; Perez, Christian; Scarlett, Rachel; Valentine, David L.

2015-03-01

Simple hydrocarbon gases containing two to four carbons (ethane, propane, and butane) are among the most abundant compounds present in petroleum reservoirs, and are introduced into the ocean through natural seepage and industrial discharge. Yet little is known about the bacterial consumption of these compounds in ocean waters. To assess the timing by which microbes metabolize these gases, we conducted a three-phase study that tested and applied a radiotracer-based method to quantify the oxidation rates of ethane, propane, and butane in fresh seawater samples. Phase 1 involved the synthesis of tritiated ethane, propane, and butane using Grignard reagents and tritiated water. Phase 2 was a systematic assessment of experimental conditions, wherein the indigenous microbial community was found to rapidly oxidize ethane, propane, and butane. Phase 3 was the application of this tritium method near the Coal Oil Point seeps, offshore California. Spatial and temporal patterns of ethane, propane, and butane oxidation down current from the hydrocarbon seeps demonstrated that >99% of these gases are metabolized within 1.3 days following initial exposure. The oxidation of ethane outpaced oxidation of propane and butane with patterns indicating the microbial community responded to these gases by rapid adaptation or growth. Methane oxidation responded the slowest in plume waters. Estimates based on the observed metabolic rates and carbon mass balance suggest that ethane, propane, and butane-consuming microorganisms may transiently account for a majority of the total microbial community in these impacted waters.

Monitoring the dynamics of syntrophic β-oxidizing bacteria during anaerobic degradation of oleic acid by quantitative PCR.

PubMed

Ziels, Ryan M; Beck, David A C; Martí, Magalí; Gough, Heidi L; Stensel, H David; Svensson, Bo H

2015-04-01

The ecophysiology of long-chain fatty acid-degrading syntrophic β-oxidizing bacteria has been poorly understood due to a lack of quantitative abundance data. Here, TaqMan quantitative PCR (qPCR) assays targeting the 16S rRNA gene of the known mesophilic syntrophic β-oxidizing bacterial genera Syntrophomonas and Syntrophus were developed and validated. Microbial community dynamics were followed using qPCR and Illumina-based high-throughput amplicon sequencing in triplicate methanogenic bioreactors subjected to five consecutive batch feedings of oleic acid. With repeated oleic acid feeding, the initial specific methane production rate significantly increased along with the relative abundances of Syntrophomonas and methanogenic archaea in the bioreactor communities. The novel qPCR assays showed that Syntrophomonas increased from 7 to 31% of the bacterial community 16S rRNA gene concentration, whereas that of Syntrophus decreased from 0.02 to less than 0.005%. High-throughput amplicon sequencing also revealed that Syntrophomonas became the dominant genus within the bioreactor microbiomes. These results suggest that increased specific mineralization rates of oleic acid were attributed to quantitative shifts within the microbial communities toward higher abundances of syntrophic β-oxidizing bacteria and methanogenic archaea. The novel qPCR assays targeting syntrophic β-oxidizing bacteria may thus serve as monitoring tools to indicate the fatty acid β-oxidization potential of anaerobic digester communities. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

40 CFR 63.10400 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2010 CFR

2010-07-01

... CATEGORIES (CONTINUED) National Emission Standards for Hospital Ethylene Oxide Sterilizers Initial Compliance... submitting an Initial Notification of Compliance Status certifying that you are venting the ethylene oxide...

Aluminum/water reactions under extreme conditions

NASA Astrophysics Data System (ADS)

Hooper, Joseph

2013-03-01

We discuss mechanisms that may control the reaction of aluminum and water under extreme conditions. We are particularly interested in the high-temperature, high-strain regime where the native oxide layer is destroyed and fresh aluminum is initially in direct contact with liquid or supercritical water. Disparate experimental data over the years have suggested rapid oxidation of aluminum is possible in such situations, but no coherent picture has emerged as to the basic oxidation mechanism or the physical processes that govern the extent of reaction. We present theoretical and computational analysis of traditional metal/water reaction mechanisms that treat diffusion through a dynamic oxide layer or reaction limited by surface kinetics. Diffusion through a fresh solid oxide layer is shown to be far too slow to have any effect on the millisecond timescale (even at high temperatures). Quantum molecular dynamics simulations of liquid Al and water surface reactions show rapid water decomposition at the interface, catalyzed by adjacent water molecules in a Grotthus-like relay mechanism. The surface reaction barriers are far too low for this to be rate-limiting in any way. With these straightforward mechanisms ruled out, we investigate two more complex possibilities for the rate-limiting factor; first, we explore the possibility that newly formed oxide remains a metastable liquid well below its freezing point, allowing for diffusion-limited reactions through the oxide shell but on a much faster timescale. The extent of reaction would then be controlled by the solidification kinetics of alumina. Second, we discuss preliminary analysis on surface erosion and turbulent mixing, which may play a prominent role during hypervelocity penetration of solid aluminum projectiles into water.

Relation between film character and wafer alignment: critical alignment issues on HV device for VLSI manufacturing

NASA Astrophysics Data System (ADS)

Lo, Yi-Chuan; Lee, Chih-Hsiung; Lin, Hsun-Peng; Peng, Chiou-Shian

1998-06-01

Several continuous splits for wafer alignment target topography conditions to improve epitaxy film alignment were applied. The alignment evaluation among former layer pad oxide thickness (250 angstrom - 500 angstrom), drive oxide thickness (6000 angstrom - 10000 angstrom), nitride film thickness (600 angstrom - 1500 angstrom), initial oxide etch (fully wet etch, fully dry etch and dry plus wet etch) will be split to this experiment. Also various epitaxy deposition recipe such as: epitaxy source (SiHCl2 or SiCHCl3) and growth rate (1.3 micrometer/min approximately 2.0 micrometer/min) will be used to optimize the process window for alignment issue. All the reflectance signal and cross section photography of alignment target during NIKON stepper alignment process will be examined. Experimental results show epitaxy recipe plays an important role to wafer alignment. Low growth rate with good performance conformity epitaxy lead to alignment target avoid washout, pattern shift and distortion. All the results (signal monitor and film character) combined with NIKON's stepper standard laser scanning alignment system will be discussed in this paper.

Effect of Growth Parameters on SnO2 Nanowires Growth by Electron Beam Evaporation Method

NASA Astrophysics Data System (ADS)

Rakesh Kumar, R.; Manjula, Y.; Narasimha Rao, K.

2018-02-01

Tin oxide (SnO2) nanowires were synthesized via catalyst assisted VLS growth mechanism by the electron beam evaporation method at a growth temperature of 450 °C. The effects of growth parameters such as evaporation rate of Tin, catalyst film thickness, and different types of substrates on the growth of SnO2 nanowires were studied. Nanowires (NWs) growth was completely seized at higher tin evaporation rates due to the inability of the catalyst particle to initiate the NWs growth. Nanowires diameters were able to tune with catalyst film thickness. Nanowires growth was completely absent at higher catalyst film thickness due to agglomeration of the catalyst film. Optimum growth parameters for SnO2 NWs were presented. Nanocomposites such as Zinc oxide - SnO2, Graphene oxide sheets- SnO2 and Graphene nanosheets-SnO2 were able to synthesize at a lower substrate temperature of 450 °C. These nanocompsoites will be useful in enhancing the capacity of Li-ion batteries, the gas sensing response and also useful in increasing the photo catalytic activity.

The Heterogeneous Oxidation of Organic Droplets -Temperature and Physical Phase Effects

NASA Astrophysics Data System (ADS)

Hung, H.; Tang, C.; Lin, L.

2008-12-01

The heterogeneous reactions of oleic acid droplets with ozone are studied at different temperatures to imitating the atmospheric condition. The reactions are monitored concomitantly by using attenuated total reflectance Fourier Transform infrared spectroscopy (ATR-FT-IR) for the organic species and UV-VIS spectrometry for the ozone concentration, in order to investigate reaction rate discrepancies reported in literature as well as the oxidation mechanism, temperature and physical phase effects. The less and semi- volatile products are identified and resolved by a liquid chromatography and a gas chromatography mass spectrometer, respectively. The identified products are predominantly composed by nananoic acid and azelaic acid and might be due to propagation reactions possibly initiated by a secondary reaction such as the stabilized Criegee intermediates reacting with oleic acid. For temperature effect, the oxidation rate decreases with temperature when the oleic acid droplets are in the same physical phases. As oleic acid turns into the solid phase, the oxidation mechanism is observed to be different from the liquid phase. Furthermore, the concentration of ozone was monitored to examine the kinetics of the oxidation reaction. The integrated ozone profile recorded by UV-VIS spectrometry shows that the consumed ozone represents only approximately 12% of total oleic acid for the solid cases at 4°C in contrast to 30% for the liquid cases at 25°C, and hence confirmed the existence of secondary reactions.

Phenyl-alpha-tert-butyl nitrone reverses mitochondrial decay in acute Chagas' disease.

PubMed

Wen, Jian-Jun; Bhatia, Vandanajay; Popov, Vsevolod L; Garg, Nisha Jain

2006-12-01

In this study, we investigated the mechanism(s) of mitochondrial functional decline in acute Chagas' disease. Our data show a substantial decline in respiratory complex activities (39 to 58%) and ATP (38%) content in Trypanosoma cruzi-infected murine hearts compared with normal controls. These metabolic alterations were associated with an approximately fivefold increase in mitochondrial reactive oxygen species production rate, substantial oxidative insult of mitochondrial membranes and respiratory complex subunits, and >60% inhibition of mtDNA-encoded transcripts for respiratory complex subunits in infected myocardium. The antioxidant phenyl-alpha-tert-butyl nitrone (PBN) arrested the oxidative damage-mediated loss in mitochondrial membrane integrity, preserved redox potential-coupled mitochondrial gene expression, and improved respiratory complex activities (47 to 95% increase) and cardiac ATP level (>or=40% increase) in infected myocardium. Importantly, PBN resulted twofold decline in mitochondrial reactive oxygen species production rate in infected myocardium. Taken together, our data demonstrate the pathological significance of oxidative stress in metabolic decay and energy homeostasis in acute chagasic myocarditis and further suggest that oxidative injuries affecting mitochondrial integrity-dependent expression and activity of the respiratory complexes initiate a feedback cycle of electron transport chain inefficiency, increased reactive oxygen species production, and energy homeostasis in acute chagasic hearts. PBN and other mitochondria-targeted antioxidants may be useful in altering mitochondrial decay and oxidative pathology in Chagas' disease.

Destruction of OPA from munitions demilitarization in supercritical water oxidation: kinetics of total organic carbon disappearance.

PubMed

Veriansyah, Bambang; Kim, Jae-Duck; Lee, Jong-Chol; Hong, Deasik

2006-01-01

The destruction of OPA from munitions demilitarization has been accomplished in supercritical water oxidation (SCWO) with oxygen as oxidant in an isothermal continuous-flow reactor. The experiments were conducted at a temperature of 689-887 K and a fixed pressure of 25 MPa, with a residence time that ranged from 7 s to 14 s. The destruction efficiency was measured by total organic carbon (TOC) conversion. At the reaction condition, the initial TOC concentrations of OPA were varied from 1.41 mmol/L to 19.57 mmol/L and the oxygen concentrations were varied from 15.03 mmol/L to 81.85 mmol/L. Experimental data showed that all the TOC conversions were >80% under the above experimental conditions. The kinetics of TOC disappearance, which is essential for the design, optimization, and control of reliable commercial SCWO reactor was developed by taking into account the dependence of the oxidant and TOC concentration on the reaction rate. A global TOC disappearance rates expression was regressed from the data of 38 experiments, to a 95% confidence level. The resulting activation energy was determined to be 44.01 +/- 1.52 kJ/mol, and the pre-exponential factor was (1.67 +/- 0.45) x 10(2) L(1.14) mmol(-0.14) s(-1). The reaction orders for the TOC and the oxidant were 0.98 +/- 0.01 and 0.16 +/- 0.02, respectively.

Kinetics of CO2 Reduction over Nonstoichiometric Ceria

PubMed Central

2015-01-01

The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

Degradation kinetics and transformation products of chlorophene by aqueous permanganate.

PubMed

Xu, Xinxin; Chen, Jing; Wang, Siyuan; Ge, Jiali; Qu, Ruijuan; Feng, Mingbao; Sharma, Virender K; Wang, Zunyao

2018-07-01

This paper evaluates the oxidation of an antibacterial agent, chlorophene (4-chloro-2-(phenylmethyl)phenol, CP), by permanganate (Mn(VII)) in water. Second-order rate constant (k) for the reaction between Mn(VII) and CP was measured as (2.05 ± 0.05) × 10 1  M -1  s -1 at pH 7.0 for an initial CP concentration of 20.0 μM and Mn(VII) concentration of 60.0 μM. The value of k decreased with increasing pH in the pH range of 5.0-7.0, and then increased with an increase in solution pH from 7.0 to 10.0. The presence of MnO 2 and Fe 3+ in water generally enhanced the removal of CP, while the effect of humic acid was not obvious. Fourteen oxidation products of CP were identified by an electrospray time-of-flight mass spectrometer, and direct oxidation, ring-opening, and decarboxylation were mainly observed in the reaction process. The initial reaction sites of CP by Mn(VII) oxidation were rationalized by density functional theory calculations. Toxicity changes of the reaction solutions were assessed by the luminescent bacteria P. phosphoreum, and the intermediate products posed a relatively low ecological risk during the degradation process. The efficient removal of CP in secondary clarifier effluent and river water demonstrated the potential application of this Mn(VII) oxidation method in water treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Secondary organic aerosol formation from isoprene photooxidation

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

2005-12-01

We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

Catalytic oxidation of gaseous reduced sulfur compounds using coal fly ash.

PubMed

Kastner, James R; Das, K C; Melear, Nathan D

2002-11-11

Activated carbon has been shown to oxidize reduced sulfur compounds, but in many cases it is too costly for large-scale environmental remediation applications. Alternatively, we theorized that coal fly ash, given its high metal content and the presence of carbon could act as an inexpensive catalytic oxidizer of reduced sulfur compounds for "odor" removal. Initial results indicate that coal fly ash can catalyze the oxidization of H(2)S and ethanethiol, but not dimethyl sulfide (DMS) and dimethyl disulfide (DMDS) at room temperature. In batch reactor systems, initial concentrations of 100-500 ppmv H(2)S or ethanethiol were reduced to 0-2 ppmv within 1-2 and 6-8 min, respectively. This was contrary to control systems without ash in which concentrations remained constant. Diethyl disulfide was formed from ethanethiol substantiating the claim that catalytic oxidation occurred. The presence of water increased the rate of adsorption/reaction of both H(2)S and ethanethiol for the room temperature reactions (23-25 degrees C). Additionally, in a continuous flow packed bed reactor, a gaseous stream containing an inlet H(2)S concentration of 400-500 ppmv was reduced to 200 ppmv at a 4.6s residence time. The removal efficiency remained at 50% for approximately 4.6h or 3500 reactor volumes. These results demonstrate the potential of using coal fly ash in reactors for removal of H(2)S and other reduced sulfur compounds.

Evolution of the chemistry of Fe bearing waters during CO2 degassing

USGS Publications Warehouse

Geroni, J.N.; Cravotta, C.A.; Sapsford, D.J.

2012-01-01

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO2 can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO2 during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO2 initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO2 by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO2 led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO2 removal at the flow rates measured.

In Situ Atomic Scale Visualization Of Surface Kinetics Driven Dynamics Of Oxide Growth On A Ni–Cr Surface

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

Luo, Langli; Zou, Lianfeng; Schreiber, Daniel K.

2016-01-20

We report in situ atomic-scale visualization of the dynamical three-dimensional (3D) growth of NiO during initial oxidation of Ni-10at%Cr using environmental transmission electron microscopy (ETEM). Despite the thermodynamic preference for Cr2O3 formation, cubic NiO oxides nucleated and grew epitaxially as the dominating oxide phase on the Ni-Cr (100) surface during initial oxidation. The growth of NiO islands proceeds through step-by-step adatom mechanism in 3D, which is sustained by surface diffusion of Ni and O atoms. Although the shapes of oxide islands are controlled by strain energy between oxide and alloy substrate, local surface kinetic variations can lead to the changemore » of surface planes of oxide islands. These results demonstrate that surface diffusion dominates initial oxidation of Ni-Cr in these test conditions.« less

Evaluating Metabolite-Related DNA Oxidation and Adduct Damage from Aryl Amines Using a Microfluidic ECL Array.

PubMed

Bist, Itti; Bhakta, Snehasis; Jiang, Di; Keyes, Tia E; Martin, Aaron; Forster, Robert J; Rusling, James F

2017-11-21

Damage to DNA from the metabolites of drugs and pollutants constitutes a major human toxicity pathway known as genotoxicity. Metabolites can react with metal ions and NADPH to oxidize DNA or participate in S N 2 reactions to form covalently linked adducts with DNA bases. Guanines are the main DNA oxidation sites, and 8-oxo-7,8-dihydro-2-deoxyguanosine (8-oxodG) is the initial product. Here we describe a novel electrochemiluminescent (ECL) microwell array that produces metabolites from test compounds and measures relative rates of DNA oxidation and DNA adduct damage. In this new array, films of DNA, metabolic enzymes, and an ECL metallopolymer or complex assembled in microwells on a pyrolytic graphite wafer are housed in dual microfluidic chambers. As reactant solution passes over the wells, metabolites form and can react with DNA in the films to form DNA adducts. These adducts are detected by ECL from a RuPVP polymer that uses DNA as a coreactant. Aryl amines also combine with Cu 2+ and NADPH to form reactive oxygen species (ROS) that oxidize DNA. The resulting 8-oxodG was detected selectively by ECL-generating bis(2,2'-bipyridine)-(4-(1,10-phenanthrolin-6-yl)-benzoic acid)Os(II). DNA/enzyme films on magnetic beads were oxidized similarly, and 8-oxodG determined by LC/MS/MS enabled array standardization. The array limit of detection for oxidation was 720 8-oxodG per 10 6 nucleobases. For a series of aryl amines, metabolite-generated DNA oxidation and adduct formation turnover rates from the array correlated very well with rodent 1/TD 50 and Comet assay results.

Electrocatalytic Water Oxidation by a Homogeneous Copper Catalyst Disfavors Single-Site Mechanisms.

PubMed

Koepke, Sara J; Light, Kenneth M; VanNatta, Peter E; Wiley, Keaton M; Kieber-Emmons, Matthew T

2017-06-28

Deployment of solar fuels derived from water requires robust oxygen-evolving catalysts made from earth abundant materials. Copper has recently received much attention in this regard. Mechanistic parallels between Cu and single-site Ru/Ir/Mn water oxidation catalysts, including intermediacy of terminal Cu oxo/oxyl species, are prevalent in the literature; however, intermediacy of late transition metal oxo species would be remarkable given the high d-electron count would fill antibonding orbitals, making these species high in energy. This may suggest alternate pathways are at work in copper-based water oxidation. This report characterizes a dinuclear copper water oxidation catalyst, {[(L)Cu(II)] 2 -(μ-OH) 2 }(OTf) 2 (L = Me 2 TMPA = bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine) in which water oxidation proceeds with high Faradaic efficiency (>90%) and moderate rates (33 s -1 at ∼1 V overpotential, pH 12.5). A large kinetic isotope effect (k H /k D = 20) suggests proton coupled electron transfer in the initial oxidation as the rate-determining step. This species partially dissociates in aqueous solution at pH 12.5 to generate a mononuclear {[(L)Cu(II)(OH)]} + adduct (K eq = 0.0041). Calculations that reproduce the experimental findings reveal that oxidation of either the mononuclear or dinuclear species results in a common dinuclear intermediate, {[LCu(III)] 2 -(μ-O) 2 } 2+ , which avoids formation of terminal Cu(IV)═O/Cu(III)-O • intermediates. Calculations further reveal that both intermolecular water nucleophilic attack and redox isomerization of {[LCu(III)] 2 -(μ-O) 2 } 2+ are energetically accessible pathways for O-O bond formation. The consequences of these findings are discussed in relation to differences in water oxidation pathways between Cu catalysts and catalysts based on Ru, Ir, and Mn.

Oxidation behavior of multiwall carbon nanotubes with different diameters and morphology

NASA Astrophysics Data System (ADS)

Mazov, Ilya; Kuznetsov, Vladimir L.; Simonova, Irina A.; Stadnichenko, Andrey I.; Ishchenko, Arkady V.; Romanenko, Anatoly I.; Tkachev, Evgeniy N.; Anikeeva, Olga B.

2012-06-01

Multiwall carbon nanotubes (MWNT) with three medium diameters (20-22, 9-13, and 6-8 nm) and different morphology were chemically oxidized using concentrated nitric acid, mixture of nitric and sulfuric acids ("mélange" solution) and mixture of sulfuric acid and hydrogen peroxide ("piranha" solution). Influence of MWNT type and structure as well as type of oxidizer on the surface composition and structure of nanotubes after oxidation was investigated. Acid-base titration, X-ray photoelectron spectroscopy and thermal gravimetric analysis were used for quantitative and qualitative investigation of surface group composition of initial and oxidized nanotubes. Amount of oxygen-containing groups on the surface of oxidized MWNT depends on the type of initial MWNT. It was found that ratio of different oxygen containing groups is less dependent on the type of oxidizer. Electrophysical properties of initial and oxidized nanotubes were investigated in temperature range 4-293 K and main types of electrical conductivity were determined. It was shown that oxidation results in decrease in electrical conductivity of all samples with simultaneous change in the conductivity mechanism. Dispersive behavior of initial and oxidized nanotubes in different commonly used solvents was investigated. It was shown that oxidation leads to the improvement of sedimentation stability of MWNT in polar solvents.

The FA pathway counteracts oxidative stress through selective protection of antioxidant defense gene promoters.

PubMed

Du, Wei; Rani, Reena; Sipple, Jared; Schick, Jonathan; Myers, Kasiani C; Mehta, Parinda; Andreassen, Paul R; Davies, Stella M; Pang, Qishen

2012-05-03

Oxidative stress has been implicated in the pathogenesis of many human diseases including Fanconi anemia (FA), a genetic disorder associated with BM failure and cancer. Here we show that major antioxidant defense genes are down-regulated in FA patients, and that gene down-regulation is selectively associated with increased oxidative DNA damage in the promoters of the antioxidant defense genes. Assessment of promoter activity and DNA damage repair kinetics shows that increased initial damage, rather than a reduced repair rate, contributes to the augmented oxidative DNA damage. Mechanistically, FA proteins act in concert with the chromatin-remodeling factor BRG1 to protect the promoters of antioxidant defense genes from oxidative damage. Specifically, BRG1 binds to the promoters of the antioxidant defense genes at steady state. On challenge with oxidative stress, FA proteins are recruited to promoter DNA, which correlates with significant increase in the binding of BRG1 within promoter regions. In addition, oxidative stress-induced FANCD2 ubiquitination is required for the formation of a FA-BRG1-promoter complex. Taken together, these data identify a role for the FA pathway in cellular antioxidant defense.

Oxidation and gum formation in diesel fuels. Interim report No. 2, 10 September 1984-30 April 1985

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

Mayo, F.R.

1985-05-03

Rates of oxygen absorption (R sub O) and gum formation (R sub g) are now related by the R sub g/ R/sub 0/ ratio, the reciprocal of the ratio previously used. The change was made because when the oxygen content of the gum is known, the R sub g/ R/sub 0/ ratio is proportional to the fraction of oxygen absorbed that appears in the gum. Oxidations of tetralin (TET) and 2-ethyl-naphthalene (EtN) at 130 C are initially fast but the rates decrease regularly. The oxidation of n-dodecane (DOD) is clearly autocatalytic; it requires the most oxygen to produce a milligrammore » of gum while EtN, among the pure hydrocarbons, requires the least. Rates of oxygen absorption for DOD at 100 C appear to be erratic. Part of the problem is autocatalysis; part is near exhaustion of oxygen. The best results are those for K92A and K92C. R/sub 0/ without t-Bu2O2 is autocatalytic. Trends in oxidations of Fuels 14 and 14A, which are different at 130 C, are not yet clear at 100, and 60 C. The important points in the above discussion are: The oxidation of DOD is autocatalytic; oxidations of TET, EtN, and Fuel 14 are self-retarding. In our oxidations of Fuel 14 with shaking, all the deposits at 100 and 130 C appear as films on glass; no deposits have yet been obtained at lower temperatures. The ratio R sub g/ R/sub 0/, still appears to be essentially constant for any fuel at a single temperature, even with large differences in R/sub 0/ from addition of t-Bu202. Thus, gum can be accumulated relatively rapidly for experimental purposes. We are accumulating new data at 43 and 60 C. These findings should assist materially in our efforts to understand and devise a test for fuel stability.« less

Multiple laser pulse ignition method and apparatus

DOEpatents

Early, J.W.

1998-05-26

Two or more laser light pulses with certain differing temporal lengths and peak pulse powers can be employed sequentially to regulate the rate and duration of laser energy delivery to fuel mixtures, thereby improving fuel ignition performance over a wide range of fuel parameters such as fuel/oxidizer ratios, fuel droplet size, number density and velocity within a fuel aerosol, and initial fuel temperatures. 18 figs.

X-ray photoelectron spectroscopic and morphologic studies of Ru nanoparticles deposited onto highly oriented pyrolytic graphite

NASA Astrophysics Data System (ADS)

Bavand, R.; Yelon, A.; Sacher, E.

2015-11-01

Ruthenium nanoparticles (Ru NPs) function as effective catalysts in specific reactions, such as methanation and Fischer-Tropsch syntheses. It is our purpose to physicochemically characterize their surfaces, at which catalysis occurs, by surface-sensitive X-ray photoelectron spectroscopy (XPS), using the symmetric peak component anaylsis technique developed in our laboratory to reveal previously hidden components. Ru NPs were deposited by evaporation (0.25-1.5 nm nominal deposition range) onto highly oriented pyrolytic graphite (HOPG). In addition to their surfaces being characterized by XPS, an indication of morphology was obtained from transmission electron microscopy (TEM). Our use of symmetric peak component XPS analysis has revealed detailed information on a previously unidentified surface oxide initially formed, as well as on the valence electronic structure and its variation with NP size, information that is of potential importance in the use of these NPs in catalysis. Each of the several Ru core XPS spectra characterized (3d, 3p and 3s) was found to be composed of three symmetric components. Together with two metal oxide O1s components, these give evidence of a rather complex, previously unidentified oxide that is initially formed. The Ru valence band (4d and 5s) spectra clearly demonstrate a loss of metallicity, a simultaneous increase of the Kubo gap, and an abrupt transfer in valence electron density from the 4d to the 5s orbitals (known as electron spill-over), as the NP size decreases below 0.5 nm. TEM photomicrographs, as a function of deposition rate, show that, at a rate that gives insufficient time for the NP condensation energy to dissipate, the initially well-separated NPs are capable of diffusing laterally and aggregating. This indicates weak NP bonding to the HOPG substrate. Carbide is formed, at both high and low deposition rates, at Ru deposition thicknesses greater than 0.25 nm, its formation explained by Ru NPs reacting with residual hydrocarbon vapor, under the influence of the heat of condensation released on Ru deposition, and not by Ru reacting with the HOPG substrate.

High rate dry etching of InGaZnO by BCl3/O2 plasma

NASA Astrophysics Data System (ADS)

Park, Wanjae; Whang, Ki-Woong; Gwang Yoon, Young; Hwan Kim, Jeong; Rha, Sang-Ho; Seong Hwang, Cheol

2011-08-01

This paper reports the results of the high-rate dry etching of indium gallium zinc oxide (IGZO) at room temperature using BCl3/O2 plasma. We achieved an etch rate of 250 nm/min. We inferred from the x-ray photoelectron spectroscopy analysis that BOx or BOClx radicals generated from BCl3/O2 plasma cause the etching of the IGZO material. O2 initiates the etching of IGZO, and Ar removes nonvolatile byproducts from the surface during the etching process. Consequently, a smooth etched surface results when these gases are added to the etch gas.

Investigation of OxProduction Rates in the Mexico City Metropolitan Area during MILAGRO

NASA Astrophysics Data System (ADS)

Dusanter, S.; Molina, L. T.; Stevens, P. S.

2009-12-01

Understanding the oxidative capacity of the atmosphere and the formation of secondary pollutants are important issues in atmospheric chemistry. For instance, the photochemical production of tropospheric ozone (O3) is of particular interest due to its detrimental effects on both human health and agricultural ecosystems. A detailed characterization of tropospheric O3 production rates will help in the development of effective control strategies. The 2006 Mexico City Metropolitan Area field campaign (MCMA-2006) was one of four components of MILAGRO (Megacity Initiative: Local And Global Research Observations) intended to collect information on the impact of megacity emissions on local, regional and global scales. In this presentation, rates of production of Ox (Ox = O3 + NO2) species during MCMA-2006 at the supersite T0 (Instituto Mexicano del Petroleo) will be presented using different approaches based on measured and modeled concentrations of ROx (OH + HO2 + RO2) radicals. In addition, we will examine both the reactivity of OH and the contribution of specific peroxy radicals to the oxidation rate of NO to estimate the contribution of groups of VOCs (alkanes, alkenes, aromatics, oxygenated and biogenic VOCs) to the total production rate of Ox species.

Kinetic phase evolution of spinel cobalt oxide during lithiation

DOE PAGES

Li, Jing; He, Kai; Meng, Qingping; ...

2016-09-15

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

Kinetic phase evolution of spinel cobalt oxide during lithiation

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

Li, Jing; He, Kai; Meng, Qingping

Spinel cobalt oxide has been proposed to undergo a multiple-step reaction during the electrochemical lithiation process. Understanding the kinetics of the lithiation process in this compound is crucial to optimize its performance and cyclability. In this work, we have utilized a low-angle annular dark-field scanning transmission electron microscopy method to visualize the dynamic reaction process in real time and study the reaction kinetics at different rates. We show that the particles undergo a two-step reaction at the single-particle level, which includes an initial intercalation reaction followed by a conversion reaction. At low rates, the conversion reaction starts after the intercalationmore » reaction has fully finished, consistent with the prediction of density functional theoretical calculations. At high rates, the intercalation reaction is overwhelmed by the subsequently nucleated conversion reaction, and the reaction speeds of both the intercalation and conversion reactions are increased. Phase-field simulations show the crucial role of surface diffusion rates of lithium ions in controlling this process. Furthermore, this work provides microscopic insights into the reaction dynamics in non-equilibrium conditions and highlights the effect of lithium diffusion rates on the overall reaction homogeneity as well as the performance.« less

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

NASA Astrophysics Data System (ADS)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.

Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: coupling of primary amines and cyanation of tertiary amines.

PubMed

Liu, Lianghui; Wang, Zikuan; Fu, Xuefeng; Yan, Chun-Hua

2012-11-16

In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide range of "green" oxidation chemistry.

Development of improved high temperature coatings for IN-792 + HF

NASA Technical Reports Server (NTRS)

Profant, D. D.; Naik, S. K.

1981-01-01

The development for t-55 l712 engine of high temperature for integral turbine nozzles with improved thermal fatigue resistance without sacrificing oxidation/corrosion protection is discussed. The program evaluated to coating systems which comprised one baseline plasma spray coating (12% Al-NiCoCrALY), three aluminide coatings including the baseline aluminide (701), two CoNiCrAly (6% Al) + aluminide systems and four NiCoCrY + aluminide coating were evaluated. The two-step coating processes were investigated since it offered the advantage of tailoring the composition as well as properly coating surfaces of an integral or segmented nozzle. Cyclic burner rig thermal fatigue and oxidation/corrosion tests were used to evaluate the candidate coating systems. The plasma sprayed 12% Al-NiCoCrAlY was rated the best coating in thermal fatigue resistance and outperformed all coatings by a factor between 1.4 to 2.5 in cycles to crack initiation. However, this coatings is not applicable to integral or segmented nozzles due to the line of sight limitation of the plasma spray process. The 6% Al-CoNiCrAlY + Mod. 701 aluminide (32 w/o Al) was rated the best coating in oxidation/corrosion resistance and was rated the second best in thermal fatigue resistance.

Strain-Rate-Free Diffusion Flames: Initiation, Properties, and Quenching

NASA Technical Reports Server (NTRS)

Fendell, Francis; Rungaldier, Harald; Gokoglu, Suleyman; Schultz, Donald

1997-01-01

For about a half century, the stabilization of a steady planar deflagration on a heat-sink-type flat-flame burner has been of extraordinary service for the theoretical modeling and diagnostic probing of combusting gaseous mixtures. However, most engineering devices and most unwanted fire involve the burning of initially unmixed reactants. The most vigorous burning of initially separated gaseous fuel and oxidizer is the diffusion flame. In this useful idealization (limiting case), the reactants are converted to product at a mathematically thin interface, so no interpenetration of fuel and oxidizer occurs. This limit is of practical importance because it often characterizes the condition of optimal performance (and sometimes environmentally objectionable operation) of a combustor. A steady planar diffusion flame is most closely approached in the laboratory in the counterflow apparatus. The utility of this simple-strain-rate flow for the modeling and probing of diffusion flames was noted by Pandya and Weinberg 35 years ago, though only in the last decade or so has its use become internationally common place. However, typically, as the strain rate a is reduced below about 20 cm(exp -1), and the diffusion-flame limit (reaction rate much faster than the flow rate) is approached, the burning is observed to become unstable in earth gravity. The advantageous steady planar flow is not available in the diffusion-flame limit in earth gravity. This is unfortunate because the typical spatial scale in a counterflow is (k/a)(sup 1/2), where k denotes a characteristic diffusion coefficient; thus, the length scale becomes large, and the reacting flow is particularly amenable to diagnostic probing, as the diffusion-flame limit is approached. The disruption of planar symmetry is owing the fact that, as the strain rate a decreases, the residence time (l/a) of the throughput in the counterflow burner increases. Observationally, when the residence time exceeds about 50 msec, the inevitably present convective (Rayleigh-Benard) instabilities, associated with hot-under-cold (flame-under-fresh-reactant) stratification of fluid in a gravitational field, have time to grow to finite amplitude during transit of the burner.

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

NASA Astrophysics Data System (ADS)

Lengke, Maggy F.; Tempel, Regina N.

2005-01-01

Arsenic sulfide (AsS (am), As 2S 3 (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH˜2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As 2S 3 (am), orpiment, AsS (am), and realgar, respectively. Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ˜1.14 to 13 times and that pH values decrease by ˜0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase. Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As 2S 3 (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH˜8 and temperature 25 to 40°C, and pyrite activation energies are ˜52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As 2S 3 (am). Low activation energies of As 2S 3 (am) indicate that diffusion may be rate controlling. Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO 3) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.

Effect of age on kinetics of nitric oxide release in rat aorta and pulmonary artery.

PubMed Central

Tschudi, M R; Barton, M; Bersinger, N A; Moreau, P; Cosentino, F; Noll, G; Malinski, T; Lüscher, T F

1996-01-01

Aging is an important determinant of vascular disease. Endothelium-derived nitric oxide (NO) is protective as a vasodilator and inhibitor of platelet function. This study was designed to directly measure effects of prolonged aging on endotheliai NO release in isolated blood vessels and to delineate differences between the systemic and pulmonary circulation. Aortas and pulmonary arteries from 5-6-mo-old (young), 18-19-mo-old (middle-aged), and 32-33-mo-old (old) normotensive female rats were used. Blood pressure and plasma estradiol-17beta (E2) remained unchanged. In isolated blood vessels, NO release was induced by the receptor-independent agonist calcium ionophore A23187 (10 micromol/liter) and measured in situ on the endothelial surface of vessels using a porphyrinic microsensor. In vessels suspended in organ chambers isometric tension was recorded. In the aorta, the initial rate of NO release and peak NO concentration were reduced in middle-aged and old rats (P < 0.0006 vs. young rats, n = 6). Furthermore, endothelium-dependent relaxations to calcium ionophore and acetylcholine (both 10(-10) - 10(-5) mol/liter) were also reduced in aortas from old as compared with young rats (n = 6, P < 0.05). The initial rate of NO release and peak NO concentration significantly correlated with maximal relaxation to calcium ionophore A23187 (correlation coefficients r - 0.916, P < 0.0018 and r = 0.961, P < 0.0001, respectively, n = 7). In pulmonary arteries, however, the initial rate of NO release as well as peak NO concentration did not decrease with age (n = 6 for each age group, NS). In both blood vessels, the NO release was unaffected by superoxide dismutase in all age groups (n = 6, NS). Thus, aging specifically reduces initial rate and peak concentrations of endothelial NO release from aorta but not pulmonary artery indicating reduced NO production. As arterial pressure did not change with aging, the chronic exposure of the aorta to higher pressure and/or pulsatility than in the pulmonary artery may be the cause. This appears important as NO plays a protective role by preventing vasoconstriction, thrombosis and atherosclerosis. PMID:8770860

Mach 1 oxidation of thoriated nickel chromium at 1204 C /2200 F/.

NASA Technical Reports Server (NTRS)

Lowell, C. E.; Sanders, W. A.

1972-01-01

Electropolished and ground samples of TD-NiCr were exposed to a 1-atm, Mach 1 gas stream at 1204 C for times up to 50 hr. The samples were subjected to both cyclic and isothermal exposure. Weight change, metal loss, X-ray diffraction, metallographic, and electron microprobe analyses were performed. Neither surface preparation nor cyclic-against-isothermal-exposure conditions had a strong effect on the oxidation behavior of the alloy. Initially, a Cr2O3 layer was formed whose volatilization resulted in a very rapid loss of metal - more than 40 microns in the first hour. At about 1 hr, the Cr2O3 layer broke down and NiO began to cover the surface. By 5 hr, the NiO had covered the surface and the rate of loss slowed. The rate-controlling step was diffusion of Cr through NiO.

Effect of ozonation on the reactivity of lignocellulose substrates in enzymatic hydrolyses to sugars

NASA Astrophysics Data System (ADS)

Ben'ko, E. M.; Manisova, O. R.; Lunin, V. V.

2013-07-01

The efficiency of pre-treatment of aspen wood with ozone for subsequent enzymatic hydrolysis into sugars is determined by the amount of absorbed ozone. The ozone absorption rate depended on the water content in the sample being ozonized and was maximum at a relative humidity of wood of ˜40%. As a result of ozone pre-treatment, the initial rate of the enzymatic hydrolysis of wood under the action of a cellulase complex increased eightfold, and the maximum yield of sugars increased tenfold depending on the ozone dose. The ozonation at ozone doses of more than 3 mol/PPU (phenylpropane structural unit of lignin) led to a decrease in the yield of sugars because of the oxidative destruction of cellulose and hemicellulose. The alkaline ozonation in 2 and 12% NaOH was inefficient because of the accompanying oxidation of carbohydrates and considerably decreased the yield of sugars.

An analysis of pump cavitation damage. [Space Shuttle main engine high pressure oxidizer turbopump

NASA Technical Reports Server (NTRS)

Brophy, M. C.; Stinebring, D. R.; Billet, M. L.

1985-01-01

The cavitation assessment for the space shuttle main engine high pressure oxidizer turbopump is documented. A model of the flow through the pump was developed. Initially, a computational procedure was used to analyze the flow through the inlet casing including the prediction of wakes downstream of the casing vanes. From these flow calculations, cavitation patterns on the inducer blades were approximated and the damage rate estimated. The model correlates the heavy damage on the housing and over the inducer with unsteady blade surface cavitation. The unsteady blade surface cavitation is due to the large incidence changes caused by the wakes of the upstream vanes. Very high cavitation damage rates are associated with this type of cavitation. Design recommendations for reducing the unsteady cavitation include removing the set of vanes closest to the inducer and modifying the remaining vanes.

A study of pump cavitation damage. [space shuttle main engine high pressure oxidizer turbopump

NASA Technical Reports Server (NTRS)

Brophy, M. C.; Stinebring, D. R.; Billet, M. L.

1983-01-01

The cavitation assessment for the space shuttle main engine high pressure oxidizer turbopump is documented. A model of the flow through the pump was developed. Initially, a computational procedure was used to analyze the flow through the inlet casing including the prediction of wakes downstream of the casing vanes. From these flow calculations, cavitation patterns on the inducer blades were approximated and the damage rate estimated. The model correlates the heavy damage on the housing and over the inducer with unsteady blade surface cavitation. The unsteady blade surface cavitation is due to the large incidence changes caused by the wakes of the upstream vanes. Very high cavitation damage rates are associated with this type of cavitation. Design recommendations for reducing the unsteady cavitation include removing the set of vanes closest to the inducer and modifying the remaining vanes.

Oxidation of benzoic acid by heat-activated persulfate: Effect of temperature on transformation pathway and product distribution.

PubMed

Zrinyi, Nick; Pham, Anh Le-Tuan

2017-09-01

Heat activates persulfate (S 2 O 8 2- ) into sulfate radical (SO 4 - ), a powerful oxidant capable of transforming a wide variety of contaminants. Previous studies have shown that an increase in temperature accelerates the rates of persulfate activation and contaminant transformation. However, few studies have considered the effect of temperature on contaminant transformation pathway. The objective of this study was to determine how temperature (T = 22-70 °C) influences the activation of persulfate, the transformation of benzoic acid (i.e., a model compound), and the distribution of benzoic acid oxidation products. The time-concentration profiles of the products suggest that benzoic acid was transformed via decarboxylation and hydroxylation mechanisms, with the former becoming increasingly important at elevated temperatures. The pathway through which the products were further oxidized was also influenced by the temperature of persulfate activation. Our findings suggest that the role of temperature in the persulfate-based treatment systems is not limited only to controlling the rates of sulfate and hydroxyl radical generation. The ability of sulfate radical to initiate decarboxylation reactions and, more broadly, fragmentation reactions, as well as the effect of temperature on these transformation pathways could be important to the transformation of a number of organic contaminants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Community structure of ammonia-oxidizing archaea and ammonia-oxidizing bacteria in soil treated with the insecticide imidacloprid.

PubMed

Cycoń, Mariusz; Piotrowska-Seget, Zofia

2015-01-01

The purpose of this experiment was to assess the effect of imidacloprid on the community structure of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) in soil using the denaturing gradient gel electrophoresis (DGGE) approach. Analysis showed that AOA and AOB community members were affected by the insecticide treatment. However, the calculation of the richness (S) and the Shannon-Wiener index (H) values for soil treated with the field rate (FR) dosage of imidacloprid (1 mg/kg soil) showed no changes in measured indices for the AOA and AOB community members. In turn, the 10∗FR dosage of insecticide (10 mg/kg soil) negatively affected the AOA community, which was confirmed by the decrease of the S and H values in comparison with the values obtained for the control soil. In the case of AOB community, an initial decline followed by the increase of the S and H values was obtained. Imidacloprid decreased the nitrification rate while the ammonification process was stimulated by the addition of imidacloprid. Changes in the community structure of AOA and AOB could be due to an increase in the concentration of N-NH4 (+), known as the most important factor which determines the contribution of these microorganisms to soil nitrification.

Community Structure of Ammonia-Oxidizing Archaea and Ammonia-Oxidizing Bacteria in Soil Treated with the Insecticide Imidacloprid

PubMed Central

Cycoń, Mariusz; Piotrowska-Seget, Zofia

2015-01-01

The purpose of this experiment was to assess the effect of imidacloprid on the community structure of ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) in soil using the denaturing gradient gel electrophoresis (DGGE) approach. Analysis showed that AOA and AOB community members were affected by the insecticide treatment. However, the calculation of the richness (S) and the Shannon-Wiener index (H) values for soil treated with the field rate (FR) dosage of imidacloprid (1 mg/kg soil) showed no changes in measured indices for the AOA and AOB community members. In turn, the 10∗FR dosage of insecticide (10 mg/kg soil) negatively affected the AOA community, which was confirmed by the decrease of the S and H values in comparison with the values obtained for the control soil. In the case of AOB community, an initial decline followed by the increase of the S and H values was obtained. Imidacloprid decreased the nitrification rate while the ammonification process was stimulated by the addition of imidacloprid. Changes in the community structure of AOA and AOB could be due to an increase in the concentration of N-NH4 +, known as the most important factor which determines the contribution of these microorganisms to soil nitrification. PMID:25705674

SWATH label-free proteomics analyses revealed the roles of oxidative stress and antioxidant defensing system in sclerotia formation of Polyporus umbellatus

NASA Astrophysics Data System (ADS)

Li, Bing; Tian, Xiaofang; Wang, Chunlan; Zeng, Xu; Xing, Yongmei; Ling, Hong; Yin, Wanqiang; Tian, Lixia; Meng, Zhixia; Zhang, Jihui; Guo, Shunxing

2017-01-01

Understanding the initiation and maturing mechanisms is important for rational manipulating sclerotia differentiation and growth from hypha of Polyporus umbellatus. Proteomes in P. umbellatus sclerotia and hyphae at initial, developmental and mature phases were studied. 1391 proteins were identified by nano-liquid chromatograph-mass spectrometry (LC-MS) in Data Dependant Acquisition mode, and 1234 proteins were quantified successfully by Sequential Window Acquisition of all THeoretical fragment ion spectra-MS (SWATH-MS) technology. There were 347 differentially expressed proteins (DEPs) in sclerotia at initial phase compared with those in hypha, and the DEP profiles were dynamically changing with sclerotia growth. Oxidative stress (OS) in sclerotia at initial phase was indicated by the repressed proteins of respiratory chain, tricarboxylic acid cycle and the activation of glycolysis/gluconeogenesis pathways were determined based on DEPs. The impact of glycolysis/gluconeogenesis on sclerotium induction was further verified by glycerol addition assays, in which 5% glycerol significantly increased sclerotial differentiation rate and biomass. It can be speculated that OS played essential roles in triggering sclerotia differentiation from hypha of P. umbellatus, whereas antioxidant activity associated with glycolysis is critical for sclerotia growth. These findings reveal a mechanism for sclerotial differentiation in P. umbellatus, which may also be applicable for other fungi.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-06-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization

NASA Astrophysics Data System (ADS)

Rout, Bapin Kumar; Brooks, Geoffrey; Akbar Rhamdhani, M.; Li, Zushu; Schrama, Frank N. H.; Overbosch, Aart

2018-03-01

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537-557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag-metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag-metal emulsion. The model's prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

Erratum to ;Coastal water column ammonium and nitrite oxidation are decoupled in summer;

NASA Astrophysics Data System (ADS)

Heiss, Elise M.; Fulweiler, Robinson W.

2017-07-01

Water column nitrification is a key process in the nitrogen cycle as it links reduced and oxidized forms of nitrogen and also provides the substrate (nitrate) needed for reactive nitrogen removal by denitrification. We measured potential water column ammonium and nitrite oxidation rates at four sites along an estuary to continental shelf gradient over two summers. In most cases, nitrite oxidation rates outpaced ammonium oxidation rates. Overall, ammonium and nitrite oxidation rates were higher outside of the estuary, and this trend was primarily driven by higher oxidation rates in deeper waters. Additionally, both ammonium and nitrite oxidation rates were impacted by different in situ variables. Ammonium oxidation rates throughout the water column as a whole were most positively correlated to depth and salinity and negatively correlated to dissolved oxygen, light, and temperature. In contrast, nitrite oxidation rates throughout the water column were negatively correlated with temperature, light and pH. Multivariate regression analysis revealed that surface (<20 m) ammonium oxidation rates were most strongly predicted by substrate (NH4+), salinity, and light, while deep (>20 m) rates were regulated by temperature, light, and [H+] (i.e. pH). In addition, surface (<20 m) nitrite oxidation rates were best explained by [H+] alone, while [H+], temperature, and dissolved oxygen all played a role in predicting deep (>20 m) nitrite oxidation rates. These results support the growing body of evidence that ammonium oxidation and nitrite oxidation are not always coupled, should be measured separately, and are influenced by different environmental conditions.

Change of brown coal oxidation kinetic characteristics by promoting additives appending in the form of copper salts

NASA Astrophysics Data System (ADS)

Larionov, K. B.; Mishakov, I. V.; Gromov, A. A.; Zenkov, A. V.

2017-11-01

Process of brown coal oxidation with 5%wt content of copper-salt additives of various nature (Cu (NO3)2, CuSO4 and Cu(CH3COO)2) was studied. The experiment has been performed by thermogravimetric analysis at a heating rate of 2.5°C/min to a maximum temperature of 600°C in the air. Analytical evaluation of oxidation process kinetic characteristics has been conducted based on the results of TGA. It has been established that addition of initiating agents leads to significant reduction in the initial ignition temperature of coal (ΔTi = 15÷40°C), shortening of the sample warm-up time to the ignition point (Δte = 6÷12 min) and reduction of the sample burning time (Δtf = 40÷54 min). The following series of additives activity affecting ignition temperature of coals has been established: Cu(CH3COO)2 > Cu(NO3)2 > CuSO4. Additionally, the opposite can be said about the effect of additives on residence time of the sample in its combustion area (CuSO4 > Cu(NO3)2 > Cu(CH3COO)2). According to mass spectrometric analysis, presence of NOx, SO2, CO2 (intense peaks at 190÷290°C) was recorded in oxidation products of modified samples, which is explained by partial or complete decomposition of salts.

Modeling of oxidation of aluminum nanoparticles by using Cabrera Mott Model

NASA Astrophysics Data System (ADS)

Ramazanova, Zamart; Zyskin, Maxim; Martirosyan, Karen

2012-10-01

Our research focuses on modeling new Nanoenergetic Gas-Generator (NGG) formulations that rapidly release a large amount of gaseous products and generates shock and pressure waves. Nanoenergetic thermite reagents include mixtures of Al and metal oxides such as bismuth trioxide and iodine pentoxide. The research problem is considered a spherically symmetric case and used the Cabrera Mott oxidation model to describe the kinetics of oxide growth on spherical Al nanoparticles for evaluating reaction time which a process of the reaction with oxidizer happens on the outer part of oxide layer of aluminum ions are getting in contact with an oxidizing agent and react. We assumed that a ball of Al of radius 20 to 50 nm is covered by a thin oxide layer 2-4 nm and is surrounded by abundant amount of oxygen stored by oxidizers. The ball is rapidly heated up to ignition temperature to initiate self-sustaining oxidation reaction. As a result highly exothermic reaction is generated. In the oxide layer of excess concentrations of electrons and ions are dependent on the electric field potential with the corresponding of the Gibbs factors and that it conducts to the solution of a nonlinear Poisson equation for the electric field potential in a moving boundary domain. Motion of the boundary is determined by the gradient of a solution on the boundary. We investigated oxidation model numerically, using the COMSOL software utilizing finite element analysis. The computing results demonstrate that oxidation rate increases with the decreasing particle radius.

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

NASA Astrophysics Data System (ADS)

Talic, Belma; Falk-Windisch, Hannes; Venkatachalam, Vinothini; Hendriksen, Peter Vang; Wiik, Kjell; Lein, Hilde Lea

2017-06-01

Manganese cobalt spinel oxides are promising materials for protective coatings for solid oxide fuel cell (SOFC) interconnects. To achieve high density such coatings are often sintered in a two-step procedure, involving heat treatment first in reducing and then in oxidizing atmospheres. Sintering the coating inside the SOFC stack during heating would reduce production costs, but may result in a lower coating density. The importance of coating density is here assessed by characterization of the oxidation kinetics and Cr evaporation of Crofer 22 APU with MnCo1.7Fe0.3O4 spinel coatings of different density. The coating density is shown to have minor influence on the long-term oxidation behavior in air at 800 °C, evaluated over 5000 h. Sintering the spinel coating in air at 900 °C, equivalent to an in-situ heat treatment, leads to an 88% reduction of the Cr evaporation rate of Crofer 22 APU in air-3% H2O at 800 °C. The air sintered spinel coating is initially highly porous, however, densifies with time in interaction with the alloy. A two-step reduction and re-oxidation heat treatment results in a denser coating, which reduces Cr evaporation by 97%.

Oxidative stress induces senescence in human mesenchymal stem cells

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

Brandl, Anita; Meyer, Matthias; Bechmann, Volker

Mesenchymal stem cells (MSCs) contribute to tissue repair in vivo and form an attractive cell source for tissue engineering. Their regenerative potential is impaired by cellular senescence. The effects of oxidative stress on MSCs are still unknown. Our studies were to investigate into the proliferation potential, cytological features and the telomere linked stress response system of MSCs, subject to acute or prolonged oxidant challenge with hydrogen peroxide. Telomere length was measured using the telomere restriction fragment assay, gene expression was determined by rtPCR. Sub-lethal doses of oxidative stress reduced proliferation rates and induced senescent-morphological features and senescence-associated {beta}-galactosidase positivity. Prolongedmore » low dose treatment with hydrogen peroxide had no effects on cell proliferation or morphology. Sub-lethal and prolonged low doses of oxidative stress considerably accelerated telomere attrition. Following acute oxidant insult p21 was up-regulated prior to returning to initial levels. TRF1 was significantly reduced, TRF2 showed a slight up-regulation. SIRT1 and XRCC5 were up-regulated after oxidant insult and expression levels increased in aging cells. Compared to fibroblasts and chondrocytes, MSCs showed an increased tolerance to oxidative stress regarding proliferation, telomere biology and gene expression with an impaired stress tolerance in aged cells.« less

The influence of iridium chemical oxidation state on the performance and durability of oxygen evolution catalysts in PEM electrolysis

NASA Astrophysics Data System (ADS)

Siracusano, S.; Baglio, V.; Grigoriev, S. A.; Merlo, L.; Fateev, V. N.; Aricò, A. S.

2017-10-01

Nanosized Ir-black (3 nm) and Ir-oxide (5 nm) oxygen evolution electrocatalysts showing high performance in polymer electrolyte membrane (PEM) water electrolysis based on Aquivion® short-side chain ionomer membrane are investigated to understand the role of the Ir oxidation state on the electrocatalytic activity and stability. Despite the smaller mean crystallite size, the Ir-black electrocatalyst shows significantly lower initial performance than the Ir-oxide. During operation at high current density, the Ir-black shows a decrease of cell potential with time whereas the Ir-oxide catalyst shows increasing cell potential resulting in a degradation rate of about 10 μV/h, approaching 1000 h. The unusual behaviour of the Ir-black results from the oxidation of metallic Ir to IrOx. The Ir-oxide catalyst shows instead a hydrated structure on the surface and a negative shift of about 0.5 eV for the Ir 4f binding energy after 1000 h electrolysis operation. This corresponds to the formation of a sub-stoichiometric Ir-oxide on the surface. These results indicate that a hydrated IrO2 with high oxidation state on the surface is favourable in decreasing the oxygen evolution overpotential. Modifications of the Ir chemical oxidation state during operation can affect significantly the catalytic activity and durability of the electrolysis system.

Planktonic Marine Iron-Oxidizers Drive Iron(III) Mineralization Under Low Oxygen Conditions

NASA Astrophysics Data System (ADS)

Luther, G. W., III; Field, E.; Findlay, A.; MacDonald, D. J.; Chan, C. S. Y.; Kato, S.

2016-02-01

Observations of modern microbes have led to several hypotheses on how microbes precipitated the extensive banded iron formations in the geologic record, but we have yet to resolve the exact microbial contributions. An initial hypotheses was that cyanobacteria produced oxygen that oxidized iron(II) abiotically; however, in modern environments such as microbial mats, where Fe(II) and O2 coexist, we commonly find microaerophilic chemolithotrophic iron(II)-oxidizing bacteria producing Fe(III) oxyhydroxides. This suggests that such iron-oxidizers could have inhabited niches in ancient coastal oceans where Fe(II) and O2 coexisted, and therefore contributed to iron deposits, but there is currently little evidence for planktonic marine iron-oxidizers in modern analogs. Here, we demonstrate successful cultivation of planktonic microaerophilic iron-oxidizing Zetaproteobacteria from the Chesapeake Bay during seasonal stratification. Iron-oxidizers were associated with low oxygen concentrations and active iron redox cycling in the oxic-anoxic transition zone (<3 µM O2, <0.2 µM H2S). While cyanobacteria were also detected in this transition zone, oxygen concentrations were too low to support significant rates of abiotic iron oxidation. Instead, cyanobacteria may be providing oxygen for microaerophilic iron(II) oxidation through a symbiotic relationship that promotes oxygen consumption rather than build-up. Our results suggest that once oxygenic photosynthesis evolved, microaerophilic chemolithotrophic iron(II)-oxidizers were likely important drivers of iron(III) mineralization in ancient oceans.

Oxidation of trichloroethylene, toluene, and ethanol vapors by a partially saturated permeable reactive barrier

NASA Astrophysics Data System (ADS)

Mahmoodlu, Mojtaba G.; Hassanizadeh, S. Majid; Hartog, Niels; Raoof, Amir

2014-08-01

The mitigation of volatile organic compound (VOC) vapors in the unsaturated zone largely relies on the active removal of vapor by ventilation. In this study we considered an alternative method involving the use of solid potassium permanganate to create a horizontal permeable reactive barrier for oxidizing VOC vapors. Column experiments were carried out to investigate the oxidation of trichloroethylene (TCE), toluene, and ethanol vapors using a partially saturated mixture of potassium permanganate and sand grains. Results showed a significant removal of VOC vapors due to the oxidation. We found that water saturation has a major effect on the removal capacity of the permeable reactive layer. We observed a high removal efficiency and reactivity of potassium permanganate for all target compounds at the highest water saturation (Sw = 0.6). A change in pH within the reactive layer reduced oxidation rate of VOCs. The use of carbonate minerals increased the reactivity of potassium permanganate during the oxidation of TCE vapor by buffering the pH. Reactive transport of VOC vapors diffusing through the permeable reactive layer was modeled, including the pH effect on the oxidation rates. The model accurately described the observed breakthrough curve of TCE and toluene vapors in the headspace of the column. However, miscibility of ethanol in water in combination with produced water during oxidation made the modeling results less accurate for ethanol. A linear relationship was found between total oxidized mass of VOC vapors per unit volume of permeable reactive layer and initial water saturation. This behavior indicates that pH changes control the overall reactivity and longevity of the permeable reactive layer during oxidation of VOCs. The results suggest that field application of a horizontal permeable reactive barrier can be a viable technology against upward migration of VOC vapors through the unsaturated zone.

The atmospheric chemistry of isoprene- and other multifunctional-nitrates

NASA Astrophysics Data System (ADS)

Perring, Anne Elizabeth

Formation of alkyl and multifunctional nitrates significantly reduces ozone production rates in their source regions, their transport and subsequent chemistry can impact secondary organic aerosol formation and NOy removal rates and they may lead to the re-release of NOx in regions far-removed from the original source. In this dissertation, the atmospheric chemistry of alkyl and multifunctional nitrates is investigated through a combination of laboratory and field measurements. In contrast to many previous studies that have focused on observations of specific individual nitrate compounds, the work described here uses a technique (Thermal Dissociation-Laser Induced Fluorescence or TD-LIF) that allows for measurements of the sum of all alkyl and multifunctional nitrates. These observations show that alkyl and multifunctional nitrates are a significant fraction of NOy in a number of different chemical regimes representing diverse hydrocarbon mixtures. In what follows, I show that their formation impacts both ozone 1 formation and NOy transport in ways that are not accounted for by currently accepted chemical mechanisms. Aircraft measurements are used to constrain nitrate yields following isoprene oxidation by OH, the atmospheric lifetimes of these nitrates, and the retention rate of the nitrate functional group upon oxidation of the initial isoprene nitrates. It is found that nitrate functionality is maintained upon further oxidation at least 75% of the time indicating that the lifetime of isoprene nitrates as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates with respect to reaction with OH. We examine the products of NO3-initiated oxidation of isoprene in a smog-chamber, propose a detailed reaction scheme, and find that nitrates are produced with a yield of 65+/-12%, the majority of which are carbonyl nitrates. We investigate the role of alkyl and multifunctional nitrates in the Mexico City plume where they are observed to be more abundant than expected given currently accepted chemical mechanisms. We investigate several possible explanations for the unexpectedly high abundances and calculate that their formation depresses ozone production in the near-field of Mexico City by as much as 30%.

Oxygen evolution from single- and multiple-turnover light pulses: temporal kinetics of electron transport through PSII in sunflower leaves.

PubMed

Oja, Vello; Eichelmann, Hillar; Laisk, Agu

2011-12-01

Oxygen evolution per single-turnover flash (STF) or multiple-turnover pulse (MTP) was measured with a zirconium O(2) analyzer from sunflower leaves at 22 °C. STF were generated by Xe arc lamp, MTP by red LED light of up to 18000 μmol quanta m(-2) s(-1). Ambient O(2) concentration was 10-30 ppm, STF and MTP were superimposed on far-red background light in order to oxidize plastoquinone (PQ) and randomize S-states. Electron (e(-)) flow was calculated as 4 times O(2) evolution. Q (A) → Q (B) electron transport was investigated firing double STF with a delay of 0 to 2 ms between the two. Total O(2) evolution per two flashes equaled to that from a single flash when the delay was zero and doubled when the delay exceeded 2 ms. This trend was fitted with two exponentials with time constants of 0.25 and 0.95 ms, equal amplitudes. Illumination with MTP of increasing length resulted in increasing O(2) evolution per pulse, which was differentiated with an aim to find the time course of O(2) evolution with sub-millisecond resolution. At the highest pulse intensity of 2.9 photons ms(-1) per PSII, 3 e(-) initially accumulated inside PSII and the catalytic rate of PQ reduction was determined from the throughput rate of the fourth and fifth e(-). A light response curve for the reduction of completely oxidized PQ was a rectangular hyperbola with the initial slope of 1.2 PSII quanta per e(-) and V (m) of 0.6 e(-) ms(-1) per PSII. When PQ was gradually reduced during longer MTP, V (m) decreased proportionally with the fraction of oxidized PQ. It is suggested that the linear kinetics with respect to PQ are apparent, caused by strong product inhibition due to about equal binding constants of PQ and PQH(2) to the Q (B) site. The strong product inhibition is an appropriate mechanism for down-regulation of PSII electron transport in accordance with rate of PQH(2) oxidation by cytochrome b(6)f. © Springer Science+Business Media B.V. 2011

Different isotope and chemical patterns of pyrite oxidation related to lag and exponential growth phases of Acidithiobacillus ferrooxidans reveal a microbial growth strategy

NASA Astrophysics Data System (ADS)

Brunner, Benjamin; Yu, Jae-Young; Mielke, Randall E.; MacAskill, John A.; Madzunkov, Stojan; McGenity, Terry J.; Coleman, Max

2008-06-01

The solution chemistry during the initial (slow increase of dissolved iron and sulfate) and main stage (rapid increase of dissolved iron and sulfate) of pyrite leaching by Acidithiobacillus ferrooxidans (Af) at a starting pH of 2.05 shows significant differences. During the initial stage, ferrous iron (Fe2+) is the dominant iron species in solution and the molar ratio of produced sulfate (SO42-) and total iron (Fetot) is 1.1, thus does not reflect the stoichiometry of pyrite (FeS2). During the main stage, ferric iron (Fe3+) is the dominant iron species in solution and the SO42-:Fetot ratio is with 1.9, close to the stoichiometry of FeS2. Another difference between initial and main stage is an initial trend to slightly higher pH values followed by a drop during the main stage to pH 1.84. These observations raise the question if there are different modes of bioleaching of pyrite, and if there are, what those modes imply in terms of leaching mechanisms. Different oxygen and sulfur isotope trends of sulfate during the initial and main stages of pyrite oxidation confirm that there are two pyrite bioleaching modes. The biochemical reactions during initial stage are best explained by the net reaction FeS2 + 3O2 ⇒ Fe2+ + SO42- + SO2(g). The degassing of sulfur dioxide (SO2) acts as sink for sulfur depleted in 34S compared to pyrite, and is the cause of the SO42-:Fetot ratio of 1.1 and the near constant pH. During the exponential phase, pyrite sulfur is almost quantitatively converted to sulfate, according to the net reaction FeS2 + 15/4O2 + 1/2H2O ⇒ Fe3+ + 2SO42- + H+. We hypothesize that the transition between the modes of bioleaching of pyrite is due to the impact of the accumulation of ferrous iron, which induces changes in the metabolic activity of Af and may act as an inhibitor for the oxidation of sulfur species. This transition defines a fundamental change in the growth strategy of Af. A mode, where bacteria gain energy by oxidation of elemental sulfur to sulfite but show little growth is switched into a mode, where bacteria gain a smaller amount of energy by the oxidation of ferrous iron, but induce much faster pyrite leaching rates due to the production of ferric iron.

Method of digesting an explosive nitro compound

DOEpatents

Shah, Manish M.

2000-01-01

The present invention is a process wherein bleaching oxidants are used to digest explosive nitro compounds. The process has an excellent reaction rate for digesting explosives and operates under multivariate conditions. Reaction solutions may be aqueous, non-aqueous or a combination thereof, and can also be any pH, but preferably have a pH between 2 and 9. The temperature may be ambient as well as any temperature above which freezing of the solution would occur and below which any degradation of the bleaching oxidant would occur or below which any explosive reaction would be initiated. The pressure may be any pressure, but is preferably ambient or atmospheric, or a pressure above a vapor pressure of the aqueous solution to avoid boiling of the solution. Because the bleaching oxidant molecules are small, much smaller than an enzyme molecule for example, they can penetrate the microstructure of plastic explosives faster. The bleaching oxidants generate reactive hydroxyl radicals, which can destroy other organic contaminants, if necessary, along with digesting the explosive nitro compound.

Real-time combustion controls and diagnostics sensors (CCADS)

DOEpatents

Thornton, Jimmy D.; Richards, George A.; Dodrill, Keith A.; Nutter, Jr., Roy S.; Straub, Douglas

2005-05-03

The present invention is directed to an apparatus for the monitoring of the combustion process within a combustion system. The apparatus comprises; a combustion system, a means for supplying fuel and an oxidizer, a device for igniting the fuel and oxidizer in order to initiate combustion, and a sensor for determining the current conducted by the combustion process. The combustion system comprises a fuel nozzle and an outer shell attached to the combustion nozzle. The outer shell defines a combustion chamber. Preferably the nozzle is a lean premix fuel nozzle (LPN). Fuel and an oxidizer are provided to the fuel nozzle at separate rates. The fuel and oxidizer are ignited. A sensor positioned within the combustion system comprising at least two electrodes in spaced-apart relationship from one another. At least a portion of the combustion process or flame is between the first and second electrodes. A voltage is applied between the first and second electrodes and the magnitude of resulting current between the first and second electrodes is determined.

Minimizing analyte electrolysis in electrospray ionization mass spectrometry using a redox buffer coated emitter electrode

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

Peintler-Krivan, Emese; Van Berkel, Gary J; Kertesz, Vilmos

2010-01-01

An emitter electrode with an electroactive poly(pyrrole) (PPy) polymer film coating was constructed for use in electrospray ionization mass spectrometry (ESI-MS). The PPy film acted as a surface-attached redox buffer limiting the interfacial potential of the emitter electrode. While extensive oxidation of selected analytes (reserpine and amodiaquine) was observed in positive ion mode ESI using a bare metal (gold) emitter electrode, the oxidation was suppressed for these same analytes when using the PPy-coated electrode. A semi-quantitative relationship between the rate of oxidation observed and the interfacial potential of the emitter electrode was shown. The redox buffer capacity, and therefore themore » lifetime of the redox buffering effect, correlated with the oxidation potential of the analyte and with the magnitude of the film charge capacity. Online reduction of the PPy polymer layer using negative ion mode ESI between analyte injections was shown to successfully restore the redox buffering capacity of the polymer film to its initial state.« less

Release and Formation of Oxidation-Related Aldehydes during Wine Oxidation.

PubMed

Bueno, Mónica; Carrascón, Vanesa; Ferreira, Vicente

2016-01-27

Twenty-four Spanish wines were subjected to five consecutive cycles of air saturation at 25 °C. Free and bound forms of carbonyls were measured in the initial samples and after each saturation. Nonoxidized commercial wines contain important and sensory relevant amounts of oxidation-related carbonyls under the form of odorless bound forms. Models relating the contents in total aldehydes to the wine chemical composition suggest that fermentation can be a major origin for Strecker aldehydes: methional, phenylacetaldehyde, isobutyraldehyde, 2-methylbutanal, and isovaleraldehyde. Bound forms are further cleaved, releasing free aldehydes during the first steps of wine oxidation, as a consequence of equilibrium shifts caused by the depletion of SO2. At low levels of free SO2, de novo formation and aldehyde degradation are both observed. The relative importance of these phenomena depends on both the aldehyde and the wine. Models relating aldehyde formation rates to wine chemical composition suggest that amino acids are in most cases the most important precursors for de novo formation.

Survival and Recovery of Methanotrophic Bacteria Starved Under Oxic and Anoxic Conditions

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1994-01-01

The effects of carbon deprivation on survival of methanotrophic bacteria were compared in cultures incubated in the presence and absence of oxygen in the starvation medium. Survival and recovery of the examined methanotrophs were generally highest for cultures starved under anoxic conditions as indicated by poststarvation measurements of methane oxidation, tetrazolium salt reduction, plate counts, and protein synthesis. Methylosinus trichosporium OB3b survived up to 6 weeks of carbon deprivation under anoxic conditions while maintaining a physiological state that allowed relatively rapid (hours) methane oxidation after substrate addition. A small fraction of cells starved under oxic and anoxic conditions (4 and 10%, respectively) survived more than 10 weeks but required several days for recovery on plates and in liquid medium. A non-spore-forming methanotroph, strain WP 12, displayed 36 to 118% of its initial methane oxidation capacity after 5 days of carbon deprivation. Oxidation rates varied with growth history prior to the experiments as well as with starvation conditions. Strain WP 12 starved under anoxic conditions showed up to 90% higher methane oxidation activity and 46% higher protein production after starvation than did cultures starved under oxic conditions. Only minor changes in biomass and niorpholow were seen for methanotrophic bacteria starved tinder anoxic conditions. In contrast, starvation under oxic conditions resulted in morphology changes and an initial 28 to 35% loss of cell protein. These data suggest that methanotrophic bacteria can survin,e carbon deprivation under anoxic conditions by using maintenance energy derived Solelyr from an anaerobic endogenous metabolism. This capability could partly explain a significant potential for methane oxidation in environments not continuously, supporting aerobic methanotrophic growth.

Unusual Mesoporous Carbonaceous Matrix Loading with Sulfur as the Cathode of Lithium Sulfur Battery with Exceptionally Stable High Rate Performance.

PubMed

Qian, Weiwei; Gao, Qiuming; Li, Zeyu; Tian, Weiqian; Zhang, Hang; Zhang, Qiang

2017-08-30

Unusual three-dimensional mesoporous carbon/reduced graphene oxide (MP-C/rGO) matrix possessing graphene nanolayer pore walls built up by three to five graphene monosheets and some carbon particles with the sizes of about 5 nm located between the graphene nanolayers was prepared by facile freeze-drying and then carbonization of the poly(vinyl alcohol) and graphene oxide mixture. The mesoporous carbonaceous MP-C/rGO sample has a high specific surface area of 661.6 m 2 g -1 , large specific pore volume of 1.54 m 3 g -1 , and focused pore size distribution of 2-10 nm. About 64 wt % sulfur could be held in the pores of the MP-C/rGO matrix. As the cathode of a Li-S battery, the MP-C/rGO/S composite showed excellent electrochemical property including a high initial specific capacity of 919 mA h g -1 at 1 C with the capacity retention ratio of 63.3% and the Coulombic efficiency above 90% after 500 cycles. Meanwhile, the initial specific capacity of 602 mA h g -1 at 5 C and remaining capacity of 391 mA h g -1 after 500 cycles with an outstanding Coulombic efficiency of 97% indicate its exceptionally stable rate performance.

Experimental and theoretical understanding of the gas phase oxidation of atmospheric amides with OH radicals: kinetics, products, and mechanisms.

PubMed

Borduas, Nadine; da Silva, Gabriel; Murphy, Jennifer G; Abbatt, Jonathan P D

2015-05-14

Atmospheric amides have primary and secondary sources and are present in ambient air at low pptv levels. To better assess the fate of amides in the atmosphere, the room temperature (298 ± 3 K) rate coefficients of five different amides with OH radicals were determined in a 1 m(3) smog chamber using online proton-transfer-reaction mass spectrometry (PTR-MS). Formamide, the simplest amide, has a rate coefficient of (4.44 ± 0.46) × 10(-12) cm(3) molec(-1) s(-1) against OH, translating to an atmospheric lifetime of ∼1 day. N-methylformamide, N-methylacetamide and propanamide, alkyl versions of formamide, have rate coefficients of (10.1 ± 0.6) × 10(-12), (5.42 ± 0.19) × 10(-12), and (1.78 ± 0.43) × 10(-12) cm(3) molec(-1) s(-1), respectively. Acetamide was also investigated, but due to its slow oxidation kinetics, we report a range of (0.4-1.1) × 10(-12) cm(3) molec(-1) s(-1) for its rate coefficient with OH radicals. Oxidation products were monitored and quantified and their time traces were fitted using a simple kinetic box model. To further probe the mechanism, ab initio calculations are used to identify the initial radical products of the amide reactions with OH. Our results indicate that N-H abstractions are negligible in all cases, in contrast to what is predicted by structure-activity relationships. Instead, the reactions proceed via C-H abstraction from alkyl groups and from formyl C(O)-H bonds when available. The latter process leads to radicals that can readily react with O2 to form isocyanates, explaining the detection of toxic compounds such as isocyanic acid (HNCO) and methyl isocyanate (CH3NCO). These contaminants of significant interest are primary oxidation products in the photochemical oxidation of formamide and N-methylformamide, respectively.

Desulfurization kinetics of molten copper by gas bubbling

NASA Astrophysics Data System (ADS)

Fukunaka, Y.; Nishikawa, K.; Sohn, H. S.; Asaki, Z.

1991-02-01

Molten copper with 0.74 wt pct sulfur content was desulfurized at 1523 K by bubbling Ar-O2 gas through a submerged nozzle. The reaction rate was significantly influenced not only by the oxygen partial pressure but also by the gas flow rate. Little evolution of SO2 gas was observed in the initial 10 seconds of the oxidation; however, this was followed by a period of high evolution rate of SO2 gas. The partial pressure of SO2 gas decreased with further progress of the desulfurization. The effect of the immersion depth of the submerged nozzle was negligible. The overall reaction is decomposed to two elementary reactions: the desulfurization and the dissolution rate of oxygen. The assumptions were made that these reactions are at equilibrium and that the reaction rates are controlled by mass transfer rates within and around the gas bubble. The time variations of sulfur and oxygen contents in the melt and the SO2 partial pressure in the off-gas under various bubbling conditions were well explained by the mathematical model combined with the reported thermodynamic data of these reactions. Based on the present model, it was anticipated that the oxidation rate around a single gas bubble was mainly determined by the rate of gas-phase mass transfer, but all oxygen gas blown into the melt was virtually consumed to the desulfurization and dissolution reactions before it escaped from the melt surface.

[Participation of oxygen in the reduction of methylviologen, photosensitized by chlorophyll, in an aqueous solution of detergent].

PubMed

Luganskaia, A N; Krasnovskiĭ, A A

1975-01-01

Dependence of chlorophyll "a" photosensitized reduction of methylviologene with tiourea on the temperature of reaction mixture was studied in aerobic conditions in triton X-100 aqueous solution. It was found that the reaction consisted of two stages: the light and dark ones. Photosensitized oxidation of tiourea with air oxygen proceeds at the temperatures up to -70 degrees C. Reduction of methylviologen is a dark stage for which diffusion processes are necessary. The role of hydrogen peroxide in the reaction studied has been investigated. It has been shown that hydrogen peroxide is not the "initiator" of the reaction which results in the reduction of methylviologen. Reduced glutation and the mixture of reduced and oxidized glutations were used as electron donors in photosensitized reaction in the presence of air oxygen. An increase of the depth and rate of the reduction of methylviologen under aerobic conditions as compared to anaerobic ones points to the formation of more active reducers than the initial electron donor.

Oxidation of Benzene by Persulfate in the Presence of Fe(III)- and Mn(IV)-Containing Oxides: Stoichiometric Efficiency and Transformation Products.

PubMed

Liu, Haizhou; Bruton, Thomas A; Li, Wei; Buren, Jean Van; Prasse, Carsten; Doyle, Fiona M; Sedlak, David L

2016-01-19

Sulfate radical (SO4(•-)) is a strong, short-lived oxidant that is produced when persulfate (S2O8(2-)) reacts with transition metal oxides during in situ chemical oxidation (ISCO) of contaminated groundwater. Although engineers are aware of the ability of transition metal oxides to activate persulfate, the operation of ISCO remediation systems is hampered by an inadequate understanding of the factors that control SO4(•-) production and the overall efficiency of the process. To address these shortcomings, we assessed the stoichiometric efficiency and products of transition metal-catalyzed persulfate oxidation of benzene with pure iron- and manganese-containing minerals, clays, and aquifer solids. For most metal-containing solids, the stoichiometric efficiency, as determined by the loss of benzene relative to the loss of persulfate, approached the theoretical maximum. Rates of production of SO4(•-) or hydroxyl radical (HO(•)) generated from radical chain reactions were affected by the concentration of benzene, with rates of S2O8(2-) decomposition increasing as the benzene concentration increased. Under conditions selected to minimize the loss of initial transformation products through reaction with radicals, the production of phenol only accounted for 30%-60% of the benzene lost in the presence of O2. The remaining products included a ring-cleavage product that appeared to contain an α,β-unsaturated aldehyde functional group. In the absence of O2, the concentration of the ring-cleavage product increased relative to phenol. The formation of the ring-cleavage product warrants further studies of its toxicity and persistence in the subsurface.

Growth of Nitrosococcus-Related Ammonia Oxidizing Bacteria Coincides with Extremely Low pH Values in Wastewater with High Ammonia Content

PubMed Central

2017-01-01

Ammonia oxidation decreases the pH in wastewaters where alkalinity is limited relative to total ammonia. The activity of ammonia oxidizing bacteria (AOB), however, typically decreases with pH and often ceases completely in slightly acidic wastewaters. Nevertheless, nitrification at low pH has been reported in reactors treating human urine, but it has been unclear which organisms are involved. In this study, we followed the population dynamics of ammonia oxidizing organisms and reactor performance in synthetic fully hydrolyzed urine as the pH decreased over time in response to a decrease in the loading rate. Populations of the β-proteobacterial Nitrosomonas europaea lineage were abundant at the initial pH close to 6, but the growth of a possibly novel Nitrosococcus-related AOB genus decreased the pH to the new level of 2.2, challenging the perception that nitrification is inhibited entirely at low pH values, or governed exclusively by β-proteobacterial AOB or archaea. With the pH shift, nitrite oxidizing bacteria were not further detected, but nitrous acid (HNO2) was still removed through chemical decomposition to nitric oxide (NO) and nitrate. The growth of acid-tolerant γ-proteobacterial AOB should be prevented, by keeping the pH above 5.4, which is a typical pH limit for the N. europaea lineage. Otherwise, the microbial community responsible for high-rate nitrification can be lost, and strong emissions of hazardous volatile nitrogen compounds such as NO are likely. PMID:28509546

Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

NASA Astrophysics Data System (ADS)

Eitel, Eryn M.; Taillefert, Martial

2017-10-01

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

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

Sanwald, Kai E.; Berto, Tobias F.; Jentys, Andreas

Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents formore » H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for SEM and AAS measurements and Dr. Udishnu Sanyal for TEM imaging. Christine Schwarz is acknowledged for technical assistance in NMR experiments.« less

Theoretical study of production of unique glasses in space

NASA Technical Reports Server (NTRS)

Larsen, D. C.

1974-01-01

Analytical functional relationships describing homogeneous nucleation and crystallization in various supercooled liquids were developed. The time and temperature dependent relationships of nucleation and crystallization (intrinsic properties) are being used to relate glass forming tendency to extrinsic parameters such as cooling rate through computer simulation. Single oxide systems are being studied initially to aid in developing workable kinetic models and to indicate the primary materials parameters affecting glass formation. The theory and analytical expressions developed for simple systems is then extended to complex oxide systems. A thorough understanding of nucleation and crystallization kinetics of glass forming systems provides a priori knowledge of the ability of a given system to form a glass.

Atomic oxygen undercutting of defects on SiO2 protected polyimide solar array blankets

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Rutledge, Sharon K.; Auer, Bruce M.; Difilippo, Frank

1990-01-01

Low Earth Orbital (LEO) atomic oxygen can oxidize SiO2-protected polyimide kapton solar array blanket material which is not totally protected as a result of pinholes or scratches in the SiO2 coatings. The probability of atomic oxygen reaction upon initial impact is low, thus inviting oxidation by secondary impacts. The secondary impacts can produce atomic oxygen undercutting which may lead to coating mechanical failure and ever increasing mass loss rates of kapton. Comparison of undercutting effects in isotropic plasma asher and directed beam tests are reported. These experimental results are compared with computational undercutting profiles based on Monte Carlo methods and their implication on LEO performance of protected polymers.

Effect of denervation and reinnervation on oxidation of 6-(C-14) glucose by rat skeletal muscle homogenates

NASA Technical Reports Server (NTRS)

Dubois, D. C.; Max, S. R.

1983-01-01

The effects of denervation and reinnervation of the rat extensor digitorum longus muscle on the oxidation of 6-(C-14) glucose to (C-14)O2 is investigated. Results show that the rate of (C-14)O2 production decreased dramatically following denervation and the decrease became significant 20 days after nerve section. The changes which occurred prior to day 20 apparently reflected the decline of muscle mass. The decreased (C-14)O2 production was found to be due to reduced capacity of the enzymatic system, while there was no change in the apparent affinity for glucose. Results of mixing experiments showed that the loss of oxidative capacity following denervation is not caused by the production of soluble inhibitors by degenerating muscle. Measurements of the (C-14)O2 revealed that oxidative metabolism recovered during reinnervation. The specific activity in reinnervated muscles displayed an 'overshoot' of approximately 50 percent, which returned to control levels by day 60. The time-course of the denervation-mediated change indicates that altered oxidative capacity is secondary to events that initiate dennervation changes in muscle, although diminished oxidative capacity may be of considerable metabolic significance in denervated muscle.

A procedure for the measurement of Oxygen Consumption Rates (OCRs) in red wines and some observations about the influence of wine initial chemical composition.

PubMed

Marrufo-Curtido, Almudena; Carrascón, Vanesa; Bueno, Mónica; Ferreira, Vicente; Escudero, Ana

2018-05-15

The rates at which wine consumes oxygen are important technological parameters for whose measurement there are not accepted procedures. In this work, volumes of 8 wines are contacted with controlled volumes of air in air-tight tubes containing oxygen-sensors and are further agitated at 25 °C until O 2 consumption is complete. Three exposure levels of O 2 were used: low (10 mg/L) and medium or high (18 or 32 mg/L plus the required amount to oxidize all wine SO 2 ). In each oxygen level, 2-4 independent segments following pseudo-first order kinetics were identified, plus an initial segment at which wine consumed O 2 very fast. Overall, multivariate data techniques identify six different Oxygen-Consumption-Rates (OCRs) as required to completely define wine O 2 consumption. Except the last one, all could be modeled from the wine initial chemical composition. Total acetaldehyde, Mn, Cu/Fe, blue and red pigments and gallic acid seem to be essential to determine these OCRs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Glass composition and solution speciation effects on stage III dissolution

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

Trivelpiece, Cory L.; Rice, Jarret A.; Pantano, Carlo G.

To understand and mitigate the onset of Stage III corrosion of multicomponent oxides waste glasses. Stage III refers to a resumption of the high initial rate of glass dissolution in some glass samples that have otherwise exhibited dissolution at the much lower residual rate for a long time (Stage II). Although the onset of Stage III is known to occur concurrently with the precipitation of particular alteration products, the root cause of the transition is still unknown. Certain glass compositions (notably AFCI) and high pH environmental conditions are also associated with this observed transition.

OH-initiated heterogeneous aging of highly oxidized organic aerosol

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

Kessler, Sean H.; Nah, Theodora; Daumit, Kelly E.

2011-12-05

The oxidative evolution (“aging”) of organic species in the atmosphere is thought to have a major influence on the composition and properties of organic particulate matter, but remains poorly understood, particularly for the most oxidized fraction of the aerosol. Here we measure the kinetics and products of the heterogeneous oxidation of highly oxidized organic aerosol, with an aim of better constraining such atmospheric aging processes. Submicron particles composed of model oxidized organics—1,2,3,4-butanetetracarboxylic acid (C{sub 8}H{sub 10}O{sub 8}), citric acid (C{sub 6}H{sub 8}O{sub 7}), tartaric acid (C{sub 4}H{sub 6}O{sub 6}), and Suwannee River fulvic acid—were oxidized by gas-phase OH in amore » flow reactor, and the masses and elemental composition of the particles were monitored as a function of OH exposure. In contrast to our previous studies of less-oxidized model systems (squalane, erythritol, and levoglucosan), particle mass did not decrease significantly with heterogeneous oxidation. Carbon content of the aerosol always decreased somewhat, but this mass loss was approximately balanced by an increase in oxygen content. The estimated reactive uptake coefficients of the reactions range from 0.37 to 0.51 and indicate that such transformations occur at rates corresponding to 1-2 weeks in the atmosphere, suggesting their importance in the atmospheric lifecycle of organic particulate matter.« less

Excellent temperature performance of spherical LiFePO4/C composites modified with composite carbon and metal oxides.

PubMed

Zhang, Bao; Zeng, Tao; Zhang, Jiafeng; Peng, Chunli; Zheng, Junchao; Chen, Guomin

2014-01-01

Nanosized spherical LiFePO4/C composite was synthesized from nanosized spherical FePO4 ·2H2O, Li2C2O4, aluminum oxide, titanium oxide, oxalic acid, and sucrose by binary sintering process. The phases and morphologies of LiFePO4/C were characterized using SEM, TEM, CV, EIS, EDS, and EDX as well as charging and discharging measurements. The results showed that the as-prepared LiFePO4/C composite with good conductive webs from nanosized spherical FePO4 ·2H2O exhibits excellent electrochemical performances, delivering an initial discharge capacity of 161.7 mAh·g(-1) at a 0.1 C rate, 152.4 mAh·g(-1) at a 1 C rate and 131.7 mAh·g(-1) at a 5 C rate, and the capacity retention of 99.1%, 98.7%, and 95.8%, respectively, after 50 cycles. Meanwhile, the high and low temperature performance is excellent for 18650 battery, maintaining capacity retention of 101.7%, 95.0%, 88.3%, and 79.3% at 55°C, 0°C, -10°C, and -20°C by comparison withthat of room temperature (25°C) at the 0.5 C rate over a voltage range of 2.2 V to 3.6 V, respectively.

A study of the wear behaviour of ion implanted pure iron

NASA Astrophysics Data System (ADS)

Goode, P. D.; Peacock, A. T.; Asher, J.

1983-05-01

The technique of Thin Layer Activation (TLA) has been used to monitor disc wear in pin-on-disc wear tests. By simultaneously monitoring the pin wear the relationship between the wear rates of the two components of the wear couple has been studied. Tests were carried out using untreated pins wearing against ion implanted and untreated pure iron discs. The ratio of pin/disc volumetric wear rates was found to be constant in tests with unimplanted discs. In the implanted case the ratio was 8 initially, rising to the unimplatned value of 24 by a sliding distance of 25 km. The relationship between pin and disc wear after nitrogen implantation of the disc was approximately independent of dose between values of 7×10 16 and 1.2×10 18 N atoms cm -2. The actual wear rates of both pin and disc were significantly lower after implantation with the greater effects being observed om the unimplanted pin. The effects are explained in terms of the model of oxidative wear. In the unimplanted case the high pin wear relative to disc wear is considered to result from the higher mean temperature of pin asperities. Implantation appears to alter the mean asperity temperatures in such a way as to reduce the oxidation rate of the pin preferentially. Alternatively the effect of the implantation could be to reduce the critical thickness for removal of oxide formed on disc asperities.

Laser shock processing effects on isothermal oxidation resistance of GH586 superalloy

NASA Astrophysics Data System (ADS)

Hua, Yinqun; Rong, Zhen; Ye, Yunxia; Chen, Kangmin; Chen, Ruifang; Xue, Qing; Liu, Haixia

2015-03-01

The oxidation is one of the main failure mode of Ni-based alloy at high temperature, laser shock processing not only can improve the mechanical properties but also the oxidation resistance. So the study on laser shock processing effects on oxidation resistance of this alloy is necessary. The aim of this paper is to investigate the effects of laser shock processing on microstructure, micro-hardness and isothermal oxidation resistance of GH586 superalloy. Scanning electron microscopy, energy-dispersive spectrum, transmission electron microscope, and X-ray diffraction technique were used to analyze the microstructure changes and the surface morphologies of the oxide scales. In addition, micro-hardness of LSP-treated samples was measured. The results show that the average grains size on the surfaces of LSP specimen was found to be significantly finer compared to the untreated one (33.3 μm vs. 18.5 μm). Highly tangled and dense dislocation arrangements and a high amount of twins have been observed. After the oxidation, the defects density (dislocations and twins) in the specimen decreased. The oxidation kinetics approximately followed a parabolic oxidation law at 800 °C and 900 °C. The oxidation layer was composed of Cr2O3, NiCr2O4, TiO2, and Al2O3, which generated more quickly on the surface treated by LSP during initial oxidation. The average oxidation rate was lower after LSP due to the dense, tiny and homogeneous oxidation layer. The results show that the specimens treated by LSP have a better high temperature oxidation resistance.

A study of the kinetics of the reduction of neptunium(VI) by acetohydroxamic acid in perchloric acid

NASA Astrophysics Data System (ADS)

Matteson, Brent S.; Precek, Martin; Paulenova, Alena

2010-03-01

The kinetics of reduction of NpO22+ to NpO2+ by acetohydroxamic acid in 1 mol·L-1perchloric acid media at 10 and 22°C were studied. The reaction rate was monitored using stopped-flow and standard infrared spectroscopy. Under conditions such that acetohydroxamic acid was in excess relative to Np, the reduction rate of NpO22+ is described by the following: where k = 2.57x103 mol-1·L·sec-1 at 10°C. However, when neptunium is in a significant molar excess relative to acetohydroxamic acid, the reduction mechanism is dictated by two distinct reactions. An initial and incomplete reduction occurs as the result of the oxidation of AHA, while a slower and partial reduction of NpO22+ is likely caused by the oxidation products of AHA. The reaction rate of this first-order mechanism was calculated as 3.7x10-4 sec-1 at 10°C and 0.001 sec-1 at 22°C.

Analysis of a gas-liquid film plasma reactor for organic compound oxidation.

PubMed

Hsieh, Kevin; Wang, Huijuan; Locke, Bruce R

2016-11-05

A pulsed electrical discharge plasma formed in a tubular reactor with flowing argon carrier gas and a liquid water film was analyzed using methylene blue as a liquid phase hydroxyl radical scavenger and simultaneous measurements of hydrogen peroxide formation. The effects of liquid flow rate, liquid conductivity, concentration of dye, and the addition of ferrous ion on dye decoloration and degradation were determined. Higher liquid flow rates and concentrations of dye resulted in less decoloration percentages and hydrogen peroxide formation due to initial liquid conductivity effects and lower residence times in the reactor. The highest decoloration energy yield of dye found in these studies was 5.2g/kWh when using the higher liquid flow rate and adding the catalyst. The non-homogeneous nature of the plasma discharge favors the production of hydrogen peroxide in the plasma-liquid interface over the chemical oxidation of the organic in the bulk liquid phase and post-plasma reactions with the Fenton catalyst lead to complete utilization of the plasma-formed hydrogen peroxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Gas generation behavior of transuranic waste under disposal conditions

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

Fujisawa, Ryutaro; Kurashige, Tetsunari; Inagaki, Yusuke

1999-07-01

The generation of hydrogen-gas from metallic waste is an important issue for the safety analysis of geological disposal facilities for transuranic (TRU) radioactive waste in Japan. The objective of this study is to clarify the gas-generation behavior of stainless steel and carbon steel in non-oxidizing alkaline synthetic groundwater (pH 12.8 and 10.5) at 30 C simulating geological disposal environments. At pH 12.8, the observed gas-generation rate from stainless steel in the initial period of immersion was 1.0 x 10{sup 2} Nml/m{sup 2}/y and 1.0 x 10 Nml/m{sup 2}/y after 200 days (N represents the standard state of gas at 0more » C and 1 atm). At pH 10.5, gas generation was not observed for 60 days in the initial period. At 60 days, the gas-generation observed was 5.0 x 10 NMl/m{sup 2}/y. After 250 days, the gas-generation rate approaches zero. At pH 12.8, the observed gas generation rate of carbon steel in the initial period of immersion was 1.5 x 10{sup 2} Nml/m{sup 2}/y and the gas generation rate began to decrease after 200 days. After 300 days, it was 25 Nml/m{sup 2}/y. At pH 10.5, the gas generation rate in the initial period was 5.0 x 10{sup 2} Nml/m{sup 2}/y and was 1.0 x 10 Nml/m{sup 2}/y after 200 days.« less

Planar Strain-Rate-Free Diffusion Flames: Initiation, Properties, and Extinction

NASA Technical Reports Server (NTRS)

Fendell, Francis; Gokoglu, Suleyman; Rungaldier, Harald; Schultz, Donald

1999-01-01

An effectively strain-rate-free diffusion flame constitutes the most vigorous laminar combustion of initially unmixed reactive gases. Such a diffusion flame is characterized by a relatively long residence time and by a relatively large characteristic length scale. If such a flame were also planar, providing high symmetry, it would be particularly suitable for experimental and theoretical investigations of key combustion phenomena, such as multicomponent diffusion, chemical kinetics, and soot inception, growth, and oxidation. Unfortunately, a planar strain-rate-free diffusion flame is highly disrupted in earth-gravity (e.g., in a counterflow-diffusion-flame apparatus) because of the very rapid onset (approx. 100 ms) of gravity-induced instability. Accordingly, a specially dedicated apparatus was designed, fabricated, and initially checked out for the examination of a planar strain-rate-free diffusion flame in microgravity. Such a diffusion flame may be formed within a hollowed-out squat container (initially configured as 25 cm x 25 cm x 9 cm), with isothermal, noncatalytic, impervious walls. At test initiation, a thin metallic sheet (approx. 1 mm in thickness) that separates the internal volume into two equal portions, each of dimensions 25 cm x 25 cm x 4.5 cm, is withdrawn, by uniform translation (approx. 50 cm/s) in its own plane, through a tightly fitting slit in one side wall. Thereupon, diluted fuel vapor (initially confined to one half-volume of the container) gains access to diluted oxygen (initially with the same pressure, density, and temperature as the fuel, but initially confined to the other half-volume). After a brief delay (approx. 10 ms), to permit limited but sufficient-for-flammability diffusional interpenetration of fuel vapor and oxidizer, burning is initiated by discharge of a line igniter, located along that side wall from which the trailing edge of the separator withdraws. The ignition spawns a triple-flame propagation across the 25 cm x 25 cm centerplane. When a diffusion flame is emplaced in the centerplane, any subsequent travel, and change in temperature, of that planar diffusion flame may be tracked, along with the effectively spatially uniform but temporally evolving pressure within the container. Eventually, nearly complete depletion of the stoichiometrically deficient reactant, along with heat loss to the container surfaces, effects extinction. These data afford an opportunity to check theoretical models of diffusion and chemical kinetics under conditions ranging from intense burning to flame out, or, alternatively, to evolve simple empirical representations of these phenomena. Thus, the project sought to utilize microgravity testing to elucidate commonly encountered phenomenology, arising in the commonly-encountered mode of combustion (whether related to heating, manufacturing, boiling, and propulsion, or to uncontrolled, free-burning fire in structures and wildland vegetation), of those commonly utilized fuels usually categorized as gaseous fuels (such as hydrogen, natural gas, and propane, which are gaseous under atmospheric conditions).

Pulsed Power Discharges in Water

NASA Astrophysics Data System (ADS)

Kratel, Axel Wolf Hendrik

An Electrohydraulic Discharge Process (EHD) for the treatment of hazardous chemical wastes in water has been developed. Liquid waste in a 4 L EHD reactor is directly exposed to high-energy pulsed electrical discharges between two submerged electrodes. The high-temperature (> 14,000 K) plasma channel created by an EHD discharge emits ultraviolet radiation, and produces an intense shock wave as it expands against the surrounding water. A simulation of the EHD process is presented along with experimental results. The simulation assumes a uniform plasma channel with a plasma that obeys the ideal gas law and the Spitzer conductivity law. The results agree with previously published data. The simulation is used to predict the total energy efficiency, energy partitioning, maximum plasma channel temperature and pressure for the Caltech Pulsed Power Facility (CPPF). The simulation shows that capacitance, initial voltage and gap length can be used to control the efficiency of the discharge. The oxidative degradation of 4-chlorophenol (4 -CP), 3,4-dichloroaniline (3,4-DCA), and 2,4,6 trinitrotoluene (TNT) in an EHD reactor was explored. The initial rates of degradation for the three substrates are described by a first-order rate equation, where k_{ it 0/} is the zero-order rate constant that accounts for direct photolysis; and k_ {it 1/} is the first-order term that accounts for oxidation in the plasma channel region. For 4-CP in the 4.0 L reactor, the values of these two rate constants are k_{it 0/} = 0.73 +/- 0.08 mu M, and k_{ it 1/} =(9.4 +/- 1.4) times 10^{-4}. For a 200 mu M 4-CP solution this corresponds to an overall intrinsic zero-order rate constant of 0.022 M s^{it -1/} , and a G-value of 4.45 times 10^{-3}. Ozone increases the rate and extent of degradation of the substrates in the EHD reactor. Combined EHD/ozone treatment of a 160 mu M TNT solution resulted in the complete degradation of TNT, and a 34% reduction of the total organic carbon (TOC). The intrinsic initial rate constant of TNT degradation was 0.024 M s^{it -1/} . The results of these experiments demonstrate the potential application of the EHD process for the treatment of hazardous wastes.

Betanodavirus induces oxidative stress-mediated cell death that prevented by anti-oxidants and zfcatalase in fish cells.

PubMed

Chang, Chih-Wei; Su, Yu-Chin; Her, Guor-Mour; Ken, Chuian-Fu; Hong, Jiann-Ruey

2011-01-01

The role of oxidative stress in the pathogenesis of RNA nervous necrosis virus infection is still unknown. Red-spotted grouper nervous necrosis virus (RGNNV) induced free radical species (ROS) production at 12-24 h post-infection (pi; early replication stage) in fish GF-1 cells, and then at middle replication stage (24-48 h pi), this ROS signal may upregulate some expressions of the anti-oxidant enzymes Cu/Zn SOD and catalase, and eventually expression of the transcription factor Nrf2. Furthermore, both antioxidants diphenyliodonium and N-acetylcysteine or overexpression of zebrafish catalase in GF-1 cells also reduced ROS production and protected cells for enhancing host survival rate due to RGNNV infection. Furthermore, localization of ROS production using esterase activity and Mitotracker staining assays found that the ROS generated can affect mitochondrial morphology changes and causes ΔΨ loss, both of which can be reversed by antioxidant treatment. Taken together, our data suggest that RGNNV induced oxidative stress response for playing dual role that can initiate the host oxidative stress defense system to upregulate expression of antioxidant enzymes and induces cell death via disrupting the mitochondrial morphology and inducing ΔΨ loss, which can be reversed by anti-oxidants and zfcatalase, which provide new insight into betanodavirus-induced ROS-mediated pathogenesis.

Superparamagnetic magnetite nanocrystals-graphene oxide nanocomposites: facile synthesis and their enhanced electric double-layer capacitor performance.

PubMed

Wang, Qihua; Wang, Dewei; Li, Yuqi; Wang, Tingmei

2012-06-01

Superparamagnetic magnetite nanocrystals-graphene oxide (FGO) nanocomposites were successfully synthesized through a simple yet versatile one-step solution-processed approach at ambient conditions. Magnetite (Fe3O4) nanocrystals (NCs) with a size of 10-50 nm were uniformly deposited on the surfaces of graphene oxide (GO) sheets, which were confirmed by transmission electron microscopy (TEM) and high-angle annular dark field scanning transmission election microscopy (HAADF-STEM) studies. FGO with different Fe3O4 loadings could be controlled by simply manipulating the initial weight ratio of the precursors. The M-H measurements suggested that the as-prepared FGO nanocomposites have a large saturation magnetizations that made them can move regularly under an external magnetic field. Significantly, FGO nanocomposites also exhibit enhanced electric double-layer capacitor (EDLC) activity compared with pure Fe3O4 NCs and GO in terms of specific capacitance and high-rate charge-discharge.

Nutrient Controls on Methane Emissions in a Permafrost Thaw Subarctic Peatland

NASA Astrophysics Data System (ADS)

Kashi, N. N.; Perryman, C. R.; Malhotra, A.; Marek, E. A.; Giesler, R.; Varner, R. K.

2015-12-01

Permafrost peatlands in northern latitudes are large reservoirs of sequestered carbon that are vulnerable to climate change. While peatlands account for a small fraction of total global land surfaces, their potential to release sequestered carbon in response to higher temperatures is of concern. Of particular relevance is the conversion of these carbon stores into methane (CH4), a strong greenhouse gas with a global warming potential 20 times greater than that of CO2 over a 100-year time frame. Here, we explore how key nutrients impact the consumption of CH4 at the Stordalen Mire in Abisko, Sweden, a discontinuous permafrost peatland with expanding thaw over the last century. Peatland CH4 emissions are highly spatially variable due to multiple emission pathways and strong dependence on several environmental factors. Among controls on CH4 emissions, such as temperature and water table depth, primary production of wetland vegetation is also a strong factor in the variability of CH4 emissions. Plant community shifts among permafrost thaw stages subsequently change nutrient cycling and availability, which in turn impacts primary production. Early stages of permafrost thaw are mosaicked with a variety of vascular plants and mosses. We analyzed potential enzymatic activities of chitinase, glucosidase, and phosphatase as proxies for organic nitrogen, carbon, and phosphorus cycling, respectively, in tandem with potential CH4 oxidation rates. In addition, stoichiometric ratios of carbon, nitrogen, and phosphorus concentrations are used to illustrate nutrient limitation controls on CH4 oxidation rates. While CH4 emissions are low throughout initial thaw stages, < 7 CH4 mg m-2 day-1, we found they had the highest rates of potential CH4 oxidation. These permafrost thaw-induced CH4 oxidation rates are 5 and 11 times higher, in the surface and depth of the peat profile respectively, than subsequent aerobic permafrost thaw stages. As CH4 emissions are low in intact permafrost peatlands, these high rates of potential CH4 oxidation indicate the importance of plant communities and the methanotrophic microbes they harbor.

Coal-Packed Methane Biofilter for Mitigation of Green House Gas Emissions from Coal Mine Ventilation Air

PubMed Central

Limbri, Hendy; Gunawan, Cindy; Thomas, Torsten; Smith, Andrew; Scott, Jason; Rosche, Bettina

2014-01-01

Methane emitted by coal mine ventilation air (MVA) is a significant greenhouse gas. A mitigation strategy is the oxidation of methane to carbon dioxide, which is approximately twenty-one times less effective at global warming than methane on a mass-basis. The low non-combustible methane concentrations at high MVA flow rates call for a catalytic strategy of oxidation. A laboratory-scale coal-packed biofilter was designed and partially removed methane from humidified air at flow rates between 0.2 and 2.4 L min−1 at 30°C with nutrient solution added every three days. Methane oxidation was catalysed by a complex community of naturally-occurring microorganisms, with the most abundant member being identified by 16S rRNA gene sequence as belonging to the methanotrophic genus Methylocystis. Additional inoculation with a laboratory-grown culture of Methylosinus sporium, as investigated in a parallel run, only enhanced methane consumption during the initial 12 weeks. The greatest level of methane removal of 27.2±0.66 g methane m−3 empty bed h−1 was attained for the non-inoculated system, which was equivalent to removing 19.7±2.9% methane from an inlet concentration of 1% v/v at an inlet gas flow rate of 1.6 L min−1 (2.4 min empty bed residence time). These results show that low-cost coal packing holds promising potential as a suitable growth surface and contains methanotrophic microorganisms for the catalytic oxidative removal of methane. PMID:24743729

Predictive Finite Rate Model for Oxygen-Carbon Interactions at High Temperature

NASA Astrophysics Data System (ADS)

Poovathingal, Savio

An oxidation model for carbon surfaces is developed to predict ablation rates for carbon heat shields used in hypersonic vehicles. Unlike existing empirical models, the approach used here was to probe gas-surface interactions individually and then based on an understanding of the relevant fundamental processes, build a predictive model that would be accurate over a wide range of pressures and temperatures, and even microstructures. Initially, molecular dynamics was used to understand the oxidation processes on the surface. The molecular dynamics simulations were compared to molecular beam experiments and good qualitative agreement was observed. The simulations reproduced cylindrical pitting observed in the experiments where oxidation was rapid and primarily occurred around a defect. However, the studies were limited to small systems at low temperatures and could simulate time scales only of the order of nanoseconds. Molecular beam experiments at high surface temperature indicated that a majority of surface reaction products were produced through thermal mechanisms. Since the reactions were thermal, they occurred over long time scales which were computationally prohibitive for molecular dynamics to simulate. The experiments provided detailed dynamical data on the scattering of O, O2, CO, and CO2 and it was found that the data from molecular beam experiments could be used directly to build a model. The data was initially used to deduce surface reaction probabilities at 800 K. The reaction probabilities were then incorporated into the direct simulation Monte Carlo (DSMC) method. Simulations were performed where the microstructure was resolved and dissociated oxygen convected and diffused towards it. For a gas-surface temperature of 800 K, it was found that despite CO being the dominant surface reaction product, a gas-phase reaction forms significant CO2 within the microstructure region. It was also found that surface area did not play any role in concentration of reaction products because the reaction probabilities were in the diffusion dominant regime. The molecular beam data at different surface temperatures was then used to build a finite rate model. Each reaction mechanism and all rate parameters of the new model were determined individually based on the molecular beam data. Despite the experiments being performed at near vacuum conditions, the finite rate model developed using the data could be used at pressures and temperatures relevant to hypersonic conditions. The new model was implemented in a computational fluid dynamics (CFD) solver and flow over a hypersonic vehicle was simulated. The new model predicted similar overall mass loss rates compared to existing models, however, the individual species production rates were completely different. The most notable difference was that the new model (based on molecular beam data) predicts CO as the oxidation reaction product with virtually no CO2 production, whereas existing models predict the exact opposite trend. CO being the dominant oxidation product is consistent with recent high enthalpy wind tunnel experiments. The discovery that measurements taken in molecular beam facilities are able to determine individual reaction mechanisms, including dependence on surface coverage, opens up an entirely new way of constructing ablation models.

Effect of electrolyte temperature on the formation of self-organized anodic niobium oxide microcones in hot phosphate-glycerol electrolyte

NASA Astrophysics Data System (ADS)

Yang, S.; Aoki, Y.; Habazaki, H.

2011-07-01

Nanoporous niobium oxide films with microcone-type surface morphology were formed by anodizing at 10 V in glycerol electrolyte containing 0.6 mol dm -3 K 2HPO 4 and 0.2 mol dm -3 K 3PO 4 in a temperature range of 428-453 K. The microcones appeared after prolonged anodizing, but the required time was largely reduced by increasing electrolyte temperature. The anodic oxide was initially amorphous at all temperatures, but crystalline oxide nucleated during anodizing. The anodic oxide microcones, which were crystalline, appeared on surface as a consequence of preferential chemical dissolution of initially formed amorphous oxide. The chemical dissolution of an initially formed amorphous layer was accelerated by increasing the electrolyte temperature, with negligible influence of the temperature on the morphology of microcones up to 448 K.

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

PubMed

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.

Electrochemical Study of Corrosion Phenomena in Zirconium Alloys

DTIC Science & Technology

2005-06-01

required reaction rates [1.1]. Based predominantly on this fact, zirconium alloys were chosen to sheath, or clad, the fuel. With the increasing demand...cathode or anode. As the oxidation and reduction reactions occur, a galvanic cell is developed. The electrons on the anode are released from the metallic...matrix as the ions are released into the aqueous solution in the initial half-cell reaction . The second half-cell reaction , taking place on the

STIR: Tailored Interfaces for High Strength Composites Across Strain Rates

DTIC Science & Technology

2013-09-02

following by the nanowire growth . For the seeding process, the fibers were dipped into a colloidal solution of ZnO nanoparticles (2nm diameter) that was...to the fabric prior to nanowire growth . The synthesis of ZnO nanowire on Kevlar fabric surface was conducted in two steps; initial seeding and...Patterson, Mohammad H. Malakooti, Henry A. Sodano. Modification of Pullout Behavior of Kevlar Fabric by Zinc Oxide Nanowire Reinforcement, Proceedings of

Rapid removal of nitrobenzene in a three-phase ozone loaded system with gas-liquid-liquid

USGS Publications Warehouse

Li, Shiyin; Zhu, Jiangpeng; Wang, Guoxiang; Ni, Lixiao; Zhang, Yong; Green, Christopher T.

2015-01-01

This study explores the removal rate of nitrobenzene (NB) using a new gas-liquid-liquid (G-L-L) three-phase ozone loaded system consisting of a gaseous ozone, an aqueous solvent phase, and a fluorinated solvent phase (perfluorodecalin, or FDC). The removal rate of NB was quantified in relation to six factors including 1) initial pH, 2) initial NB dosage, 3) gaseous ozone dosage, 4) free radical scavenger, 5) FDC pre-aerated gaseous ozone, and 6) reuse of FDC. The NB removal rate is positively affected by the first three factors. Compared with the conventional gas-liquid (water) (G-L) two-phase ozonation system, the free radical scavenger (tertiary butyl alcohol) has much less influence on the removal rate of NB in the G-L-L system. The FDC loaded ozone acts as an ozone reservoir and serves as the main reactive phase in the G-L-L three-phase system. The reuse of FDC has little influence on the removal rate of NB. These experimental results suggest that the oxidation efficiency of ozonation in the G-L-L three-phase system is better than that in the conventional G-L two-phase system.

Graphene oxide hydrogel as a restricted-area nanoreactor for synthesis of 3D graphene-supported ultrafine TiO2 nanorod nanocomposites for high-rate lithium-ion battery anodes

NASA Astrophysics Data System (ADS)

Cheng, Jianli; Gu, Guifang; Ni, Wei; Guan, Qun; Li, Yinchuan; Wang, Bin

2017-07-01

Three-dimensional graphene-supported TiO2 nanorod nanocomposites (3D GS-TNR) are prepared using graphene oxide hydrogel as a restricted-area nanoreactor in the hydrothermal process, in which well-distributed TiO2 nanorods with a width of approximately 5 nm and length of 30 nm are conformally embedded in the 3D interconnected graphene network. The 3D graphene oxide not only works as a restricted-area nanoreactor to constrain the size, distribution and morphology of the TiO2; it also work as a highly interconnected conducting network to facilitate electrochemical reactions and maintain good structural integration when the nanocomposites are used as anode materials in lithium-ion batteries. Benefiting from the nanostructure, the 3D GS-TNR nanocomposites show high capacity and excellent long-term cycling capability at high current rates. The 3D GS-TNR composites deliver a high initial charge capacity of 280 mAh g-1 at 0.2 C and maintain a reversible capacity of 115 mAh g-1, with a capacity retention of 83% at 20 C after 1000 cycles. Meanwhile, compared with that of previously reported TiO2-based materials, the 3D GS-TNR nanocomposites show much better performance, including higher capacity, better rate capability and long-term cycling stability.

PRELIMINARY REPORT: EFFECTS OF IRRADIATION AND THERMAL EXPOSURE ON ELASTOMERIC SEALS FOR CASK TRANSPORTATION AND STORAGE

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

Verst, C.; Skidmore, E.; Daugherty, W.

2014-05-30

A testing and analysis approach to predict the sealing behavior of elastomeric seal materials in dry storage casks and evaluate their ability to maintain a seal under thermal and radiation exposure conditions of extended storage and beyond was developed, and initial tests have been conducted. The initial tests evaluate the aging response of EPDM elastomer O-ring seals. The thermal and radiation exposure conditions of the CASTOR® V/21 casks were selected for testing as this cask design is of interest due to its widespread use, and close proximity of the seals to the fuel compared to other cask designs leading tomore » a relatively high temperature and dose under storage conditions. A novel test fixture was developed to enable compression stress relaxation measurements for the seal material at the thermal and radiation exposure conditions. A loss of compression stress of 90% is suggested as the threshold at which sealing ability of an elastomeric seal would be lost. Previous studies have shown this value to be conservative to actual leakage failure for most aging conditions. These initial results indicate that the seal would be expected to retain sealing ability throughout extended storage at the cask design conditions, though longer exposure times are needed to validate this assumption. The high constant dose rate used in the testing is not prototypic of the decreasingly low dose rate that would occur under extended storage. The primary degradation mechanism of oxidation of polymeric compounds is highly dependent on temperature and time of exposure, and with radiation expected to exacerbate the oxidation.« less

On the possibility to grow zinc oxide-based transparent conducting oxide films by hot-wire chemical vapor deposition

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

Abrutis, Adulfas, E-mail: adulfas.abrutis@chf.vu.lt; Silimavicus, Laimis; Kubilius, Virgaudas

Hot-wire chemical vapor deposition (HW-CVD) was applied to grow zinc oxide (ZnO)-based transparent conducting oxide (TCO) films. Indium (In)-doped ZnO films were deposited using a cold wall pulsed liquid injection CVD system with three nichrome wires installed at a distance of 2 cm from the substrate holder. The wires were heated by an AC current in the range of 0–10 A. Zn and In 2,2,6,6-tetramethyl-3,5-heptanedionates dissolved in 1,2-dimethoxyethane were used as precursors. The hot wires had a marked effect on the growth rates of ZnO, In-doped ZnO, and In{sub 2}O{sub 3} films; at a current of 6–10 A, growth rates weremore » increased by a factor of ≈10–20 compared with those of traditional CVD at the same substrate temperature (400 °C). In-doped ZnO films with thickness of ≈150 nm deposited on sapphire-R grown at a wire current of 9 A exhibited a resistivity of ≈2 × 10{sup −3} Ωcm and transparency of >90% in the visible spectral range. These initial results reveal the potential of HW-CVD for the growth of TCOs.« less

Employing Synergetic Effect of Doping and Thin Film Coating to Boost the Performance of Lithium-Ion Battery Cathode Particles

PubMed Central

Patel, Rajankumar L.; Jiang, Ying-Bing; Choudhury, Amitava; Liang, Xinhua

2016-01-01

Atomic layer deposition (ALD) has evolved as an important technique to coat conformal protective thin films on cathode and anode particles of lithium ion batteries to enhance their electrochemical performance. Coating a conformal, conductive and optimal ultrathin film on cathode particles has significantly increased the capacity retention and cycle life as demonstrated in our previous work. In this work, we have unearthed the synergetic effect of electrochemically active iron oxide films coating and partial doping of iron on LiMn1.5Ni0.5O4 (LMNO) particles. The ionic Fe penetrates into the lattice structure of LMNO during the ALD process. After the structural defects were saturated, the iron started participating in formation of ultrathin oxide films on LMNO particle surface. Owing to the conductive nature of iron oxide films, with an optimal film thickness of ~0.6 nm, the initial capacity improved by ~25% at room temperature and by ~26% at an elevated temperature of 55 °C at a 1C cycling rate. The synergy of doping of LMNO with iron combined with the conductive and protective nature of the optimal iron oxide film led to a high capacity retention (~93% at room temperature and ~91% at 55 °C) even after 1,000 cycles at a 1C cycling rate. PMID:27142704

Enhanced electrochemical performance of Li-rich layered cathode materials via chemical activation of Li2MnO3 component and formation of spinel/carbon coating layer

NASA Astrophysics Data System (ADS)

Pang, Shengli; Xu, Kaijie; Wang, Yonggang; Shen, Xiangqian; Wang, Wenzhi; Su, Yanjing; Zhu, Meng; Xi, Xiaoming

2017-10-01

Li-rich layered oxides are promising cathode materials for advanced Li-ion batteries because of their high specific capacity and operating potential. In this work, the Li-rich layered oxide Li1·2Mn0·54Ni0·13Co0·13O2 (LMNC), is modified via a carbonization-reduction process (yielding the corresponding reduced compound denoted LMNC-R). Compared to the pristine oxide, LMNC-R delivers significantly enhanced initial discharge capacity/columbic efficiency, remarkably improved rate performance with an accelerated Li+ diffusion rate, and significantly increased capacity/voltage retention. The specific energy density and energy retention after 100 cycles increase from 378.2 Wh kg-1 and 47.7% for LMNC to 572.0 Wh kg-1 and 71.3%, respectively, for LMNC-R. The enhancement in the electrochemical performance of LMNC-R can be attributed to the synchronous formation of the oxygen non-stoichiometric Li2MnO3-δ component and to the carbon/spinel double coating layer in the material that resulted from the post-treatment process. Thus, the carbonization-reduction modification process can be used to tailor the structural evolution procedure and to suppress the metal ion dissolution of the Li-rich layered oxide during cycling.

Initial oxidation of pure and K doped NiTi shape memory alloys

NASA Astrophysics Data System (ADS)

Tollefsen, H.; Raaen, S.

2009-06-01

Initial oxidation of pure and K doped nitinol has been studied by photoelectron spectroscopy. The composition of the TiOx layer that forms on the surface is found to depend on the temperature during oxidation. The oxidation at high temperatures results in enhanced formation of lower oxides, whereas TiO2 predominates for oxidation at lower temperatures, e.g., 70 °C. Submonolayer coverage of K on NiTi enhances the formation of TiO2 on the expense of lower oxides, which is of consequence for formation of a protective oxide layer and biocompatibility. Oxidation in the martensitic phase was found to be independent of temperature for temperatures between -40 and 10 °C, whereas in the austenitic phase the oxide growth is thermally activated.

Oxidation of a new Biogenic VOC: Chamber Studies of the Atmospheric Chemistry of Methyl Chavicol

NASA Astrophysics Data System (ADS)

Bloss, William; Alam, Mohammed; Adbul Raheem, Modinah; Rickard, Andrew; Hamilton, Jacqui; Pereira, Kelly; Camredon, Marie; Munoz, Amalia; Vazquez, Monica; Vera, Teresa; Rodenas, Mila

2013-04-01

The oxidation of volatile organic compounds (VOCs) leads to formation of ozone and SOA, with consequences for air quality, health, crop yields, atmospheric chemistry and radiative transfer. Recent observations have identified Methyl Chavicol ("MC": Estragole; 1-allyl-4-methoxybenzene, C10H12O) as a major BVOC above pine forests in the USA, and oil palm plantations in Malaysian Borneo. Palm oil cultivation, and hence MC emissions, may be expected to increase with societal food and bio fuel demand. We present the results of a series of simulation chamber experiments to assess the atmospheric fate of MC. Experiments were performed in the EUPHORE facility, monitoring stable product species, radical intermediates, and aerosol production and composition. We determine rate constants for reaction of MC with OH and O3, and ozonolysis radical yields. Stable product measurements (FTIR, PTRMS, GC-SPME) are used to determine the yields of stable products formed from OH- and O3- initiated oxidation, and to develop an understanding of the initial stages of the MC degradation chemistry. A surrogate mechanism approach is used to simulate MC degradation within the MCM, evaluated in terms of ozone production measured in the chamber experiments, and applied to quantify the role of MC in the real atmosphere.

Mechanistic and kinetic investigation on OH-initiated oxidation of tetrabromobisphenol A.

PubMed

He, Maoxia; Li, Xin; Zhang, Shiqing; Sun, Jianfei; Cao, Haijie; Wang, Wenxing

2016-06-01

Detailed mechanism of the OH-initiated transformation of tetrabromobisphenol A (TBBPA) has been investigated by quantum chemical methods in this paper. Abstraction reactions of hydrogen atoms from the OH groups and CH3 groups of TBBPA are the dominant pathways of the initial reactions. The produced phenolic-type radical and alkyl-type radical may transfer to 4,4'-(ethene-1,1-diyl)bis(2,6-dibromophenol), 4-acetyl-2,6-dibromophenol and 2,6-dibromobenzoquinone at high temperature. In water, major products are 2,6-dibromo-p-hydroquinone, 4-isopropylene-2,6-dibromophenol and 4-(2-hydroxyisopropyl)-2,6-dibromophenol resulting from the addition reactions. Total rate constants of the initial reaction are 1.02 × 10(-12) cm(3) molecule(-1) s(-1) in gas phase and 1.93 × 10(-12) cm(3) molecule(-1) s(-1) in water at 298 K. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ovarian tumor-initiating cells display a flexible metabolism

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

Anderson, Angela S.; Roberts, Paul C.; Frisard, Madlyn I.

2014-10-15

An altered metabolism during ovarian cancer progression allows for increased macromolecular synthesis and unrestrained growth. However, the metabolic phenotype of cancer stem or tumor-initiating cells, small tumor cell populations that are able to recapitulate the original tumor, has not been well characterized. In the present study, we compared the metabolic phenotype of the stem cell enriched cell variant, MOSE-L{sub FFLv} (TIC), derived from mouse ovarian surface epithelial (MOSE) cells, to their parental (MOSE-L) and benign precursor (MOSE-E) cells. TICs exhibit a decrease in glucose and fatty acid oxidation with a concomitant increase in lactate secretion. In contrast to MOSE-L cells,more » TICs can increase their rate of glycolysis to overcome the inhibition of ATP synthase by oligomycin and can increase their oxygen consumption rate to maintain proton motive force when uncoupled, similar to the benign MOSE-E cells. TICs have an increased survival rate under limiting conditions as well as an increased survival rate when treated with AICAR, but exhibit a higher sensitivity to metformin than MOSE-E and MOSE-L cells. Together, our data show that TICs have a distinct metabolic profile that may render them flexible to adapt to the specific conditions of their microenvironment. By better understanding their metabolic phenotype and external environmental conditions that support their survival, treatment interventions can be designed to extend current therapy regimens to eradicate TICs. - Highlights: • Ovarian cancer TICs exhibit a decreased glucose and fatty acid oxidation. • TICs are more glycolytic and have highly active mitochondria. • TICs are more resistant to AICAR but not metformin. • A flexible metabolism allows TICs to adapt to their microenvironment. • This flexibility requires development of specific drugs targeting TIC-specific changes to prevent recurrent TIC outgrowth.« less

SiGe-on-insulator fabricated via germanium condensation following high-fluence Ge+ ion implantation

NASA Astrophysics Data System (ADS)

Anthony, R.; Haddara, Y. M.; Crowe, I. F.; Knights, A. P.

2017-08-01

Germanium condensation is demonstrated using a two-step wet oxidation of germanium implanted Silicon-On-Insulator (SOI). Samples of 220 nm thick SOI are implanted with a nominal fluence of 5 × 1016 cm-2 Ge+ at an energy of 33 keV. Primary post-implantation wet oxidation is performed initially at 870 °C for 70 min, with the aim of capping the sample without causing significant dose loss via Ge evaporation through the sample surface. This is followed by a secondary higher temperature wet oxidation at either 900 °C, 1000 °C, or 1080 °C. The germanium retained dose and concentration profile, and the oxide thickness is examined after primary oxidation, and various secondary oxidation times, using Rutherford backscattering analysis. A mixed SiGe oxide is observed to form during the primary oxidation followed by a pure silicon oxide after higher temperature secondary oxidation. The peak germanium concentration, which varies with secondary oxidation condition, is found to range from 43 at. % to 95 at. %, while the FWHM of the Ge profile varies from 13 to 5 nm, respectively. It is also observed that both the diffusion of germanium and the rate of oxidation are enhanced at 870 and 900 °C compared to equilibrium expectations. Transmission electron microscopy of a representative sample with secondary oxidation at 1080 °C for 20 min shows that the SiGe layer is crystalline in nature and seeded from the underlying silicon. Raman spectroscopy is used to determine residual strain in the SiGe region following secondary oxidation. The strain is compressive in nature and increases with Ge concentration to a maximum of approximately 1% in the samples probed. In order to elucidate the physical mechanisms, which govern the implantation-condensation process, we fit the experimental profiles of the samples with a model that uses a modified segregation boundary condition; a modified linear rate constant for the oxidation; and an enhanced diffusion coefficient of germanium where the enhancement is inversely proportional to the temperature and decays with increasing time. Comparison of the modeled and experimental results shows reasonable agreement and allows conclusions to be made regarding the dominant physical mechanisms, despite the semi-empirical nature of the model used.

Experimental Study and Mathematical Modeling of Self-Sustained Kinetic Oscillations in Catalytic Oxidation of Methane over Nickel.

PubMed

Lashina, Elena A; Kaichev, Vasily V; Saraev, Andrey A; Vinokurov, Zakhar S; Chumakova, Nataliya A; Chumakov, Gennadii A; Bukhtiyarov, Valerii I

2017-09-21

The self-sustained kinetic oscillations in the oxidation of CH 4 over Ni foil have been studied at atmospheric pressure using an X-ray diffraction technique and mass spectrometry. It has been shown that the regular oscillations appear under oxygen-deficient conditions; CO, CO 2 , H 2 , and H 2 O are detected as the products. According to in situ X-ray diffraction measurements, nickel periodically oxidizes to NiO initiating the reaction-rate oscillations. To describe the oscillations, we have proposed a five-stage mechanism of the partial oxidation of methane over Ni and a corresponding three-variable kinetic model. The mechanism considers catalytic methane decomposition, dissociative adsorption of oxygen, transformation of chemisorbed oxygen to surface nickel oxide, and reaction of adsorbed carbon and oxygen species to form CO. Analysis of the kinetic model indicates that the competition of two processes, i.e., the oxidation and the carbonization of the catalyst surface, is the driving force of the self-sustained oscillations in the oxidation of methane. We have compared this mechanism with the detailed 18-stage mechanism described previously by Lashina et al. (Kinetics and Catalysis 2012, 53, 374-383). It has been shown that both kinetic mechanisms coupled with a continuous stirred-tank reactor model describe well the oscillatory behavior in the oxidation of methane under non-isothermal conditions.

Spatial variation of charge and sulfur oxidation state in a surface gradient affects plasma proteins adsorption

PubMed Central

Ding, Yong-Xue; Streitmatter, Seth; Wright, Bryon E.; Hlady, Vladimir

2010-01-01

A gradient of negative surface charge based on 1-D spatial variation from surface sulfhydryl to mixed sulfhydryl-sulfonate moities was prepared by controlled UV oxidation of 3-mercaptopropylsilane monolayer on fused silica. Adsorption of three human plasma proteins, albumin (HSA), immunoglobulin G (IgG), and fibrinogen (Fgn) onto such surface gradient was studied using spatially-resolved total internal reflection fluorescence (TIRF) and autoradiography. Adsorption was measured from dilute solutions equivalent to 1/100 (TIRF, autoradiography), and 1/500 and 1/1000 (autoradiography) of protein’s physiological concentrations in plasma. All three proteins adsorbed more to the non-oxidized sulfhydryl region than to the oxidized, mixed sulfhydryl-sulfonate region of the gradient. In the case of HSA the adsorption contrast along the gradient was largest when the adsorption took place from more dilute protein solutions. Increasing the concentration to 1/100 of protein plasma concentration eliminated the effect of the gradient on HSA adsorption and to the lesser extent on IgG adsorption. In the case of Fgn the greatest adsorption contrast was observed at the highest concentration used. Based on adsorption kinetics, the estimated binding affinity of HSA for the sulfhydryl region what twice the affinity for the mixed sulfhydryl-sulfonate region of the gradient. For IgG and Fgn the initial adsorption was transport-limited and the initial adsorption rates approached the computed flux of the protein to the surface. PMID:20568822

Co2+-exchange mechanism of birnessite and its application for the removal of Pb2+ and As(III).

PubMed

Yin, Hui; Liu, Fan; Feng, Xionghan; Liu, Mingming; Tan, Wenfeng; Qiu, Guohong

2011-11-30

Co-containing birnessites were obtained by ion exchange at different initial concentrations of Co(2+). Ion exchange of Co(2+) had little effect on birnessite crystal structure and micromorphology, but resulted in an increase in specific surface areas from 19.26 to 33.35 m(2)g(-1), and a decrease in both crystallinity and manganese average oxidation state. It was due to that Mn(IV) in the layer structure was reduced to Mn(III) during the oxidation process of Co(2+) to Co(III). The hydroxyl groups on the surface of Co-containing birnessites gradually decreased with an increase of Co/Mn molar ratio owing to the occupance of Co(III) into vacancies and the location of large amounts of Co(2+/3+) and Mn(2+/3+) above/below the vacant sites. This greatly accounted for the monotonous reduction in Pb(2+) adsorption capacity, from 2538 mmol kg(-1) for the unmodified birnessite to 1500 mmol kg(-1) for the Co(2+) ion-exchanged birnessite with a Co/Mn molar ratio of 0.16. The amount of As(III) oxidized by birnessite was enhanced after ion exchange, but the apparent initial reaction rate was greatly decreased. The present work demonstrates that Co(2+) ion exchange has great influence on the adsorption and oxidation behavior of inorganic toxic metal ions by birnessite in water environments. Copyright © 2011 Elsevier B.V. All rights reserved.

Reactivity of Metal Oxide Sorbents for Removal of H{sub 2}S

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

Kwon, K.C.; Crowe, E.R.

1996-12-31

Removal of hydrogen sulfide contained in hot coal gases produced from integrated gasification combined cycle power generation systems is required to protect downstream combustion turbines from being corroded with sulfur compounds. Removal of sulfur compounds from hot coal gas products is investigated by using various metal oxide sorbents and membrane separation methods. The main requirements of these metal oxide sorbents are durability and high sulfur loading capacity during absorption-regeneration cycles. In this research, durable metal oxide sorbents were formulated. Reactivity of the formulated metal oxide sorbents with simulated coal gas mixtures was examined to search for an ideal sorbent formulationmore » with a high-sulfur loading capacity suitable for removal of hydrogen sulfide from coal gases. The main objectives of this research are to formulate durable metal oxide sorbents with high-sulfur loading capacity by a physical mixing method, to investigate reaction kinetics on the removal of sulfur compounds from coal gases at high temperature and pressure, to study reaction kinetics on the regeneration of sulfided sorbents, to identify effects of hydrogen partial pressures and moisture on equilibrium/dynamic absorption of hydrogen sulfide into formulated metal oxide sorbents as well as initial reaction rates of H{sub 2}S with formulated metal oxide sorbents, and to evaluate intraparticular diffusivity of H{sub 2}S into formulated sorbents at various reaction conditions. The metal oxide sorbents such as TU-1, TU-19, TU-24, TU-25 and TU-28 were formulated with zinc oxide powder as an active sorbent ingredient, bentonite as a binding material and titanium oxide as a supporting metal oxide.« less

Auger electron spectroscopy study of initial stages of oxidation in a copper - 19.6-atomic-percent-aluminum alloy

NASA Technical Reports Server (NTRS)

Ferrante, J.

1973-01-01

Auger electron spectroscopy was used to examine the initial stages of oxidation of a polycrystalline copper - 19.6 a/o-aluminum alloy. The growth of the 55-eV aluminum oxide peak and the decay of the 59-, 62-, and 937-eV copper peaks were examined as functions of temperature, exposure, and pressure. Pressures ranged from 1x10 to the minus 7th power to 0.0005 torr of O2. Temperatures ranged from room temperature to 700 C. A completely aluminum oxide surface layer was obtained in all cases. Complete disappearance of the underlying 937-eV copper peak was obtained by heating at 700 C in O2 at 0.0005 torr for 1 hr. Temperature studies indicated that thermally activated diffusion was important to the oxidation studies. The initial stages of oxidation followed a logarithmic growth curve.

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid.

PubMed

Lederer, Madeline R; Staniec, Allison R; Coates Fuentes, Zoe L; Van Ry, Daryl A; Hinrichs, Ryan Z

2016-12-08

Biogenic volatile organic compounds (BVOCs), including the monoterpene limonene, are a major source of secondary organic aerosol (SOA). While gas-phase oxidation initiates the dominant pathway for BVOC conversion to SOA, recent studies have demonstrated that biogenic hydrocarbons can also directly react with acidic droplets. To investigate whether mineral dust may facilitate similar reactive uptake of biogenic hydrocarbons, we studied the heterogeneous reaction of limonene with mineral substrates using condensed-phase infrared spectroscopy and identified the formation of irreversibly adsorbed organic products. For kaolinite, Arizona Test Dust, and silica at 30% relative humidity, GC-MS identified limonene-1,2-diol as the dominant product with total organic surface concentrations on the order of (3-5) × 10 18 molecules m -2 . Experiments with 18 O-labeled water support a mechanism initiated by oxidation of limonene by surface redox sites forming limonene oxide followed by water addition to the epoxide to form limonenediol. Limonene uptake on α-alumina, γ-alumina, and montmorillonite formed additional products in high yield, including carveol, carvone, limonene oxide, and α-terpineol. To model tropospheric processing of mineral aerosol, we also exposed each mineral substrate to gaseous nitric acid prior to limonene uptake and identified similar surface adsorbed products that were formed at rates 2 to 5 times faster than without nitrate coatings. The initial rate of reaction was linearly dependent on gaseous limonene concentration between 5 × 10 12 and 5 × 10 14 molecules cm -3 (0.22-20.5 ppm) consistent with an Eley-Rideal-type mechanism in which gaseous limonene reacts directly with reactive surface sites. Increasing relative humidity decreased the amount of surface adsorbed products indicating competitive adsorption of surface adsorbed water. Using a laminar flow tube reactor we measured the uptake coefficient for limonene on kaolinite at 25% RH to range from γ = 5.1 × 10 -6 to 9.7 × 10 -7 . After adjusting for reactive surface areas, we estimate uptake coefficients for limonene on HNO 3 -processed mineral aerosol on the order of (1-6) × 10 -6 . Although this heterogeneous reaction will not impact the atmospheric lifetime of gaseous limonene, it does provide a new pathway for mineral aerosol to acquire secondary organic matter from biogenic hydrocarbons, which in turn will alter the physical properties of mineral dust.

Oxidation of the odorous compound 2,4,6-trichloroanisole by UV activated persulfate: Kinetics, products, and pathways.

PubMed

Luo, Congwei; Jiang, Jin; Ma, Jun; Pang, Suyan; Liu, Yongze; Song, Yang; Guan, Chaoting; Li, Juan; Jin, Yixin; Wu, Daoji

2016-06-01

The transformation efficiency and products of an odorous compound 2,4,6-trichloroanisole (TCA) at the wavelength of 254 nm in the presence of persulfate were investigated for the first time. The effects of water matrix (i.e., natural organic matter (NOM), pH, carbonate/bicarbonate (HCO3(-)/CO3(2-)), and chloride ions (Cl(-))) were evaluated. The second order rate constant of TCA reacting with sulfate radical (SO4(-)) was determined to be (3.72 ± 0.10) × 10(9) M(-1) s(-1). Increasing dosage of persulfate increased the observed pseudo-first-order rate constant for TCA degradation (kobs), and the contribution of SO4(-) to TCA degradation was much higher than that of HO at each experimental condition. Degradation rate of TCA decreased with pH increasing from 4.0 to 9.0, which could be explained by the lower radical scavenging effect of dihydrogen phosphate than hydrogen phosphate in acidic condition (pH < 6). NOM significantly decreased kobs due to the effects of radical scavenging and UV absorption with the former one being dominant. kobs decreased from 2.32 × 10(-3) s(-1) to 0.92 × 10(-3) s(-1) with the CO3(2-)/HCO3(-) concentration increased from 0.5 mM to 10 mM in the UV/persulfate process, while kobs slightly decreased from 2.54 × 10(-3) s(-1) in the absence of Cl(-) to 2.10 × 10(-3) s(-1) in the presence of 10 mM Cl(-). Most of these kinetic results could be described by a steady-state kinetic model. Furthermore, liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry at powerful precursor ion scan approach was used to selectively detect oxidation products of TCA. It was found that 2,4,6-trichorophenol (TCP) was the major oxidation product (i.e., the initial yield of TCP was above 90%). The second order rate constant between TCP and SO4(-) was estimated to be (4.16 ± 0.20) × 10(9) M(-1) s(-1). In addition, three products (i.e., 2,6-dichloro-1,4-benzoquinone and two aromatic ring-opening products) were detected in the reaction of TCP with SO4(-), which also appeared in the oxidation of TCA in the UV/persulfate process. A tentative pathway was proposed, where the initial one-electron oxidation of TCA by SO4(-) and further reactions (e.g., ipso-hydroxylation and aromatic ring-cleavage) of the formed cation intermediate TCA were involved. Copyright © 2016. Published by Elsevier Ltd.

Iron dynamics: Transformation of Fe(II)/Fe(III) during injection of natural organic matter in a sandy aquifer

NASA Astrophysics Data System (ADS)

Liang, Liyuan; McCarthy, John F.; Jolley, Louwanda W.; McNabb, J. Andrew; Mehlhorn, Tonia L.

1993-05-01

The dynamics of dissolved, colloidal, and deposited iron phases were examined during a forced-gradient field experiment. The experiment involved the injection of oxygenated water containing high levels of natural organic matter (NOM) into a sandy aquifer. The initial redox potential of the aquifer favored Fe(II) in the groundwater. The changes in the concentrations of Fe(II) and Fe(III) were observed in sampling wells. Under the increased dissolved oxygen (DO) conditions, Fe(II) oxygenation was rapid, resulting in the formation of Fe(III) (hydr) oxide colloids. The oxidation follows the rate law as given in STUMM and MORGAN (1981): d[ Fe(II)] /dt = - k obs[ O2( aq)] /[ H+] 2[ Fe(II)] , with a rate constant, kobs to be 1.9 × 10 -12 M min -1. For an averaged pH and DO of the groundwater, the half time of Fe(II) oxidation is 49 h. The NOM was postulated to stabilize the newly formed colloids, thereby increasing the turbidity in the groundwater. The additional increase in the colloidal fraction of Fe(III) oxide suggested that transport of the colloidal particles was occurring. At those locations where DO remained constantly low, the turbidity increase was moderate, and up to 80% of Fe(III) was in the dissolved phase (< 3000 mol. wt). The latter observation was attributed to the presence of NOM, forming Fe(III)-organic complexes. In addition, NOM may play a role in the oxygen consumption through a Fe(II)/Fe(III) catalyzed oxidation of organic matter as outlined by STUMM and MORGAN (1981, p. 469). In this mechanism, Fe(II) oxidation is slow, maintaining a near constant Fe(II) concentration, in agreement with field data. The overall increase in Fe(III) under low DO conditions was postulated to be a combination of (1) slow oxidation, (2) ligand-promoted and catalytic dissolution of deposited iron phases, and (3) the transport of newly formed iron oxide colloids along flow paths.

Preliminary study on optimization of pH, oxidant and catalyst dose for high COD content: solar parabolic trough collector

PubMed Central

2013-01-01

In the present study, solar photocatalytic oxidation has been investigated through laboratory experiments as an alternative to conventional secondary treatment for the organic content reduction of high COD wastewater. Experiments have been performed on synthetic high COD wastewater for solar photocatalytic oxidation using a parabolic trough reactor. Parameters affecting the oxidation of organics have been investigated. The experimental design followed the sequence of dark adsorption studies of organics, followed by photolytic studies (in absence of catalyst) and finally photocatalytic studies in presence and absence of additional oxidant (H2O2). All the experimental studies have been performed at pH values of 2, 4, 6,8,10 and the initial pH value of the wastewater (normal pH). For photocatalytic studies, TiO2 has been used as a photocatalyst. Optimization of catalyst dose, pH and H2O2 concentration has been done. Maximum reduction of organic content was observed at the normal pH value of the wastewater (pH = 6.8). The reaction rate was significantly enhanced in presence of hydrogen peroxide. The optimum pH other than the Normal was in the alkaline range. Acidic pH was not found to be favourable for organic content reduction. pH was found to be a dominant factor affecting reaction rate even in presence of H2O2 as an additional oxidant. Also, the solar detoxification process was effective in treating a waste with a COD level of more than 7500 mg/L, which is a otherwise a difficult waste to treat. It can therefore be used as a treatment step in the high organic wastewater treatment during the primary stage also as it effectively reduces the COD content by 86%. PMID:23369352

Middle atmosphere NO/x/ production due to ion propulsion induced radiation belt proton precipitation

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Jackman, C. H.

1980-01-01

The suggestion that keV Ar(+) resulting from ion propulsion operations during solar power satellite construction could cause energetic proton precipitation from the inner radiation belt is examined to determine if such precipitation could cause significant increases in middle atmosphere nitric oxide concentrations thereby adversely affecting stratospheric ozone. It is found that the initial production rate of NO (mole/cu cm-sec) at 50 km is 130 times that due to nitrous oxide reacting with excited oxygen. However, since the time required to empty the inner belt of protons is about 1 sec and short compared to the replenishment time due to neutron decay, precipitation of inner radiation belt protons will have no adverse atmospheric environmental effect.

Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

PubMed

Minakata, Daisuke; Crittenden, John

2011-04-15

The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

Characterization and Electrochromic Properties of Vanadium Oxide Thin Films Prepared via Spray Pyrolysis

NASA Astrophysics Data System (ADS)

Mousavi, M.; Kompany, A.; Shahtahmasebi, N.; Bagheri-Mohagheghi, M.-M.

2013-08-01

Vanadium oxide thin films were grown on glass substrates using spray pyrolysis technique. The effects of substrate temperature, vanadium concentration in the initial solution and the solution spray rate on the nanostructural and the electrochromic properties of deposited films are investigated. Characterization and the electrochromic measurements were carried out using X-ray diffraction, scanning electron microscopy and cyclic voltammogram. XRD patterns showed that the prepared films have polycrystalline structure and are mostly mixed phases of orthorhombic α-V2O5 along with minor β-V2O5 and V4O9 tetragonal structures. The preferred orientation of the deposited films was found to be along [101] plane. The cyclic voltammogram results obtained for different samples showed that only the films with 0.2 M solution concentration, 5 ml/min solution spray rate and 450°C substrate temperature exhibit two-step electrochromic properties. The results show a correlation between cycle voltammogram, morphology and resistance of the films.

Crystallization of copper metaphosphate glass

NASA Technical Reports Server (NTRS)

Bae, Byeong-Soo; Weinberg, Michael C.

1993-01-01

The effect of the valence state of copper in copper metaphosphate glass on the crystallization behavior and glass transition temperature has been investigated. The crystallization of copper metaphosphate is initiated from the surface and its main crystalline phase is copper metaphosphate (Cu(PO)3),independent of the (Cu sup 2+)/(Cu(total)). However, the crystal morphology, the relative crystallization rates, and their temperature dependences are affected by the (Cu sup 2+)/(Cu (total)) ratio in the glass. On the other hand, the totally oxidized glass crystallizes from all over the surface. The relative crystallization rate of the reduced glass to the totally oxidized glass is large at low temperature, but small at high temperature. The glass transition temperature of the glass increases as the (Cu sup 2+)/(Cu(total)) ratio is raised. It is also found that the atmosphere used during heat treatment does not influence the crystallization of the reduced glass, except for the formation of a very thin CuO surface layer when heated in air.

Role of nitrification in the biodegradation of selected artificial sweetening agents in biological wastewater treatment process.

PubMed

Tran, N H; Nguyen, V T; Urase, T; Ngo, H H

2014-06-01

The biodegradation of the six artificial sweetening agents including acesulfame (ACE), aspartame (ASP), cyclamate (CYC), neohesperidindihydrochalcone (NHDC), saccharin (SAC), and sucralose (SUC) by nitrifying activated sludge was first examined. Experimental results showed that ASP and NHDC were the most easily degradable compounds even in the control tests. CYC and SAC were efficiently biodegraded by the nitrifying activated sludge, whereas ACE and SUC were poorly removed. However, the biodegradation efficiencies of the ASs were increased with the increase in initial ammonium concentrations in the bioreactors. The association between nitrification and co-metabolic degradation was investigated and a linear relationship between nitrification rate and co-metabolic biodegradation rate was observed for the target artificial sweeteners (ASs). The contribution of heterotrophic microorganisms and autotrophic ammonia oxidizers in biodegradation of the ASs was elucidated, of which autotrophic ammonia oxidizers played an important role in the biodegradation of the ASs, particularly with regards to ACE and SUC. Copyright © 2014 Elsevier Ltd. All rights reserved.

Aggregation of a Monoclonal Antibody Induced by Adsorption to Stainless Steel

PubMed Central

Bee, Jared S.; Davis, Michele; Freund, Erwin; Carpenter, John F.; Randolph, Theodore W.

2014-01-01

Stainless steel is a ubiquitous surface in therapeutic protein production equipment and is also present as the needle in some pre-filled syringe biopharmaceutical products. Stainless steel microparticles can cause of aggregation of a monoclonal antibody (mAb). The initial rate of mAb aggregation was second-order in steel surface area and zero-order in mAb concentration, generally consistent with a bimolecular surface aggregation being the rate-limiting step. Polysorbate 20 (PS20) suppressed the aggregation yet was unable to desorb the firmly bound first layer of protein that adsorbs to the stainless steel surface. Also, there was no exchange of mAb from the first adsorbed layer to the bulk phase, suggesting that the aggregation process actually occurs on subsequent adsorption layers. No oxidized Met residues were detected in the mass spectrum of a digest of a highly aggregated mAb, although there was five-fold increase in carbonyl groups due to protein oxidation. PMID:19725039

Effect of delignification upon in vitro digestion of forage cellulose.

PubMed

Darcy, B K; Belyea, R L

1980-10-01

Orchardgrass forages harvested at two maturities (early and late) were ground through two screens (1 and 8 mm) and digested in vitro as intact forage and forage delignified by permanganate oxidation. Initial and residual cell wall, initial and residual cellulose and potentially digestible cellulose were greater in late intact forage than in the early. In the delignified forage, late cut forage had less residual cellulose than did the early, but initial and potentially digestible cellulose were similar. Particle size had less consistent and smaller effects upon cell wall and cellulose than did maturity. Cellulose of intact orchardgrass was 64% digested at 72 h vs 94% for cellulose of delignified orchardgrass. Digestion rate of cellulose was .0197 and .0220 logn units/hr for early and late cut intact forage and .0554 and .0719 logn units/hr for early and late cut delignified forage. Removal of the inhibitory effects of lignin increased the amount of digestible cellulose, increased the rate at which cellulose degraded and decreased the indigestible cellulose residue. Reduction in lignin could greatly improve forage intake and utilization at moderate levels of animal production.

Ferrate(VI) enhanced photocatalytic oxidation of pollutants in aqueous TiO2 suspensions.

PubMed

Sharma, Virender K; Graham, Nigel J D; Li, Xiang-Zhong; Yuan, Bao-Ling

2010-02-01

Photocatalytic oxidation using UV irradiation of TiO(2) has been studied extensively and has many potential industrial applications, including the degradation of recalcitrant contaminants in water and wastewater treatment. A limiting factor in the oxidation process is the recombination of conduction band electrons (e(-)(cb)) with electron holes (h(vb)(+)) on the irradiated TiO(2) surface; thus, in aqueous conditions, the presence of an effective electron scavenger will be beneficial to the efficiency of the oxidation process. Ferrate (FeO(4)(2-)) has received much recent attention as a water treatment chemical since it behaves simultaneously as an oxidant and coagulant. The combination of ferrate [Fe(VI)] with UV/TiO(2) photocatalysis offers an oxidation synergism arising from the Fe(VI) scavenging of e(-)(cb) and the corresponding beneficial formation of Fe(V) from the Fe(VI) reduction. This paper reviews recent studies concerning the photocatalytic oxidation of problematic pollutants with and without ferrate. The paper reviews the published results of laboratory experiments designed to follow the photocatalytic degradation of selected contaminants of environmental significance and the influence of the experimental conditions (e.g. pH, reactant concentrations and dissolved oxygen). The specific compounds are as follows: ammonia, cyanate, formic acid, bisphenol-A, dibutyl- and dimethyl-phthalate and microcystin-LR. The principal focus in these studies has been on the rates of reaction rather than on reaction pathways and products. The presence of UV/TiO(2) accelerates the chemical reduction of ferrate, and the reduction rate decreases with pH owing to deprotonation of ferrate ion. For all the selected contaminant substances, the photocatalytic oxidation rate was greater in the presence of ferrate, and this was believed to be synergistic rather than additive. The presence of dissolved oxygen in solution reduced the degradation rate of dimethyl phthalate in the ferrate/photocatalysis system. In the study of microcystin-LR, it was evident that an optimal ferrate concentration exists, whereby higher Fe(VI) concentrations above the optimum leads to a reduction in microcystin-LR degradation. In addition, the rate of microcystin-LR degradation was found to be strongly dependent on pH and was greatest at pH 6. The initial rate of photocatalytic reduction under different conditions was analysed using a Langmuirian form. Decrease in rates in the presence of dissolved oxygen may be due to competition between oxygen and ferrate as electron scavengers and to non-productive radical species interactions. The reaction between ferrate(VI) and microcystins-LR in the pH range of 6.0-10.0 is most likely controlled by the protonated Fe(VI) species, HFeO(4)(-). The photocatalytic oxidation of selected, recalcitrant contaminants was found to be significantly greater in the presence of ferrate, arising from the role of ferrate in inhibiting the h(vb)(+)-e(-)(cb) pair recombination on TiO(2) surfaces and the corresponding generation of highly oxidative Fe(V) species. The performance of the ferrate/photocatalysis system is strongly influenced by the reaction conditions, particularly the pH and dissolved oxygen concentration, arising from the complex nature of the interactions between the catalyst and the solution. Overall, the treatment performance of the Fe(VI)-TiO(2)-UV system is generally superior to alternative chemical oxidation methods. The formation of intermediate Fe(V) species in the photocatalytic reduction of ferrate(VI) requires confirmation, and a method involving electron paramagnetic resonance spectroscopy could be applied for this. The reactivity of Fe(V) with the selected contaminants is required in order to better understand the role of ferrate in the Fe(VI)-TiO(2)-UV oxidation system. To increase the practical utility of the system, it is recommended that future studies involving the photocatalytic oxidation of pollutants in the presence of ferrate(VI) should focus on developing modified TiO(2) surfaces that are photocatalytic under visible light conditions.

Three-dimensional three-phase model for simulation of hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification in an oxidation ditch.

PubMed

Lei, Li; Ni, Jinren

2014-04-15

A three-dimensional three-phase fluid model, supplemented by laboratory data, was developed to simulate the hydrodynamics, oxygen mass transfer, carbon oxidation, nitrification and denitrification processes in an oxidation ditch. The model provided detailed phase information on the liquid flow field, gas hold-up distribution and sludge sedimentation. The three-phase model described water-gas, water-sludge and gas-sludge interactions. Activated sludge was taken to be in a pseudo-solid phase, comprising an initially separated solid phase that was transported and later underwent biological reactions with the surrounding liquidmedia. Floc parameters were modified to improve the sludge viscosity, sludge density, oxygen mass transfer rate, and carbon substrate uptake due to adsorption onto the activated sludge. The validation test results were in very satisfactory agreement with laboratory data on the behavior of activated sludge in an oxidation ditch. By coupling species transport and biological process models, reasonable predictions are made of: (1) the biochemical kinetics of dissolved oxygen, chemical oxygen demand (COD) and nitrogen variation, and (2) the physical kinematics of sludge sedimentation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Oxidation behavior of FeAl+Hf,Zr,B

NASA Technical Reports Server (NTRS)

Smialek, James L.; Doychak, Joseph

1988-01-01

The oxidation behavior of Fe-40Al-1Hf, Fe-40Al-1Hf-0.4B, and Fe-40Al-0.1Zr-0.4B (at. percent) alloys was characterized after 900, 1000, and 100 C exposures. Isothermal tests revealed parabolic kinetics after a period of transitional theta-alumina scale growth. The parabolic growth rates for the subsequent alpha-alumina scales were about five times higher than those for NiAl+0.1Zr alloys. The isothermally grown scales showed a propensity toward massive scale spallation due to both extensive rumpling from growth stresses and to an inner layer of HfO2. Cyclic oxidation for 200 1-hr cycles produced little degradation at 900 or 1000 C, but caused significant spallation at 1100 C in the form of small segments of the outer scale. The major difference in the cyclic oxidation of the three FeAl alloys was increased initial spallation for FeAl+Zr,B. Although these FeAl alloys showed many similarities to NiAl alloys, they were generally less oxidation resistant. It is believed that this resulted from nonoptimal levels of dopants and larger thermal expansion mismatch stresses.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-02-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Cobalt oxide-carbon nanosheet nanoarchitecture as an anode for high-performance lithium-ion battery.

PubMed

Wang, Huanlei; Mao, Nan; Shi, Jing; Wang, Qigang; Yu, Wenhua; Wang, Xin

2015-02-04

To improve the electrochemical performance of cobalt oxide owing to its inherent poor electrical conductivity and large volume expansion/contraction, Co3O4-carbon nanosheet hybrid nanoarchitectures were synthesized by a facile and scalable chemical process. However, it is still a challenge to control the size of Co3O4 particles down to ∼5 nm. Herein, we created nanosized cobalt oxide anchored 3D arrays of carbon nanosheets by the control of calcination condition. The uniformly dispersed Co3O4 nanocrystals on carbon nanosheets held a diameter down to ∼5 nm. When tested as anode materials for lithium-ion batteries, high lithium storage over 1200 mAh g(-1) is achieved, whereas high rate capability with capacity of about 390 mAh g(-1) at 10 A g(-1) is maintained through nanoscale diffusion distances and interconnected porous structure. After 500 cycles, the cobalt oxide-carbon nansheets hybrid display a reversible capacity of about 970 mAh g(-1) at 1 A g(-1). The synergistic effect between nanosized cobalt oxide and sheetlike interconnected carbon nanosheets lead to the greatly improved specific capacity and the initial Coulombic efficiency of the hybrids.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

PubMed Central

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-01-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

[Fructose as a factor of Carbonyl and oxidative stress development and accelerated aging in the yeast Saccharomyces].

PubMed

Lozins'ka, L M; Semchyshyn, G M

2011-01-01

Excessive and prolonged consumption of fructose may lead to the development of metabolic disorders. However, the mechanisms of disturbances are still discussed. In the present work, the budding yeast Saccharomyces cerevisiae has been used as a model to compare the effects of prolonged consumption of different concentrations of glucose and fructose on certain physiology-biochemical parameters of eukaryotes. It has been shown that the yeast growth, their metabolic activity, intracellular level of glycogen and oxidized proteins were higher in cells grown on fructose. The observation is consistent with the data on a higher in vitro ability of fructose than glucose to initiate glycation which products of which are highly reactive a-dicarbonyl compounds and activated oxygen forms. Thus the intensity of carbonyl and oxidative stress is higher in cells grown on fructose. This can explain a higher rate of aging of yeast consuming fructose as a source of carbon and energy as compared to cells growing on glucose. However, carbohydrate restriction used in this study ham- pered the accumulation of glycogen and oxidized proteins and did not reveal any difference between markers of aging and carbonyl and oxidative stress in yeast grown on glucose and fructose.

Microbial degradation of [C14C]polystyrene and 1,3-diphenylbutane.

PubMed

Sielicki, M; Focht, D D; Martin, J P

1978-07-01

Microbial degradation of [beta-14C]polystyrene and 1,3-diphenylbutane, a compound structurally representing the smallest repeating unit of styrene (dimer), was investigated in soil and liquid enrichment cultures. Degradation rates in soil, as determined by 14CO2 evolution from applied [14C]polystyrene, varied from 1.5 to 3.0% for a 4-month period. Although relatively low, these percentages were 15 to 30 times greater than values previously reported. Enrichment cultures, containing 1,3-diphenylbutane as the only carbon souce, were used to determine the mechanisms of microbial oxidation of the polymer chain ends. Metabolism of 1,3-diphenylbutane appeared to involve the attack by a monooxygenease to form 2-phenyl-4-hydroxyphenylbutane followed by a further oxidation and subsequent fission of the benzene ring to yield 4-phenylvaleric acid and an unidentified 5-carbon fragment via the classic meta-fission pathway. Phenylacetic acid was probably formed from 4-phenylvaleric acid by subsequent beta-oxidation of the side chain, methyl-oxidation and decarboxylation. An initial examination of the population of microorganisms in the diphenylbutane enrichment cultures indicated that these oxidative reactions are carried out by common soil microorganism of the genera Bacillus, Pseudomonas, Micrococcus, and Nocardia.

Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

NASA Astrophysics Data System (ADS)

Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

2016-09-01

Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

Multiple transformation pathways of p-arsanilic acid to inorganic arsenic species in water during UV disinfection.

PubMed

Li, Suqi; Xu, Jing; Chen, Wei; Yu, Yingtan; Liu, Zizheng; Li, Jinjun; Wu, Feng

2016-09-01

p-Arsanilic acid (p-ASA) is widely used in China as livestock and poultry feed additive for promoting animal growth. The use of organoarsenics poses a potential threat to the environment because it is mostly excreted by animals in its original form and can be transformed by UV-Vis light excitation. This work examined the initial rate and efficiency of p-ASA phototransformation under UV-C disinfection lamp. Several factors influencing p-ASA phototransformation, namely, pH, initial concentration, temperature, as well as the presence of NaCl, NH4(+), and humic acid, were investigated. Quenching experiments and LC-MS were performed to investigate the mechanism of p-ASA phototransformation. Results show that p-ASA was decomposed to inorganic arsenic (including As(III) and As(V)) and aromatic products by UV-C light through direct photolysis and indirect oxidation. The oxidation efficency of p-ASA by direct photosis was about 32%, and those by HO and (1)O2 were 19% and 49%, respectively. Cleavage of the arsenic-benzene bond through direct photolysis, HO oxidation or (1)O2 oxidation results in simultaneous formation of inorganic As(III), As(IV), and As(V). Inorganic As(III) is oxidized to As(IV) and then to As(V) by (1)O2 or HO. As(IV) can undergo dismutation or simply react with oxygen to produce As(V) as well. Reactions of the organic moieties of p-ASA produce aniline, aminophenol and azobenzene derivatives as main products. The photoconvertible property of p-ASA implies that UV disinfection of wastewaters from poultry and swine farms containing p-ASA poses a potential threat to the ecosystem, especially agricultural environments. Copyright © 2016. Published by Elsevier B.V.

Oxidative phosphorylation flexibility in the liver of mice resistant to high-fat diet-induced hepatic steatosis.

PubMed

Poussin, Carinne; Ibberson, Mark; Hall, Diana; Ding, Jun; Soto, Jamie; Abel, E Dale; Thorens, Bernard

2011-09-01

To identify metabolic pathways that may underlie susceptibility or resistance to high-fat diet-induced hepatic steatosis. We performed comparative transcriptomic analysis of the livers of A/J and C57Bl/6 mice, which are, respectively, resistant and susceptible to high-fat diet-induced hepatosteatosis and obesity. Mice from both strains were fed a normal chow or a high-fat diet for 2, 10, and 30 days, and transcriptomic data were analyzed by time-dependent gene set enrichment analysis. Biochemical analysis of mitochondrial respiration was performed to confirm the transcriptomic analysis. Time-dependent gene set enrichment analysis revealed a rapid, transient, and coordinate upregulation of 13 oxidative phosphorylation genes after initiation of high-fat diet feeding in the A/J, but not in the C57Bl/6, mouse livers. Biochemical analysis using liver mitochondria from both strains of mice confirmed a rapid increase by high-fat diet feeding of the respiration rate in A/J but not C57Bl/6 mice. Importantly, ATP production was the same in both types of mitochondria, indicating increased uncoupling of the A/J mitochondria. Together with previous data showing increased expression of mitochondrial β-oxidation genes in C57Bl/6 but not A/J mouse livers, our present study suggests that an important aspect of the adaptation of livers to high-fat diet feeding is to increase the activity of the oxidative phosphorylation chain and its uncoupling to dissipate the excess of incoming metabolic energy and to reduce the production of reactive oxygen species. The flexibility in oxidative phosphorylation activity may thus participate in the protection of A/J mouse livers against the initial damages induced by high-fat diet feeding that may lead to hepatosteatosis.

Sonocatalytic degradation of malachite green oxalate by a semiconductor metal oxide nanocatalyst.

PubMed

Bhavani, R; Sivasamy, A

2016-12-01

Advanced Oxidation Process (AOP) technologies are considered to be better technique for the degradation or mineralization of many recalcitrant compounds and pollutants. In the present study heterogeneous sonocatalytic degradation of a model organic compound such as Malachite green oxalate (MGO) was carried out in the aqueous phase. Zinc oxide nanorods were prepared by precipitation method employing zinc acetates as precursors and were characterized by FT-IR, XRD, FE-SEM and EDAX analysis. Degradation of MGO in the aqueous phase was studied in detail under the sonocatalytic process. Effects of pH, dye concentration, oxidant concentration, kinetics and effect of electrolytes on dye degradation were carried out to check the efficiency of the sonocatalyst. Effect of energy input on the degradation processes was also investigated. The degradation of dye molecules were monitored by UV-visible spectrophotometer and Chemical Oxygen demand (COD). The dye molecules were readily degraded at above 90% in the pH range 5.0-7.0 under ultrasound with zinc oxide nanorods. The interference of electrolytes like NaCl, KCl, Na 2 CO 3 , NaHCO 3 and MgSO 4 on the degradation of dye molecules were also studied on the sonocatalytic degradation of MGO. From the kinetic studies it was observed that at lower initial concentration of dye molecules the degradation efficiency was above 90%. The rate of the reaction decreased on increasing the initial dye concentrations of the dye molecules. It was observed that the complete mineralization of dye molecules was achieved without the formation of toxic by-products. The reusability of the catalyst also showed the effective degradation of the dye molecules up to five cycles without loss of the catalytic activities. Copyright © 2015 Elsevier Inc. All rights reserved.

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation.

PubMed

Wan, Wei; Pepping, Troy J; Banerji, Tuhin; Chaudhari, Sanjeev; Giammar, Daniel E

2011-01-01

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations. Copyright © 2010 Elsevier Ltd. All rights reserved.

The performance and decolourization kinetics of O3/H2O2 oxidation of reactive green 19 dye in wastewater

NASA Astrophysics Data System (ADS)

Sabri, S. N.; Abidin, C. Z. A.; Fahmi; Kow, S. H.; Razali, N. A.

2018-03-01

The degradations characteristic of azo dye Reactive Green 19 (RG19) was investigated using advanced oxidation process (AOPs). It was evaluated based on colour and chemical oxygen demand (COD) removal. The effect of operational parameters such as initial dye concentration, initial dosage of hydrogen peroxide (H2O2), contact time, and pH was also being studied. The samples were treated by ozonation (O3) and peroxone O3/H2O2 process. Advanced oxidation processes (AOPs) involve two stages of oxidation; firstly is the formation of strong oxidant and secondly the reaction of organic contaminants in water. In addition, the term advanced oxidation is referring to the processes in which oxidation of organic contaminants occurs primarily through reactions with hydroxyl radicals. There are several analyses that use to determine the efficiency of the treatment process, which are UV-Vis absorption spectra, COD, Fourier Transform Infrared (FT-IR), and pH. The results demonstrated that the ozone oxidation was efficient in decolourization and good in mineralization, based on the reduction of colour and COD. Additionally, results indicate that H2O2 is able to perform better than ozonation in order to decolourize the dye wastewater with 0.5 mL H2O2/L dye dosage of H2O2 at different initial concentration, initial pH, with contact time.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

PubMed

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

Sulfur oxidation to sulfate coupled with electron transfer to electrodes by Desulfuromonas strain TZ1

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

Zhang, T; Bain, TS; Barlett, MA

2014-01-02

Microbial oxidation of elemental sulfur with an electrode serving as the electron acceptor is of interest because this may play an important role in the recovery of electrons from sulfidic wastes and for current production in marine benthic microbial fuel cells. Enrichments initiated with a marine sediment inoculum, with elemental sulfur as the electron donor and a positively poised (+300 mV versus Ag/AgCl) anode as the electron acceptor, yielded an anode biofilm with a diversity of micro-organisms, including Thiobacillus, Sulfurimonas, Pseudomonas, Clostridium and Desulfuromonas species. Further enrichment of the anode biofilm inoculum in medium with elemental sulfur as the electronmore » donor and Fe(III) oxide as the electron acceptor, followed by isolation in solidified sulfur/Fe(III) medium yielded a strain of Desulfuromonas, designated strain TZ1. Strain TZ1 effectively oxidized elemental sulfur to sulfate with an anode serving as the sole electron acceptor, at rates faster than Desulfobulbus propionicus, the only other organism in pure culture previously shown to oxidize S with current production. The abundance of Desulfuromonas species enriched on the anodes of marine benthic fuel cells has previously been interpreted as acetate oxidation driving current production, but the results presented here suggest that sulfur-driven current production is a likely alternative.« less

Stable isotopes and iron oxide mineral products as markers of chemodenitrification.

PubMed

Jones, L Camille; Peters, Brian; Lezama Pacheco, Juan S; Casciotti, Karen L; Fendorf, Scott

2015-03-17

When oxygen is limiting in soils and sediments, microorganisms utilize nitrate (NO3-) in respiration--through the process of denitrification--leading to the production of dinitrogen (N2) gas and trace amounts of nitrous (N2O) and nitric (NO) oxides. A chemical pathway involving reaction of ferrous iron (Fe2+) with nitrite (NO2-), an intermediate in the denitrification pathway, can also result in production of N2O. We examine the chemical reduction of NO2- by Fe(II)--chemodenitrification--in anoxic batch incubations at neutral pH. Aqueous Fe2+ and NO2- reacted rapidly, producing N2O and generating Fe(III) (hydr)oxide mineral products. Lepidocrotite and goethite, identified by synchrotron X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, were produced from initially aqueous reactants, with two-line ferrihydrite increasing in abundance later in the reaction sequence. Based on the similarity of apparent rate constants with different mineral catalysts, we propose that the chemodenitrification rate is insensitive to the type of Fe(III) (hydr)oxide. With stable isotope measurements, we reveal a narrow range of isotopic fractionation during NO2- reduction to N2O. The location of N isotopes in the linear N2O molecule, known as site preference, was also constrained to a signature range. The coexistence of Fe(III) (hydr)oxide, characteristic 15N and 18O fractionation, and N2O site preference may be used in combination to qualitatively distinguish between abiotic and biogenically emitted N2O--a finding important for determining N2O sources in natural systems.

Mach 1 oxidation of thoriated nickel chromium at 1204 C (2200 F)

NASA Technical Reports Server (NTRS)

Lowell, C. E.; Sanders, W. A.

1971-01-01

TD NiCr was exposed to a Mach 1, 1-atmosphere gas stream at 1204 C for times up to 50 hours. Weight change, metal thickness loss, X-ray diffraction, metallographic, and electron microprobe analyses were made. Neither surface preparation nor thermal cycling had an appreciable effect on the results. Initially, Cr2O3 formed and volatilized, allowing a rapid metal loss rate of 40 microns per hour. After about 1 hour the Cr2O3 broke down, resulting in an NiO overgrowth. The metal loss rate then slowed to 2.5 microns per hour and remained constant to 50 hours.

Effect of UV and UV/H2O2 in the presence of chloramines on NDMA formation potential of tramadol.

PubMed

Radjenovic, Jelena; Farré, Maria José; Gernjak, Wolfgang

2012-08-07

This study evaluates the effect of UV-C and UV-C/H(2)O(2) in the presence of chloramines on the N-nitrosodimethylamine formation potential (NDMA FP) of tramadol as a model precursor. The experiments were performed at high initial concentrations of TMDL (i.e., 20 mg/L) in order to elucidate the structures of TMDL byproducts. Twenty-four byproducts were identified in UV-C, UV-C/monochloramine, and UV/H(2)O(2)/monochloramine oxidation of tramadol using MS(3) capabilities of a hybrid quadrupole-linear ion trap mass spectrometer, combined with online hydrogen/deuterium (H/D) exchange experiments. Oxidative cleavage of methoxy and methoxybenzene moiety, O-demethylation, hydroxylation, and cyclohexane ring-opening were identified as major reaction mechanisms of tramadol in UV oxidation. Addition of monochloramine decreased the degradation rates of tramadol and its byproducts and yielded several monochlorinated derivatives. The oxidation rates were significantly enhanced in the presence of H(2)O(2), and byproducts of oxidative benzene ring-opening were detected. The majority of the identified byproducts are likely to have a higher NDMA FP than the parent compound due to a reduced steric hindrance and/or insertion of electron-donating hydroxyl groups in the N,N-dimethylamine side chain. This was confirmed by the results of NDMA FP tests, which showed that the formation of NDMA was enhanced up to four times depending on the process conditions in UV alone and in UV and UV/H(2)O(2) in the presence of monochloramine. Prolonged oxidation by hydroxyl radicals in UV/H(2)O(2)/monochloramine process mineralized some of the byproducts and slightly reduced the NDMA FP at the end of the treatment. The obtained degradation pathway of tramadol allowed the correlation of changes in NDMA FP during oxidation with its major oxidative transformation reactions. This manuscript demonstrates the significance of oxidation byproducts as NDMA precursors and emphasizes the need for their consideration when evaluating the evolution of NDMA FP during oxidative treatment.

Wet air oxidation induced enhanced biodegradability of distillery effluent.

PubMed

Malik, S N; Saratchandra, T; Tembhekar, P D; Padoley, K V; Mudliar, S L; Mudliar, S N

2014-04-01

The present study reports the feasibility of Wet Air Oxidation (WAO) as a pretreatment option for enhanced biodegradation of complex distillery effluent. Initially, the distillery effluent was pretreated by WAO at different process conditions (pressure, temperature and time) to facilitate enhancement in the biodegradability index (BI = BOD5: COD ratio). The biodegradability of WAO pretreated effluent was evaluated by subjecting it to aerobic biodegradation and anaerobic followed by aerobic biodegradation. Aerobic biodegradation of pretreated effluent with enhanced biodegradability index (BI = 0.4-0.8) showed enhanced COD reduction of up to 67.7%, whereas the untreated effluent (BI = 0.17) indicated poor COD reduction of only 22.5%. Anaerobic followed by aerobic biodegradation of pretreated effluent has shown up to 87.9% COD reduction, while the untreated effluent has shown only 43.1% COD reduction. Bio-kinetic parameters also confirmed the increased rate of bio-oxidation at enhanced BIs. The results indicate that the WAO pretreatment facilitates enhanced bio-oxidation/bio-degradation of complex effluents like the distillery spent wash. Copyright © 2014 Elsevier Ltd. All rights reserved.

Reduced graphene oxide supported highly porous V2O5 spheres as a high-power cathode material for lithium ion batteries.

PubMed

Rui, Xianhong; Zhu, Jixin; Sim, Daohao; Xu, Chen; Zeng, Yi; Hng, Huey Hoon; Lim, Tuti Mariana; Yan, Qingyu

2011-11-01

Reduced graphene oxide (rGO) supported highly porous polycrystalline V(2)O(5) spheres (V(2)O(5)/rGO) were prepared by using a solvothermal approach followed by an annealing process. Initially, reduced vanadium oxide (rVO) nanoparticles with sizes in the range of 10-50 nm were formed through heterogeneous nucleation on rGO sheets during the solvothermal process. These rVO nanoparticles were oxidized to V(2)O(5) after the annealing process in air at 350 °C and assembled into polycrystalline porous spheres with sizes of 200-800 nm. The weight ratio between the rGO and V(2)O(5) is tunable by changing the weight ratio of the precursors, which in turn affects the morphology of V(2)O(5)/rGO composites. The V(2)O(5)/rGO composites display superior cathode performances with highly reversible specific capacities, good cycling stabilities and excellent rate capabilities (e.g. 102 mA h g(-1) at 19 C).

Physical and oxidative removal of organics during Fenton treatment of mature municipal landfill leachate.

PubMed

Deng, Yang

2007-07-19

Municipal landfill leachate, especially mature leachate, may disrupt the performance of moderately-sized municipal activated sludge wastewater treatment plants, and likewise tend to be recalcitrant to biological pretreatment. Recently, Fenton methods have been investigated for chemical treatment or pre-treatment of mature leachate. In this paper, the results of laboratory tests to determine the roles of oxidation and coagulation in reducing the organic content of mature leachate during Fenton treatment are presented. The efficiencies of chemical oxygen demand (COD) oxidation and coagulation were tested, and the ratio of COD removal by oxidation to that by coagulation was assessed, under various operating conditions. Low initial pH, appropriate relative and absolute Fenton reagent dosages, aeration, and stepwise addition of reagents increased COD removal by oxidation and the importance of oxidation relative to coagulation. Simultaneous aeration and stepwise reagent addition allowed comparable treatment without initial acidification pH, due to the generation of acidic organic intermediates and the continuous input of CO2. On the other hand, high COD oxidation efficiency and low ferrous dosage inhibited COD removal by coagulation. At significantly high oxidation efficiency, overall COD reduction decrease slightly due to low coagulation efficiency. Under the most favorable conditions (initial pH 3, molar ratio [H(2)O(2)]/[Fe2+]=3, [H2O2]=240 mM, and six dosing steps), 61% of the initial COD was removed, and the ratio of COD removal oxidation to coagulation was 0.75. Results highlighted the synergistic roles of oxidation and coagulation in Fenton treatment of mature leachate, and the role of oxidation in controlling the efficiency of removal of COD by coagulation.

Development and validation of sensitive kinetic spectrophotometric method for the determination of moxifloxacin antibiotic in pure and commercial tablets

NASA Astrophysics Data System (ADS)

Ashour, Safwan; Bayram, Roula

2015-04-01

New, accurate, sensitive and reliable kinetic spectrophotometric method for the assay of moxifloxacin hydrochloride (MOXF) in pure form and pharmaceutical formulations has been developed. The method involves the oxidative coupling reaction of MOXF with 3-methyl-2-benzothiazolinone hydrazone hydrochloride monohydrate (MBTH) in the presence of Ce(IV) in an acidic medium to form colored product with lambda max at 623 and 660 nm. The reaction is followed spectrophotometrically by measuring the increase in absorbance at 623 nm as a function of time. The initial rate and fixed time methods were adopted for constructing the calibration curves. The linearity range was found to be 1.89-40.0 μg mL-1 for initial rate and fixed time methods. The limit of detection for initial rate and fixed time methods is 0.644 and 0.043 μg mL-1, respectively. Molar absorptivity for the method was found to be 0.89 × 104 L mol-1 cm-1. Statistical treatment of the experimental results indicates that the methods are precise and accurate. The proposed method has been applied successfully for the estimation of moxifloxacin hydrochloride in tablet dosage form with no interference from the excipients. The results are compared with the official method.

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation.

PubMed

Minero, Claudio; Maurino, Valter; Bono, Francesca; Pelizzetti, Ezio; Marinoni, Angela; Mailhot, Gilles; Carlotti, Maria Eugenia; Vione, Davide

2007-08-01

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.

Oxidative dissolution of pyrite surfaces by hexavalent chromium: Surface site saturation and surface renewal

NASA Astrophysics Data System (ADS)

Graham, Andrew M.; Bouwer, Edward J.

2012-04-01

In-situ reduction of toxic Cr(VI) to nontoxic Cr(III) represents an important natural attenuation process for Cr(VI)-impacted environments. This study investigates the stoichiometry and kinetics of Cr(VI) reduction by pyrite, a reduced iron-sulfur mineral ubiquitous in recent estuarine and marine sediments. Pyrite suspensions at surface loadings of 0.28-2.10 m2/L (typical of estuarine or marine sediments) were capable of completely reducing 7-120 μM Cr(VI) on the timescale of minutes to days, with the time to reaction completion decreasing with increasing pyrite loading, decreasing initial Cr(VI) concentration, and decreasing suspension pH. Analysis of metal species (Cr and Fe) and sulfur species in solution and at the mineral surface indicated that Cr(VI) oxidatively dissolved the pyrite surface, releasing ferrous iron and sulfate into solution as the reaction progressed. Surface disulfide groups were postulated as the Cr(VI)-reactive surface entity. Net production or consumption of aqueous Fe(II) was shown to depend upon the relative rates of proton-promoted Fe(II) release, Fe(II) release due to oxidative dissolution of pyrite in the presence of Cr(VI), and Fe(II) consumption due to homogeneous reaction with Cr(VI). Kinetics of Cr(VI) reduction by pyrite displayed a biphasic pattern, and the time to reaction completion increased dramatically with increasing initial Cr(VI) concentration. Rapid Cr(VI) removal occurred early in the reaction progress, attributable to Cr(VI) loss under an adsorption-limited regime. Slow, approximately zero-order, Cr(VI) removal occurred over the bulk of the time courses, and corresponded to Cr(VI) removal under surface site saturation conditions. Stoichiometric Cr(VI) reduction was able to proceed under surface site limited conditions owing to regeneration of reactive surface sites following desorption/dissolution of oxidized surface products, as demonstrated in repeat Cr(VI)-spiking experiments. The role of surface passivation was evaluated by comparing rates of Cr(VI) reduction in the presence and absence of the Cr(III)-complexing agent citrate. While citrate addition significantly enhanced Cr(III) solubility, rates of Cr(VI) reduction were only marginally accelerated, suggesting that Cr(OH)3(s) coatings did not completely block access of Cr(VI) to reactive surface sites on pyrite. Given the rapid rates of Cr(VI) reduction with pyrite under pH and surface coverage conditions typical of natural environments, we propose that Cr(VI) reduction by pyrite be considered in fate and transport models for Cr in contaminated sediments.

Detailed mechanism of toluene oxidation and comparison with benzene

NASA Technical Reports Server (NTRS)

Bittker, David A.

1988-01-01

A detailed mechanism for the oxidation of toluene in both argon and nitrogen dilutents is presented. The mechanism was used to compute experimentally ignition delay times for shock-heated toluene-oxygen-argon mixtures with resonably good success over a wide range of initial temperatures and pressures. Attempts to compute experimentally measured concentration profiles for toluene oxidation in a turbulent reactor were partially successful. An extensive sensitivity analysis was performed to determine the reactions which control the ignition process and the rates of formation and destruction of various species. The most important step was found to be the reaction of toluene with molecular oxygen, followed by the reactions of hydroperoxyl and atomic oxygen with benzyl radicals. These findings contrast with the benzene oxidation, where the benzene-molecular oxygen reaction is quite unimportant and the reaction of phenyl with molecular oxygen dominates. In the toluene mechanism the corresponding reaction of benzyl radicals with oxygen is unimportant. Two reactions which are important in the oxidation of benzene also influence the oxidation of toluene for several conditions. These are the oxidations of phenyl and cyclopentadienyl radicals by molecular oxygen. The mechanism presented successfully computes the decrease of toluene concentration with time in the nitrogen diluted turbulent reactor. This fact, in addition to the good prediction of ignition delay times, shows that this mechanism can be used for modeling the ignition and combustion process in practical, well-mixed combustion systems.

Remediation of TCE-contaminated groundwater using acid/BOF slag enhanced chemical oxidation.

PubMed

Tsai, T T; Kao, C M; Wang, J Y

2011-04-01

The objective of this study was to evaluate the potential of applying acid/H(2)O(2)/basic oxygen furnace slag (BOF slag) and acid/S(2)O(8)(2-)/BOF slag systems to enhance the chemical oxidation of trichloroethylene (TCE)-contaminated groundwater. Results from the bench-scale study indicate that TCE oxidation via the Fenton-like oxidation process can be enhanced with the addition of BOF slag at low pH (pH=2-5.2) and neutral (pH=7.1) conditions. Because the BOF slag has iron abundant properties (14% of FeO and 6% of Fe(2)O(3)), it can be sustainably reused for the supplement of iron minerals during the Fenton-like or persulfate oxidation processes. Results indicate that higher TCE removal efficiency (84%) was obtained with the addition of inorganic acid for the activation of Fenton-like reaction compared with the experiments with organic acids addition (with efficiency of 10-15% lower) (BOF slag=10gL(-1); initial pH=5.2). This could be due to the fact that organic acids would compete with TCE for available oxidants. Results also indicate that the pH value had a linear correlation with the observed first-order decay constant of TCE, and thus, lower pH caused a higher TCE oxidation rate. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enhancing the Oxidation Stability of Polydivinylbenzene Films via Residual Pendant Vinyl Passivation

DOE PAGES

Lepro, Xavier; Ehrmann, Paul; Rodriguez, Jennifer; ...

2018-01-11

Polydivinylbenzene (PDVB) is a thermally stable, optically transparent, crosslinked polymer that until recently has been difficult to synthesize as a thin film. With the recent demonstration of initiated chemical vapor deposition (iCVD) of thin PDVB films, a renewed interest in the material properties of PDVB has developed. In particular, attention is now focused on its oxidation pathways and long-term stability under the desired application use conditions. In this paper, we report on the thermal and environmental stability of PDVB films and show that unreacted pendant vinyl groups drive polymer oxidation upon exposure to either air or light. We demonstrate thatmore » such vinyls can be effectively passivated by a simple ex-situ thermal annealing at ca. 300 °C in inert atmosphere that induces an 87% reduction of the PDVB oxidation rate in air and slows light (λ=405 nm) induced oxidation by 56%. While the thermal annealing is less effective at preventing oxidation under higher energy (λ = 365 nm) UV light, we demonstrate that this aging pathway is based on the presence of reactive oxygen species rather than traditional photo-oxidation. Finally, vinyl removal through ex-situ thermal annealing improves the chemical stability of iCVD PDVB to continuous air (over 500 days) or light (70 hours) exposure and offers a simple option to improve its environmental aging resistance which is important for long-term protective applications.« less

Betanodavirus Induces Oxidative Stress-Mediated Cell Death That Prevented by Anti-Oxidants and Zfcatalase in Fish Cells

PubMed Central

Chang, Chih-Wei; Su, Yu-Chin; Her, Guor-Mour; Ken, Chuian-Fu; Hong, Jiann-Ruey

2011-01-01

The role of oxidative stress in the pathogenesis of RNA nervous necrosis virus infection is still unknown. Red-spotted grouper nervous necrosis virus (RGNNV) induced free radical species (ROS) production at 12–24 h post-infection (pi; early replication stage) in fish GF-1 cells, and then at middle replication stage (24–48 h pi), this ROS signal may upregulate some expressions of the anti-oxidant enzymes Cu/Zn SOD and catalase, and eventually expression of the transcription factor Nrf2. Furthermore, both antioxidants diphenyliodonium and N-acetylcysteine or overexpression of zebrafish catalase in GF-1 cells also reduced ROS production and protected cells for enhancing host survival rate due to RGNNV infection. Furthermore, localization of ROS production using esterase activity and Mitotracker staining assays found that the ROS generated can affect mitochondrial morphology changes and causes ΔΨ loss, both of which can be reversed by antioxidant treatment. Taken together, our data suggest that RGNNV induced oxidative stress response for playing dual role that can initiate the host oxidative stress defense system to upregulate expression of antioxidant enzymes and induces cell death via disrupting the mitochondrial morphology and inducing ΔΨ loss, which can be reversed by anti-oxidants and zfcatalase, which provide new insight into betanodavirus-induced ROS-mediated pathogenesis. PMID:21991373

In vitro measurements of oxygen consumption rates in hTERT-RPE cells exposed to low levels of red light

NASA Astrophysics Data System (ADS)

Wigle, Jeffrey C.; Castellanos, Cherry C.

2016-03-01

Exposure to 2.88 J/cm2 of red light induces an adaptive response against a lethal pulse of 2.0 μm laser radiation in hTERT-RPE cells in vitro, but not in a knockdown mutant for vascular endothelial growth factor c (VEGF-C). The generally accepted initiation sequence for photobiomodulation is that absorption of red light by cytochome c oxidase (CCOX) of the electron transport chain increases the binding affinity of CCOX for O2 vs. nitric oxide (NO). This results in displacement of NO by O2 in the active site of CCOX, thereby increasing cellular respiration and intracellular ATP. We've previously reported that red-light exposure induces a small, but consistently reproducible, increase in NO levels in these cells. But the relative importance of NO and oxidative phosphorylation is unclear because little is known about the relative contributions of NO and ATP to the response. However, if NO dissociation from CCOX actually increases oxidative phosphorylation, one should see a corresponding increase in oxygen consumption. A Seahorse Extracellular Flux Analyzer was used to measure oxygen consumption rates (OCR) in normal and mutant cells as a proxy for oxidative phosphorylation. Both basal respiration and maximum respiration rates in normal cells are significantly higher than in the mutant. The normal cells have a significant amount of "excess capacity," whereas the VEGF-C(KD) have little or none. The OCR in exposed normal cells is lower than in unexposed cells when measured immediately after exposure. The exposures used for these experiments had no effect on the OCR in mutant cells.

Thermal barrier coating life prediction model development

NASA Technical Reports Server (NTRS)

Sheffler, K. D.; Demasi, J. T.

1985-01-01

A methodology was established to predict thermal barrier coating life in an environment simulative of that experienced by gas turbine airfoils. Specifically, work is being conducted to determine failure modes of thermal barrier coatings in the aircraft engine environment. Analytical studies coupled with appropriate physical and mechanical property determinations are being employed to derive coating life prediction model(s) on the important failure mode(s). An initial review of experimental and flight service components indicates that the predominant mode of TBC failure involves thermomechanical spallation of the ceramic coating layer. This ceramic spallation involves the formation of a dominant crack in the ceramic coating parallel to and closely adjacent to the metal-ceramic interface. Initial results from a laboratory test program designed to study the influence of various driving forces such as temperature, thermal cycle frequency, environment, and coating thickness, on ceramic coating spalling life suggest that bond coat oxidation damage at the metal-ceramic interface contributes significantly to thermomechanical cracking in the ceramic layer. Low cycle rate furnace testing in air and in argon clearly shows a dramatic increase of spalling life in the non-oxidizing environments.

In vitro degradation and biocompatibility of a strontium-containing micro-arc oxidation coating on the biodegradable ZK60 magnesium alloy

NASA Astrophysics Data System (ADS)

Lin, Xiao; Yang, Xiaoming; Tan, Lili; Li, Mei; Wang, Xin; Zhang, Yu; Yang, Ke; Hu, Zhuangqi; Qiu, Jianhong

2014-01-01

Magnesium alloys are promising biodegradable implant candidates for orthopedic application. In the present study, a phosphate-based micro-arc oxidation (MAO) coating was applied on the ZK60 alloy to decrease its initial degradation rate. Strontium (Sr) was incorporated into the coating in order to improve the bioactivity of the coating. The in vitro degradation studies showed that the MAO coating containing Sr owned a better initial corrosion resistance, which was mainly attributed to the superior inner barrier layer, and a better long-term protective ability, probably owning to its larger thickness, superior inner barrier layer and the superior apatite formation ability. The degradation of MAO coating was accompanied by the formation of degradation layer and Ca-P deposition layer. The in vitro cell tests demonstrated that the incorporation of Sr into the MAO coating enhanced both the proliferation of preosteoblast cells and the alkaline phosphatase activity of the murine bone marrow stromal cells. In conclusion, the MAO coating with Sr is a promising surface treatment for the biodegradable magnesium alloys.

Ignition in an Atomistic Model of Hydrogen Oxidation.

PubMed

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

2017-03-02

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

Effect of Iron(II) on Arsenic Sequestration by δ-MnO 2 : Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy

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

Wu, Yun; Li, Wei; Sparks, Donald L.

2015-10-18

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO 2) in the presence of Fe(II)more » prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO 4 3–) and calcium (Ca 2+). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.« less

Effect of Iron(II) on Arsenic Sequestration by δ-MnO2: Desorption Studies Using Stirred-Flow Experiments and X-Ray Absorption Fine-Structure Spectroscopy.

PubMed

Wu, Yun; Li, Wei; Sparks, Donald L

2015-11-17

Arsenic (As) mobility in the environment is greatly affected by its oxidation state and the degree to which it is sorbed on metal oxide surfaces. Manganese (Mn) and iron (Fe) oxides are ubiquitous solids in terrestrial systems and have high sorptive capacities for many trace metals, including As. Although numerous studies have studied the effects of As adsorption and desorption onto Fe and Mn oxides individually, the fate of As within mixed systems representative of natural environments has not been resolved. In this research, As(III) was initially reacted with a poorly crystalline phyllomanganate (δ-MnO2) in the presence of Fe(II) prior to desorption. This initial reaction resulted in the sorption of both As(III) and As(V) on mixed Fe/Mn-oxides surfaces. A desorption study was carried out using two environmentally significant ions, phosphate (PO4(3-)) and calcium (Ca(2+)). Both a stirred-flow technique and X-ray absorption fine-structure spectroscopy (XAFS) analysis were used to investigate As desorption behavior. Results showed that when As(III)/Fe(II) = 1:1 in the initial reaction, only As(V) was desorbed, agreeing with a previous study showing that As(III) is not associated with the Fe/Mn-oxides. When As(III)/Fe(II) = 1:10 in the initial reaction, both As(III) and As(V) can be desorbed from the Fe/Mn-oxide surface, and more As(III) is desorbed than As(V). Neither of the desorbents used in this study completely removed As(III) or As(V) from the Fe/Mn-oxides surface. However, the As desorption fraction decreases with increasing Fe(II) concentration in the initial reactions.

Gaseous oxidized mercury dry deposition measurements in the southwestern USA: a comparison between Texas, eastern Oklahoma, and the Four Corners area.

PubMed

Sather, Mark E; Mukerjee, Shaibal; Allen, Kara L; Smith, Luther; Mathew, Johnson; Jackson, Clarence; Callison, Ryan; Scrapper, Larry; Hathcoat, April; Adam, Jacque; Keese, Danielle; Ketcher, Philip; Brunette, Robert; Karlstrom, Jason; Van der Jagt, Gerard

2014-01-01

Gaseous oxidized mercury (GOM) dry deposition measurements using aerodynamic surrogate surface passive samplers were collected in central and eastern Texas and eastern Oklahoma, from September 2011 to September 2012. The purpose of this study was to provide an initial characterization of the magnitude and spatial extent of ambient GOM dry deposition in central and eastern Texas for a 12-month period which contained statistically average annual results for precipitation totals, temperature, and wind speed. The research objective was to investigate GOM dry deposition in areas of Texas impacted by emissions from coal-fired utility boilers and compare it with GOM dry deposition measurements previously observed in eastern Oklahoma and the Four Corners area. Annual GOM dry deposition rate estimates were relatively low in Texas, ranging from 0.1 to 0.3 ng/m(2)h at the four Texas monitoring sites, similar to the 0.2 ng/m(2)h annual GOM dry deposition rate estimate recorded at the eastern Oklahoma monitoring site. The Texas and eastern Oklahoma annual GOM dry deposition rate estimates were at least four times lower than the highest annual GOM dry deposition rate estimate previously measured in the more arid bordering western states of New Mexico and Colorado in the Four Corners area.

The mechanism of deceleration of nucleation and crystal growth by the small addition of transition metals to lithium disilicate glasses

PubMed Central

Thieme, Katrin; Avramov, Isak; Rüssel, Christian

2016-01-01

The addition of small amounts of niobium or tantalum oxide to lithium disilicate glass provokes a drastic decrease of the steady-state nucleation rates and the crystal growth velocities. The viscosity of the residual glassy matrix is considered as a function of the crystallization degree in the course of a non-isothermal crystallization. For simplification, a homogeneous distribution of the added oxides in the glass matrix is assumed. While the viscosity initially decreases, it significantly increases again for higher crystallization degrees hindering crystal growth. However, it was shown that the additives are enriched at the crystal interface. Several possible reasons for the inhibition of nucleation and growth kinetics such as viscosity, interfacial energy crystal/glassy phase, thermodynamic driving force or impingement rate are discussed. Since the crystallization front is blocked by the additives the impingement rate is decreased with increasing additive concentration. Since small concentrations of Nb2O5 and Ta2O5 have a drastic effect on the nucleation, these components should be enriched at the interface crystal/glass. This will only take place, if it leads to a decrease in the interfacial energy. Since this effect alone should result in an increase of the nucleation rate, it must be overcompensated by kinetic effects. PMID:27150844

Are there intergenerational and population-specific effects of oxidative stress in sockeye salmon (Oncorhynchus nerka)?

PubMed

Taylor, Jessica J; Wilson, Samantha M; Sopinka, Natalie M; Hinch, Scott G; Patterson, David A; Cooke, Steven J; Willmore, William G

2015-06-01

Intergenerational effects of stress have been reported in a wide range of taxa; however, few researchers have examined the intergenerational consequences of oxidative stress. Oxidative stress occurs in living organisms when reactive oxygen species remain unquenched by antioxidant defense systems and become detrimental to cells. In fish, it is unknown how maternal oxidative stress and antioxidant capacity influence offspring quality. The semelparous, migratory life history of Pacific salmon (Oncorhynchus spp.) provides a unique opportunity to explore intergenerational effects of oxidative stress. This study examined the effects of population origin on maternal and developing offspring oxidative stress and antioxidant capacity, and elucidated intergenerational relationships among populations of sockeye salmon (Oncorhynchus nerka) with varying migration effort. For three geographically distinct populations of Fraser River sockeye salmon (British Columbia, Canada), antioxidant capacity and oxidative stress were measured in adult female plasma, heart, brain, and liver, as well as in developing offspring until time of emergence. Maternal and offspring oxidative stress and antioxidant capacity varied among populations but patterns were not consistent across tissue/developmental stage. Furthermore, maternal oxidative stress and antioxidant capacity did not affect offspring oxidative stress and antioxidant capacity across any of the developmental stages or populations sampled. Our results revealed that offspring develop their endogenous antioxidant systems at varying rates across populations; however, this variability is overcome by the time of emergence. While offspring may be relying on maternally derived antioxidants in the initial stages of development, they rapidly develop their own antioxidant systems (mainly glutathione) during later stages of development. Copyright © 2015 Elsevier Inc. All rights reserved.

[Kinetics modeling and reaction mechanism of ferrate(VI) oxidation of triclosan].

PubMed

Yang, Bin; Ying, Guang-Guo; Zhao, Jian-Liang

2011-09-01

Triclosan (TCS) is a broad-spectrum antibacterial agent widely used in many personal care products. We investigated oxidation of TCS by aqueous ferrate Fe(VI) to determine reaction kinetics, interpreted the reaction mechanism by a linear free-energy relationship, and evaluated the degradation efficiency. Second-order reaction kinetics was used to model Fe (VI) oxidation of TCS, with the apparent second-order rate constant (k(app)) being 531.9 L x (mol x s)(-1) at pH 8.5 and (24 +/- 1) degrees C. The half life (t1/2) is 25.8 s for an Fe( VI) concentration of 10 mg x L(-1). The rate constants of the reaction decrease with increasing pH values. These pH-dependent variations in k(app) could be distributed by considering species-specific reactions between Fe(VI) species and acid-base species of an ionizable TCS. Species-specific second-order reaction rate constants, k, were determined for reaction of HFeO4(-) with each of TCS's acid-base species. The value of k determined for neutral TCS was (4.1 +/- 3.5) x 10(2) L x (mol x s)(-1), while that measured for anionic TCS was (1.8 +/- 0.1) x 10(4) L x (mol x s)(-1). The reaction between HFeO4(-) and the dissociated TCS controls the overall reaction. A linear free-energy relationship illustrated the electrophilic oxidation mechanism. Fe (VI) reacts initially with TCS by electrophilic attack at the latter's phenol moiety. At a n[Fe(VI)]: n(TCS) > 7: 1, complete removal of TCS was achieved. And lower concentration of the humic acid could enhance the k(app) of Fe( VI) with TCS. In conclusion, Fe(VI) oxidation technology appears to be a promising tool for applications of WWTPs effluents and other decontamination processes.

Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

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

Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.

2014-06-02

The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction ofmore » S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.« less

Controlling the Degradation of Bioresorbable Polymers

NASA Astrophysics Data System (ADS)

Moritz, Istvan; Crowley, Brian; Brundage, Elizabeth; Rende, Deniz; Ozisik, Rahmi

Bioresorbable polymers play a vital role in the development of implantable materials that are used in surgical procedures, controlled drug delivery systems; and tissue engineering scaffolds. The half-life of common bioresorbable polymers ranges from 3 to over 12 months and slow bioresorption rates of these polymers restrict their use to a limited set of applications. The use of embedded enzymes was previously proposed to control the degradation rate of bioresorbable polymers, and was shown to decrease average degradation time to about 0.5 months. In this study, electromagnetic actuation of iron oxide magnetic nanoparticles embedded in an encapsulant polymer, poly(ethyleneoxide), PEO, was employed to initiate enzyme assisted degradation of bioresorbable polymer poly(caprolactone), PCL. Results indicate that the internal temperature of iron oxide magnetic nanoparticle doped PEO samples can be increased via an alternating magnetic field, and temperature increase depends strongly on nanoparticle concentration and magnetic field parameters. The temperature achieved is sufficient to relax the PEO matrix and to enable the diffusion of enzymes from PEO to a surrounding PCL matrix. Current studies are directed at measuring the degradation rate of PCL due to the diffused enzyme. This material is based upon work supported by the National Science Foundation under Grant No. CMMI-1538730.

Bioleaching of Ilmenite and Basalt in the Presence of Iron-oxidizing and Iron-scavenging Bacteria

NASA Astrophysics Data System (ADS)

Navarrete, J. U.; Cappelle, I.; Borrok, D.; Isru-Bio Team

2010-12-01

Understanding the biogeochemical processes that control mineral weathering rates is not only important for Earth systems, but may be a useful for developing technologies for the in-situ utilization of resources from other planets, moons, and asteroids. Traditional techniques that may be used to extract metals like iron, titanium, and aluminum from planetary rocks have large energy and/or hardware requirements that may not always be feasible. In this study, we performed biotic and abiotic leaching experiments with basalt and ilmenite (FeTiO3) to determine whether bacteria increased elemental leaching rates. Our secondary objectives were (1) to determine whether Acidithiobacillus ferrooxidans, an Fe-oxidizing bacterial strain, could grow on the low concentrations of ferrous Fe generated by the available substrates, and (2) to determine whether Pseudomonas mendocina, a heterotrophic Fe-scavenging bacteria, could grow on the low concentrations of nutrient elements generated by the available substrates. Experimental results demonstrate that the Fe(II) leached from ilmenite was rapidly depleted and replaced by Fe(III) in the presence of the Fe-oxidizing bacteria. The Fe in the abiotic control system remained as Fe(II) over the entire duration of the experiment. This suggests that the bacteria were able to grow using the Fe(II) from ilmenite (and the metal-free growth media) as a substrate. The iron-oxidizing bacteria were also able to grow in the presence of basaltic rock types; however the elemental release rates of Si, Ca, and Al in the presence of A. ferrooxidans were actually the same or lower than those from the abiotic control experiments. This may be attributable to the metabolically active bacteria creating a thick altered layer at the mineral surface that decreased the rate of diffusion or it may be caused in part by adsorption or precipitation of Fe(III) onto the existing mineral surfaces. Blending of the basaltic rock with ilmenite to further stimulate the bacterial metabolisms by providing additional Fe(II) resulted in a slight increase in Si, Ca, and Al release rates. For example, Si was released at an initial rate of 6.6e-12 mol/m2*s in the biotic experiments, while Si leached from the abiotic control at a rate of 4.0e-12mol/m2*s. Additional experiments utilizing P. mendocina, a heterotrophic organism capable of using siderophores to scavenge Fe from refractory minerals, are underway. Results from these experiments will be presented and compared to the results obtained for the iron-oxidizing systems.

Influence of uranium hydride oxidation on uranium metal behaviour

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

Patel, N.; Hambley, D.; Clarke, S.A.

2013-07-01

This work addresses concerns that the rapid, exothermic oxidation of active uranium hydride in air could stimulate an exothermic reaction (burning) involving any adjacent uranium metal, so as to increase the potential hazard arising from a hydride reaction. The effect of the thermal reaction of active uranium hydride, especially in contact with uranium metal, does not increase in proportion with hydride mass, particularly when considering large quantities of hydride. Whether uranium metal continues to burn in the long term is a function of the uranium metal and its surroundings. The source of the initial heat input to the uranium, ifmore » sufficient to cause ignition, is not important. Sustained burning of uranium requires the rate of heat generation to be sufficient to offset the total rate of heat loss so as to maintain an elevated temperature. For dense uranium, this is very difficult to achieve in naturally occurring circumstances. Areas of the uranium surface can lose heat but not generate heat. Heat can be lost by conduction, through contact with other materials, and by convection and radiation, e.g. from areas where the uranium surface is covered with a layer of oxidised material, such as burned-out hydride or from fuel cladding. These rates of heat loss are highly significant in relation to the rate of heat generation by sustained oxidation of uranium in air. Finite volume modelling has been used to examine the behaviour of a magnesium-clad uranium metal fuel element within a bottle surrounded by other un-bottled fuel elements. In the event that the bottle is breached, suddenly, in air, it can be concluded that the bulk uranium metal oxidation reaction will not reach a self-sustaining level and the mass of uranium oxidised will likely to be small in relation to mass of uranium hydride oxidised. (authors)« less

Nano lead oxide and epdm composite for development of polymer based radiation shielding material: Gamma irradiation and attenuation tests

NASA Astrophysics Data System (ADS)

Özdemir, T.; Güngör, A.; Akbay, I. K.; Uzun, H.; Babucçuoglu, Y.

2018-03-01

It is important to have a shielding material that is not easily breaking in order to have a robust product that guarantee the radiation protection of the patients and radiation workers especially during the medical exposure. In this study, nano sized lead oxide (PbO) particles were used, for the first time, to obtain an elastomeric composite material in which lead oxide nanoparticles, after the surface modification with silane binding agent, was used as functional material for radiation shielding. In addition, the composite material including 1%, 5%, 10%, 15% and 20% weight percent nano sized lead oxide was irradiated with doses of 81, 100 and 120 kGy up to an irradiation period of 248 days in a gamma ray source with an initial dose rate of 21.1 Gy/h. Mechanical, thermal properties of the irradiated materials were investigated using DSC, DMA, TGA and tensile testing and modifications in thermal and mechanical properties of the nano lead oxide containing composite material via gamma irradiation were reported. Moreover, effect of bismuth-III oxide addition on radiation attenuation of the composite material was investigated. Nano lead oxide and bismuth-III oxide particles were mixed with different weight ratios. Attenuation tests have been conducted to determine lead equivalent values for the developed composite material. Lead equivalent thickness values from 0.07 to 0.65 (2-6 mm sample thickness) were obtained.

Growth of ZnOx:Al by high-throughput CVD at atmospheric pressure

NASA Astrophysics Data System (ADS)

Illiberi, A.; Simons, P. J. P. M.; Kniknie, B.; van Deelen, J.; Theelen, M.; Zeman, M.; Tijssen, M.; Zijlmans, W.; Steijvers, H. L. A. H.; Habets, D.; Janssen, A. C.; Beckers, E. H. A.

2012-05-01

Aluminum doped zinc oxide films (ZnOx:Al) have been deposited on a moving glass substrate by a metalorganic CVD process at atmospheric pressure in an in-line industrial type reactor. Tertiary-butanol has been used as an oxidant for diethylzinc and trimethylaluminium as the dopant gas. The effect of the deposition temperature (from 380 to 540 °C) on the deposition rate has been investigated by a numerical code, where a gas phase reaction among tertiary-butanol and diethylzinc is assumed to occur. The structural (crystallinity and morphology) properties of the films as a function of the deposition temperature have been analyzed by using X-ray diffraction and Scanning Electron Microscopy. A maximum growth rate of ˜11 nm/s was found at a deposition temperature of 480 °C, for which ZnOx:Al films show (002) preferential orientation, good crystalline quality and a naturally rough surface. ZnOx:Al films deposited at 480 °C are also highly conductive (R<10 Ω/□ for film thicknesses above 1050 nm) and transparent (>85% in the visible range). These films have been used as front transparent conductive oxide layers in p i n a-Si:H solar cells, achieving an initial efficiency approaching 8%.

Concentration-dependent photodegradation kinetics and hydroxyl-radical oxidation of phenicol antibiotics.

PubMed

Li, Kai; Zhang, Peng; Ge, Linke; Ren, Honglei; Yu, Chunyan; Chen, Xiaoyang; Zhao, Yuanfeng

2014-09-01

Thiamphenicol and florfenicol are two phenicol antibiotics widely used in aquaculture and are ubiquitous as micropollutants in surface waters. The present study investigated their photodegradation kinetics, hydroxyl-radical (OH) oxidation reactivities and products. Firstly, the photolytic kinetics of the phenicols in pure water was studied as a function of initial concentrations (C0) under UV-vis irradiation (λ>200nm). It was found that the kinetics was influenced by C0. A linear plot of the pseudo-first-order rate constant vs C0 was observed with a negative slope. Secondly, the reaction between the phenicol antibiotics and OH was examined with a competition kinetic method under simulated solar irradiation (λ>290nm), which quantified their bimolecular reaction rate constants of (2.13±0.02)×10(9)M(-1)s(-1) and (1.82±0.10)×10(9)M(-1)s(-1) for thiamphenicol and florfenicol, respectively. Then the corresponding OH oxidated half-lives in sunlit surface waters were calculated to be 90.5-106.1h. Some main intermediates were formed from the reaction, which suggested that the two phenicols underwent hydroxylation, oxygenation and dehydrogenation when OH existed. These results are of importance to assess the phenicol persistence in wastewater treatment and sunlit surface waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

Regime Shift and Microbial Dynamics in a Sequencing Batch Reactor for Nitrification and Anammox Treatment of Urine ▿†

PubMed Central

Bürgmann, Helmut; Jenni, Sarina; Vazquez, Francisco; Udert, Kai M.

2011-01-01

The microbial population and physicochemical process parameters of a sequencing batch reactor for nitrogen removal from urine were monitored over a 1.5-year period. Microbial community fingerprinting (automated ribosomal intergenic spacer analysis), 16S rRNA gene sequencing, and quantitative PCR on nitrogen cycle functional groups were used to characterize the microbial population. The reactor combined nitrification (ammonium oxidation)/anammox with organoheterotrophic denitrification. The nitrogen elimination rate initially increased by 400%, followed by an extended period of performance degradation. This phase was characterized by accumulation of nitrite and nitrous oxide, reduced anammox activity, and a different but stable microbial community. Outwashing of anammox bacteria or their inhibition by oxygen or nitrite was insufficient to explain reactor behavior. Multiple lines of evidence, e.g., regime-shift analysis of chemical and physical parameters and cluster and ordination analysis of the microbial community, indicated that the system had experienced a rapid transition to a new stable state that led to the observed inferior process rates. The events in the reactor can thus be interpreted to be an ecological regime shift. Constrained ordination indicated that the pH set point controlling cycle duration, temperature, airflow rate, and the release of nitric and nitrous oxides controlled the primarily heterotrophic microbial community. We show that by combining chemical and physical measurements, microbial community analysis and ecological theory allowed extraction of useful information about the causes and dynamics of the observed process instability. PMID:21724875

Hydrogenated TiO 2@reduced graphene oxide sandwich-like nanosheets for high voltage supercapacitor applications

DOE PAGES

Pham, Viet Hung; Nguyen-Phan, Thuy-Duong; Tong, Xiao; ...

2017-10-09

Hydrogenated TiO 2 has recently attracted considerable attention as potential electrode materials for supercapacitors due to its abundance, low cost, high conductivity, remarkable rate capability, and outstanding long-term cycling stability. In this paper, we demonstrate the synthesis of hydrogenated TiO 2 nanoparticles anchored on reduced graphene oxide nanosheets (HTG) in the form of sandwich-like nanosheet composites. Further, we explored their implementation as electrode materials for high voltage, symmetric supercapacitors, operating in the voltage window of 0–1.8 V. The HTGs were prepared by a sol-gel method, followed by hydrogenation in the temperature range 300–500 °C. Of the prepared composites, HTG preparedmore » at 400 °C exhibited the largest specific capacitance of 51 F g -1 at the current density of 1.0 A g -1 and excellent rate capability with 82.5% capacitance retention as the current density increased 40-fold, from 0.5 to 20.0 A g -1. HTG's excellent rate capability was attributed to its sandwich-like nanostructure, in which ultrasmall hydrogenated TiO 2 nanoparticles densely anchored onto both surfaces of the two-dimensional reduced graphene oxide sheets. Moreover, HTG-based supercapacitors also exhibited long-term cycling stability with the retention over 80% of its initial capacitance after 10,000 cycles. Finally, these properties suggest that HTG is a promising electrode material for the scalable manufacture of high-performance supercapacitors.« less

High areal capacity, micrometer-scale amorphous Si film anode based on nanostructured Cu foil for Li-ion batteries

NASA Astrophysics Data System (ADS)

Si, Wenping; Sun, Xiaolei; Liu, Xianghong; Xi, Lixia; Jia, Yandong; Yan, Chenglin; Schmidt, Oliver G.

2014-12-01

We report a feasible design to fabricate micrometer-scale Si films deposited on nanostructured Cu foil as high areal capacity anodes for Li-ion batteries with excellent cycling performance. Nanostructured copper oxides are prepared by anodic oxidation of Cu foil in alkaline solution. The resultant copper oxide nanofibers function as matrix for thick Si films (1-2 μm) loading. Metallic Cu nanofibers are obtained by in-situ electrochemical reduction at low potentials, which work as electrical highways for fast electron transport and a reliable mechanical matrix to accommodate volume changes during lithium-silicon alloy/dealloy processes. The engineered thick Si film anode exhibit both high areal capacity (0.48 mAh cm-2 for 1 μm Si film and 0.6 mAh cm-2 for 2 μm Si film after 200 cycles at 0.225 mA cm-2) and excellent rate capability (0.52 mAh cm-2 at 1.05 mA cm-2 for 2 μm Si film). The 2 μm silicon film electrode is able to recover to the initial value of 1 mAh cm-2 when the current rate is set back to 0.15 mA cm-2 even after cycling at high current rates. The reported concept can be a general method for high-loading-film electrodes, which is industrial scalable and compatible with current battery manufacturing processes.

Hydrogenated TiO 2@reduced graphene oxide sandwich-like nanosheets for high voltage supercapacitor applications

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

Pham, Viet Hung; Nguyen-Phan, Thuy-Duong; Tong, Xiao

Hydrogenated TiO 2 has recently attracted considerable attention as potential electrode materials for supercapacitors due to its abundance, low cost, high conductivity, remarkable rate capability, and outstanding long-term cycling stability. In this paper, we demonstrate the synthesis of hydrogenated TiO 2 nanoparticles anchored on reduced graphene oxide nanosheets (HTG) in the form of sandwich-like nanosheet composites. Further, we explored their implementation as electrode materials for high voltage, symmetric supercapacitors, operating in the voltage window of 0–1.8 V. The HTGs were prepared by a sol-gel method, followed by hydrogenation in the temperature range 300–500 °C. Of the prepared composites, HTG preparedmore » at 400 °C exhibited the largest specific capacitance of 51 F g -1 at the current density of 1.0 A g -1 and excellent rate capability with 82.5% capacitance retention as the current density increased 40-fold, from 0.5 to 20.0 A g -1. HTG's excellent rate capability was attributed to its sandwich-like nanostructure, in which ultrasmall hydrogenated TiO 2 nanoparticles densely anchored onto both surfaces of the two-dimensional reduced graphene oxide sheets. Moreover, HTG-based supercapacitors also exhibited long-term cycling stability with the retention over 80% of its initial capacitance after 10,000 cycles. Finally, these properties suggest that HTG is a promising electrode material for the scalable manufacture of high-performance supercapacitors.« less

Effects of Alloyed Metal on the Catalysis Activity of Pt for Ethanol Partial Oxidation: Adsorption and Dehydrogenation on Pt3M (M=Pt, Ru, Sn, Re, Rh, and Pd)

PubMed Central

Xu, Zhen-Feng; Wang, Yixuan

2011-01-01

The adsorption and dehydrogenation reactions of ethanol over bimetallic clusters, Pt3M (M = Pt, Ru, Sn, Re, Rh, and Pd), have been extensively investigated with density functional theory. Both the α-hydrogen and hydroxyl adsorptions on Pt as well as on the alloyed transition metal M sites of PtM were considered as initial reaction steps. The adsorptions of ethanol on Pt and M sites of some PtM via the α-hydrogen were well established. Although the α-hydrogen adsorption on Pt site is weaker than the hydroxyl, the potential energy profiles show that the dehydrogenation via the α-hydrogen path has much lower energy barrier than that via the hydroxyl path. Generally for the α-hydrogen path the adsorption is a rate-determining-step because of rather low dehydrogenation barrier for the α-hydrogen adsorption complex (thermodynamic control), while the hydroxyl path is determined by its dehydrogenation step (kinetic control). The effects of alloyed metal on the catalysis activity of Pt for ethanol partial oxidation, including adsorption energy, energy barrier, electronic structure, and eventually rate constant were discussed. Among all of the alloyed metals only Sn enhances the rate constant of the dehydrogenation via the α-hydrogen path on the Pt site of Pt3Sn as compared with Pt alone, which interprets why the PtSn is the most active to the oxidation of ethanol. PMID:22102920

Control of aerosol contaminants in indoor air: combining the particle concentration reduction with microbial inactivation.

PubMed

Grinshpun, Sergey A; Adhikari, Atin; Honda, Takeshi; Kim, Ki Youn; Toivola, Mika; Rao, K S Ramchander; Reponen, Tiina

2007-01-15

An indoor air purification technique, which combines unipolar ion emission and photocatalytic oxidation (promoted by a specially designed RCI cell), was investigated in two test chambers, 2.75 m3 and 24.3 m3, using nonbiological and biological challenge aerosols. The reduction in particle concentration was measured size selectively in real-time, and the Air Cleaning Factor and the Clean Air Delivery Rate (CADR) were determined. While testing with virions and bacteria, bioaerosol samples were collected and analyzed, and the microorganism survival rate was determined as a function of exposure time. We observed that the aerosol concentration decreased approximately 10 to approximately 100 times more rapidly when the purifier operated as compared to the natural decay. The data suggest that the tested portable unit operating in approximately 25 m3 non-ventilated room is capable to provide CADR-values more than twice as great than the conventional closed-loop HVAC system with a rating 8 filter. The particle removal occurred due to unipolar ion emission, while the inactivation of viable airborne microorganisms was associated with photocatalytic oxidation. Approximately 90% of initially viable MS2 viruses were inactivated resulting from 10 to 60 min exposure to the photocatalytic oxidation. Approximately 75% of viable B. subtilis spores were inactivated in 10 min, and about 90% or greater after 30 min. The biological and chemical mechanisms that led to the inactivation of stress-resistant airborne viruses and bacterial spores were reviewed.

pH-Dependent Singlet O2 Oxidation Kinetics of Guanine and 9-Methylguanine: An Online Mass Spectrometry and Spectroscopy Study Combined with Theoretical Exploration.

PubMed

Lu, Wenchao; Sun, Yan; Zhou, Wenjing; Liu, Jianbo

2018-01-11

We report a kinetic and mechanistic study on the title reactions, in which 1 O 2 was generated by the reaction of H 2 O 2 with Cl 2 and bubbled into an aqueous solution of guanine and 9-methylguanine (9MG) at different pH values. Oxidation kinetics and product branching ratios were measured using online electrospray ionization mass spectrometry coupled with absorption and emission spectrophotometry, and product structures were determined by collision-induced dissociation (CID) tandem mass spectrometry. Experiments revealed strong pH dependence of the reactions. The oxidation of guanine is noticeable only in basic solution, while the oxidation of 9MG is weak in acidic solution, increases in neutral solution, and becomes intensive in basic solution. 5-Guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp) were detected as the major oxidation products of guanine and 9MG, and Sp became dominant in basic solution. A reaction intermediate was captured in mass spectra, and assigned to gem-diol on the basis of CID measurements. This intermediate served as the precursor for the formation of Gh. After taking into account solution compositions at each pH, first-order oxidation rate constants were extracted for individual species: that is, 3.2-3.6 × 10 7 M -1 s -1 for deprotonated guanine, and 1.2 × 10 6 and 4.6-4.9 × 10 7 M -1 s -1 for neutral and deprotonated 9MG, respectively. Guided by approximately spin-projected density-functional-theory-calculated reaction potential energy surfaces, the kinetics for the initial 1 O 2 addition to guanine and 9MG was evaluated using transition state theory (TST). The comparison between TST modeling and experiment confirms that 1 O 2 addition is rate-limiting for oxidation, which forms endoperoxide and peroxide intermediates as determined in previous measurements of the same systems in the gas phase.

Oxidation of aquatic pollutants by ferrous-oxalate complexes under dark aerobic conditions.

PubMed

Lee, Jaesang; Kim, Jungwon; Choi, Wonyong

2014-06-15

This study evaluates the ability of Fe(II)-oxalate complexes for the generation of OH through oxygen reduction and the oxidative degradation of aquatic pollutants under dark aerobic conditions (i.e., with oxygen but without light). The degradation of 4-chlorophenol (4-CP) was rapid in the mixture of Fe(2+) and oxalate prepared using ultrapure water, but was absent without either Fe(2+) or oxalate. The formation of Fe(II)-oxalate complexes enables two-electron reduction of oxygen to generate H2O2 and subsequent production of OH. The significant inhibition of 4-CP degradation in the presence of H2O2 and OH scavenger confirms such mechanisms. The degradation experiments with varying [Fe(2+)], [oxalate], and initial pH demonstrated that the degradation rate depends on [Fe(II)(Ox)2(2-)], but the degree of degradation is primarily determined by [Fe(II)(Ox)2(2-)]+[Fe(II)(Ox)(0)]. Efficient degradation of diverse aquatic pollutants, especially phenolic pollutants, was observed in the Fe(II)-oxalate complexes system, wherein the oxidation efficacy was primarily correlated with the reaction rate constant between pollutant and OH. The effect of various organic ligands (oxalate, citrate, EDTA, malonate, and acetate) on the degradation kinetics of 4-CP was investigated. The highest efficiency of oxalate for the oxidative degradation is attributed to its high capability to enhance the reducing power and low reactivity with OH. Copyright © 2014 Elsevier B.V. All rights reserved.

Volatile organic compound conversion by ozone, hydroxyl radicals, and nitrate radicals in residential indoor air: Magnitudes and impacts of oxidant sources

NASA Astrophysics Data System (ADS)

Waring, Michael S.; Wells, J. Raymond

2015-04-01

Indoor chemistry may be initiated by reactions of ozone (O3), the hydroxyl radical (OH), or the nitrate radical (NO3) with volatile organic compounds (VOC). The principal indoor source of O3 is air exchange, while OH and NO3 formation are considered as primarily from O3 reactions with alkenes and nitrogen dioxide (NO2), respectively. Herein, we used time-averaged models for residences to predict O3, OH, and NO3 concentrations and their impacts on conversion of typical residential VOC profiles, within a Monte Carlo framework that varied inputs probabilistically. We accounted for established oxidant sources, as well as explored the importance of two newly realized indoor sources: (i) the photolysis of nitrous acid (HONO) indoors to generate OH and (ii) the reaction of stabilized Criegee intermediates (SCI) with NO2 to generate NO3. We found total VOC conversion to be dominated by reactions both with O3, which almost solely reacted with D-limonene, and also with OH, which reacted with D-limonene, other terpenes, alcohols, aldehydes, and aromatics. VOC oxidation rates increased with air exchange, outdoor O3, NO2 and D-limonene sources, and indoor photolysis rates; and they decreased with O3 deposition and nitric oxide (NO) sources. Photolysis was a strong OH formation mechanism for high NO, NO2, and HONO settings, but SCI/NO2 reactions weakly generated NO3 except for only a few cases.

HbE/β-Thalassemia and Oxidative Stress: The Key to Pathophysiological Mechanisms and Novel Therapeutics.

PubMed

Hirsch, Rhoda Elison; Sibmooh, Nathawut; Fucharoen, Suthat; Friedman, Joel M

2017-05-10

Oxidative stress and generation of free radicals are fundamental in initiating pathophysiological mechanisms leading to an inflammatory cascade resulting in high rates of morbidity and death from many inherited point mutation-derived hemoglobinopathies. Hemoglobin (Hb)E is the most common point mutation worldwide. The β E -globin gene is found in greatest frequency in Southeast Asia, including Thailand, Malaysia, Indonesia, Vietnam, Cambodia, and Laos. With the wave of worldwide migration, it is entering the gene pool of diverse populations with greater consequences than expected. While HbE by itself presents as a mild anemia and a single gene for β-thalassemia is not serious, it remains unexplained why HbE/β-thalassemia (HbE/β-thal) is a grave disease with high morbidity and mortality. Patients often exhibit defective physical development, severe chronic anemia, and often die of cardiovascular disease and severe infections. Recent Advances: This article presents an overview of HbE/β-thal disease with an emphasis on new findings pointing to pathophysiological mechanisms derived from and initiated by the dysfunctional property of HbE as a reduced nitrite reductase concomitant with excess α-chains exacerbating unstable HbE, leading to a combination of nitric oxide imbalance, oxidative stress, and proinflammatory events. Additionally, we present new therapeutic strategies that are based on the emerging molecular-level understanding of the pathophysiology of this and other hemoglobinopathies. These strategies are designed to short-circuit the inflammatory cascade leading to devastating chronic morbidity and fatal consequences. Antioxid. Redox Signal. 26, 794-813.

Mitochondrial DNA Damage Initiates Acute Lung Injury and Multi-Organ System Failure Evoked in Rats by Intra-Tracheal Pseudomonas Aeruginosa.

PubMed

Lee, Yann-Leei; Obiako, Boniface; Gorodnya, Olena M; Ruchko, Mykhaylo V; Kuck, Jamie L; Pastukh, Viktor M; Wilson, Glenn L; Simmons, Jon D; Gillespie, Mark N

2017-07-01

Although studies in rat cultured pulmonary artery endothelial cells, perfused lungs, and intact mice support the concept that oxidative mitochondrial (mt) DNA damage triggers acute lung injury (ALI), it has not yet been determined whether enhanced mtDNA repair forestalls development of ALI and its progression to multiple organ system failure (MOSF). Accordingly, here we examined the effect of a fusion protein construct targeting the DNA glycosylase, Ogg1, to mitochondria in a rat model intra-tracheal Pseudomonas aeruginosa (strain 103; PA103)-induced ALI and MOSF. Relative to controls, animals given PA103 displayed increases in lung vascular filtration coefficient accompanied by transient lung tissue oxidative mtDNA damage and variable changes in mtDNA copy number without evidence of nuclear DNA damage. The approximate 40% of animals surviving 24 h after bacterial administration exhibited multiple organ dysfunction, manifest as increased serum and tissue-specific indices of kidney and liver failure, along with depressed heart rate and blood pressure. While administration of mt-targeted Ogg1 to control animals was innocuous, the active fusion protein, but not a DNA repair-deficient mutant, prevented bacteria-induced increases in lung tissue oxidative mtDNA damage, failed to alter mtDNA copy number, and attenuated lung endothelial barrier degradation. These changes were associated with suppression of liver, kidney, and cardiovascular dysfunction and with decreased 24 h mortality. Collectively, the present findings indicate that oxidative mtDNA damage to lung tissue initiates PA103-induced ALI and MOSF in rats.

HbE/β-Thalassemia and Oxidative Stress: The Key to Pathophysiological Mechanisms and Novel Therapeutics

PubMed Central

Sibmooh, Nathawut; Fucharoen, Suthat

2017-01-01

Abstract Significance: Oxidative stress and generation of free radicals are fundamental in initiating pathophysiological mechanisms leading to an inflammatory cascade resulting in high rates of morbidity and death from many inherited point mutation-derived hemoglobinopathies. Hemoglobin (Hb)E is the most common point mutation worldwide. The βE-globin gene is found in greatest frequency in Southeast Asia, including Thailand, Malaysia, Indonesia, Vietnam, Cambodia, and Laos. With the wave of worldwide migration, it is entering the gene pool of diverse populations with greater consequences than expected. Critical Issues: While HbE by itself presents as a mild anemia and a single gene for β-thalassemia is not serious, it remains unexplained why HbE/β-thalassemia (HbE/β-thal) is a grave disease with high morbidity and mortality. Patients often exhibit defective physical development, severe chronic anemia, and often die of cardiovascular disease and severe infections. Recent Advances: This article presents an overview of HbE/β-thal disease with an emphasis on new findings pointing to pathophysiological mechanisms derived from and initiated by the dysfunctional property of HbE as a reduced nitrite reductase concomitant with excess α-chains exacerbating unstable HbE, leading to a combination of nitric oxide imbalance, oxidative stress, and proinflammatory events. Future Directions: Additionally, we present new therapeutic strategies that are based on the emerging molecular-level understanding of the pathophysiology of this and other hemoglobinopathies. These strategies are designed to short-circuit the inflammatory cascade leading to devastating chronic morbidity and fatal consequences. Antioxid. Redox Signal. 26, 794–813. PMID:27650096

Intra-puff CO and CO 2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

NASA Astrophysics Data System (ADS)

Crawford, Danielle R.; Parrish, Milton E.; Gee, Diane L.; Harward, Charles N.

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO 2 as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1 s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO 2 intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO 2 deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy.

PubMed

Crawford, Danielle R; Parrish, Milton E; Gee, Diane L; Harward, Charles N

2007-05-01

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.

Role of Nuclear Factor Erythroid 2-Related Factor 2 in Diabetic Nephropathy

PubMed Central

Min, Xu; Xu, Xiaohong

2017-01-01

Diabetic nephropathy (DN) is manifested as increased urinary protein level, decreased glomerular filtration rate, and final renal dysfunction. DN is the leading cause of end-stage renal disease worldwide and causes a huge societal healthcare burden. Since satisfied treatments are still limited, exploring new strategies for the treatment of this disease is urgently needed. Oxidative stress takes part in the initiation and development of DN. In addition, nuclear factor erythroid 2-related factor 2 (Nrf2) plays a key role in the cellular response to oxidative stress. Thus, activation of Nrf2 seems to be a new choice for the treatment of DN. In current review, we discussed and summarized the therapeutic effects of Nrf2 activation on DN from both basic and clinical studies. PMID:28512642

Reactive oxygen species produced by NADPH oxidase and mitochondrial dysfunction in lung after an acute exposure to Residual Oil Fly Ashes

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

Magnani, Natalia D.; Marchini, Timoteo; Vanasco, Virginia

2013-07-01

Reactive O{sub 2} species production triggered by particulate matter (PM) exposure is able to initiate oxidative damage mechanisms, which are postulated as responsible for increased morbidity along with the aggravation of respiratory diseases. The aim of this work was to quantitatively analyse the major sources of reactive O{sub 2} species involved in lung O{sub 2} metabolism after an acute exposure to Residual Oil Fly Ashes (ROFAs). Mice were intranasally instilled with a ROFA suspension (1.0 mg/kg body weight), and lung samples were analysed 1 h after instillation. Tissue O{sub 2} consumption and NADPH oxidase (Nox) activity were evaluated in tissuemore » homogenates. Mitochondrial respiration, respiratory chain complexes activity, H{sub 2}O{sub 2} and ATP production rates, mitochondrial membrane potential and oxidative damage markers were assessed in isolated mitochondria. ROFA exposure was found to be associated with 61% increased tissue O{sub 2} consumption, a 30% increase in Nox activity, a 33% increased state 3 mitochondrial O{sub 2} consumption and a mitochondrial complex II activity increased by 25%. During mitochondrial active respiration, mitochondrial depolarization and a 53% decreased ATP production rate were observed. Neither changes in H{sub 2}O{sub 2} production rate, nor oxidative damage in isolated mitochondria were observed after the instillation. After an acute ROFA exposure, increased tissue O{sub 2} consumption may account for an augmented Nox activity, causing an increased O{sub 2}{sup ·−} production. The mitochondrial function modifications found may prevent oxidative damage within the organelle. These findings provide new insights to the understanding of the mechanisms involving reactive O{sub 2} species production in the lung triggered by ROFA exposure. - Highlights: • Exposure to ROFA alters the oxidative metabolism in mice lung. • The augmented Nox activity contributes to the high tissue O{sub 2} consumption. • Exposure to ROFA produces alterations in mitochondrial function. • ΔΨ{sub m} decrease in state 3 may be responsible for the decreased ATP production. • Mild uncoupling prevents mitochondrial oxidative damage.« less

Atmospheric oxidation mechanism of chlorobenzene.

PubMed

Wu, Runrun; Wang, Sainan; Wang, Liming

2014-09-01

The atmospheric oxidation mechanism of chlorobenzene (CB) initiated by the OH radicals is investigated at M06-2X/6-311++G(2df, 2p) and ROCBS-QB3 levels. The oxidation is initiated by OH addition to the ortho (∼50%), para (∼33%) and meta (∼17%) positions, forming CB-OH adducts as R2, R3, and R4; while the ipso-addition is negligible (∼0.2%). The reactions of the CB-OH adducts with the atmospheric oxygen are further investigated in detail by coupling the unimolecular reaction rate theory calculations with master-equation (RRKM-ME). The CB-OH adducts react with O2 either by irreversible H-abstraction to form chlorophenol and HO2 or by reversible additions to form CB-OH-O2 radicals, which subsequently cyclize to bicyclic radicals. RRKM-ME calculations show that the addition reactions of CB-OH and O2 at the atmospheric pressure are close to but not yet reach their high-pressure-limits. The RRKM-ME simulations predict the yields of 93%, 38%, and 74% for ortho-, meta- and para-chlorophenols from the reactions of O2 with R2, R3 and R4, being lower than their high-pressure-limit yields of 95%, 48%, an 80%, respectively. Overall, the yield of chlorophenols is determined as 72% at the atmospheric pressure. Copyright © 2014 Elsevier Ltd. All rights reserved.

Diurnal variation of nitric oxide in the upper stratosphere

NASA Technical Reports Server (NTRS)

Kondo, Y.; Aimedieu, P.; Pirre, M.; Ramaroson, R.; Matthews, W. A.

1990-01-01

Two recent measurements of the temporal variation of nitric oxide at constant altitude near 40 km are reported. The observations were made at float altitude with a balloon-borne chemiluminescence detector together with in situ ozone measurements. The first measurement was made at 44 N on September 17, 1987, at an altitude of 40 km from before sunrise until 1000 LT. The second observation was made at the same latitude on June 18, 1988, at 39 km from 0800 to 1230 LT. At an altitude of 40 km, nitric oxide was observed to start increasing very rapidly at sunrise when the solar zenith angle reached about 95 deg. After the rapid initial buildup, the rate of NO increase stabilized for 3 hours at about 1.2 ppbv/hour. Near 1100 LT at 39 km in summer, the NO mixing ratio was observed to become nearly constant. These features of the diurnal variation of NO are in accord with the temporal variation expected from a time-dependent zero-dimensional photochemical model.

Zn2+-Doped Polyaniline/Graphene Oxide as Electrode Material for Electrochemical Supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Hui; Tang, Jing; Chen, Yong; Liu, Jian; Pu, Jinjuan; Li, Qi

2017-10-01

Electrodes based on Zn2+-doped polyaniline/graphene oxide (Zn2+/PANI/GO) were synthesized on stainless steel mesh substrates in H2SO4 solution via electrochemical codeposition. Different concentrations of graphene oxide (GO) were incorporated into the films to improve the electrochemical performance of the electrodes. Electrochemical properties of the films were tested by cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy, in a three-electrode system. The maximum specific capacitance of the Zn2+/PANI/GO film with a GO concentration of 15 mg L-1 was found to be 1266 F g-1 at a scan rate of 3 mV s-1. This value was higher than that of a Zn2+ doped polyaniline (Zn2+/PANI) film (814 F g-1). The Zn2+/PANI/GO film also showed good cycling stability, retaining over 86% of its initial capacitance after 1000 cycles. These results indicate that the Zn2+/PANI/GO composites can be applied as high performance supercapacitor electrodes.

Stability of Silica- and Enzyme-Treated Palm Oil Under Deep Frying Conditions.

PubMed

Karim, Nur Azwani Ab; Noor, Ahmadilfitri Md; Lee, Yee-Ying; Lai, Oi-Ming

2015-12-01

The oxidative and thermal stability of low diglycerides palm oil produced via silica treatment (sPO) and enzymatic treatment (ePO) compared with standard quality palm oil (SQ) and premium quality palm oil (PQ) was investigated. Both of the oils displayed better oxidative stability compared with SQ as well as significantly higher (P < 0.05) thermal resistance and oxidative strength than SQ and PQ due to lower amounts of partial glycerides. Although the initial induction periods (IPs) of sPO and ePO were significantly lower compared with SQ and PQ, both the oils showed slower drops in their IP values. The darkening effect after frying was significantly (P < 0.05) slower in sPO compared with SQ, PQ, and ePO. Besides, there is no difference p > 0.05 in the rate of FFA formation between sPO and PQ. The anisidine value and peroxide values were lowest in sPO, followed by ePO, PQ, and SQ. © 2015 Institute of Food Technologists®

How environmental and genetic factors combine to cause autism: A redox/methylation hypothesis.

PubMed

Deth, Richard; Muratore, Christina; Benzecry, Jorge; Power-Charnitsky, Verna-Ann; Waly, Mostafa

2008-01-01

Recently higher rates of autism diagnosis suggest involvement of environmental factors in causing this developmental disorder, in concert with genetic risk factors. Autistic children exhibit evidence of oxidative stress and impaired methylation, which may reflect effects of toxic exposure on sulfur metabolism. We review the metabolic relationship between oxidative stress and methylation, with particular emphasis on adaptive responses that limit activity of cobalamin and folate-dependent methionine synthase. Methionine synthase activity is required for dopamine-stimulated phospholipid methylation, a unique membrane-delimited signaling process mediated by the D4 dopamine receptor that promotes neuronal synchronization and attention, and synchrony is impaired in autism. Genetic polymorphisms adversely affecting sulfur metabolism, methylation, detoxification, dopamine signaling and the formation of neuronal networks occur more frequently in autistic subjects. On the basis of these observations, a "redox/methylation hypothesis of autism" is described, in which oxidative stress, initiated by environment factors in genetically vulnerable individuals, leads to impaired methylation and neurological deficits secondary to reductions in the capacity for synchronizing neural networks.

Catalyst supports for polymer electrolyte fuel cells.

PubMed

Subban, Chinmayee; Zhou, Qin; Leonard, Brian; Ranjan, Chinmoy; Edvenson, Heather M; Disalvo, F J; Munie, Semeret; Hunting, Janet

2010-07-28

A major challenge in obtaining long-term durability in fuel cells is to discover catalyst supports that do not corrode, or corrode much more slowly than the current carbon blacks used in today's polymer electrolyte membrane fuel cells. Such materials must be sufficiently stable at low pH (acidic conditions) and high potential, in contact with the polymer membrane and under exposure to hydrogen gas and oxygen at temperatures up to perhaps 120 degrees C. Here, we report the initial discovery of a promising class of doped oxide materials for this purpose: Ti(1-x)M(x)O(2), where M=a variety of transition metals. Specifically, we show that Ti(0.7)W(0.3)O(2) is electrochemically inert over the appropriate potential range. Although the process is not yet optimized, when Pt nanoparticles are deposited on this oxide, electrochemical experiments show that hydrogen is oxidized and oxygen reduced at rates comparable to those seen using a commercial Pt on carbon black support.

Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Catalyst for the Alcohol Oxidation Reaction

PubMed Central

Yi, Chae S.; Zeczycki, Tonya N.; Guzei, Ilia A.

2008-01-01

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was synthesized in two steps from the monomeric complex (PCy3)(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C6H4CH2OH (ρ = −0.45) and p-X-C6H4CH(OH)CH3 (ρ = +0.22) (X = OMe, CH3, H, Cl, CF3). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH3] (K0.5 = 0.34 M; Hill coefficient, n = 4.2±0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols. PMID:18726005

Thermal fatigue and oxidation data of superalloys including directionally solidified eutectics

NASA Technical Reports Server (NTRS)

Hill, V. L.; Humphreys, V. E.

1977-01-01

Thermal fatigue and oxidation data were obtained on 61 specimens, representing 15 discrete alloy compositions or fabricating techniques and three coating systems. Conventionally fabricated alloys included V57, MM 200, Rene 77, Rene 125, MM 246, MM 509, IN-738, IN-792 + Hf, and MM 200 + Hf. The directionally solidified alloys were MM 200, MM 200 single crystal, MM 200 bicrystal, cellular gamma/gamma' - delta) and lamellar gamma/gamma' - delta. The coatings systems included NiCrAlY on IN-738, In-792 + Hf, MM 200 DS, MM 200 DS single crystal, and cellular gamma/gamma' - delta and NiCrAlY/Pt on lamellar gamma/gamma' - delta. Crack initiation survival rates were recorded for all alloys, with and without coatings. All uncoated alloys, except MM 509, exhibited significant oxidation weight loss in 75,000 to 15,000 cycles. MM 509 specimens had weight losses only slightly higher than coated specimens through 7,500 cycles. All coated specimens had low weight loss.

Optimization of Lipase-Mediated Synthesis of 1-Nonene Oxide Using Phenylacetic Acid and Hydrogen Peroxide

PubMed Central

Abdulmalek, Emilia; Arumugam, Mahashanon; Basri, Mahiran; Rahman, Mohd Basyaruddin Abdul

2012-01-01

Herein, an efficient epoxidation of 1-nonene is described. In a simple epoxidation system, commercially available Novozym 435, an immobilized Candida antarctica lipase B, and hydrogen peroxide (H2O2) were utilized to facilitate the in situ oxidation of phenylacetic acid to the corresponding peroxy acid which then reacted with 1-nonene to give 1-nonene oxide with high yield and selectivity. The aliphatic terminal alkene was epoxidised efficiently in chloroform to give an excellent yield (97%–99%) under the optimum reaction conditions, including temperature (35 °C), initial H2O2 concentration (30%), H2O2 amount (4.4 mmol), H2O2 addition rate (one step), acid amount (8.8 mmol), and stirring speed (250 rpm). Interestingly, the enzyme was stable under the single-step addition of H2O2 with a catalytic activity of 190.0 Ug−1. The entire epoxidation process was carried out within 12 h using a conventional water bath shaker. PMID:23202943

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

NASA Technical Reports Server (NTRS)

Whitten, G. Z.; Hogo, H.

1976-01-01

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

Passive aerobic treatment of net-alkaline, iron-laden drainage from a flooded underground anthracite mine, Pennsylvania, USA

USGS Publications Warehouse

Cravotta, C.A.

2007-01-01

This report evaluates the results of a continuous 4.5-day laboratory aeration experiment and the first year of passive, aerobic treatment of abandoned mine drainage (AMD) from a typical flooded underground anthracite mine in eastern Pennsylvania, USA. During 1991-2006, the AMD source, locally known as the Otto Discharge, had flows from 20 to 270 L/s (median 92 L/s) and water quality that was consistently suboxic (median 0.9 mg/L O2) and circumneutral (pH ??? 6.0; net alkalinity >10) with moderate concentrations of dissolved iron and manganese and low concentrations of dissolved aluminum (medians of 11, 2.2, and <0.2 mg/L, respectively). In 2001, the laboratory aeration experiment demonstrated rapid oxidation of ferrous iron (Fe 2+) without supplemental alkalinity; the initial Fe2+ concentration of 16.4 mg/L decreased to less than 0.5 mg/L within 24 h; pH values increased rapidly from 5.8 to 7.2, ultimately attaining a steady-state value of 7.5. The increased pH coincided with a rapid decrease in the partial pressure of carbon dioxide (PCO2) from an initial value of 10 -1.1atm to a steady-state value of 10-3.1atm. From these results, a staged aerobic treatment system was conceptualized consisting of a 2 m deep pond with innovative aeration and recirculation to promote rapid oxidation of Fe2+, two 0.3 m deep wetlands to facilitate iron solids removal, and a supplemental oxic limestone drain for dissolved manganese and trace-metal removal. The system was constructed, but without the aeration mechanism, and began operation in June 2005. During the first 12 months of operation, estimated detention times in the treatment system ranged from 9 to 38 h. However, in contrast with 80-100% removal of Fe2+ over similar elapsed times during the laboratory aeration experiment, the treatment system typically removed less than 35% of the influent Fe2+. Although concentrations of dissolved CO2 decreased progressively within the treatment system, the PCO2 values for treated effluent remained elevated (10-2.4 to 10-1.7atm). The elevated PCO 2 maintained the pH within the system at values less than 7 and hence slowed the rate of Fe2+ oxidation compared to the aeration experiment. Kinetic models of Fe2+ oxidation that consider effects of pH and dissolved O2 were incorporated in the geochemical computer program PHREEQC to evaluate the effects of detention time, pH, and other variables on Fe2+ oxidation and removal rates. These models and the laboratory aeration experiment indicate that performance of this and other aerobic wetlands for treatment of net-alkaline AMD could be improved by aggressive, continuous aeration in the initial stage to decrease PCO 2, increase pH, and accelerate Fe2+ oxidation. ?? 2007 Springer-Verlag.

Fabrication of mesoporous metal oxide coated-nanocarbon hybrid materials via a polyol-mediated self-assembly process

NASA Astrophysics Data System (ADS)

Feng, Bingmei; Wang, Huixin; Wang, Dongniu; Yu, Huilong; Chu, Yi; Fang, Hai-Tao

2014-11-01

After clarifying the formation mechanism of a typical metal glycolate precipitate, Ti glycolate, in a polyol-mediated synthesis using acetone as a precipitation medium, we describe a simple template-free approach based on an ethylene glycol-mediated synthesis to fabricate mesoporous metal oxide coated-nanocarbon hybrid materials including TiO2 coated-carbon nanotube (CNT), SnO2 coated-CNT, Cu2O/CuO coated-CNT and TiO2 coated-graphene sheet (GS). In the approach, metal oxide precursors, metal glycolates, were first deposited on CNTs or GSs, and subsequently transformed to the metal oxide coatings by pyrolysis or hydrolysis. By a comparison between the characterization of two TiO2-CNT hybrid materials using carboxylated CNTs and pristine CNTs without carboxyl groups, the driving force for initiating the deposition of metal glycolates on the carboxylated CNTs is confirmed to be the hydrogen bonding between the carboxyl groups and the polymer chains in metal glycolate sols. The electrochemical performances of the mesoporous TiO2 coated-carboxylated CNTs and TiO2-pristine CNT hybrid materials were investigated. The results show that the mesoporous TiO2 coated-carboxylated CNT with a uniform core-shell nanostructure exhibits substantial improvement in the rate performance in comparison with its counterpart from 0.5 C to 100 C because of its higher electronic conductivity and shorter diffusion path for the lithium ion. At the extremely high rate of 100 C, the specific capacity of TiO2 of the former reaches 85 mA h g-1, twice as high as that of the latter.After clarifying the formation mechanism of a typical metal glycolate precipitate, Ti glycolate, in a polyol-mediated synthesis using acetone as a precipitation medium, we describe a simple template-free approach based on an ethylene glycol-mediated synthesis to fabricate mesoporous metal oxide coated-nanocarbon hybrid materials including TiO2 coated-carbon nanotube (CNT), SnO2 coated-CNT, Cu2O/CuO coated-CNT and TiO2 coated-graphene sheet (GS). In the approach, metal oxide precursors, metal glycolates, were first deposited on CNTs or GSs, and subsequently transformed to the metal oxide coatings by pyrolysis or hydrolysis. By a comparison between the characterization of two TiO2-CNT hybrid materials using carboxylated CNTs and pristine CNTs without carboxyl groups, the driving force for initiating the deposition of metal glycolates on the carboxylated CNTs is confirmed to be the hydrogen bonding between the carboxyl groups and the polymer chains in metal glycolate sols. The electrochemical performances of the mesoporous TiO2 coated-carboxylated CNTs and TiO2-pristine CNT hybrid materials were investigated. The results show that the mesoporous TiO2 coated-carboxylated CNT with a uniform core-shell nanostructure exhibits substantial improvement in the rate performance in comparison with its counterpart from 0.5 C to 100 C because of its higher electronic conductivity and shorter diffusion path for the lithium ion. At the extremely high rate of 100 C, the specific capacity of TiO2 of the former reaches 85 mA h g-1, twice as high as that of the latter. Electronic supplementary information (ESI) available. See DOI: 10.1039/C4NR04254A

In vivo imaging of free radicals produced by multivitamin-mineral supplements.

PubMed

Rabovsky, Alexander B; Buettner, Garry R; Fink, Bruno

2015-12-01

Redox active minerals in dietary supplements can catalyze unwanted and potentially harmful oxidations. To determine if this occurs in vivo we employed electron paramagnetic (EPR) imaging. We used 1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine (CPH) as a reporter for one-electron oxidations, e.g . free radical-mediated oxidations; the one-electron oxidation product of CPH, 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (CP • ), is a nitroxide free radical that is relatively persistent in vivo and detectable by EPR. As model systems, we used research formulations of vitamin mineral supplements (RVM) that are typical of commercial products. In in vitro experiments, upon suspension of RVM in aqueous solution, we observed: (1) the uptake of oxygen in the solution, consistent with oxidation of the components in the RVM; (2) the ascorbate free radical, a real-time indicator of ongoing oxidations; and (3) when amino acid/oligosaccharide (AAOS; glycinate or aspartate with non-digestible oligofructose) served as the matrix in the RVM, the rate of oxidation was significantly slowed. In a murine model, EPR imaging showed that the ingestion of RVM along with CPH results in the one-electron oxidation of CPH by RVM in the digestive system. The resulting CP • distributes throughout the body. Inclusion of AAOS in the RVM formulation diminished the oxidation of CPH to CP • in vivo. These data demonstrate that typical formulations of multivitamin/multimineral dietary supplements can initiate the oxidation of bystander substances and that AAOS-complexes of essential redox active metals, e.g . copper and iron, have reduced ability to catalyze free radical formation and associated detrimental oxidations when a part of a multivitamin/multimineral formulation.

In vivo imaging of free radicals produced by multivitamin-mineral supplements

PubMed Central

Buettner, Garry R.; Fink, Bruno

2015-01-01

Background Redox active minerals in dietary supplements can catalyze unwanted and potentially harmful oxidations. Methods To determine if this occurs in vivo we employed electron paramagnetic (EPR) imaging. We used 1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine (CPH) as a reporter for one-electron oxidations, e.g. free radical-mediated oxidations; the one-electron oxidation product of CPH, 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (CP•), is a nitroxide free radical that is relatively persistent in vivo and detectable by EPR. As model systems, we used research formulations of vitamin mineral supplements (RVM) that are typical of commercial products. Results In in vitro experiments, upon suspension of RVM in aqueous solution, we observed: (1) the uptake of oxygen in the solution, consistent with oxidation of the components in the RVM; (2) the ascorbate free radical, a real-time indicator of ongoing oxidations; and (3) when amino acid/oligosaccharide (AAOS; glycinate or aspartate with non-digestible oligofructose) served as the matrix in the RVM, the rate of oxidation was significantly slowed. In a murine model, EPR imaging showed that the ingestion of RVM along with CPH results in the one-electron oxidation of CPH by RVM in the digestive system. The resulting CP• distributes throughout the body. Inclusion of AAOS in the RVM formulation diminished the oxidation of CPH to CP• in vivo. Conclusions These data demonstrate that typical formulations of multivitamin/multimineral dietary supplements can initiate the oxidation of bystander substances and that AAOS-complexes of essential redox active metals, e.g. copper and iron, have reduced ability to catalyze free radical formation and associated detrimental oxidations when a part of a multivitamin/multimineral formulation. PMID:26705481

Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex.

PubMed

Lam, William W Y; Man, Wai-Lun; Wang, Yi-Ning; Lau, Tai-Chu

2008-08-04

The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.

Kinetics and mechanism of auto- and copper-catalyzed oxidation of 1,4-naphthohydroquinone.

PubMed

Yuan, Xiu; Miller, Christopher J; Pham, A Ninh; Waite, T David

2014-06-01

Although quinones represent a class of organic compounds that may exert toxic effects both in vitro and in vivo, the molecular mechanisms involved in quinone species toxicity are still largely unknown, especially in the presence of transition metals, which may both induce the transformation of the various quinone species and result in generation of harmful reactive oxygen species. In this study, the oxidation of 1,4-naphthohydroquinone (NH2Q) in the absence and presence of nanomolar concentrations of Cu(II) in 10 mM NaCl solution over a pH range of 6.5-7.5 has been investigated, with detailed kinetic models developed to describe the predominant mechanisms operative in these systems. In the absence of copper, the apparent oxidation rate of NH2Q increased with increasing pH and initial NH2Q concentration, with concomitant oxygen consumption and peroxide generation. The doubly dissociated species, NQ(2-), has been shown to be the reactive species with regard to the one-electron oxidation by O2 and comproportionation with the quinone species, both generating the semiquinone radical (NSQ(·-)). The oxidation of NSQ(·-) by O2 is shown to be the most important pathway for superoxide (O2(·-)) generation with a high intrinsic rate constant of 1.0×10(8)M(-1)s(-1). Both NSQ(·-) and O2(·-) served as chain-propagating species in the autoxidation of NH2Q. Cu(II) is capable of catalyzing the oxidation of NH2Q in the presence of O2 with the oxidation also accelerated by increasing the pH. Both the uncharged (NH2Q(0)) and the mono-anionic (NHQ(-)) species were found to be the kinetically active forms, reducing Cu(II) with an intrinsic rate constant of 4.0×10(4) and 1.2×10(7)M(-1)s(-1), respectively. The presence of O2 facilitated the catalytic role of Cu(II) by rapidly regenerating Cu(II) via continuous oxidation of Cu(I) and also by efficient removal of NSQ(·-) resulting in the generation of O2(·-). The half-cell reduction potentials of various redox couples at neutral pH indicated good agreement between thermodynamic and kinetic considerations for various key reactions involved, further validating the proposed mechanisms involved in both the autoxidation and the copper-catalyzed oxidation of NH2Q in circumneutral pH solutions. Copyright © 2014 Elsevier Inc. All rights reserved.