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Sample records for heat-activated persulfate oxidation

  1. Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process.

    PubMed

    Fan, Yan; Ji, Yuefei; Kong, Deyang; Lu, Junhe; Zhou, Quansuo

    2015-12-30

    Sulfamethazine (SMZ) is widely used in livestock feeding and aquaculture as an antibiotic agent and growth promoter. Widespread occurrence of SMZ in surface water, groundwater, soil and sediment has been reported. In this study, degradation of SMZ by heat-activated persulfate (PS) oxidation was investigated in aqueous solution. Experimental results demonstrated that SMZ degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing concentration of PS and temperature. Radical scavenging tests revealed that the predominant oxidizing species was SO4·(-) with HO playing a less important role. Aniline moiety in SMZ molecule was confirmed to be the reactive site for SO4·(-) attack by comparison with substructural analogs. Nontarget natural water constituents affected SMZ removal significantly, e.g., Cl(-) and HCO3(-) improved the degradation while fulvic acid reduced it. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). 6 products derived from sulfonamide S--N bond cleavage, aniline moiety oxidation and Smiles-type rearrangement were identified, and transformation pathways of SMZ oxidation were proposed. Results reveal that heat-activated PS oxidation could be an efficient approach for remediation of water contaminated by SMZ and related sulfonamides. PMID:26151383

  2. Heat-activated persulfate oxidation of PFOA, 6:2 fluorotelomer sulfonate, and PFOS under conditions suitable for in-situ groundwater remediation.

    PubMed

    Park, Saerom; Lee, Linda S; Medina, Victor F; Zull, Aaron; Waisner, Scott

    2016-02-01

    PFOA (perfluorooctanoic acid) oxidation (0.121-6.04 μM) by heat-activated persulfate was evaluated at 20-60 °C with 4.2-84 mM [Formula: see text] and in the presence of soluble fuel components to assess feasibility for in-situ remediation of groundwater. 6:2 fluorotelomer sulfonic acid/sulfonate (6:2 FTSA) and PFOS (perfluorooctanesulfonic acid) persulfate oxidation was also evaluated in a subset of conditions given their co-occurrence at many sites. High performance liquid chromatography electron spray tandem mass spectrometry was used for organic analysis and fluoride was measured using a fluoride-specific electrode. PFOA pseudo-1st order transformation rates (k1,PFOA) increased with increasing temperature (half-lives from 0.1 to 7 d for 60 to 30 °C) sequentially removing CF2 groups ('unzipping') to shorter chain perfluoroalkyl carboxylic acids (PFCAs) and F(-). At 50 °C, a 5-fold increase in [Formula: see text] led to a 5-fold increase in k1,PFOA after which self-scavenging by sulfate radicals decreased the relative rate of increase with more [Formula: see text] . Benzene, toluene, ethylbenzene and xylene did not affect k1,PFOA even at 40 times higher molar concentrations than PFOA. A modeling approach to explore pathways strongly supported that for 6:2 FTSA, both the ethyl linkage and CF2-CH2 bond of 6:2 FTSA oxidize simultaneously, resulting in a ratio of ∼25/75 PFHpA/PFHxA. The effectiveness of heat-activated [Formula: see text] on PFOA oxidation was reduced in a soil slurry; therefore, repeated persulfate injections are required to efficiently achieve complete oxidation in the field. However, PFOS remained unaltered even at higher activation temperatures, thus limiting the sole use of heat-activated persulfate for perfluoroalkyl substances removal in the field. PMID:26692515

  3. Persulfate Oxidation of Gasoline Compounds

    NASA Astrophysics Data System (ADS)

    Sra, K.; Thomson, N.; Barker, J.

    2009-05-01

    In situ chemical oxidation (ISCO) using persulfate is a promising remediation technology that can be potentially applied to a wide range of organic contaminants. Gasoline compounds are of particular interest because they extensively impact the soil and groundwater, and are highly persistent and toxic. In this investigation, destruction of specific gasoline compounds (benzene, toluene, ethylbenzenes, xylenes, trimethylbenzenes (TMBs) and naphthalene), and fractions (F1 and F2) by activated and inactivated persulfate was studied at the bench-scale. Aqueous phase batch reactors (25 mL) for inactivated systems employed persulfate at two concentrations (1 or 20 g/L), and activated systems were conducted with a persulfate concentration of 20 g/L. In the activated systems, the ability of hydrogen peroxide or chelated-ferrous as an activator was examined at two experimental conditions (peroxide molar ratio 0.1 and 1.0 with respect to persulfate; and citric acid chelated ferrous at 150 and 600 mg/L). All treatments and controls contained an initial gasoline concentration of approximately 25 mg/L and were run in triplicate. Sampling for gasoline compounds was conducted over <28 day reaction period. The controls showed insignificant degradation for all the gasoline compounds and fractions examined while inactivated persulfate at 1 g/L showed little (<10%) decrease in the concentration of gasoline compounds over the 28 day reaction period. Inactivated persulfate at 20 g/L demonstrated a significant decrease in the aqueous concentration of BTEX (>99%), TMB (>94%) and naphthalene (>71%). Oxidation of the F1 fraction (>94%) was more pronounced than the F2 fraction (>80%), and >93% TPH was oxidized. Use of peroxide as an activator at a molar ratio of 0.1 improved the destruction of TMBs (>99%) and naphthalene (>85%) while maintaining the high removal of BTEX (>99%) compounds. Increase in activator strength (molar ratio 1.0) decreased the destruction of xylenes (>86%) and TMBs (>81%). The decrease in concentration of all the compounds was higher for a molar ratio of 1.0 (<27%) as compared with a molar ratio of 0.1 (<11%). The activation by ferrous concentration resulted in higher oxidation of compounds (except naphthalene) as compared with unactivated or peroxide activated persulfate. 1,3,5-TMB was completed oxidized after 4 days using higher chelated ferrous concentration and after 12 days using lower chelated ferrous concentration for persulfate activation. In general, increase in chelated ferrous concentration resulted in higher oxidation of the gasoline compounds. While oxidation of F1 fraction was similar for two ferrous activation conditions, the oxidation of F2 fraction was lower when ferrous activation at 600 mg/L was employed. Use of persulfate at high dosages by itself or in combination with higher doses of chelated ferrous or optimum doses of peroxide as an activator seems to be a viable option for remediation of gasoline compounds examined in this study. Persulfate appears to be particularly effective in the oxidation of BTEX compounds, but may require ferrous activation for a complete oxidation of TMBs and peroxide activation for oxidation of naphthalene.

  4. Degradation of toluene, ethylbenzene, and xylene using heat and chelated-ferrous iron activated persulfate oxidation

    NASA Astrophysics Data System (ADS)

    Mondal, P.; Sleep, B.

    2014-12-01

    Toluene, ethylbenze, and xylene (TEX) are common contaminants in the subsurface. Activated persulfate has shown promise for degrading a wide variety of organic compounds. However, studies of persulfate application for in situ degradation of TEX and effects on the subsequent bioremediation are limited. In this work, degradation studies of TEX in aqueous media and soil are being conducted using heat activated and chelated-ferrous iron activated persulfate oxidation in batch and flow-through column experiments. In the batch experiments, sodium persulfate is being used at different concentrations to provide an initial persulfate to TEX molar ratios between 10:1 and 100:1. Sodium persulfate solutions are being activated at 20, 37, 60, and 80 oC temperatures for the heat activated oxidation. For the chelated-ferrous iron activated oxidation, ferrous iron and citric acid, both are being used at concentration of 5 mM. In the experiments with soil slurry, a soil to water ratio of 1 to 5 is being used. Flow through water saturated column experiments are being conducted with glass columns (45 cm in length and 4 cm in diameter) uniformly packed with soils, and equilibrated with water containing TEX at the target concentrations. Both the heat activation and chelated-ferrous iron activation of persulfate are being employed in the column experiments. Future experiments are planned to determine the suitability of persulfate oxidation of TEX on the subsequent biodegradation using batch microcosms containing TEX degrading microbial cultures. In these experiments, the microbial biomass will be monitored using total phospholipids, and the microbial community will be determined using quantitative real-time polymerase chain reaction (qPCR) on the extracted DNA. This study is expected to provide suitable operating conditions for in situ chemical oxidation of TEX with activated persulfate followed by bioremediation.

  5. Rapid persulfate oxidation predicts PAH bioavailability in soils and sediments

    SciTech Connect

    Cuypers, C.; Grotenhuis, T.; Joziasse, J.; Rulkens, W.

    2000-05-15

    Persulfate oxidation was validated as a method to predict polycyclic aromatic hydrocarbon (PAH) bioavailability in soils and sediments. It was demonstrated for 14 field contaminated soils and sediments that residual PAH concentrations after a short (3 h) persulfate oxidation correspond well to residual PAH concentrations after 21 days of biodegradation. Persulfate oxidation of samples that had first been subjected to biodegradation yielded only limited additional PAH oxidation. This implies that oxidation and biodegradation removed approximately the same PAH fraction. Persulfate oxidation thus provides a good and rapid method for the prediction of PAH bioavailability. Thermogravimetric analysis of oxidized and untreated samples showed that persulfate oxidation primarily affected expanded organic matter. The results indicate that this expanded organic matter contained mainly readily bioavailable PAHs.

  6. Lipid extraction from microalgae cell using persulfate-based oxidation.

    PubMed

    Seo, Yeong Hwan; Sung, Mina; Oh, You-Kwan; Han, Jong-In

    2016-01-01

    In this study, persulfate, a solid-type oxidant, was adopted as a substitute for hydrogen peroxide in extracting lipid from microalgae biomass. Microalgae cells were concentrated at pH 3 and with 200mg/L of ferric chloride, conditions which can activate oxidants such as hydrogen peroxide and persulfate. At a persulfate concentration of 2mM and a reaction temperature of 90°C, exceedingly high extraction efficiency over 95% was obtained, which was higher than with 0.5% hydrogen peroxide at the same temperature. This result showed that persulfate is sufficiently powerful and incomparably cheap enough to replace the potent yet expensive oxidant. It appears that combining iron-based coagulation and persulfate-based lipid extraction is indeed a competitive approach that can possibly lighten the process burden for the microalgae-derived biodiesel production. PMID:26614226

  7. Release of chromium from soils with persulfate chemical oxidation.

    PubMed

    Kaur, Kawalpreet; Crimi, Michelle

    2014-01-01

    An important part of the evaluation of the effectiveness of persulfate in situ chemical oxidation (ISCO) for treating organic contaminants is to identify and understand its potential impact on metal co-contaminants in the subsurface. Chromium is a redox-sensitive and toxic metal the release of which poses considerable risk to human health. The objective of this study was to investigate the impact of persulfate chemical oxidation on the release of chromium from three soils varying in physical-chemical properties. Soils were treated with unactivated and activated persulfate [activated with Fe(II), Fe(II)-EDTA, and alkaline pH] at two different concentrations (i.e., 41 mM and 2.1 mM persulfate) for 48 h and 6 months and were analyzed for release of chromium. Results show that release of chromium with persulfate chemical oxidation depends on the soil type and the activation method. Sandy soil with low oxidant demand released more chromium compared to soils with high oxidant demand. More chromium was released with alkaline pH activation. Alkaline pH and high Eh conditions favor oxidation of Cr(III) to Cr(VI), which is the main mechanism of release of chromium with persulfate chemical oxidation. Unactivated and Fe(II)-activated persulfate decreased pH and at low pH in absence of EDTA chromium release is not a concern. These results indicate that chromium release can be anticipated based on the given site and treatment conditions, and ISCO system can be designed to minimize potential chromium release when treating soils and groundwater contaminated with both organic and metal contaminants. PMID:24028318

  8. Microwave-enhanced persulfate oxidation to treat mature landfill leachate.

    PubMed

    Chou, Yu-Chieh; Lo, Shang-Lien; Kuo, Jeff; Yeh, Chih-Jung

    2015-03-01

    Microwave oxidation process (MOP) was evaluated for treatment of landfill leachate. Kinetics of persulfate oxidation in MOP, effects of pH and persulfate doses on fates of derivative organic acids, and the energy cost of MOP were evaluated. The results showed that total organic carbon (TOC) removal of 79.4%, color removal of 88.4%, and UV254 removal of 77.1% were reached at MOP 550 W/85 °C within 30 min. The kinetics of oxidation by MOP followed the first-order reaction. For a given persulfate dose, the reaction rate increased with the microwave power setting (775 W>550 W>325 W>128 W) with reaction rate constants ranging from 10(-5) to 10(-2) min(-1). The adverse effects on reaction rates under higher microwave power settings and high persulfate doses are plausibly caused by excessive persulfate oxidation and self-scavenging termination of free radicals. During the MOP treatment, TOC/COD ratio dropped with time and an 86.7% reduction in TOC/COD ratio after 120 min at pH 7. Oxalic acid was the major derivative and its concentrations were higher under acidic conditions. Malic, lactic, and acetic acids were formed and soon degraded, and the solution pH has an insignificant effect on their fates. The energy cost of MOP (USD$6.03/m(3)) is essentially similar to that of conventional heating oxidation (CHO) (USD$6.10/m(3)). PMID:25463221

  9. Degradation of 1,4-dioxane in water with heat- and Fe(2+)-activated persulfate oxidation.

    PubMed

    Zhao, Long; Hou, Hong; Fujii, Ayuko; Hosomi, Masaaki; Li, Fasheng

    2014-06-01

    This research investigated the 1,4-dioxane (1,4-D) degradation efficiency and rate during persulfate oxidation at different temperatures, with and without Fe(2+) addition, also considering the effect of pH and persulfate concentration on the oxidation of 1,4-D. Degradation pathways for 1,4-D have also been proposed based on the decomposition intermediates and by-products. The results indicate that 1,4-D was completely degraded with heat-activated persulfate oxidation within 3-80 h. The kinetics of the 1,4-D degradation process fitted well to a pseudo-first-order reaction model. Temperature was identified as the most important factor influencing the 1,4-D degradation rate during the oxidation process. As the temperature increased from 40 to 60 C, the degradation rate improved significantly. At 40 C, the addition of Fe(2+) also increased the 1,4-D degradation rate. Interestingly, at 50 and 60 C, the 1,4-D degradation rate decreased slightly with the addition of Fe(2+). This reduced degradation rate may be attributed to the rapid conversion of Fe(2+) to Fe(3+) and the production of an Fe(OH)3 precipitate which limited the ultimate oxidizing capability of persulfate with Fe(2+) under higher temperatures. Higher persulfate concentrations led to higher 1,4-D degradation rates, but pH adjustment had no significant effect on the 1,4-D degradation rate. The identification of intermediates and by-products in the aqueous and gas phases showed that acetaldehyde, acetic acid, glycolaldehyde, glycolic acid, carbon dioxide, and hydrogen ion were generated during the persulfate oxidation process. A carbon balance analysis showed that 96 and 93% of the carbon from the 1,4-D degradation were recovered as by-products with and without Fe(2+) addition, respectively. Overall, persulfate oxidation of 1,4-D is promising as an economical and highly efficient technology for treatment of 1,4-D-contaminated water. PMID:24590601

  10. Persulfate oxidation of MTBE- and chloroform-spent granular activated carbon.

    PubMed

    Huling, Scott G; Ko, Saebom; Park, Saehan; Kan, Eunsung

    2011-09-15

    Activated persulfate (Na(2)S(2)O(8)) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H(2)O(2)-persulfate binary mixtures. H(2)O(2) may serve multiple roles in oxidation mechanisms including Fenton-driven oxidation, and indirect activation of persulfate through thermal or ferrous iron activation mechanisms. More frequent, lower volume applications of persulfate solution (i.e., the persulfate loading rate), higher solid/solution ratio (g GAC mL(-1) solution), and higher persulfate concentration (mass loading) resulted in greater MTBE oxidation and removal. Chloroform oxidation was more effective in URV GAC compared to F400 GAC. This study provides baseline conditions that can be used to optimize pilot-scale persulfate-driven regeneration of contaminant-spent GAC. PMID:21782339

  11. Evaluation of persulfate oxidative wet scrubber for removing BTEX gases.

    PubMed

    Liang, Chenju; Chen, Yan-Jyun; Chang, Keng-Jung

    2009-05-30

    Soil vapor extraction (SVE) coupled with air sparging of groundwater is a method commonly used to remediate soil and groundwater contaminated with volatile organic petroleum contaminants such as gasoline. These hazardous contaminants are mainly attributable to the compounds-benzene, toluene, ethylbenzene, and xylenes (known collectively as BTEX). Exhaust gas from SVE may contain BTEX, and therefore must be treated before being discharged. This study evaluated the use of iron-activated persulfate chemical oxidation in conjunction with a wet scrubbing system, i.e., a persulfate oxidative scrubber (POS) system, to destroy BTEX gases. The persulfate anions can be activated by citric acid (CA) chelated Fe(2+) to generate sulfate radicals (SO(4)(*-), E degrees =2.4V), which may rapidly degrade BTEX in the aqueous phase and result in continuous destruction of the BTEX gases. The results show that persulfate activation occurred as a result of continuous addition of the citric acid chelated Fe(2+) activator, which readily oxidized the dissolved BTEX. Based on initial results from the aqueous phase, a suitable Fe(2+)/CA molar ratio of 5/3 was determined and used to initiate activation in the subsequent POS system tests. In the POS system, using persulfate as a scrubber solution and with activation by injecting Fe(2+)/CA activators under two testing conditions, varying iron concentrations and pumping rates, resulted in an approximate 50% removal of BTEX gases. During the course of the tests which in corporate activation, a complete destruction of BTEX was achieved in the aqueous phase. It is noted that no removal of BTEX occurred in the control tests which did not include activation. The results of this study would serve as a reference for future studies into the practical chemical oxidation of waste gas streams. PMID:18829165

  12. Oxidation of polyvinyl alcohol by persulfate activated with heat, Fe2+, and zero-valent iron.

    PubMed

    Oh, Seok-Young; Kim, Hyeong-Woo; Park, Jun-Mo; Park, Hung-Suck; Yoon, Chohee

    2009-08-30

    The oxidation of polyvinyl alcohol (PVA) by persulfate (S(2)O(8)(2-)) activated with heat, Fe(2+), and zero-valent iron (Fe(0)) was investigated via batch experiments. It was hypothesized that elevated temperature and the addition of Fe(2+) or Fe(0) into a persulfate-water system could enhance the oxidation of PVA by activated persulfate. Increasing the temperature from 20 to 60 degrees C or 80 degrees C accelerated the oxidation rate of PVA, which achieved complete oxidation in 30 and 10 min, respectively. At 20 degrees C, the addition of Fe(2+) or Fe(0) to the persulfate-water system significantly enhanced the oxidation of PVA. The optimal persulfate-to-Fe(2+) or Fe(0) molar ratio was found to be 1:1. Complete oxidation of PVA was obtained by Fe(0)-activated persulfate in 2h. Synergistic activation of persulfate by heat and Fe(2+) or Fe(0) was also shown to enhance the oxidation of PVA in the persulfate-water system. By using GC-MS analysis, an oxidation product of PVA was identified as vinyl acetic acid (C(4)H(6)O(2)), which is readily biodegradable. Our results suggest that the oxidative treatment of PVA by activated persulfate is a viable option for the pretreatment of PVA-laden wastewater to enhance its biodegradability. PMID:19285795

  13. Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil.

    PubMed

    Liao, Xiaoyong; Zhao, Dan; Yan, Xiulan; Huling, Scott G

    2014-07-15

    The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed in the soil. Oxy-PAHs including 1H-phenalen-1-one, 9H-fluoren-9-one, and 1,8-naphthalic anhydride were also produced during persulfate oxidation of PAHs. Concentration of 1,8-naphthalic anhydride at 4h in thermally activated (50C) persulfate oxidation (TAPO) treatment increased 12.7 times relative to the oxidant-free control. Additionally, the oxy-PAHs originally present and those generated during oxidation can be oxidized by unactivated or thermally activated persulfate oxidation. For example, 9H-fluoren-9-one concentration decreased 99% at 4h in TAPO treatment relative to the control. Thermally activated persulfate resulted in greater oxy-PAHs removal than unactivated persulfate. Overall, both unactivated and thermally activated persulfate oxidation of PAH-contaminated soil reduced PAH mass, and oxidized most of the reaction byproducts. Consequently, this treatment process could limit environmental risk related to the parent compound and associated reaction byproducts. PMID:24862467

  14. UV-activated persulfate oxidation and regeneration of NOM-Saturated granular activated carbon.

    PubMed

    An, Dong; Westerhoff, Paul; Zheng, Mengxin; Wu, Mengyuan; Yang, Yu; Chiu, Chao-An

    2015-04-15

    A new method of ultraviolet light (UV) activated persulfate (PS) oxidation was investigated to regenerate granular activated carbon (GAC) in drinking water applications. The improvements in iodine and methylene blue numbers measured in the GAC after ultraviolet- (UV) activated persulfate suggested that the GAC preloaded with natural organic matter (NOM) was chemically regenerated. An experimental matrix for UV-activated persulfate regeneration included a range of persulfate doses and different UV wavelengths. Over 87% of the initial iodine number for GAC was restored under the optimum conditions, perfulfate dosage 60 g/L and UV exposure 1.75 10(4) mJ/cm(2). The persulfate dosages had little effect on the recovery of the methylene blue number, which was approximately 65%. Persulfate activation at 185 nm was superior to activation at 254 nm. UV activation of persulfate in the presence of GAC produced acid, lowering the solution pH. Higher persulfate concentrations and UV exposure resulted in greater GAC regeneration. Typical organic and inorganic byproducts (e.g., benzene compounds and sulfate ions) were measured as a component of treated water quality safety. This study provides a proof-of-concept that can be used to optimize pilot-scale and full-scale UV-activated persulfate for regeneration of NOM-saturated GAC. PMID:25697692

  15. Defluorination of Aqueous Perfluorooctanesulfonate by Activated Persulfate Oxidation

    PubMed Central

    Yang, Shewei; Cheng, Jianhua; Sun, Jian; Hu, Yongyou; Liang, Xiaoyan

    2013-01-01

    Activated persulfate oxidation technologies based on sulfate radicals were first evaluated for defluorination of aqueous perfluorooctanesulfonate (PFOS). The influences of catalytic method, time, pH and K2S2O8 amounts on PFOS defluorination were investigated. The intermediate products during PFOS defluorination were detected by using LC/MS/MS. The results showed that the S2O82− had weak effect on the defluorination of PFOS, while the PFOS was oxidatively defluorinated by sulfate radicals in water. The defluorination efficiency of PFOS under various treatment was followed the order: HT (hydrothermal)/K2S2O8 > UV (ultraviolet)/K2S2O8 > Fe2+/K2S2O8 > US (ultrasound)/K2S2O8. Low pH was favorable for the PFOS defluorination with sulfate radicals. Increase in the amount of S2O82− had positive effect on PFOS defluorination. However, further increase in amounts of S2O82− caused insignificant improvement in PFOS defluorination due to elimination of sulfate radicals under high concentration of S2O82−. CF3(CF2)nCOOH (n = 0–6) were detected as intermediates during PFOS defluorination. Sulfate radicals oxidation and hydrolysis were the main mechanisms involved in defluorination process of PFOS. PMID:24116016

  16. Green mechanochemical oxidative decomposition of powdery decabromodiphenyl ether with persulfate.

    PubMed

    Huang, Aizhen; Zhang, Zhimin; Wang, Nan; Zhu, Lihua; Zou, Jing

    2016-01-25

    A method was developed for efficiently degrading powdery decabromodiphenyl ether (BDE209) by using mechanochemical (MC) activation of persulfate (PS). Characteristic Raman spectra of BDE209 corresponding to CBr and CO bonds were decreased in intensity and finally disappeared as the MC reaction proceeded. The BDE209 removal was influenced by the molar ratio of PS to BDE209, the mass ratio of milling ball to reaction mixtures, the ball size, and the ball rotation speed. Under optimal conditions, the new method could achieve a complete degradation, debromination and mineralization of BDE209 within 3h of milling. However, the degradation removal (or debromination efficiency) was decreased to only 51.7% (15.6%) and 67.8% (31.5%) for the use of CaO and peroxymonosulfate, respectively. The analyses of products demonstrated that once the degradation was initiated, BDE209 molecules were deeply debrominated and fully mineralized in the MC-PS system. The strong oxidizing ability of this system was due to the reactive sulfate radicals generated from the MC-enhanced activation of PS, which was confirmed with electron spin resonance spectroscopy. Because no toxic low brominated polybrominated diphenyl ethers were accumulated as byproducts, the proposed MC oxidative degradation method will have promising applications in the treatment of solid BDE209 at high concentrations. PMID:26474378

  17. Activation of Persulfate by Iron Filings and Oxidation of 1,4-Dioxane

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Zhong, H.; Yan, N.; Brusseau, M. L.

    2014-12-01

    The use of iron filings to promote in-situ activation of persulfate for permeable reactive barrier systems is investigated with batch and column experiments. The application of the approach was illustrated for oxidation of 1,4-dioxane. The results of the batch experiments showed that in the absence of the iron filings both persulfate decomposition and dioxane degradation were slow, with pseudo first-order half-lives of 160 d-1 and 6.3 d-1, respectively. In the presence of the iron filings, persulfate decomposition and dioxane degradation was much faster, with reductions in concentrations of 86% and 34% in the first 30 minutes, respectively. Approximately 10% of the dioxane injected into a column packed with iron filings was degraded. Analysis of persulfate and sulfate concentrations in the column effluent produced balanced total sulfur. The rate coefficient obtained from the column experiments was similar to the value obtained from the batch experiments.

  18. Recovery of Phenanthrene-Degrading Bacteria After Simulated In Situ Persulfate Oxidation in Contaminated Soil

    PubMed Central

    Richardson, Stephen D.; Lebron, Benjamin L.; Miller, Cass T.; Aitken, Michael D.

    2010-01-01

    A continuous-flow column study was conducted to investigate the long-term effects of persulfate oxidation on the abundance and activity of the indigenous microbial community and phenanthrene-degrading bacteria in contaminated soil from a former manufactured gas plant (MGP) site. Approximately six pore volumes of a 20 g/L persulfate solution were introduced into the column, followed by simulated groundwater for 500 d. Soil samples were collected from the surface of the soil bed and along the column length immediately before and after persulfate injection and up to 500 d following injection. Exposure to persulfate led to a two- to three-log reduction in total bacterial 16S rRNA genes, severe inhibition of 14C-acetate mineralization (as a measure of general microbial activity), and a decrease in community diversity. However, relatively rapid recovery of both bacterial gene abundance and activity was observed within 30 d after persulfate exposure. Mineralization of 14C-phenanthrene was also inhibited but did not recover until 100 d post-oxidation. Known phenanthrene-degrading bacterial groups decreased to below detection limits throughout the column, with recovery times from 100 d to 500 d after persulfate injection. These findings suggest that coupling biological processes with persulfate oxidation is possible, although recovery of specific contaminant degraders may occur much later than the general microbial community recovers. Furthermore, the use of total bacterial quantity or non-specific measures of activity as a surrogate for the recovery of contaminant degraders may be inappropriate for evaluating the compatibility of chemical treatment with subsequent bioremediation. PMID:21162560

  19. Persulfate Oxidation Regeneration of Granular Activated Carbon: Reversible Impacts on Sorption Behavior

    EPA Science Inventory

    Chemical oxidation regeneration of granular activated carbon (GAC) is a developing technology that can be carried out utilizing thermally-activated persulfate. During chemical regeneration of GAC, aggressive oxidative conditions lead to high acidity (pH < 2) and the accumulation ...

  20. Comparative Study on Oxidative Treatments of NAPL Containing Chlorinated Ethanes and Ethenes using Hydrogen Peroxide and Persulfate in Soils

    EPA Science Inventory

    The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H2O2–persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand,...

  1. Comparative Study on Oxidative Treatments of NAPL Containing Chlorinated Ethanes and Ethenes using Hydrogen Peroxide and Persulfate in Soils

    EPA Science Inventory

    The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H2O2persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand,...

  2. Carbon isotope fractionation of chlorinated ethenes during oxidation by Fe2+ activated persulfate.

    PubMed

    Marchesi, Massimo; Aravena, Ramon; Sra, Kanwartej S; Thomson, Neil R; Otero, Neus; Soler, Albert; Mancini, Silvia

    2012-09-01

    The increased use of persulfate (S(2)O(8)(2-)) for in situ chemical oxidation to treat groundwater and soils contaminated by chlorinated hydrocarbon compounds (CHCs) requires unbiased methods to assess treatment performance. Stable carbon isotope analysis offers a potential tool for assessing the in situ treatment performance of persulfate at sites contaminated with CHCs. This study investigated the extent of C isotope fractionation during oxidation of tetrachloroethene (PCE), trichloroethene (TCE) and cis-dichloroethene (cis-DCE) by persulfate activated by ferrous ion (Fe(2+)). An average carbon isotope enrichment factor ?(bulk) of -4.9 for PCE, -3.6 for TCE and -7.6 for cis-DCE were obtained in batch experiments. Variations in the initial S(2)O(8)(2-)/Fe(2+)/CHC molar ratios did not result in any significant differences in carbon isotope fractionation. The occurrence of carbon isotope fractionation during oxidation and the lack of dependence of enrichment factors upon the S(2)O(8)(2-)/Fe(2+)/CHC molar ratio demonstrate that carbon isotope analysis can potentially be used at contaminated sites as an additional technique to estimate treatment efficacy during oxidation of CHCs by Fe(2+) activated persulfate. PMID:22814410

  3. Influences of carbonate and chloride ions on persulfate oxidation of trichloroethylene at 20 degrees C.

    PubMed

    Liang, Chenju; Wang, Zih-Sin; Mohanty, Nihar

    2006-11-01

    Application of in situ chemical oxidation (ISCO) involves application of oxidants to contaminants such as trichloroethylene (TCE) in soil or groundwater in place. Successful application of ISCO at a hazardous waste site requires understanding the scavenging reactions that could take place at the site to better optimize the oxidation of target contaminants and identification of site conditions where ISCO using persulfate may not be applicable. Additionally, estimation of the oxidant dose at a site would need identification of groundwater constituents such as alkalinity and chlorides that may scavenge radicals and therefore use up the oxidant that is targeted for the contaminant(s). The objective of this study was to investigate the influence of various levels of chloride and carbonates on persulfate oxidation of TCE at 20 degrees C under controlled conditions in a laboratory. Based on the results of the laboratory experiments, both chloride and alkalinity were shown to have scavenging effects on the rate of oxidation of TCE. It was found that at a neutral pH, persulfate oxidation of TCE was not affected by the presence of bicarbonate/carbonate concentrations within the range of 0-9.20 mM. However, the TCE degradation rate was seen to reduce with an increase in the level of carbonate species and at elevated pHs. TCE degradation in the presence of chlorides revealed no effect on the degradation rate especially at chloride levels below 0.2 M. However, at chloride levels greater than 0.2 M, TCE degradation rate was seen to reduce with an increase in the chloride ion concentration. Prior to application of persulfate as an oxidant, a site should be screened for the presence of scavengers to evaluate the potential of meeting target cleanup goals within a desirable timeframe at the site. PMID:17014891

  4. Remediation of nitrobenzene contaminated soil by combining surfactant enhanced soil washing and effluent oxidation with persulfate.

    PubMed

    Yan, Jingchun; Gao, Weiguo; Qian, Linbo; Han, Lu; Chen, Yun; Chen, Mengfang

    2015-01-01

    The combination of surfactant enhanced soil washing and degradation of nitrobenzene (NB) in effluent with persulfate was investigated to remediate NB contaminated soil. Aqueous solution of sodium dodecylbenzenesulfonate (SDBS, 24.0 mmol L-1) was used at a given mass ratio of solution to soil (20:1) to extract NB contaminated soil (47.3 mg kg-1), resulting in NB desorption removal efficient of 76.8%. The washing effluent was treated in Fe2+/persulfate and Fe2+/H2O2 systems successively. The degradation removal of NB was 97.9%, being much higher than that of SDBS (51.6%) with addition of 40.0 mmol L-1 Fe2+ and 40.0 mmol L-1 persulfate after 15 min reaction. The preferential degradation was related to the lone pair electron of generated SO4-, which preferably removes electrons from aromatic parts of NB over long alkyl chains of SDBS through hydrogen abstraction reactions. No preferential degradation was observed in OH based oxidation because of its hydrogen abstraction or addition mechanism. The sustained SDBS could be reused for washing the contaminated soil. The combination of the effective surfactant-enhanced washing and the preferential degradation of NB with Fe2+/persulfate provide a useful option to remediate NB contaminated soil. PMID:26266532

  5. Remediation of Nitrobenzene Contaminated Soil by Combining Surfactant Enhanced Soil Washing and Effluent Oxidation with Persulfate

    PubMed Central

    Yan, Jingchun; Gao, Weiguo; Qian, Linbo; Han, Lu; Chen, Yun; Chen, Mengfang

    2015-01-01

    The combination of surfactant enhanced soil washing and degradation of nitrobenzene (NB) in effluent with persulfate was investigated to remediate NB contaminated soil. Aqueous solution of sodium dodecylbenzenesulfonate (SDBS, 24.0 mmol L-1) was used at a given mass ratio of solution to soil (20:1) to extract NB contaminated soil (47.3 mg kg-1), resulting in NB desorption removal efficient of 76.8%. The washing effluent was treated in Fe2+/persulfate and Fe2+/H2O2 systems successively. The degradation removal of NB was 97.9%, being much higher than that of SDBS (51.6%) with addition of 40.0 mmol L-1 Fe2+ and 40.0 mmol L-1 persulfate after 15 min reaction. The preferential degradation was related to the lone pair electron of generated SO4?, which preferably removes electrons from aromatic parts of NB over long alkyl chains of SDBS through hydrogen abstraction reactions. No preferential degradation was observed in OH based oxidation because of its hydrogen abstraction or addition mechanism. The sustained SDBS could be reused for washing the contaminated soil. The combination of the effective surfactant-enhanced washing and the preferential degradation of NB with Fe2+/persulfate provide a useful option to remediate NB contaminated soil. PMID:26266532

  6. Effect of persulfate on the oxidation of benzotriazole and humic acid by e-beam irradiation.

    PubMed

    Roshani, Babak; Leitner, Nathalie Karpel Vel

    2011-06-15

    These days, the use of persulfate in advanced oxidation processes (AOPs) has gained more attention as an emerging clean and efficient technology to degrade the organic pollutants. The objective of this study was to investigate the effect of the addition of persulfate on the oxidation of benzotriazole (BT) and humic acids (HAs) by irradiation. The degradation of BT (3.7 ?M) was followed under the influence of persulfate addition (200-500 ?M) in combination with a fixed radiation dose (15 Gy) in the absence and presence of HA (5 and 20mg/L) in deionized water. The main results obtained in this study on the degradation of BT in the presence of HA showed a different effect of S(2)O(8)(2-) addition during irradiation, depending on whether HA are oxidized or not-oxidized. (1) An inhibitory effect of S(2)O(8)(2-) was observed in the presence of non-oxidized HA. (2) The removal of BT was generally more important during irradiation in the presence of S(2)O(8)(2-) when HA is pre-oxidized. This could be explained by the different structures of humic acids. These differences of structures of HA were identified by physico-chemical parameters such as the absorbance in the UV (254 nm), the fluorescence and the SUVA measurement. PMID:21514992

  7. In situ chemical oxidation of contaminated groundwater by persulfate: decomposition by Fe(III)- and Mn(IV)-containing oxides and aquifer materials.

    PubMed

    Liu, Haizhou; Bruton, Thomas A; Doyle, Fiona M; Sedlak, David L

    2014-09-01

    Persulfate (S2O8(2-)) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4(-)) and hydroxyl radical (HO()) over time scales of several weeks at rates that were 2-20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants. PMID:25133603

  8. In Situ Chemical Oxidation of Contaminated Groundwater by Persulfate: Decomposition by Fe(III)- and Mn(IV)-Containing Oxides and Aquifer Materials

    PubMed Central

    2015-01-01

    Persulfate (S2O82–) is being used increasingly for in situ chemical oxidation (ISCO) of organic contaminants in groundwater, despite an incomplete understanding of the mechanism through which it is converted into reactive species. In particular, the decomposition of persulfate by naturally occurring mineral surfaces has not been studied in detail. To gain insight into the reaction rates and mechanism of persulfate decomposition in the subsurface, and to identify possible approaches for improving its efficacy, the decomposition of persulfate was investigated in the presence of pure metal oxides, clays, and representative aquifer solids collected from field sites in the presence and absence of benzene. Under conditions typical of groundwater, Fe(III)- and Mn(IV)-oxides catalytically converted persulfate into sulfate radical (SO4•–) and hydroxyl radical (HO•) over time scales of several weeks at rates that were 2–20 times faster than those observed in metal-free systems. Amorphous ferrihydrite was the most reactive iron mineral with respect to persulfate decomposition, with reaction rates proportional to solid mass and surface area. As a result of radical chain reactions, the rate of persulfate decomposition increased by as much as 100 times when benzene concentrations exceeded 0.1 mM. Due to its relatively slow rate of decomposition in the subsurface, it can be advantageous to inject persulfate into groundwater, allowing it to migrate to zones of low hydraulic conductivity where clays, metal oxides, and contaminants will accelerate its conversion into reactive oxidants. PMID:25133603

  9. 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. PMID:26452660

  10. The Persulfate Process for the Mediated Oxidation of Organic Pollutants

    NASA Astrophysics Data System (ADS)

    Vatistas, N.; Comninellis, Ch.

    The electrochemical treatment of effluents with conventional anodic materials is not very efficient in terms of organic pollutant oxidation and produces a large amount of oxygen. These results can be enhanced by mediated oxidation that produces stronger oxidants than oxygen which oxidize the organic pollutants. New electrode materials like, boron-doped diamond (BDD) shows a high selectivity toward organic pollutants and the oxygen is not easily produced. Consequently the contribution of mediated oxidation cannot be excluded, but probably occurs in a different way. This chapter re-examines at the light of the present knowledge the mediated oxidation with the BDD anode, tests the used mediated oxidation method, and proposes an alternative method to increase the positive contribution of this oxidation during electrochemical treatment with BDD anodes.

  11. Chemical Oxidation of Complex PAH Mixtures by Base-activated Sodium Persulfate

    NASA Astrophysics Data System (ADS)

    Hauswirth, S.; Miller, C. T.

    2013-12-01

    In situ chemical oxidation (ISCO) is an attractive approach for the remediation of recalcitrant soil and groundwater contaminants. One oxidant that has received significant recent attention is sodium persulfate, which has several advantages, including a relatively long lifetime in porous media, the ability to destroy a wide-range of chemical contaminants, and a high oxidation potential. In this study, we investigated the chemical mechanisms associated with base-activated persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) and assessed the applicability of persulfate to the remediation of porous media contaminated with non-aqueous phase liquid (NAPL) PAH mixtures. Batch experiments were conducted to determine the oxidation kinetics for individual PAH compounds, synthetic PAH mixtures, and manufactured gas plant (MGP) tars. Additional experiments were conducted with added surfactants (Triton X-100, Triton X-45, and Tween 80) to increase PAH mass transfer from the NAPL to the aqueous phase, and with radical scavengers (ethanol and tert-butyl alcohol) to identify the reactive species responsible for degradation. Degradation of total PAHs in the NAPL experiments was as high as 70%. The addition of surfactant increased initial PAH degradation rates, but also greatly increased the rate of base consumption, thereby reducing the overall fraction degraded. The degradation of individual PAHs within the NAPLs varied significantly, with the masses of some compounds remaining largely unchanged. The results of the radical scavenger and single PAH experiments suggest that the observed pattern of degradation in PAH mixtures is the result of a combination of mass transfer considerations and competition for radical species.

  12. Optimization of stabilized leachate treatment using ozone/persulfate in the advanced oxidation process

    SciTech Connect

    Abu Amr, Salem S.; Aziz, Hamidi Abdul; Adlan, Mohd Nordin

    2013-06-15

    Highlights: ► Ozone and persulfate reagent (O{sub 3}/S{sub 2}O{sub 8}{sup 2-}) was used to treat stabilized leachate. ► Central composite design (CCD) with response surface methodology (RSM) was applied. ► Operating variables including ozone and persulfate dosage, pH variance, and reaction time. ► Optimum removal of COD, color, and NH{sub 3}–N was 72%, 96%, and 76%, respectively. ► A good value of ozone consumption (OC) obtained with 0.60 (kg O{sub 3}/kg COD). - Abstract: The objective of this study was to investigate the performance of employing persulfate reagent in the advanced oxidation of ozone to treat stabilized landfill leachate in an ozone reactor. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as ozone and persulfate dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following four responses proved to be significant with very low probabilities (<0.0001): COD, color, NH{sub 3}–N, and ozone consumption (OC). The obtained optimum conditions included a reaction time of 210 min, 30 g/m{sup 3} ozone, 1 g/1 g COD{sub 0}/S{sub 2}O{sub 8}{sup 2-} ratio, and pH 10. The experimental results were corresponded well with predicted models (COD, color, and NH{sub 3}–N removal rates of 72%, 96%, and 76%, respectively, and 0.60 (kg O{sub 3}/kg COD OC). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as ozone only and persulfate S{sub 2}O{sub 8}{sup 2-} only, to evaluate its effectiveness. The combined method (i.e., O{sub 3}/S{sub 2}O{sub 8}{sup 2-}) achieved higher removal efficiencies for COD, color, and NH{sub 3}–N compared with other studied applications. Furthermore, the new method is more efficient than ozone/Fenton in advanced oxidation process in the treatment of the same studied leachate.

  13. Treatability assessment of polycyclic aromatic hydrocarbons contaminated marine sediments using permanganate, persulfate and Fenton oxidation processes.

    PubMed

    Shih, Yu-Jen; Binh, Nguyen Thanh; Chen, Chiu-Wen; Chen, Chih-Feng; Dong, Cheng-Di

    2016-05-01

    Various chemical oxidation techniques, such as potassium permanganate (KMnO4), sodium persulfate (Na2S2O8), Fenton (H2O2/Fe(2+)), and the modified persulfate and Fenton reagents (activated by ferrous complexes), were carried out to treat marine sediments that were contaminated with polycyclic aromatic hydrocarbons (PAHs) and dredged from Kaohsiung Harbor in Taiwan. Experimental results revealed that KMnO4 was the most effective of the tested oxidants in PAH degradation. Owing to the high organic matter content in the sediment that reduced the efficiencies of Na2S2O8 and regular Fenton reactions, a large excess of oxidant was required. Nevertheless, KH2PO4, Na4P2O7 and four chelating agents (EDTA, sodium citrate, oxalic acid, and sodium oxalate) were utilized to stabilize Fe(II) in activating the Na2S2O8 and Fenton oxidations, while Fe(II)-citrate remarkably promoted the PAH degradation. Increasing the molecular weight and number of rings of PAH did not affect the overall removal efficiencies. The correlation between the effectiveness of the oxidation processes and the physicochemical properties of individual PAH was statistically analyzed. The data implied that the reactivity of PAH (electron affinity and ionization potential) affected its treatability more than did its hydrophobicity (Kow, Koc and Sw), particularly using experimental conditions under which PAHs could be effectively oxidized. PMID:26915591

  14. Ultrasonic-assisted chemical oxidative cutting of multiwalled carbon nanotubes with ammonium persulfate in neutral media

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Wang, Tingmei

    2009-12-01

    A new, facile, and mild approach was developed to cut the conventional long and entangled multiwalled carbon nanotubes (MWCNTs) to short and dispersed ones with length of less than 1 ?m by ultrasonic-assisted chemical oxidation with ammonium persulfate (APS) in neutral aqueous solution at room temperature. The resulting products were characterized with Fourier transform infrared (FTIR), Raman, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and transmission electron microscope (TEM) techniques. The shortened MWCNTs formed stable dispersion state in water without the help of surfactants that provided possibility for further functionalizations and applications.

  15. Persulfate Oxidation of MTBE- and Chloroform-Spent Granular Activated Carbon

    EPA Science Inventory

    Activated persulfate (Na2S2O8) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H2O2persulfate binary mixtur...

  16. Persulfate Oxidation of MTBE- and Chloroform-Spent Granular Activated Carbon

    EPA Science Inventory

    Activated persulfate (Na2S2O8) regeneration of methyl tert-butyl ether (MTBE) and chloroform-spent GAC was evaluated in this study. Thermal-activation of persulfate was effective and resulted in greater MTBE removal than either alkaline-activation or H2O2–persulfate binary mixtur...

  17. Comparative study on oxidative treatments of NAPL containing chlorinated ethanes and ethenes using hydrogen peroxide and persulfate in soils.

    PubMed

    Ko, Saebom; Crimi, Michelle; Marvin, Bruce K; Holmes, Victor; Huling, Scott G

    2012-10-15

    The goal of this study was to assess the oxidation of NAPL in soil, 30% of which were composed of chlorinated ethanes and ethenes, using catalyzed hydrogen peroxide (CHP), activated persulfate (AP), and H(2)O(2)-persulfate (HP) co-amendment systems. Citrate, a buffer and iron ligand, was amended to the treatment system to enhance oxidative treatment. Four activation/catalysis methods were employed: (1) oxidant only, (2) oxidant-citrate, (3) oxidant-iron(II), and (4) oxidant-citrate-iron(II). The NAPL treatment effectiveness was the greatest in the CHP reactions, the second in HP, and the third in AP. The effective activation and catalysis methods depended on the oxidant types; oxidant only for CHP and HP and oxidant-citrate-iron for AP. The treatability trend of chlorinated ethanes and ethenes in the soil mixture was as follows: trichloroethene > tetrachloroethene > dichloroethane > trichloroethane > tetrachloroethane. A significant fraction of persulfate remained in the oxidation systems after the 2-day reaction period, especially in the citrate-iron(II) AP. In general, oxidation systems that included citrate maintained a post-treatment pH in the range of 7-9. A final pH of AP oxidation systems was acidic (pH 2-3), where a molar ratio of citrate-iron(II) was less than 1.8 and where no citrate was amended. PMID:22658989

  18. Efficient degradation of trichloroethylene in water using persulfate activated by reduced graphene oxide-iron nanocomposite.

    PubMed

    Ahmad, Ayyaz; Gu, Xiaogang; Li, Li; Lv, Shuguang; Xu, Yisheng; Guo, Xuhong

    2015-11-01

    Graphene oxide (GO) and nano-sized zero-valent iron-reduced graphene oxide (nZVI-rGO) composite were prepared. The GO and nZVI-rGO composite were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), energy-dispersive spectroscopy (EDS), and Raman spectroscopy. The size of nZVI was about 6nm as observed by TEM. The system of nZVI-rGO and persulfate (PS) was used for the degradation of trichloroethylene (TCE) in water, and showed 26.5% more efficiency as compared to nZVI/PS system. The different parameters were studied to determine the efficiency of nZVI-rGO to activate the PS system for the TCE degradation. By increasing the PS amount, TCE removal was also improved while no obvious effect was observed by varying the catalyst loading. Degradation was decreased as the TCE initial concentration was increased from 20 to 100mg/L. Moreover, when initial solution pH was increased, efficiency deteriorated to 80%. Bicarbonate showed more negative effect on TCE removal among the solution matrix. To better understand the effects of radical species in the system, the scavenger tests were performed. The SO4 (-) and O2 (-) were predominant species responsible for TCE removal. The nZVI-rGO-activated PS process shows potential applications in remediation of highly toxic organic contaminants such as TCE present in the groundwater. Graphical abstract Persulfate activated by reduced graphene oxide and nano-sized zero-valent iron composite can be used for efficient degradation of trichloroethylene (TCE) in water. PMID:26162447

  19. Contaminated Groundwater Remediation by Catalyzed Hydrogen Peroxide and Persulfate Oxidants System

    NASA Astrophysics Data System (ADS)

    Yan, N.; Wang, Y.; Brusseau, M. L.

    2014-12-01

    A binary oxidant system, catalyzed hydrogen peroxide (H2O2) coupled with persulfate (S2O82-), was investigated for use in in-situ chemical oxidation (ISCO) applications. Trichloroethene (TCE) and 1,4-dioxane were used as target contaminants. Batch experiments were conducted to investigate the catalytic efficiency between ferrous ion (Fe2+) and base (NaOH), oxidant decomposition rates, and contaminant degradation efficiency. For the base-catalyzed H2O2-S2O82- system, oxidant release was moderate and sustained over the entire test period of 96 hours. Conversely, the oxidants were depleted within 24 hours for the Fe2+-catalyzed system. Solution pH decreased slightly for the Fe2+-catalyzed system, whereas the pH increased for the base-catalyzed system. The rates of degradation for TCE and 1,4-dioxane are compared as a function of system conditions. The results of this study indicate that the binary H2O2-S2O82- oxidant system is effective for oxidation of the tested contaminants.

  20. Increased formation of halomethanes during chlorination of chloramphenicol in drinking water by UV irradiation, persulfate oxidation, and combined UV/persulfate pre-treatments.

    PubMed

    Wenhai, Chu; Tengfei, Chu; Erdeng, Du; Deng, Yang; Yingqing, Guo; Naiyun, Gao

    2016-02-01

    Ultraviolet/persulfate (UV/PS) has been widely used to generate sulfate radicals for degradation of water organic pollutants in previous studies. However, its impacts on disinfection byproduct formation during post-chlorination of degraded compounds is unclear. The objective of this study was to evaluate the impacts of UV irradiation, PS oxidation, and the combined UV/PS advanced oxidation process (AOP) pre-treatments on halomethane formation during the following chlorination of chloramphenicol (CAP), a model antibiotic commonly found in wastewater-impacted water. Results showed that CAP could be transformed to more trichloromethane (TCM) than monochloromethane (MCM) and dichloromethane (DCM) in the presence of excess chlorine. UV photolysis, PS oxidation and UV/PS AOP all directly decomposed CAP to produce halomethanes (HMs) before post-chlorination. Moreover, UV and UV/PS pre-treatments both enhanced the formation of all the HMs in the subsequent chlorination. PS pre-oxidation decreased the TCM formation during post-chlorination, but increased the yields of MCM, DCM and total HMs. UV pre-irradiation significantly increased the bromide utilization of HMs, whereas UV/PS pre-oxidation decreased the bromine incorporation and utilization of HMs from the chlorination of CAP in a low-bromide water. UV irradiation, PS oxidation, and UV/PS AOP can inactivate pathogens and degrade organic pollutants, but this benefit should be weighed against a potential risk of the increased halomethane formation from degraded organic pollutants with and without post-chlorination. PMID:26513530

  1. Performance of combined sodium persulfate/H2O2 based advanced oxidation process in stabilized landfill leachate treatment.

    PubMed

    Hilles, Ahmed H; Abu Amr, Salem S; Hussein, Rim A; El-Sebaie, Olfat D; Arafa, Anwaar I

    2016-01-15

    A combination of persulfate and hydrogen peroxide (S2O8(2-)/H2O2) was used to oxidizelandfill leachate. The reaction was performed under varying S2O8(2-)/H2O2 ratio (g/g), S2O8(2-)/H2O2 dosages (g/g), pH, and reaction time (minutes), so as to determine the optimum operational conditions. Results indicated that under optimum operational conditions (i.e. 120 min of oxidation using a S2O8(2-)/H2O2 ratio of 1 g/1.47 g at a persulfate and hydrogen peroxide dosage of 5.88 g/50 ml and8.63 g/50 ml respectively, at pH 11) removal of 81% COD and 83% NH3-N was achieved. In addition, the biodegradability (BOD5/COD ratio) of the leachate was improved from 0.09 to 0.17. The results obtained from the combined use of (S2O8(2-)/H2O2) were compared with those obtained with sodium persulfate only, hydrogen peroxide only and sodium persulfate followed by hydrogen peroxide. The combined method (S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with the other methods using a single oxidizing agent. Additionally, the study has proved that the combination of S2O8(2-)/H2O2 is more efficient than the sequential use of sodium persulfate followed by hydrogen peroxide in advanced oxidation processes aiming at treatingstabilizedlandfill leachate. PMID:26580899

  2. Thermo activated persulfate oxidation of antibiotic sulfamethoxazole and structurally related compounds.

    PubMed

    Ji, Yuefei; Fan, Yan; Liu, Kuo; Kong, Deyang; Lu, Junhe

    2015-12-15

    The widespread occurrence of sulfonamides (e.g., sulfamethoxazole) in natural environment has raised growing concerns due to their potential to induce antibiotic-resistant genes. In this study, the degradation of SMX and related sulfonamides by thermo activated persulfate (PS) oxidation was investigated. Experimental results demonstrated that SMX degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing temperature and pH. The presence of bicarbonate manifested promoting effect on SMX degradation while fulvic acid reduced it. Radical scavenging tests revealed that the predominant oxidizing species was SO4(-) at neutral pH. Aniline moiety in SMX molecule was confirmed to be the primary reactive site for SO4(-) attack by comparison with substructural analogues. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). A total of 7 products derived from hydroxylation, sulfonamide S-N bond cleavage, aniline moiety oxidation and coupling reaction were identified, and transformation pathways of SMX oxidation were proposed. Degradation of sulfonamides was appreciably influenced by the heterocyclic ring present in the molecules. Results reveal that thermo activated PS oxidation could be an efficient approach for remediation of water contaminated by SMX and related sulfonamides. PMID:26378726

  3. Mechanism of the quenching of the tris(bipyridine)ruthenium(II) emission by persulfate: implications for photoinduced oxidation reactions.

    PubMed

    Lewandowska-Andralojc, A; Polyansky, D E

    2013-10-10

    A revised mechanism for the oxidation of the excited state of Ru(bpy)3(2+) with the persulfate anion is described in this work. The formation of the precursor complex in the electron transfer reaction involves ion pairing between the metal complex in ground and excited states and S2O8(2-). The equilibrium constant for the ion-pair formation (K(IP) = 2.7 M(-1)) was determined from electrochemical measurements and analysis of thermal reaction between Ru(bpy)3(2+) and persulfate. It was found to be consistent with the calculated value estimated from the Debye-Hückel model. The analysis of rate constants for reactions between persulfate and various metal complexes indicates that thermal and photochemical reactions most likely proceed through a common pathway. Extremely high reorganization energy (ca. 3.54 eV) for the electron transfer obtained from fitting experimental data with the Marcus equation is indicative of significant nuclear reorganization during the electron transfer step. In view of these results the electron transfer can be described as dissociative probably involving substantial elongation or complete scission of the O-O bond. The proposed model accurately describes experimental results for the quenching of *Ru(bpy)3(2+) over a wide range of persulfate concentrations and resolves some discrepancies between the values of K(IP) and k(et) previously reported. The implications of various factors such as the ionic strength and dielectric constant of the medium are discussed in relation to measurements of the quantum yields in photodriven oxidation reactions employing the Ru(bpy)3(2+)/persulfate couple. PMID:24040757

  4. Oxidative degradation of diclofenac by thermally activated persulfate: implication for ISCO.

    PubMed

    Chen, Jiabin; Qian, Yajie; Liu, Hongmei; Huang, Tianyin

    2016-02-01

    Diclofenac (DCF), one of the typically recalcitrant pharmaceuticals, has been frequently detected in groundwater in recent years. This work investigated the performance of DCF degradation by thermally activated persulfate (PS) to further understand its application in in situ chemical oxidation (ISCO) for DCF-contaminated groundwater. The effects of various factors, including activation temperature, solution pH, PS/DCF ratio, and common constitutes, e.g., HCO3 (-), Cl(-) and humic acid, and the toxicity of transformation products were evaluated. The results indicated that the oxidation of DCF was well-fitted with a pseudo-first-order kinetic model, and the rate constants increased with the elevated temperatures. The rate constants from 50-70 °C were further fitted to the Arrhenius equation, yielding an activation energy of 157.63 kJ·mol(-1). In addition, the oxidation of DCF was highly pH-dependent, with the rate constants rapidly decreased from pH 5 to 7, then slightly increased at the alkaline pH. The presence of a low dosage of Cl(-) (0-10 mM) promoted the degradation of DCF, whereas high Cl(-) addition (>10 mM) inhibited DCF degradation. HCO3 (-) exhibited a negligible effect on DCF removal, while natural organic matters, e.g., humic acids, lightly inhibited DCF degradation. The rapid degradation of DCF was also confirmed in the real groundwater sample, which might be attributed to the pH drop during the reaction. Moreover, the radical quenching experiments revealed that sulfate radicals (SO4 (·-)) was the dominant reactive species for DCF oxidation. Finally, the acute toxicity of the DCF solution, as tested with a bioluminescent assay, was gradually decreased during the reaction, indicating that a thermally activated PS oxidation was a promising alternative approach for DCF-contaminated groundwater remediation. PMID:26498962

  5. Studies on oxidative radiolysis of ibuprofen in presence of potassium persulfate

    NASA Astrophysics Data System (ADS)

    Paul (Guin), Jhimli; Naik, D. B.; Bhardwaj, Y. K.; Varshney, Lalit

    2014-07-01

    The radiolysis of ibuprofen (IBP), a model pharmaceutical compound, was studied by gamma irradiation in an aqueous solution in the presence and absence of potassium persulfate (K2S2O8). The extent of mineralization was investigated by measuring the UV-visible spectra, decrease in the chemical oxygen demand (COD) and the total organic carbon (TOC) content of aqueous IBP solution at different doses. The gamma radiolysis, in the presence of K2S2O8, required much lesser dose compared to in the absence of K2S2O8 for the same extent of mineralization of aqueous IBP solution. The pulse radiolysis of IBP was carried out under different radiolytic conditions to understand the mechanism of efficient mineralization of IBP during gamma radiolysis in the presence of K2S2O8. It was found that unlike OH radical, SO4- radical preferentially produces benzyl type of radicals via the formation of the benzene radical cation. The results concluded that the gamma radiolysis in presence of K2S2O8 could be one of the efficient advanced oxidation processes for degradation of pharmaceutical compounds present in the aqueous solution.

  6. Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant.

    PubMed

    Hori, Hisao; Yamamoto, Ari; Hayakawa, Etsuko; Taniyasu, Sachi; Yamashita, Nobuyoshi; Kutsuna, Shuzo; Kiatagawa, Hiroshi; Arakawa, Ryuichi

    2005-04-01

    Photochemical decomposition of persistent perfluorocarboxylic acids (PFCAs) in water by use of persulfate ion (S2O8(2-)) was examined to develop a technique to neutralize stationary sources of PFCAs. Photolysis of S2O8(2-) produced highly oxidative sulfate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs bearing C4-C8 perfluoroalkyl groups. The major products were F- and CO2; also, small amounts of PFCAs with shorter than initial chain lengths were detected in the reaction solution. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was completely decomposed by a photochemical system with 50 mM S2O8(2-) and 4 h of irradiation from a 200-W xenon-mercury lamp. The initial PFOA decomposition rate was 11 times higherthan with photolysis alone. All sulfur-containing species in the reaction solution were eventually transformed to sulfate ions by this method. This method was successfully applied to the decomposition of perfluorononanoic acid contained in a floor wax solution. PMID:15871280

  7. Degradation efficiencies of azo dye Acid Orange 7 by the interaction of heat, UV and anions with common oxidants: persulfate, peroxymonosulfate and hydrogen peroxide.

    PubMed

    Yang, Shiying; Wang, Ping; Yang, Xin; Shan, Liang; Zhang, Wenyi; Shao, Xueting; Niu, Rui

    2010-07-15

    In this paper, the degradation of azo dye Acid Orange 7 (AO7) by three common peroxides (persulfate (PS), peroxymonosulfate (PMS) or hydrogen peroxide (H(2)O(2))) under various activation conditions, i.e., heat (25-80 degrees C), UV light (254 nm), or anions (SO(4)(2-), NO(3)(-), CO(3)(2-), HCO(3)(-), HPO(4)(2-), and Cl(-)), was investigated. The order of AO7 degradation efficiencies by heat activation is PS>PMS>H(2)O(2). PS oxidation activated by heat (>50 degrees C) is an effective degradation technology, while PMS and H(2)O(2) are hardly activated. When assisted by UV, peroxides could all be activated and degrade AO7 quickly. The order is PS>H(2)O(2)>PMS. We activated peroxides, for the first time, by using some anions and compared the subsequently degradation efficiencies of AO7. It was found that PMS could be activated by some anions, but PS and H(2)O(2) cannot. The activation efficiencies of PMS by SO(4)(2-) and NO(3)(-) are negligible, whereas remarkable by HCO(3)(-), HPO(4)(2-), Cl(-) and CO(3)(2-). For HCO(3)(-), HPO(4)(2-) and Cl(-), the activation efficiencies become higher with the increase of anion concentration. For CO(3)(2-), however, the activation efficiency is higher at lower concentration. PMID:20371151

  8. 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 ?,?-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. PMID:26687229

  9. Remediation of phenanthrene-contaminated soil by simultaneous persulfate chemical oxidation and biodegradation processes.

    PubMed

    Mora, Vernica C; Madueo, Laura; Peluffo, Marina; Rosso, Janina A; Del Panno, Mara T; Morelli, Irma S

    2014-06-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds with carcinogenic and/or mutagenic potential. To address the limitations of individual remediation techniques and to achieve better PAH removal efficiencies, the combination of chemical and biological treatments can be used. The degradation of phenanthrene (chosen as a model of PAH) by persulfate in freshly contaminated soil microcosms was studied to assess its impact on the biodegradation process and on soil properties. Soil microcosms contaminated with 140mg/kgDRY SOIL of phenanthrene were treated with different persulfate (PS) concentrations 0.86-41.7g/kgDRY SOIL and incubated for 28days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28days of treatment. Genetic diversity analysis of the soil microcosm bacterial community was performed by PCR amplification of bacterial 16S rDNA fragments followed by denaturing gradient gel electrophoresis (DGGE). The addition of PS in low concentrations could be an interesting biostimulatory strategy that managed to shorten the lag phase of the phenanthrene biological elimination, without negative effects on the physicochemical and biological soil properties, improving the remediation treatment. PMID:24595755

  10. Selective oxidative degradation of toluene for the recovery of surfactant by an electro/Fe?/persulfate process.

    PubMed

    Long, Anhua; Zhang, Hui

    2015-08-01

    An electro/Fe(2+)/persulfate process has been conducted for toluene removal from surfactant (SDS) flushing solution, and the pseudo-second-order reaction rate constant (k2 value) of toluene removal has been optimized by a response surface methodology (RSM). The results indicated that in this process, the reaction between persulfate and externally added Fe(2+) generates sulfate-free radicals, and at the same time, Fe(2+) is electro-regenerated at the cathode by the reduction of Fe(3+). RSM based on Box-Behnken design (BBD) has been applied to analyze the experimental variables, of which the concentrations of persulfate and Fe(2+) showed a positive effect on the rate constant of toluene removal, whereas the concentration of SDS showed a negative effect. The interactions between pairs of variables proved to be significant, such as between SDS, persulfate, and Fe(2+) concentrations. ANOVA results confirmed that the proposed models were accurate and reliable for analysis of the variables of the electro/Fe(2+)/persulfate process. The shapes of the 3D response surfaces and contour plots showed that the SDS, persulfate, and Fe(2+) concentrations substantially affected the k2 value of toluene removal. The results indicated that increasing persulfate or Fe(2+) concentration increased the k2 value, whereas increasing SDS concentration decreased the k2 value. The reaction intermediates have been identified by GC-MS, and a plausible degradation pathway for toluene degradation is proposed. PMID:25847443

  11. Persistence of persulfate in uncontaminated aquifer materials.

    PubMed

    Sra, Kanwartej S; Thomson, Neil R; Barker, Jim F

    2010-04-15

    Batch and stop-flow column experiments were performed to estimate persulfate decomposition kinetic parameters in the presence of seven well-characterized aquifer materials. Push-pull tests were conducted in a sandy aquifer to represent persulfate decomposition under in situ conditions. The decomposition of persulfate followed a first-order rate law for all aquifer materials investigated. Reaction rate coefficients (k(obs)) increased by an order of magnitude when persulfate concentration was reduced from 20 g/L to 1 g/L, due to ionic strength effects. The column experiments yielded higher k(obs) than batch experiments due to the lower oxidant to solids mass ratio. The kinetic model developed from the batch test data was able to reproduce the observed persulfate temporal profiles from the push-pull tests. The estimated k(obs) indicate that unactivated persulfate is a persistent oxidant for the range of aquifer materials explored with half-lives ranging from 2 to 600 d. PMID:20205387

  12. The Feasibility Study of Persulfate Oxidation to Regenerating of Spent Granular Activated Carbon

    EPA Science Inventory

    Chemical oxidation is a developing technology used to regenerate contaminant-spent GAC. Chemical regeneration of GAC represents a viable option to thermal regeneration methods that are energy intensive resulting in significant consumption of fossil fuels and production of greenho...

  13. Thermally activated persulfate oxidation regeneration of NOM- and MTBE- spent granular activated carbon

    EPA Science Inventory

    Chemical oxidation is a developing technology used to regenerate contaminant-spent GAC. Chemical regeneration of GAC represents a viable option to thermal regeneration methods that are energy intensive resulting in significant consumption of fossil fuels and production of greenho...

  14. Impact of persulfate and ultraviolet light activated persulfate pre-oxidation on the formation of trihalomethanes, haloacetonitriles and halonitromethanes from the chlor(am)ination of three antibiotic chloramphenicols.

    PubMed

    Chu, Wenhai; Chu, Tengfei; Bond, Tom; Du, Erdeng; Guo, Yingqing; Gao, Naiyun

    2016-04-15

    Persulfate oxidation processes, with and without activation using ultraviolet light (respectively UV/PS and PS) have the potential to degrade anthropogenic chemicals in water. However, little is known about the impact of PS or UV/PS pre-oxidation on downstream formation of disinfection by-products (DBPs). In this study the three antibiotic chloramphenicols (chloramphenicol and two of its analogues [thiamphenicol and florfenicol], referred to collectively as CAPs), which frequently occur in wastewater-impacted source waters used by drinking water treatment plants, were selected as model antibiotic compounds. The formation of carbonaceous and nitrogenous disinfection by-products, including halomethanes, haloacetonitriles and halonitromethanes, during chlorination and chloramination preceded by PS and UV/PS was investigated. No significant concentrations of haloacetonitriles and halonitromethanes were detected during chlorination. During chloramination chloramphenicol formed a considerable amount of dichloronitromethane (e.g., 3.44 ± 0.33% mol/mol at NH2Cl dose = 1 mM) and trichloronitromethane (e.g., 0.79 ± 0.07% mol/mol at NH2Cl dose = 1 mM), compared with THM and HAN formation. PS pre-oxidation achieved a statistically significant reduction in trichloromethane formation from chlorination, and in HAN and HNM formation from chloramination. Although UV/PS slightly increased dichloroacetonitrile formation during chloramination, it significantly decreased dichloronitromethane and trichloronitromethane formation during chloramination. Overall, the use of PS and UV/PS has the potential to have contrasting impacts on DBP formation in heavily wastewater-impacted waters, depending on the disinfection method. Hence, their application needs to be carefully balanced against the downstream effect on DBP formation. PMID:26894475

  15. Effect of metal oxides on the reactivity of persulfate/Fe(II) in the remediation of diesel-contaminated soil and sand.

    PubMed

    Do, Si-Hyun; Kwon, Yong-Jae; Kong, Sung-Ho

    2010-10-15

    The effect of metal oxides on the ability of persulfate (PS) with Fe(II) to remediate diesel-contaminated soil was investigated. In both natural soil and purchased sand, the highest diesel degradation occurred at pH 3 and the optimum molar ratio of PS/Fe(II) was 100:1 (i.e. 500 mM PS to 5 mM Fe(II)). Moreover, adding Fe(II) increased PS reactivity more in soil than it did in sand, indicating the involvement of metal oxides in the soil matrix. Evaluating the effects of metal oxides (i.e. goethite, hematite, magnetite, and manganese oxide) on the reactivity of PS with/without Fe(II) in a system containing diesel-contaminated sand revealed that manganese oxide increased PS activity the most and that the highest diesel degradation by PS occurred when both manganese oxide and Fe(II) were used as activators. XRD did not show the transformation of manganese oxide in the presence of Fe(II). SEM-EDS showed the association of Fe(II) on the surface of manganese oxide, and ICP analysis revealed that almost all the added Fe(II) adsorbed to manganese oxide but almost none adsorbed to iron oxides under acidic conditions. Therefore, the high reactivity of PS could be due to the high density of Fe(II) over the surface of manganese oxide. PMID:20633989

  16. Oxidation of 2,4-dichlorophenol by non-radical mechanism using persulfate activated by Fe/S modified carbon nanotubes.

    PubMed

    Cheng, Xin; Guo, Hongguang; Zhang, Yongli; Liu, Yang; Liu, Hongwei; Yang, Ying

    2016-05-01

    The aim of this study was to develop a new approach for the activation of persulfate (PS) based on carbon nanotubes (CNTs). Fe/S modified carbon nanotubes (Fe/S-CNTs) were synthesized via impregnation-precipitation in the aqueous-phase synthesis method. The morphologies and chemical states of the catalysts were characterized and 2,4-dichlorophenol (2,4-DCP) was selected to investigate the degradation performance using Fe/S-CNTs with PS. The results reveal that the Fe/S-CNTs catalysts can significantly accelerate the removal of 2,4-DCP compared to single PS or PS/CNTs. The catalytic capacity is also enhanced by S modification and is affected by the solution pH. The iron loading content, PS concentration and catalyst dosage could play important roles in the degradation. A non-radical process of 2,4-DCP degradation is demonstrated for the first time in the results of the radical scavengers and chloride ionic, as well as persulfate decomposition. It is suggested that PS is first bonded with the sp(2)-hybridized system and activated by iron oxide particles and iron-sulfur complexes, then it reacts rapidly with the adsorbed 2,4-DCP. PMID:26897564

  17. Persulfate injection into a gasoline source zone.

    PubMed

    Sra, Kanwartej S; Thomson, Neil R; Barker, Jim F

    2013-07-01

    One pore volume of unactivated sodium persulfate was delivered into an emplaced gasoline residual source zone at CFB Borden. Concentrations of inorganic species (S2O8(2-), SO4(2-), Na(+), dissolved inorganic carbon (DIC)) and selected gasoline compounds (benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) were monitored across a transect equipped with 90 multilevel sampling points for >10months post-injection. Mass loading (M?) of compounds constructed from the transect data was used for assessment purposes. Breakthrough of inorganic species was observed when the injection slug crossed the monitoring transect. An increase in [Formula: see text] indicated persulfate consumption during oxidation of gasoline compounds or degradation due to the interaction with aquifer materials. M?DIC increased by >100% suggesting some mineralization of gasoline compounds during treatment. Mass loading for all the monitored gasoline compounds reduced by 46 to 86% as the inorganic slug crossed the monitoring transect. The cumulative mass discharge across the monitoring transect was 19 to 58% lower than that expected without persulfate injection. After the inorganic injection slug was flushed from the source zone a partial rebound (40 to 80% of baseline levels) of mass discharge of the monitored gasoline compounds was observed. The ensemble of data collected provides insight into the fate and transport of the injected persulfate solution, and the accompanying treatment of a gasoline the source zone. PMID:23660235

  18. Persulfate injection into a gasoline source zone

    NASA Astrophysics Data System (ADS)

    Sra, Kanwartej S.; Thomson, Neil R.; Barker, Jim F.

    2013-07-01

    One pore volume of unactivated sodium persulfate was delivered into an emplaced gasoline residual source zone at CFB Borden. Concentrations of inorganic species (S2O82 -, SO42 -, Na+, dissolved inorganic carbon (DIC)) and selected gasoline compounds (benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) were monitored across a transect equipped with 90 multilevel sampling points for > 10 months post-injection. Mass loading (M?) of compounds constructed from the transect data was used for assessment purposes. Breakthrough of inorganic species was observed when the injection slug crossed the monitoring transect. An increase in M indicated persulfate consumption during oxidation of gasoline compounds or degradation due to the interaction with aquifer materials. M increased by > 100% suggesting some mineralization of gasoline compounds during treatment. Mass loading for all the monitored gasoline compounds reduced by 46 to 86% as the inorganic slug crossed the monitoring transect. The cumulative mass discharge across the monitoring transect was 19 to 58% lower than that expected without persulfate injection. After the inorganic injection slug was flushed from the source zone a partial rebound (40 to 80% of baseline levels) of mass discharge of the monitored gasoline compounds was observed. The ensemble of data collected provides insight into the fate and transport of the injected persulfate solution, and the accompanying treatment of a gasoline the source zone.

  19. Electrokinetic delivery of persulfate to remediate PCBs polluted soils: effect of injection spot.

    PubMed

    Fan, Guangping; Cang, Long; Fang, Guodong; Qin, Wenxiu; Ge, Liqiang; Zhou, Dongmei

    2014-12-01

    Persulfate-based in situ chemical oxidation (ISCO) is a promising technique for the remediation of organic compounds contaminated soils. Electrokinetics (EK) provides an alternative method to deliver oxidants into the target zones especially in low permeable-soil. In this study, the flexibility of delivering persulfate by EK to remediate polychlorinated biphenyls (PCBs) polluted soil was investigated. 20% (w/w) of persulfate was injected at the anode, cathode and both electrodes to examine its transport behaviors under electrical field, and the effect of field inversion process was also evaluated. The results showed that high dosage of persulfate could be delivered into S4 section (near cathode) by electroosmosis when persulfate was injected from anode, 30.8% of PCBs was removed from the soil, and the formed hydroxyl precipitation near the cathode during EK process impeded the transportation of persulfate. In contrast, only 18.9% of PCBs was removed with the injection of persulfate from cathode, although the breakthrough of persulfate into the anode reservoir was observed. These results indicated that the electroosmotic flow is more effective for the transportation of persulfate into soil. The addition of persulfate from both electrodes did not significantly facilitate the PCBs oxidation as well as the treatment of electrical field reversion, the reinforced negative depolarization function occurring in the cathode at high current consumed most of the oxidant. Furthermore, it was found that strong acid condition near the anode favored the oxidation of PCBs by persulfate and the degradation of PCBs was in consistent with the oxidation of Soil TOC in EK/persulfate system. PMID:25193794

  20. Mechanistic study of photo-oxidation of Bisphenol-A (BPA) with hydrogen peroxide (H2O2) and sodium persulfate (SPS).

    PubMed

    Sharma, Jyoti; Mishra, I M; Kumar, Vineet

    2016-01-15

    The removal of Bisphenol-A (BPA) from contaminated water using advanced oxidation methods such as UV-C assisted oxidation by hydrogen peroxide (H2O2) and sodium persulfate (SPS) has been reported by the authors earlier (Sharma etal., 2015a). In the present study, the authors report the removal of BPA from aqueous solution by the above two methods and its degradation mechanism. UV-C light (254nm wavelength, 40W power) was applied to BPA contaminated water at natural pH (pHN) under room temperature conditions. Experiments were carried out with the initial BPA concentration in the range of 0.04mM-0.31mM and the oxidant/BPA molar ratio in the range of 294:1-38:1 for UV-C/H2O2 and 31.5-4.06:1 for UV-C/SPS systems. The removal of BPA enhanced with decreasing BPA concentration. The total organic carbon also decreased with the UV-C irradiation time under optimum conditions ([H2O2]0=11.76mM; [SPS]0=1.26mM; temperature (293C). Competition of BPA for reaction with HO or [Formula: see text] radicals at its higher concentrations results in a decrease in the removal of BPA. The intermediates with smaller and higher molecular weights than that of BPA were found in the treated water. Based on GC-MS and FTIR spectra of the reaction mixture, the formation of hydroxylated by-products testified the HO mediated oxidation pathway in the BPA degradation, while the formation of quinones and phenoxy phenols pointed to the [Formula: see text] dominating pathway through the formation of hydroxycyclohexadienyl (HCHD) and BPA phenoxyl radicals. The main route of BPA degradation is the hydroxylation followed by dehydration, coupling and ring opening reactions. PMID:26468603

  1. pH dependence of persulfate activation by EDTA/Fe(III) for degradation of trichloroethylene

    NASA Astrophysics Data System (ADS)

    Liang, Chenju; Liang, Ching-Ping; Chen, Chi-Chin

    2009-05-01

    The ability of free ferrous ion activated persulfate (S 2O 82-) to generate sulfate radicals (SO 4- rad ) for the oxidation of trichloroethylene (TCE) is limited by the scavenging of SO 4- rad with excess Fe 2+ and a quick conversion of Fe 2+ to Fe 3+. This study investigated the applicability of ethylene-diamine-tetra-acetic acid (EDTA) chelated Fe 3+ in activating persulfate for the destruction of TCE in aqueous phase under pH 3, 7 and 10. Fe 3+ and EDTA alone did not appreciably degrade persulfate. The presence of TCE in the EDTA/Fe 3+ activated persulfate system can induce faster persulfate and EDTA degradation due to iron recycling to activate persulfate under a higher pH condition. Increasing the pH leads to increases in pseudo-first-order-rate constants for TCE, S 2O 82- and EDTA degradations, and Cl generation. Accordingly, the experiments at pH 10 with different EDTA/Fe 3+ molar ratios indicated that a 1/1 ratio resulted in a remarkably higher degradation rate at the early stage of reaction as compared to results by other ratios. Higher persulfate dosage under the EDTA/Fe 3+ molar ratio of 1/1 resulted in greater TCE degradation rates. However, increases in persulfate concentration may also lead to an increase in the rate of persulfate consumption.

  2. Ultrasound and heat enhanced persulfate oxidation activated with Fe(0) aggregate for the decolorization of C.I. Direct Red 23.

    PubMed

    Weng, Chih-Huang; Tsai, Kuen-Lung

    2016-03-01

    Effluents from the paper printing and textile industries are often heavily contaminated with azo dyes. Azo dyes are difficult to oxidize biologically. This work investigated the decolorization of an azo dye, C.I. Direct Red 23 (DR23), by persulfate (PS) activated with Fe(0) aggregates (PS/Fe(0)). Ultrasound (US) and heat were used as enhancement tools in the PS oxidation system. Neither US-activated PS nor thermally activated PS was effective in oxidizing DR23. However, the decolorization was significantly enhanced by PS/Fe(0) combined with US (PS/Fe(0)/US) or heat (PS/Fe(0)/55 °C). Approximately 95% decolorization of 1×10(-4) M DR23 was achieved within 15 min in the PS/Fe(0)/US system at an initial pH of 6.0, PS of 5×10(-3) M, Fe(0) of 0.5 g/L and US irradiation of 106 W/cm(2) (60 kHz). Complete decolorization was achieved within 10 min in the Fe(0)/PS/55 °C system. The rate of decolorization doubled when US was introduced in the PS/Fe(0) system during the treatment of different initial dye concentrations. The dependence of dye and true color (ADMI) depletion on PS concentration has been discussed. DR23 was completely degraded based on the disappearance of aromatic groups of UV-vis spectra and the variation of TOC mineralization. The observed pseudo-first-order decolorization rate was substantially enhanced by increasing temperature. The Arrhenius activation energy for the PS activated with Fe(0) was estimated as 8.98 kcal/mol, implying that higher temperature is beneficial for the DR23 decolorization. The addition of US into the PS/Fe(0) system did not incur a substantial increase in electricity, whereas the mineralization of DR23 occurred quickly. Thus, both PS/Fe(0)/US and heated PS/Fe(0) systems are practically feasible for the effective degradation of the direct azo dye in textile wastewater. PMID:26584979

  3. Fenton- and Persulfate-driven Regeneration of Contaminant-spent Granular Activated Carbon

    EPA Science Inventory

    Fenton- or persulfate-driven chemical oxidation regeneration of spent granular activated carbon (GAC) involves the combined, synergistic use of two treatment technologies: adsorption of organic chemicals onto GAC and chemical oxidation regeneration of the spent-GAC. Environmental...

  4. LaCoO3 acting as an efficient and robust catalyst for photocatalytic water oxidation with persulfate.

    PubMed

    Yamada, Yusuke; Yano, Kentaro; Hong, Dachao; Fukuzumi, Shunichi

    2012-04-28

    Cobalt-containing metal oxides [perovskites (LaCoO(3), NdCoO(3), YCoO(3), La(0.7)Sr(0.3)CoO(3)), spinel (Co(3)O(4)) and wolframite (CoWO(4))] have been examined as catalysts for photocatalytic water oxidation with Na(2)S(2)O(8) and [Ru(bpy)(3)](2+) as an electron acceptor and a photosensitizer, respectively. Catalysts with the perovskite structure exhibited higher catalytic activity as compared with the catalysts with the spinel and wolframite structures. LaCoO(3), which stabilizes Co(III) species in the perovskite structure, exhibited the highest catalytic activity in the photocatalytic water oxidation compared with CoWO(4), Co(3)O(4) and La(0.7)Sr(0.3)CoO(3) which contain Co(II) or Co(IV) species in the matrices. The high catalytic reactivity of LaCoO(3) possessing perovskite structure was maintained in NdCoO(3) and YCoO(3) which exclusively contain Co(III) species. Thus, the catalytic activity of Co ions can be controlled by the additional metal ions, which leads to development of highly reactive and robust catalysts for the photocatalytic water oxidation. PMID:22415556

  5. Electrokinetic delivery of persulfate to remediate PCBs polluted soils: Effect of different activation methods.

    PubMed

    Fan, Guangping; Cang, Long; Gomes, Helena I; Zhou, Dongmei

    2016-02-01

    Persulfate-based in-situ chemical oxidation (ISCO) for the remediation of organic polluted soils has gained much interest in last decade. However, the transportation of persulfate in low-permeability soil is very low, which limits its efficiency in degrading soil pollutants. Additionally, the oxidation-reduction process of persulfate with organic contaminants takes place slowly, while, the reaction will be greatly accelerated by the production of more powerful radicals once it is activated. Electrokinetic remediation (EK) is a good way for transporting persulfate in low-permeability soil. In this study, different activation methods, using zero-valent iron, citric acid chelated Fe(2+), iron electrode, alkaline pH and peroxide, were evaluated to enhance the activity of persulfate delivered by EK. All the activators and the persulfate were added in the anolyte. The results indicated that zero-valent iron, alkaline, and peroxide enhanced the transportation of persulfate at the first stage of EK test, and the longest delivery distance reached sections S4 or S5 (near the cathode) on the 6th day. The addition of activators accelerated decomposition of persulfate, which resulted in the decreasing soil pH. The mass of persulfate delivered into the soil declined with the continuous decomposition of persulfate by activation. The removal efficiency of PCBs in soil followed the order of alkaline activation>peroxide activation>citric acid chelated Fe(2+) activation>zero-valent iron activation>without activation>iron electrode activation, and the values were 40.5%, 35.6%, 34.1%, 32.4%, 30.8% and 30.5%, respectively. The activation effect was highly dependent on the ratio of activator and persulfate. PMID:26347936

  6. Effect and mechanism of persulfate activated by different methods for PAHs removal in soil.

    PubMed

    Zhao, Dan; Liao, Xiaoyong; Yan, Xiulan; Huling, Scott G; Chai, Tuanyao; Tao, Huan

    2013-06-15

    The influence of persulfate activation methods on polycyclic aromatic hydrocarbons (PAHs) degradation was investigated and included thermal, citrate chelated iron, and alkaline, and a hydrogen peroxide (H?O?)-persulfate binary mixture. Thermal activation (60 C) resulted in the highest removal of PAHs (99.1%) and persulfate consumption during thermal activation varied (0.45-1.38 g/kg soil). Persulfate consumption (0.91-1.22 g/kg soil) and PAHs removal (73.3-82.9%) varied using citrate chelated iron. No significant differences in oxidant consumption and PAH removal was measured in the H?O?-persulfate binary mixture and alkaline activated treatment systems, relative to the unactivated control. Greater removal of high molecular weight PAHs was measured with persulfate activation. Electron spin resonance spectra indicated the presence of hydroxyl radicals in thermally activated systems; weak hydroxyl radical activity in the H?O?-persulfate system; and superoxide radicals were predominant in alkaline activated systems. Differences in oxidative ability of the activated persulfate were related to different radicals generated during activation. PMID:23618659

  7. Optimization of leachate treatment using persulfate/H2O2 based advanced oxidation process: case study: Deir El-Balah Landfill Site, Gaza Strip, Palestine.

    PubMed

    Hilles, Ahmed H; Abu Amr, Salem S; Hussein, Rim A; Arafa, Anwar I; El-Sebaie, Olfat D

    2016-01-01

    The objective of this study was to investigate the performance of employing H2O2 reagent in persulfate activation to treat stabilized landfill leachate. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as persulfate and H2O2 dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following two responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD) and NH3-N removal. The obtained optimum conditions included a reaction time of 116 min, 4.97 g S2O8(2-), 7.29 g H2O2 dosage and pH 11. The experimental results were corresponding well with predicted models (COD and NH3-N removal rates of 81% and 83%, respectively). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as persulfate only and H2O2 only, to evaluate its effectiveness. The combined method (i.e., /S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with other studied applications. PMID:26744940

  8. Mineralization of aniline in aqueous solution by electrochemical activation of persulfate.

    PubMed

    Chen, Wen-Shing; Huang, Chi-Pin

    2015-04-01

    Oxidative degradation of aniline in aqueous solution was carried out by coupling electrolysis with persulfate oxidation, in which a synergistic effect occurred. Experiments were performed under a batch-wise mode to evaluate the influence of various operation parameters on the electrolytic behavior, such as acidity of aqueous solution, temperature, electrode potential, persulfate anion concentration and nitrogen/oxygen gas dosage. The aniline pollutants could be almost entirely mineralized by means of electro-activated persulfate oxidation, wherein sulfate radicals were presumed to be principal oxidizing agents. Besides, electrogenerated hydrogen peroxide originated from cathodic reduction of oxygen, supplied chiefly by anodic oxidation of water, would contribute partially for decomposition of aniline. On the whole, the electro-activated persulfate process is a very promising method for treatment of aniline in wastewater. PMID:25576128

  9. Remediation of hexachlorocyclohexanes by electrochemically activated persulfates.

    PubMed

    Wac?awek, Stanis?aw; Anto, Vojtech; Hrabk, Pavel; ?ernk, Miroslav; Elliott, Daniel

    2016-01-01

    Hexachlorocyclohexane (HCH) isomers represent a family of formerly widely utilized pesticides that are persistent, capable of undergoing long-range transport and tend to bioaccumulate in human and animal tissue. Their widespread global utilization coupled with a propensity to adversely impact human health and the environment translates into an urgent need to develop feasible methodologies by which to treat HCH-impacted groundwater and soil. The present study was conducted to evaluate the efficacy of two persulfate-based oxidants: peroxydisulfate (S2O8 (2-), PDS) and peroxymonosulfate (HSO5 (-), PMS) activated by electrochemical processes (EC) to treat HCH-impacted environmental media. This research demonstrated that the optimal experimental conditions (oxidant dose and electrical current) were 2mM PDS and 20mA for an aqueous solution of 4?M of summed HCHs (?HCH). GC/MS full scan analysis revealed the presence of 2,4,6-trichlorophenol as the only detectable intermediate formed during electro-activated PDS treatment of ?HCH. The investigated method was tested on leachate from a known HCHs-impacted site in Hajek, Czech Republic which contained 106?g/l of ?HCH and 129?g/l of chlorobenzenes. Results from batch treatment showed positive results for electro-activated PDS but only negligible effectiveness for electro-activated PMS. In addition to explaining the efficacy of the electro-activated PDS, this research also explored the basis for the differing reactivities of these two persulfates. PMID:26336848

  10. In-situ activation of persulfate by iron filings and degradation of 1,4-dioxane.

    PubMed

    Zhong, Hua; Brusseau, Mark L; Wang, Yake; Yan, Ni; Quig, Lauren; Johnson, Gwynn R

    2015-10-15

    Activation of persulfate by iron filings and subsequent degradation of 1,4-dioxane (dioxane) was studied in both batch-reactor and column systems to evaluate the potential of a persulfate-enhanced permeable reactive barrier (PRB) system for combined oxidative-reductive removal of organic contaminants from groundwater. In batch experiments, decomposition of persulfate to sulfate and degradation of dioxane both occurred rapidly in the presence of iron filings. Conversely, dioxane degradation by persulfate was considerably slower in the absence of iron filings. For the column experiments, decomposition and retardation of persulfate was observed for transport in the columns packed with iron filings, whereas no decomposition or retardation was observed for transport in columns packed with a reference quartz sand. Both sulfate production and dioxane degradation were observed for the iron-filings columns, but not for the sand column. The pH of the column effluent increased temporarily before persulfate breakthrough, and significant increases in both ferrous and ferric iron coincided with persulfate breakthrough. Multiple species of free radicals were produced from persulfate activation as determined by electron paramagnetic resonance (EPR) spectroscopy. The impact of the oxidation process on solution composition and iron-filings surface chemistry was examined using ICP-MS, SEM-EDS, and XRD analyses. A two-stage reaction mechanism is proposed to describe the oxidation process, consisting of a first stage of rapid, solution-based, radical-driven decomposition of dioxane and a second stage governed by rate-limited surface reaction. The results of this study show successful persulfate activation using iron filings, and the potential to apply an enhanced PRB method for improving in-situ removal of organic contaminants from groundwater. PMID:26141426

  11. Targeted proteomic analyses of nasal lavage fluid in persulfate-challenged hairdressers with bleaching powder-associated rhinitis.

    PubMed

    Mrtstedt, Harriet; Ali, Neserin; Kredal, Monica; Jacobsson, Helene; Rietz, Emelie; Diab, Kerstin Kronholm; Nielsen, Jrn; Jnsson, Bo A G; Lindh, Christian H

    2015-02-01

    Hairdressers have an increased risk for developing airway symptoms, for example, asthma and rhinitis. Persulfates, which are oxidizing agents in bleaching powder, are considered important causal agents for these symptoms. However, the underlying mechanisms are unclear. The aim was therefore to measure proteomic changes in nasal lavage fluid from persulfate-challenged subjects to identify proteins potentially involved in the pathogenesis of bleaching powder-associated rhinitis or candidate effect biomarkers for persulfate. Also, oxidized peptides were measured to evaluate their usefulness as biomarkers for persulfate exposure or effect, for example, oxidative stress. Samples from hairdressers with and without bleaching powder-associated rhinitis were analyzed with liquid chromatography tandem mass spectrometry using selected reaction monitoring to target 246 proteins and five oxidized peptides. Pathway analysis was applied to obtain a functional overview of the proteins. Several proteins involved in biologically meaningful pathways, functions, or disorders, for example, inflammatory responses, oxidative stress, epithelium integrity, and dermatological disorders, changed after the persulfate challenge. A list with nine proteins that appeared to be affected by the persulfate challenge and should be followed up was defined. An albumin peptide containing oxidized tryptophan increased 2 h and 5 h after the challenge but not after 20 min, which indicates that such peptides may be useful as oxidative stress biomarkers. PMID:25546367

  12. Electrolytic Manipulation of Persulfate Reactivity by Iron Electrodes for TCE Degradation in Groundwater

    PubMed Central

    Yuan, Songhu; Liao, Peng; Alshawabkeh, Akram N.

    2014-01-01

    Activated persulfate oxidation is an effective in situ chemical oxidation process for groundwater remediation. However, reactivity of persulfate is difficult to manipulate or control in the subsurface causing activation before reaching the contaminated zone and leading to a loss of chemicals. Furthermore, mobilization of heavy metals by the process is a potential risk. An effective approach using iron electrodes is thus developed to manipulate the reactivity of persulfate in situ for trichloroethylene (TCE) degradation in groundwater, and to limit heavy metals mobilization. TCE degradation is quantitatively accelerated or inhibited by adjusting the current applied to the iron electrode, following k1 = 0.00053Iv + 0.059 (?122 A/m3 ? Iv ? 244 A/m3) where k1 and Iv are the pseudo first-order rate constant (min?1) and volume normalized current (A/m3), respectively. Persulfate is mainly decomposed by Fe2+ produced from the electrochemical and chemical corrosion of iron followed by the regeneration via Fe3+ reduction on the cathode. SO4? and OH co-contribute to TCE degradation, but OH contribution is more significant. Groundwater pH and oxidation-reduction potential can be restored to natural levels by the continuation of electrolysis after the disappearance of contaminants and persulfate, thus decreasing adverse impacts such as the mobility of heavy metals in the subsurface. PMID:24328192

  13. Leaching of Calcareous Bornite Ore in Ammoniacal Solution Containing Ammonium Persulfate

    NASA Astrophysics Data System (ADS)

    Liu, Zhi-xiong; Yin, Zhou-lan; Chen, Yi-guang; Xiong, Li-zhi

    2014-12-01

    The leaching process of copper from calcareous bornite ore using ammonium persulfate as an oxidant in ammoniacal solution was investigated. The effects of stirring speed, temperature, initial concentration of ammonia and ammonium persulfate, and liquid-to-solid (L/S) ratio on the extraction percentage of copper from bornite ore were studied. The results show that the optimum leaching conditions for bornite ore with a maximum extraction of copper 88.9 pct are temperature 313.15 K (40 C), reaction time 4 hours, stirring speed 600 r /min, L/S ratio 7/1 cm3/g, initial concentration of ammonia 2.0 mol/dm3, and ammonium persulfate 3.0 mol/dm3.

  14. Advanced oxidation of the commercial nonionic surfactant octylphenol polyethoxylate TritonTM X-45 by the persulfate/UV-C process: effect of operating parameters and kinetic evaluation

    NASA Astrophysics Data System (ADS)

    Arslan-Alaton, Idil; Olmez-Hanci, Tugba; Genc, Bora; Dursun, Duygu

    2013-03-01

    This study explored the potential use of a sulfate radical (SO4?-)-based photochemical oxidation process to treat the commercial nonionic surfactant octylphenol polyethoxylate (OPPE) TritonTMX-45. For this purpose, the effect of initial S2O82- (0-5.0 mM) and OPPE (10-100 mg/L) concentrations on OPPE and its organic carbon content (TOC) removal were investigated at an initial reaction pH of 6.5. Results indicated that very fast OPPE degradation (100%) accompanied with high TOC abatement rates (90%) could be achieved for 10 and 20 mg/L aqueous OPPE at elevated S2O82- concentrations (>2.5 mM). S2O82-/UV-C treatment was still capable of complete OPPE removal up to an initial concentration of 40 mg/L in the presence of 2.5 mM S2O82-. On the other hand, TOC removal efficiencies dropped down to only 40% under the same reaction conditions. S2O82-/UV-C oxidation of OPPE was also compared with the relatively well-known and established H2O2/UV-C oxidation process. Treatment results showed that the performance of S2O82-/UV-C was comparable to that of H2O2/UV-C oxidation for the degradation and mineralization of OPPE. In order to elucidate the relative reactivity and selectivity of SO4?- and HO?, bimolecular reaction rate coefficients of OPPE with SO4?- and HO? were determined by employing competition kinetics with aqueous phenol (47 ?M) selected as the reference compound. The first-order abatement rate coefficient obtained for OPPE during S2O82-/UV-C oxidation (0.044 min-1) was found to be significantly lower than that calculated for phenol (0.397 min-1). In the case of H2O2/UV-C oxidation however, similar first-order abatement rate coefficients were obtained for both OPPE (0.087 min-1) and phenol (0.140 min-1). Second-order reaction rate coefficients for OPPE with SO4?- and HO? were determined as 9.8?108 M-1s-1 and 4.1?109 M-1s-1, respectively. The kinetic study also revealed that the selectivity of SO4?- was found to be significantly higher than that of HO?.

  15. Degradation of ciprofloxacin and sulfamethoxazole by ferrous-activated persulfate: implications for remediation of groundwater contaminated by antibiotics.

    PubMed

    Ji, Yuefei; Ferronato, Corinne; Salvador, Arnaud; Yang, Xi; Chovelon, Jean-Marc

    2014-02-15

    The wide occurrence of antibiotics in groundwater raised great scientific interest as well as public awareness in recent years due to their potential ability to spread antibiotic resistant gene and pose risk to humans. The present study investigated the ferrous ion (Fe(II)) activated decomposition of persulfate (S2O8(2-)), as a potential in situ chemical oxidation (ISCO) approach, for remediation of groundwater contaminated by antibiotics. Fe(II)-persulfate mediated ciprofloxacin (CIP) degradation was found to be more efficient than sulfamethoxazole (SMX) at near neutral pH (pH6.0), probably due to the higher electric density in CIP molecule and its ability to form complex with Fe(II) as a ligand. Hydroxyl (HO) and sulfate radical (SO4(-)) were determined to be responsible for the degradation of CIP and SMX in Fe(II)-persulfate system by molecular probes. No enhancement in the degradation of CIP was observed when citrate (CA), ethylenediaminetetraacetate (EDTA) and (S,S)-ethylenediamine-N,N'-disuccinate (EDDS) were used as Fe(II) chelating agents in Fe(II)-persulfate system. For SMX, CA and EDTA accelerated the degradation by Fe(II)-persulfate. Degradation of antibiotics in river water matrix was nearly the same as that in Milli-Q water, implying the possibility of using Fe(II)-persulfate for antibiotics depletion under environmentally relevant condition. A comparison of the degradation efficiency of SMX with other sulfonamides and sulfanilic acid indicated that the heterocyclic ring has a large impact on the degradation of sulfonamides. Transformation products of CIP and SMX by Fe(II)-persulfate were analyzed by solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) technique. Based on the intermediate products, Fe(II)-persulfate mediated CIP degradation pathways were tentatively proposed. PMID:24342085

  16. Field Application of a Rapid Spectrophotometric Method for Determination of Persulfate in Soil

    PubMed Central

    Cunningham, Colin J.; Pitschi, Vanessa; Anderson, Peter; Barry, D. A.; Patterson, Colin; Peshkur, Tanya A.

    2013-01-01

    Remediation of hydrocarbon contaminated soils can be performed both in situ and ex situ using chemical oxidants such as sodium persulfate. Standard methods for quantifying persulfate require either centrifugation or prolonged settling times. An optimized soil extraction procedure was developed for persulfate involving simple water extraction using a modified disposable syringe. This allows considerable saving of time and removes the need for centrifugation. The extraction time was reduced to only 5 min compared to 15 min for the standard approach. A comparison of the two approaches demonstrated that each provides comparable results. Comparisons were made using high (93 g kg?1 soil) and low (9.3 g kg?1 soil) additions of sodium persulfate to a petroleum hydrocarbon-contaminated soil, as well as sand spiked with diesel. Recoveries of 951% and 9610% were observed with the higher application rate in the contaminated soil and spiked sand, respectively. Corresponding recoveries of 865% and 11719% were measured for the lower application rate. Results were obtained in only 25 min and the method is well suited to batch analyses. In addition, it is suitable for application in a small field laboratory or even a mobile, vehicle-based system, as it requires minimal equipment and reagents. PMID:23776446

  17. Developing slow-release persulfate candles to treat BTEX contaminated groundwater.

    PubMed

    Kambhu, Ann; Comfort, Steve; Chokejaroenrat, Chanat; Sakulthaew, Chainarong

    2012-10-01

    The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technology. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated groundwater. Laboratory-scale candles were prepared by heating and mixing Na(2)S(2)O(8) with paraffin in a 2.25 to 1 ratio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO(4) or zerovalent iron (ZVI) and wax. By treating benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid transformation of all contaminants. By using (14)C-labeled benzoic acid and benzene, we also confirmed mineralization (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking persulfate and ZVI candles on top of each other in a saturated sand tank (14142.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, benzoic acid or benzene concentrations (C(o)=1 mM) decreased by >90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater. PMID:22776257

  18. Removal of carbamazepine from aqueous solution using sono-activated persulfate process.

    PubMed

    Wang, Songlin; Zhou, Ning

    2016-03-01

    This study investigated systematically the removal of carbamazepine (CBZ) in solution using the combination of ultrasound and persulfate anions to identify the factors affecting the kinetics of the process. The effects of reaction time, initial persulfate anion concentration, initial CBZ concentration, ultrasonic power input, solution pH and temperature on CBZ removal efficiency were examined. The sulfate radical oxidation of CBZ in the presence of ultrasonic irradiation showed a significant synergistic effect on CBZ removal. It is found that up to 89.4% CBZ removal efficiency was achieved after 120 min reaction. The removal process of CBZ in solution could be described using pseudo-first-order kinetics. In this system, sulfate radicals (SO4(-)) were considered to be the mainly oxidant to remove CBZ while ultrasound power input could affect CBZ removal efficiency significantly. Changing solution pH influenced the CBZ removal efficiency and the best performance would be achieved at pH 5.0. PMID:26584993

  19. Activated persulfate for organic chemical degradation: A review.

    PubMed

    Matzek, Laura W; Carter, Kimberly E

    2016-05-01

    Activated persulfate reactions have widespread application for groundwater and environmental remediation, as many of these reactions involve destruction of environmental contaminants. Within the last five years, knowledge of activated persulfate degradation reactions has grown to include novel means of activating persulfate for enhanced removal of organic species. These current studies cover a long list of organic analytes, including pharmaceuticals, pesticides, halogenated compounds and dyes. An extensive review of recently published experimental parameters and results for the destruction of organic compounds via activated persulfate is presented. Focus is placed on emerging methodologies and manipulation of traditional activation techniques. Knowledge gaps are identified and discussed, as despite the number of publications on this subject, more broad-reaching guidelines are needed for optimizing applications of activated persulfate in water treatment. PMID:26938680

  20. Removal of 1,1,1-trichloroethane from aqueous solution by a sono-activated persulfate process.

    PubMed

    Li, Bingzhi; Li, Lin; Lin, Kuangfei; Zhang, Wei; Lu, Shuguang; Luo, Qishi

    2013-05-01

    1,1,1-Trichloroethane (TCA), labeled as a priority pollutant by the Environmental Protection Agency (EPA) of China, can be removed from groundwater by sonochemical oxidation. The sonochemical oxidation of TCA in the presence of persulfate (PS) showed a significant synergistic effect. The operational parameters, ultrasonic frequency, PS/TCA molar ratio, radical scavenger, inorganic anions (Cl(-), CO(3)(2-), HCO(3)(-) and NO(3)(-)) and humic acid (HA), were evaluated during the investigation of the sonochemical reaction. The results showed that the degradation of TCA followed pseudo-first-order kinetics, and the rate constant was found to increase with increasing ultrasonic frequency but to decrease with both an increasing PS/TCA molar ratio and an increasing concentration of inorganic anions. With a concentration of 4.46mg/L of HA in solution, an enhanced effect was observed. Further addition of HA retarded the degradation rate of TCA. TCA could be eliminated almost completely by sono-activated persulfate oxidation, with sulfate and hydroxyl radicals serving as the principal oxidants as confirmed by the addition of radical scavengers. Eleven chlorinated degradation intermediates were detected and quantified by purge and trap gas chromatography coupled with mass spectrometry (P&T-GC-MS) in the absence of pH buffer. Three TCA degradation pathways were therefore proposed. In conclusion, the sono-activated persulfate oxidation process appears to be a highly promising technique for the remediation of TCA-contaminated groundwater. PMID:23266439

  1. [Influence of the Application of Activated Persulfate on Municipal Sludge Conditioning].

    PubMed

    Xu, Xin; Pu, Wen-hong; Shi, Ya-fei; Yu, Wen-bo; Zhang, Shi-nan; Song, Jian; Zhang, Hao; He, Shu; Yang, Chang-zhu; Yang, Jia-kuan

    2015-11-01

    The water content of dewatered sewage sludge can decrease at about 80% by traditional sludge dewatering technologies. High water content has negative impacts on the sequent sludge disposal with a stricter standard. The sulfate free radical SO4(*-), generated by activated persulfate, is a powerful oxidant. This article found that it could improve sludge dewatering properties by using the Fe2+ activated sodium persulfate (SPS). The results showed that when using Fe2+ 25.88 mg x g(-1) (based on dry sludge solid) and S2 O8(2-) 80 mg x g(-1) (the mole ratio of Fe2+ to S2 O8(2-) was 1.1 : 1) for sludge conditioning, it could reduce the capillary suction time (CST) and specific resistance to filtration (RSF) of sludge, increased the protein and ploysaccharide as well as the COD concentration in the filtrate. The further research showed that this method could change the zeta potential of sludge, increased the sludge particle specific surface area, and made flocs become a loose layered structure from dense clusters, which was beneficial to improve the sludge dewaterability. PMID:26911010

  2. Leaching of a copper flotation concentrate with ammonium persulfate in an autoclave system

    NASA Astrophysics Data System (ADS)

    Deniz Turan, M.; Soner Altundo?an, H.

    2014-09-01

    The leaching behavior of a copper flotation concentrate was investigated using ammonium persulfate (APS) in an autoclave system. The decomposition products of APS, active oxygen, and acidic medium were used to extract metals from the concentrate. Leaching experiments were performed to compare the availability of APS as an oxidizing agent for leaching of the concentrate under atmospheric conditions and in an autoclave system. Leaching temperature and APS concentration were found to be important parameters in both leaching systems. Atmospheric leaching studies showed that the metal extractions increased with the increase in APS concentration and temperature (up to 333 K). A similar tendency was determined in the autoclave studies up to 423 K. It was also determined that the metal extractions decreased at temperatures above 423 K due to the passivation of the particle surface by molten elemental sulfur. The results showed that higher copper extractions could be achieved using an autoclave system.

  3. 76 FR 28419 - Persulfates From the People's Republic of China: Final Results of the 2009-2010 Antidumping Duty...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-17

    ... Results of the 2009-2010 Antidumping Duty Administrative Review, 76 FR 13358 (March 11, 2011... covered by this review are persulfates, including ammonium, potassium, and sodium persulfates. The... 8 . Potassium persulfates are currently classifiable under subheading 2833.40.10 of the...

  4. Peroxone activated persulfate treatment of 1,4-dioxane in the presence of chlorinated solvent co-contaminants.

    PubMed

    Eberle, Dylan; Ball, Raymond; Boving, Thomas B

    2016-02-01

    1,4-dioxane is often found as a co-contaminant with chlorinated volatile organic compounds (VOCs) at solvent release sites such as landfills, solvent recycling facilities, or fire training areas. Historically, soil and groundwater samples were not routinely analyzed for 1,4-dioxane and therefore the number of known 1,4-dioxane sites is still increasing. Due to its co-occurrence with chlorinated compounds, remediation strategies are needed that simultaneously treat both 1,4-dioxane as well as chlorinated VOC co-contaminants. In this proof of concept laboratory study, the fate of 1,4-dioxane was examined during the targeted destruction of aqueous phase VOC, using a peroxone activated persulfate (PAP) chemical oxidation method. Bench-scale experiments were carried out to evaluate the treatability of 1,4-dioxane as both a single-contaminant and in the presence of trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single-contaminant batch systems followed pseudo-first-order reaction kinetics and even at the most dilute oxidant concentration lasted for at least 13 days. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least, was: TCE>1,4-dioxane>1,1,1-TCA. Oxidation rates were up to 87% slower in a mixture of these three compounds. Although additional tests are necessary, our data suggest that PAP oxidation of 1,4-dioxane might aid in the cleanup of VOC contaminated sites. PMID:26408980

  5. Fe/S doped granular activated carbon as a highly active heterogeneous persulfate catalyst toward the degradation of Orange G and diethyl phthalate.

    PubMed

    Pu, Mengjie; Ma, Yongwen; Wan, Jinquan; Wang, Yan; Huang, Mingzhi; Chen, Yangmei

    2014-03-15

    Fe/S doped granular activated carbon (Fe/SGAC) was synthesized with ferric nitrate, Na2S2O3 and (NH4)2S2O8 via an impregnation-precipitation, reduction-oxidation combining with aqueous-phase synthesis method treatment. Surface density of functional groups, surface area changes as well as the chemical state inside Fe/SGAC catalyst were studied by Boehm titration, N2 adsorption and X-ray photoelectron spectroscopy (XPS). The reactivity of the catalysts was tested by degrading Orange G (OG) and diethyl phthalate (DEP). The Fe/SGAC catalysts could significantly enhance the removal rate of OG as compared to persulfate alone and PS/GAC. And the catalytic capacity was also enhanced by S doping. But the degradation of DEP under the similar condition was inhibited by adsorption process because of the different hydrophobicities of OG and DEP molecule. Fe2O3/FeOOH (Fe(3+)) (represents ferrihydrite) together with FeO/Fe3O4 (Fe(2+)) and Fe2O3-satellite, which provide the new active site for persulfate catalyst was found to be the major components of iron element in Fe/SGAC catalyst; the existence of FeS2(S(-)) for sulfur element verified the assumption that the doped S element promoted the electron transfer between the persulfate species and iron oxide at the interface. COD removal experiment further confirmed that mostly contaminant removal was owed to the Fe/SGAC catalytic persulfate oxidation process. PMID:24461853

  6. Degradation and dechlorination of pentachlorophenol by microwave-activated persulfate.

    PubMed

    Qi, Chengdu; Liu, Xitao; Zhao, Wei; Lin, Chunye; Ma, Jun; Shi, Wenxiao; Sun, Qu; Xiao, Hao

    2015-03-01

    The degradation performance of pentachlorophenol (PCP) by the microwave-activated persulfate (MW/PS) process was investigated in this study. The results indicated that degradation efficiency of PCP in the MW/PS process followed pseudo-first-order kinetics, and compared with conventional heating, microwave heating has a special effect of increasing the reaction rate and reducing the process time. A higher persulfate concentration and reaction temperature accelerated the PCP degradation rate. Meanwhile, increasing the pH value and ionic strength of the phosphate buffer slowed down the degradation rate. The addition of ethanol and tert-butyl alcohol as hydroxyl radical and sulfate radical scavengers proved that the sulfate radicals were the dominant active species in the MW/PS process. Gas chromatography-mass spectrometry (GC-MS) was employed to identify the intermediate products, and then a plausible degradation pathway involving dechlorination, hydrolysis, and mineralization was proposed. The acute toxicity of PCP, as tested with Photobacterium phosphoreum, Vibrio fischeri, and Vibrio qinghaiensis, was negated quickly during the MW/PS process, which was in agreement with the nearly complete mineralization of PCP. These results showed that the MW/PS process could achieve a high mineralization level in a short time, which provided an efficient way for PCP elimination from wastewater. PMID:25328098

  7. The control of emerging haloacetamide DBP precursors with UV/persulfate treatment.

    PubMed

    Chu, Wenhai; Li, Dongmei; Gao, Naiyun; Templeton, Michael R; Tan, Chaoqun; Gao, Yuqiong

    2015-04-01

    Haloacetamides (HAcAms), an emerging class of nitrogen-containing disinfection byproducts (N-DBPs) of health concern in drinking water, have been reported to occur in treated drinking waters at low ?g/L levels typically. The objective of this study was to examine the potential of an ultraviolet light/persulfate (UV/PS) oxidation technology to reduce the precursors of HAcAms and also minimize the formation of other N-DBPs upon subsequent chlorination. Low-pressure UV photolysis alone and PS pre-oxidation alone did not significantly affect HAcAm formation, however UV/PS pre-oxidation achieved a statistically significant reduction in HAcAm formation and also reduced bromine incorporation into the HAcAms. UV/PS also showed a good performance in removing the precursors of haloacetonitriles and halonitromethanes prior to chlorination. Therefore, UV/PS has the potential to minimize the formation of a range of N-DBPs in organic nitrogen-rich waters where N-DBP precursors are prevalent. However, these benefits should be weighed against the potential drawbacks of increased bromate and sulfate formation, particularly in high-bromide waters. PMID:25267364

  8. Determination of an Effective Perfluorinated Compounds (PFCs) Oxidation Method

    NASA Astrophysics Data System (ADS)

    Siriwardena, D. P.; Crimi, M.; Holsen, T.; Bellona, C.

    2014-12-01

    Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are a stable synthetic class of chemicals ubiquitously spread in environmental media (i.e. air, soil, biota, surface water and groundwater). The substances' strong polar carbon-fluorine bonds and their high thermal and chemical stability make them resistant to biological, chemical, and physical degradation. The purpose of this research is to identify the most effective oxidation method to treat perfluorinated compounds (PFCs) and their by-products that is suitable for in situ application. The laboratory oxidation study focuses on the more commonly detected and studied long-chain (C-8) PFAS; perfluorooctanoic acids (PFOA) and perfluorooctane sulfonic acid (PFOS). Existing research evaluating oxidizing treatment effectiveness on perfluoroalkyl sulfoinoic acids (PFSAs) is limited. A review of the literature and results from preliminary studies indicate that activated persulfate and catalyzed hydrogen peroxide propagation (CHP) reactions appear to be promising oxidants for PFOA. It has been demonstrated that the reactivity of superoxide in water increases in the presence of hydrogen peroxide (H2O2) and solids. Superoxide generated in CHP reactions degrades PFOA seemingly similar to superoxide-mediated destruction of the perhalogenated compounds.The goal of this study is to look at conditions that promote generation of superoxide and look at PFASs treatment effectiveness and byproduct generation. CHP reactions are conducted with varying amount of H2O2 and Fe(III) to determine the optimum conditions for PFC degradation. Results will be compared to those of another experiment using manganese dioxide as a CHP catalyst with varied H2O2 concentration to generate superoxide to degrade PFASs. Activated persulfate conditions to be compared include alkaline pH activation, heat activation, and dual oxidation (combined H2O2 and persulfate ). This presentation will focus on a comparison of oxidation effectiveness under the varied reaction conditions as well as on the oxidation intermediates and byproducts generated toward improved understanding of the potential for and limitations of in situ chemical oxidation (ISCO) for treatment of PFCs.

  9. Sodium persulfate-assisted mechanochemical degradation of tetrabromobisphenol A: Efficacy, products and pathway.

    PubMed

    Liu, Xitao; Zhang, Xiaohui; Zhang, Kunlun; Qi, Chengdu

    2016-05-01

    In recent years, activated persulfate (PS) oxidation has been developed as a new advanced oxidation process for the degradation of organic pollutants. On the other hand, the mechanochemical method has exhibited a unique advantage in dealing with chemical wastes. The degradation of tetrabromobisphenol A (TBBPA), a widely used brominated flame retardant (BFR), in wastes has attracted considerable attention. In this study, the efficacy of a CaO-mechanochemical (CaO-MC) treatment system assisted by the addition of PS for the degradation of TBBPA was investigated. Under the optimum reaction conditions with a mole ratio of PS:CaO = 1:4 and less than 12.5% of TBBPA by mass, the degradation and debromination of TBBPA were completed within 2 h, while the mineralization was completed within 4 h. Characterization of the milled sample by XRD revealed that CaSO4 crystallization occurred. The TG results illustrate that there was little organic matter left after 4 h of milling. Raman and FT-IR spectra exhibited the TBBPA destruction process and disappearance of the organic groups. Through analysis by LC/MS/MS, seventeen intermediates were identified. The mechanism of TBBPA degradation by the PS-assisted CaO-MC treatment system was explained from two aspects, the course of crystallization and the degradation of TBBPA by activated PS, and two parallel initiation pathways were proposed. PMID:26359264

  10. Rapid and simple spectrophotometric determination of persulfate in water by microwave assisted decolorization of Methylene Blue.

    PubMed

    Zhao, Lajuan; Yang, Shiying; Wang, Leilei; Shi, Chao; Huo, Meiqing; Li, Yan

    2015-05-01

    A rapid and simple method for determination of persulfate in aqueous solution was developed. The method is based on the rapid reaction of persulfate with Methylene Blue (MB) via domestic microwave activation, which can promote the activation of persulfate and decolorize MB quickly. The depletion of MB at 644 nm (the maximum absorption wavelength of MB) is in proportion to the increasing concentration of persulfate in aqueous solution. Linear calibration curve was obtained in the range 0-1.5 mmol/L, with a limit of detection of 0.0028 mmol/L. The reaction time is rapid (within 60 sec), which is much shorter than that used for conventional methods. Compared with existing analytical methods, it need not any additives, especially colorful Fe2+, and need not any pretreatment for samples, such as pH adjustment. PMID:25968279

  11. Activated Persulfate Treatment of 1,4-Dioxane in the Presence of Chlorinated Solvent Co-contaminants

    NASA Astrophysics Data System (ADS)

    Boving, T. T.; Eberle, D. E. H.; Ball, R.

    2014-12-01

    1,4-dioxane is an emerging groundwater contaminant and a likely human carcinogen. Due to its history as a stabilizer in chlorinated solvents, 1,4-dioxane is often found as a co-contaminant at solvent releases sites such as landfills, solvent recycling facilities, vapor decreasing operations, and fire-training areas. Historically, 1,4-dioxane was not routinely analyzed for at solvent release sites. The lack of analyses and the limitations of the analyses that were performed (i.e. high reporting limits) means that the scale of 1,4-dioxane subsurface contamination is still emerging. With the number of known 1,4-dioxane sites increasing, the need for cost effective 1,4-dioxane remediation technologies is rising as well. Remediation strategies that are capable of treating both 1,4-dioxane as well as chlorinated co-contaminants are of particular importance, especially when treating mixed-waste source zones. In the present study, we examined the fate of 1,4-dioxane during the targeted remediation of aqueous phase volatile organic compounds (VOC) using an activated persulfate based ISCO method (OxyZone®). Bench scale laboratory experiments are used to evaluate the treatability of 1,4-dioxane both as a single compound and in the presence of trichloroethene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. Preliminary results are promising and show that OxyZone® is persistent and long lived, with oxidation of 1,4-dioxane continuing more than 12 days after initial dosage, even at dilute oxidant concentrations. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single compound batch systems followed pseudo first order reaction kinetics. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least was: TCE > 1,4-Dioxane > 1,1,1-TCA. Experiments examining the destruction of 1,4-dioxane in the presence of TCE and 1,1,1-TCA are ongoing. The final results of this study will be presented.

  12. 76 FR 13358 - Persulfates From the People's Republic of China: Preliminary Results of the 2009-2010 Antidumping...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-11

    ... Republic of China, 62 FR 36259 (July 7, 1997) (``Persulfates Order and Amended Final''), amended by Notice of Amended Antidumping Duty Order: Persulfates From the People's Republic of China, 62 FR 39212 (July..., or Suspended Investigation; Opportunity To Request Administrative Review, 75 FR 38074 (July 1,...

  13. Is it possible to remediate a BTEX contaminated chalky aquifer by in situ chemical oxidation?

    PubMed

    Lemaire, Julien; Croze, Vronique; Maier, Joachim; Simonnot, Marie-Odile

    2011-08-01

    An industrial coating site in activity located on a chalky plateau, contaminated by BTEX (mainly xylenes, no benzene), is currently remediated by in situ chemical oxidation (ISCO). We present the bench scale study that was conducted to select the most appropriate oxidant. Ozone and catalyzed hydrogen peroxide (Fenton's reaction) were discarded since they were incompatible with plant activity. Permanganate, activated percarbonate and activated persulfate were tested. Batch experiments were run with groundwater and groundwater-chalk slurries with these three oxidants. Total BTEX degradation in groundwater was reached with all the oxidants. The molar ratios [oxidant]:[Fe(2+)]:[BTEX] were 100:0:1 with permanganate, 100:100:1 with persulfate and 25:100:1 with percarbonate. Precipitation of either manganese dioxide or iron carbonate (siderite) occurred. The best results with chalk slurries were obtained with permanganate at the molar ratio 110:0:1 and activated persulfate at the molar ratio 110:110:1. To avoid precipitation, persulfate was also used without activation at the molar ratio 140:1. Natural Oxidant Demand measured with both oxidants was lower than 5% of initial oxidant contents. Activated percarbonate was not appropriate because of radical scavenging by carbonated media. Permanganate and persulfate were both effective at oxidant concentrations of ca 1 g kg(-1) with permanganate and 1.8 g kg(-1) with persulfate and adapted to site conditions. Activation of persulfate was not mandatory. This bench scale study proved that ISCO remediation of a chalky aquifer contaminated by mainly xylenes was possible with permanganate and activated or unactivated persulfate. PMID:21733544

  14. Advances in heat-activated cooling systems

    SciTech Connect

    Worek, W.M.; Novosel, D.; Collier, R.K.

    1996-08-01

    Regulatory issues are fundamentally changing the heating, ventilation, and air-conditioning (HVAC) market. Growing concerns about indoor air quality, the phase-out of traditional refrigerants, and renewed emphasis on energy efficiency threaten the future of traditional vapor-compression refrigeration cycles. The air conditioner of the future will have to efficiently provide increased amounts of ventilation air, avoid the use of chlorofluorocarbons or similar compounds, provide cool unsaturated air below 70% relative humidity, maintain relative humidity in the conditioned space at 50% year-round, and reduce or eliminate air contaminants. This new air conditioner must also minimize initial, operating, and maintenance costs yet keep electric demand low. Recent advances in heat-activated cooling system have led to the development of several systems that perform better than conventional electric-driven unitary air conditioners. One heat-activated cooling system, an open-cycle desiccant system, has begun to enter the air-conditioning market. An open-cycle desiccant system dehumidifies and cools air directly, providing greater efficiency and less pollution.

  15. Variability in carbon isotope fractionation of trichloroethene during degradation by persulfate activated with zero-valent iron: Effects of inorganic anions.

    PubMed

    Liu, Yunde; Zhou, Aiguo; Gan, Yiqun; Li, Xiaoqian

    2016-04-01

    Stable carbon isotope analysis has the potential to be used for assessing the performance of in situ remediation of organic contaminants. Successful application of this isotope technique requires understanding the magnitude and variability in carbon isotope fractionation associated with the reactions under consideration. This study investigated the influence of inorganic anions (sulfate, bicarbonate, and chloride) on carbon isotope fractionation of trichloroethene (TCE) during its degradation by persulfate activated with zero-valent iron. The results demonstrated that the significant carbon isotope fractionation (enrichment factors ε ranging from -3.4±0.3 to -4.3±0.3‰) was independent on the zero-iron dosage, sulfate concentration, and bicarbonate concentration. However, the ε values (ranging from -7.0±0.4 to -13.6±1.2‰) were dependent on the chloride concentration, indicating that chloride could significantly affect carbon isotope fractionation during TCE degradation by persulfate activated with zero-valent iron. The dependence of ε values on chloride concentration, indicated that TCE degradation mechanisms may be different from the degradation mechanism caused by sulfate radical (SO4(-)). Ignoring the effect of chloride on ε value may cause numerous uncertainties in quantitative assessment of the performance of the in situ chemical oxidation (ISCO). PMID:26784392

  16. The synthesized and thermally modified Mn-Ca-FeOOH composite in persulfate system: Its role to discolor methylene blue

    NASA Astrophysics Data System (ADS)

    Jo, Young-Hoon; Hong, Seong-Ho; Park, Tae-Jin; Do, Si-Hyun

    2014-05-01

    Methylene blue (MB) discoloration was performed using persulfate (PS) activated with the synthesized composites. Four types of composites, which were synthesized by the immobilization of Mn on iron oxides (hematite and goethite) using either NaOH or Ca(OH)2, were evaluated as PS activator. The synthesized Mn-Ca-FeOOH composite was selected and it was thermally modified at 300 and 700 C (denoted Mn-Ca-FeOOH_300 and Mn-Ca-FeOOH_700). The BET surface area of Mn-Ca-FeOOH_300 was similar to that of Mn-Ca-FeOOH while that of Mn-Ca-FeOOH_700 was dramatically lower. XRD and XPS analysis indicated that the thermal modification transformed iron oxides from goethite to hematite and changed amorphous manganese oxide to crystalline. MB discoloration at pH 3 indicated that Mn-Ca-FeOOH acted as an oxidant to degrade MB, and the thermally modified composites (i.e. Mn-Ca-FeOOH_300 and Mn-Ca-FeOOH_700) acted as a catalyst to activate PS. Moreover, incomplete MB discoloration was observed in PS/composite system at pH 3. However, a whole tested wavelength of MB was reduced when MB discoloration was tested in PS/composite system above pH 7. Moreover, the increasing pH of solution increased MB discoloration. The higher MB discoloration in heterogeneous system at pH 12 could suggest that superoxide anion (O2-) was dominant reactive oxygen species.

  17. Development of crosslinked methylcellulose hydrogels for soft tissue augmentation using an ammonium persulfate-ascorbic acid redox system.

    PubMed

    Gold, Gittel T; Varma, Devika M; Taub, Peter J; Nicoll, Steven B

    2015-12-10

    Hydrogels composed of methylcellulose are candidate materials for soft tissue reconstruction. Although photocrosslinked methylcellulose hydrogels have shown promise for such applications, gels crosslinked using reduction-oxidation (redox) initiators may be more clinically viable. In this study, methylcellulose modified with functional methacrylate groups was polymerized using an ammonium persulfate (APS)-ascorbic acid (AA) redox initiation system to produce injectable hydrogels with tunable properties. By varying macromer concentration from 2% to 4% (w/v), the equilibrium moduli of the hydrogels ranged from 1.47 0.33 to 5.31 0.71 kPa, on par with human adipose tissue. Gelation time was found to conform to the ISO standard for injectable materials. Cellulase treatment resulted in complete degradation of the hydrogels within 24h, providing a reversible corrective feature. Co-culture with human dermal fibroblasts confirmed the cytocompatibility of the gels based on DNA measurements and Live/Dead imaging. Taken together, this evidence indicates that APS-AA redox-polymerized methylcellulose hydrogels possess properties beneficial for use as soft tissue fillers. PMID:26428151

  18. Photocatalysis assisted by peroxymonosulfate and persulfate for benzotriazole degradation: effect of pH on sulfate and hydroxyl radicals.

    PubMed

    Ahmadi, Mehdi; Ghanbari, Farshid; Moradi, Mahsa

    2015-01-01

    Recently, notable attempts have been devoted to removing emerging pollutants from water resources. Benzotriazole (BTA) as an emerging pollutant has widely been detected in the aquatic environment and water resources. In the current work, peroxymonosulfate (PMS) and persulfate (PS) were added to a TiO2/UV system for BTA degradation, as electron acceptors to overcome recombination of hole and electron. Additions of PMS and PS to the photocatalysis process considerably increased removal efficiency. The rate constants of UV/TiO2/PMS, UV/TiO2/PS and UV/TiO2 were 0.0217 min(-1), 0.0152 min(-1) and 0.0052 min(-1) respectively. The results showed that pH significantly affected the UV/TiO2/PMS system while it marginally affected UV/TiO2/PS. Scavenging experiments using alcohols indicated that in acidic pH, the dominant oxidant was sulfate radical in both systems. The contribution of hydroxyl radical in BTA degradation was boosted at alkaline and neutral conditions especially in the UV/TiO2/PMS system. Moreover, other scavenging experiments implied that reaction of radicals occurred at both the catalyst surface and in solution. The mineralization results showed that PMS and PS significantly increased chemical oxygen demand and total organic carbon removal efficiencies. In general, presence of PMS in the photocatalysis process had a better performance compared to PS in terms of BTA removal and mineralization. PMID:26606105

  19. Oxidation of Aromatic Aldehydes Using Oxone

    ERIC Educational Resources Information Center

    Gandhari, Rajani; Maddukuri, Padma P.; Thottumkara, Vinod K.

    2007-01-01

    The experiment demonstrating the feasibility of using water as a solvent for organic reactions which highlights the cost and environmental benefits of its use is presented. The experiment encourages students to think in terms of the reaction mechanism of the oxidation of aldehydes knowing that potassium persulfate is the active oxidant in Oxone

  20. Oxidation of Aromatic Aldehydes Using Oxone

    ERIC Educational Resources Information Center

    Gandhari, Rajani; Maddukuri, Padma P.; Thottumkara, Vinod K.

    2007-01-01

    The experiment demonstrating the feasibility of using water as a solvent for organic reactions which highlights the cost and environmental benefits of its use is presented. The experiment encourages students to think in terms of the reaction mechanism of the oxidation of aldehydes knowing that potassium persulfate is the active oxidant in Oxone…

  1. Reduction of diffusive contaminant emissions from a dissolved source in a lower permeability layer by sodium persulfate treatment.

    PubMed

    Cavanagh, Bridget A; Johnson, Paul C; Daniels, Eric J

    2014-12-16

    Residual contamination contained in lower permeability zones is difficult to remediate and can, through diffusive emissions to adjacent higher permeability zones, result in long-term impacts to groundwater. This work investigated the effectiveness of oxidant delivery for reducing diffusive emissions from lower permeability zones. The experiment was conducted in a 1.2 m tall 1.2 m wide 6 cm thick tank containing two soil layers having 3 orders of magnitude contrast in hydraulic conductivity. The lower permeability layer initially contained dissolved methyl tert-butyl ether (MTBE) and benzene, toluene, ethylbenzene, and p-xylenes (BTEX). The treatment involved delivery of 10% w/w nonactivated sodium persulfate (Na2S2O8) solution to the high permeability layer for 14 days. The subsequent diffusion into the lower permeability layer and contaminant emission response were monitored for about 240 days. The S2O8(2-) diffused about 14 cm at 1% w/w into the lower permeability layer during the 14 day delivery and continued diffusing deeper into the layer as well as back toward the higher-lower permeability interface after delivery ceased. Over 209 days, the S2O8(2-) diffused 60 cm into the lower permeability layer, the BTEX mass and emission rate were reduced by 95-99%, and the MTBE emission rate was reduced by 63%. The overall treatment efficiency was about 60-110 g-S2O8(2-)delivered/g-hydrocarbon oxidized, with a significant fraction of the oxidant delivered likely lost by back-diffusion and not involved in hydrocarbon destruction. PMID:25386986

  2. Removal of 2-MIB and geosmin using UV/persulfate: contributions of hydroxyl and sulfate radicals.

    PubMed

    Xie, Pengchao; Ma, Jun; Liu, Wei; Zou, Jing; Yue, Siyang; Li, Xuchun; Wiesner, Mark R; Fang, Jingyun

    2015-02-01

    2-methylisoborneol (2-MIB) and geosmin are two odor-causing compounds that are difficult to remove and the cause of many consumer complaints. In this study, we assessed the degradation of 2-MIB and geosmin using a UV/persulfate process for the first time. The results showed that both 2-MIB and geosmin could be degraded effectively using this process. The process was modeled based on steady-state assumption with respect to the odor-causing compounds and either hydroxyl or sulfate radicals. The second order rate constants for 2-MIB and geosmin reacting with the sulfate radical (SO4(-)) were estimated to be (4.20.6)נ10(8)M(-1)s(-1) and (7.60.6)נ10(8)M(-1)s(-1) respectively at a pH of 7.0. The contributions of the hydroxyl radical (OH) to 2-MIB and geosmin degradation were 3.5 times and 2.0 times higher, respectively, than the contribution from SO4(-) in Milli-Q water with 2mM phosphate buffer at pH 7.0. The pseudo-first-order rate constants (ko(s)) of both 2-MIB and geosmin increased with increasing dosages of persulfate. Although pH did not affect the degradation of 2-MIB and geosmin directly, different scavenging effects of hydrogen phosphate and dihydrogen phosphate resulted in higher values of ko(s) for both 2-MIB and geosmin in acidic condition. Bicarbonate and natural organic matter (NOM) inhibited the degradation of both 2-MIB and geosmin dramatically through consuming OH and SO4(-) and were likely to be the main radical scavengers in natural waters when using UV/persulfate process to control 2-MIB and geosmin. PMID:25486622

  3. Heat-activated cooling devices: A guidebook for general audiences

    SciTech Connect

    Wiltsee, G.

    1994-02-01

    Heat-activated cooling is refrigeration or air conditioning driven by heat instead of electricity. A mill or processing facility can us its waste fuel to air condition its offices or plant; using waste fuel in this way can save money. The four basic types of heat-activated cooling systems available today are absorption cycle, desiccant system, steam jet ejector, and steam turbine drive. Each is discussed, along with cool storage and biomass boilers. Steps in determining the feasibility of heat-activated cooling are discussed, as are biomass conversion, system cost and integration, permits, and contractor selection. Case studies are given.

  4. Removal of elemental mercury from flue gas by thermally activated ammonium persulfate in a bubble column reactor.

    PubMed

    Liu, Yangxian; Wang, Qian

    2014-10-21

    In this article, a novel technique on removal of elemental mercury (Hg(0)) from flue gas by thermally activated ammonium persulfate ((NH4)(2)S(2)O(8)) has been developed for the first time. Some experiments were carried out in a bubble column reactor to evaluate the effects of process parameters on Hg(0) removal. The mechanism and kinetics of Hg(0) removal are also studied. The results show that the parameters, (NH4)(2)S(2)O(8) concentration, activation temperature and solution pH, have significant impacts on Hg(0) removal. The parameters, Hg(0), SO2 and NO concentration, only have small effects on Hg(0) removal. Hg(0) is removed by oxidations of (NH4)(2)S(2)O(8), sulfate and hydroxyl free radicals. When (NH4)(2)S(2)O(8) concentration is more than 0.1 mol/L and solution pH is lower than 9.71, Hg(0) removal by thermally activated (NH4)(2)S(2)O(8) meets a pseudo-first-order fast reaction with respect to Hg(0). However, when (NH4)(2)S(2)O(8) concentration is less than 0.1 mol/L or solution pH is higher than 9.71, the removal process meets a moderate speed reaction with respect to Hg(0). The above results indicate that this technique is a feasible method for emission control of Hg(0) from flue gas. PMID:25251199

  5. Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment.

    PubMed

    Marchesi, Massimo; Thomson, Neil R; Aravena, Ramon; Sra, Kanwartej S; Otero, Neus; Soler, Albert

    2013-09-15

    The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S?O?(2-)) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ?12. An increase in the NaOH:S?O?(2-) molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ?5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S?O?(2-) molar ratio of -7.0 0.2 was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S?O?(2-) molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system. PMID:23747463

  6. 78 FR 13891 - Persulfates From China; Institution of a Five-Year Review Concerning the Antidumping Duty Order...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-03-01

    ... From the Federal Register Online via the Government Publishing Office INTERNATIONAL TRADE... Persulfates From China AGENCY: United States International Trade Commission. ACTION: Notice. SUMMARY: The... amended at 74 FR 2847 (January 16, 2009). \\1\\ No response to this request for information is required if...

  7. Improvement of phenol photodegradation efficiency by a combined g-C3N4/Fe(III)/persulfate system.

    PubMed

    Hu, Jian-Yang; Tian, Ke; Jiang, Hong

    2016-04-01

    Graphite-like C3N4 (g-C3N4) is an efficient visible-light-driven photocatalyst commonly used in dye decolorization with very poor photocatalytic efficiency for degrading recalcitrant organic pollutants, such as phenol. In this study, we designed a g-C3N4/Fe(III)/persulfate system to significantly improve the phenol photodegradation efficacy by combining photocatalysis and light Fenton interaction. The phenol removal ratio and degradation rate of the g-C3N4/Fe(III)/persulfate system are 16.5- and 240-fold higher than those of individual g-C3N4 system. Sulfate radicals [Formula: see text] and H2O2 are detected in the g-C3N4/Fe(III)/persulfate system, suggesting that both radical decomposition and light Fenton interaction play important roles in phenol degradation. The efficient coupled photocatalytic system of g-C3N4 combined with Fe(III) and persulfate shows significant potential for application in large-scale degradation of environmental pollutants. PMID:26802260

  8. Perfluorooctanoic Acid Degradation Using UV-Persulfate Process: Modeling of the Degradation and Chlorate Formation.

    PubMed

    Qian, Yajie; Guo, Xin; Zhang, Yalei; Peng, Yue; Sun, Peizhe; Huang, Ching-Hua; Niu, Junfeng; Zhou, Xuefei; Crittenden, John C

    2016-01-19

    In this study, we investigated the destruction and by-product formation of perfluorooctanoic acid (PFOA) using ultraviolet light and persulfate (UV-PS). Additionally, we developed a first-principles kinetic model to simulate both PFOA destruction and by-product and chlorate (ClO3(-)) formation in ultrapure water (UW), surface water (SW), and wastewater (WW). PFOA degradation was significantly suppressed in the presence of chloride and carbonate species and did not occur until all the chloride was converted to ClO3(-) in UW and for low DOC concentrations in SW. The model was able to simulate the PS decay, pH changes, radical concentrations, and ClO3(-) formation for UW and SW. However, our model was unable to simulate PFOA degradation well in WW, possibly from PS activation by NOM, which in turn produced sulfate radicals. PMID:26686982

  9. Chemical modification of chitin by grafting with polystyrene using ammonium persulfate initiator.

    PubMed

    Abu Naim, Ahmedy; Umar, Abdulganiyu; Sanagi, Mohd Marsin; Basaruddin, Noraimi

    2013-11-01

    Chitin was successfully grafted with polystyrene by free radical mechanism using ammonium persulfate (APS) initiator. The reaction was carried out in aqueous medium. The effect of pH, chitin:monomer weight ratio, APS, reaction time and reaction temperature were investigated. The results showed that the optimum conditions for grafting of polystyrene were found as follows: pH 7, chitin:monomer weight ratio of 1:3, 0.4 g of APS, reaction temperature of 60 C and reaction time 2 h. The graft copolymer was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA) and differential scanning electron microscopy (DSC). Gel permeation chromatography (GPC) analysis carried out on the hydrolyzed graft copolymer showed that the Mn and Mw were 6.339510(4) g/mol and 1.6928310(5) g/mol, respectively, with polydispersity index of 2.7. PMID:24053848

  10. Combining in situ chemical oxidation, stabilization, and anaerobic bioremediation in a single application to reduce contaminant mass and leachability in soil.

    PubMed

    Cassidy, Daniel P; Srivastava, Vipul J; Dombrowski, Frank J; Lingle, James W

    2015-10-30

    Laboratory batch reactors were maintained for 32 weeks to test the potential for an in situ remedy that combines chemical oxidation, stabilization, and anaerobic bioremediation in a single application to treat soil from a manufactured gas plant, contaminated with polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). Portland cement and slaked lime were used to activate the persulfate and to stabilize/encapsulate the contaminants that were not chemically oxidized. Native sulfate-reducing bacteria degraded residual contaminants using the sulfate left after persulfate activation. The ability of the combined remedy to reduce contaminant mass and leachability was compared with NaOH-activated persulfate, stabilization, and sulfate-reducing bioremediation as stand-alone technologies. The stabilization amendments increased pH and temperature sufficiently to activate the persulfate within 1 week. Activation with both stabilization amendments and NaOH removed between 55% and 70% of PAH and BTEX. However, combined persulfate and stabilization significantly reduced the leachability of residual BTEX and PAH compared with NaOH activation. Sulfide, 2-naphthoic acid, and the abundance of subunit A of the dissimilatory sulfite reductase gene (dsrA) were used to monitor native sulfate-reducing bacteria, which were negatively impacted by activated persulfate, but recovered completely within weeks. PMID:26093352

  11. Friedel-Crafts Amidoalkylation via Thermolysis and Oxidative Photocatalysis

    PubMed Central

    Dai, Chunhui; Meschini, Francesco; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

    2012-01-01

    Friedel-Crafts amidoalkylation was achieved by oxidation of dialkylamides using persulfate (S2O82?) in the presence of the visible light catalyst, Ru(bpy)3Cl2, at room temperature, via a reactive N-acyliminium intermediate. Alternatively, mild heating of the dialkylamides and persulfate afforded a metal and Lewis acid-free Friedel-Crafts amidoalkylation. Alcohols and electronrich arenes served as effective nucleophiles, forming new CO or CC bonds. In general, photocatalysis provided higher yields and better selectivities. PMID:22458307

  12. Activation of persulfate/copper by hydroxylamine via accelerating the cupric/cuprous redox couple.

    PubMed

    Zhou, Peng; Zhang, Jing; Liang, Juan; Zhang, Yongli; Liu, Ya; Liu, Bei

    2016-01-01

    Cuprous copper [Cu(I)] reacts with sodium persulfate (PDS) to generate sulfate radical SO4(-)•, but it has been seldom investigated owing to its instability and difficulty in dissolving it. This study proposes a new method to regenerate Cu(I) from cupric copper [Cu(II)] by addition of hydroxylamine (HA) to induce the continuous production of radicals through active PDS, and investigates the resulting enhanced methyl orange (MO) degradation efficiency and mechanism in the new system. HA accelerated the degradation of MO markedly in the pH range from 6.0 to 8.0 in the HA/Cu(II)/PDS process. Both SO4(-)• and hydroxyl radicals (•OH) were considered as the primary reactive radicals in the process. The MO degradation in the HA/Cu(II)/PDS process can be divided into three stages: the fast stage, the transitory stage, and the low stage. MO degradation was enhanced with increased dosage of PDS. Although high dosage of HA could accelerate the transformation of the Cu(II)/Cu(I) cycle to produce more reactive radicals, excess HA can quench the reactive radicals. This study indicates that through a copper-redox cycling mechanism by HA, the production of SO4(-)• and •OH can be strongly enhanced, and the effective pH range can be expanded to neutral conditions. PMID:26877030

  13. Kinetics and mechanism investigation on the destruction of oxytetracycline by UV-254nm activation of persulfate.

    PubMed

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

    2016-03-15

    Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (kobs) was found to be the highest at near neutral pH conditions (pH 5.5-8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu(2+). Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO4(-) reaction including hydroxylation (+16Da), demethylation (-14Da), decarbonylation (-28Da) and dehydration (-18Da). This study suggests that UV-254nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC. PMID:26686482

  14. Degradation of flumequine in aqueous solution by persulfate activated with common methods and polyhydroquinone-coated magnetite/multi-walled carbon nanotubes catalysts.

    PubMed

    Feng, Mingbao; Qu, Ruijuan; Zhang, Xiaoling; Sun, Ping; Sui, Yunxia; Wang, Liansheng; Wang, Zunyao

    2015-11-15

    In recent years, flumequine (FLU) has been ubiquitously detected in surface waters and municipal wastewaters. In light of its potential negative impacts to aquatic species, growing concern has been arisen for the removal of this antibiotic from natural waters. In this study, the kinetics, degradation mechanisms and pathways of aqueous FLU by persulfate (PS) oxidation were systematically determined. Three common activation methods, including heat, Fe(2+) and Cu(2+), and a novel heterogeneous catalyst, namely, polyhydroquinone-coated magnetite/multi-walled carbon nanotubes (Fe3O4/MWCNTs/PHQ), were investigated to activate PS for FLU removal. It was found that these three common activators enhanced FLU degradation obviously, while several influencing factors, such as solution pH, inorganic ions (especially HCO3(-) at 5 mmol/L) and dissolved organic matter extracts, exerted their different effects on FLU removal. The catalysts were characterized, and an efficient catalytic degradation performance, high stability and excellent reusability were observed. The measured total organic carbon levels suggested that FLU can be effectively mineralized by using the catalysts. Radical mechanism was studied by combination of the quenching tests and electron paramagnetic resonance analysis. It was assumed that sulfate radicals predominated in the activation of PS with Fe3O4/MWCNTs/PHQ for FLU removal, while hydroxyl radicals also contributed to the catalytic oxidation process. In addition, a total of fifteen reaction intermediates of FLU were identified, from which two possible pathways were proposed involving hydroxylation, decarbonylation and ring opening. Overall, this study represented a systematical evaluation regarding the transformation process of FLU by PS, and showed that the heterogeneous catalysts can efficiently activate PS for FLU removal from the water environment. PMID:26281959

  15. Investigation of the toxicity of common oxidants used in advanced oxidation processes and their quenching agents.

    PubMed

    Olmez-Hanci, Tugba; Arslan-Alaton, Idil; Dursun, Duygu

    2014-08-15

    The inhibitory effect of commonly known oxidants and their quenching agents was investigated by employing a battery of toxicity tests. Hydrogen peroxide toxicity could be effectively eliminated by the enzyme catalase, whereas sodium thiosulfate and ascorbic acid were recommended as suitable quenching agents for the removal of the oxidants persulfate and peroxymonosulfate in the Vibrio fischeri bioassays. None of the studied quenching agents was found to be suitable for persulfate and peroxymonosulfate in the Daphnia magna bioassays since high inhibitory effects were obtained for both oxidants. In the case of Pseudokirchneriella subcapitata, manganese dioxide powder should be used as an alternative quenching agent to catalase, since this enzyme exhibited a highly toxic effect towards these microalgae. Sodium sulfite, which is extensively used as a quenching agent, was not appropriate for quenching peroxymonosulfate in all studied bioassays. PMID:24996151

  16. Photocatalytic Synthesis of Dihydrobenzofurans by Oxidative [3+2] Cycloaddition of Phenols**

    PubMed Central

    Blum, Travis R.; Zhu, Ye; Nordeen, Sarah A.; Yoon, Tehshik P.

    2014-01-01

    We report a protocol for oxidative [3+2] cycloadditions of phenols and alkenes applicable to the modular synthesis of a large family of dihydrobenzofuran natural products. Visible light-activated transition metal photocatalysis enables the use of ammonium persulfate as an easily handled, benign terminal oxidant. The broad range of organic substrates that are readily oxidized by photoredox catalysis suggests that this strategy may be applicable to a variety of useful oxidative transformations. PMID:25155300

  17. In-Situ Chemical Reduction and Oxidation of VOCs in Groundwater: Groundwater Treatability Studies

    NASA Technical Reports Server (NTRS)

    Keith, Amy; Glasgow, Jason; McCaleh, Rececca C. (Technical Monitor)

    2001-01-01

    This paper presents NASA Marshall Space Flight Center's treatability studies for volatile organic compounds in groundwater. In-Situ groundwater treatment technologies include: 1) Chemical Reduction(Ferox); 2) Chemical Oxidation (Fenton Reagents, Permanganate, and Persulfate); and 3) Thermal (Dynamic Underground Stripping, Six-Phase Heating). This paper is presented in viewgraph form.

  18. Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

    EPA Science Inventory

    In-situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming ground-water contaminants into less harmful byproducts. Due to oxidant persistence, ground water samples collected at hazardous waste sites may contain o...

  19. Microbial dynamics during and after in situ chemical oxidation of chlorinated solvents.

    PubMed

    Sutton, Nora B; Atashgahi, Siavash; van der Wal, Jurgen; Wijn, Geert; Grotenhuis, Tim; Smidt, Hauke; Rijnaarts, Huub H M

    2015-01-01

    In situ chemical oxidation (ISCO) followed by a bioremediation step is increasingly being considered as an effective biphasic technology. Information on the impact of chemical oxidants on organohalide respiring bacteria (OHRB), however, is largely lacking. Therefore, we used quantitative PCR (qPCR) to monitor the abundance of OHRB (Dehalococcoides mccartyi, Dehalobacter, Geobacter, and Desulfitobacterium) and reductive dehalogenase genes (rdh; tceA, vcrA, and bvcA) at a field location contaminated with chlorinated solvents prior to and following treatment with sodium persulfate. Natural attenuation of the contaminants tetrachloroethene (PCE) and trichloroethene (TCE) observed prior to ISCO was confirmed by the distribution of OHRB and rdh genes. In wells impacted by persulfate treatment, a 1 to 3 order of magnitude reduction in the abundances of OHRB and complete absence of rdh genes was observed 21 days after ISCO. Groundwater acidification (pH<3) and increase in the oxidation reduction potential (>500 mV) due to persulfate treatment were significant and contributed to disruption of the microbial community. In wells only mildly impacted by persulfate, a slight stimulation of the microbial community was observed, with more than 1 order of magnitude increase in the abundance of Geobacter and Desulfitobacterium 36 days after ISCO. After six months, regeneration of the OHRB community occurred, however, neither D. mccartyi nor any rdh genes were observed, indicating extended disruption of biological natural attenuation (NA) capacity following persulfate treatment. For full restoration of biological NA activity, additional time may prove sufficient; otherwise addition electron donor amendment or bioaugmentation may be required. PMID:24898385

  20. Potential for in situ chemical oxidation of acid extractable organics in oil sands process affected groundwater.

    PubMed

    Sohrabi, V; Ross, M S; Martin, J W; Barker, J F

    2013-11-01

    The process of bitumen extraction from oil sands in Alberta, Canada leads to an accumulation of toxic acid-extractable organics (AEOs) in oil sands process water (OSPW). Infiltration of OSPW from tailings ponds and from their retaining sand dykes and subsequent transport towards surface water has occurred. Given the apparent lack of significant natural attenuation of AEOs in groundwater, remediation may be required. This laboratory study evaluates the potential use of unactivated persulfate and permanganate as in situ oxidation agents for remediation of AEOs in groundwater. Naphthenic acids (NAs; CnH2n+zO2), which are a component of the acutely toxic AEOs, were degraded by both oxidants in OSPW samples. Permanganate oxidation yielded some residual dissolved organic carbon (DOC) whereas persulfate mineralized the AEO compounds with less residual DOC. Acid-extractable organics from oxidized OSPW had essentially no Microtox toxicity. PMID:24054134

  1. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory : evaluation of alkaline persulfate digestion as an alternative to Kjeldahl digestion for determination of total and dissolved nitrogen and phosphorus in water

    USGS Publications Warehouse

    Patton, Charles J.; Kryskalla, Jennifer R.

    2003-01-01

    Alkaline persulfate digestion was evaluated and validated as a more sensitive, accurate, and less toxic alternative to Kjeldahl digestion for routine determination of nitrogen and phosphorus in surface- and ground-water samples in a large-scale and geographically diverse study conducted by U.S. Geological Survey (USGS) between October 1, 2001, and September 30, 2002. Data for this study were obtained from about 2,100 surface- and ground-water samples that were analyzed for Kjeldahl nitrogen and Kjeldahl phosphorus in the course of routine operations at the USGS National Water Quality Laboratory (NWQL). These samples were analyzed independently for total nitrogen and total phosphorus using an alkaline persulfate digestion method developed by the NWQL Methods Research and Development Program. About half of these samples were collected during nominally high-flow (April-June) conditions and the other half were collected during nominally low-flow (August-September) conditions. The number of filtered and whole-water samples analyzed from each flow regime was about equal.By operational definition, Kjeldahl nitrogen (ammonium + organic nitrogen) and alkaline persulfate digestion total nitrogen (ammonium + nitrite + nitrate + organic nitrogen) are not equivalent. It was necessary, therefore, to reconcile this operational difference by subtracting nitrate + nitrite concentra-tions from alkaline persulfate dissolved and total nitrogen concentrations prior to graphical and statistical comparisons with dissolved and total Kjeldahl nitrogen concentrations. On the basis of two-population paired t-test statistics, the means of all nitrate-corrected alkaline persulfate nitrogen and Kjeldahl nitrogen concentrations (2,066 paired results) were significantly different from zero at the p = 0.05 level. Statistically, the means of Kjeldahl nitrogen concentrations were greater than those of nitrate-corrected alkaline persulfate nitrogen concentrations. Experimental evidence strongly suggests, however, that this apparent low bias resulted from nitrate interference in the Kjeldahl digestion method rather than low nitrogen recovery by the alkaline persulfate digestion method. Typically, differences between means of Kjeldahl nitrogen and nitrate-corrected alkaline persulfate nitrogen in low-nitrate concentration (< 0.1 milligram nitrate nitrogen per liter) subsets of filtered surface- and ground-water samples were statistically equivalent to zero at the p =level.Paired analytical results for dissolved and total phosphorus in Kjeldahl and alkaline persulfate digests were directly comparable because both digestion methods convert all forms of phosphorus in water samples to orthophosphate. On the basis of two-population paired t-test statistics, the means of all Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations (2,093 paired results) were not significantly different from zero at the p = 0.05 level. For some subsets of these data, which were grouped according to water type and flow conditions at the time of sample collection, differences between means of Kjeldahl phosphorus and alkaline persulfate phosphorus concentrations were not equivalent to zero at the p = 0.05 level. Differences between means of these subsets, however, were less than the method detection limit for phosphorus (0.007 milligram phosphorus per liter) by the alkaline persulfate digestion method, and were therefore analytically insignificant.This report provides details of the alkaline persulfate digestion procedure, interference studies, recovery of various nitrogen- and phosphorus-containing compounds, and other analytical figures of merit. The automated air-segmented continuous flow methods developed to determine nitrate and orthophosphate in the alkaline persulfate digests also are described. About 125 microliters of digested sample are required to determine nitrogen and phosphorus in parallel at a rate of about 100 samples per hour with less than 1-percent sample in

  2. Pentachlorophenol removal from aqueous solutions by microwave/persulfate and microwave/H2O2: a comparative kinetic study

    PubMed Central

    2014-01-01

    Pentachlorophenol (PCP) is one of the most fungicides and pesticides used in wood protection. Poisoning from PCP may be happened in dermal absorption, and respiration or ingestion. With regard to health and environmental effects of PCP, many methods were studied for its removal. Microwave assisted other methods are environmental friendly, safety, and economical method, therefore, in this study; a modified domestic microwave assisted hydrogen peroxide (MW/H2O2) and sodium persulfate (MW/SPS) was used for PCP removal from aqueous solutions. PCP removal rate was measured under different factors such as pH, energy intensity, SPS, H2O2 concentration, Tert- butyl alcohol (TBA) and chemical oxygen demand (COD). The concentration changes of PCP were determined using spectrophotometer and HPLC spectra, respectively. The best removal PCP rate obtained in condition of pH of 11, 0.02 mol L?1 of SPS, 0.2 mol L?1 of H2O2 and energy intensity of 600 W. Moreover, COD removals in MW/H2O2 and MW/SPS process were 83% and 94%, respectively, also TBA test decreased 15% and 3% of PCP removal in MW/SPS and MW/H2O2 processes respectively. Experimental results indicated that sulfate radical was stronger than hydroxyl radical and examinations order reaction was in first order. In this study, was cleared that MW/SPS process was more effective than MW/H2O2 process in PCP removal. PMID:25018879

  3. Degradation of methyl orange by ozone in the presence of ferrous and persulfate ions in a rotating packed bed.

    PubMed

    Ge, Deming; Zeng, Zequan; Arowo, Moses; Zou, Haikui; Chen, Jianfeng; Shao, Lei

    2016-03-01

    This work investigated the degradation of methyl orange by ozone in the presence of ferrous and persulfate ions (O3/Fe(2+)/S2O8(2-)) in a rotating packed bed. The effects of various operating parameters such as initial pH, rotational speed, gas-liquid ratio, ozone inlet concentration and reaction temperature on the degradation rate of methyl orange were studied with an aim to optimize the operation conditions. Results reveal that the degradation rate increased with an increase in rotational speed, gas-liquid ratio and ozone inlet concentration, and reached a maximum at 25 °C and initial pH 4. Contrast experiments involving ozone and ferrous ions (O3/Fe(2+)) were also carried out, and the results show approximately 10% higher degradation rate and COD removal in the O3/Fe(2+)/S2O8(2-) process than in the O3/Fe(2+) process. Additionally, the intermediates of the degradation process were analyzed to ascertain the degradation products. PMID:26741546

  4. Oxidative Alkaline leaching of Americium from simulated high-level nuclear waste sludges

    SciTech Connect

    Reed, Wendy A.; Garnov, Alexander Yu.; Rao, Linfeng; Nash, Kenneth L.; Bond, Andrew H.

    2004-01-23

    Oxidative alkaline leaching has been proposed to pre-treat the high-level nuclear waste sludges to remove some of the problematic (e.g., Cr) and/or non-radioactive (e.g., Na, Al) constituents before vitrification. It is critical to understand the behavior of actinides, americium and plutonium in particular, in oxidative alkaline leaching. We have studied the leaching behavior of americium from four different sludge simulants (BiPO{sub 4}, BiPO{sub 4 modified}, Redox, PUREX) using potassium permanganate and potassium persulfate in alkaline solutions. Up to 60% of americium sorbed onto the simulants is leached from the sludges by alkaline persulfate and permanganate. The percentage of americium leached increases with [NaOH] (between 1.0 and 5.0 M). The initial rate of americium leaching by potassium persulfate increases in the order BiPO{sub 4} sludge < Redox sludge < PUREX sludge. The data are most consistent with oxidation of Am{sup 3+} in the sludge to either AmO{sub 2}{sup +} or AmO{sub 2}{sup 2+} in solution. Though neither of these species is expected to exhibit long-term stability in solution, the potential for mobilization of americium from sludge samples would have to be accommodated in the design of any oxidative leaching process for real sludge samples.

  5. Demonstration of the Enhanced Disinfection of E. coli Water Contamination by Associated Solar Irradiation with Potassium Persulfate

    PubMed Central

    GHANIZADEH, Ghader; NASERI ARA, Ali; ESMAILI, Davoud; MASOUMBEIGI, Hossein

    2015-01-01

    Background: Tremendous amount of researches have investigated the issue of water photodisnfection. The aim of this research is to illustrate the influences of bacterial density, turbidity, exposure time and potassium persulfate (KPS) dosage on the efficacy of associated solar disinfection (SODIS) with KPS for E. coli (ATCC: 25922) eradication as an efficient and inexpensive process. Methods: Desired bacterial density and turbidity was achieved by spiking of 0.5 Mc Farland (1.5×108 cell/ml) and sterile soil slurry in 1 liter of the commercially bottled water. Results: The highest value of UVA solar irradiation measured at 13.30 p.m was 5510 μW/Cm2. Increase of bacterial density from 1000 to 1500 cell/ml led to an increase in disinfection lapse time, except in 2 mMol/l KPS. Spiking of 0.1 mMol/l of KPS was not effective; however, increase of KPS dosage from 0.1 mMol/l to 0.7, 1.5 and 2 mMol/l led to the enhancement of disinfection time from 4 h to 3 h and 1 h, respectively. For bacterial density of 1000 cell/ml, increasing KPS dosage up to 0.7 mMol/l had no improved effect; however, beyond this dosage the disinfection time decreased to 1 h. Without KPS and up to 150 NTU within 4 h exposure time, E. coli disinfection was completed. In 2 mMol/l KPS and 1000 and 1500 cell/ml, the 2 h contact time was sufficient up to 150 and 100 NTU, respectively; moreover, complete disinfection was not achieved at higher turbidity. Conclusion: Association of KPS with SODIS can lead to decreasing of water disinfection time. PMID:26576351

  6. Novel High-Viscosity Polyacrylamidated Chitosan for Neural Tissue Engineering: Fabrication of Anisotropic Neurodurable Scaffold via Molecular Disposition of Persulfate-Mediated Polymer Slicing and Complexation

    PubMed Central

    Kumar, Pradeep; Choonara, Yahya E.; du Toit, Lisa C.; Modi, Girish; Naidoo, Dinesh; Pillay, Viness

    2012-01-01

    Macroporous polyacrylamide-grafted-chitosan scaffolds for neural tissue engineering were fabricated with varied synthetic and viscosity profiles. A novel approach and mechanism was utilized for polyacrylamide grafting onto chitosan using potassium persulfate (KPS) mediated degradation of both polymers under a thermally controlled environment. Commercially available high molecular mass polyacrylamide was used instead of the acrylamide monomer for graft copolymerization. This grafting strategy yielded an enhanced grafting efficiency (GE = 92%), grafting ratio (GR = 263%), intrinsic viscosity (IV = 5.231 dL/g) and viscometric average molecular mass (MW = 1.63 106 Da) compared with known acrylamide that has a GE = 83%, GR = 178%, IV = 3.901 dL/g and MW = 1.22 106 Da. Image processing analysis of SEM images of the newly grafted neurodurable scaffold was undertaken based on the polymer-pore threshold. Attenuated Total Reflectance-FTIR spectral analyses in conjugation with DSC were used for the characterization and comparison of the newly grafted copolymers. Static Lattice Atomistic Simulations were employed to investigate and elucidate the copolymeric assembly and reaction mechanism by exploring the spatial disposition of chitosan and polyacrylamide with respect to the reactional profile of potassium persulfate. Interestingly, potassium persulfate, a peroxide, was found to play a dual role initially degrading the polymerspolymer slicingthereby initiating the formation of free radicals and subsequently leading to synthesis of the high molecular mass polyacrylamide-grafted-chitosan (PAAm-g-CHT)polymer complexation. Furthermore, the applicability of the uniquely grafted scaffold for neural tissue engineering was evaluated via PC12 neuronal cell seeding. The novel PAAm-g-CHT exhibited superior neurocompatibility in terms of cell infiltration owing to the anisotropic porous architecture, high molecular mass mediated robustness, superior hydrophilicity as well as surface charge due to the acrylic chains. Additionally, these results suggested that the porous PAAm-g-CHT scaffold may act as a potential neural cell carrier. PMID:23203044

  7. Influence of persulfate ions on the removal of phenol in aqueous solution using electron beam irradiation.

    PubMed

    Boukari, Sahidou O B; Pellizzari, Fabien; Karpel Vel Leitner, Nathalie

    2011-01-30

    The removal of phenol (Co = 100 ?M) during electron beam irradiation was studied in pure water and in the presence of HCO(3)(-) and Br(-) ions. It was found that the introduction of S(2)O(8)(2-) ions (1mM), by generating SO(4)(-) radicals increases the radiation yield of phenol removal. 90% removal of phenol was obtained with radiation doses 600 and 1200 Gy with and without S(2)O(8)(2-) ions respectively. This system induced smaller oxygen consumption with smaller concentration of catechol and hydroquinone found in the solution. HCO(3)(-) and Br(-) have an inhibiting effect in the presence as in the absence of S(2)O(8)(2-). In most cases, the introduction of S(2)O(8)(2-) ions in water radiolysis system can advantageously increase the yield of organic compounds removal by oxidation. PMID:21093981

  8. Activating persulfate by Fe? coupling with weak magnetic field: performance and mechanism.

    PubMed

    Xiong, Xinmei; Sun, Bo; Zhang, Jing; Gao, Naiyun; Shen, Jimin; Li, Jialing; Guan, Xiaohong

    2014-10-01

    Weak magnetic field (WMF) and Fe(0) were proposed to activate PS synergistically (WMF-Fe(0)/PS) to degrade dyes and aromatic contaminants. The removal rates of orange G (OG) by WMF-Fe(0)/PS generally decreased with increasing initial pH (3.0-10.0) and increased with increasing Fe(0) (0.5-3.0 mM) or PS dosages (0.5-3.0 mM). Compared to its counterpart without WMF, the WMF-Fe(0)/PS process could induce a 5.4-28.2 fold enhancement in the removal rate of OG under different conditions. Moreover, the application of WMF significantly enhanced the decolorization rate and the mineralization of OG. The degradation rates of caffeine, 4-nitrophenol, benzotriazole and diuron by Fe(0)/PS were improved by 2.1-11.1 fold due to the superimposed WMF. Compared to many other sulfate radical-based advanced oxidation technologies under similar reaction conditions, WMF-Fe(0)/PS technology could degrade selected organic contaminants with much greater rates. Sulfate radical was identified to be the primary radical species responsible for the OG degradation at pH 7.0 in WMF-Fe(0)/PS process. This study unraveled that the presence of WMF accelerated the corrosion rate of Fe(0) and thus promoted the release of Fe(2+), which induced the increased production of sulfate radicals from PS and promoted the degradation of organic contaminants. Employing WMF to enhance oxidation capacity of Fe(0)/PS is a novel, efficient, promising and environmental-friendly method since it does not need extra energy and costly reagents. PMID:24934323

  9. A pain-inducing centipede toxin targets the heat activation machinery of nociceptor TRPV1

    NASA Astrophysics Data System (ADS)

    Yang, Shilong; Yang, Fan; Wei, Ningning; Hong, Jing; Li, Bowen; Luo, Lei; Rong, Mingqiang; Yarov-Yarovoy, Vladimir; Zheng, Jie; Wang, Kewei; Lai, Ren

    2015-09-01

    The capsaicin receptor TRPV1 ion channel is a polymodal nociceptor that responds to heat with exquisite sensitivity through an unknown mechanism. Here we report the identification of a novel toxin, RhTx, from the venom of the Chinese red-headed centipede that potently activates TRPV1 to produce excruciating pain. RhTx is a 27-amino-acid small peptide that forms a compact polarized molecule with very rapid binding kinetics and high affinity for TRPV1. We show that RhTx targets the channel's heat activation machinery to cause powerful heat activation at body temperature. The RhTx-TRPV1 interaction is mediated by the toxin's highly charged C terminus, which associates tightly to the charge-rich outer pore region of the channel where it can directly interact with the pore helix and turret. These findings demonstrate that RhTx binding to the outer pore can induce TRPV1 heat activation, therefore providing crucial new structural information on the heat activation machinery.

  10. A pain-inducing centipede toxin targets the heat activation machinery of nociceptor TRPV1

    PubMed Central

    Yang, Shilong; Yang, Fan; Wei, Ningning; Hong, Jing; Li, Bowen; Luo, Lei; Rong, Mingqiang; Yarov-Yarovoy, Vladimir; Zheng, Jie; Wang, KeWei; Lai, Ren

    2015-01-01

    The capsaicin receptor TRPV1 ion channel is a polymodal nociceptor that responds to heat with exquisite sensitivity through an unknown mechanism. Here we report the identification of a novel toxin, RhTx, from the venom of the Chinese red-headed centipede that potently activates TRPV1 to produce excruciating pain. RhTx is a 27-amino-acid small peptide that forms a compact polarized molecule with very rapid binding kinetics and high affinity for TRPV1. We show that RhTx targets the channel's heat activation machinery to cause powerful heat activation at body temperature. The RhTx–TRPV1 interaction is mediated by the toxin's highly charged C terminus, which associates tightly to the charge-rich outer pore region of the channel where it can directly interact with the pore helix and turret. These findings demonstrate that RhTx binding to the outer pore can induce TRPV1 heat activation, therefore providing crucial new structural information on the heat activation machinery. PMID:26420335

  11. A pain-inducing centipede toxin targets the heat activation machinery of nociceptor TRPV1.

    PubMed

    Yang, Shilong; Yang, Fan; Wei, Ningning; Hong, Jing; Li, Bowen; Luo, Lei; Rong, Mingqiang; Yarov-Yarovoy, Vladimir; Zheng, Jie; Wang, KeWei; Lai, Ren

    2015-01-01

    The capsaicin receptor TRPV1 ion channel is a polymodal nociceptor that responds to heat with exquisite sensitivity through an unknown mechanism. Here we report the identification of a novel toxin, RhTx, from the venom of the Chinese red-headed centipede that potently activates TRPV1 to produce excruciating pain. RhTx is a 27-amino-acid small peptide that forms a compact polarized molecule with very rapid binding kinetics and high affinity for TRPV1. We show that RhTx targets the channel's heat activation machinery to cause powerful heat activation at body temperature. The RhTx-TRPV1 interaction is mediated by the toxin's highly charged C terminus, which associates tightly to the charge-rich outer pore region of the channel where it can directly interact with the pore helix and turret. These findings demonstrate that RhTx binding to the outer pore can induce TRPV1 heat activation, therefore providing crucial new structural information on the heat activation machinery. PMID:26420335

  12. [The significance of heat activation for the testing of bioindicators on surviving microorganisms exposed to formaldehyde].

    PubMed

    Spicher, G; Borchers, U

    1988-05-01

    Heat activation is a special phenomenon: After an additional heat treatment, a larger share of the bacterial spores which had been exposed to formaldehyde proves to be viable than without such heat activation. Model studies have been performed to test the effects of heat activation on the examination of bioindicators and test objects for surviving organisms. Test objects (cotton threads of 1 cm length) contaminated with spores of Bacillus stearothermophilus were used for these trials. The test objects were exposed to a 2% formaldehyde solution at 60 degrees C. After periods of action of 30, 45, 60 ... and 105 min, formaldehyde adhering to the test objects was neutralized. For testing these objects for surviving organisms, they were placed into a nutrient medium and incubated for 40 days at 56 degrees C. The investigation consisted of 2 parallel test series which only differed in one single point. In one series, the test objects were incubated at 56 degrees C as soon as they had been placed into the nutrient solution. In the other series, the test objects were exposed to a temperature of 95 degrees C for 1 h (heat activation) before starting incubation. The culture tubes were checked daily to see whether signs of growth (turbidity and deposits) could be observed. The frequencies of test objects with surviving organisms depending on the period of action of formaldehyde and the period of incubation determined in this way are based on the examination of 72 test objects each. Without heat activation, the share of test objects on which surviving test organisms could be detected, increased slowly with the period of incubation. Only after 30 days the counts did not increase any more when continuing the incubation (cf. Fig. 1). In the test series in which the spores had been subjected to heat activation before the incubation period, useful results were obtained already after 3 days. They only changed slightly when incubation was continued. Moreover, the frequency of test objects on which surviving organisms could be detected was always considerably higher than without heat activation. When the frequency of test objects with surviving organisms was plotted against the period of action of formaldehyde (cf. Fig. 2A), S-shaped curves resulted.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:3138833

  13. Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

    PubMed

    Sharma, Jyoti; Mishra, I M; Kumar, Vineet

    2015-06-01

    This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254nm and 40W power (Io=1.26נ10(-6)Es(-1)) at its natural pH and a temperature of 293C. With an optimum persulfate concentration of 1.26mM, the UV/S2O8(2-) process resulted in ?95% BPA removal after 240min of irradiation. The optimum BPA removal was found to be ?85% with a H2O2 concentration of 11.76mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307kWh/m(3)) EE/O in comparison to UV/H2O2 system (509kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system. PMID:25889275

  14. Nitrogen-Doped Reduced Graphene Oxide as a Bifunctional Material for Removing Bisphenols: Synergistic Effect between Adsorption and Catalysis.

    PubMed

    Wang, Xiaobo; Qin, Yanlei; Zhu, Lihua; Tang, Heqing

    2015-06-01

    Nitrogen modified reduced graphene oxide (N-RGO) was prepared by a hydrothermal method. The nitrogen modification enhanced its adsorption and catalysis ability. For an initial bisphenol concentration of 0.385 mmol L(-1), the adsorption capacity of N-RGO was evaluated as 1.56 and 1.43 mmol g(-1) for bisphenol A (BPA) and 1.43 mmol g(-1) for bisphenol F (BPF), respectively, both of which were about 1.75 times that (0.90 and 0.84 mmol g(-1)) on N-free RGO. N-RGO could activate persulfate, producing strong oxidizing sulfate radicals. The apparent degradation rate constant of BPA on N-RGO was 0.71 min(-1), being about 700 times that (0.001 min(-1)) on N-free RGO. In mixtures of various phenols, the degradation rate constant of each phenol was linearly increased with its adsorption capacity. A simultaneous use of N-RGO and persulfate yielded fast and efficient removal of bisphenols. The use of N-RGO (120 mg L(-1)) and persulfate (0.6 mmol L(-1)) almost completely removed the added bisphenols (0.385 mmol L(-1)) at pH 6.6 within 17 min. A mechanism study indicated that the adsorption enriched the pollutant, and the catalytically generated sulfate radicals rapidly degrade the adsorbed pollutant, accelerating in turn the adsorption of residual pollutant. PMID:25943004

  15. Carbon isotopic analysis of dissolved organic carbon in produced water brines by wet chemical oxidation and cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Conaway, C.; Kharaka, Y. K.; Saad, N.

    2012-12-01

    We have adapted the Picarro iTOC CRDS isotope analyzer for analysis of produced water brines via wet chemical persulfate oxidation. In particular, we developed strategies and techniques for overcoming the limitation imposed by low oxidation efficiencies due to the chloride ion interference with persulfate oxidation. These techniques are important for understanding the origin of dissolved organic carbon in subsurface fluids from oilfields, as a tracer of fracking fluids in groundwater, and in interpreting changes in groundwater DOC as a result of microbial activity including oil biodegradation or microbially enhanced oil recovery. We describe the limitations of this new instrument for the analysis of DOC in brines including sample requirements, matrix effects, and the effect of DOC composition on reaction efficiency and isotopic measurements. We compare strategies including anion exchange cartridges, persulfate reactant concentrations, and reaction time. The CRDS analysis of DOC in brines is a useful tool for understanding the origin and fate of DOC and is a potentially powerful tool to identifiy evidence of contamination due to hydrofracturing chemicals that have a distinctive carbon isotopic signature relative to natural brine.

  16. Exploration of the Role of Heat Activation in Enhancing Serpentine Carbon Sequestration Reactions

    SciTech Connect

    McKelvy, M.J.; Chizmeshya, A.V.G.; Diefenbacher, J.; Bearat, H.; Wolf, G.

    2005-03-29

    As compared with other candidate carbon sequestration technologies, mineral carbonation offers the unique advantage of permanent disposal via geologically stable and environmentally benign carbonates. The primary challenge is the development of an economically viable process. Enhancing feedstock carbonation reactivity is key. Heat activation dramatically enhances aqueous serpentine carbonation reactivity. Although the present process is too expensive to implement, the materials characteristics and mechanisms that enhance carbonation are of keen interest for further reducing cost. Simultaneous thermogravimetric and differential thermal analysis (TGA/DTA) of the serpentine mineral lizardite was used to isolate a series of heat-activated materials as a function of residual hydroxide content at progressively higher temperatures. Their structure and composition are evaluated via TGA/DTA, X-ray powder diffraction (including phase analysis), and infrared analysis. The meta-serpentine materials that were observed to form ranged from those with longer range ordering, consistent with diffuse stage-2 like interlamellar order, to an amorphous component that preferentially forms at higher temperatures. The aqueous carbonation reaction process was investigated for representative materials via in situ synchrotron X-ray diffraction. Magnesite was observed to form directly at 15 MPa CO{sub 2} and at temperatures ranging from 100 to 125 C. Carbonation reactivity is generally correlated with the extent of meta-serpentine formation and structural disorder.

  17. Exploration of the role of heat activation in enhancing serpentine carbon sequestration reactions.

    PubMed

    McKelvy, Michael J; Chizmeshya, Andrew V G; Diefenbacher, Jason; Barat, Hamdallah; Wolf, George

    2004-12-15

    As compared with other candidate carbon sequestration technologies, mineral carbonation offers the unique advantage of permanent disposal via geologically stable and environmentally benign carbonates. The primary challenge is the development of an economically viable process. Enhancing feedstock carbonation reactivity is key. Heat activation dramatically enhances aqueous serpentine carbonation reactivity. Although the present process is too expensive to implement, the materials characteristics and mechanisms that enhance carbonation are of keen interest for further reducing cost. Simultaneous thermogravimetric and differential thermal analysis (TGA/DTA) of the serpentine mineral lizardite was used to isolate a series of heat-activated materials as a function of residual hydroxide content at progressively higher temperatures. Their structure and composition are evaluated via TGA/DTA, X-ray powder diffraction (including phase analysis), and infrared analysis. The meta-serpentine materials that were observed to form ranged from those with longer range ordering, consistent with diffuse stage-2 like interlamellar order, to an amorphous component that preferentially forms at higher temperatures. The aqueous carbonation reaction process was investigated for representative materials via in situ synchrotron X-ray diffraction. Magnesite was observed to form directly at 15 MPa CO2 and at temperatures ranging from 100 to 125 degrees C. Carbonation reactivity is generally correlated with the extent of meta-serpentine formation and structural disorder. PMID:15669355

  18. The heat-activated solderless passivation (HASP) technique for correcting nonpassive-fitting bars without soldering.

    PubMed

    Ford, Thomas G

    2003-01-01

    The fabrication of a cast noble alloy overdenture bar entails a variety of clinical and laboratory steps, each of which can potentially generate distortions that result in the non-passive fit of the finished product. Traditional laboratory procedures to correct the misfit of cast bars entail sectioning the bar, then reconnecting the bar segments by soldering or welding. After such procedures, research has shown that the bar may still not fit passively on the implant abutments in the patient's mouth. In addition, the overall structure of the bar would be weaker at the mended joints. The heat-activated solderless passivation (HASP) technique involves a two-step process of correcting the master cast, then attaching the cast bar to a soldering index and applying heat to relax the metal until the tensile forces of the retention screws pull the bar into a passive fit. PMID:12704951

  19. Adsorption mechanism of cationic surfactants onto acid- and heat-activated sepiolites.

    PubMed

    Sabah, E; Turan, M; Celik, M S

    2002-09-01

    Systematic adsorption tests were carried out to determine the uptake of typical quaternary amines, dodecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide and a primary amine, dodecylamine hydrochloride by sepiolite. Bottle adsorption tests conducted with untreated, acid- and heat-activated sepiolites exhibit two distinct regions. The first stage is characterized by low rate and governed through an ion exchange process between ammonium ions and magnesium ions in the octahedral sheet. The second stage is ascribed to a combination of chain-chain interactions through Van der Waals forces and ion exchange process. Despite several-fold increases in surface areas upon activation, surprisingly no improvement in adsorption is observed. The observed differences are explained on the basis of partial collapse of the sepiolite crystal structure, the removal of zeolitic and bound waters and modification of the pore size distribution of sepiolite upon treatments. PMID:12405404

  20. Direct trifluoromethylthiolation of unactivated C(sp(3))-H using silver(I) trifluoromethanethiolate and potassium persulfate.

    PubMed

    Wu, Hao; Xiao, Zhiwei; Wu, Junhui; Guo, Yong; Xiao, Ji-Chang; Liu, Chao; Chen, Qing-Yun

    2015-03-23

    A practical and efficient method for the direct trifluoromethylthiolation of unactivated C(sp(3) )?H bonds by AgSCF3 /K2 S2 O8 under mild conditions is described. The reaction has a good functional-group tolerance and good selectivity. Initial mechanistic investigations indicate that the reaction may involve a radical process in which K2 S2 O8 plays key roles in both the activation of the C(sp(3) )?H bond and the oxidation of AgSCF3 . PMID:25707945

  1. A novel three-dimensional spherical CuBi2O4 consisting of nanocolumn arrays with persulfate and peroxymonosulfate activation functionalities for 1H-benzotriazole removal

    NASA Astrophysics Data System (ADS)

    Oh, Wen-Da; Lua, Shun-Kuang; Dong, Zhili; Lim, Teik-Thye

    2015-04-01

    A novel CuBi2O4 consisting of self-assembled spherical nanocolumn arrays (CuB-H) was synthesized via a facile hydrothermal method. It was further modified by controlling the Cu : Bi ratio during synthesis to become an efficient bi-functional catalyst (CuB-2.5) activated persulfate (PS) and peroxymonosulfate (PMS) for 1H-benzotriazole (BTZ) removal. Characterization of CuB-2.5 using XRD, FESEM, FTIR, BET and XPS revealed that it was morphologically similar to CuB-H and the molecular formula, as determined from the XRD results, was Cu1.2Bi1.6O3.6 with 2.4% w/w of CuO. The CuB-2.5 catalyst exhibited superior performance for BTZ removal via PS and PMS activations over the Cu2+ (aq.), CuO, CuBi2O4 (CuB-M, microsphere) and CuB-H. The performance of CuB-2.5 was investigated at different initial PS/PMS dosages, initial catalyst loadings and initial BTZ concentrations. Interestingly, it was found that the inter- and intra-molecular hydrogen bondings play prominent roles in the BTZ removal mechanism in both the PS and PMS systems. Meanwhile, it is relatively easy to activate PMS, leading to a faster BTZ removal rate over the PS system. The intermediate products of BTZ degradation produced from the PS and PMS systems were similar, indicating a similar degradation pathway. The catalyst could still retain its morphology and can be reused multiple times.A novel CuBi2O4 consisting of self-assembled spherical nanocolumn arrays (CuB-H) was synthesized via a facile hydrothermal method. It was further modified by controlling the Cu : Bi ratio during synthesis to become an efficient bi-functional catalyst (CuB-2.5) activated persulfate (PS) and peroxymonosulfate (PMS) for 1H-benzotriazole (BTZ) removal. Characterization of CuB-2.5 using XRD, FESEM, FTIR, BET and XPS revealed that it was morphologically similar to CuB-H and the molecular formula, as determined from the XRD results, was Cu1.2Bi1.6O3.6 with 2.4% w/w of CuO. The CuB-2.5 catalyst exhibited superior performance for BTZ removal via PS and PMS activations over the Cu2+ (aq.), CuO, CuBi2O4 (CuB-M, microsphere) and CuB-H. The performance of CuB-2.5 was investigated at different initial PS/PMS dosages, initial catalyst loadings and initial BTZ concentrations. Interestingly, it was found that the inter- and intra-molecular hydrogen bondings play prominent roles in the BTZ removal mechanism in both the PS and PMS systems. Meanwhile, it is relatively easy to activate PMS, leading to a faster BTZ removal rate over the PS system. The intermediate products of BTZ degradation produced from the PS and PMS systems were similar, indicating a similar degradation pathway. The catalyst could still retain its morphology and can be reused multiple times. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01428j

  2. The Effects of Heat Activation on Bacillus Spore Germination, with Nutrients or under High Pressure, with or without Various Germination Proteins

    PubMed Central

    Luu, Stephanie; Cruz-Mora, Jose; Setlow, Barbara; Feeherry, Florence E.; Doona, Christopher J.

    2015-01-01

    Nutrient germination of spores of Bacillus species occurs through germinant receptors (GRs) in spores' inner membrane (IM) in a process stimulated by sublethal heat activation. Bacillus subtilis spores maximum germination rates via different GRs required different 75C heat activation times: 15 min for l-valine germination via the GerA GR and 4 h for germination with the l-asparagineglucosefructoseK+ mixture via the GerB and GerK GRs, with GerK requiring the most heat activation. In some cases, optimal heat activation decreased nutrient concentrations for half-maximal germination rates. Germination of spores via various GRs by high pressure (HP) of 150 MPa exhibited heat activation requirements similar to those of nutrient germination, and the loss of the GerD protein, required for optimal GR function, did not eliminate heat activation requirements for maximal germination rates. These results are consistent with heat activation acting primarily on GRs. However, (i) heat activation had no effects on GR or GerD protein conformation, as probed by biotinylation by an external reagent; (ii) spores prepared at low and high temperatures that affect spores' IM properties exhibited large differences in heat activation requirements for nutrient germination; and (iii) spore germination by 550 MPa of HP was also affected by heat activation, but the effects were relatively GR independent. The last results are consistent with heat activation affecting spores' IM and only indirectly affecting GRs. The 150- and 550-MPa HP germinations of Bacillus amyloliquefaciens spores, a potential surrogate for Clostridium botulinum spores in HP treatments of foods, were also stimulated by heat activation. PMID:25681191

  3. Heterogeneous Degradation of Organic Pollutants by Persulfate Activated by CuO-Fe3O4: Mechanism, Stability, and Effects of pH and Bicarbonate Ions.

    PubMed

    Lei, Yang; Chen, Chuh-Shun; Tu, Yao-Jen; Huang, Yao-Hui; Zhang, Hui

    2015-06-01

    Magnetic CuO-Fe3O4 composite was fabricated by a simple hydrothermal method and characterized as a heterogeneous catalyst for phenol degradation. The effects of pH and bicarbonate ions on catalytic activity were extensively evaluated in view of the practical applications. The results indicated that an increase of solution pH and the presence of bicarbonate ions were beneficial for the removal of phenol in the CuO-Fe3O4 coupled with persulfate (PS) process. Almost 100% mineralization of 0.1 mM phenol can be achieved in 120 min by using 0.3 g/L CuO-Fe3O4 and 5.0 mM PS at pH 11.0 or in the presence of 3.0 mM bicarbonate. The positive effect of bicarbonate ion is probably due to the suppression of copper leaching as well as the formation of Cu(III). The reuse of catalyst at pH0 11.0 and 5.6 showed that the catalyst remains a high level of stability at alkaline condition (e.g., pH0 11.0). On the basis of the characterization of catalyst, the results of metal leaching and EPR studies, it is suggested that phenol is mainly destroyed by the surface-adsorbed radicals and Cu(III) resulting from the reaction between PS and Cu(II) on the catalyst. Taking into account the widespread presence of bicarbonate ions in waste streams, the CuO-Fe3O4/PS system may provide some new insights for contaminant removal from wastewater. PMID:25955238

  4. Selective disruption of high sensitivity heat activation but not capsaicin activation of TRPV1 channels by pore turret mutations.

    PubMed

    Cui, Yuanyuan; Yang, Fan; Cao, Xu; Yarov-Yarovoy, Vladimir; Wang, KeWei; Zheng, Jie

    2012-04-01

    The capsaicin receptor transient receptor potential vanilloid (TRPV)1 is a highly heat-sensitive ion channel. Although chemical activation and heat activation of TRPV1 elicit similar pungent, painful sensation, the molecular mechanism underlying synergistic activation remains mysterious. In particular, where the temperature sensor is located and whether heat and capsaicin share a common activation pathway are debated. To address these fundamental issues, we searched for channel mutations that selectively affected one form of activation. We found that deletion of the first 10 amino acids of the pore turret significantly reduced the heat response amplitude and shifted the heat activation threshold, whereas capsaicin activation remained unchanged. Removing larger portions of the turret disrupted channel function. Introducing an artificial sequence to replace the deleted region restored sensitive capsaicin activation in these nonfunctional channels. The heat activation, however, remained significantly impaired, with the current exhibiting diminishing heat sensitivity to a level indistinguishable from that of a voltage-gated potassium channel, Kv7.4. Our results demonstrate that heat and capsaicin activation of TRPV1 are structurally and mechanistically distinct processes, and the pore turret is an indispensible channel structure involved in the heat activation process but is not part of the capsaicin activation pathway. Synergistic effect of heat and capsaicin on TRPV1 activation may originate from convergence of the two pathways on a common activation gate. PMID:22412190

  5. Innovative Protocols for in SITU MTBE Degradation by Using Molecular Probes-An Enhanced Chemical-Bio Oxidation Technique

    SciTech Connect

    Paul Fallgren

    2009-02-20

    In situ chemical oxidation (ISCO) is a common technology to cleanup petroleum hydrocarbon-contaminated soils and groundwater. Sodium percarbonate (SPC) is an oxidant which is activated by iron (Fe) to produce Fenton-like reactions. Western Research Institute, in conjunction with Regenesis and the U.S. Department of Energy, conducted a study that investigated the performance of a 'safe' oxidant, SPC, to cleanup groundwater and soils contaminated with petroleum hydrocarbons and associated contaminants (e.g., MTBE). Results from a field pilot test in Frenchglen, Oregon showed VOC concentrations in groundwater decreased substantially within 2 weeks after injecting activated SPC (RegenOx). A protocol was established for determining RegenOx TOD in soils and groundwater. Total oxidant demand tests were necessary to determine the correct dosage of RegenOx to apply in the field and sufficiently degrade the contaminants of concern. Bench studies with RegenOx showed this technology was effective in degrading diesel fuel and 1,4-dioxane. The Fe-silica activator (RegenOx Part B) was tested with another oxidant, sodium persulfate. Bench tests results showed the combination of sodium persulfate and RegenOx Part B was effective in reducing PCE, MTBE, benzene, and n-heptane concentrations in water. Overall, the results of this project indicated that most petroleum contaminants in soil and groundwater can be sufficiently degraded using the RegenOx technology.

  6. Process for the oxidation of materials in water at supercritical temperatures utilizing reaction rate enhancers

    SciTech Connect

    Swallow, K.C.; Killilea, W.R.; Hong, G.T.; Bourhis, A.L.

    1993-08-03

    A method is described for substantially completely oxidizing combustible materials in which an aqueous stream bearing the combustible materials is reacted in the presence of an oxidant comprising diatomic oxygen and at a temperature greater than the critical temperature of water and at a pressure greater than about 25 bar, within a reactor for a period of less than about 5 minutes to produce a reaction product stream, wherein the reaction is initiated in the presence of a rate enhancer comprising at least one oxidizing agent in addition to said oxidant selected from the group consisting of ozone, hydrogen peroxide, salts containing persulfate, salts containing permanganate, nitric acid, salts containing nitrate, oxyacids of chlorine and their corresponding salts, hypochlorous acid, salts containing hypochlorite, chlorous acid, salts containing chlorite, chloric acid, salts containing chlorate, perchloric acid, and salts containing perchlorate.

  7. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    PubMed

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts. PMID:26130568

  8. Effects of chemical oxidants on perfluoroalkyl acid transport in one-dimensional porous media columns.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2015-02-01

    In situ chemical oxidation (ISCO) is a remediation approach that is often used to remediate soil and groundwater contaminated with fuels and chlorinated solvents. At many aqueous film-forming foam-impacted sites, perfluoroalkyl acids (PFAAs) can also be present at concentrations warranting concern. Laboratory experiments were completed using flow-through one-dimensional columns to improve our understanding of how ISCO (i.e., activated persulfate, permanganate, or catalyzed hydrogen peroxide) could affect the fate and transport of PFAAs in saturated porous media. While the resultant data suggest that standard ISCO is not a viable remediation strategy for PFAA decomposition, substantial changes in PFAA transport were observed upon and following the application of ISCO. In general, activated persulfate decreased PFAA transport, while permanganate and catalyzed hydrogen peroxide increased PFAA transport. PFAA sorption increased in the presence of increased aqueous polyvalent cation concentrations or decreased pH. The changes in contaminant mobility were greater than what would be predicted on the basis of aqueous chemistry considerations alone, suggesting that the application of ISCO results in changes to the porous media matrix (e.g., soil organic matter quality) that also influence transport. The application of ISCO is likely to result in changes in PFAA transport, where the direction (increased or decreased transport) and magnitude are dependent on PFAA characteristics, oxidant characteristics, and site-specific factors. PMID:25621878

  9. Catalytic-Oxidative Leaching of Low-Grade Complex Zinc Ore by Cu (II) Ions Produced from Copper Ore in Ammonia-Ammonium Sulfate Solution

    NASA Astrophysics Data System (ADS)

    Liu, Zhi Xiong; Yin, Zhou Lan; Hu, Hui Ping; Chen, Qi Yuan

    2012-10-01

    The catalytic-oxidative leaching of a mixed ore, which consists of low-grade oxide copper ore and oxide zinc ore containing ZnS, was investigated in ammonia-ammonium sulfate solution. The effect of the main parameters, such as mass ratio of copper ore to zinc ore, liquid-to-solid ratio, concentration of lixivant, leaching time, and temperature, was studied. The optimal leaching conditions with a maximum extraction of Cu 92.6 pct and Zn 85.5 pct were determined as follows: the mass ratio of copper ore to zinc ore 4/10 g/g, temperature 323.15 K (50 C), leaching time 6 hours, stirring speed 500 r/min, liquid-to-solid ratio 3.6/1 cm3/g, concentration of lixivant including ammonia 2.0 mol/dm3, ammonium sulfate 1.0 mol/dm3, and ammonium persulfate 0.3 mol/dm3. It was found that ZnS in the oxide zinc ore could be extracted with Cu(II) ion, which was produced from copper ore and was used as the catalyst in the presence of ammonium persulfate.

  10. The influence of a non-aqueous phase liquid (NAPL) and chemical oxidant application on perfluoroalkyl acid (PFAA) fate and transport.

    PubMed

    McKenzie, Erica R; Siegrist, Robert L; McCray, John E; Higgins, Christopher P

    2016-04-01

    One dimensional column experiments were conducted using saturated porous media containing residual trichloroethylene (TCE) to understand the effects of non-aqueous phase liquids (NAPLs) and chemical oxidation on perfluoroalkyl acid (PFAA) fate and transport. Observed retardation factors and data from supporting batch studies suggested that TCE provides additional sorption capacity that can increase PFAA retardation (i.e., decreased mobility), though the mechanisms remain unclear. Treatment with persulfate activated with FeCl2 and citric acid, catalyzed hydrogen peroxide (CHP), or permanganate did not result in oxidative transformations of PFAAs. However, impacts on PFAA sorption were apparent, and enhanced sorption was substantial in the persulfate-treated columns. In contrast, PFAA transport was accelerated in permanganate- and CHP-treated columns. Ultimately, PFAA transport in NAPL contaminated groundwater is likely influenced by porous media properties, NAPL characteristics, and water quality properties, each of which can change due to chemical oxidant treatment. For contaminated sites for which ISCO is a viable treatment option, changes to PFAA transport and the implications thereof should be included as a component of the remediation evaluation and selection process. PMID:26854608

  11. Miniaturized dielectric barrier discharge carbon atomic emission spectrometry with online microwave-assisted oxidation for determination of total organic carbon.

    PubMed

    Han, Bingjun; Jiang, Xiaoming; Hou, Xiandeng; Zheng, Chengbin

    2014-07-01

    A simple, rapid, and portable system consisted of a laboratory-built miniaturized dielectric barrier discharge atomic emission spectrometer and a microwave-assisted persulfate oxidation reactor was developed for sensitive flow injection analysis or continuous monitoring of total organic carbon (TOC) in environmental water samples. The standard/sample solution together with persulfate was pumped to the reactor to convert organic compounds to CO2, which was separated from liquid phase and transported to the spectrometer for detection of the elemental specific carbon atomic emission at 193.0 nm. The experimental parameters were systematically investigated. A limit of detection of 0.01 mg L(-1) (as C) was obtained based on a 10 mL sample injection volume, and the precision was better than 6.5% (relative standard deviation, RSD) at 0.1 mg L(-1). The system was successfully applied for TOC analysis of real environmental water samples. The obtained TOC value of 30 test samples agreed well with those by the standard high-temperature combustion coupled nondispersive infrared absorption method. Most importantly, the system showed good capability of in situ continuous monitoring of total organic carbon in environmental water. PMID:24862626

  12. Destruction of cyanobacterial toxin cylindrospermopsin by hydroxyl radicals and sulfate radicals using UV-254 nm activation of hydrogen peroxide, persulfate and peroxymonosulfate

    EPA Science Inventory

    Abstract: With increasing worldwide incidence of toxic cyanobacterial blooms in bodies of water, cylindrospermopsin (CYN) has become a significant concern to public health and water management officials. In this study, the removal of CYN by UV-254 nm-mediated advanced oxidation ...

  13. Homogeneous Photocatalytic Water Oxidation with a Dinuclear Co(III)-Pyridylmethylamine Complex.

    PubMed

    Ishizuka, Tomoya; Watanabe, Atsuko; Kotani, Hiroaki; Hong, Dachao; Satonaka, Kenta; Wada, Tohru; Shiota, Yoshihito; Yoshizawa, Kazunari; Ohara, Kazuaki; Yamaguchi, Kentaro; Kato, Satoshi; Fukuzumi, Shunichi; Kojima, Takahiko

    2016-02-01

    A bis-hydroxo-bridged dinuclear Co(III)-pyridylmethylamine complex (1) was synthesized and the crystal structure was determined by X-ray crystallography. Complex 1 acts as a homogeneous catalyst for visible-light-driven water oxidation by persulfate (S2O8(2-)) as an oxidant with [Ru(II)(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer affording a high quantum yield (44%) with a large turnover number (TON = 742) for O2 formation without forming catalytically active Co-oxide (CoOx) nanoparticles. In the water-oxidation process, complex 1 undergoes proton-coupled electron-transfer (PCET) oxidation as a rate-determining step to form a putative dinuclear bis-?-oxyl Co(III) complex (2), which has been suggested by DFT calculations. Catalytic water oxidation by 1 using [Ru(III)(bpy)3](3+) as an oxidant in a H2(16)O and H2(18)O mixture was examined to reveal an intramolecular O-O bond formation in the two-electron-oxidized bis-?-oxyl intermediate, prior to the O2 evolution. PMID:26810593

  14. Metalloporphyrin-sensitized photooxidation of water to oxygen on the surface of colloidal iridium oxides. Photochemical and pulse radiolytic studies

    SciTech Connect

    Nahor, G.S.; Neta, P. ); Hambright, P. ); Thompson, A.N. Jr. ); Harriman, A. )

    1989-08-10

    Derivatives of TSPP (tetrakis(4-sulfonatophenyl)porphyrin) were prepared and tested as photosensitizers for oxidation of water to oxygen on the surface of colloidal iridium oxide. Triplet quantum yields, energies, and lifetimes were measured by laser flash photolysis. Rate constants for quenching the porphyrin triplet state with O{sub 2} and with persulfate ions were also determined. The rates of interaction between the porphyrin radical cations and colloidal IrO{sub x} particles were measured by pulse radiolysis for several of the compounds. The one-electron oxidation potentials of the porphyrins, measured by cyclic voltammetry, were varied between 0.7 and 1.4 V vs. NHE by using different metal centers and by substitution on the phenyl rings. Illumination of a porphyrin in the presence of sodium persulfate and an IrO{sub x} colloid resulted in generation of O{sub 2} in a process that was strongly dependent upon pH and upon the nature of the photosensitizer in the same manner as the kinetics determined by pulse radiolysis. The rate of O{sub 2} production under any conditions could be explained on the basis of thermodynamic criteria relating to either of the individual quenching or water oxidation steps. Zn porphyrins (0.9 < E{sub {1/2}} < 1.02 V) effected O{sub 2} production only in alkaline solution, whereas PdTSPP (E{sub {1/2}} = 1.1 V) gave efficient O{sub 2} evolution even in neutral solution. Further increase in E{sub 1/2}, as achieved with InTSPP (E{sub {1/2}} = 1.16 V), lowers the threshold pH for O{sub 2} evolution, and pulse radiolysis experiments confirmed that the radical cation of this porphyrin is the most reactive toward the catalyst, reacting at diffusion-controlled rates even in acidic solutions. However, the rate of O{sub 2} formation with InTSPP was very low due to the inefficient photochemistry arising from the incomplete quenching of this less-reducing porphyrin triplet state by persulfate ions.

  15. A combined coarse-grained and all-atom simulation of TRPV1 channel gating and heat activation.

    PubMed

    Zheng, Wenjun; Qin, Feng

    2015-05-01

    The transient receptor potential (TRP) channels act as key sensors of various chemical and physical stimuli in eukaryotic cells. Despite years of study, the molecular mechanisms of TRP channel activation remain unclear. To elucidate the structural, dynamic, and energetic basis of gating in TRPV1 (a founding member of the TRPV subfamily), we performed coarse-grained modeling and all-atom molecular dynamics (MD) simulation based on the recently solved high resolution structures of the open and closed form of TRPV1. Our coarse-grained normal mode analysis captures two key modes of collective motions involved in the TRPV1 gating transition, featuring a quaternary twist motion of the transmembrane domains (TMDs) relative to the intracellular domains (ICDs). Our transition pathway modeling predicts a sequence of structural movements that propagate from the ICDs to the TMDs via key interface domains (including the membrane proximal domain and the C-terminal domain), leading to sequential opening of the selectivity filter followed by the lower gate in the channel pore (confirmed by modeling conformational changes induced by the activation of ICDs). The above findings of coarse-grained modeling are robust to perturbation by lipids. Finally, our MD simulation of the ICD identifies key residues that contribute differently to the nonpolar energy of the open and closed state, and these residues are predicted to control the temperature sensitivity of TRPV1 gating. These computational predictions offer new insights to the mechanism for heat activation of TRPV1 gating, and will guide our future electrophysiology and mutagenesis studies. PMID:25918362

  16. A combined coarse-grained and all-atom simulation of TRPV1 channel gating and heat activation

    PubMed Central

    Qin, Feng

    2015-01-01

    The transient receptor potential (TRP) channels act as key sensors of various chemical and physical stimuli in eukaryotic cells. Despite years of study, the molecular mechanisms of TRP channel activation remain unclear. To elucidate the structural, dynamic, and energetic basis of gating in TRPV1 (a founding member of the TRPV subfamily), we performed coarse-grained modeling and all-atom molecular dynamics (MD) simulation based on the recently solved high resolution structures of the open and closed form of TRPV1. Our coarse-grained normal mode analysis captures two key modes of collective motions involved in the TRPV1 gating transition, featuring a quaternary twist motion of the transmembrane domains (TMDs) relative to the intracellular domains (ICDs). Our transition pathway modeling predicts a sequence of structural movements that propagate from the ICDs to the TMDs via key interface domains (including the membrane proximal domain and the C-terminal domain), leading to sequential opening of the selectivity filter followed by the lower gate in the channel pore (confirmed by modeling conformational changes induced by the activation of ICDs). The above findings of coarse-grained modeling are robust to perturbation by lipids. Finally, our MD simulation of the ICD identifies key residues that contribute differently to the nonpolar energy of the open and closed state, and these residues are predicted to control the temperature sensitivity of TRPV1 gating. These computational predictions offer new insights to the mechanism for heat activation of TRPV1 gating, and will guide our future electrophysiology and mutagenesis studies. PMID:25918362

  17. Temporal stability of solid oxidizers at high temperature and humidity. Memorandum report

    SciTech Connect

    Pellenbarg, R.E.; Dotson, D.A.

    1985-09-30

    Chemical Warfare/Biological Warfare (CW/BW) decontamination operations may rely on aqueous solutions prepared from stored solid oxidizers. Needed are data defining the shipboard storage stability of candidate oxidizers. Therefore, the stability of a series of potential decontaminants has been examined at high temperature (90 + C) and humidity (95 + % R.H.). The loss of oxidizing capacity in aliquots of the oxidizers was followed with time by iodometric titration. Calcium hypochlorite lost over 99% of its oxidizing capacity in less than two days, whereas lithium hypochlorite retained one-third oxidizing capacity for approximately twenty days. Sodium perborate, and sodium persulfate were very hygroscopic and unstable with time. H-48 decomposed in approximately two days, while sodium isocyanurate lost about 80% of its oxidizing capacity in two weeks. The data presented documents severe stability problems of one sort or another with all the materials tested, although overall the sodium isocyanurate appeared to be the more stable candidate undr extreme conditions. In any case, packaging and storage considerations are shown to be important for any potential decontaminant to be stored under environmentally severe conditions.

  18. Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods.

    PubMed

    Zhang, Kaitao; Sun, Peipei; Liu, He; Shang, Shibin; Song, Jie; Wang, Dan

    2016-03-15

    Two kinds of carboxylated cellulose nanocrystals (CCNs) were prepared by using ultrasonic assisted 2,2,6,6-tetramethylpiperidinyl-1-oxy radical (TEMPO) mediated oxidation and one-step ammonium persulfate (APS) oxidation, which were denoted as TEMPO-oxidized CCNs (TO-CCNs) and APS-oxidized CCNs (AO-CCNs), respectively. The effects of oxidant content on the yield, carboxyl content, degree of polymerization (DPv) and morphology of the oxidized celluloses in the two oxidation methods were studied. Furthermore, the chemical structure, crystallinity and thermal stability of TO-CCNs and AO-CCNs were evaluated and compared by Fourier transformed infrared spectra, X-ray diffraction and thermogravimetric analyses. The results showed that with increase of oxidant content in the two methods, the carboxyl groups on the surfaces of TO-CCNs and AO-CCNs were both improved. And a remarkable decline of the DPv of cellulose sample also appeared in the two oxidative treatments. In addition, AO-CCNs exhibited a higher crystallinity and an enhanced thermal stability compared with TO-CCNs. PMID:26794758

  19. Oxidative degradation of food dye E133 Brilliant Blue FCF Liquid chromatography-electrospray mass spectrometry identification of the degradation pathway.

    PubMed

    Gosetti, F; Gianotti, V; Angioi, S; Polati, S; Marengo, E; Gennaro, M C

    2004-10-29

    This paper is devoted to the evaluation of the degradation pathway of the E133 Brilliant Blue FCF (C.I. 42090) that is largely used in the food industry. The degradation is studied in oxidation conditions obtained by addition of potassium persulfate at different persulfate to dye molar ratios under natural sunlight irradiation. The degradation pathway of the dye passes through a species coloured in dark blue and then gives rise to uncoloured species. Due to the low volatility and the poor thermal stability of the dye, reversed-phase liquid chromatography associated to mass spectrometry and tandom mass spectrometry was employed to follow the kinetics of degradation and identify some intermediates. The identification of organic species still present in the decoloured dye and the value of COD obtained in these conditions show evidence that complete decolorization does not correspond to complete mineralisation. No direct information of toxicity is available for the uncoloured degradation products but the further formation of aromatic amines can not be excluded. PMID:15553166

  20. Solid-liquid separation of oxidized americium from fission product lanthanides

    NASA Astrophysics Data System (ADS)

    Shehee, T. C.; Martin, L. R.; Nash, K. L.

    2010-03-01

    The separation of americium from the lanthanides and curium is a requirement if transmutation of americium is to be performed in advanced nuclear fuel cycles. Oxidation of Am3+ to AmO2+ or AmO22+ may allow separation of Am from Ln and Cm in one step, since the lanthanides and curium do not have higher oxidation states as accessible. Two possible solid-liquid separation methods have been developed to address this difficult separation. Under acidic conditions using oxone or persulfate, the oxidation and retention of tracer Am in the aqueous phase has been observed with a separation factor of 11 1. Most of these studies have been conducted using 237NpO2(NO3), 233UO2(NO3)2, 238Pu(NO3)4 and 241Am(NO3)3 at radiotracer concentrations. Lanthanides precipitate as the sodium or potassium europium double sulfate salt. Under basic conditions, ozone oxidation of Am(CO3)OH(s) solubilizes Am from a lanthanide carbonate hydroxide solid phase to the aqueous phase as the AmO2(CO3)34-or AmO2(CO3)35- species. For the ozone oxidation of the americium tracer a separation factor of 1.6 0.8 and 47 2 for the oxidation/separation in Na2CO3 and NaHCO3 respectively.

  1. Self-flocculated powdered activated carbon with different oxidation methods and their influence on adsorption behavior.

    PubMed

    Gong, Zailin; Li, Shujin; Ma, Jun; Zhang, Xiangdong

    2016-03-01

    The commercial powdered activated carbon (PAC) has been selectively oxidized by two methods. The two oxidized methods are wet oxidation with ammonium persulfate and thermal treatment after acidification with hydrochloride acid, respectively. The two oxidized PAC were then functionalized with thermoresponsive poly (N-isopropylacrylamide) (PNIPAM) in aqueous solution at ambient temperature. Comparing the two oxidized PAC products and their grafted derivatives, the oxidized PAC modified with thermal treatment after acidification shows larger surface area of 1184m(2)/g and better adsorption of bisphenol A. Its derivative also exhibits relatively large surface area and adsorption capacity after grafted with PNIPAM. The maximum surface adsorption capacity simulated under Langmuir Models reached 156mg/g. In addition, the grafted PAC products show self-flocculation behaviors with rapid response to temperature because of the thermal phase transition and entanglement behaviors of PNIPAM. The present study provides a new way to obtain carboxyl-rich activated carbon with large surface area and better adsorption capacity. The retrievable grafted PAC with good self-flocculation effect responsive to temperature will have high potential application in water remediation which requires pre-heating and emergency water treatment in the wild. PMID:26551226

  2. Methods of analysis by the U.S. Geological Survey National Water Quality Laboratory : determination of nonpurgeable suspended organic carbon by wet-chemical oxidation and infrared spectrometry

    USGS Publications Warehouse

    Burkhardt, Mark R.; Kammer, James A.; Jha, Virendra K.; O'Mara-Lopez, Peggy G.; Woodworth, Mark T.

    1997-01-01

    Precision and accuracy results are described for the determination of nonpurgeable suspended organic carbon (SOC) by silver-filter filtration, wet-chemical oxidation, and infrared determination of hte resulting carbon dioxide (CO2) used at the U.S. Geological Survey's nationalWater Quality Laboratory. An aliquot of raw water isfiltered through a 0.45-micrometer silver filter. The trapped organic material is oxidized using phosphoric acid and potassium persulfate in a scaled glass ampule,and the rseulting CO2 is measured by an infrared CO2 detector. The amount of CO3 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the sample. The SOC method detection limit for routine analysis is 0.2 milligram per liter. The average percent recovery is 97.1 percent and the average standard deviation is 11 percent.

  3. Synthesis of electromagnetic functionalized Fe3O4 microspheres/polyaniline composites by two-step oxidative polymerization.

    PubMed

    Cui, Chenkui; Du, Yunchen; Li, Tianhao; Zheng, Xiaoying; Wang, Xiaohong; Han, Xijiang; Xu, Ping

    2012-08-01

    Composites consisting of Fe(3)O(4) microspheres (FMS) and polyaniline (PANI), FMS/PANI, have been successfully prepared through a two-step oxidative polymerization of aniline monomers in the presence of Fe(3)O(4) microspheres. In our two-step polymerization technique, Fe(3+) and ammonium persulfate (APS) are used as the oxidants in each step. It is discovered that the two-step oxidative process plays a dominant role in the morphology of these composites: aniline oligomers oxidized by Fe(3+) are mainly produced in the first stage, and "egg-like" PANI aggregates are obtained in the second stage. It can be found that embedding Fe(3)O(4) microspheres in the polymer matrixes will not only modulate the complex permittivity but also produce magnetic resonance and loss in the composites. Therefore, the characteristic impedance and reflection loss of these composites are greatly improved. Especially, the composite with equal amount of FMS and PANI, FMS/PANI(50), displays very strong reflection loss over a wide frequency range that can be manipulated by the absorber thickness. More importantly, the composites prepared from the two-step chemical oxidative polymerization using hierarchical magnetic materials have better microwave absorption and environmental stability as compared with those composites from Fe(3)O(4) nanoparticles, one-step oxidative polymerization, and physical mixture. We believe the two-step oxidative polymerization technique can be a novel route for the design and preparation of lightweight and highly effective microwave absorbers in the future. PMID:22800337

  4. Component analysis of dyads designed for light-driven water oxidation.

    PubMed

    Kohler, Lars; Kaveevivitchai, Nattawut; Zong, Ruifa; Thummel, Randolph P

    2014-01-21

    A series of seven dyad molecules have been prepared utilizing a [Ru(tpy)(NN)I](+) type oxidation catalyst (NN = 2,5-di(pyrid-2'-yl) pyrazine (1), 2,5-di-(1',8'-dinaphthyrid-2'-yl) pyrazine (2), or 4,6-di-(1',8'-dinaphthyrid-2'-yl) pyrimidine (3). The other bidentate site of the bridging ligand was coordinated with 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), or a substituted derivative. These dinuclear complexes were characterized by their (1)H NMR spectra paying special attention to protons held in the vicinity of the electronegative iodide. In one case, 10a, the complex was also analyzed by single crystal X-ray analysis. The electronic absorption spectra of all the complexes were measured and reported as well as emission properties for the sensitizers. Oxidation and reduction potentials were measured and excited state redox properties were calculated from this data. Turnover numbers, initial rates, and induction periods for oxygen production in the presence of a blue LED light and sodium persulfate as a sacrificial oxidant were measured. Similar experiments were run without irradiation. Dyad performance correlated well with the difference between the excited state reduction potential of the photosensitizer and the ground state oxidation potential of the water oxidation dyad. The most active system was one having 5,6-dibromophen as the auxiliary ligand, and the least active system was the one having 4,4'-dimethylbpy as the auxiliary ligand. PMID:24364791

  5. Nitrogen- and Sulfur-Codoped Hierarchically Porous Carbon for Adsorptive and Oxidative Removal of Pharmaceutical Contaminants.

    PubMed

    Tian, Wenjie; Zhang, Huayang; Duan, Xiaoguang; Sun, Hongqi; Tade, Moses O; Ang, Ha Ming; Wang, Shaobin

    2016-03-23

    Heteroatom (nitrogen and sulfur)-codoped porous carbons (N-S-PCs) with high surface areas and hierarchically porous structures were successfully synthesized via direct pyrolysis of a mixture of glucose, sodium bicarbonate, and thiourea. The resulting N-S-PCs exhibit excellent adsorption abilities and are highly efficient for potassium persulfate activation when employed as catalysts for the oxidative degradation of sulfachloropyridazine (SCP) solutions. The adsorption capacities of N-S-PC-2 (which contains 4.51 atom % nitrogen and 0.22 atom % sulfur and exhibits SBET of 1608 m(2) g(-1)) are 73, 7, and 3 times higher than those of graphene oxide, reduced graphene oxide, and commercial single-walled carbon nanotube, respectively. For oxidation, the reaction rate constant of N-S-PC-2 is 0.28 min(-1). This approach not only contributes to the large-scale production and application of high-quality catalysts in water remediation but also provides an innovative strategy for the production of heteroatom-doped PCs for energy applications. PMID:26937827

  6. The chimeric approach reveals that differences in the TRPV1 pore domain determine species-specific sensitivity to block of heat activation.

    PubMed

    Papakosta, Marianthi; Dalle, Carine; Haythornthwaite, Alison; Cao, Lishuang; Stevens, Edward B; Burgess, Gillian; Russell, Rachel; Cox, Peter J; Phillips, Stephen C; Grimm, Christian

    2011-11-11

    The capsaicin-, heat-, and proton-activated ion channel TRPV1, a member of the transient receptor potential cation channel family is a polymodal nociceptor. For almost a decade, TRPV1 has been explored by the pharmaceutical industry as a potential target for example for pain conditions. Antagonists which block TRPV1 activation by capsaicin, heat, and protons were developed by a number of pharmaceutical companies. The unexpected finding of hyperthermia as an on-target side effect in clinical studies using polymodal TRPV1 antagonists has prompted companies to search for ways to circumvent hyperthermia, for example by the development of modality-selective antagonists. The significant lack of consistency of the pharmacology of many TRPV1 antagonists across different species has been a further obstacle. JYL-1421 for example was shown to block capsaicin and heat responses in human and monkey TRPV1 while it was largely ineffective in blocking heat responses in rat TRPV1. These findings suggested structural dissimilarities between different TRPV1 species relevant for small compound antagonism for example of heat activation. Using a chimeric approach (human and rat TRPV1) in combination with a novel FLIPR-based heat activation assay and patch-clamp electrophysiology we have identified the pore region as being strongly linked to the observed species differences. We demonstrate that by exchanging the pore domains JYL-1421, which is modality-selective in rat can be made modality-selective in human TRPV1 and vice-versa. PMID:21911503

  7. The Chimeric Approach Reveals That Differences in the TRPV1 Pore Domain Determine Species-specific Sensitivity to Block of Heat Activation*

    PubMed Central

    Papakosta, Marianthi; Dalle, Carine; Haythornthwaite, Alison; Cao, Lishuang; Stevens, Edward B.; Burgess, Gillian; Russell, Rachel; Cox, Peter J.; Phillips, Stephen C.; Grimm, Christian

    2011-01-01

    The capsaicin-, heat-, and proton-activated ion channel TRPV1, a member of the transient receptor potential cation channel family is a polymodal nociceptor. For almost a decade, TRPV1 has been explored by the pharmaceutical industry as a potential target for example for pain conditions. Antagonists which block TRPV1 activation by capsaicin, heat, and protons were developed by a number of pharmaceutical companies. The unexpected finding of hyperthermia as an on-target side effect in clinical studies using polymodal TRPV1 antagonists has prompted companies to search for ways to circumvent hyperthermia, for example by the development of modality-selective antagonists. The significant lack of consistency of the pharmacology of many TRPV1 antagonists across different species has been a further obstacle. JYL-1421 for example was shown to block capsaicin and heat responses in human and monkey TRPV1 while it was largely ineffective in blocking heat responses in rat TRPV1. These findings suggested structural dissimilarities between different TRPV1 species relevant for small compound antagonism for example of heat activation. Using a chimeric approach (human and rat TRPV1) in combination with a novel FLIPR-based heat activation assay and patch-clamp electrophysiology we have identified the pore region as being strongly linked to the observed species differences. We demonstrate that by exchanging the pore domains JYL-1421, which is modality-selective in rat can be made modality-selective in human TRPV1 and vice-versa. PMID:21911503

  8. The Effect of Al2O3 Addition on the Thermal Diffusivity of Heat Activated Acrylic Resin

    PubMed Central

    Atla, Jyothi; Manne, Prakash; Gopinadh, A.; Sampath, Anche; Muvva, Suresh Babu; Kishore, Krishna; Sandeep, Chiramana; Chittamsetty, Harika

    2013-01-01

    Aim: This study aimed at investigating the effect of adding 5% to 20% by weight aluminium oxide powder (Al2O3) on thermal diffusivity of heat–polymerized acrylic resin. Material and Methods: Twenty five cylindrical test specimens with an embedded thermocouple were used to determine thermal diffusivity over a physiologic temperature range (0 to 70°C). The specimens were divided into five groups (5 specimens/group) which were coded A to E. Group A was the control group (unmodified acrylic resin specimens). The specimens of the remaining four groups were reinforced with 5%, 10%, 15%, and 20% Al2O3 by weight. Results were analysed by using one–way analysis of variance (ANOVA). Results: Test specimens which belonged to Group E showed the highest mean thermal diffusivity value of 10.7mm2/sec, followed by D (9.09mm2/sec), C (8.49mm2/sec), B(8.28mm2/sec) and A(6.48mm2/sec) groups respectively. Thermal diffusivities of the reinforced acrylic resins were found to be significantly higher than that of the unmodified acrylic resin. Thermal diffusivity was found to increase in proportion to the weight percentage of alumina filler. Conclusion: Al2O3 fillers have potential to provide increased thermal diffusivity. Increasing the heat transfer characteristics of the acrylic resin base material could lead to more patient satisfaction. PMID:24086917

  9. NF-TiO? photocatalysis of amitrole and atrazine with addition of oxidants under simulated solar light: emerging synergies, degradation intermediates, and reusable attributes.

    PubMed

    Andersen, Joel; Pelaez, Miguel; Guay, Lisa; Zhang, Zhaohong; O'Shea, Kevin; Dionysiou, Dionysios D

    2013-09-15

    In order to investigate sustainable alternatives to current water treatment methods, the effect of NF-titania film thickness and subsequent photocatalysis in combination with oxidants was examined under simulated solar light. Such a combination presents a theoretical possibility for a synergistic interaction between the photocatalyst and the oxidant (activation of the oxidant by the catalyst under conditions under which it may not conventionally be activated). To investigate, peroxymonosulfate (PMS) and persulfate (PS) were used as oxidants, and two pesticides, amitrole and atrazine, were used as target contaminants. In the absence of a film, activation of PMS under simulated solar conditions is demonstrated by removal of atrazine, whereas PS provided minimal removal, suggesting inefficient activation. Combining photocatalytic films with PMS and PS manifested synergies for both oxidants. The effect was most pronounced for PS since PMS already underwent significant activation without the photocatalyst. Amitrole degradation results indicated a lack of removal of amitrole by activated PS alone, suggesting that this sulfate radical-based treatment technology may be ineffective for the removal of amitrole. The NF-TiO? films demonstrated reusability under solar light both with and without oxidants. Finally, the degradation intermediates were analyzed, and a new intermediate appeared upon incorporating oxidants into the system. PMID:23811632

  10. Visible light-driven water oxidation promoted by host-guest interaction between photosensitizer and catalyst with a high quantum efficiency.

    PubMed

    Li, Hua; Li, Fei; Zhang, Biaobiao; Zhou, Xu; Yu, Fengshou; Sun, Licheng

    2015-04-01

    A highly active supramolecular system for visible light-driven water oxidation was developed with cyclodextrin-modified ruthenium complex as the photosensitizer, phenyl-modified ruthenium complexes as the catalysts, and sodium persulfate as the sacrificial electron acceptor. The catalysts were found to form 1:1 host-guest adducts with the photosensitizer. Stopped-flow measurement revealed the host-guest interaction is essential to facilitate the electron transfer from catalyst to sensitizer. As a result, a remarkable quantum efficiency of 84% was determined under visible light irradiation in neutral aqueous phosphate buffer. This value is nearly 1 order of magnitude higher than that of noninteraction system, indicating that the noncovalent incorporation of sensitizer and catalyst is an appealing approach for efficient conversion of solar energy into fuels. PMID:25799114

  11. Treatment of hydrocarbon contamination under flow through conditions by using magnetite catalyzed chemical oxidation.

    PubMed

    Usman, M; Faure, P; Lorgeoux, C; Ruby, C; Hanna, K

    2013-01-01

    Soil pollution by hydrocarbons (aromatic and aliphatic hydrocarbons) is a major environmental issue. Various treatments have been used to remove them from contaminated soils. In our previous studies, the ability of magnetite has been successfully explored to catalyze chemical oxidation for hydrocarbon remediation in batch slurry system. In the present laboratory study, column experiments were performed to evaluate the efficiency of magnetite catalyzed Fenton-like (FL) and activated persulfate (AP) oxidation for hydrocarbon degradation. Flow-through column experiments are intended to provide a better representation of field conditions. Organic extracts isolated from three different soils (an oil-contaminated soil from petrochemical industrial site and two soils polluted by polycyclic aromatic hydrocarbon (PAH) originating from coking plant sites) were spiked on sand. After solvent evaporation, spiked sand was packed in column and was subjected to oxidation using magnetite as catalyst. Oxidant solution was injected at a flow rate of 0.1 mL min(-1) under water-saturated conditions. Organic analyses were performed by GC-mass spectrometry, GC-flame ionization detector, and micro-Fourier transform infrared spectroscopy. Significant abatement of both types of hydrocarbons (60-70 %) was achieved after chemical oxidation (FL and AP) of organic extracts. No significant by-products were formed during oxidation experiment, underscoring the complete degradation of hydrocarbons. No selective degradation was observed for FL with almost similar efficiency towards all hydrocarbons. However, AP showed less reactivity towards higher molecular weight PAHs and aromatic oxygenated compounds. Results of this study demonstrated that magnetite-catalyzed chemical oxidation can effectively degrade both aromatic and aliphatic hydrocarbons (enhanced available contaminants) under flow-through conditions. PMID:22684901

  12. Ratiometric Signaling of Hypochlorite by the Oxidative Cleavage of Sulfonhydrazide-Based Rhodamine-Dansyl Dyad.

    PubMed

    Lee, Hyo Jin; Cho, Min Jeoung; Chang, Suk-Kyu

    2015-09-01

    A reaction-based probe 1 for hypochlorite signaling was designed by the conjugation of two fluorophores, rhodamine and dansyl moieties, by the reaction of rhodamine B base with dansylhydrazine. Probe 1 exhibited pronounced hypochlorite-selective chromogenic and fluorescent signaling behavior over other oxidants used in practical applications, such as hydrogen peroxide, peracetic acid, and ammonium persulfate, as well as commonly encountered metal ions and anions. Signaling was attributed to the hypochlorite-induced oxidative cleavage of the sulfonhydrazide linkage of the probe. In particular, favorable ratiometric fluorescence signaling was possible by utilizing the emissions of the two fluorophores. A detection limit of 1.13 × 10(-6) M (0.058 ppm) was estimated for the determination of hypochlorite. A paper-based test strip was prepared and was used as a semiquantitative indicator for the presence of hypochlorite in aqueous solutions. The probe was also successfully applied for the determination of hypochlorite in practical tap water samples. PMID:26313428

  13. Erythromycin oxidation and ERY-resistant Escherichia coli inactivation in urban wastewater by sulfate radical-based oxidation process under UV-C irradiation.

    PubMed

    Michael-Kordatou, I; Iacovou, M; Frontistis, Z; Hapeshi, E; Dionysiou, D D; Fatta-Kassinos, D

    2015-11-15

    This study evaluates the feasibility of UV-C-driven advanced oxidation process induced by sulfate radicals SO4(.)- in degrading erythromycin (ERY) in secondary treated wastewater. The results revealed that 10 mg L(-1) of sodium persulfate (SPS) can result in rapid and complete antibiotic degradation within 90 min of irradiation, while ERY decay exhibited a pseudo-first-order kinetics pattern under the different experimental conditions applied. ERY degradation rate was strongly affected by the chemical composition of the aqueous matrix and it decreased in the order of: ultrapure water (kapp = 0.55 min(-1)) > bottled water (kapp = 0.26 min(-1)) > humic acid solution (kapp = 0.05 min(-1)) > wastewater effluents (kapp = 0.03 min(-1)). Inherent pH conditions (i.e. pH 8) yielded an increased ERY degradation rate, compared to that observed at pH 3 and 5. The contribution of hydroxyl and sulfate radicals (HO. and SO4(.)-) on ERY degradation was found to be ca. 37% and 63%, respectively. Seven transformation products (TPs) were tentatively elucidated during ERY oxidation, with the 14-membered lactone ring of the ERY molecule being intact in all cases. The observed phytotoxicity against the tested plant species can potentially be attributed to the dissolved effluent organic matter (dEfOM) present in wastewater effluents and its associated-oxidation products and not to the TPs generated from the oxidation of ERY. This study evidences the potential use of the UV-C/SPS process in producing a final treated effluent with lower phytotoxicity (<10%) compared to the untreated wastewater. Finally, under the optimum experimental conditions, the UV-C/SPS process resulted in total inactivation of ERY-resistant Escherichia coli within 90 min. PMID:26360228

  14. PEGylated liposomes with NGR ligand and heat-activable cell-penetrating peptide-doxorubicin conjugate for tumor-specific therapy.

    PubMed

    Yang, Yanfang; Yang, Yang; Xie, Xiangyang; Cai, Xingshi; Zhang, Hui; Gong, Wei; Wang, Zhiyuan; Mei, Xingguo

    2014-05-01

    Cell-penetrating peptides (CPPs) mediated tumor-oriented nanocarriers have been widely studied by researchers recently. However, applications of CPPs invivo were usually hampered by their loss in untargeted tissues and enzymatic degradation. These shortfalls required strategies to camouflage CPPs before their arrival at the targeted site. In this work, we constructed a thermosensitive liposome (TSL) containing Asparagines-Glycine-Arginine (NGR) peptide as the targeting moiety and heat-activable cell-penetrating peptide-doxorubicin conjugate for enhancing specific cancer therapy. Different to the masking strategies of CPPs reported, CPPs existing in conjugation form of CPPs and doxorubicin (CPP-Dox) were hidden in TSL to cloak and protect CPPs. Meanwhile, NGR moiety and local tumor hyperthermia were utilized to achieve specific targeting of CPPs to the tumor. The nanocarrier (CPP-Dox/NGR-TSL) prepared in this work possessed suitable physiochemical properties such as small particle size of about 90nm, high drug encapsulation efficiency of approximately 95%, good stability in the medium containing 10% fetal bovine serum (FBS) and so on. Invitro experiments on Human fibrosarcoma cells (HT-1080) and human breast adenocarcinoma cells (MCF-7) verified the specific targeting ability and enhanced intracellular drug delivery of the liposomes to HT-1080 cells. Furthermore, comparing with NGR-targeted TSL containing Dox (Dox/NGR-TSL), the results of intravenous administration showed CPP-Dox/NGR-TSL significantly inhibited tumor growth in nude mice xenografted HT-1080 tumors and excellent body safety. In conclusion, the nanocarrier constructed in this study would be a safe and efficiently drug delivery system for specific cancer treatment. PMID:24565519

  15. Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Annual report, October 1, 1980-September 30, 1981

    SciTech Connect

    Hirschon, A.S.; Zevely, J.; Mayo, F.R.

    1981-11-12

    The objective of this project is to determine the structure of bituminous coal by determining the proportions of the various kinds of connecting bonds and how they can best be broken. Results obtained during the past quarter are presented for the following tasks: (1) extractions and fractionations of coal products which covers pyridine extraction, fractionation of TIPS fractions, EDA extraction of Illinois No. 6 coal and swelling ratios of coal samples; (2) experiments on breakable single bonds which cover reactions of ethylenediamine and model ethers, reaction of pyridine-extracted coal with Me/sub 3/SiI, Baeyer-Villiger oxidations, reaction to diphenylmethane with 15% HNO/sub 3/, cleavage of TIPS with ZnI/sub 2/, and cleavage of black acids; and (3) oxygen oxidation No. 18. Some of the highlights of these studies are: (1) some model ethers are not cleaved by EDA under extraction conditions; (2) oxidation of diaryl ketones with m-chloroperbenzoic acid and saponification of the resulting esters in promising for identifying ketones, (3) treatment of a black acid with pyridine hydroiodide reduced the acid's molecular weight and increased its solubility in pyridine, but treatment with ZnI/sub 2/ was ineffective; (4) in comparison with 0.1 M K/sub 2/S/sub 2/O/sub 8/, 0.01 M persulfate is relatively ineffective in accelerating oxidation of BnNH/sub 2/-extracted coal in water suspension. 2 figures, 3 tables.

  16. Magnesium Oxide

    MedlinePLUS

    Magnesium is an element your body needs to function normally. Magnesium oxide may be used for different reasons. Some ... to relieve heartburn, sour stomach, or acid indigestion. Magnesium oxide also may be used as a laxative ...

  17. Ethylene Oxide

    Cancer.gov

    At room temperature, ethylene oxide is a flammable colorless gas with a sweet odor. It is used primarily to produce other chemicals, including antifreeze. In smaller amounts, ethylene oxide is used as a pesticide and a sterilizing agent. The ability of ethylene oxide to damage DNA makes it an effective sterilizing agent but also accounts for its cancer-causing activity.

  18. Design, synthesis, and characterization of materials for controlled line deposition, environmental remediation, and doping of porous manganese oxide material

    NASA Astrophysics Data System (ADS)

    Calvert, Craig A.

    This thesis covers three topics: (1) coatings formed from sol-gel phases, (2) environmental remediation, and (3) doping of a porous manganese oxide. Synthesis, characterization, and application were investigated for each topic. Line-formations were formed spontaneously by self-assembly from vanadium sol-gels and other metal containing solutions on glass substrates. The solutions were prepared by the dissolution of metal oxide or salt in water. A more straightforward method is proposed than used in previous work. Analyses using optical microscopy, atomic force microscopy, scanning electron microscopy, energy-dispersive X-ray analysis, and infrared spectroscopy showed discreet lines whose deposition could be controlled by varying the concentration. A mechanism was developed from the observed results. Microwave heating, the addition of graphite rods, and oxidants, can enhance HCB remediation from soil. To achieve remediation, a TeflonRTM vessel open to the atmosphere along with an oxidant, potassium persulfate (PerS) or potassium hydroxide, along with uncoated or aluminum oxide coated, graphite rods were heated in a research grade microwave oven. Microwave heating was used to decrease the heating time, and graphite rods were used to increase the absorption of the microwave energy by providing thermal centers. The results showed that the percent HCB removed was increased by adding graphite rods and oxidants. Tungsten, silver, and sulfur were investigated as doping agents for K--OMS-2. The synthesis of these materials was carried out with a reflux method. The doping of K--OMS-2 led to changes in the properties of a tungsten doped K--OMS-2 had an increased resistivity, the silver doped material showed improved epoxidation of trans-stilbene, and the addition of sulfur produced a paper-like material. Rietveld refinement of the tungsten doped K--OMS-2 showed that the tungsten was doped into the framework.

  19. The carbonate radical is a site-selective oxidizing agent of guanine in double-stranded oligonucleotides.

    PubMed

    Shafirovich, V; Dourandin, A; Huang, W; Geacintov, N E

    2001-07-01

    The carbonate radical anion (CO(3)) is believed to be an important intermediate oxidant derived from the oxidation of bicarbonate anions and nitrosoperoxocarboxylate anions (formed in the reaction of CO(2) with ONOO(-)) in cellular environments. Employing nanosecond laser flash photolysis methods, we show that the CO(3) anion can selectively oxidize guanines in the self-complementary oligonucleotide duplex d(AACGCGAATTCGCGTT) dissolved in air-equilibrated aqueous buffer solution (pH 7.5). In these time-resolved transient absorbance experiments, the CO(3) radicals are generated by one-electron oxidation of the bicarbonate anions (HCO(3)(-)) with sulfate radical anions (SO(4)) that, in turn, are derived from the photodissociation of persulfate anions (S(2)O(8)(2-)) initiated by 308-nm XeCl excimer laser pulse excitation. The kinetics of the CO(3) anion and neutral guanine radicals, G(-H)( small middle dot), arising from the rapid deprotonation of the guanine radical cation, are monitored via their transient absorption spectra (characteristic maxima at 600 and 315 nm, respectively) on time scales of microseconds to seconds. The bimolecular rate constant of oxidation of guanine in this oligonucleotide duplex by CO(3) is (1.9 +/- 0.2) x 10(7) m(-1) s(-1). The decay of the CO(3) anions and the formation of G(-H)( small middle dot) radicals are correlated with one another on the millisecond time scale, whereas the neutral guanine radicals decay on time scales of seconds. Alkali-labile guanine lesions are produced and are revealed by treatment of the irradiated oligonucleotides in hot piperidine solution. The DNA fragments thus formed are identified by a standard polyacrylamide gel electrophoresis assay, showing that strand cleavage occurs at the guanine sites only. The biological implications of these oxidative processes are discussed. PMID:11320091

  20. Improved method for the determination of nonpurgeable suspended organic carbon in natural water by silver filter filtration, wet chemical oxidation, and infrared spectrometry

    USGS Publications Warehouse

    Burkhardt, M.R.; Brenton, R.W.; Kammer, J.A.; Jha, V.K.; O'Mara-Lopez, P. G.; Woodworth, M.T.

    1999-01-01

    Precision and accuracy are reported for the first time for the analysis of nonpurgeable suspended organic carbon by silver membrane filtration followed by wet chemical oxidation. A water sample is pressure filtered through a 0.45-??m-pore-size, 47-mm-diameter silver membrane filter. The silver membrane filter then is cut into ribbons and placed in a flame-sealable glass ampule. The organic material trapped on the membrane filter strips is acidified, purged with oxygen to remove inorganic carbonates and volatile organic compounds, and oxidized to carbon dioxide (CO2) using phosphoric acid and potassium persulfate in the sealed glass ampule. The resulting CO2 is measured by a nondispersive infrared CO2 detector. The amount of CO2 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the environmental water sample. The quantitation and method detection limit for routine analysis is 0.2 mg/L. The average percent recovery in five representative matrices was 97 ?? 11%. The errors associated with sampling and sample preparation of nonpurgeable suspended organic carbon are also described.Precision and accuracy are reported for the first time for the analysis of nonpurgeable suspended organic carbon by silver membrane filtration followed by wet chemical oxidation. A water sample is pressure filtered through a 0.45-??m-pore-size, 47-mm-diameter silver membrane filter. The silver membrane filter then is cut into ribbons and placed in a flame-sealable glass ampule. The organic material trapped on the membrane filter strips is acidified, purged with oxygen to remove inorganic carbonates and volatile organic compounds, and oxidized to carbon dioxide (CO2) using phosphoric acid and potassium persulfate in the sealed glass ampule. The resulting CO2 is measured by a nondispersive infrared CO2 detector. The amount of CO2 is proportional to the concentration of chemically oxidizable nonpurgeable organic carbon in the environmental water sample. The quantitation and method detection limit for routine analysis is 0.2 mg/L. The average percent recovery in five representative matrices was 97??11%. The errors associated with sampling and sample preparation of nonpurgeable suspended organic carbon are also described.

  1. Treating organic pollutants in urban runoff using slow-release oxidants and storm pipes: A field investigation

    NASA Astrophysics Data System (ADS)

    Eyerdom, T. J.; Lee, E.; Kim, Y.

    2013-12-01

    Non-point source (NPS) contamination is a major concern for urban aquatic environments. This study tested the efficacy of using slow-release oxidants emplaced in storm pipes for treating organic pollutants in urban storm runoff through proof-of-concept laboratory tests and a field demonstration test in Athens, OH. Release rates of slow-release persulfate (SR-PS), slow-release hydrogen pyroxide (SR-HP), and slow-release iron (SR-Fe) were estimated through column tests. Runoff samples were collected at a storm pipe discharge point in the study area for 3 storm events having different prior drought periods to establish baseline concentrations of organic pollutants. Samples were analyzed for Methyl-tert-butyl-ether (MTBE), Naphthalene, and total organic carbon contents. The proof-of-concept flow-through test demonstrated that up 90% of pollutants can be removed by the SR-PS/Fe within 20 minutes of reaction time. The SR-PS/HP/Fe forms are emplaced in several storm drains where the pollutants would have ~15 minutes of reaction with the oxidants released from the slow-release forms. Preliminary results suggest that the SR-PS/HP/Fe forms installed in the storm pipes can reduce NPS pollutants in the urban storm runoff in a sustainable manner.

  2. Development of Alkaline Oxidative Dissolution Methods for Chromium (III) Compounds Present in Hanford Site Tank Sludges

    SciTech Connect

    Delegard, Calvin H.; Krot, N N.; Shilov, V P.; Fedoseev, A M.; Budantseva, N A.; Nikonov, M V.; Yusov, A B.; Garnov, A Y.; Charushnikova, I A.; Perminov, V P.; Astafurova, L N.; Lapitskaya, T S.; Makarenkov, V I.

    1999-07-02

    The high-level radioactive waste sludge in the underground storage tanks at the Hanford Site contains various chromium solid phases. Dissolution and removal of chromium from tank waste sludges is desirable prior to high-level waste vitrification because increased volume is required to incorporate the residual chromium. Unfortunately, dissolution of chromium from the sludge to form Cr(OH){sub 4}{sup -} through treatment with heated NaOH solution (also used to dissolve aluminum phases and metathesize phosphates to sodium salts) generally has been unsuccessful in tests with both simulated and genuine Hanford waste sludges. Oxidative dissolution of the Cr(III) compounds to form soluble chromate has been proposed as an alternative chromium solid phase dissolution method and results of limited prior testing have been reported. The present systematic tests investigated oxygen gas, hydrogen peroxide, and sodium persulfate oxidants to dissolve Cr(III) under alkaline conditions to form soluble chromate. Permanganate and ozone also were considered for testing but were thought to be of secondary interest because of the insoluble residue (MnO{sub 2} from permanganate) and complex equipment (necessary to generate ozone) implicit with use of these reagents. The oxygen and hydrogen peroxide reagents leave no condensable residue and sodium persulfate only leaves soluble sodium sulfate. Crystalline Cr(OH){sub 3}, various hydrothermally aged amorphous Cr(III) oxide hydrates, mixed Fe(III)/Cr(III) oxide hydrates, and nickel and iron Cr(III) spinels, all of which have been identified or are likely constituents in Hanford tank wastes, were prepared and characterized for the dissolution tests. The effects of reagent and hydroxide concentrations, reaction temperature, and transition metal catalysts on reaction progress were investigated for each reagent as functions of reaction time. Reaction progress was measured by monitoring chromate concentration. Oxidation of chromium compounds by dissolved oxygen was found to increase linearly with oxygen partial pressure and NaOH concentration. The rate also increased with temperature at low activation energy, 26-36 kJ/mol, reflecting the opposing influences of decreasing oxygen volubility and increasing underlying chemical reaction rate. The reaction apparently proceeds by way of dissolved Cr(III) species, is catalyzed by Ni(II), and is slower for the hydrothermally aged materials. Dissolution rates ranged from about 7 x 10{sup -5} to 2.4 x 10{sup -4} moles Cr(III)/liter-hour in 80 C, 3-M NaOH with one atmosphere pure oxygen for the various Cr(III) compounds tested. These low dissolution rates commend the use of oxygen reagent to waste tank processing where extended residence times maybe practical. Oxidative dissolution of Cr(III) compounds by hydrogen peroxide was hampered in the presence of greater than 0.5 g Fe(III)/liter and other catalysts for H{sub 2}O{sub 2} decomposition and was less effective for materials that had undergone prolonged aging at high temperatures. Leaching was optimized at low excess NaOH and high temperatures (activation energy of {approx}82 kJ/mol). To prevent excessive loss of H{sub 2}O{sub 2} to catalytic decomposition, the peroxide reagent must be added slowly and with intense stirring. Treatment of waste solids with H{sub 2}O{sub 2} may only be attractive for freshly formed Cr(III) hydroxides [formed, for example, by alkaline metathesis of Cr(III)-bearing sludges] in the absence of decomposition catalysts such as Fe(III).

  3. Oxidative shielding or oxidative stress?

    PubMed

    Naviaux, Robert K

    2012-09-01

    In this review I report evidence that the mainstream field of oxidative damage biology has been running fast in the wrong direction for more than 50 years. Reactive oxygen species (ROS) and chronic oxidative changes in membrane lipids and proteins found in many chronic diseases are not the result of accidental damage. Instead, these changes are the result of a highly evolved, stereotyped, and protein-catalyzed "oxidative shielding" response that all eukaryotes adopt when placed in a chemically or microbially hostile environment. The machinery of oxidative shielding evolved from pathways of innate immunity designed to protect the cell from attack and limit the spread of infection. Both oxidative and reductive stress trigger oxidative shielding. In the cases in which it has been studied explicitly, functional and metabolic defects occur in the cell before the increase in ROS and oxidative changes. ROS are the response to disease, not the cause. Therefore, it is not the oxidative changes that should be targeted for therapy, but rather the metabolic conditions that create them. This fresh perspective is relevant to diseases that range from autism, type 1 diabetes, type 2 diabetes, cancer, heart disease, schizophrenia, Parkinson's disease, and Alzheimer disease. Research efforts need to be redirected. Oxidative shielding is protective and is a misguided target for therapy. Identification of the causal chemistry and environmental factors that trigger innate immunity and metabolic memory that initiate and sustain oxidative shielding is paramount for human health. PMID:22700427

  4. Metal ions as potential regulatory factors in the biosynthesis of red hair pigments: a new benzothiazole intermediate in the iron or copper assisted oxidation of 5-S-cysteinyldopa.

    PubMed

    Di Donato, Paola; Napolitano, Alessandra; Prota, Giuseppe

    2002-06-01

    In the presence of iron or copper ions, the course of the oxidation in air of 5-S-cysteinyldopa (1), the main biosynthetic precursor of pheomelanins and trichochromes, was markedly changed affording two main products. One of these was identified as the oxobenzothiazine 8, previously obtained under nonphysiologically relevant conditions, while the other was characterized as the novel hydroxybenzothiazole 9. Besides 8 and 9, carboxylated and noncarboxylated benzothiazine products were obtained by persulfate oxidation of 1 in the presence of iron or copper ions. The ratio of formation yields of carboxylated/noncarboxylated benzothiazines, determined after reduction of the mixture, was lower than that of the control reaction run in the absence of metal ions, and much lower than that of the oxidation carried out in the presence of zinc ions, in agreement with a recent report. Notably, 8 and 9 were formed in variable yields under different oxidation conditions including tyrosinase/O(2), peroxidase/hydrogen peroxide, and the hydrogen peroxide/or (9E,11Z,13S)-13-hydroperoxyoctadeca-9,11-dienoic acid/Fe(III) systems. Mechanistic routes to 8 and 9 were proposed based on the results of experiments involving in situ generation of labile benzothiazine intermediates. Overall, these results allow to formulate an improved biosynthetic scheme in which metal ions act as critical regulatory factors determining pheomelanin vs. trichochromes formation. PMID:12049796

  5. Use of Advanced Oxidation and Aerobic Degradation for Remediation of Various Hydrocarbon Contaminates

    SciTech Connect

    Paul Fallgren

    2009-03-06

    Western Research Institute in conjunction with Sierra West Consultants, Inc., Tetra Tech, Inc., and the U.S. Department of Energy conducted laboratory and field studies to test different approaches to enhance degradation of hydrocarbons and associated contaminants. WRI in conjunction with Sierra West Consultants, Inc., conducted a laboratory and field study for using ozone to treat a site contaminated with MTBE and other hydrocarbons. Results from this study demonstrate that a TOD test can be used to resolve the O{sub 3} dosage problem by establishing a site-specific benchmark dosage for field ozone applications. The follow-up testing of the laboratory samples provided indications that intrinsic biodegradation could be stimulated by adding oxygen. Laboratory studies also suggests that O3 dosage in the full-scale field implementation could be dialed lower than stoichiometrically designed to eliminate the formation of Cr(VI). WRI conducted a study involving a series of different ISCO oxidant applications to diesel-contaminated soil and determined the effects on enhancing biodegradation to degrade the residual hydrocarbons. Soils treated with permanganate followed by nutrients and with persulfate followed by nutrients resulted in the largest decrease in TPH. The possible intermediates and conditions formed from NOM and TPH oxidation by permanganate and activated persulfate favors microbial TPH degrading activity. A 'passive-oxidation' method using microbial fuel cell (MFC) technology was conducted by WRI in conjunction with Tetra Tech, Inc., to degrade MTBE in groundwater. These experiments have demonstrated that a working MFC (i.e., one generating power) could be established in the laboratory using contaminated site water or buffered media inoculated with site water and spiked with MTBE, benzene, or toluene. Electrochemical methods were studied by WRI with goal of utilizing low voltage and amperage electrical sources for 'geo-oxidation' of organic contaminants. The results from a study with TCE contaminated-clay indicate that electrochemically inducing reductive dechlorination of TCE in a saturated matrix may offer an effective and viable alternative to remediation TCE and other contaminants with potential of being reduced. Another study focused on steel wool oxidation to electrochemically increase population of hydrocarbon-degrading denitrifying bacteria. Significantly larger denitrifying activity was observed in the cathode chamber of a treatment unit setup like an MFC with steel wool as the anode. This enhanced nitrate reduction could be due to direct electron utilization by denitrifying bacteria on the cathode, thereby stimulating microbial denitrification or a combination of electron transfer directly to NO{sub 3}{sup -} and electron transfer to nitrate reducing bacteria, which may serve as a type of bio-catalyst on the cathode for nitrate reduction. Overall, the studies conducted under Task 72 demonstrated different innovative methods to enhance petroleum hydrocarbon degradation and associated contaminants.

  6. Chemical Conversion of PON to Nitrous Oxide for Nitrogen Isotopic Analysis : High- Sensitivity Tracer Assay for Nitrogen Fixation

    NASA Astrophysics Data System (ADS)

    Tsunogai, U.; Kido, T.; Hirota, A.; Ohkubo, S.; Komatsu, D. D.; Nakagawa, F.

    2006-12-01

    We present a method for high-sensitivity nitrogen isotopic analysis of particulate organic nitrogen (PON) in seawater and freshwater, for the aim of measuring the rate of nitrogen fixation through 15N2 tracer technique for samples that contain low numeric abundance of organisms. The method composed of the traditional oxidation/reduction methods: such as oxidation of PON to nitrate using persulfate, the reduction of nitrate to nitrite using spongy cadmium, and further reduction of nitrite to nitrous oxide using sodium azide in an acetic acid buffer. Then, Nitrous oxide is purged from the water and trapped cryogenically with subsequent release into a gas chromatography column to analyze stable nitrogen isotopic compositions using a continuous-flow isotope ratio mass spectrometer. A standard deviation less than 0.3 for nitrogen was found for PON samples containing more than 80 nmolN, with a blank nitrogen of 20 nmolN. Nitrogen isotopic fractionation were consistent within each batch of analysis. Besides, we found that we can also determine nitrogen isotopic compositions of total dissolved nitrogen (TDN, sum of NO3-, NO2-, ammonium, and DON), by applying the method for filtrate samples. Our method may prove to obtain isotopic information for lower quantities of PON and TDN than other methods, so that we can reduce quantities of water samples needed for incubation to determine the nitrogen fixation rate in both seawater and freshwater. Besides, the method is also useful to determine the rate of nitrogen fixation by the small size fraction in ocean. We will also present the results obtained at western subtropical North Pacific to support our conclusions.

  7. Oxidant gases

    SciTech Connect

    Evans, M.J.

    1984-01-01

    The acute and chronic action of the oxidant gases ozone, nitrogen dioxide and oxygen on the morphological appearance of cells of the alveolar and bronchiolar epithelium is reviewed. Type I cells of the alveolar and ciliated cells of the bronchiolar epithelium appear to be sensitive targets for the oxidant gases. The degree of damage is influenced by age, nutritional status and the development of tolerance.

  8. Mechanisms of oxidation of guanine in DNA by carbonate radical anion, a decomposition product of nitrosoperoxycarbonate.

    PubMed

    Lee, Young Ae; Yun, Byeong Hwa; Kim, Seog K; Margolin, Yelena; Dedon, Peter C; Geacintov, Nicholas E; Shafirovich, Vladimir

    2007-01-01

    Peroxynitrite is produced during inflammation and combines rapidly with carbon dioxide to yield the unstable nitrosoperoxycarbonate, which decomposes (in part) to CO(3) (.-) and (.)NO(2) radicals. The CO(3) (.-) radicals oxidize guanine bases in DNA through a one-electron transfer reaction process that ultimately results in the formation of stable guanine oxidation products. Here we have explored these mechanisms, starting with a spectroscopic study of the kinetics of electron transfer from 20-22mer double-stranded oligonucleotides to CO(3) (.-) radicals, together with the effects of base sequence on the formation of the end-products in runs of one, two, or three contiguous guanines. The distributions of these alkali-labile lesions were determined by gel electrophoresis methods. The cascade of events was initiated through the use of 308 nm XeCl excimer laser pulses to generate CO(3) (.-) radicals by an established method based on the photodissociation of persulfate to sulfate radicals and the oxidation of bicarbonate. Although the Saito model (Saito et al., J. Am. Chem. Soc. 1995, 117, 6406-6407) predicts relative ease of one-electron oxidations in DNA, following the trend 5'-GGG > 5'-GG > 5'-G, we found that the rate constants for CO(3) (.-)-mediated oxidation of guanines in these sequence contexts (k(5)) showed only small variation within a narrow range [(1.5-3.0)x10(7) M(-1) s(-1)]. In contrast, the distributions of the end-products are dependent on the base sequence context and are higher at the 5'-G in 5'-GG sequences and at the first two 5'-guanines in the 5'-GGG sequences. These effects are attributed to a combination of initial hole distributions among the contiguous guanines and the subsequent differences in chemical reaction yields at each guanine. The lack of dependence of k(5) on sequence context indicates that the one-electron oxidation of guanine in DNA by CO(3) (.-) radicals occurs by an inner-sphere mechanism. PMID:17335089

  9. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T. (Cambridge, MA); Lahr, David L. (Cambridge, MA)

    2010-11-09

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

  10. Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation, chemical and advanced oxidation processes.

    PubMed

    Bagal, Manisha V; Gogate, Parag R

    2013-09-01

    In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3-6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3-11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H2O2), ferrous activated persulfate (HC/Na2S2O8/FeSO4) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO4/H2O2), advanced Fenton (HC/Fe/H2O2) and Fenton-like process (HC/CuO/H2O2) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes. PMID:23538121

  11. Nitric oxide

    Integrated Risk Information System (IRIS)

    Nitric oxide ; CASRN 10102 - 43 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  12. Merphos oxide

    Integrated Risk Information System (IRIS)

    Merphos oxide ; CASRN 78 - 48 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effe

  13. Thallium oxide

    Integrated Risk Information System (IRIS)

    Thallium oxide ; CASRN 1314 - 32 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  14. Propylene oxide

    Integrated Risk Information System (IRIS)

    Propylene oxide ; CASRN 75 - 56 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  15. NITROGEN OXIDES

    EPA Science Inventory

    This report is a review of current knowledge of the environmental health basis for control of manmade sources of nitrogen oxide emissions. The literature review covered the period through 1974. The principal subject areas considered in the report include: sources and control of a...

  16. ALTERNATIVE OXIDANTS

    EPA Science Inventory

    This chapter reports on the efforts of the USEPA to study chloramines, chlorine dioxide and ozone as alternative oxidants/disinfectants to chlorine for the control of disinfection by-rpdocuts (DBPs) in drinking water. It examines the control of DBPs like trihalomethanes and haloa...

  17. PREFACE: Semiconducting oxides Semiconducting oxides

    NASA Astrophysics Data System (ADS)

    Catlow, Richard; Walsh, Aron

    2011-08-01

    Semiconducting oxides are amongst the most widely studied and topical materials in contemporary condensed matter science, with interest being driven both by the fundamental challenges posed by their electronic and magnetic structures and properties, and by the wide range of applications, including those in catalysis and electronic devices. This special section aims to highlight recent developments in the physics of these materials, and to show the link between developing fundamental understanding and key application areas of oxide semiconductors. Several aspects of the physics of this wide and expanding range of materials are explored in this special section. Transparent semiconducting oxides have a growing role in several technologies, but challenges remain in understanding their electronic structure and the physics of charge carriers. A related problem concerns the nature of redox processes and the reactions which interconvert defects and charge carriers—a key issue which may limit the extent to which doping strategies may be used to alter electronic properties. The magnetic structures of the materials pose several challenges, while surface structures and properties are vital in controlling catalytic properties, including photochemical processes. The field profits from and exploits a wide range of contemporary physical techniques—both experimental and theoretical. Indeed, the interplay between experiment and computation is a key aspect of contemporary work. A number of articles describe applications of computational methods whose use, especially in modelling properties of defects in these materials, has a long and successful history. Several papers in this special section relate to work presented at a symposium within the European Materials Research Society (EMRS) meeting held in Warsaw in September 2010, and we are grateful to the EMRS for supporting this symposium. We would also like to thank the editorial staff of Journal of Physics: Condensed Matter for their help in producing this special section. We hope that it conveys some of the excitement and significance of the field. Semiconducting oxides contents Chemical bonding in copper-based transparent conducting oxides: CuMO2 (M = In, Ga, Sc) K G Godinho, B J Morgan, J P Allen, D O Scanlon and G W Watson Electrical properties of (Ba, Sr)TiO3 thin films with Pt and ITO electrodes: dielectric and rectifying behaviourShunyi Li, Cosmina Ghinea, Thorsten J M Bayer, Markus Motzko, Robert Schafranek and Andreas Klein Orientation dependent ionization potential of In2O3: a natural source for inhomogeneous barrier formation at electrode interfaces in organic electronicsMareike V Hohmann, Péter Ágoston, André Wachau, Thorsten J M Bayer, Joachim Brötz, Karsten Albe and Andreas Klein Cathodoluminescence studies of electron irradiation effects in n-type ZnOCasey Schwarz, Yuqing Lin, Max Shathkin, Elena Flitsiyan and Leonid Chernyak Resonant Raman scattering in ZnO:Mn and ZnO:Mn:Al thin films grown by RF sputteringM F Cerqueira, M I Vasilevskiy, F Oliveira, A G Rolo, T Viseu, J Ayres de Campos, E Alves and R Correia Structure and electrical properties of nanoparticulate tungsten oxide prepared by microwave plasma synthesisM Sagmeister, M Postl, U Brossmann, E J W List, A Klug, I Letofsky-Papst, D V Szabó and R Würschum Charge compensation in trivalent cation doped bulk rutile TiO2Anna Iwaszuk and Michael Nolan Deep level transient spectroscopy studies of n-type ZnO single crystals grown by different techniquesL Scheffler, Vl Kolkovsky, E V Lavrov and J Weber Microstructural and conductivity changes induced by annealing of ZnO:B thin films deposited by chemical vapour depositionC David, T Girardeau, F Paumier, D Eyidi, B Lacroix, N Papathanasiou, B P Tinkham, P Guérin and M Marteau Multi-component transparent conducting oxides: progress in materials modellingAron Walsh, Juarez L F Da Silva and Su-Huai Wei Thickness dependence of the strain, band gap and transport properties of epitaxial In2O3 thin films grown on Y-stabilised ZrO2(111) K H L Zhang, V K Lazarov, T D Veal, F E Oropeza, C F McConville, R G Egdell and A Walsh Hydrogenated cation vacancies in semiconducting oxidesJ B Varley, H Peelaers, A Janotti and C G Van de Walle Reactive force field simulation of proton diffusion in BaZrO3 using an empirical valence bond approachPaolo Raiteri, Julian D Gale and Giovanni Bussi Conductivity in transparent oxide semiconductorsP D C King and T D Veal A theoretical study of a ZnO graphene analogue: adsorption on Ag(111) and hydrogen transportIlker Demiroglu, Daniele Stradi, Francesc Illas and Stefan T Bromley The interplay between dopants and oxygen vacancies in the magnetism of V-doped TiO2 Ricardo Grau-Crespo and Udo Schwingenschlögl Electron and hole stability in GaN and ZnOAron Walsh, C Richard A Catlow, Martina Miskufova and Alexey A Sokol Holes bound as small polarons to acceptor defects in oxide materials: why are their thermal ionization energies so high?O F Schirmer

  18. DNA lesions derived from the site selective oxidation of Guanine by carbonate radical anions.

    PubMed

    Joffe, Avrum; Geacintov, Nicholas E; Shafirovich, Vladimir

    2003-12-01

    Carbonate radical anions are potentially important oxidants of nucleic acids in physiological environments. However, the mechanisms of action are poorly understood, and the end products of oxidation of DNA by carbonate radicals have not been characterized. These oxidation pathways were explored in this work, starting from the laser pulse-induced generation of the primary radical species to the identification of the stable oxidative modifications (lesions). The cascade of events was initiated by utilizing 308 nm XeCl excimer laser pulses to generate carbonate radical anions on submicrosecond time scales. This laser flash photolysis method involved the photodissociation of persulfate to sulfate radical anions and the one electron oxidation of bicarbonate anions by the sulfate radicals to yield the carbonate radical anions. The latter were monitored by their characteristic transient absorption band at 600 nm. The rate constants of reactions of carbonate radicals with oligonucleotides increase in the ascending order: 5'-d(CCATCCTACC) [(5.7 +/- 0.6) x 10(6) M(-)(1) s(-)(1)] < 5'-d(TATAACGTTATA), self-complementary duplex [(1.4 +/- 0.2) x 10(7) M(-)(1) s(-)(1)] < 5'-d(CCATCGCTACC [(2.4 +/- 0.3) x 10(7) M(-)(1) s(-)(1)] < 5'-d(CCATC[8-oxo-G]CTACC) [(3.2 +/- 0.4) x 10(8) M(-)(1) s(-)(1)], where 8-oxo-G is 8-oxo-7,8-dihydroguanine, the product of a two electron oxidation of guanine. This remarkable enhancement of the rate constants is correlated with the presence of either G or 8-oxo-G bases in the oligonucleotides. The rate constant for the oxidation of G in a single-stranded oligonuclotide is faster by a factor of approximately 2 than in the double-stranded form. The site selective oxidation of G and 8-oxo-G residues by carbonate radicals results in the formation of unique end products, the diastereomeric spiroiminodihydantoin (Sp) lesions, the products of a four electron oxidation of guanine. These lesions, formed in high yields (40-60%), were isolated by reversed phase HPLC and identified by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. These assignments were supported by the characteristic circular dichroism spectra of opposite signs of the two lesions. The oxidation of guanine to Sp diastereomers occurs, at least in part, via the formation of 8-oxo-G lesions as intermediates. The Sp lesions can be considered as the terminal products of the oxidation of G and 8-oxo-G in DNA by carbonate radical anions. The mechanistic aspects and biological implications of these site selective reactions in DNA initiated by carbonate radicals are discussed. PMID:14680366

  19. Oxidation resistance of silicon ceramics

    NASA Technical Reports Server (NTRS)

    Yasutoshi, H.; Hirota, K.

    1984-01-01

    Oxidation resistance, and examples of oxidation of SiC, Si3N4 and sialon are reviewed. A description is given of the oxidation mechanism, including the oxidation product, oxidation reaction and the bubble size. The oxidation reactions are represented graphically. An assessment is made of the oxidation process, and an oxidation example of silicon ceramics is given.

  20. Thermally exfoliated graphite oxide

    NASA Technical Reports Server (NTRS)

    Prud'Homme, Robert K. (Inventor); Aksay, Ilhan A. (Inventor); Abdala, Ahmed (Inventor)

    2011-01-01

    A modified graphite oxide material contains a thermally exfoliated graphite oxide with a surface area of from about 300 sq m/g to 2600 sq m/g, wherein the thermally exfoliated graphite oxide displays no signature of the original graphite and/or graphite oxide, as determined by X-ray diffraction.

  1. Electrochemical oxidation of cholesterol

    PubMed Central

    2015-01-01

    Summary Indirect cholesterol electrochemical oxidation in the presence of various mediators leads to electrophilic addition to the double bond, oxidation at the allylic position, oxidation of the hydroxy group, or functionalization of the side chain. Recent studies have proven that direct electrochemical oxidation of cholesterol is also possible and affords different products depending on the reaction conditions. PMID:25977713

  2. Nitric oxide inhibition strategies

    PubMed Central

    Wong, Vivian (Wai Chong); Lerner, Ethan

    2015-01-01

    Nitric oxide is involved in many physiologic processes. There are efforts, described elsewhere in this volume, to deliver nitric oxide to tissues as a therapy. Nitric oxide also contributes to pathophysiologic processes. Inhibiting nitric oxide or its production can thus also be of therapeutic benefit. This article addresses such inhibitory strategies. PMID:26634146

  3. Numerical simulation of in-situ chemical oxidation (ISCO) and biodegradation of petroleum hydrocarbons using a coupled model for bio-geochemical reactive transport

    NASA Astrophysics Data System (ADS)

    Marin, I. S.; Molson, J. W.

    2013-05-01

    Petroleum hydrocarbons (PHCs) are a major source of groundwater contamination, being a worldwide and well-known problem. Formed by a complex mixture of hundreds of organic compounds (including BTEX - benzene, toluene, ethylbenzene and xylenes), many of which are toxic and persistent in the subsurface and are capable of creating a serious risk to human health. Several remediation technologies can be used to clean-up PHC contamination. In-situ chemical oxidation (ISCO) and intrinsic bioremediation (IBR) are two promising techniques that can be applied in this case. However, the interaction of these processes with the background aquifer geochemistry and the design of an efficient treatment presents a challenge. Here we show the development and application of BIONAPL/Phreeqc, a modeling tool capable of simulating groundwater flow, contaminant transport with coupled biological and geochemical processes in porous or fractured porous media. BIONAPL/Phreeqc is based on the well-tested BIONAPL/3D model, using a powerful finite element simulation engine, capable of simulating non-aqueous phase liquid (NAPL) dissolution, density-dependent advective-dispersive transport, and solving the geochemical and kinetic processes with the library Phreeqc. To validate the model, we compared BIONAPL/Phreeqc with results from the literature for different biodegradation processes and different geometries, with good agreement. We then used the model to simulate the behavior of sodium persulfate (NaS2O8) as an oxidant for BTEX degradation, coupled with sequential biodegradation in a 2D case and to evaluate the effect of inorganic geochemistry reactions. The results show the advantages of a treatment train remediation scheme based on ISCO and IBR. The numerical performance and stability of the integrated BIONAPL/Phreeqc model was also verified.

  4. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland (Lakewood, CO); Liu, Ping (Irvine, CA); Smith, R. Davis (Golden, CO)

    2009-07-14

    Photo-oxidation catalysts and methods for cleaning a metal-based catalyst are disclosed. An exemplary catalyst system implementing a photo-oxidation catalyst may comprise a metal-based catalyst, and a photo-oxidation catalyst for cleaning the metal-based catalyst in the presence of light. The exposure to light enables the photo-oxidation catalyst to substantially oxidize absorbed contaminants and reduce accumulation of the contaminants on the metal-based catalyst. Applications are also disclosed.

  5. Biofiltration of nitric oxide

    SciTech Connect

    Davidova, Y.B.; Schroeder, E.D.; Chang, D.P.Y.

    1997-12-31

    Results of recent experiments on nitrogen transformations in biofilters suggest that oxides of nitrogen may be both oxidized or reduced within these systems. Under the proper conditions, nitric oxide (+2) can be reduced to molecular nitrogen (0) through microbial denitrification, or nitric oxide can be sequentially oxidized to nitrite (+3) and then to nitrate (+5) through microbial nitrification. There are major implications of these findings for the use of biofilters as air pollution control devices since economical NO{sub x} control technologies may be possible and should be exploited. Oxidation of ammonia ({minus}3) to nitrite (+3) by bacteria of the genus Nitrosomonas and oxidation of nitrite (+3) to nitrate (+5) by bacteria of the genus Nitrobacter are ubiquitous reactions in soil and natural waters. The intermediates, nitrous oxide (+1) and nitric oxide (+2) are potentially oxidizable by nitrifying bacteria in the presence of atmospheric concentration of oxygen. The oxidation of nitric oxide within a biofilter was demonstrated. The authors have observed removal up to 70% in laboratory scale aerobic biofilters with a NO feed of 80 ppmv and an empty bed contact time of 12 minutes. Nitric oxide removal appears to be linear with nitric oxide concentration. Removal rates are a function of the flow rate of the gas, suggesting diffusion limitations. The biofilter system was sensitive to pH changes resulting from nitrification. Improved removal efficiency at shorter contact times may be possible with increased biomass and better distribution.

  6. Fatty acid oxidation and isoprostanes: oxidative strain and oxidative stress.

    PubMed

    Basu, Samar

    2010-01-01

    Oxidative stress is implicated as one of the key causes underlying many diseases. Free radicals are important constituents of basal physiology. Assessment of free radicals or the end products of their action has proved to be difficult. Consequently, authentication of the contribution of free radicals to physiology and pathology has usually been equivocal. Isoprostanes are biosynthesized in vivo, predominantly through free radical attack on arachidonic acid and are now regarded as robust biomarkers of oxidative stress in vivo. Isoprostanes are associated with many human diseases, and their concentration is altered over the course of normal human pregnancy, but their (patho)physiological roles have not yet been clearly defined. Measurement of F(2)-isoprostanes in body fluids could offer a unique analytical opportunity to study the role of free radicals in physiology and pathophysiology in order to comprehend both oxidative strain and oxidative stress. PMID:20363116

  7. Oxidative stress in neurodegeneration.

    PubMed

    Shukla, Varsha; Mishra, Santosh K; Pant, Harish C

    2011-01-01

    It has been demonstrated that oxidative stress has a ubiquitous role in neurodegenerative diseases. Major source of oxidative stress due to reactive oxygen species (ROS) is related to mitochondria as an endogenous source. Although there is ample evidence from tissues of patients with neurodegenerative disorders of morphological, biochemical, and molecular abnormalities in mitochondria, it is still not very clear whether the oxidative stress itself contributes to the onset of neurodegeneration or it is part of the neurodegenerative process as secondary manifestation. This paper begins with an overview of how oxidative stress occurs, discussing various oxidants and antioxidants, and role of oxidative stress in diseases in general. It highlights the role of oxidative stress in neurodegenerative diseases like Alzheimer's, Parkinson's, and Huntington's diseases and amyotrophic lateral sclerosis. The last part of the paper describes the role of oxidative stress causing deregulation of cyclin-dependent kinase 5 (Cdk5) hyperactivity associated with neurodegeneration. PMID:21941533

  8. Oxidative stress and anxiety

    PubMed Central

    Rammal, Hassan; Soulimani, Rachid

    2009-01-01

    High O2 consumption, modest antioxidant defenses and a lipid-rich constitution make the brain highly vulnerable to redox imbalances. Oxidative damage in the brain causes nervous system impairment. Recently, oxidative stress has also been implicated in depression, anxiety disorders and high anxiety levels. The findings which establish a link between oxidative stress and pathological anxiety have inspired a number of other recent studies focusing on the link between oxidative status and normal anxiety and also on a possible causal relationship between cellular oxidative stress and emotional stress. This review examines the recent discoveries made on the link between oxidative status and normal anxiety levels and the putative role of oxidative stress in genesis of anxiety. We discuss the different opinions and questions that exist in the field and review the methodological approaches that are being used to determine a causal relationship between oxidative and emotional stress. PMID:20357926

  9. Electrolytic oxidation of anthracite

    USGS Publications Warehouse

    Senftle, F.E.; Patton, K.M.; Heard, I., Jr.

    1981-01-01

    An anthracite slurry can be oxidized only with difficulty by electrolytic methods in which aqueous electrolytes are used if the slurry is confined to the region of the anode by a porous pot or diaphragm. However, it can be easily oxidized if the anthracite itself is used as the anode. No porous pot or diaphragm is needed. Oxidative consumption of the coal to alkali-soluble compounds is found to proceed preferentially at the edges of the aromatic planes. An oxidation model is proposed in which the chief oxidants are molecular and radical species formed by the electrolytic decomposition of water at the coal surface-electrolyte interface. The oxidation reactions proposed account for the opening of the aromatic rings and the subsequent formation of carboxylic acids. The model also explains the observed anisotropic oxidation and the need for the porous pot or diaphragm used in previous studies of the oxidation of coal slurries. ?? 1981.

  10. Bridged graphite oxide materials

    NASA Technical Reports Server (NTRS)

    Herrera-Alonso, Margarita (Inventor); McAllister, Michael J. (Inventor); Aksay, Ilhan A. (Inventor); Prud'homme, Robert K. (Inventor)

    2010-01-01

    Bridged graphite oxide material comprising graphite sheets bridged by at least one diamine bridging group. The bridged graphite oxide material may be incorporated in polymer composites or used in adsorption media.

  11. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael (Naperville, IL); Ahmed, Shabbir (Bolingbrook, IL); Kumar, Romesh (Naperville, IL); Doshi, Rajiv (Downers Grove, IL)

    2000-01-01

    A two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion. The dehydrogenation portion is a group VIII metal and the oxide-ion conducting portion is selected from a ceramic oxide crystallizing in the fluorite or perovskite structure. There is also disclosed a method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.

  12. Zirconium Oxide Nanostructures Prepared by Anodic Oxidation

    SciTech Connect

    Dang, Ying Yi; Bhuiyan, Md S; Paranthaman, Mariappan Parans

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic films can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide film to flake off. Further studies are needed to define the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  13. ZIRCONIUM OXIDE NANOSTRUCTURES PREPARED BY ANODIC OXIDATION

    SciTech Connect

    Dang, Y. Y.; Bhuiyan, M.S.; Paranthaman, M. P.

    2008-01-01

    Zirconium oxide is an advanced ceramic material highly useful for structural and electrical applications because of its high strength, fracture toughness, chemical and thermal stability, and biocompatibility. If highly-ordered porous zirconium oxide membranes can be successfully formed, this will expand its real-world applications, such as further enhancing solid-oxide fuel cell technology. Recent studies have achieved various morphologies of porous zirconium oxide via anodization, but they have yet to create a porous layer where nanoholes are formed in a highly ordered array. In this study, electrochemical methods were used for zirconium oxide synthesis due to its advantages over other coating techniques, and because the thickness and morphology of the ceramic fi lms can be easily tuned by the electrochemical parameters, such as electrolyte solutions and processing conditions, such as pH, voltage, and duration. The effects of additional steps such as pre-annealing and post-annealing were also examined. Results demonstrate the formation of anodic porous zirconium oxide with diverse morphologies, such as sponge-like layers, porous arrays with nanoholes ranging from 40 to 75 nm, and nanotube layers. X-ray powder diffraction analysis indicates a cubic crystallographic structure in the zirconium oxide. It was noted that increased voltage improved the ability of the membrane to stay adhered to the zirconium substrate, whereas lower voltages caused a propensity for the oxide fi lm to fl ake off. Further studies are needed to defi ne the parameters windows that create these morphologies and to investigate other important characteristics such as ionic conductivity.

  14. Mechanism of N(5)-ethyl-flavinium cation formation upon electrochemical oxidation of N(5)-ethyl-4a-hydroxyflavin pseudobase.

    PubMed

    Sichula, Vincent; Hu, Ying; Mirzakulova, Ekaterina; Manzer, Samuel F; Vyas, Shubham; Hadad, Christopher M; Glusac, Ksenija D

    2010-07-29

    We investigated the oxidation behavior of 5-ethyl-4a-hydroxy-3-methyl-4a,5-dihydrolumiflavin (pseudobase Et-FlOH) in acetonitrile with the aim of determining if the two-electron oxidized Et-FlOH(2+) undergoes a release of hydroxyl cation and the production of 5-ethyl-3methyllumiflavinium cation (Et-Fl(+)). The focus of this work is to investigate the possibility of using Et-FlOH as a catalyst for water oxidation. The cyclic voltammetry demonstrates that Et-FlOH exhibits two one-electron oxidation potentials at +0.95 and +1.4 V versus normal hydrogen electrode (NHE), with the second oxidation potential being irreversible. The production of Et-Fl(+) is observed in the cyclic voltammetry of Et-FlOH and has been previously assigned to the release of OH(+) from the two-electron oxidized Et-FlOH(2+). The results of our study show that this is not the case: (i) we performed bulk electrolysis of the electrolyte solution at +2 V and then added Et-FlOH to the electrolyzed solution. We found that Et-Fl(+) is produced from this solution, even though Et-FlOH itself was not oxidized; (ii) reactions of Et-FlOH with chemical oxidants (ceric ammonium nitrate, nitrosyl tetrafluoroborate, and tetrabutylammonium persulfate) demonstrate that Et-Fl(+) production occurs only in the presence of strong Lewis acids, such as Ce(4+) and NO(+) ions. On the basis of these results, we propose that the production of Et-Fl(+) in the electrochemistry of Et-FlOH occurs because of the shift in the Et-FlOH/Et-Fl(+) acid-base equilibrium in the presence of protons released during anodic oxidation. We identified two sources of protons: (i) oxidation of traces of water present in the acetonitrile releases oxygen and protons and (ii) two-electron oxidized Et-FlOH(2+) releases protons located on the N(5)-alkyl chain. The release of protons from Et-FlOH(2+) was confirmed by cyclic voltammetry of Et-FlOH in the presence of pyridine as a base. The first oxidation peak of Et-FlOH at +0.95 V is reversible in the absence of pyridine. The addition of pyridine leads to the shift of the oxidation potential to a less positive value, which is consistent with a proton-coupled electron transfer (PCET). Furthermore, the anodic current increases, and the cathodic peak becomes irreversible, giving rise to two additional reduction peaks at -0.2 and -1 V. The same reduction peaks were observed in the high scan rate cyclic voltammogram of Et-FlOH in the absence of pyridine, implying that the release of protons indeed occurs from Et-FlOH(2+). To determine which functional group of Et-FlOH(.+) is the source of protons, we performed DFT calculations at the B3LYP/6-311++G** level of theory for a reaction of Et-FlOH(.+) with pyridine and identified two proton sources: (i) the >N-CH(2)- group of the N(5) alkyl chain and (ii) the -OH group in the 4a-position of the radical cation. Because the appearance of new reduction peaks at -0.2 and -1.0 V occurs in the model compound that lacks -OH protons (Et-FlOMe), we conclude that the proton removal occurs predominantly from the >N-CH(2)- moiety. PMID:20597524

  15. Acute in vivo toxicity mitigation of PEI-coated maghemite nanoparticles using controlled oxidation and surface modifications toward siRNA delivery.

    PubMed

    Israel, Liron Limor; Lellouche, Emmanuel; Ostrovsky, Stella; Yarmiayev, Valeria; Bechor, Moshe; Michaeli, Shulamit; Lellouche, Jean-Paul Moshe

    2015-07-22

    A ceric ammonium nitrate (CAN)-based doping step was used for the fabrication of core maghemite nanoparticles (NPs) that enabled the obtainment of colloid particles with a view to a high-level nanoparticle (NP) surface doping by Ce(III/IV). Such doping of Ce(III/IV) cations enables one to exploit their quite rich coordination chemistry for ligand coordinative binding. In fact, they were shown to act as powerful Lewis acid centers for attaching any organic (Lewis base) ligand such as a 25 kDa branched PEI polymer. Resulting conPEI25-CAN-γ-Fe2O3 NPs have been fully characterized before a successful implementation of siRNA loading and cell delivery/gene silencing using a well-known dual luciferase system. This attractive result emphasized their significant potential as an NP platform technology toward additional MRI and/or drug delivery (peptide)-relating end applications. However, due to their high positive charge, PEI polymers can cause severe in vivo toxicity due to their interaction with negatively charged red blood cells (RBC), resulting in RBC aggregation and lysis, leading to thrombosis and, finally, to animal death. In order to mitigate these acute toxic effects, two different types of surface modifications were performed. One modification included the controlled oxidation of 0.1-5% of the PEI amines before or after conjugation to the NPs, using hydrogen peroxide or potassium persulfate. The other type of modification was the addition of a second biocompatible polyanionic polymer to the PEI grafted NPs, based on the concept of a layer-by-layer (LbL) technique. This modification is based on the coordination of another polyanionic polymer on the NPs surface in order to create a combined hybrid PEI and polyanionic polymer nanosystem. In both cases, the surface modification successfully mitigated the NP acute in vivo toxicity, without compromising the silencing efficiency. PMID:26120905

  16. Oxidation Resistant Graphite Studies

    SciTech Connect

    W. Windes; R. Smith

    2014-07-01

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

  17. Biomimetic Water-Oxidation Catalysts: Manganese Oxides.

    PubMed

    Kurz, Philipp

    2016-01-01

    The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnOx. This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnOx. The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn (III/IV)-oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials. In the outlook, the challenges of catalyst screenings (and hence the identification of a "best MnOx catalyst") are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnOx materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future. PMID:25980320

  18. Barium oxide, calcium oxide, magnesia, and alkali oxide free glass

    DOEpatents

    Lu, Peizhen Kathy; Mahapatra, Manoj Kumar

    2013-09-24

    A glass composition consisting essentially of about 10-45 mole percent of SrO; about 35-75 mole percent SiO.sub.2; one or more compounds from the group of compounds consisting of La.sub.2O.sub.3, Al.sub.2O.sub.3, B.sub.2O.sub.3, and Ni; the La.sub.2O.sub.3 less than about 20 mole percent; the Al.sub.2O.sub.3 less than about 25 mole percent; the B.sub.2O.sub.3 less than about 15 mole percent; and the Ni less than about 5 mole percent. Preferably, the glass is substantially free of barium oxide, calcium oxide, magnesia, and alkali oxide. Preferably, the glass is used as a seal in a solid oxide fuel/electrolyzer cell (SOFC) stack. The SOFC stack comprises a plurality of SOFCs connected by one or more interconnect and manifold materials and sealed by the glass. Preferably, each SOFC comprises an anode, a cathode, and a solid electrolyte.

  19. The Oxidation of Pyrrole.

    PubMed

    Howard, James K; Rihak, Kieran J; Bissember, Alex C; Smith, Jason A

    2016-01-01

    The dearomatization of heterocycles has been a powerful means for producing functional molecules in synthesis. In the case of pyrroles, reductive methods (such as the Birch reduction) have been most widely exploited, while oxidative methods are generally dismissed as too difficult or unpredictable to be useful. However, since the early twentieth century considerable research has been carried out on the controlled oxidation of pyrroles to give highly functionalized products, using a variety of oxidants. This review presents a summary of all work up until the present day in the area of pyrrole oxidation, looking at the use of peroxide, singlet oxygen, hypervalent iodine reagents, a range or organic and inorganic oxidants, and electrochemical approaches. It also offers some perspective on the potential future role of pyrrole oxidation in synthesis. PMID:26294175

  20. Design for Oxidation Resistance

    NASA Technical Reports Server (NTRS)

    Smialek, James L.; Schaeffer, Jon C.; Barrett, Charles A.

    1997-01-01

    Alloys intended for use in high-temperature environment rely on the formation of a continuous, compact, slow-growing oxide layer for oxidation and hot corrosion resistance. To be protective, this oxide layer must be chemically, thermodynamically stable. Successful alloy design for oxidative environment is best achieved by developing alloys that are capable of forming adherent scales of either alumina (Al2O3), chromia (Cr2O3), or silica (SiO2). In this article, emphasis has been placed on the issue related to high-temperature oxidation of superalloys used in gas turbine engine application. Despite the complexity of these alloys, optimal performance has been associated with protective alumina scale formation. As will be described below, both compositional makeup and protective coatings play key role in providing oxidation protection. Other high-temperature materials described include nickel and titanium aluminide intermetallics, refractory metal, and ceramics.

  1. Plasma oxidation of polymers

    SciTech Connect

    Moss, S.J.; Jolly, A.M.; Tighe, B.J.

    1986-12-01

    The rates of plasma oxidation have been measured for homopolymers of several monomers and for copolymers of methyl methacrylate with styrene and vinyl naphthalene. Their results show that relatively small amounts of the aromatic component in the copolymer convey substantially increased resistance to plasma oxidation. Current knowledge of the mechanisms of plasma oxidation is reviewed and new mechanistic explanations are suggested. The implications for improved design of plasma-developable resists systems are considered.

  2. METAL OXIDE NANOPARTICLES

    SciTech Connect

    FERNANDEZ-GARCIA,M.; RODGRIGUEZ, J.A.

    2007-10-01

    This chapter covers the fundamental science, synthesis, characterization, physicochemical properties and applications of oxide nanomaterials. Explains fundamental aspects that determine the growth and behavior of these systems, briefly examines synthetic procedures using bottom-up and top-down fabrication technologies, discusses the sophisticated experimental techniques and state of the art theory results used to characterize the physico-chemical properties of oxide solids and describe the current knowledge concerning key oxide materials with important technological applications.

  3. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott (Dublin, CA); Wang, Ruiping (Fremont, CA); Derouane, Eric (Liverpool, GB)

    2003-01-01

    The present invention is a mixed oxide solid solution containing a tetravalent and a pentavalent cation that can be used as a support for a metal combustion catalyst. The invention is furthermore a combustion catalyst containing the mixed oxide solid solution and a method of making the mixed oxide solid solution. The tetravalent cation is zirconium(+4), hafnium(+4) or thorium(+4). In one embodiment, the pentavalent cation is tantalum(+5), niobium(+5) or bismuth(+5). Mixed oxide solid solutions of the present invention exhibit enhanced thermal stability, maintaining relatively high surface areas at high temperatures in the presence of water vapor.

  4. Oxidants and oxidation in the Earth's atmosphere

    NASA Technical Reports Server (NTRS)

    1995-01-01

    The 1994 BOC Priestley Conference was held at Bucknell University in Lewisburg, Pennsylvania, from June 24 through June 27, 1994. This conference, managed by the American Chemical Society (ACS), was a joint celebration with the Royal Society of Chemistry (RSC) commemorating Joseph Priestley's arrival in the U.S. and his discovery of oxygen. The basic theme of the conference was 'Oxidants and Oxidation in the Earth's Atmosphere,' with a keynote lecture on the history of ozone. A distinguished group of U.S. and international atmospheric chemists addressed the issues dominating current research and policy agendas. Topics crucial to the atmospheric chemistry of global change and local and regional air pollution were discussed. The program for the conference included four technical sessions on the following topics: (1) Oxidative Fate of Atmospheric Pollutants; (2) Photochemical Smog and Ozone; (3) Stratospheric Ozone; and (4) Global Tropospheric Ozone.

  5. UV Induced Oxidation of Nitric Oxide

    NASA Technical Reports Server (NTRS)

    Parrish, Clyde, F. (Inventor); Luecke, Dale E. (Inventor)

    2007-01-01

    Nitric oxide in a gaseous stream is converted to nitrogen dioxide using oxidizing species generated at least in part using in situ UV radiation sources. The sources of the oxidizing species include oxygen and/or hydrogen peroxide. The oxygen may be a component of the gaseous stream or added to the gaseous stream, preferably near a UV radiation source, and is converted to ozone by the UV irradiation. The hydrogen peroxide is decomposed through a combination of vaporization and UV irradiation. The hydrogen peroxide is preferably stored at stable concentration levels, i.e., approximately 50% by volume and increased in concentration in a continuous process preceding vaporization within the flow channel of the gaseous stream and in the presence of the UV radiation sources.

  6. Catalytic process for formaldehyde oxidation

    NASA Technical Reports Server (NTRS)

    Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); D'Ambrosia, Christine M. (Inventor)

    1996-01-01

    Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  7. Monolithic metal oxide transistors.

    PubMed

    Choi, Yongsuk; Park, Won-Yeong; Kang, Moon Sung; Yi, Gi-Ra; Lee, Jun-Young; Kim, Yong-Hoon; Cho, Jeong Ho

    2015-04-28

    We devised a simple transparent metal oxide thin film transistor architecture composed of only two component materials, an amorphous metal oxide and ion gel gate dielectric, which could be entirely assembled using room-temperature processes on a plastic substrate. The geometry cleverly takes advantage of the unique characteristics of the two components. An oxide layer is metallized upon exposure to plasma, leading to the formation of a monolithic source-channel-drain oxide layer, and the ion gel gate dielectric is used to gate the transistor channel effectively at low voltages through a coplanar gate. We confirmed that the method is generally applicable to a variety of sol-gel-processed amorphous metal oxides, including indium oxide, indium zinc oxide, and indium gallium zinc oxide. An inverter NOT logic device was assembled using the resulting devices as a proof of concept demonstration of the applicability of the devices to logic circuits. The favorable characteristics of these devices, including (i) the simplicity of the device structure with only two components, (ii) the benign fabrication processes at room temperature, (iii) the low-voltage operation under 2 V, and (iv) the excellent and stable electrical performances, together support the application of these devices to low-cost portable gadgets, i.e., cheap electronics. PMID:25777338

  8. OXIDANT-PRECURSOR RELATIONSHIPS

    EPA Science Inventory

    New methods of ambient air analysis were used to define more clearly the relationships between oxidants and their precursors. Non-methane hydrocarbons, NOx, O2, and oxidants were measured at the same time and location (Riverside, California). The ambient air data presented in thi...

  9. Redefining oxidative stress.

    PubMed

    Jones, Dean P

    2006-01-01

    Oxidative stress is often defined as an imbalance of pro-oxidants and antioxidants, which can be quantified in humans as the redox state of plasma GSH/GSSG. Plasma GSH redox in humans becomes oxidized with age, in response to oxidative stress (chemotherapy, smoking), and in common diseases (type 2 diabetes, cardiovascular disease). However, data also show that redox of plasma GSH/GSSG is not equilibrated with the larger plasma cysteine/cystine (Cys/CySS) pool, indicating that the "balance" of pro-oxidants and antioxidants cannot be defined by a single entity. The major cellular thiol/disulfide systems, including GSH/GSSG, thioredoxin- 1 (-SH(2)/-SS-), and Cys/CySS, are not in redox equilibrium and respond differently to chemical toxicants and physiologic stimuli. Individual signaling and control events occur through discrete redox pathways rather than through mechanisms that are directly responsive to a global thiol/disulfide balance such as that conceptualized in the common definition of oxidative stress. Thus, from a mechanistic standpoint, oxidative stress may be better defined as a disruption of redox signaling and control. Adoption of such a definition could redirect research to identify key perturbations of redox signaling and control and lead to new treatments for oxidative stress-related disease processes. PMID:16987039

  10. Stabilized chromium oxide film

    DOEpatents

    Nyaiesh, A.R.; Garwin, E.L.

    1986-08-04

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150A are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  11. Stabilized chromium oxide film

    DOEpatents

    Garwin, Edward L. (Los Altos, CA); Nyaiesh, Ali R. (Palo Alto, CA)

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  12. Lagoons and Oxidation Ponds.

    ERIC Educational Resources Information Center

    O'Brien, W. J.

    1978-01-01

    Presents the 1978 literature review of wastewater treatment. This review covers lagoons and oxidation ponds, and it includes some areas such as improving the effluents from ponds, stabilization ponds, aerated lagoons, and oxidation ditches. A list of 36 references is also presented. (HM)

  13. Reducible oxide based catalysts

    DOEpatents

    Thompson, Levi T.; Kim, Chang Hwan; Bej, Shyamal K.

    2010-04-06

    A catalyst is disclosed herein. The catalyst includes a reducible oxide support and at least one noble metal fixed on the reducible oxide support. The noble metal(s) is loaded on the support at a substantially constant temperature and pH.

  14. OXIDATION OF CHLORINATED ETHANES

    EPA Science Inventory

    The oxidation products of seven chlorinated ethanes were identified using Fourier Transform Spectroscopy and long path infrared techniques. Photo-oxidation of each chlorinated ethane was initiated by chlorine atoms in one atmosphere of dry air. The chlorinated reaction products i...

  15. Organic Oxidations Using Geomimicry.

    PubMed

    Yang, Ziming; Hartnett, Hilairy E; Shock, Everett L; Gould, Ian R

    2015-12-18

    Oxidations of phenylacetic acid to benzaldehyde, benzyl alcohol to benzaldehyde, and benzaldehyde to benzoic acid have been observed, in water as the solvent and using only copper(II) chloride as the oxidant. The reactions are performed at 250 C and 40 bar, conditions that mimic hydrothermal reactions that are geochemically relevant. Speciation calculations show that the oxidizing agent is not freely solvated copper(II) ions, but complexes of copper(II) with chloride and carboxylate anions. Measurements of the reaction stoichiometries and also of substituent effects on reactivity allow plausible mechanisms to be proposed. These oxidation reactions are relevant to green chemistry in that they proceed in high chemical yield in water as the solvent and avoid the use of toxic heavy metal oxidizing reagents. PMID:26561976

  16. [Oxidative stress and magnesium].

    PubMed

    Hasebe, Naoyuki

    2005-02-01

    The generation of reactive oxygen species and other free radicals during metabolism is a necessary and normal process that ideally is compensated for by an elaborate endogenous antioxidant system. However, due to many environmental, lifestyle, and pathological situations, excess radicals can accumulate, resulting in oxidative stress. Oxidative stress has been related to cardiovascular disease, cancer, and other chronic diseases that account for a major portion of deaths today. Antioxidants are compounds that hinder the oxidative processes and thereby delay or prevent oxidative stress. In this sense, magnesium is one of the physiological, efficient antioxidant. Magnesium plays a role in more than 300 enzymatic reactions and is critically involved in energy metabolism, glucose utilization, protein synthesis, fatty acid synthesis and breakdown, ATPase functions, and virtually all hormonal reactions. This article summarizes the process of oxidative stress and the pathways by which it relates to magnesium. PMID:15692157

  17. Oxidation characteristics of molybdenum-zirconium oxide cermets

    NASA Technical Reports Server (NTRS)

    Heitzinger, B.

    1984-01-01

    The oxidation of molybdenum is affected by the factors of temperature, the oxygen pressure in the oxidizing atmosphere, and the time of exposure. Studies of the oxidation characteristics of Mo show that the oxidation rate increases strongly when the temperature exceeds 600 C. Investigations of the behavior of cermets with various percentages of zirconium oxide are discussed, taking into account oxidation conditions at temperatures under and above the melting point of molybdenum trioxide.

  18. Biocompatibility of Graphene Oxide

    NASA Astrophysics Data System (ADS)

    Wang, Kan; Ruan, Jing; Song, Hua; Zhang, Jiali; Wo, Yan; Guo, Shouwu; Cui, Daxiang

    2011-12-01

    Herein, we report the effects of graphene oxides on human fibroblast cells and mice with the aim of investigating graphene oxides' biocompatibility. The graphene oxides were prepared by the modified Hummers method and characterized by high-resolution transmission electron microscope and atomic force microscopy. The human fibroblast cells were cultured with different doses of graphene oxides for day 1 to day 5. Thirty mice divided into three test groups (low, middle, high dose) and one control group were injected with 0.1, 0.25, and 0.4 mg graphene oxides, respectively, and were raised for 1 day, 7 days, and 30 days, respectively. Results showed that the water-soluble graphene oxides were successfully prepared; graphene oxides with dose less than 20 ?g/mL did not exhibit toxicity to human fibroblast cells, and the dose of more than 50 ?g/mL exhibits obvious cytotoxicity such as decreasing cell adhesion, inducing cell apoptosis, entering into lysosomes, mitochondrion, endoplasm, and cell nucleus. Graphene oxides under low dose (0.1 mg) and middle dose (0.25 mg) did not exhibit obvious toxicity to mice and under high dose (0.4 mg) exhibited chronic toxicity, such as 4/9 mice death and lung granuloma formation, mainly located in lung, liver, spleen, and kidney, almost could not be cleaned by kidney. In conclusion, graphene oxides exhibit dose-dependent toxicity to cells and animals, such as inducing cell apoptosis and lung granuloma formation, and cannot be cleaned by kidney. When graphene oxides are explored for in vivo applications in animal or human body, its biocompatibility must be considered.

  19. Oxide Nanocrystal Model Catalysts.

    PubMed

    Huang, Weixin

    2016-03-15

    Model catalysts with uniform and well-defined surface structures have been extensively employed to explore structure-property relationships of powder catalysts. Traditional oxide model catalysts are based on oxide single crystals and single crystal thin films, and the surface chemistry and catalysis are studied under ultrahigh-vacuum conditions. However, the acquired fundamental understandings often suffer from the "materials gap" and "pressure gap" when they are extended to the real world of powder catalysts working at atmospheric or higher pressures. Recent advances in colloidal synthesis have realized controlled synthesis of catalytic oxide nanocrystals with uniform and well-defined morphologies. These oxide nanocrystals consist of a novel type of oxide model catalyst whose surface chemistry and catalysis can be studied under the same conditions as working oxide catalysts. In this Account, the emerging concept of oxide nanocrystal model catalysts is demonstrated using our investigations of surface chemistry and catalysis of uniform and well-defined cuprous oxide nanocrystals and ceria nanocrystals. Cu2O cubes enclosed with the {100} crystal planes, Cu2O octahedra enclosed with the {111} crystal planes, and Cu2O rhombic dodecahedra enclosed with the {110} crystal planes exhibit distinct morphology-dependent surface reactivities and catalytic properties that can be well correlated with the surface compositions and structures of exposed crystal planes. Among these types of Cu2O nanocrystals, the octahedra are most reactive and catalytically active due to the presence of coordination-unsaturated (1-fold-coordinated) Cu on the exposed {111} crystal planes. The crystal-plane-controlled surface restructuring and catalytic activity of Cu2O nanocrystals were observed in CO oxidation with excess oxygen. In the propylene oxidation reaction with O2, 1-fold-coordinated Cu on Cu2O(111), 3-fold-coordinated O on Cu2O(110), and 2-fold-coordinated O on Cu2O(100) were identified as the active sites, respectively, to produce acrolein, propylene oxide, and CO2. Ceria rods enclosed with the {110} and {100} crystal planes, ceria cubes enclosed with the {100} crystal planes, and ceria octahedra enclosed with the {111} crystal planes exhibit distinct morphology-dependent oxygen vacancy concentrations and structures that can be well correlated with the surface compositions and structures of exposed crystal planes. Consequently, the metal-ceria interactions, structures, and catalytic performances of ceria-supported catalysts depend on the CeO2 morphology. Our results comprehensively reveal the morphology-dependent surface chemistry and catalysis of oxide nanocrystals that not only greatly deepen the fundamental understanding of oxide catalysis but also demonstrate a morphology-engineering strategy to optimize the catalytic performance of oxide catalysts. These results adequately exemplify the concept of oxide nanocrystal model catalysts for the fundamental investigations of oxide catalysis without the "materials gap" and "pressure gap". With the structure-catalytic property relationships learned from oxide nanocrystal model catalyst studies and the advancement of controlled-synthesis methods, it is promising to realize the structural design and controlled synthesis of novel efficient oxide catalysts in the future. PMID:26938790

  20. NEPTUNIUM OXIDE PROCESSING

    SciTech Connect

    Jordan, J; Watkins, R; Hensel, S

    2009-05-27

    The Savannah River Site's HB-Line Facility completed a campaign in which fifty nine cans of neptunium oxide were produced and shipped to the Idaho National Laboratory in the 9975 shipping container. The neptunium campaign was divided into two parts: Part 1 which consisted of oxide made from H-Canyon neptunium solution which did not require any processing prior to conversion into an oxide, and Part 2 which consisted of oxide made from additional H-Canyon neptunium solutions which required processing to purify the solution prior to conversion into an oxide. The neptunium was received as a nitrate solution and converted to oxide through ion-exchange column extraction, precipitation, and calcination. Numerous processing challenges were encountered in order make a final neptunium oxide product that could be shipped in a 9975 shipping container. Among the challenges overcome was the issue of scale: translating lab scale production into full facility production. The balance between processing efficiency and product quality assurance was addressed during this campaign. Lessons learned from these challenges are applicable to other processing projects.

  1. Oxidative stress in COPD.

    PubMed

    Kirkham, Paul A; Barnes, Peter J

    2013-07-01

    Oxidative stress is now recognized as a major predisposing factor in the pathogenesis of COPD. Existing therapies for COPD are ineffective at halting disease progression, with bronchodilators being the mainstay of pharmacotherapy, providing symptomatic relief only. It is, therefore, important for a better understanding of the underlying mechanisms by which oxidative stress drives disease pathogenesis to develop novel and more effective therapies. Antioxidant capacity in COPD is substantially reduced as a result of cigarette smoking and exacerbations, with oxidative stress persisting long after the cessation of cigarette smoking or exacerbation, due to the continued production of reactive oxygen species from endogenous sources. We discuss (1) how oxidative stress arises in the lung, (2) how it is neutralized, (3) what genetic factors may predispose to the development of COPD, and (4) how this impacts inflammation and autoimmunity in the development of emphysema and small airways disease. Finally, various strategies have been considered to neutralize the increased oxidative burden present in COPD. This review highlights why current antioxidant strategies have so far failed and what promising alternatives are on the horizon. Moreover, a number of studies have shown that there is no single "magic bullet" to combat oxidative stress, but instead a combination therapy, targeting oxidative stress in the various subcellular compartments, may prove to be more effective in COPD. PMID:23880677

  2. Transpassive oxidation of pyrite

    SciTech Connect

    Zhu, Ximeng; Bodily, D.M.; Wadsworth, M.E. . College of Mines and Earth Sciences)

    1993-07-01

    The electrochemical behavior of mineral and coal pyrites in basic borate/sulfate solutions was investigated using cyclic voltammetry with both stationary and rotating disk electrode. Emphasis was centered on transpassive oxidation. In the transpassive region, 0.4 to 0.8 V (SCE), aggressive oxidation of pyrite occurred. The reaction products in this region are Fe(III) oxides, sulfate ion, and partially oxidized sulfur intermediates. The formation of sulfur and polysulfides was identified by in situ Raman spectroscopy. Exposure of pyrite to anodic potentials higher than the transpassive region resulted in rapid oxidation of sulfur intermediates to sulfate ion. The effect of electrode rotation speed, electrode precondition time, and upper potential of the scan in the transpassive region was observed to be critical to the formation of sulfur intermediates. Sulfur intermediates, formed in the transpassive region, dramatically affected subsequent oxidation reactions occurring in the lower potential region. The magnitude of two dominant oxidation peaks, a ferrous hydroxide peak and an iron sulfide peak, observed in this region correlated directly with the quantity of sulfur intermediates formed in the transpassive region. This effect was less pronounced for coal pyrites compared to mineral pyrite.

  3. Mercuric oxide poisoning

    MedlinePLUS

    Mercuric oxide may be found in some: Button batteries (batteries containing mercury are no longer sold in the ... long-term injury Any person who swallowed a battery will need immediate x-rays to make sure ...

  4. Oxidative Tritium Decontamination System

    DOEpatents

    Gentile, Charles A. (Plainsboro, NJ), Guttadora, Gregory L. (Highland Park, NJ), Parker, John J. (Medford, NJ)

    2006-02-07

    The Oxidative Tritium Decontamination System, OTDS, provides a method and apparatus for reduction of tritium surface contamination on various items. The OTDS employs ozone gas as oxidizing agent to convert elemental tritium to tritium oxide. Tritium oxide vapor and excess ozone gas is purged from the OTDS, for discharge to atmosphere or transport to further process. An effluent stream is subjected to a catalytic process for the decomposition of excess ozone to diatomic oxygen. One of two configurations of the OTDS is employed: dynamic apparatus equipped with agitation mechanism and large volumetric capacity for decontamination of light items, or static apparatus equipped with pressurization and evacuation capability for decontamination of heavier, delicate, and/or valuable items.

  5. Chemistry of phospholipid oxidation.

    PubMed

    Reis, Ana; Spickett, Corinne M

    2012-10-01

    The oxidation of lipids has long been a topic of interest in biological and food sciences, and the fundamental principles of non-enzymatic free radical attack on phospholipids are well established, although questions about detail of the mechanisms remain. The number of end products that are formed following the initiation of phospholipid peroxidation is large, and is continually growing as new structures of oxidized phospholipids are elucidated. Common products are phospholipids with esterified isoprostane-like structures and chain-shortened products containing hydroxy, carbonyl or carboxylic acid groups; the carbonyl-containing compounds are reactive and readily form adducts with proteins and other biomolecules. Phospholipids can also be attacked by reactive nitrogen and chlorine species, further expanding the range of products to nitrated and chlorinated phospholipids. Key to understanding the mechanisms of oxidation is the development of advanced and sensitive technologies that enable structural elucidation. Tandem mass spectrometry has proved invaluable in this respect and is generally the method of choice for structural work. A number of studies have investigated whether individual oxidized phospholipid products occur in vivo, and mass spectrometry techniques have been instrumental in detecting a variety of oxidation products in biological samples such as atherosclerotic plaque material, brain tissue, intestinal tissue and plasma, although relatively few have achieved an absolute quantitative analysis. The levels of oxidized phospholipids in vivo is a critical question, as there is now substantial evidence that many of these compounds are bioactive and could contribute to pathology. The challenges for the future will be to adopt lipidomic approaches to map the profile of oxidized phospholipid formation in different biological conditions, and relate this to their effects in vivo. This article is part of a Special Issue entitled: Oxidized phospholipids-their properties and interactions with proteins. PMID:22342938

  6. Controlled CO preferential oxidation

    DOEpatents

    Meltser, M.A.; Hoch, M.M.

    1997-06-10

    Method is described for controlling the supply of air to a PROX (PReferential OXidation for CO cleanup) reactor for the preferential oxidation in the presence of hydrogen wherein the concentration of the hydrogen entering and exiting the PROX reactor is monitored, the difference there between correlated to the amount of air needed to minimize such difference, and based thereon the air supply to the PROX reactor adjusted to provide such amount and minimize such difference. 2 figs.

  7. Silver(II) Oxide or Silver(I,III) Oxide?

    ERIC Educational Resources Information Center

    Tudela, David

    2008-01-01

    The often called silver peroxide and silver(II) oxide, AgO or Ag[subscript 2]O[subscript 2], is actually a mixed oxidation state silver(I,III) oxide. A thermochemical cycle, with lattice energies calculated within the "volume-based" thermodynamic approach, explain why the silver(I,III) oxide is more stable than the hypothetical silver(II) oxide.

  8. Silver(II) Oxide or Silver(I,III) Oxide?

    ERIC Educational Resources Information Center

    Tudela, David

    2008-01-01

    The often called silver peroxide and silver(II) oxide, AgO or Ag[subscript 2]O[subscript 2], is actually a mixed oxidation state silver(I,III) oxide. A thermochemical cycle, with lattice energies calculated within the "volume-based" thermodynamic approach, explain why the silver(I,III) oxide is more stable than the hypothetical silver(II) oxide.…

  9. Enargite oxidation: A review

    NASA Astrophysics Data System (ADS)

    Lattanzi, Pierfranco; Da Pelo, Stefania; Musu, Elodia; Atzei, Davide; Elsener, Bernhard; Fantauzzi, Marzia; Rossi, Antonella

    2008-01-01

    Enargite, Cu 3AsS 4, is common in some deposit types, e.g. porphyry systems and high sulphidation epithermal deposits. It is of environmental concern as a potential source of arsenic. In this communication, we review the current knowledge of enargite oxidation, based on the existing literature and our own original data. Explicit descriptions of enargite oxidation in natural environments are scarce. The most common oxidized alteration mineral of enargite is probably scorodite, FeAsO 4.2H 2O, with iron provided most likely by pyrite, a phase almost ubiquitously associated with enargite. Other secondary minerals after enargite include arsenates such as chenevixite, Cu 2Fe 2(AsO 4) 2(OH) 4.H 2O, and ceruleite, Cu 2Al 7(AsO 4) 4.11.5H 2O, and sulphates such as brochantite, Cu 4(SO 4)(OH) 6, and posnjakite, Cu 4(SO 4)(OH) 6·H 2O. Detailed studies of enargite field alteration at Furtei, Sardinia, suggest that most alteration occurs through dissolution, as testified by the appearance of etch pits at the surface of enargite crystals. However, apparent replacement by scorodite and cuprian melanterite was observed. Bulk oxidation of enargite in air is a very slow process. However, X-ray photoelectron spectroscopy (XPS) reveals subtle surface changes. From synchrotron-based XPS it was suggested that surface As atoms react very fast, presumably by forming bonds with oxygen. Conventional XPS shows the formation, on aged samples, of a nanometer-size alteration layer with an appreciably distinct composition with respect to the bulk. Mechanical activation considerably increases enargite reactivity. In laboratory experiments at acidic to neutral pH, enargite oxidation/dissolution is slow, although it is accelerated by the presence of ferric iron and/or bacteria such as Acidithiobacillus ferrooxidans and Sulfolobus BC. In the presence of sulphuric acid and ferric iron, the reaction involves dissolution of Cu and formation of native sulphur, subsequently partly oxidized to sulphate. At alkaline pH, the reactivity of enargite is apparently slightly greater. XPS spectra of surfaces conditioned at pH 11 have been interpreted as evidence of formation of a number of surface species, including cupric oxide and arsenic oxide. Treatment with hypochlorite solutions at pH 12.5 quickly produces a coating of cupric oxide. Electrochemical oxidation of enargite typically involves low current densities, confirming that the oxidation process is slow. Important surface changes occur only at high applied potentials, e.g. + 0.74 V vs. SHE. It is confirmed that, at acidic pH, the dominant process is Cu dissolution, accompanied (at + 0.56 V vs. SHE, pH = 1) by formation of native sulphur. At alkaline pH, a number of surface products have been suggested, including copper and arsenic oxides, and copper arsenates. XPS studies of the reacted surfaces demonstrate the evolution of Cu from the monovalent to the divalent state, the formation of As-O bonds, and the oxidation of sulphur to polysulphide, sulphite and eventually sulphate. In most natural and quasi-natural (mining) situations, it is expected that enargite reactivity will be slow. Moreover, it is likely that the release of arsenic will be further slowed down by at least temporary trapping in secondary phases. Therefore, an adequate management of exposed surfaces and wastes should minimize the environmental impact of enargite-bearing deposits. In spite of an increasing body of data, there are several gaps in our knowledge of enargite oxidation. The exact nature of most mechanisms and products remains poorly constrained, and there is a lack of quantitative data on the dependence on parameters such as pH and dissolved oxygen.

  10. Staphylococcal response to oxidative stress

    PubMed Central

    Gaupp, Rosmarie; Ledala, Nagender; Somerville, Greg A.

    2012-01-01

    Staphylococci are a versatile genus of bacteria that are capable of causing acute and chronic infections in diverse host species. The success of staphylococci as pathogens is due in part to their ability to mitigate endogenous and exogenous oxidative and nitrosative stress. Endogenous oxidative stress is a consequence of life in an aerobic environment; whereas, exogenous oxidative and nitrosative stress are often due to the bacteria's interaction with host immune systems. To overcome the deleterious effects of oxidative and nitrosative stress, staphylococci have evolved protection, detoxification, and repair mechanisms that are controlled by a network of regulators. In this review, we summarize the cellular targets of oxidative stress, the mechanisms by which staphylococci sense oxidative stress and damage, oxidative stress protection and repair mechanisms, and regulation of the oxidative stress response. When possible, special attention is given to how the oxidative stress defense mechanisms help staphylococci control oxidative stress in the host. PMID:22919625

  11. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1997-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  12. Metal oxide-polymer composites

    NASA Technical Reports Server (NTRS)

    Wellinghoff, Stephen T. (Inventor)

    1994-01-01

    A method of making metal oxide clusters in a single stage by reacting a metal oxide with a substoichiometric amount of an acid in the presence of an oxide particle growth terminator and solubilizer. A method of making a ceramer is also disclosed in which the metal oxide clusters are reacted with a functionalized polymer. The resultant metal oxide clusters and ceramers are also disclosed.

  13. Stabilized tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2008-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  14. Switching Oxide Traps

    NASA Technical Reports Server (NTRS)

    Oldham, Timothy R.

    2003-01-01

    We consider radiation-induced charge trapping in SiO2 dielectric layers, primarily from the point of view of CMOS devices. However, SiO2 insulators are used in many other ways, and the same defects occur in other contexts. The key studies, which determined the nature of the oxide charge traps, were done primarily on gate oxides in CMOS devices, because that was the main radiation problem in CMOS at one time. There are two major reviews of radiation-induced oxide charge trapping already in the literature, which discuss the subject in far greater detail than is possible here. The first of these was by McLean et al. in 1989, and the second, ten years later, was intended as an update, because of additional, new work that had been reported. Basically, the picture that has emerged is that ionizing radiation creates electron-hole pairs in the oxide, and the electrons have much higher mobility than the holes. Therefore, the electrons are swept out of the oxide very rapidly by any field that is present, leaving behind any holes that escape the initial recombination process. These holes then undergo a polaron hopping transport toward the Si/SiO2 interface (under positive bias). Near the interface, some fraction of them fall into deep, relatively stable, long-lived hole traps. The nature and annealing behavior of these hole traps is the main focus of this paper.

  15. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir (Bolingbrook, IL); Kumar, Romesh (Naperville, IL); Krumpelt, Michael (Naperville, IL)

    1999-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  16. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir (Bolingbrook, IL); Kumar, Romesh (Naperville, IL); Krumpelt, Michael (Naperville, IL)

    2001-01-01

    A partial oxidation reformer comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell.

  17. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-24

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  18. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, S.; Kumar, R.; Krumpelt, M.

    1999-08-17

    A partial oxidation reformer is described comprising a longitudinally extending chamber having a methanol, water and an air inlet and an outlet. An igniter mechanism is near the inlets for igniting a mixture of methanol and air, while a partial oxidation catalyst in the chamber is spaced from the inlets and converts methanol and oxygen to carbon dioxide and hydrogen. Controlling the oxygen to methanol mole ratio provides continuous slightly exothermic partial oxidation reactions of methanol and air producing hydrogen gas. The liquid is preferably injected in droplets having diameters less than 100 micrometers. The reformer is useful in a propulsion system for a vehicle which supplies a hydrogen-containing gas to the negative electrode of a fuel cell. 7 figs.

  19. Oxidation in rheumatoid arthritis

    PubMed Central

    Hitchon, Carol A; El-Gabalawy, Hani S

    2004-01-01

    Oxygen metabolism has an important role in the pathogenesis of rheumatoid arthritis. Reactive oxygen species (ROS) produced in the course of cellular oxidative phosphorylation, and by activated phagocytic cells during oxidative bursts, exceed the physiological buffering capacity and result in oxidative stress. The excessive production of ROS can damage protein, lipids, nucleic acids, and matrix components. They also serve as important intracellular signaling molecules that amplify the synovial inflammatoryproliferative response. Repetitive cycles of hypoxia and reoxygenation associated with changes in synovial perfusion are postulated to activate hypoxia-inducible factor-1? and nuclear factor-?B, two key transcription factors that are regulated by changes in cellular oxygenation and cytokine stimulation, and that in turn orchestrate the expression of a spectrum of genes critical to the persistence of synovitis. An understanding of the complex interactions involved in these pathways might allow the development of novel therapeutic strategies for rheumatoid arthritis. PMID:15535839

  20. Enhanced mercury oxidation

    SciTech Connect

    Gretta, W.J.; Wu, S.; Kikkawa, H.

    2009-06-15

    A new catalyst offers a new way to enhance mercury control from bituminous coal-fired power plants. Hitachi has developed an SCR catalyst which satisfies high Hg{sup 0} oxidation and low SO{sub 2} oxidation requirements under high temperatures (716 to 770 F). This triple action catalysts, TRAC can significantly enhance mercury oxidation and reduce or eliminate the need for additional mercury control measures such as activated carbon injection. After laboratory testing, pilot-scale tests confirmed an activity of 1.4-1.7 times higher than that of conventional SCR catalyst. The new catalyst has been successfully applied in a commercial PRB-fired boiler without the need for halogens to be added to the fuel feed or flue gas. 2 figs.

  1. Microbial Formaldehyde Oxidation

    SciTech Connect

    Timothy J. Donohue

    2004-12-09

    This project analyzed how cells sense and generate energy from formaldehyde oxidation. Formaldehyde is a toxin that is produced naturally, chemically or by metabolism of a wide variety of methyl-containing compounds. Our goals are to identify how cells sense the presence of this toxic compound and determine how they generate energy and nutrients from the oxidation of formaldehyde. This research capitalizes on the role of the Rhodobacter sphaeroides glutathione dependent formaldehyde dehydrogenase (GSH FDH) in a formaldehyde oxidation pathway that is apparently found in a wide variety of microbes, plants and animals. Thus, our findings illustrate what is required for a large variety of cells to metabolize this toxic compound. A second major focus of our research is to determine how cells sense the presence of this toxic compound and control the expression of gene products required for its detoxification.

  2. Ethylene Oxide Gaseous Sterilization

    PubMed Central

    Ernst, Robert R.; Shull, James J.

    1962-01-01

    The duration of the equilibration period between admission of water vapor and subsequent introduction of gaseous ethylene oxide to an evacuated sterilizer chamber was studied with respect to its effect on the inactivation of spores of Bacillus subtilis var. niger under simulated practical conditions. Introduction of a water-adsorbing cotton barrier between the spores and an incoming gas mixture of water vapor and ethylene oxide caused a marked increase in the observed thermochemical death time of the spore populations. This effect was negated by admission of water vapor one or more minutes prior to introduction of ethylene oxide gas. Increases in temperature and relative humidity of the system promoted passage of water vapor through the cotton barriers and diminished their effect. PMID:13890660

  3. Nonaqueous Catalytic Water Oxidation

    SciTech Connect

    Chen, Zuofeng; Concepcion, Javier J.; Luo, Hanlin; Hull, Jonathan F.; Paul, Amit; Meyer, Thomas J.

    2010-11-23

    The complex [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] and its 4,4'-(PO3H2CH2)2bpy derivative on oxide electrodes are water oxidation catalysts in propylene carbonate and 2,2,2-trifluoroethanol (TFE) to which water has been added as a limiting reagent. The rate of water oxidation is greatly enhanced relative to that with water as the solvent and occurs by a pathway that is first-order in H2O; an additional pathway that is first-order in acetate appears when TFE is used as the solvent.

  4. Nitroalkane Oxidation by Streptomycetes

    PubMed Central

    Dhawale, Motiram R.; Hornemann, Ulfert

    1979-01-01

    Crude cell-free extracts of nine strains of Streptomyces tested for nitroalkane-oxidizing activity showed production of nitrous acid from 2-nitropropane, 1-nitropropane, nitroethane, nitromethane, and 3-nitropropionic acid. These substrates were utilized in most strains but to a decreasing extent in the order given, and different strains varied in their relative efficiency of oxidation. p-Nitrobenzoic acid, p-aminobenzoic acid, enteromycin, and ω-nitro-l-arginine were not attacked. d-Amino acid oxidase, glucose oxidase, glutathione S-transferase, and xanthine oxidase, enzymes potentially responsible for the observed oxidations in crude cellfree extracts, were present at concentrations too low to play any significant role. A nitroalkane-oxidizing enzyme from streptozotocin-producing Streptomyces achromogenes subsp. streptozoticus was partially purified and characterized. It catalyzes the oxidative denitrification of 2-nitropropane as follows: 2CH3CH(NO2)CH3 + O2 → 2CH3COCH3 + 2HNO2. At the optimum pH of 7.5 of the enzyme, 2-nitropropane was as good a substrate as its sodium salt; t-nitrobutane was not a substrate. Whereas Tiron, oxine, and nitroxyl radical acted as potent inhibitors of this enzyme, superoxide dismutase was essentially without effect. Sodium peroxide abolished a lag phase in the progress curve of the enzyme and afforded stimulation, whereas sodium superoxide did not affect the reaction. Reducing agents, such as glutathione, reduced nicotinamide adenine dinucleotide, and nicotinamide adenine dinucleotide phosphate, reduced form, as well as thiol compounds, were strongly inhibitory, but cyanide had no effect. The S. achromogenes enzyme at the present stage of purification is similar in many respects to the enzyme 2-nitropropane dioxygenase from Hansenula mrakii. The possible involvement of the nitroalkane-oxidizing enzyme in the biosynthesis of antibiotics that contain a nitrogen-nitrogen bond is discussed. PMID:33965

  5. Molecular water oxidation catalyst

    DOEpatents

    Gratzel, Michael (St. Sulpice, CH); Munavalli, Shekhar (Bel Air, MD); Pern, Fu-Jann (Lakewood, CO); Frank, Arthur J. (Lakewood, CO)

    1993-01-01

    A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

  6. Tetraalykylammonium polyoxoanionic oxidation catalysts

    DOEpatents

    Ellis, Paul E. (Downingtown, PA); Lyons, James E. (Wallingford, PA); Myers, Jr., Harry K. (Cochranville, PA); Shaikh, Shahid N. (Media, PA)

    1998-01-01

    Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H.sub.e-z (n-C.sub.4 H.sub.9).sub.4 N!.sub.z (XM.sub.11 M'O.sub.39).sup.-e The M' (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

  7. Tetraalykylammonium polyoxoanionic oxidation catalysts

    DOEpatents

    Ellis, Paul E.; Lyons, James E.; Myers, Jr., Harry K.; Shaikh, Shahid N.

    1998-01-01

    Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H.sub.e-z ›(n-C.sub.4 H.sub.9).sub.4 N!.sub.z (XM.sub.11 M'O.sub.39).sup.-e The M' (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

  8. Tetraalklylammonium polyoxoanionic oxidation catalysts

    DOEpatents

    Ellis, P.E.; Lyons, J.E.; Myers, H.K. Jr.; Shaikh, S.N.

    1998-10-06

    Alkanes are catalytically oxidized in air or oxygen using iron-substituted polyoxoanions (POAs) of the formula: H{sub e{minus}z}[(n-C{sub 4}H{sub 9}){sub 4}N]{sub z}(XM{sub 11}M{prime}O{sub 39}){sup {minus}e}. The M{prime} (e.g., iron(III)/iron(II)) reduction potential of the POAs is affected by selection of the central atom X and the framework metal M, and by the number of tetrabutyl-ammonium groups. Decreased Fe(III)/Fe(II) reduction potential has been found to correlate to increased oxidation activity.

  9. Krypton oxides under pressure

    NASA Astrophysics Data System (ADS)

    Zaleski-Ejgierd, Patryk; Lata, Pawel M.

    2016-02-01

    Under high pressure, krypton, one of the most inert elements is predicted to become sufficiently reactive to form a new class of krypton compounds; krypton oxides. Using modern ab-initio evolutionary algorithms in combination with Density Functional Theory, we predict the existence of several thermodynamically stable Kr/O species at elevated pressures. In particular, our calculations indicate that at approx. 300 GPa the monoxide, KrO, should form spontaneously and remain thermo- and dynamically stable with respect to constituent elements and higher oxides. The monoxide is predicted to form non-molecular crystals with short Kr-O contacts, typical for genuine chemical bonds.

  10. Krypton oxides under pressure

    PubMed Central

    Zaleski-Ejgierd, Patryk; Lata, Pawel M.

    2016-01-01

    Under high pressure, krypton, one of the most inert elements is predicted to become sufficiently reactive to form a new class of krypton compounds; krypton oxides. Using modern ab-initio evolutionary algorithms in combination with Density Functional Theory, we predict the existence of several thermodynamically stable Kr/O species at elevated pressures. In particular, our calculations indicate that at approx. 300 GPa the monoxide, KrO, should form spontaneously and remain thermo- and dynamically stable with respect to constituent elements and higher oxides. The monoxide is predicted to form non-molecular crystals with short Kr-O contacts, typical for genuine chemical bonds. PMID:26830129

  11. Krypton oxides under pressure.

    PubMed

    Zaleski-Ejgierd, Patryk; Lata, Pawel M

    2016-01-01

    Under high pressure, krypton, one of the most inert elements is predicted to become sufficiently reactive to form a new class of krypton compounds; krypton oxides. Using modern ab-initio evolutionary algorithms in combination with Density Functional Theory, we predict the existence of several thermodynamically stable Kr/O species at elevated pressures. In particular, our calculations indicate that at approx. 300 GPa the monoxide, KrO, should form spontaneously and remain thermo- and dynamically stable with respect to constituent elements and higher oxides. The monoxide is predicted to form non-molecular crystals with short Kr-O contacts, typical for genuine chemical bonds. PMID:26830129

  12. Low temperature oxidation of plutonium

    SciTech Connect

    Nelson, Art J.; Roussel, Paul

    2013-05-15

    The initial oxidation of gallium stabilized {delta}-plutonium metal at 193 K has been followed using x-ray photoelectron spectroscopy. On exposure to Langmuir quantities of oxygen, plutonium rapidly forms a trivalent oxide followed by a tetravalent plutonium oxide. The growth modes of both oxides have been determined. Warming the sample in vacuum, the tetravalent oxide reduces to the trivalent oxide. The kinetics of this reduction reaction have followed and the activation energy has been determined to be 38.8 kJ mol{sup -1}.

  13. Uranium oxidation: characterization of oxides formed by reaction with water

    SciTech Connect

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

    1983-04-27

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

  14. Conformations of Organophosphine Oxides.

    PubMed

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P; Gordon, Mark S; Windus, Theresa L

    2015-08-13

    The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P-C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 force field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes-an essential part of understanding the chemistry of these compounds. The predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3. PMID:26186383

  15. Conformations of organophosphine oxides

    DOE PAGESBeta

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P.; Gordon, Mark S.; Windus, Theresa L.

    2015-07-17

    The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 forcemore » field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.« less

  16. Tributyltin oxide (TBTO)

    Integrated Risk Information System (IRIS)

    Tributyltin oxide ( TBTO ) ; CASRN 56 - 35 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarc

  17. Diesel engine exhaust oxidizer

    SciTech Connect

    Kammel, R.A.

    1992-06-16

    This patent describes a diesel engine exhaust oxidizing device. It comprises: an enclosure having an inlet for receiving diesel engine exhaust, a main flow path through the enclosure to an outlet of the enclosure, a by-ass through the enclosure, and a microprocessor control means.

  18. Oxidative stress in myopia.

    PubMed

    Francisco, Bosch-Morell; Salvador, Mrida; Amparo, Navea

    2015-01-01

    Myopia affected approximately 1.6 billion people worldwide in 2000, and it is expected to increase to 2.5 billion by 2020. Although optical problems can be corrected by optics or surgical procedures, normal myopia and high myopia are still an unsolved medical problem. They frequently predispose people who have them to suffer from other eye pathologies: retinal detachment, glaucoma, macular hemorrhage, cataracts, and so on being one of the main causes of visual deterioration and blindness. Genetic and environmental factors have been associated with myopia. Nevertheless, lack of knowledge in the underlying physiopathological molecular mechanisms has not permitted an adequate diagnosis, prevention, or treatment to be found. Nowadays several pieces of evidence indicate that oxidative stress may help explain the altered regulatory pathways in myopia and the appearance of associated eye diseases. On the one hand, oxidative damage associated with hypoxia myopic can alter the neuromodulation that nitric oxide and dopamine have in eye growth. On the other hand, radical superoxide or peroxynitrite production damage retina, vitreous, lens, and so on contributing to the appearance of retinopathies, retinal detachment, cataracts and so on. The objective of this review is to suggest that oxidative stress is one of the key pieces that can help solve this complex eye problem. PMID:25922643

  19. Tributyltin oxide (TBTO)

    Integrated Risk Information System (IRIS)

    TOXICOLOGICAL REVIEW TRIBUTYLTIN OXIDE ( CAS No . 56 - 35 - 9 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) July 1997 . U.S . Environmental Protection Agency Washington D.C . TABLE OF CONTENTS Contributors and Reviewers Foreword 1.0 Introduction 1 2.0 Chemica

  20. Highly oxidized superconductors

    DOEpatents

    Morris, D.E.

    1994-09-20

    Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known synthesis in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed. 16 figs.

  1. Highly oxidized superconductors

    DOEpatents

    Morris, Donald E. (Kensington, CA)

    1994-01-01

    Novel superconducting materials in the form of compounds, structures or phases are formed by performing otherwise known syntheses in a highly oxidizing atmosphere rather than that created by molecular oxygen at atmospheric pressure or below. This leads to the successful synthesis of novel superconducting compounds which are thermodynamically stable at the conditions under which they are formed.

  2. Doped zinc oxide microspheres

    DOEpatents

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1993-12-14

    A new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel. 4 figures.

  3. CONTROLLING SULFUR OXIDES

    EPA Science Inventory

    This Research Summary describes EPA's program to develop new and improve existing technologies for sulfur oxides control. As we increasingly turn to coal as the primary utility and industrial fuel, while trying to deal with the problems of acid precipitation, visibility degradati...

  4. Hydrous oxide activated charcoal

    SciTech Connect

    Weller, J.P.

    1987-09-08

    This patent describes a process for preparing of an ion exchanger, comprising: treating an ionically inert activated charcoal porous support with an aqueous solution of metal oxychloride selected from the group consisting of zirconium and titanium oxychlorides so as to impregnate the pores of the support with the solution; separating the treated support from excess metal oxychloride solution; converting the metal oxychloride to a hydrous metal oxide precipitate in the pores of the support at a pH above 8 and above the pH whereat the hydrous metal oxide and activated charcoal support have opposite zeta potentials and sufficient to hydrolyze the metal oxychloride. It also describes a process for preparing an ion exchanger comprising: treating granulated activated charcoal with a concentrated solution of a metal oxychloride from the group consisting of zirconium and titanium oxychlorides, degassing the mixture; and treating the resultant mixture with a base selected from the group consisting of ammonium hydroxide and alkali metal hydroxides so as to precipitate the oxychloride within the pores of the activated carbon granules as hydrous metal oxide at a pH above 8 and above the pH whereat the hydrous metal oxide and activated charcoal have opposite zeta potentials.

  5. Grazing and Nitrous Oxide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrous oxide emission rates are typically measured using bottom up methods which involve placing airtight chambers over the soil surface and measuring the change in gas concentration over short time periods (e.g., 15-60 min.). Emission rates vary substantially both spatially and temporally and ma...

  6. Sulfite-oxidizing enzymes.

    PubMed

    Kappler, Ulrike; Enemark, John H

    2015-03-01

    Sulfite-oxidizing enzymes (SOEs) are molybdenum enzymes that exist in almost all forms of life where they carry out important functions in protecting cells and organisms against sulfite-induced damage. Due to their nearly ubiquitous presence in living cells, these enzymes can be assumed to be evolutionarily ancient, and this is reflected in the fact that the basic domain architecture and fold structure of all sulfite-oxidizing enzymes studied so far are similar. The Mo centers of all SOEs have five-coordinate square pyramidal coordination geometry, which incorporates a pyranopterin dithiolene cofactor. However, significant differences exist in the quaternary structure of the enzymes, as well as in the kinetic properties and the nature of the electron acceptors used. In addition, some SOEs also contain an integral heme group that participates in the overall catalytic cycle. Catalytic turnover involves the paramagnetic Mo(V) oxidation state, and EPR spectroscopy, especially high-resolution pulsed EPR spectroscopy, provides detailed information about the molecular and electronic structure of the Mo center and the Mo-based sulfite oxidation reaction. PMID:25261289

  7. Oxidative Stress in Myopia

    PubMed Central

    Francisco, Bosch-Morell; Salvador, Mérida; Amparo, Navea

    2015-01-01

    Myopia affected approximately 1.6 billion people worldwide in 2000, and it is expected to increase to 2.5 billion by 2020. Although optical problems can be corrected by optics or surgical procedures, normal myopia and high myopia are still an unsolved medical problem. They frequently predispose people who have them to suffer from other eye pathologies: retinal detachment, glaucoma, macular hemorrhage, cataracts, and so on being one of the main causes of visual deterioration and blindness. Genetic and environmental factors have been associated with myopia. Nevertheless, lack of knowledge in the underlying physiopathological molecular mechanisms has not permitted an adequate diagnosis, prevention, or treatment to be found. Nowadays several pieces of evidence indicate that oxidative stress may help explain the altered regulatory pathways in myopia and the appearance of associated eye diseases. On the one hand, oxidative damage associated with hypoxia myopic can alter the neuromodulation that nitric oxide and dopamine have in eye growth. On the other hand, radical superoxide or peroxynitrite production damage retina, vitreous, lens, and so on contributing to the appearance of retinopathies, retinal detachment, cataracts and so on. The objective of this review is to suggest that oxidative stress is one of the key pieces that can help solve this complex eye problem. PMID:25922643

  8. Conformations of organophosphine oxides

    SciTech Connect

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P.; Gordon, Mark S.; Windus, Theresa L.

    2015-07-17

    The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 force field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.

  9. Doped zinc oxide microspheres

    DOEpatents

    Arnold, Jr., Wesley D. (Oak Ridge, TN); Bond, Walter D. (Knoxville, TN); Lauf, Robert J. (Oak Ridge, TN)

    1993-01-01

    A new composition and method of making same for a doped zinc oxide microsphere and articles made therefrom for use in an electrical surge arrestor which has increased solid content, uniform grain size and is in the form of a gel.

  10. CONTROLLING NITROGEN OXIDES

    EPA Science Inventory

    Recent research indicates that nitrogen oxides (NOx) could be one of the most troublesome air pollutants of the 1980's. More than 20 million metric tons of NOx are annually polluting our air as a result of the widespread combustion of fossil fuels in power plants, industrial boil...

  11. Active oxide nanophotonics

    NASA Astrophysics Data System (ADS)

    Dicken, Matthew J.

    Materials that can be manipulated electrically or mechanically to induce a change in their intrinsic properties are highly relevant when suitably integrated with current technologies. These "active" materials, such as oxide-based ferroelectrics or materials with easily accessible changes of phase, find extensive use as mechanical resonators, solid-state memories, and optical modulators. Barium titanate, a tetragonal ferroelectric at room temperature, is a prime example of a material both mechanically and optically active. This thesis deals primarily with the deposition of active, oxide-based materials and their integration into device structures where either the mechanical or optical properties are exploited. The technologically interesting paradigms within which these active oxide materials have been investigated are microelectromechanical systems, plasmonics, and metamaterials. Microelectromechanical systems are devices that have been micromachined and rely on an applied voltage to induce a mechanical response. Mechanically active materials, such as piezoelectrics or ferroelectrics, can increase the response of these devices. Plasmonics deals with electromagnetic waves resonantly coupled into free electron oscillations at a metal-dielectric interface or metal nanoparticle. Coupling to these resonant modes allows surface plasmon polaritons to propagate along the metal with a nonlinear dispersion. Metamaterials are ordered, subwavelength, metal inclusions in a dielectric, which respond collectively to electromagnetic radiation. This response can yield a material permittivity or permeability not found in nature. The optical properties of metamaterials lead to effects such as negative index response and super lensing, and can be used to design optical cloaking structures. Here, devices utilizing these effects are investigated with an eye toward tuning or switching their resonant response using optically active oxide thin films. This manuscript follows the evolution of active oxide thin films from deposition, through design of plasmonic devices and active metamaterials, finite difference modeling of these structures, and finally experimental validation. First, deposition and material integration techniques for oxide-based thin films will be discussed. The role of molecular beam epitaxy, pulsed laser deposition, and ion beam assisted deposition as material growth techniques are investigated. Development of a multitude of oxide materials using these techniques including barium titanate, strontium ruthenate, vanadium oxide, and magnesium oxide will be covered. The following two sections deal with the mechanical and optical properties of barium titanate thin films as they are studied and utilized to design and fabricate active devices. Films were characterized mechanically, using nanoindentation and piezoresponse force microscopy, and optically with variable angle spectroscopic ellipsometry. The subsequent section deals with the design, fabrication, and experimental validation of an active optical device based on surface plasmon polariton wavevector modulation via electrooptic modulation of a barium titanate thin film. Interferometers based on pairs of parallel slits fabricated in silver films on barium titanate are used to investigate optical modulation due to both domain switching and the electrooptic effect. Finally, active metamaterials are discussed through the investigation of a new material, vanadium oxide, as it is deposited and characterized, and the results used to design and fabricate active, split-ring resonator metamaterial structures.

  12. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Colin P. Horwitz; Terrence J. Collins

    2003-10-22

    The design of new, high efficiency and cleaner burning engines is strongly coupled with the removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from fuels. Oxidative desulfurization (ODS) wherein these dibenzothiophene derivatives are oxidized to their corresponding sulfoxides and sulfones is an approach that has gained significant attention. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) convert in a catalytic process dibenzothiophene and its derivatives to the corresponding sulfoxides and sulfones rapidly at moderate temperatures (60 C) and ambient pressure. The reaction can be performed in both an aqueous system containing an alcohol (methanol, ethanol, or t-butanol) to solubilize the DBT and in a two-phase hydrocarbon/aqueous system where the alcohol is present in both phases and facilitates the oxidation. Under a consistent set of conditions using the FeBF{sub 2} TAML activator, the degree of conversion was found to be t-butanol > methanol > ethanol. In the cases of methanol and ethanol, both the sulfoxide and sulfone were observed while for t-butanol only the sulfone was detected. In the two-phase system, the alcohol may function as an inverse phase transfer agent. The oxidation was carried out using two different TAML activators. In homogeneous solution, approximately 90% oxidation of the DBT could be achieved using the prototype TAML activator, FeB*, by sonicating the solution at near room temperature. In bi-phasic systems conversions as high as 50% were achieved using the FeB* TAML activator and hydrogen peroxide at 100 C. The sonication method yielded only {approx}6% conversion but this may have been due to mixing.

  13. Oxidative phosphorylation revisited.

    PubMed

    Nath, Sunil; Villadsen, John

    2015-03-01

    The fundamentals of oxidative phosphorylation and photophosphorylation are revisited. New experimental data on the involvement of succinate and malate anions respectively in oxidative phosphorylation and photophosphorylation are presented. These new data offer a novel molecular mechanistic explanation for the energy coupling and ATP synthesis carried out in mitochondria and chloroplast thylakoids. The mechanism does not suffer from the flaws in Mitchell's chemiosmotic theory that have been pointed out in many studies since its first appearance 50 years ago, when it was hailed as a ground-breaking mechanistic explanation of what is perhaps the most important process in cellular energetics. The new findings fit very well with the predictions of Nath's torsional mechanism of energy transduction and ATP synthesis. It is argued that this mechanism, based on at least 15 years of experimental and theoretical work by Sunil Nath, constitutes a fundamentally different theory of the energy conversion process that eliminates all the inconsistencies in Mitchell's chemiosmotic theory pointed out by other authors. It is concluded that the energy-transducing complexes in oxidative phosphorylation and photosynthesis are proton-dicarboxylic acid anion cotransporters and not simply electrogenic proton translocators. These results necessitate revision of previous theories of biological energy transduction, coupling, and ATP synthesis. The novel molecular mechanism is extended to cover ATP synthesis in prokaryotes, in particular to alkaliphilic and haloalkaliphilic bacteria, essentially making it a complete theory addressing mechanistic, kinetic, and thermodynamic details. Finally, based on the new interpretation of oxidative phosphorylation, quantitative values for the P/O ratio, the amount of ATP generated per redox package of the reduced substrates, are calculated and compared with experimental values for fermentation on different substrates. It is our hope that the presentation of oxidative phosphorylation and photophosphorylation from a wholly new perspective will rekindle scientific discussion of a key process in bioenergetics and catalyze new avenues of research in a truly interdisciplinary field. PMID:25384602

  14. Nanostructured transition metal oxides useful for water oxidation catalysis

    DOEpatents

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  15. OXIDATIVE TREATMENT OF INDUSTRIAL WASTEWATER

    EPA Science Inventory

    This paper defines industrial waste treatment process as falling into categories of oxidative destruction, reductive destruction, and non-destructive, separation operations. The various oxidative approaches, including biological, chemical and thermal methods, are then discussed i...

  16. Experiments with Unusual Oxidation States

    ERIC Educational Resources Information Center

    Kauffman, G. B.

    1975-01-01

    Describes four synthesis experiments, adapted for the general chemistry laboratory, in which compounds in unusual oxidation are prepared. The abnormal oxidation states involved in the synthesis products are: silver (II), chromium (II), lead (IV), and bromine (I). (MLH)

  17. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2012-09-11

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  18. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2013-04-16

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  19. Staged membrane oxidation reactor system

    DOEpatents

    Repasky, John Michael; Carolan, Michael Francis; Stein, VanEric Edward; Chen, Christopher Ming-Poh

    2014-05-20

    Ion transport membrane oxidation system comprising (a) two or more membrane oxidation stages, each stage comprising a reactant zone, an oxidant zone, one or more ion transport membranes separating the reactant zone from the oxidant zone, a reactant gas inlet region, a reactant gas outlet region, an oxidant gas inlet region, and an oxidant gas outlet region; (b) an interstage reactant gas flow path disposed between each pair of membrane oxidation stages and adapted to place the reactant gas outlet region of a first stage of the pair in flow communication with the reactant gas inlet region of a second stage of the pair; and (c) one or more reactant interstage feed gas lines, each line being in flow communication with any interstage reactant gas flow path or with the reactant zone of any membrane oxidation stage receiving interstage reactant gas.

  20. REVIEW OF PLUTONIUM OXIDATION LITERATURE

    SciTech Connect

    Korinko, P.

    2009-11-12

    A brief review of plutonium oxidation literature was conducted. The purpose of the review was to ascertain the effect of oxidation conditions on oxide morphology to support the design and operation of the PDCF direct metal oxidation (DMO) furnace. The interest in the review was due to a new furnace design that resulted in oxide characteristics that are different than those of the original furnace. Very little of the published literature is directly relevant to the DMO furnace operation, which makes assimilation of the literature data with operating conditions and data a convoluted task. The oxidation behavior can be distilled into three regimes, a low temperature regime (RT to 350 C) with a relatively slow oxidation rate that is influenced by moisture, a moderate temperature regime (350-450 C) that is temperature dependent and relies on more or less conventional oxidation growth of a partially protective oxide scale, and high temperature oxidation (> 500 C) where the metal autocatalytically combusts and oxidizes. The particle sizes obtained from these three regimes vary with the finest being from the lowest temperature. It is surmised that the slow growth rate permits significant stress levels to be achieved that help break up the oxides. The intermediate temperatures result in a fairly compact scale that is partially protective and that grows to critical thickness prior to fracturing. The growth rate in this regime may be parabolic or paralinear, depending on the oxidation time and consequently the oxide thickness. The high temperature oxidation is invariant in quiescent or nearly quiescent conditions due to gas blanketing while it accelerates with temperature under flowing conditions. The oxide morphology will generally consist of fine particles (<15 {micro}m), moderately sized particles (15 < x < 250 {micro}m) and large particles (> 250 {micro}m). The particle size ratio is expected to be < 5%, 25%, and 70% for fine, medium and large particles, respectively, for metal temperatures in the 500-600 C range.

  1. Tailoring oxidation degrees of graphene oxide by simple chemical reactions

    SciTech Connect

    Wang Gongkai; Sun Xiang; Lian Jie; Liu Changsheng

    2011-08-01

    High quality graphene oxide (GO) with controllable degrees of oxidation was synthesized by simple chemical reactions inspired by approaches to unzip single wall carbon nanotubes using strong oxidizing agents. As compared to the conventional Hummers method, these reactions are less exo-therm involved without emission of toxic gases. The structural characteristics of the synthesized GO with various oxidation degrees were evaluated by x-ray diffraction, x-ray photoelectron spectroscopy, Raman spectroscopy, thermal gravimetric analysis, and UV-vis-IR spectroscopy. GO with tailored degrees of oxidation displays tunable optoelectronic properties and may have a significant impact on developing graphene- or GO-based platforms for various technological applications.

  2. Doped palladium containing oxidation catalysts

    DOEpatents

    Mohajeri, Nahid

    2014-02-18

    A supported oxidation catalyst includes a support having a metal oxide or metal salt, and mixed metal particles thereon. The mixed metal particles include first particles including a palladium compound, and second particles including a precious metal group (PMG) metal or PMG metal compound, wherein the PMG metal is not palladium. The oxidation catalyst may also be used as a gas sensor.

  3. Entropy-stabilized oxides

    NASA Astrophysics Data System (ADS)

    Rost, Christina M.; Sachet, Edward; Borman, Trent; Moballegh, Ali; Dickey, Elizabeth C.; Hou, Dong; Jones, Jacob L.; Curtarolo, Stefano; Maria, Jon-Paul

    2015-09-01

    Configurational disorder can be compositionally engineered into mixed oxide by populating a single sublattice with many distinct cations. The formulations promote novel and entropy-stabilized forms of crystalline matter where metal cations are incorporated in new ways. Here, through rigorous experiments, a simple thermodynamic model, and a five-component oxide formulation, we demonstrate beyond reasonable doubt that entropy predominates the thermodynamic landscape, and drives a reversible solid-state transformation between a multiphase and single-phase state. In the latter, cation distributions are proven to be random and homogeneous. The findings validate the hypothesis that deliberate configurational disorder provides an orthogonal strategy to imagine and discover new phases of crystalline matter and untapped opportunities for property engineering.

  4. Entropy-stabilized oxides

    PubMed Central

    Rost, Christina M.; Sachet, Edward; Borman, Trent; Moballegh, Ali; Dickey, Elizabeth C.; Hou, Dong; Jones, Jacob L.; Curtarolo, Stefano; Maria, Jon-Paul

    2015-01-01

    Configurational disorder can be compositionally engineered into mixed oxide by populating a single sublattice with many distinct cations. The formulations promote novel and entropy-stabilized forms of crystalline matter where metal cations are incorporated in new ways. Here, through rigorous experiments, a simple thermodynamic model, and a five-component oxide formulation, we demonstrate beyond reasonable doubt that entropy predominates the thermodynamic landscape, and drives a reversible solid-state transformation between a multiphase and single-phase state. In the latter, cation distributions are proven to be random and homogeneous. The findings validate the hypothesis that deliberate configurational disorder provides an orthogonal strategy to imagine and discover new phases of crystalline matter and untapped opportunities for property engineering. PMID:26415623

  5. Enzymatic Oxidation of Methane

    SciTech Connect

    Sirajuddin, S; Rosenzweig, AC

    2015-04-14

    Methane monooxygenases (MMOs) are enzymes that catalyze the oxidation of methane to methanol in methanotrophic bacteria. As potential targets for new gas-to-liquid methane bioconversion processes, MMOs have attracted intense attention in recent years. There are two distinct types of MMO, a soluble, cytoplasmic MMO (sMMO) and a membrane-bound, particulate MMO (pMMO). Both oxidize methane at metal centers within a complex, multisubunit scaffold, but the structures, active sites, and chemical mechanisms are completely different. This Current Topic review article focuses on the overall architectures, active site structures, substrate reactivities, proteinprotein interactions, and chemical mechanisms of both MMOs, with an emphasis on fundamental aspects. In addition, recent advances, including new details of interactions between the sMMO components, characterization of sMMO intermediates, and progress toward understanding the pMMO metal centers are highlighted. The work summarized here provides a guide for those interested in exploiting MMOs for biotechnological applications.

  6. Silver oxide cells

    SciTech Connect

    Nagaura, T.

    1983-09-20

    The silver oxide cell is constructed so as to dispose, at the cathode side, of a cathodic material layer composed of AgO and a reducing layer for reducing AgO and, at the anode side, of an anodic material layer and an electrolyte layer in a container composed of a cathode can an anode cap and a gasket. The cathodic material layer is covered at the surface thereof with a reduced layer formed by the reduction of AgO. The silver oxide cell enables a discharge on the single voltage level as in Ag/sub 2/O cells, and is appropriate for large-scale production and favorable in workability.

  7. Lipid oxidation on foods.

    PubMed

    St Angelo, A J

    1996-02-01

    This review discusses the basic chemical reactions that affect food flavor quality. Although there are many reactions that can lead to the deterioration of quality in foods, this review focuses on lipid oxidation and how it adversely affects flavor principals. It also presents technological advances for studying the basic mechanism of lipid oxidation, for measuring its intensity, and for retaining food quality. The food commodities that provide the subject matter for this review include vegetable oils, legumes, cereal grains, eggs, beef, lamb, poultry, seafoods, and catfish. The methodologies for assessing food quality form a multidisciplinary approach that includes primarily instrumental analysis by direct gas chromatography, chemical analysis by the TBA test, and sensory analysis by quantitative descriptive determinations. The author hopes that the information presented in this review is applicable to food commodities not discussed. PMID:8744604

  8. Entropy-stabilized oxides.

    PubMed

    Rost, Christina M; Sachet, Edward; Borman, Trent; Moballegh, Ali; Dickey, Elizabeth C; Hou, Dong; Jones, Jacob L; Curtarolo, Stefano; Maria, Jon-Paul

    2015-01-01

    Configurational disorder can be compositionally engineered into mixed oxide by populating a single sublattice with many distinct cations. The formulations promote novel and entropy-stabilized forms of crystalline matter where metal cations are incorporated in new ways. Here, through rigorous experiments, a simple thermodynamic model, and a five-component oxide formulation, we demonstrate beyond reasonable doubt that entropy predominates the thermodynamic landscape, and drives a reversible solid-state transformation between a multiphase and single-phase state. In the latter, cation distributions are proven to be random and homogeneous. The findings validate the hypothesis that deliberate configurational disorder provides an orthogonal strategy to imagine and discover new phases of crystalline matter and untapped opportunities for property engineering. PMID:26415623

  9. Electrochemical oxidation of chlorophenols

    SciTech Connect

    Polcaro, A.M.; Palmas, S.

    1997-05-01

    Electrochemical 2-chlorophenol and 2,6-dichlorophenol removal from aqueous solutions using porous carbon felt anodes was investigated. Operating variables including current input, ratio between electrode and solution volumes, and initial pollutant concentration were considered in order to determine their influence on the faradic efficiency of the process. The byproducts of the oxidation reaction were identified, and their concentration was determined during the electrolysis. The experimental results showed that a satisfactory detoxification, consisting of removal of cyclic chlorinated compounds, could be accomplished by means of this electrochemical method with a faradic efficiency of 30% under optimized conditions. A mathematical model based on the reaction between chlorophenols adsorbed on the carbon fibers of the electrode and hydroxyl radicals produced by anodic oxidation of water has been proposed in order to interpret the experimental behavior of the system under different operating conditions.

  10. Chemical oxidizers treat wastewater

    SciTech Connect

    Stephenson, F.A. )

    1992-12-01

    Based on the inherent benefits of these original oxidation systems, a second generation of advanced oxidation processes (AOPs) has emerged. These processes combine key features of the first generation technologies with more sophisticated advances in UV technology, such as the new pulsed plasma xenon flash lamp that emits high-energy, high-intensity UV light. Second generation systems can be equipped with a transmittance controller to prevent lamp fouling or scaling. The coupling of the first generation's technology with the new UV sources provides the rapid destruction of chlorinated and nonchlorinated hydrocarbons and humic acids from contaminated water. It also is effective in the treatment of organic laden gases from soil vapor extraction systems. AOPs may promote the oxidation (and subsequent removal) of heavy metals in water, though few data are available to verify the claim. The success of AOPs, including ozonation with UV light, hydrogen peroxide with UV light and advanced photolysis, is linked with their creation of hydroxyl-free radicals (OH[center dot]) that are effective in eliminating contaminants such as formaldehyde, chlorinated hydrocarbons and chlorinated solvents. Hydroxyl free-radicals are consumed in microsecond reactions and exhibit little substrate selectivity with the exception of halogenated alkanes such as chloroform. They can act as chain carriers. Given their power, hydroxyl free-radicals react with virtually all organic solutes more quickly (especially in water) than any other oxidants, except fluorine. There are projects that have found the combination of some AOPs to be the most efficient organic destruction techniques for the job. For example, one project successfully remediated groundwater contaminated with gasoline and Number 2 diesel through successive treatments of ozone and hydrogen peroxide with ultraviolet light, followed by granular activated carbon. 5 refs., 2 tabs.

  11. Ultra supercritical steamside oxidation

    SciTech Connect

    Holcomb, Gordon R.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Cramer, Stephen D.; Ziomek-Moroz, Margaret

    2005-01-01

    Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions, Current goals of the U.S. Department of Energys Advanced Power Systems Initiatives include coal generation at 60% efficiency, which would require steam temperatures of up to 760C. This research examines the steamside oxidation of advanced alloys for use in USC systems, with emphasis placed on alloys for high- and intermediate-pressure turbine sections.

  12. Hemoglobin oxidative stress

    NASA Astrophysics Data System (ADS)

    Croci, S.; Ortalli, I.; Pedrazzi, G.; Passeri, G.; Piccolo, P.

    2000-07-01

    Venous blood obtained from healthy donors and from patients suffering from breast cancer have been treated with acetylphenylhydrazine (APH) for different time. Mssbauer spectra of the packed red cells have been recorded and compared. The largest difference occurs after 50 min of treatment with APH where the patient samples show a broad spectral pattern indicating an advanced hemoglobin oxidation. These results may have some relevance in early cancer diagnosis.

  13. Oxidation, Reduction, and Deoxygenation

    NASA Astrophysics Data System (ADS)

    Madsen, Robert

    In this chapter, methods for oxidation, reduction, and deoxygenation of carbohydrates are presented. In most cases, the reactions have been used on aldoses and their derivatives including glycosides, uronic acids, glycals, and other unsaturated monosaccharides. A number of reactions have also been applied to aldonolactones. The methods include both chemical and enzymatic procedures and some of these can be applied for regioselective transformation of unprotected or partially protected carbohydrates.

  14. Thermopower in Cobalt Oxides

    NASA Astrophysics Data System (ADS)

    Koshibae, Wataru; Tsutsui, Kenji; Maekawa, Sadamichi

    2001-03-01

    Recently, Terasaki et al., [PRB56, R12685 (1997).] have discovered large thermopower in the layered compound NaCo_2O_4, and proposed that the compound is of importance in view of potential application in thermoelectric devices which convert heat into energy. Some other cobalt oxides also show large thermopower. It is, therefore, of importance to examine the origin of the large thermopower. We have examined the thermopower in the cobalt oxides theoretically using Heikes formula. The formula indicates that the thermopower is governed by the change of degeneracy per added carrier. In the cobalt oxides, carriers have characteristic degeneracy due to spin and orbital degrees of freedom caused by strong correlation. The motion of carriers causes the motion of the degeneracy, which depends on the difference of degeneracy between local electronic states of Co^3+ and Co^4+ ions. Then, we find the thermopower (Q) in the cobalt oxides to be Q=-k_B\\over eln (g_3\\over g_4x\\over 1-x) , where g3 and g4 denote the degeneracies of Co^3+ and Co^4+ ions, respectively, and x is the concentration of Co^4+ ions. When we apply the theory to NaCo_2O_4, the large positive thermopower is obtained assuming low-spin(LS) state of Co^3+ and LS (and/or high-spin) state of Co^4+ ions. These ionic states have been observed by the magnetic susceptibility and NMR measurements [R.Ray et al., PRB 59, 9454 (1999).] in NaCo_2O_4. The ionic states and the observed large thermopower are consistent with our theory.

  15. Oxidative Stress in Malaria

    PubMed Central

    Percrio, Sandro; Moreira, Danilo R.; Gomes, Bruno A. Q.; Ferreira, Michelli E. S.; Gonalves, Ana Carolina M.; Laurindo, Paula S. O. C.; Vilhena, Thyago C.; Dolabela, Maria F.; Green, Michael D.

    2012-01-01

    Malaria is a significant public health problem in more than 100 countries and causes an estimated 200 million new infections every year. Despite the significant effort to eradicate this dangerous disease, lack of complete knowledge of its physiopathology compromises the success in this enterprise. In this paper we review oxidative stress mechanisms involved in the disease and discuss the potential benefits of antioxidant supplementation as an adjuvant antimalarial strategy. PMID:23208374

  16. Oxidative neuronal injury

    PubMed Central

    Chu, Charleen T.; Levinthal, David J.; Kulich, Scott M.; Chalovich, Elisabeth M.; DeFranco, Donald B.

    2007-01-01

    The extracellular signal regulated protein kinases (ERK1/2) are essential for normal development and functional plasticity of the central nervous system. However, a growing number of recent studies in models of cerebral ischemia, brain trauma and neurodegenerative diseases implicate a detrimental role for ERK1/2 signaling during oxidative neuronal injury. Neurons undergoing oxidative stress-related injuries typically display a biphasic or sustained pattern of ERK1/2 activation. A variety of potential targets of reactive oxygen species and reactive nitrogen species could contribute to ERK1/2 activation. These include cell surface receptors, G proteins, upstream kinases, protein phosphatases and proteasome components, each of which could be direct or indirect targets of reactive oxygen or nitrogen species, thereby modulating the duration and magnitude of ERK1/2 activation. Neuronal oxidative stress also appears to influence the subcellular trafficking and/or localization of activated ERK1/2. Differences in compartmentalization of phosphorylated ERK1/2 have been observed in diseased or injured human neurons and in their respective animal and cell culture model systems. We propose that differential accessibility of ERK1/2 to downstream targets, which is dictated by the persistent activation of ERK1/2 within distinct subcellular compartments, underlies the neurotoxic responses that are driven by this kinase. PMID:15153095

  17. Oxide Ferromagnetic Semiconductors

    NASA Astrophysics Data System (ADS)

    Ogale, Satishchandra

    2006-03-01

    The field of oxide ferromagnetic semiconductors has witnessed tremendous interest and activity over the past few years, especially in the context of realization of intrinsic oxide based diluted magnetic semiconductors (O-DMS). In this talk I will review the important developments in this field, highlighting apparent successes, concerns and questions. Research results obtained by various groups on a number of systems such as transition element (especially Co, Mn, Cr) doped TiO2, ZnO, La1-xSrxTiO3, HfO2 will be discussed including some related device efforts involving spin transport and field induced modulation of magnetization. Some cases of undoped or dual doped oxide films will also be addressed. In the light of the potentially serious possibility of extrinsic effects in most systems the significance of the choice and implementation of an appropriate characterization scheme will also be highlighted. Collaborators : T. Venkatesan, Nigel Browning, Y. V. Idzerda, R. Ramesh, D. K. Kundaliya, S. X. Zhang, L. F. Fu, S. Dhar, A. Lussier, S. R. Shinde, Y. Zhao, M. S. R. Rao, T. Zhao.

  18. Nonisostructural complex oxide heteroepitaxy

    SciTech Connect

    Wong, Franklin J. Ramanathan, Shriram

    2014-07-01

    The authors present an overview of the fundamentals and representative examples of the growth of epitaxial complex oxide thin films on structurally dissimilar substrates. The authors will delineate how the details of particular crystal structures and symmetry of different oxide surfaces can be employed for a rational approach to the synthesis of nonisostructural epitaxial heterostructures. The concept of oxygen eutaxy can be widely applied. Materials combinations will be split into three categories, and in all cases the films and substrates occur in different crystal structures: (1) common translational and rotational symmetry between the film and substrate planes; (2) translational symmetry mismatch between the substrates and films that is distinct from a simple mismatch in lattice parameters; and (3) rotational symmetry mismatch. In case (1), in principle single-crystalline thin films can be attained despite the films and substrates possessing different crystal structures. In case (2), antiphase boundaries will be prevalent in the thin films. In case (3), thin-film rotational variants that are joined by tilt boundaries will be present. Diffraction techniques to determine crystallographic alignment and epitaxial variants are discussed, and transmission electron microscopy studies to investigate extended defects in the thin films will also be reviewed. The authors end with open problems in this field regarding the structure of oxide interfaces that can be topics for future research.

  19. Sulfur oxides scrubbing process

    SciTech Connect

    Reeder, P.E.

    1986-07-15

    A process is described for removing sulfur oxides and solid particulates from a gaseous effluent. The steps of the process consist of: contacting within a venturi structure a gaseous effluent containing sulfur oxides with a liquid scrubbing mixture; passing the admixture of the gaseous effluent and liquid scrubbing mixture through a constricted passage of the venturi structure to increase the velocity thereof; separating the admixture into a liquid portion and a gas portion; delivering the gas portion of the separation step to a packed tower beneath the packed section thereof; contacting the gas portion with liquid scrubbing mixture in the packed section of the tower to form a gaseous overhead effluent substantially free of sulfur oxides and a bottoms liquid; combining the bottom liquid from the packed section of the tower with the liquid portion from the separating step to form a combined liquid bottoms; adjusting the pH of the combined liquid bottoms with a basic solution to form a liquid scrubbing mixture, the basic solution selected from the group consisting of alkali metal hydroxides, ammonium hydroxide, and ammonia; and dividing the liquid scrubbing mixture into a tower bottoms products, a first recycle stream providing the liquid scrubbing mixture to the first contacting step, and a second recycle stream providing the liquid scrubbing mixture to the second contacting step.

  20. Oxidation in a temperature gradient

    SciTech Connect

    Holcomb, Gordon R.; Covino, Bernard S., Jr.; Russell, James H.

    2001-01-01

    The effects of a temperature gradient and heat flux on point defect diffusion in protective oxide scales were examined. Irreversible thermodynamics were used to expand Fick's first law of diffusion to include a heat flux term--a Soret effect. Oxidation kinetics were developed for the oxidation of cobalt and for nickel doped with chromium. Research in progress is described to verify the effects of a heat flux by oxidizing pure cobalt in a temperature gradient above 800 C, and comparing the kinetics to isothermal oxidation. The tests are being carried out in the new high temperature gaseous corrosion and corrosion/erosion facility at the Albany Research Center.

  1. Oxidized Phosphatidylserine: Production and Bioactivities

    PubMed Central

    Matsura, Tatsuya

    2014-01-01

    Recent development of analytical methods for lipid hydroperoxides and preparation of highly pure lipid hydroperoxides have revealed the important new pathophysiological roles of oxidized phospholipids. Generation of reactive oxygen species and subsequent oxidative stress leads to random oxidation of membrane phospholipids. However, recent studies have reported that anionic phospholipid molecules such as phosphatidylserine (PS) and cardiolipin are preferentially oxidized during apoptosis, resulting in efficient apoptosis execution and apoptotic cell clearance by phagocytes. This review is exclusively focused on selective production of oxidized PS (oxPS) during apoptosis as well as the novel roles of oxPS under pathophysiological conditions. PMID:25901098

  2. Lipid oxidation induced oxidative degradation of cereal beta-glucan.

    PubMed

    Wang, Yu-Jie; Mäkelä, Noora; Maina, Ndegwa Henry; Lampi, Anna-Maija; Sontag-Strohm, Tuula

    2016-04-15

    In food systems, lipid oxidation can cause oxidation of other molecules. This research for the first time investigated oxidative degradation of β-glucan induced by lipid oxidation using an oil-in-water emulsion system which simulated a multi-phased aqueous food system containing oil and β-glucan. Lipid oxidation was monitored using peroxide value and hexanal production while β-glucan degradation was evaluated by viscosity and molecular weight measurements. The study showed that while lipid oxidation proceeded, β-glucan degradation occurred. Emulsions containing β-glucan, oil and ferrous ion showed significant viscosity and molecular weight decrease after 1week of oxidation at room temperature. Elevated temperature (40°C) enhanced the oxidation reactions causing higher viscosity drop. In addition, the presence of β-glucan appeared to retard the hexanal production in lipid oxidation. The study revealed that lipid oxidation may induce the degradation of β-glucan in aqueous food systems where β-glucan and lipids co-exist. PMID:26675874

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

    SciTech Connect

    Vogt, Patrick; Bierwagen, Oliver

    2015-02-23

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

  4. Hysteresis-free high rate reactive sputtering of niobium oxide, tantalum oxide, and aluminum oxide

    SciTech Connect

    Särhammar, Erik Berg, Sören; Nyberg, Tomas

    2014-07-01

    This work reports on experimental studies of reactive sputtering from targets consisting of a metal and its oxide. The composition of the targets varied from pure metal to pure oxide of Al, Ta, and Nb. This combines features from both the metal target and oxide target in reactive sputtering. If a certain relation between the metal and oxide parts is chosen, it may be possible to obtain a high deposition rate, due to the metal part, and a hysteresis-free process, due to the oxide part. The aim of this work is to quantify the achievable boost in oxide deposition rate from a hysteresis-free process by using a target consisting of segments of a metal and its oxide. Such an increase has been previously demonstrated for Ti using a homogeneous substoichiometric target. The achievable gain in deposition rate depends on transformation mechanisms from oxide to suboxides due to preferential sputtering of oxygen. Such mechanisms are different for different materials and the achievable gain is therefore material dependent. For the investigated materials, the authors have demonstrated oxide deposition rates that are 1.5–10 times higher than what is possible from metal targets in compound mode. However, although the principle is demonstrated for oxides of Al, Ta, and Nb, a similar behavior is expected for most oxides.

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

    NASA Astrophysics Data System (ADS)

    Vogt, Patrick; Bierwagen, Oliver

    2015-02-01

    The hetero-epitaxial growth of the n-type semiconducting oxides ?-Ga2O3, In2O3, and SnO2 on c- and r-plane sapphire was performed by plasma-assisted molecular beam epitaxy. The growth-rate and desorbing flux from the substrate were measured in-situ under various oxygen to metal ratios by laser reflectometry and quadrupole mass spectrometry, respectively. These measurements clarified the role of volatile sub-oxide formation (Ga2O, In2O, and SnO) during growth, the sub-oxide stoichiometry, and the efficiency of oxide formation for the three oxides. As a result, the formation of the sub-oxides decreased the growth-rate under metal-rich growth conditions and resulted in etching of the oxide film by supplying only metal flux. The flux ratio for the exclusive formation of the sub-oxide (e.g., the p-type semiconductor SnO) was determined, and the efficiency of oxide formation was found to be the highest for SnO2, somewhat lower for In2O3, and the lowest for Ga2O3. Our findings can be generalized to further oxides that possess related sub-oxides.

  6. Iridium oxide-polymer nanocomposite electrode materials for water oxidation.

    PubMed

    Lattach, Youssef; Rivera, Juan Francisco; Bamine, Tahya; Deronzier, Alain; Moutet, Jean-Claude

    2014-08-13

    Nanocomposite anode materials for water oxidation have been readily synthesized by electrodeposition of iridium oxide nanoparticles into poly(pyrrole-alkylammonium) films, previously deposited onto carbon electrodes by oxidative electropolymerization of a pyrrole-alkylammonium monomer. The nanocomposite films were characterized by electrochemistry, transmission electron microscopy, and atomic force microscopy. They showed an efficient electrocatalytic activity toward the oxygen evolution reaction. Data from Tafel plots have demonstrated that the catalytic activity of the iridium oxide nanoparticles is maintained following their inclusion in the polymer matrix. Bulk electrolysis of water at carbon foam modified electrodes have shown that the iridium oxide-polymer composite presents a higher catalytic activity and a better operational stability than regular oxide films. PMID:25045786

  7. Oxidative stress and oxidative damage in chemical carcinogenesis

    SciTech Connect

    Klaunig, James E. Wang Zemin; Pu Xinzhu; Zhou Shaoyu

    2011-07-15

    Reactive oxygen species (ROS) are induced through a variety of endogenous and exogenous sources. Overwhelming of antioxidant and DNA repair mechanisms in the cell by ROS may result in oxidative stress and oxidative damage to the cell. This resulting oxidative stress can damage critical cellular macromolecules and/or modulate gene expression pathways. Cancer induction by chemical and physical agents involves a multi-step process. This process includes multiple molecular and cellular events to transform a normal cell to a malignant neoplastic cell. Oxidative damage resulting from ROS generation can participate in all stages of the cancer process. An association of ROS generation and human cancer induction has been shown. It appears that oxidative stress may both cause as well as modify the cancer process. Recently association between polymorphisms in oxidative DNA repair genes and antioxidant genes (single nucleotide polymorphisms) and human cancer susceptibility has been shown.

  8. Semiconducting transition metal oxides

    NASA Astrophysics Data System (ADS)

    Lany, Stephan

    2015-07-01

    Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using as an example the diversity of possible atomic and magnetic configurations of the O vacancy in TiO2, and the high levels of hole doping in Co2ZnO4 due to a self-doping mechanism that originates from the multivalence of Co.

  9. Novel Photocatalytic Metal Oxides

    SciTech Connect

    Smith, Robert W.; Mei, Wai-Ning; Sabirianov, Renat; Wang, Lu

    2012-08-31

    The principal short-term objective is to develop improved solid-state photocatalysts for the decomposition of water into hydrogen gas using ultraviolet and visible solar radiation. We will pursue our objective by modeling candidate metal oxides through computer simulations followed by synthesis of promising candidates. We will characterize samples through standard experimental techniques. The long-term objective is to provide a more efficient source of hydrogen gas for fixed-site hydrogen fuel cells, particularly for energy users in remote locations.

  10. Heterogeneous Oxidation of Catechol.

    PubMed

    Pillar, Elizabeth A; Zhou, Ruixin; Guzman, Marcelo I

    2015-10-15

    Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air-solid interface under variable relative humidity (RH = 0-90%). The maximum reactive uptake coefficient of O3(g) by catechol ?O3 = (7.49 0.35) 10(-6) occurs for 90% RH. Upon exposure of ca. 104-?m thick catechol films to O3(g) mixing ratios between 230 ppbv and 25 ppmv, three main reaction pathways are observed. (1) The cleavage of the 1,2 carbon-carbon bond at the air-solid interface resulting in the formation of cis,cis-muconic acid via primary ozonide and hydroperoxide intermediates. Further direct ozonolysis of cis,cis-muconic yields glyoxylic, oxalic, crotonic, and maleic acids. (2) A second pathway is evidenced by the presence of Baeyer-Villiger oxidation products including glutaconic 4-hydroxy-2-butenoic and 5-oxo-2-pentenoic acids during electrospray ionization mass spectrometry (MS) and ion chromatography MS analyses. (3) Finally, indirect oxidation by in situ produced hydroxyl radical (HO()) results in the generation of semiquinone radical intermediates toward the synthesis of polyhydoxylated aromatic rings such as tri-, tetra-, and penta-hydroxybenzene. Remarkably, heavier polyhydroxylated biphenyl and terphenyl products present in the extracted oxidized films result from coupling reactions of semiquinones of catechol and its polyhydroxylated rings. The direct ozonolysis of 1,2,3- and 1,2,4-trihydroxybenezene yields 2- and 3-hydroxy-cis,cis-muconic acid, respectively. The production of 2,4- or 3,4-dihdroxyhex-2-enedioic acid is proposed to result from the sequential processing of cis,cis-muconic acid, 2- and 3-hydroxy-cis,cis-muconic acid. Overall, these reactions contribute precursors to form aqueous SOA from aromatics in atmospheric aerosols and brown clouds. PMID:26403273

  11. PLATES WITH OXIDE INSERTS

    DOEpatents

    West, J.M.; Schumar, J.F.

    1958-06-10

    Planar-type fuel assemblies for nuclear reactors are described, particularly those comprising fuel in the oxide form such as thoria and urania. The fuel assembly consists of a plurality of parallel spaced fuel plate mennbers having their longitudinal side edges attached to two parallel supporting side plates, thereby providing coolant flow channels between the opposite faces of adjacent fuel plates. The fuel plates are comprised of a plurality of longitudinally extending tubular sections connected by web portions, the tubular sections being filled with a plurality of pellets of the fuel material and the pellets being thermally bonded to the inside of the tubular section by lead.

  12. Electrolytic oxide reduction system

    SciTech Connect

    Wiedmeyer, Stanley G; Barnes, Laurel A; Williamson, Mark A; Willit, James L; Berger, John F

    2015-04-28

    An electrolytic oxide reduction system according to a non-limiting embodiment of the present invention may include a plurality of anode assemblies, a plurality of cathode assemblies, and a lift system configured to engage the anode and cathode assemblies. The cathode assemblies may be alternately arranged with the anode assemblies such that each cathode assembly is flanked by two anode assemblies. The lift system may be configured to selectively engage the anode and cathode assemblies so as to allow the simultaneous lifting of any combination of the anode and cathode assemblies (whether adjacent or non-adjacent).

  13. Arsenic doped zinc oxide

    SciTech Connect

    Volbers, N.; Lautenschlaeger, S.; Leichtweiss, T.; Laufer, A.; Graubner, S.; Meyer, B. K.; Potzger, K.; Zhou Shengqiang

    2008-06-15

    As-doping of zinc oxide has been approached by ion implantation and chemical vapor deposition. The effect of thermal annealing on the implanted samples has been investigated by using secondary ion mass spectrometry and Rutherford backscattering/channeling geometry. The crystal damage, the distribution of the arsenic, the diffusion of impurities, and the formation of secondary phases is discussed. For the thin films grown by vapor deposition, the composition has been determined with regard to the growth parameters. The bonding state of arsenic was investigated for both series of samples using x-ray photoelectron spectroscopy.

  14. Oxidative Metabolism in Muscle

    NASA Astrophysics Data System (ADS)

    Ferrari, M.; Binzoni, T.; Quaresima, V.

    1997-06-01

    Oxidative metabolism is the dominant source of energy for skeletal muscle. Near-infrared spectroscopy allows the non-invasive measurement of local oxygenation, blood flow and oxygen consumption. Although several muscle studies have been made using various near-infrared optical techniques, it is still difficult to interpret the local muscle metabolism properly. The main findings of near-infrared spectroscopy muscle studies in human physiology and clinical medicine are summarized. The advantages and problems of near-infrared spectroscopy measurements, in resting and exercising skeletal muscles studies, are discussed through some representative examples.

  15. Zinc Oxide Nanophotonics

    NASA Astrophysics Data System (ADS)

    Choi, Sumin; Aharonovich, Igor

    2015-12-01

    The emerging field of nanophotonics initiated a dedicated study of single photon sources and optical resonators in new class of materials. One such material is zinc oxide (ZnO) that has been long considered only for classical light-emitting applications. However, it recently showed promise for quantum photonics technologies. In this review, we highlight the recent advances in studying single emitters in ZnO, engineering of optical cavities and practical nanophotonics devices including nanolasers and electrically triggered devices. We finalize with an outlook at this promising area, as well as provide perspectives and open questions in solid state nanophotonics employing ZnO.

  16. Semiconducting transition metal oxides.

    PubMed

    Lany, Stephan

    2015-07-22

    Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using as an example the diversity of possible atomic and magnetic configurations of the O vacancy in TiO(2), and the high levels of hole doping in Co(2)ZnO(4) due to a self-doping mechanism that originates from the multivalence of Co. PMID:26126022

  17. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOEpatents

    Dunning, John S.; Alman, David E.

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800 C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800 C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700 C. at a low cost

  18. Oxidation resistant alloys, method for producing oxidation resistant alloys

    DOEpatents

    Dunning, John S. (Corvallis, OR); Alman, David E. (Salem, OR)

    2002-11-05

    A method for producing oxidation-resistant austenitic alloys for use at temperatures below 800.degree. C. comprising of: providing an alloy comprising, by weight %: 14-18% chromium, 15-18% nickel, 1-3% manganese, 1-2% molybdenum, 2-4% silicon, 0% aluminum and the balance being iron; heating the alloy to 800.degree. C. for between 175-250 hours prior to use in order to form a continuous silicon oxide film and another oxide film. The method provides a means of producing stainless steels with superior oxidation resistance at temperatures above 700.degree. C. at a low cost

  19. Role of oxidative stress and nitric oxide in atherothrombosis

    PubMed Central

    Lubos, Edith; Handy, Diane E.; Loscalzo, Joseph

    2008-01-01

    During the last decade basic and clinical research has highlighted the central role of reactive oxygen species (ROS) in cardiovascular disease. Enhanced production or attenuated degradation of ROS leads to oxidative stress, a process that affects endothelial and vascular function, and contributes to vascular disease. Nitric oxide (NO), a product of the normal endothelium, is a principal determinant of normal endothelial and vascular function. In states of inflammation, NO production by the vasculature increases considerably and, in conjunction with other ROS, contributes to oxidative stress. This review examines the role of oxidative stress and NO in mechanisms of endothelial and vascular dysfunction with an emphasis on atherothrombosis. PMID:18508590

  20. Oxidative stress and lung diseases.

    PubMed

    Maselli, R; Grembiale, R D; Pelaia, G; Cuda, G

    2002-01-01

    Several different lung diseases are characterized by an oxidant/antioxidant imbalance, which is a major cause of cell damage. Oxidative stress activates a complex network of intracellular signal transduction pathways involved in the regulation of transcription factors such as nuclear factor kappa B (NF-kappa B) and activator protein-1 (AP-1). Within this context, a key role is played by mitogen-activated protein kinases (MAPK), which are highly expressed by pulmonary endothelial and airway epithelial cells. By exposing these cell lines to oxidant agents, our group has shown that oxidative stress leads to a significant MAPK activation, which can be effectively inhibited by corticosteroids. We believe that studies such as ours may contribute to further elucidate the molecular events underlying the therapeutic action of these drugs in many respiratory disorders caused by oxidative/proinflammatory pathogenic mechanisms. In addition, our findings may help to unveil new anti-oxidant treatments based on MAPK modulation. PMID:12619379

  1. A germanate transparent conductive oxide

    PubMed Central

    Mizoguchi, Hiroshi; Kamiya, Toshio; Matsuishi, Satoru; Hosono, Hideo

    2011-01-01

    Wide bandgap conductors such as In2O3 and ZnO are used as transparent conducting oxides (TCOs). To date, TCOs are realized using post transition metal cations with largely spread s-orbitals such as In3+, Sn4+, Zn2+ and Cd2+. On the other hand, no good electronic conductor has been realized in oxides of Al, Si and Ge. Here we report the conversion of an oxide of Ge into a good electronic conductor by employing the concept of superdegeneracy. We find that cubic SrGeO3, synthesized under high pressure, displays a direct bandgap of 3.5?eV, a carrier mobility of 12?cm2(Vs)?1, and conductivities of 3?Scm?1 (DC) and 400?Scm?1 (optical conductivity). This is the first Ge-based electronic conductive oxide, and expands the family of TCOs from ionic oxides to covalent oxides. PMID:21915112

  2. Growth, characterization and reactivity studies: Oxide films, metal-oxide films and layered oxide films

    NASA Astrophysics Data System (ADS)

    Oh, Weon Sik

    This work presents studies of the growth, characterization and reactivity of oxide thin films, metal-oxide films and layered oxide films under vacuum conditions. The growth mode of the films, the geometric, electronic and chemical properties of overlayers and supports as well as the thermal stability of the overlayers were studied using the techniques and methodology of surface science. These model studies provide a convenient approach to understanding oxide surfaces and interfaces on the atomic scale. Epitaxial titanium oxide and calcium oxide films were synthesized on a refractory substrate, Mo(100), by vapor deposition of metals in the presence of an oxygen background and characterized by various surface analytical techniques. The 90 A thick titanium oxide film is stoichiometric. LEED and STM results show a (2sqrt{2}sqrt{2})R45sp reconstruction of the TiOsb2(001) film upon annealing. CaO films grow stoichiometrically on the Mo(100) with (100) orientation. The interfacial reactions between oxide thin films and refractory metal substrates were investigated. The thermal stability of an oxide overlayer is found to be mainly dependent upon the heat of formation and film thicknesses of the oxide. The growth mode, electronic and chemical properties of Au clusters supported on the TiOsb2(001)/Mo(100) surface were studied to understand the catalytic properties of Au supported catalysts. The bonding of Au on TiOsb2/Mo(100) is weak and Au clusters easily agglomerate upon annealing. Finally, layered binary thin-film oxides of NiO, MgO and CaO were studied as models to understand how the lattice constant mismatch influences the growth, thermal stability and chemical properties of the layered oxides. The influence of MgO and CaO on the NO adsorption on NiO was also studied and correlated to the growth mode of the mixed oxides.

  3. Transparent conducting oxide nanotubes.

    PubMed

    Alivov, Yahya; Singh, Vivek; Ding, Yuchen; Nagpal, Prashant

    2014-09-26

    Thin film or porous membranes made of hollow, transparent, conducting oxide (TCO) nanotubes, with high chemical stability, functionalized surfaces and large surface areas, can provide an excellent platform for a wide variety of nanostructured photovoltaic, photodetector, photoelectrochemical and photocatalytic devices. While large-bandgap oxide semiconductors offer transparency for incident light (below their nominal bandgap), their low carrier concentration and poor conductivity makes them unsuitable for charge conduction. Moreover, materials with high conductivity have nominally low bandgaps and hence poor light transmittance. Here, we demonstrate thin films and membranes made from TiO2 nanotubes heavily-doped with shallow Niobium (Nb) donors (up to 10%, without phase segregation), using a modified electrochemical anodization process, to fabricate transparent conducting hollow nanotubes. Temperature dependent current-voltage characteristics revealed that TiO2 TCO nanotubes, doped with 10% Nb, show metal-like behavior with resistivity decreasing from 6.5נ10(-4) ?cm at T=300 K (compared to 6.5נ10(-1) ?cm for nominally undoped nanotubes) to 2.2נ10(-4) ?cm at T=20 K. Optical properties, studied by reflectance measurements, showed light transmittance up to 90%, within wavelength range 400 nm-1000 nm. Nb doping also improves the field emission properties of TCO nanotubes demonstrating an order of magnitude increase in field-emitter current, compared to undoped samples. PMID:25180635

  4. Low Temperature Oxidation Catalyst

    NASA Technical Reports Server (NTRS)

    1995-01-01

    One day soon homeowners everywhere may be protected from deadly carbon monoxide fumes, thanks to a device invented at NASA Langley Research Center in Hampton, Va. It uses a new class of low-temperature oxidation catalysts to convert carbon monoxide to non-toxic carbon dioxide at room temperature. It can also remove formaldehyde from the air. The catalysts initially were developed for research involving carbon dioxide lasers. Industry already has shown an interest. Rochester Gas and Electric Co., of Rochester, N.Y., has an agreement with NASA Langley to develop a product for habitable spaces such as homes, cars and aircraft. The Mantic Corp., of Salt Lake City, Utah, plans to use them in breathing apparatus, such as firefighter masks. The catalysts also have applications as trace-gas detectors, and in cold-engine emission control. To work, the catalysts - tin oxide and platinum - are applied to a surface. Air passing over the surface reacts with the catalysts, transforming carbon monoxide and formaldehyde. The device requires no energy for operation, doesn't need to be plugged in, has no moving parts and lasts a long time.

  5. [Oxidative stress and atherosclerosis].

    PubMed

    Stark, Jlia

    2015-07-12

    Atherosclerosis is a leading cause of death in developed countries. Genetic susceptibility and environmental factors play a role in the pathogenesis. Most of these factors lead to endothelial dysfunction and other pro-atherogenic processes by causing oxidative stress. Atherosclerosis typically develops at the curved and branched regions of the arterial tree, where the laminar blood flow is disturbed. This leads to increased permeability of the endothelium to low density lipoprotein molecules, which accumulate in the intima and are oxidised by vascular cells. Oxidised low density lipoprotein takes part in many phases of atherogenesis: stimulates the binding of monocytes to the endothelium, foam cell formation, the development of plaques, plaque destabilization and thrombotic complications. Since oxidative stress plays an important role in atherogenesis, it has been suggested that antioxidant molecules might have anti-atherogenic function. Many clinical investigations have shown that antioxidants such as N-acetylcystein, vitamin E and C, folic acid, and estrogens can prevent atherosclerosis, however, randomized studies failed to confirm this effect. PMID:26149503

  6. Graphene oxide nanocolloids.

    PubMed

    Luo, Jiayan; Cote, Laura J; Tung, Vincent C; Tan, Alvin T L; Goins, Philip E; Wu, Jinsong; Huang, Jiaxing

    2010-12-22

    Graphene oxide (GO) nanocolloids-sheets with lateral dimension smaller than 100 nm-were synthesized by chemical exfoliation of graphite nanofibers, in which the graphene planes are coin-stacked along the length of the nanofibers. Since the upper size limit is predetermined by the diameter of the nanofiber precursor, the size distribution of the GO nanosheets is much more uniform than that of common GO synthesized from graphite powders. The size can be further tuned by the oxidation time. Compared to the micrometer-sized, regular GO sheets, nano GO has very similar spectroscopic characteristics and chemical properties but very different solution properties, such as surface activity and colloidal stability. Due to higher charge density originating from their higher edge-to-area ratios, aqueous GO nanocolloids are significantly more stable. Dispersions of GO nanocolloids can sustain high-speed centrifugation and remain stable even after chemical reduction, which would result in aggregates for regular GO. Therefore, nano GO can act as a better dispersing agent for insoluble materials (e.g., carbon nanotubes) in water, creating a more stable colloidal dispersion. PMID:21105686

  7. Enzymes of respiratory iron oxidation

    SciTech Connect

    Blake, R. II.

    1991-01-01

    This report focuses on the progress made in three areas of research concerned with enzymes involved in respiratory iron oxidation. The three areas are as follows: development of an improved procedure for the routine large scale culture of iron oxidizing chemolithotrophs based on the in-situ electrolysis of the soluble iron in the growth medium; to perform iron oxidation kinetic studies on whole cells using the oxygen electrode; and to identify, separate, purify, and characterize the individual cellular components.

  8. Metabolism of Nitrogen Oxides in Ammonia-Oxidizing Bacteria

    NASA Astrophysics Data System (ADS)

    Kozlowski, J.; Stein, L. Y.

    2014-12-01

    Ammonia-oxidizing bacteria (AOB) are key microorganisms in the transformation of nitrogen intermediates in most all environments. Until recently there was very little work done to elucidate the physiology of ammonia-oxidizing bacteria cultivated from variable trophic state environments. With a greater variety of ammonia-oxidizers now in pure culture the importance of comparative physiological and genomic analysis is crucial. Nearly all known physiology of ammonia-oxidizing bacteria lies within the Nitrosomonas genus with Nitrosomonas europaea strain ATCC 19718 as the model. To more broadly characterize and understand the nature of obligate ammonia chemolithotrophy and the contribution of AOB to production of nitrogen oxides, Nitrosomonas spp. and Nitrosospira spp. isolated from variable trophic states and with sequenced genomes, were utilized. Instantaneous ammonia- and hydroxylamine-oxidation kinetics as a function of oxygen and substrate concentration were measured using an oxygen micro-sensor. The pathway intermediates nitric oxide and nitrous oxide were measured in real time using substrate-specific micro-sensors to elucidate whether production of these molecules is stoichiometric with rates of substrate oxidation. Genomic inventory was compared among the strains to identify specific pathways and modules to explain physiological differences in kinetic rates and production of N-oxide intermediates as a condition of their adaptation to different ammonium concentrations. This work provides knowledge of how nitrogen metabolism is differentially controlled in AOB that are adapted to different concentrations of ammonium. Overall, this work will provide further insight into the control of ammonia oxidizing chemolithotrophy across representatives of the Nitrosomonas and Nitrosospira genus, which can then be applied to examine additional genome-sequenced AOB isolates.

  9. Zinc oxide varistors and/or resistors

    DOEpatents

    Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

    1993-07-27

    Varistors and/or resistors are described that include doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  10. Zinc oxide varistors and/or resistors

    DOEpatents

    Arnold, Jr., Wesley D. (Oak Ridge, TN); Bond, Walter D. (Knoxville, TN); Lauf, Robert J. (Oak Ridge, TN)

    1993-01-01

    Varistors and/or resistors that includes doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.

  11. Continuous lengths of oxide superconductors

    DOEpatents

    Kroeger, Donald M. (Knoxville, TN); List, III, Frederick A. (Andersonville, TN)

    2000-01-01

    A layered oxide superconductor prepared by depositing a superconductor precursor powder on a continuous length of a first substrate ribbon. A continuous length of a second substrate ribbon is overlaid on the first substrate ribbon. Sufficient pressure is applied to form a bound layered superconductor precursor powder between the first substrate ribbon and the second substrate ribbon. The layered superconductor precursor is then heat treated to establish the oxide superconducting phase. The layered oxide superconductor has a smooth interface between the substrate and the oxide superconductor.

  12. Buried oxide layer in silicon

    DOEpatents

    Sadana, Devendra Kumar; Holland, Orin Wayne

    2001-01-01

    A process for forming Silicon-On-Insulator is described incorporating the steps of ion implantation of oxygen into a silicon substrate at elevated temperature, ion implanting oxygen at a temperature below 200.degree. C. at a lower dose to form an amorphous silicon layer, and annealing steps to form a mixture of defective single crystal silicon and polycrystalline silicon or polycrystalline silicon alone and then silicon oxide from the amorphous silicon layer to form a continuous silicon oxide layer below the surface of the silicon substrate to provide an isolated superficial layer of silicon. The invention overcomes the problem of buried isolated islands of silicon oxide forming a discontinuous buried oxide layer.

  13. Correlated oxides: Metals amassing transparency

    NASA Astrophysics Data System (ADS)

    Poeppelmeier, Kenneth R.; Rondinelli, James M.

    2016-02-01

    Conducting complex oxides with correlated electrons at room temperature offer a less explored materials platform for the high conductivity and optical transparency needed for ultrathin invisible circuitry.

  14. Mesoporous Mn- and La-doped cerium oxide/cobalt oxide mixed metal catalysts for methane oxidation.

    PubMed

    Vickers, Susan M; Gholami, Rahman; Smith, Kevin J; MacLachlan, Mark J

    2015-06-01

    New precious-metal-free mesoporous materials were investigated as catalysts for the complete oxidation of methane to carbon dioxide. Mesoporous cobalt oxide was first synthesized using KIT-6 mesoporous silica as a hard template. After removal of the silica, the cobalt oxide was itself used as a hard template to construct cerium oxide/cobalt oxide composite materials. Furthermore, cerium oxide/cobalt oxide composite materials doped with manganese and lanthanum were also prepared. All of the new composite materials retained the hierarchical long-range order of the original KIT-6 template. Temperature-programmed oxidation measurements showed that these cerium oxide/cobalt oxide and doped cerium oxide/cobalt oxide materials are effective catalysts for the total oxidation of methane, with a light-off temperature (T50%) of ?400 C observed for all of the nanostructured materials. PMID:26000732

  15. HYDROCARBON OXIDATION OVER VANADIUM PHOSPHORUS OXIDE CATALYST USING HYDROGEN PEROXIDE

    EPA Science Inventory

    Selective oxidation of hydrocarbons is one of the very important and challenging areas in industrial chemistry due to the wide ranging utility of the resulting oxygenates in fine chemical synthesis. Most of the existing processes for their oxidations employ toxic and often stoich...

  16. Catalysis by Thin Oxide Films and Oxide Nanoparticles

    NASA Astrophysics Data System (ADS)

    Rupprechter, Günther; Penner, Simon

    Model systems for transition and noble metal oxide catalysts, either as thin films or nanoparticles, were prepared by vacuum-deposition of oxides or oxidation of metals (particles, thin films, single crystals). These systems, including Ga2O3, In2O3, V2O3, V2O5, Nb2O5, Pd5O4 and PdO, are well suited for atomic scale characterization by surface-specific methods and for catalytic tests. Investigations of structure and composition were carried out by HRTEM, AFM, STM, SAED, LEED, EDX, XPS and DFT. In many cases, the surface structure of oxides does not coincide with truncations of the known bulk structures. The adsorption properties of the oxide models, in particular those of defects such as oxygen vacancies or step edges, were examined by vibrational spectroscopy (FTIR and SFG) and thermal desorption spectroscopy (TPD) of probe molecules (CO, H2, propane and propene). Together with XPS, quantification of surface coverage was performed. The catalytic activity and selectivity of the model oxides at (near) ambient gas pressure were investigated by microreactor studies of methanol steam reforming (MSR), (inverse) water gas shift (WGS) and CO oxidation. The structural/compositional flexibility of oxides leads to significant challenges in their characterization but also imparts them with exceptional catalytic properties.

  17. The Oxidative Aging of Model Oxidized Organic Aerosol Systems

    NASA Astrophysics Data System (ADS)

    Kessler, S. H.; Daumit, K. E.; Nah, T.; Smith, J. D.; Worsnop, D. R.; Wilson, K. R.; Kroll, J. H.

    2011-12-01

    Modeling and predictions of the behavior of highly oxidized organic aerosol components in the atmosphere often fall short in describing such systems, in part because of the difficulty of accessing appropriately high levels of oxidation (equivalent to one or two weeks in the atmosphere) in a laboratory setting. In this work, we present results from the heterogeneous oxidation by hydroxyl radicals (OH) of particles composed of pure citric, tartaric, or 1,2,3,4-butanetetracarboxylic acid, as well as a fulvic acid sample, in a flow tube reactor. The combination of highly oxidized reagent compounds and high concentrations of OH within the reactor allow us to access very high degrees of oxidation relative to previous studies. As OH exposure increases, an increase in carbon oxidation state and a decrease in overall carbon content are observed, consistent with reaction types in which carbon-carbon bonds are broken and molecules become volatilized. At very high exposure levels, however, changes in both oxidation state and carbon content begin to slow. This evolving recalcitrance of OA constituents suggests a framework to determine under what circumstances oxidative aging will strongly affect atmospheric particle evolution.

  18. EDITORIAL: Oxide semiconductors

    NASA Astrophysics Data System (ADS)

    Kawasaki, M.; Makino, T.

    2005-04-01

    Blue or ultraviolet semiconducting light-emitting diodes have the potential to revolutionize illumination systems in the near-future. Such industrial need has propelled the investigation of several wide-gap semiconducting materials in recent years. Commercial applications include blue lasers for DVD memory and laser printers, while military applications are also expected. Most of the material development has so far been focused on GaN (band gap 3.5 eV at 2 K), and ZnSe (2.9 eV) because these two representative direct transition semiconductors are known to be bright emitting sources. GaN and GaN-based alloys are emerging as the winners in this field because ZnSe is subject to defect formation under high current drive. On the other hand, another II-VI compound, ZnO, has also excited substantial interest in the optoelectronics-oriented research communities because it is the brightest emitter of all, owing to the fact that its excitons have a 60 meV binding energy. This is compared with 26 meV for GaN and 20 meV for ZnSe. The stable excitons could lead to laser action based on their recombination even at temperatures well above room temperature. ZnO has additional major properties that are more advantageous than other wide-gap materials: availability of large area substrates, higher energy radiation stability, environmentally-friendly ingredients, and amenability to wet chemical etching. However, ZnO is not new to the semiconductor field as exemplified by several studies made during the 1960s on structural, vibrational, optical and electrical properties (Mollwo E 1982 Landolt-Boernstein New Series vol 17 (Berlin: Springer) p 35). In terms of devices, the luminescence from light-emitting diode structures was demonstrated in which Cu2O was used as the p-type material (Drapak I T 1968 Semiconductors 2 624). The main obstacle to the development of ZnO has been the lack of reproducible p-type ZnO. The possibility of achieving epitaxial p-type layers with the aid of thermal non-equilibrium growth has rekindled the recent extensive investigation and progress in the field of ZnO epitaxy. In this special issue, Ohtomo and Tsukazaki, Cho et al, and Yi et al, respectively, describe the various fabrication processes such as pulsed laser deposition, molecular-beam epitaxy and metal-organic chemical vapour deposition. It should be noted that the last work among the above-mentioned papers has the potential to pave the way to nano-technology based on ZnO. This material has found other important applications as well, such as transparent conducting oxides (TCO). This field has a long research history, as is reviewed by Minami. Relatively speaking, ZnO was one of the earliest crystals (after Si, Ge, and InSb) to be prepared in a pure form, and the resultant long research history has given rise to the availability of large-area substrates. Recent progress in this topic is explained by two representative groups of authors in this field: Nause and Nemeth at Cermet Inc., and Maeda et al at Tokyo Denpa Co. Ltd. In order to overcome the bottleneck of p-type conduction and control the material's properties, a clear understanding of the physical processes in ZnO is necessary. Look et al are known as the first group to report on the growth and properties of p-type ZnO layers with a valid and reasonable set of experimental data (2002 Appl. Phys. Lett. 81 1830). Here, Look contributes a more comprehensive review to this issue. Optical studies on single crystals were conducted and are reviewed here by Meyer et al and Chichibu et al. Band-gap engineering and fabrication of heterojunction or quantum structures are important technological issues. It should be emphasized that by choosing an appropriate set of concentrations (x and y), perfect lattice-matching between MgxZn1-xO and CdyZn1-yO can be attained (Makino T et al 2001 Appl. Phys. Lett. 78 1237). Exciton properties of multiple quantum well structures are reported by Makino et al in this issue. Other than growth of p-type layers, ferromagnetic behaviour in transition-metal doped oxide is also fuelling renewed interest from the spintronic point of view. Since some of the related reports remain controversial, a critical discussion of the magnetic properties of these doped oxides is made by Fukumura et al. Before the observation of electro-luminescence from the ZnO p-n homojunction reported by Tsukazaki et al (2005 Nature Mater. 4 42), the afore-mentioned advantages have been explored and exploited by alternative methods, such as heteroepitaxy in which p-n heterostructures can be obtained by depositing n-type ZnO films on other p-type oxides while still utilizing ZnO as their active layer. Researchers in Hosono's group observed the high-intensity band-edge emission from such heterostructures for the first time (Ohta H et al 2000 Appl. Phys. Lett. 77 475). They have also successfully extended their research fields to the development of a transparent oxide transistor based on homologous compounds, which is reviewed by Kamiya and Hosono in this special issue. As can be seen from these demonstrations, the advantage of oxides is, of course, based on the fact that many elements in the periodic table can form compounds with oxygen. Since the discovery of high-temperature superconductors, these multi-component oxides have exploited the new field known as the science of strongly correlated-electron materials, whose recent progress is reviewed by Inoue. Although the collection of papers included in this special issue covers a good cross-section of the development of oxide semiconductors and correlated-electron oxides to date, this is not meant to be exhaustive. There are a number of unavoidable omissions, such as theoretical studies except for some theoretical predictions on the room-temperature Bose-Einstein condensation of exciton-polaritons found in the article by Chichibu et al. We hope this issue promotes further development of this exciting field. The guest editors would like to thank the publishing team of Semiconductor Science and Technology at IoPP (Claire Bedrock, Barbara Bostock, Chris Hall, and Julie Stott).

  19. Sulfite oxidizing enzymes

    PubMed Central

    Feng, Changjian; Tollin, Gordon; Enemark, John H.

    2007-01-01

    Sulfite oxidizing enzymes are essential mononuclear molybdenum (Mo) proteins involved in sulfur metabolism of animals, plants and bacteria. There are three such enzymes presently known: (1) sulfite oxidase (SO) in animals, (2) SO in plants, and (3) sulfite dehydrogenase (SDH) in bacteria. X-ray crystal structures of enzymes from all three sources (chicken SO, Arabidopsis thaliana SO, and Starkeya novella SDH) show nearly identical square pyramidal coordination around the Mo atom, even though the overall structures of the proteins and the presence of additional cofactors vary. This structural information provides a molecular basis for studying the role of specific amino acids in catalysis. Animal SO catalyzes the final step in the degradation of sulfur-containing amino acids and is critical in detoxifying excess sulfite. Human SO deficiency is a fatal genetic disorder that leads to early death, and impaired SO activity is implicated in sulfite neurotoxicity. Animal SO and bacterial SDH contain both Mo and heme domains, whereas plant SO only has the Mo domain. Intraprotein electron transfer (IET) between the Mo and Fe centers in animal SO and bacterial SDH is a key step in the catalysis, which can be studied by laser flash photolysis in the presence of deazariboflavin. IET studies on animal SO and bacterial SDH clearly demonstrate the similarities and differences between these two types of sulfite oxidizing enzymes. Conformational change is involved in the IET of animal SO, in which electrostatic interactions may play a major role in guiding the docking of the heme domain to the Mo domain prior to electron transfer. In contrast, IET measurements for SDH demonstrate that IET occurs directly through the protein medium, which is distinctly different from that in animal SO. Point mutations in human SO can result in significantly impaired IET or no IET, thus rationalizing their fatal effects. The recent developments in our understanding of sulfite oxidizing enzyme mechanisms that are driven by a combination of molecular biology, rapid kinetics, pulsed electron paramagnetic resonance (EPR), and computational techniques are the subject of this review. PMID:17459792

  20. Ferromagnet / superconductor oxide superlattices

    NASA Astrophysics Data System (ADS)

    Santamaria, Jacobo

    2006-03-01

    The growth of heterostructures combining oxide materials is a new strategy to design novel artificial multifunctional materials with interesting behaviors ruled by the interface. With the (re)discovery of colossal magnetoresistance (CMR) materials, there has been renewed interest in heterostructures involving oxide superconductors and CMR ferromagnets where ferromagnetism (F) and superconductivity (S) compete within nanometric distances from the interface. In F/S/F structures involving oxides, interfaces are especially complex and various factors like interface disorder and roughness, epitaxial strain, polarity mismatch etc., are responsible for depressed magnetic and superconducting properties at the interface over nanometer length scales. In this talk I will focus in F/S/F structures made of YBa2Cu3O7 (YBCO) and La0.7Ca0.3MnO3 (LCMO). The high degree of spin polarization of the LCMO conduction band, together with the d-wave superconductivity of the YBCO make this F/S system an adequate candidate for the search of novel spin dependent effects in transport. We show that superconductivity at the interface is depressed by various factors like charge transfer, spin injection or ferromagnetic superconducting proximity effect. I will present experiments to examine the characteristic distances of the various mechanisms of superconductivity depression. In particular, I will discuss that the critical temperature of the superconductor depends on the relative orientation of the magnetization of the F layers, giving rise to a new giant magnetoresistance effect which might be of interest for spintronic applications. Work done in collaboration with V. Peña^1, Z. Sefrioui^1, J. Garcia-Barriocanal^1, C. Visani^1, D. Arias^1, C. Leon^1 , N. Nemes^2, M. Garcia Hernandez^2, S. G. E. te Velthuis^3, A. Hoffmann^3, M. Varela^4, S. J. Pennycook^4. Work supported by MCYT MAT 2005-06024, CAM GR- MAT-0771/2004, UCM PR3/04-12399 Work at Argonne supported by the Department of Energy, Basic Energy Sciences, contract No.W-31-109-ENG-38. ^1GFMC, Departamento de F'isica Aplicada III, Universidad Complutense de Madrid, 28040 Madrid, Spain ^2Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC). 28049 Cantoblanco. Madrid. ^3Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, USA ^4Condensed Matter Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6031, USA

  1. The oxidation behavior of Co-15 wt % Cr alloy containing dispersed oxides formed by internal oxidation

    SciTech Connect

    Hou, P.Y.; Shui, Z.R.; Stringer, J.

    1991-12-01

    Internal oxidation pretreatments of Co-15wt%Cr and Co-15wt%Cr-1wt%Ti were carried out using a Rhines pack in quartz, in mullite and in alumina. A dispersion of titanium oxide particles formed in the Ti-containing alloy as a result of the internal oxidation. However, silicon also diffused into all treated specimens when the pretreatments were carried out in quartz or in mullite. The effect of various pretreatments on the subsequent oxidation of these alloys was studied at 1000{degree}C, and compared with that of Co-15wt%Cr-1wt%Si alloy. The main purpose of this study was to determine the relative effectiveness of the dispersed oxide particles and the contaminated silicon on the selective oxidation of chromium. It was found that the oxidation behavior of both treated alloys were strongly affected by the degree of silicon contamination. Selective oxidation of chromium to form a nearly continuous protective Cr{sub 2}O{sub 3} scale was achieved with greater than 0.4wt% silicon. The presence of dispersed particles reduced initial oxidation rate, but was ineffective in promoting Cr{sub 2}O{sub 3} scale formation.

  2. Effects of Oxidation on Oxidation-Resistant Graphite

    SciTech Connect

    Windes, William; Smith, Rebecca; Carroll, Mark

    2015-05-01

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

  3. Structural Characterization of Oxidized Glycerophosphatidylserine: Evidence of Polar Head Oxidation

    NASA Astrophysics Data System (ADS)

    Maciel, Elisabete; da Silva, Raquel Nunes; Simes, Cludia; Domingues, Pedro; Domingues, M. Rosrio M.

    2011-10-01

    Non-oxidized phosphatidylserine (PS) is known to play a key role in apoptosis but there is considerable research evidence suggesting that oxidized PS also plays a role in this event, leading to the increasing interest in studying PS oxidative modifications. In this work, different PS (1-palmitoyl-2-linoleoyl-sn-glycero-3-phospho-L-serine (PLPS), 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine (POPS), and 1,2-dipalmitoyl-sn-glycero-3-phospho-L-serine (DPPS) were oxidized in vitro by hydroxyl radical, generated under Fenton reaction conditions, and the reactions were monitored by ESI-MS in negative mode. Oxidation products were then fractionated by thin layer chromatography (TLC) and characterized by tandem mass spectrometry (MS/MS). This approach allowed the identification of hydroxyl, peroxy, and keto derivatives due to oxidation of unsaturated fatty acyl chains. Oxidation products due to oxidation of serine polar head were also identified. These products, with lower molecular weight than the non-modified PS, were identified as [M - 29 - H]- (terminal acetic acid), [M - 30 - H]- (terminal acetamide), [M - 13 - H]- (terminal hydroperoxyacetaldehyde), and [M - 13 - H]- (terminal hydroxyacetaldehyde plus hydroxy fatty acyl chain). Phosphatidic acid was also formed in these conditions. These findings confirm the oxidation of the serine polar head induced by the hydroxyl radical. The identification of these modifications may be a valuable tool to evaluate phosphatidylserine alteration under physiopathologic conditions and also to help understand the biological role of phosphatidylserine oxidation in the apoptotic process and other biological functions.

  4. Oxidation pathways underlying the pro-oxidant effects of apigenin.

    PubMed

    Andueza, Aitor; Garca-Garzn, Antonia; Ruiz de Galarreta, Marina; Ansorena, Eduardo; Iraburu, Mara J; Lpez-Zabalza, Mara J; Martnez-Irujo, Juan J

    2015-10-01

    Apigenin, a natural flavone, is emerging as a promising compound for the treatment of several diseases. One of the hallmarks of apigenin is the generation of intracellular reactive oxygen species (ROS), as judged by the oxidation of reduced dichlorofluorescein derivatives seen in many cell types. This study aimed to reveal some mechanisms by which apigenin can be oxidized and how apigenin-derived radicals affect the oxidation of 5-(and-6)-chloromethyl-2',7'-dichlorodihydrofluorescein (H(2)DCF), a probe usually employed to detect intracellular ROS. Apigenin induced a rapid oxidation of H(2)DCF in two different immortalized cell lines derived from rat and human hepatic stellate cells. However, apigenin did not generate ROS in these cells, as judged by dihydroethidium oxidation and extracellular hydrogen peroxide production. In cell-free experiments we found that oxidation of apigenin leads to the generation of a phenoxyl radical, which directly oxidizes H(2)DCF with catalytic amounts of hydrogen peroxide. The net balance of the reaction was the oxidation of the probe by molecular oxygen due to redox cycling of apigenin. This flavonoid was also able to deplete NADH and glutathione by a similar mechanism. Interestingly, H(2)DCF oxidation was significantly accelerated by apigenin in the presence of horseradish peroxidase and xanthine oxidase, but not with other enzymes showing peroxidase-like activity, such as cytochrome c or catalase. We conclude that in cells treated with apigenin oxidation of reduced dichlorofluorescein derivatives does not measure intracellular ROS and that pro- and antioxidant effects of flavonoids deduced from these experiments are inconclusive and must be confirmed by other techniques. PMID:26119779

  5. Operation of staged membrane oxidation reactor systems

    DOEpatents

    Repasky, John Michael

    2012-10-16

    A method of operating a multi-stage ion transport membrane oxidation system. The method comprises providing a multi-stage ion transport membrane oxidation system with at least a first membrane oxidation stage and a second membrane oxidation stage, operating the ion transport membrane oxidation system at operating conditions including a characteristic temperature of the first membrane oxidation stage and a characteristic temperature of the second membrane oxidation stage; and controlling the production capacity and/or the product quality by changing the characteristic temperature of the first membrane oxidation stage and/or changing the characteristic temperature of the second membrane oxidation stage.

  6. Main Oxidizer Valve Design

    NASA Technical Reports Server (NTRS)

    Addona, Brad; Eddleman, David

    2015-01-01

    A developmental Main Oxidizer Valve (MOV) was designed by NASA-MSFC using additive manufacturing processes. The MOV is a pneumatically actuated poppet valve to control the flow of liquid oxygen to an engine's injector. A compression spring is used to return the valve to the closed state when pneumatic pressure is removed from the valve. The valve internal parts are cylindrical in shape, which lends itself to traditional lathe and milling operations. However, the valve body represents a complicated shape and contains the majority of the mass of the valve. Additive manufacturing techniques were used to produce a part that optimized mass and allowed for design features not practical with traditional machining processes.

  7. Ultra Supercritical Steamside Oxidation

    SciTech Connect

    Holcomb, Gordon R.; Cramer, Stephen D.; Covino, Bernard S., Jr.; Bullard, Sophie J.; Ziomek-Moroz, Malgorzata

    2005-01-01

    Ultra supercritical (USC) power plants offer the promise of higher efficiencies and lower emissions, which are goals of the U.S. Department of Energy's Advanced Power Systems Initiatives. Most current coal power plants in the U.S. operate at a maximum steam temperature of 538 C. However, new supercritical plants worldwide are being brought into service with steam temperatures of up to 620 C. Current Advanced Power Systems goals include coal generation at 60% efficiency, which require steam temperatures of up to 760 C. This research examines the steamside oxidation of advanced alloys for use in USC systems, with emphasis placed on alloys for high- and intermediate-pressure turbine sections. Initial results of this research are presented.

  8. Polymorphism of phosphoric oxide

    USGS Publications Warehouse

    Hill, W.L.; Faust, G.T.; Hendricks, S.B.

    1943-01-01

    The melting points and monotropic relationship of three crystalline forms of phosphoric oxide were determined by the method of quenching. Previous vapor pressure data are discussed and interpreted to establish a pressure-temperature diagram (70 to 600??) for the one-component system. The system involves three triple points, at which solid, liquid and vapor (P4O10) coexist in equilibrium, namely: 420?? and 360 cm., 562?? and 43.7 cm. and 580?? and 55.5 cm., corresponding to the hexagonal, orthorhombic and stable polymorphs, respectively, and at least two distinct liquids, one a stable polymer of the other, which are identified with the melting of the stable form and the hexagonal modification, respectively. Indices of refraction of the polymorphs and glasses were determined. The density and the thermal, hygroscopic and structural properties of the several phases are discussed.

  9. Preface: Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Willmott, Phil

    2008-07-01

    Although the history of metal oxides and their surfaces goes back several decades to landmark studies, such as Mott and Peierls' explanation of electrical insulation in materials that are predicted in band theory to be conducting, or the observation by Morin of the superfast metal-to-insulator transition in vanadium dioxide, it is only in the last two decades that the world of condensed matter physics has become increasingly dominated by research into complex metal oxides. This has been driven most notably by an attempt to better understand and describe the fundamental physical processes behind their seemingly endless spectrum of properties, which in turn has also led to the discovery of novel phenomena, most prominently demonstrated by the discovery of high-temperature superconductivity in 1986, colossal magnetoresistance in 1994, and most recently, the formation of a two-dimensional conducting layer at the interface between two band insulators in 2004. One important reason why metal oxides, particularly in the form of thin films, have become such a popular subject for basic condensed matter research is that they offer a uniquely versatile materials base for the development of novel technologies. They owe this versatility both to the many different elemental combinations that lead to structurally similar forms, and also to the fact that in many cases, the strong interaction between the valence electrons means that there is a subtle interplay between structure and magnetic and electronic properties. This aspect has led in recent years to the birth or renaissance of research fields such as spintronics, orbital ordering, and multiferroics. Surfaces and interfaces are especially interesting in these strongly-correlated electron systems, where the rearrangement of electrical charge resulting from a minimization of surface or interfacial energy can have unexpected and often exciting consequences. Indeed, as the drive to miniaturize devices well below the micron size continues, the fraction of material constituting `non-bulklike' properties is becoming increasingly significant. On the other hand, the degree of sophistication needed to understand and predict these complex systems has driven a complementary thrust in theoretical modelling, beginning as long ago as 1963, with Hubbard's addition to the tight-binding model of the formulation of conduction in terms of a hopping integral. The present level of understanding is now so advanced that theory and experiment are no longer so distinct, both gaining further insights from one another. The aim of this special issue in the Journal of Physics: Condensed Matter is to convey to the reader the most up-to-date understanding of the physics of the surfaces, interfaces, and thin films of complex metal oxides, in a clear and accessible manner. The order of the 16 contributions reflects the broad range of disciplines within this field, beginning with general considerations and theoretical models, continuing with film growth techniques and characterization, and concluding with material types and devices. It is fairly safe to assume that research in this area will enjoy as illustrious and long-lived a future as it has had a past. As such, it is hoped that this contribution will accurately reflect this status in the first decade of the 21st Century and long provide a reference for physicists continuing on this exciting Odyssey.

  10. Phosphine oxide surfactants revisited.

    PubMed

    Stubenrauch, Cosima; Preisig, Natalie; Laughlin, Robert G

    2016-04-01

    This review summarizes everything we currently know about the nonionic surfactants alkyl dimethyl (CnDMPO) and alkyl diethyl (CnDEPO) phosphine oxide (PO surfactants). The review starts with the synthesis and the general properties (Section 2) of these compounds and continues with their interfacial properties (Section 3) such as surface tension, surface rheology, interfacial tension and adsorption at solid surfaces. We discuss studies on thin liquid films and foams stabilized by PO surfactants (Section 4) as well as studies on their self-assembly into lyotropic liquid crystals and microemulsions, respectively (Section 5). We aim at encouraging colleagues from both academia and industry to take on board PO surfactants whenever possible and feasible because of their broad variety of excellent properties. PMID:26869216

  11. High temperature oxidation resistant cermet compositions

    NASA Technical Reports Server (NTRS)

    Phillips, W. M. (Inventor)

    1976-01-01

    Cermet compositions are designed to provide high temperature resistant refractory coatings on stainless steel or molybdenum substrates. A ceramic mixture of chromium oxide and aluminum oxide form a coating of chromium oxide as an oxidation barrier around the metal particles, to provide oxidation resistance for the metal particles.

  12. Ceramic oxide powders and the formation thereof

    DOEpatents

    Katz, J.L.; Chenghung Hung.

    1993-12-07

    Ceramic oxide powders and a method for their preparation. Ceramic oxide powders are obtained using a flame process whereby two or more precursors of ceramic oxides are introduced into a counterflow diffusion flame burner wherein said precursors are converted into ceramic oxide powders. The morphology, particle size, and crystalline form of the ceramic oxide powders are determined by process conditions. 14 figures.

  13. Ceramic oxide powders and the formation thereof

    DOEpatents

    Katz, Joseph L. (Baltimore, MD); Hung, Cheng-Hung (Baltimore, MD)

    1993-01-01

    Ceramic oxide powders and a method for their preparation. Ceramic oxide powders are obtained using a flame process whereby two or more precursors of ceramic oxides are introduced into a counterflow diffusion flame burner wherein said precursors are converted into ceramic oxide powders. The morphology, particle size, and crystalline form of the ceramic oxide powders are determined by process conditions.

  14. Wet oxidation of a spacecraft model waste

    NASA Technical Reports Server (NTRS)

    Johnson, C. C.; Wydeven, T.

    1985-01-01

    Wet oxidation was used to oxidize a spacecraft model waste under different oxidation conditions. The variables studied were pressure, temperature, duration of oxidation, and the use of one homogeneous and three heterogeneous catalysts. Emphasis is placed on the final oxidation state of carbon and nitrogen since these are the two major components of the spacecraft model waste and two important plant nutrients.

  15. INSULIN SENSITIZERS AND OXIDATIVE STRESS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The leading causes of oxidative stress include hyperglycemia, hyperinsulinemia and insulin resistance and it may be postulated that oxidative stress represents the common pathway through which hyperglycemia and insulin resistance induce depressed insulin action. Two factors that have been shown to...

  16. Biochemistry of dissimilatory sulfur oxidation

    SciTech Connect

    Blake, R. II.

    1992-01-01

    Our goals of this research are to define the substrate oxidation pathways, the electron transport mechanisms, and the modes of energy conservation employed during the dissimilatory oxidation of sulfur by thiobacilli. We have purified APS reductase to electrophoratic homogeneity from cell-free extracts of Thiobacillus denitrificans. Sufficient protein is available to initiate the production of polyclonal antibodies and to perform the kinetic experiments.

  17. Oxidative Imbalance and Anxiety Disorders

    PubMed Central

    R, Krolow; D. M, Arcego; C, Noschang; S. N, Weis; C, Dalmaz

    2014-01-01

    The oxidative imbalance appears to have an important role in anxiety development. Studies in both humans and animals have shown a strong correlation between anxiety and oxidative stress. In humans, for example, the increased malondialdehyde levels and discrepancies in antioxidant enzymes in erythrocytes have been observed. In animals, several studies also show that anxiety-like behavior is related to the oxidative imbalance. Moreover, anxiety-like behavior can be caused by pharmacological-induced oxidative stress. Studies using knockout or overexpression of antioxidant enzymes have shown a relationship between anxiety-like behavior and oxidative stress. Related factors of oxidative stress that could influence anxious behavior are revised, including impaired function of different mitochondrial proteins, inflammatory cytokines, and neurotrophic factors. It has been suggested that a therapy specifically focus in reducing reactive species production may have a beneficial effect in reducing anxiety. However, the neurobiological pathways underlying the effect of oxidative stress on anxiety symptoms are not fully comprehended. The challenge now is to identify the oxidative stress mechanisms likely to be involved in the induction of anxiety symptoms. Understanding these pathways could help to clarify the neurobiology of the anxiety disorder and provide tools for new discovery in therapies and preventive strategies. PMID:24669212

  18. ENGINEERING BULLETIN: CHEMICAL OXIDATION TREATMENT

    EPA Science Inventory

    Oxidation destroys hazardous contaminants by chemically converting them to nonhazardous or less toxic compounds that are ideally more stable, less mobile, and/or inert. However, under some conditions, other hazardous compounds may be formed. The oxidizing agents most commonly use...

  19. Automated analysis of oxidative metabolites

    NASA Technical Reports Server (NTRS)

    Furner, R. L. (inventor)

    1974-01-01

    An automated system for the study of drug metabolism is described. The system monitors the oxidative metabolites of aromatic amines and of compounds which produce formaldehyde on oxidative dealkylation. It includes color developing compositions suitable for detecting hyroxylated aromatic amines and formaldehyde.

  20. Catalysts for low temperature oxidation

    DOEpatents

    Toops, Todd J.; Parks, III, James E.; Bauer, John C.

    2016-03-01

    The invention provides a composite catalyst containing a first component and a second component. The first component contains nanosized gold particles. The second component contains nanosized platinum group metals. The composite catalyst is useful for catalyzing the oxidation of carbon monoxide, hydrocarbons, oxides of nitrogen, and other pollutants at low temperatures.

  1. Metal oxide films on metal

    DOEpatents

    Wu, Xin D. (Los Alamos, NM); Tiwari, Prabhat (Los Alamos, NM)

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  2. New infrared transparent oxide glasses

    NASA Astrophysics Data System (ADS)

    Weber, Richard; Tangeman, Jean; Hiera, Kirsten; Scheunemann, Richard; Kim, Jungyun

    2005-05-01

    Glass materials based on rare earth oxides and aluminum oxide can provide a combination of infrared transparency, strength, hardness, and environmental stability in a formable material. This article describes a new family of rare earth oxide-aluminum oxide glass materials that can be made by casting from melts formed in platinum crucibles. The glasses transmit light in the wavelength range from 0.3 to 5 ?m in sections of ~0.3 cm, they have a Vickers hardness of 800-1000, and exhibit excellent environmental stability typical of refractory oxide materials. The composition of the glass can be adjusted to achieve refractive indices in the range 1.7-1.8 and Abbe numbers of 30-60. The materials are promising candidates for passive optical elements or as a host for optically active ions such as Yb or Nd that provide laser action or absorb at laser line wavelengths.

  3. BRCA1 and Oxidative Stress

    PubMed Central

    Yi, Yong Weon; Kang, Hyo Jin; Bae, Insoo

    2014-01-01

    The breast cancer susceptibility gene 1 (BRCA1) has been well established as a tumor suppressor and functions primarily by maintaining genome integrity. Genome stability is compromised when cells are exposed to oxidative stress. Increasing evidence suggests that BRCA1 regulates oxidative stress and this may be another mechanism in preventing carcinogenesis in normal cells. Oxidative stress caused by reactive oxygen species (ROS) is implicated in carcinogenesis and is used strategically to treat human cancer. Thus, it is essential to understand the function of BRCA1 in oxidative stress regulation. In this review, we briefly summarize BRCA1’s many binding partners and mechanisms, and discuss data supporting the function of BRCA1 in oxidative stress regulation. Finally, we consider its significance in prevention and/or treatment of BRCA1-related cancers. PMID:24704793

  4. Oxidation and photooxidation of asphalts

    SciTech Connect

    Mill, T.; Tse, D. )

    1990-07-01

    Oxidation of asphalt is a major cause of pavement failure owing to hardening of the asphalt binder with accompanying changes in viscosity, separation of components, embrittlement and loss of cohesion and adhesion of the asphalt in the mix. However oxidation of asphalt-aggregate mixes at high temperature is deliberately done to partly harden the mix prior to laydown; hardening then continues during cooling. Excessive hardening at this point is undesirable because of embrittlement and cracking. Slow oxidation of asphalt continues during the service life of the roadbed at a rate that appears to be partly determined by the void volume of the roadbed, as well as the properties of the asphalt and (possibly) the properties of the aggregate. The authors focused their efforts on understanding the mechanistic basis for slow oxidation of asphalt under service conditions in order to predict how rapidly an asphalt will oxidize, based on its composition, and to find better ways to inhibit the process under service conditions.

  5. Engelhard expands oxidation catalysts portfolio

    SciTech Connect

    Rotman, D.

    1997-02-26

    Engelhard says its agreement earlier this month to market Amoco Chemical`s proprietary maleic anhydride catalyst reflects an effort to expand its speciality catalysts business (CW, Feb. 19, p.5). In particular, the company says it is looking for additional alliances to bolster its oxidation catalysts portfolio. {open_quotes}There are some areas of oxidation catalysis that are reasonably attractive,{close_quotes} says Paul Lamb, marketing director/chemical catalysts. He says that while Engelhard is not interested in commodity oxidation catalysts, such as those used to make sulfuric acid, it does want to boost offerings for higher-value oxidation catalysts. Engelhard is collaborating with Geon to offer oxychlorination catalysts for making ethylene dichloride. It also markets oxidation catalysts for vinyl acetate production.

  6. Novel method for controlled oxidation

    SciTech Connect

    Benjamin, B.M.; Raaen, V.F.

    1981-03-29

    A novel method for the oxidative degradation of coal or other organic material is described. The procedure is potentially useful for structure determination. As originally conceived, this method was intended for use with aqueous potassium permanganate as oxidant, but it is equally applicable with other oxidizing agents. Sodium hypochlorite can be substituted for KMnO, except that controlling the pH and monitoring the end point become more difficult. Results with potassium permanganate only are described here but sodium hypochlorite was tried. An advantageous feature of the method is the simultaneous removal of soluble products from further contact with oxidizing agent as the oxidizing agent attacks the substrate. In principle, the experimental approach resembles that of column chromatography. The compounds were characterized by nuclear magnetic resonance measurements, and gas chromatography.

  7. Atomistic details of oxide surfaces and surface oxidation: the example of copper and its oxides

    NASA Astrophysics Data System (ADS)

    Gattinoni, Chiara; Michaelides, Angelos

    2015-11-01

    The oxidation and corrosion of metals are fundamental problems in materials science and technology that have been studied using a large variety of experimental and computational techniques. Here we review some of the recent studies that have led to significant advances in our atomic-level understanding of copper oxide, one of the most studied and best understood metal oxides. We show that a good atomistic understanding of the physical characteristics of cuprous (Cu2O) and cupric (CuO) oxide and of some key processes of their formation has been obtained. Indeed, the growth of the oxide has been shown to be epitaxial with the surface and to proceed, in most cases, through the formation of oxide nano-islands which, with continuous oxygen exposure, grow and eventually coalesce. We also show how electronic structure calculations have become increasingly useful in helping to characterise the structures and energetics of various Cu oxide surfaces. However a number of challenges remain. For example, it is not clear under which conditions the oxidation of copper in air at room temperature (known as native oxidation) leads to the formation of a cuprous oxide film only, or also of a cupric overlayer. Moreover, the atomistic details of the nucleation of the oxide islands are still unknown. We close our review with a brief perspective on future work and discuss how recent advances in experimental techniques, bringing greater temporal and spatial resolution, along with improvements in the accuracy, realism and timescales achievable with computational approaches make it possible for these questions to be answered in the near future.

  8. Nitric oxide signaling in plants.

    PubMed

    Shapiro, Allan D

    2005-01-01

    Plants have four nitric oxide synthase (NOS) enzymes. NOS1 appears mitochondrial, and inducible nitric oxide synthase (iNOS) chloroplastic. Distinct peroxisomal and apoplastic NOS enzymes are predicted. Nitrite-dependent NO synthesis is catalyzed by cytoplasmic nitrate reductase or a root plasma membrane enzyme, or occurs nonenzymatically. Nitric oxide undergoes both catalyzed and uncatalyzed oxidation. However, there is no evidence of reaction with superoxide, and S-nitrosylation reactions are unlikely except during hypoxia. The only proven direct targets of NO in plants are metalloenzymes and one metal complex. Nitric oxide inhibits apoplastic catalases/ascorbate peroxidases in some species but may stimulate these enzymes in others. Plants also have the NO response pathway involving cGMP, cADPR, and release of calcium from internal stores. Other known targets include chloroplast and mitochondrial electron transport. Nitric oxide suppresses Fenton chemistry by interacting with ferryl ion, preventing generation of hydroxyl radicals. Functions of NO in plant development, response to biotic and abiotic stressors, iron homeostasis, and regulation of respiration and photosynthesis may all be ascribed to interaction with one of these targets. Nitric oxide function in drought/abscisic acid (ABA)-induction of stomatal closure requires nitrate reductase and NOS1. Nitric oxide synthasel likely functions to produce sufficient NO to inhibit photosynthetic electron transport, allowing nitrite accumulation. Nitric oxide is produced during the hypersensitive response outside cells undergoing programmed cell death immediately prior to loss of plasma membrane integrity. A plasma membrane lipid-derived signal likely activates apoplastic NOS. Nitric oxide diffuses within the apoplast and signals neighboring cells via hydrogen peroxide (H2O2)-dependent induction of salicylic acid biosynthesis. Response to wounding appears to involve the same NOS and direct targets. PMID:16492476

  9. 78 FR 64244 - Persulfates From China; Revised Schedule for the Subject Investigation

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-10-28

    ... From the Federal Register Online via the Government Publishing Office INTERNATIONAL TRADE... International Trade Commission. ACTION: Notice. DATES: Effective Date: October 22, 2013. FOR FURTHER INFORMATION CONTACT: Angela M. W. Newell (202-708-5409), Office of Investigations, U.S. International Trade...

  10. 78 FR 14591 - Persulfates From China; Correction to Notice of institution

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-03-06

    ..., 2013 (78 FR 13891), the Commission published a notice of institution of a five-year review concerning... may also be obtained by accessing its internet server ( http://www.usitc.gov ). The public record...

  11. Oxidative decarboxylation of diclofenac by manganese oxide bed filter.

    PubMed

    Huguet, Mélissa; Deborde, Marie; Papot, Sébastien; Gallard, Hervé

    2013-09-15

    Diclofenac (DCF) was eliminated by fast chemical oxidation on natural manganese oxide in a column reactor. Identification of transformation by-products of DCF by HPLC-UV-MS(n) gave evidence of decarboxylation, iminoquinone formation and dimerization. The fast oxidation of DCF is also accompanied by a strong adsorption of organic carbon that was explained by the sorption of dimer products on the surface of manganese oxide. Decarboxylation and dimerization increased the hydrophobic interactions with manganese oxide and reduced the presence of potentially toxic by-products in the effluent. The rate of oxidation was first order with respect to DCF and was slowed down by the presence of organic buffer MOPS (3-morpholinopropane-1-sulfonic acid). The first order rate constant in absence of MOPS was extrapolated by considering a surface site-binding model and MOPS as a co-adsorbate. The rate constant was 0.818 min(-1) at pH 7 and 10 mM NaCl corresponding to empty bed residence time of 50 s only for 50% removal of DCF. Rate constants increased when pH decreased from pH 8.0 to 6.5 and when ionic strength increased. Manganese oxide bed filter can be considered as an alternative treatment for polishing waste water effluent or for remediation of contaminated groundwater. PMID:23850215

  12. Reproductive benefit of oxidative damage: an oxidative stress "malevolence"?

    PubMed

    Poljsak, B; Milisav, I; Lampe, T; Ostan, I

    2011-01-01

    High levels of reactive oxygen species (ROS) compared to antioxidant defenses are considered to play a major role in diverse chronic age-related diseases and aging. Here we present an attempt to synthesize information about proximate oxidative processes in aging (relevant to free radical or oxidative damage hypotheses of aging) with an evolutionary scenario (credited here to Dawkins hypotheses) involving tradeoffs between the costs and benefits of oxidative stress to reproducing organisms. Oxidative stress may be considered a biological imperfection; therefore, the Dawkins' theory of imperfect adaptation of beings to environment was applied to the role of oxidative stress in processes like famine and infectious diseases and their consequences at the molecular level such as mutations and cell signaling. Arguments are presented that oxidative damage is not necessarily an evolutionary mistake but may be beneficial for reproduction; this may prevail over its harmfulness to health and longevity in evolution. Thus, Dawkins' principle of biological "malevolence" may be an additional biological paradigm for explaining the consequences of oxidative stress. PMID:21969876

  13. Lipid oxidation-induced oxidation in emu and ostrich myoglobins.

    PubMed

    Nair, M N; Suman, S P; Li, S; Joseph, P; Beach, C M

    2014-02-01

    Emu and ostrich are ratites gaining increasing popularity as sources of low-fat meats. Secondary products of lipid oxidation, such as 4-hydroxy-2-nonenal (HNE), compromise myoglobin redox stability in a species-specific manner. However, the molecular basis of lipid oxidation-induced oxidation in ratite myoglobins has not been investigated. Therefore, our objective was to characterize lipid oxidation-induced oxidation in ratite myoglobins, in comparison with beef myoglobin. At physiological condition (pH7.4, 37 C) HNE accelerated (P<0.05) oxidation of emu, ostrich, and beef oxymyoglobins. Autoxidation and HNE-induced oxidation were greater (P<0.05) in ostrich oxymyoglobin than in emu and beef oxymyoglobins. Mass spectrometric analyses revealed that HNE formed mono-adduct with both emu and ostrich myoglobins after 6h of incubation. Tandem mass spectrometry demonstrated that HNE adducted histidine 36 in ostrich myoglobin, whereas histidines 34 and 36 were adducted in emu myoglobin. The results indicate that primary structure of ratite myoglobins influences their redox stability in the presence of prooxidants. PMID:24231676

  14. New developments in oxidative fermentation.

    PubMed

    Adachi, O; Moonmangmee, D; Toyama, H; Yamada, M; Shinagawa, E; Matsushita, K

    2003-02-01

    Oxidative fermentations have been well established for a long time, especially in vinegar and in L-sorbose production. Recently, information on the enzyme systems involved in these oxidative fermentations has accumulated and new developments are possible based on these findings. We have recently isolated several thermotolerant acetic acid bacteria, which also seem to be useful for new developments in oxidative fermentation. Two different types of membrane-bound enzymes, quinoproteins and flavoproteins, are involved in oxidative fermentation, and sometimes work with the same substrate but produce different oxidation products. Recently, there have been new developments in two different oxidative fermentations, D-gluconate and D-sorbitol oxidations. Flavoproteins, D-gluconate dehydrogenase, and D-sorbitol dehydrogenase were isolated almost 2 decades ago, while the enzyme involved in the same oxidation reaction for D-gluconate and D-sorbitol has been recently isolated and shown to be a quinoprotein. Thus, these flavoproteins and a quinoprotein have been re-assessed for the oxidation reaction. Flavoprotein D-gluconate dehydrogenase and D-sorbitol dehydrogenase were shown to produce 2-keto- D-gluconate and D-fructose, respectively, whereas the quinoprotein was shown to produce 5-keto- D-gluconate and L-sorbose from D-gluconate and D-sorbitol, respectively. In addition to the quinoproteins described above, a new quinoprotein for quinate oxidation has been recently isolated from Gluconobacter strains. The quinate dehydrogenase is also a membrane-bound quinoprotein that produces 3-dehydroquinate. This enzyme can be useful for the production of shikimate, which is a convenient salvage synthesis system for many antibiotics, herbicides, and aromatic amino acids synthesis. In order to reduce energy costs of oxidative fermentation in industry, several thermotolerant acetic acid bacteria that can grow up to 40 degrees C have been isolated. Of such isolated strains, some thermotolerant Acetobacter species were found to be useful for vinegar fermentation at a high temperature such 38-40 degrees C, where mesophilic strains showed no growth. They oxidized higher concentrations of ethanol up to 9% without any appreciable lag time, while alcohol oxidation with mesophilic strains was delayed or became almost impossible under such conditions. Several useful Gluconobacter species of thermotolerant acetic acid bacteria are also found, especially L-erythrulose-producing strains and cyclic alcohol-oxidizing strains. Gluconobacter frateurii CHM 43 is able to rapidly oxidize meso-erythritol at 37 degrees C leading to the accumulation of L-erythrulose, which may replace dihydroxyacetone in cosmetics. G. frateuriiCHM 9 is able to oxidize cyclic alcohols to their corresponding cyclic ketones or aliphatic ketones, which are known to be useful for preparing many different physiologically active compounds such as oxidized steroids or oxidized bicyclic ketones. The enzymes involved in these meso-erythritol and cyclic alcohol oxidations have been purified and shown to be a similar type of membrane-bound quinoproteins, consisting of a high molecular weight single peptide. This is completely different from another quinoprotein, alcohol dehydrogenase of acetic acid bacteria, which consists of three subunits including hemoproteins. PMID:12664142

  15. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  16. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  17. 40 CFR 721.10375 - Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide, copolymer...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (generic). 721.10375... Substances § 721.10375 Hydroxypropyl methacrylate, reaction products with propylene oxide and ethylene oxide... products with propylene oxide and ethylene oxide, copolymer with N-vinyl caprolactam (PMN P-10-200)...

  18. The oxidation of carbon monoxide using tin oxide based catalysts

    NASA Technical Reports Server (NTRS)

    Sampson, Christopher F.; Jorgensen, Norman

    1990-01-01

    The preparation conditions for precious metal/tin oxide catalysts were optimized for maximum carbon monoxide/oxygen recombination efficiency. This was achieved by controlling the tin digestion, the peptization to form the sol, the calcination process and the method of adding the precious metals. Extensive studies of the tin oxide structure were carried out over the temperature range 20 to 500 C in air or hydrogen environments using Raman scattering and X ray diffraction. Adsorbed species on tin oxide, generated in an environment containing carbon monoxide, gave rise to a Raman band at about 1600 cm(exp -1) which was assigned to carbonaceous groups, possible carbonate.

  19. Catalyst for Decomposition of Nitrogen Oxides

    NASA Technical Reports Server (NTRS)

    Schryer, David R. (Inventor); Jordan, Jeffrey D. (Inventor); Akyurtlu, Ates (Inventor); Akyurtlu, Jale (Inventor)

    2015-01-01

    This invention relates generally to a platinized tin oxide-based catalyst. It relates particularly to an improved platinized tin oxide-based catalyst able to decompose nitric oxide to nitrogen and oxygen without the necessity of a reducing gas.

  20. EFFECTS OF PHOTOCHEMICAL OXIDANTS ON PLANTS

    EPA Science Inventory

    Photochemical oxidants are found in 'photochemical smog' which is a complex mixture of primary and secondary air pollutants. The photochemical oxidants are secondary air pollutants formed by the action of sunlight on nitrogen oxides and reactive hydrocarbons, their precursors. Th...

  1. The oxidation and corrosion of ODS alloys

    NASA Technical Reports Server (NTRS)

    Lowell, Carl E.; Barrett, Charles A.

    1990-01-01

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

  2. Urinary Biomarkers of Oxidative Status

    PubMed Central

    Ilyasova, Dora; Scarbrough, Peter; Spasojevic, Ivan

    2012-01-01

    Oxidative damage produced by reactive oxygen species (ROS) has been implicated in the etiology and pathology of many health conditions, including a large number of chronic diseases. Urinary biomarkers of oxidative status present a great opportunity to study redox balance in human populations. With urinary biomarkers, specimen collection is non-invasive and the organic/metal content is low, which minimizes the artifactual formation of oxidative damage to molecules in specimens. Also, urinary levels of the biomarkers present intergraded indices of redox balance over a longer period of time compared to blood levels. This review summarizes the criteria for evaluation of biomarkers applicable to epidemiological studies and evaluation of several classes of biomarkers that are formed non-enzymatically: oxidative damage to lipids, proteins, DNA, and allantoin, an oxidative product of uric acid. The review considers formation, metabolism, and exertion of each biomarker, available data on validation in animal and clinical models of oxidative stress, analytical approaches, and their intra- and inter-individual variation. The recommended biomarkers for monitoring oxidative status over time are F2-isoprostanes and 8-oxodG. For inter-individual comparisons, F2-isoprostanes are recommended, whereas urinary 8-oxodG levels may be confounded by differences in the DNA repair capacity. Promising urinary biomarkers include allantoin, acrolein-lysine, and dityrosine. PMID:22683781

  3. Manganese oxidation by Leptothrix discophora.

    PubMed Central

    Boogerd, F C; de Vrind, J P

    1987-01-01

    Cells of Leptothrix discophora SS1 released Mn2+-oxidizing factors into the medium during growth in batch culture. Manganese was optimally oxidized when the medium was buffered with HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid) at pH 7.5. Manganese-oxidizing activity in the culture medium in which this strain had been grown previously was sensitive to heat, phosphate, Tris, NaN3, HgCl2 NaCl, sodium dodecyl sulfate, and pronase; 0.5 mol of O2 was consumed per mol of MnO2 formed. During Mn2+ oxidation, protons were liberated. With sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two protein-containing bands were detected in the spent culture medium. One band had an apparent molecular weight of 110,000 and was predominant in Mn2+-oxidizing activity. The second product (Mr 85,000) was only detected in some cases and probably represents a proteolytic breakdown moiety of the 110,000-Mr protein. The Mn2+-oxidizing factors were associated with the MnO2 aggregates that had been formed in spent culture medium. After solubilization of this MnO2 with ascorbate, Mn2+-oxidizing activity could be recovered. Images PMID:3804969

  4. Status of Graphite Oxidation Work

    SciTech Connect

    Rebecca Smith

    2010-05-01

    Data were developed to compare the extent of structural damage associated with high temperature exposure to an air leak. Two materials, NBG-18 graphite and unpurified PCEA graphite have been tested as of this report. The scope was limited to isothermal oxidation at a single temperature, 750°C. Ambient post-oxidation compression strength testing was performed for three levels of burn off (1%, 5%, and 10% mass loss) for two leak scenarios: 100% air and 10% air in helium. Temperature, gas flow, and dynamic mass loss oxidation conditions were monitored and recorded for each sample. The oxidation period was controlled with flow of inert gas during the thermal ramp and upon cool down with a constant 10 liter per minute flow maintained throughout furnace operation. Compressive strengths of parallel un-oxidized samples were tested to assess the relative mass loss effects. In addition to baseline samples matching the un-oxidized dimensions of the oxidized samples, two sets of mechanically reduced samples were prepared. One set was trimmed to achieve the desired mass loss by removing an effectively uniform depth from the geometric surface of the sample. The other set was cored to produce a full penetration axial hole down the center of each sample.

  5. Oxidative Stress and Insulin Resistance

    PubMed Central

    Park, Kyong; Gross, Myron; Lee, Duk-Hee; Holvoet, Paul; Himes, John H.; Shikany, James M.; Jacobs, David R.

    2009-01-01

    OBJECTIVE Although cumulative evidence suggests that increased oxidative stress may lead to insulin resistance in vivo or in vitro, community-based studies are scarce. This study examined the longitudinal relationships of oxidative stress biomarkers with the development of insulin resistance and whether these relationships were independent of obesity in nondiabetic young adults. RESEARCH DESIGN AND METHODS Biomarkers of oxidative stress (F2-isoprostanes [F2Isop] and oxidized LDL [oxLDL]), insulin resistance (the homeostasis model assessment of insulin resistance [HOMA-IR]), and various fatness measures (BMI, waist circumference, and estimated percent fat) were obtained in a population-based observational study (Coronary Artery Risk Development in Young Adults) and its ancillary study (Young Adult Longitudinal Trends in Antioxidants) during 20002006. RESULTS There were substantial increases in estimated mean HOMA-IR over time. OxLDL and F2Isop showed little association with each other. Mean evolving HOMA-IR increased with increasing levels of oxidative stress markers (P < 0.001 for oxLDL and P = 0.06 for F2Isop), measured in 20002001. After additional adjustment for adiposity, a positive association between oxLDL and HOMA-IR was strongly evident, whereas the association between F2Isop and HOMA-IR was not. CONCLUSIONS We observed positive associations between each of two oxidative stress markers and insulin resistance. The association with oxidized LDL was independent of obesity, but that with F2Isop was not. PMID:19389821

  6. Protein Oxidation Products as Biomarkers.

    PubMed

    Grune, Tilman

    2014-10-01

    Oxidative stress is associated with aging and most degenerative diseases: it contributes to clinical complications, organ failure and mortality. Furthermore, oxidative damage accumulation in macromolecules has been considered as a cause of cellular damage and pathology. Interestingly, it is unknown whether and to what extent oxidative stress contributes to the clinical worsening and most importantly, no common strategy exists about its measurement. This is partially due to the fact that many methods of measuring oxidative stress have proven unreliable and no single method exists enabling objective determination and characterization of oxidative stress in clinical settings whether in aging or in chronic disease. Some methods basing on the measurement of lipid peroxidation, as the determination of F2-isoprostanes or malondialdehyde, or on the measurement of DNA/RNA damage, as 8-hydroxydesoxyguanosine or 8-hydroxydesoxyguanine, are widely used to determine oxidative stress and gain more and more acceptance or are reliable supportive parameters. A set of methods exists for clinical set-ups based on the measurement of protein oxidation or oxidative protein modification. Some of these methods are gaining more and more acceptance due to the development of easy to use and stable methods. This includes the long known method of protein carbonyl determination in various methodological variations, but also the use of the determination of protein-based nitrotyrosine or HNE-modified proteins. All these methods can be used in clinical set-ups, but special care has to be taken on chemical and biological sample stability. It should be mentioned, that no single method, however, is yet alone able to characterize oxidative stress under clinical conditions and, therefore, various combinations of damage parameters are the most promising tools. PMID:26461416

  7. Oxidation kinetics of aluminum diboride

    NASA Astrophysics Data System (ADS)

    Whittaker, Michael L.; Sohn, H. Y.; Cutler, Raymond A.

    2013-11-01

    The oxidation characteristics of aluminum diboride (AlB2) and a physical mixture of its constituent elements (Al+2B) were studied in dry air and pure oxygen using thermal gravimetric analysis to obtain non-mechanistic kinetic parameters. Heating in air at a constant linear heating rate of 10 C/min showed a marked difference between Al+2B and AlB2 in the onset of oxidation and final conversion fraction, with AlB2 beginning to oxidize at higher temperatures but reaching nearly complete conversion by 1500 C. Kinetic parameters were obtained in both air and oxygen using a model-free isothermal method at temperatures between 500 and 1000 C. Activation energies were found to decrease, in general, with increasing conversion for AlB2 and Al+2B in both air and oxygen. AlB2 exhibited O2-pressure-independent oxidation behavior at low conversions, while the activation energies of Al+2B were higher in O2 than in air. Differences in the composition and morphology between oxidized Al+2B and AlB2 suggested that Al2O3-B2O3 interactions slowed Al+2B oxidation by converting Al2O3 on aluminum particles into a Al4B2O9 shell, while the same Al4B2O9 developed a needle-like morphology in AlB2 that reduced oxygen diffusion distances and increased conversion. The model-free kinetic analysis was critical for interpreting the complex, multistep oxidation behavior for which a single mechanism could not be assigned. At low temperatures, moisture increased the oxidation rate of Al+2B and AlB2, but both appear to be resistant to oxidation in cool, dry environments.

  8. [Oxidative stress and pseudoexfoliation glaucoma].

    PubMed

    Schlötzer-Schrehardt, U

    2010-02-01

    Pseudoexfoliation (PEX) glaucoma is the most common identifiable cause of open-angle glaucoma worldwide, comprising the majority of glaucoma in some countries. The underlying disorder, PEX syndrome, is a generalised, genetically determined, elastotic process of the extracellular matrix characterised by the excessive production and progressive accumulation of a fibrillar material in various tissues including the outflow pathways. Increasing evidence suggests that the oxidative-antioxidative balance is disturbed in patients with PEX syndrome/glaucoma, both in the anterior segment and throughout the body, and that the resulting oxidative stress constitutes a major mechanism involved in the pathophysiology of this fibrotic process. Significantly reduced levels of antioxidants, such as ascorbic acid, glutathione, trace elements, antioxidative enzymes, and total antioxidative capacity in aqueous humor and serum suggest a faulty antioxidative defense system in PEX patients. The down-regulation of antioxidative enzymes in anterior segment tissues also indicates an inadequate cytoprotection against oxidative stress. Concomitantly, levels of oxidants such as hydrogen peroxide or nitric oxide, and oxidative stress markers, including lipid peroxidation products, degradation products of oxidated and methylated proteins, advanced glycation end products, and homocysteine are significantly increased in aqueous humor, tissues, and serum. The available data suggest that chronic oxidative stress in combination with weakened cytoprotective and repair strategies affects the abnormal matrix metabolism by induction of a persistent pro-inflammatory state and activation of the profibrotic growth factor TGF-beta1. Oxidative stress, therefore, appears to represent a modifiable risk factor in the management of patients with PEX syndrome/glaucoma. PMID:20155654

  9. Chemiluminescence of nitric oxide

    NASA Technical Reports Server (NTRS)

    Sharp, W. E.; Rusch, D. W.

    1981-01-01

    Measurements of the intensities of the delta and gamma bands of nitric oxide in the nighttime terrestrial thermosphere are presented and used to infer the rate coefficient for the transition from the C 2 Pi to the A 2 Sigma + states. The nightglow spectrum was observed between 1900 and 2300 A at a resolution of 15 A by a rocket-borne scanning 1/4-m spectrometer pointing north at an apogee of 150 km. Progressions of the delta, gamma and epsilon bands are identified on the spectra by the construction of synthetic spectra, and the contributions of resonance fluorescence to the total band intensities are calculated. Finally, the ratio of the sum of the gamma bands for v-prime = 0 to the sum of the delta bands for v-prime = 0 is used to derive a branching ratio of 0.21 + or - 0.04 to the A 2 Sigma + state, which yields a probability for the C-A transition of 5.6 + or - 1.5 x to the 6th/sec.

  10. Mixed oxide fuel development

    SciTech Connect

    Leggett, R.D.; Omberg, R.P.

    1987-05-08

    This paper describes the success of the ongoing mixed-oxide fuel development program in the United States aimed at qualifying an economical fuel system for liquid metal cooled reactors. This development has been the cornerstone of the US program for the past 20 years and has proceeded in a deliberate and highly disciplined fashion with high emphasis on fuel reliability and operational safety as major features of an economical fuel system. The program progresses from feature testing in EBR-II to qualifying full size components in FFTF under fully prototypic conditions to establish a basis for extending allowable lifetimes. The development program started with the one year (300 EFPD) core, which is the FFTF driver fuel, continued with the demonstration of a two year (600 EFPD) core and is presently evaluating a three year (900 EFPD) fuel system. All three of these systems, consistent with other LMR fuel programs around the world, use fuel pellets gas bonded to a cladding tube that is assembled into a bundle and fitted into a wrapper tube or duct for ease of insertion into a core. The materials of construction progressed from austenitic CW 316 SS to lower swelling austenitic D9 to non swelling ferritic/martensitic HT9. 6 figs., 2 tabs.

  11. Alcohol oxidation by flavoenzymes.

    PubMed

    Romero, Elvira; Gadda, Giovanni

    2014-08-01

    This review article describes the occurrence, general properties, and substrate specificity of the flavoenzymes belonging to the glucose-methanol-choline oxidoreductase superfamily and the l-?-hydroxyacid dehydrogenase family. Most of these enzymes catalyze the oxidations of hydroxyl groups, yielding carbonyl moieties. Over the years, carbanion, hydride transfer, and radical mechanisms have been discussed for these enzymes, and the main experimental evidences supporting these mechanisms are presented here. Regardless of the chemical nature of the organic substrate (i.e., activated and non-activated alcohols), a hydride transfer mechanism appears to be the most plausible for the flavoenzymes acting on CH-OH groups. The reaction of most of these enzymes likely starts with proton abstraction from the substrate hydroxyl group by a conserved active site histidine. Among the different approaches carried out to determine the chemical mechanisms with physiological substrates, primary substrate and solvent deuterium kinetic isotope effect studies have provided the most unambiguous evidences. It is expected that the numerous studies reported for these enzymes over the years will be instrumental in devising efficient industrial biocatalysts and drugs. PMID:25372761

  12. Nitric oxide nanoparticles

    PubMed Central

    Schairer, David O.; Martinez, Luis R.; Blecher, Karin; Chouake, Jason S.; Nacharaju, Parimala; Gialanella, Philip; Friedman, Joel M.; Nosanchuk, Joshua D.; Friedman, Adam J.

    2012-01-01

    Nitric oxide (NO) is a critical component of host defense against invading pathogens; however, its therapeutic utility is limited due to a lack of practical delivery systems. Recently, a NO-releasing nanoparticulate platform (NO-np) was shown to have in vitro broad-spectrum antimicrobial activity and in vivo pre-clinical efficacy in a dermal abscess model. To extend these findings, both topical (TP) and intralesional (IL) NO-np administration was evaluated in a MRSA intramuscular murine abscess model and compared with vancomycin. All treatment arms accelerated abscess clearance clinically, histologically, and by microbiological assays on both days 4 and 7 following infection. However, abscesses treated with NO-np via either route demonstrated a more substantial, statistically significant decrease in bacterial survival based on colony forming unit assays and histologically revealed less inflammatory cell infiltration and preserved muscular architecture. These data suggest that the NO-np may be an effective addition to our armament for deep soft tissue infections. PMID:22286699

  13. Oxidants from Pulverized Minerals

    NASA Astrophysics Data System (ADS)

    Martel, L. M. V.

    2007-06-01

    Joel Hurowitz (previously at State University of New York at Stony Brook and now at the Jet Propulsion Laboratory), Nick Tosca, Scott McLennan, and Martin Schoonen (SUNY at Stony Brook) studied the production of hydrogen peroxide from freshly pulverized minerals in solution. Their experiments focused on olivine, augite, and labradorite; silicate minerals of basaltic planetary surfaces, such as the Moon and Mars, that are exposed to the intense crushing and grinding of impact cratering processes. The hydrogen peroxide produced in the experiments was enough to adequately explain the oxidizing nature of Martian regolith first determined by the Viking Landers and the results suggest, for the first time, that mechanically activated mineral surfaces may be an important part of the overall explanation for the Viking Lander biology experiment results. Hurowitz and coauthors further showed that when the pulverized minerals are heat-treated to high temperature under vacuum (to cause dehydroxylation) there is almost a 20 times increase in hydrogen peroxide production, a result which may be highly relevant to lunar dust. These careful studies demonstrate the importance of and concern about reactive dusts on planetary surfaces from two standpoints: the health of astronauts on surface maneuvers who may inadvertently breath it and the viability of possible Martian organic species to survive in such a corrosive, antiseptic surface environment.

  14. Nitric oxide and memory.

    PubMed

    Susswein, Abraham J; Katzoff, Ayelet; Miller, Nimrod; Hurwitz, Itay

    2004-04-01

    Nitric oxide (NO) is widely used in neural circuits giving rise to learning and memory. NO is an unusual neurotransmitter in its modes of release and action. Is its association with learning and memory related to its unusual properties? Reviewing the literature might allow the formulation of a general principle on how NO and memory are related. However, other than confirming that there is indeed a strong association between NO and memory, no simple rules emerge on the role of NO in learning and memory. The effects of NO are not associated with a particular stage or form of memory and are highly dependent on species, strain, and behavior or training paradigm. Nonetheless, a review does provide hints on why NO is associated with learning and memory. Unlike transmitters acting via receptors expressed only in neurons designed to respond to the transmitter, NO is a promiscuous signal that can affect a wide variety of neurons, via many molecular mechanisms. In circuits giving rise to learning and memory, it may be useful to signal some events via a promiscuous messenger having widespread effects. However, each circuit will use the promiscuous signal in a different way, to achieve different ends. PMID:15070489

  15. Oxidative demethylation of 2-picolines on vanadium oxide catalysts

    SciTech Connect

    Suvorov, B.V.; Glubokovskikh, L.K.; Demin, V.V.; Kan, I.I.

    1988-07-10

    One of the known methods for the preparation of pyridine is based on the dealkylation of alkylpyridines in the presence of vanadium-containing catalysts, molecular oxygen and steam. By using the oxidative demethylation of 2-picoline in the presence of steam on a fused vanadium(V) oxide, pyridine can be obtained in a yield of up to 88% of theory. To lower the consumption of vanadium(V) oxide and increase the thermostability of the catalyst, they studied the possible use of V/sub 2/O/sub 5/ catalysts on various carriers (diatomite, silica gel, porcelain balls), including the industrially produced brand SVD and SVS catalysts. The SVS brand catalyst has a satisfactory activity and selectivity in the oxidation demethylation of 2-picoline into pyridine. Under optimal conditions, pyridine is formed on this catalyst in a yield of 88% of the theoretical.

  16. 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.

  17. Tryptophan oxidation in proteins exposed to thiocyanate-derived oxidants.

    PubMed

    Bonifay, Vincent; Barrett, Tessa J; Pattison, David I; Davies, Michael J; Hawkins, Clare L; Ashby, Michael T

    2014-12-15

    Human defensive peroxidases, including lactoperoxidase (LPO) and myeloperoxidase (MPO), are capable of catalyzing the oxidation of halides (X(-)) by H2O2 to give hypohalous acids (HOX) for the purpose of cellular defense. Substrate selectivity depends upon the relative abundance of the halides, but the pseudo-halide thiocyanate (SCN(-)) is a major substrate, and sometimes the exclusive substrate, of all defensive peroxidases in most physiologic fluids. The resulting hypothiocyanous acid (HOSCN) has been implicated in cellular damage via thiol oxidation. While thiols are believed to be the primary target of HOSCN in vivo, Trp residues have also been implicated as targets for HOSCN. However, the mechanism involved in HOSCN-mediated Trp oxidation was not established. Trp residues in proteins appeared to be susceptible to oxidation by HOSCN, whereas free Trp and Trp residues in small peptides were found to be unreactive. We show that HOSCN-induced Trp oxidation is dependent on pH, with oxidation of free Trp, and Trp-containing peptides observed when the pH is below 2. These conditions mimic those employed previously to precipitate proteins after treatment with HOSCN, which accounts for the discrepancy in the results reported for proteins versus free Trp and small peptides. The reactant in these cases may be thiocyanogen ((SCN)2), which is produced by comproportionation of HOSCN and SCN(-) at low pH. Reaction of thiocyanate-derived oxidants with protein Trp residues at low pH results in the formation of a number of oxidation products, including mono- and di-oxygenated derivatives, which are also formed with other hypohalous acids. Our data suggest that significant modification of Trp by HOSCN in vivo is likely to have limited biological relevance. PMID:25172223

  18. Nitric oxide and oxidative stress in placental explant cultures.

    PubMed

    Goncalves, Juvic M; Casart, Ysabel C; Camejo, Mara I

    2016-02-01

    Placental explant culture, and cellular cytolysis and cellular differentiation have been previously studied. However, oxidative stress and nitric oxide profiles have not been evaluated in these systems. The aim of this study was to determine the release of lipid peroxidation and nitric oxide from placental explants cultured over a seven day period. Placental explants were maintained for seven days in culture and the medium was changed every 24 hours. The response was assessed in terms of syncytiotrophoblast differentiation (human chorionic gonadotropin, hCG), cellular cytolysis (lactate dehydrogenase, LDH), oxidative stress (thiobarbituric acid reactive substances, TBARS), and nitric oxide (NO). Levels of hCG increased progressively from day two to attain its highest level on days four and five after which it decreased gradually. In contrast, the levels of LDH, TBARS, and NO were elevated in the early days of placental culture when new syncytiotrophoblast from cytotrophoblast were forming and also in the last days of culture when tissue was declining. In conclusion, the levels of NO and lipid peroxidation follow a pattern similar to LDH and contrary to hCG. Future placental explant studies to evaluate oxidative stress and NO should consider the physiological changes inherent during the time of culture. PMID:26366632

  19. Alkali oxide-tantalum, niobium and antimony oxide ionic conductors

    NASA Technical Reports Server (NTRS)

    Roth, R. S.; Brower, W. S.; Parker, H. S.; Minor, D. B.; Waring, J. L.

    1975-01-01

    The phase equilibrium relations of four systems were investigated in detail. These consisted of sodium and potassium antimonates with antimony oxide and tantalum and niobium oxide with rubidium oxide as far as the ratio 4Rb2O:llB2O5 (B=Nb, Ta). The ternary system NaSbO3-Sb2O4-NaF was investigated extensively to determine the actual composition of the body centered cubic sodium antimonate. Various other binary and ternary oxide systems involving alkali oxides were examined in lesser detail. The phases synthesized were screened by ion exchange methods to determine mobility of the mobility of the alkali ion within the niobium, tantalum or antimony oxide (fluoride) structural framework. Five structure types warranted further investigation; these structure types are (1) hexagonal tungsten bronze (HTB), (2) pyrochlore, (3) the hybrid HTB-pyrochlore hexagonal ordered phases, (4) body centered cubic antimonates and (5) 2K2O:3Nb2O5. Although all of these phases exhibit good ion exchange properties only the pyrochlore was prepared with Na(+) ions as an equilibrium phase and as a low porosity ceramic. Sb(+3) in the channel interferes with ionic conductivity in this case, although relatively good ionic conductivity was found for the metastable Na(+) ion exchanged analogs of RbTa2O5F and KTaWO6 pyrochlore phases.

  20. Investigation of Mixed Oxide Catalysts for NO Oxidation

    SciTech Connect

    Szanyi, Janos; Karim, Ayman M.; Pederson, Larry R.; Kwak, Ja Hun; Mei, Donghai; Tran, Diana N.; Herling, Darrell R.; Muntean, George G.; Peden, Charles HF; Howden, Ken; Qi, Gongshin; Li, Wei

    2014-12-09

    The oxidation of engine-generated NO to NO2 is an important step in the reduction of NOx in lean engine exhaust because NO2 is required for the performance of the LNT technology [2], and it enhances the activities of ammonia selective catalytic reduction (SCR) catalysts [1]. In particular, for SCR catalysts an NO:NO2 ratio of 1:1 is most effective for NOx reduction, whereas for LNT catalysts, NO must be oxidized to NO2 before adsorption on the storage components. However, NO2 typically constitutes less than 10% of NOx in lean exhaust, so catalytic oxidation of NO is essential. Platinum has been found to be especially active for NO oxidation, and is widely used in DOC and LNT catalysts. However, because of the high cost and poor thermal durability of Pt-based catalysts, there is substantial interest in the development of alternatives. The objective of this project, in collaboration with partner General Motors, is to develop mixed metal oxide catalysts for NO oxidation, enabling lower precious metal usage in emission control systems. [1] M. Koebel, G. Madia, and M. Elsener, Catalysis Today 73, 239 (2002). [2] C. H. Kim, G. S. Qi, K. Dahlberg, and W. Li, Science 327, 1624 (2010).

  1. Structure, adhesion, and stability of metal/oxide and oxide/oxide interfaces

    SciTech Connect

    Lad, R.J.

    1992-11-01

    Studies of structural, electronic, and chemical properties of metal/oxide and oxide/oxide interfaces were performed on well-defined interfaces that created by depositing ultra-thin potassium and aluminum films and their oxides onto single crystal TiO[sub 2] and NiO surfaces. Work focused on determining the structure, growth mechanisms, and morphologies of metal and oxide films as they are deposited an single crystal oxide surfaces using RHEED and atomic force microscopy probing electronic structure, bonding and chemical interactions at the interfaces using x-ray and uv photoelectron spectroscopies (XPS, UPS) and Auger electron spectroscopy (AES), and understanding factors affecting stability and reactivity of the interface regions including the role of defects and impurities. Results indicate that kinetic effects have an important influence on interface structure and composition, and they also show that defects in the oxide substrate induce new electronic states at the interface which play a major role in cation-anion bonding and interface interactions. The results establish a link between electronic and chemical bonding properties and the interface structure and morphology, which is required to successfully manipulate the interfacial properties of advanced ceramic materials.

  2. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    EPA Science Inventory

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

  3. MTBE OXIDATION BY BIFUNCTIONAL ALUMINUM

    EPA Science Inventory

    Bifunctional aluminum, prepared by sulfating zero-valent aluminum with sulfuric acid, has a dual functionality of simultaneously decomposing both reductively- and oxidatively-degradable contaminants. In this work, the use of bifunctional aluminum for the degradation of methyl te...

  4. Oxidation dynamics of aluminum nanorods

    SciTech Connect

    Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya

    2015-02-23

    Aluminum nanorods (Al-NRs) are promising fuels for pyrotechnics due to the high contact areas with oxidizers, but their oxidation mechanisms are largely unknown. Here, reactive molecular dynamics simulations are performed to study thermally initiated burning of oxide-coated Al-NRs with different diameters (D = 26, 36, and 46 nm) in oxygen environment. We found that thinner Al-NRs burn faster due to the larger surface-to-volume ratio. The reaction initiates with the dissolution of the alumina shell into the molten Al core to generate heat. This is followed by the incorporation of environmental oxygen atoms into the resulting Al-rich shell, thereby accelerating the heat release. These results reveal an unexpectedly active role of the alumina shell as a “nanoreactor” for oxidation.

  5. COPD: balancing oxidants and antioxidants

    PubMed Central

    Fischer, Bernard M; Voynow, Judith A; Ghio, Andrew J

    2015-01-01

    Chronic obstructive pulmonary disease (COPD) is one of the most common chronic illnesses in the world. The disease encompasses emphysema, chronic bronchitis, and small airway obstruction and can be caused by environmental exposures, primarily cigarette smoking. Since only a small subset of smokers develop COPD, it is believed that host factors interact with the environment to increase the propensity to develop disease. The major pathogenic factors causing disease include infection and inflammation, protease and antiprotease imbalance, and oxidative stress overwhelming antioxidant defenses. In this review, we will discuss the major environmental and host sources for oxidative stress; discuss how oxidative stress regulates chronic bronchitis; review the latest information on genetic predisposition to COPD, specifically focusing on oxidant/antioxidant imbalance; and review future antioxidant therapeutic options for COPD. The complexity of COPD will necessitate a multi-target therapeutic approach. It is likely that antioxidant supplementation and dietary antioxidants will have a place in these future combination therapies. PMID:25673984

  6. Oxides having high energy densities

    DOEpatents

    Ceder, Gerbrand; Kang, Kisuk

    2013-09-10

    Certain disclosed embodiments generally relate to oxide materials having relatively high energy and/or power densities. Various aspects of the embodiments are directed to oxide materials having a structure B.sub.i(M.sub.jY.sub.k)O.sub.2, for example, a structure Li.sub.j(Ni.sub.jY.sub.k)O.sub.2 such as Li(Ni.sub.0.5Mn.sub.0.5)O.sub.2. In this structure, Y represents one or more atoms, each independently selected from the group consisting of alkaline earth metals, transition metals, Group 14 elements, Group 15, or Group 16 elements. In some embodiments, such an oxide material may have an O3 crystal structure, and/or a layered structure such that the oxide comprises a plurality of first, repeating atomic planes comprising Li, and a plurality of second, repeating atomic planes comprising Ni and/or Y.

  7. Synthetic chemistry with nitrous oxide.

    PubMed

    Severin, Kay

    2015-10-01

    This review article summarizes efforts to use nitrous oxide (N2O, 'laughing gas') as a reagent in synthetic chemistry. The focus will be on reactions which are carried out in homogeneous solution under (relatively) mild conditions. First, the utilization of N2O as an oxidant is discussed. Due to the low intrinsic reactivity of N2O, selective oxidation reactions of highly reactive compounds are possible. Furthermore, it is shown that transition metal complexes can be used to catalyze oxidation reactions, in some cases with high turnover numbers. In the final part of this overview, the utilization of N2O as a building block for more complex molecules is discussed. It is shown that N2O can be used as an N-atom donor for the synthesis of interesting organic molecules such as triazenes and azo dyes. PMID:26104268

  8. Electrostatic doping in oxide heterostructures

    NASA Astrophysics Data System (ADS)

    Lee, Jaekwang; Demkov, Alexander A.

    2008-03-01

    Recent experiments on perovskite heterostructures grown by molecular beam epitaxy or pulsed laser deposition suggest the possibility of creating high mobility two dimensional electron gas at the oxide/oxide interface. However, the origin of charge in these insulating materials is still not clear and deemed controversial. We report a first-principles study of SrTiO3/LaAlO3 heterostructures using density functional theory at the LDA+U level. We consider the energetics and electronic structure of the junction, while focusing on the role of electrostatics. Our results suggest that a complex balance of the crystal filed, Jahn-Teller effect, lattice dynamics and internal electric field result in the robust electrostatic doping for carefully chosen thickness of the polar oxide. We explore the possible uses of this effect in other oxide-based heterostructures.

  9. Millisecond Oxidation of Alkanes

    SciTech Connect

    Scott Han

    2011-09-30

    This project was undertaken in response to the Department of Energy's call to research and develop technologies 'that will reduce energy consumption, enhance economic competitiveness, and reduce environmental impacts of the domestic chemical industry.' The current technology at the time for producing 140 billion pounds per year of propylene from naphtha and Liquified Petroleum Gas (LPG) relied on energy- and capital-intensive steam crackers and Fluidized Catalytic Cracking (FCC) units. The propylene is isolated from the product stream in a costly separation step and subsequently converted to acrylic acid and other derivatives in separate production facilities. This project proposed a Short Contact Time Reactor (SCTR)-based catalytic oxydehydrogenation process that could convert propane to propylene and acrylic acid in a cost-effective and energy-efficient fashion. Full implementation of this technology could lead to sizeable energy, economic and environmental benefits for the U. S. chemical industry by providing up to 45 trillion BTUs/year, cost savings of $1.8 billion/year and a combined 35 million pounds/year reduction in environmental pollutants such as COx, NOx, and SOx. Midway through the project term, the program directive changed, which approval from the DOE and its review panel, from direct propane oxidation to acrylic acid at millisecond contact times to a two-step process for making acrylic acid from propane. The first step was the primary focus, namely the conversion of propane to propylene in high yields assisted by the presence of CO2. The product stream from step one was then to be fed directly into a commercially practiced propylene-to-acrylic acid tandem reactor system.

  10. Activating Nonreducible Oxides via Doping.

    PubMed

    Nilius, Niklas; Freund, Hans-Joachim

    2015-05-19

    Nonreducible oxides are characterized by large band gaps and are therefore unable to exchange electrons or to form bonds with surface species, explaining their chemical inertness. The insertion of aliovalent dopants alters this situation, as new electronic states become available in the gap that may be involved in charge-transfer processes. Consequently, the adsorption and reactivity pattern of doped oxides changes with respect to their nondoped counterparts. This Account describes scanning tunneling microscopy (STM) and photoelectron spectroscopy (XPS) experiments that demonstrate the impact of dopants on the physical and chemical properties of well-defined crystalline oxide films. For this purpose, MgO and CaO as archetypical rocksalt oxides have been loaded either with high-valence (Mo, Cr) or low-valence dopants (Li). While the former generate filled states in the oxide band gap and serve as electron donors, the latter produce valence-band holes and give rise to an acceptor response. The dopant-related electronic states and their polarization effect on the surrounding host material are explored with XPS and STM spectroscopy on nonlocal and local scales. Moreover, charge-compensating defects were found to develop in the oxide lattice, such as Ca and O vacancies in Mo- and Li-doped CaO films, respectively. These native defects are able to trap the excess charges of the impurities and therefore diminish the desired doping effect. If noncompensated dopants reside in the host lattice, electron exchange with surface species is observed. Mo ions in CaO, for example, were found to donate electrons to surface Au atoms. The anionic Au strongly binds to the CaO surface and nucleates in the form of monolayer islands, in contrast to the 3D growth prevailing on pristine oxides. Charge transfer is also revealed for surface O2 that traps one Mo electron by forming a superoxo-species. The activated oxygen is characterized by a reinforced binding to the surface, an elongated O-O bond length, and a reduced barrier for dissociation, and represents an important intermediate for oxidation reactions. The charge-transfer processes described here are quenched if Li is inserted into the oxide lattice, neutralizing the effect of the extra electrons. The specific behavior of doped oxides has been explored on a mechanistic level, i.e. on thin-film model systems at ultrahigh vacuum and low temperature. We believe, however, that our results are transferrable to realistic conditions and doping might thus develop into a powerful method to improve the performance of nonreducible oxides in surface-catalyzed reactions. PMID:25894859

  11. Preparation and properties of electrically conducting ceramics based on indium oxide-rare earth oxides-hafnium oxides

    SciTech Connect

    Marchant, D.D.; Bates, J.L.

    1983-09-01

    Electrically conducting refractory oxides based on adding indium oxide to rare earth-stabilized hafnium oxide are being studied for use in magnetohydrodynamic (MHD) generators, fuel cells, and thermoelectric generators. The use of indium oxide generally increases the electrical conductivity. The results of measurements of the electrical conductivity and data on corrosion resistance in molten salts are presented.

  12. Oxidation protection coatings for polymers

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Sovey, J. S.; Banks, B. A. (inventors)

    1985-01-01

    A polymeric substrate is coated with a metal oxide film to provide oxidation protection in low Earth orbital environments. The film contains about 4 volume percent polymer to provide flexibility. A coil of polymer material moves through an ion beam as it is fed between reels. The ion beam first cleans the polymer material surface and then sputters the film material from a target onto this surface.

  13. Enzymes of respiratory iron oxidation

    SciTech Connect

    Blake, R. II.

    1992-01-01

    This report describes experimental progress in characterizing and identifying redox proteins in a number of iron-oxidizing bacteria. Sections of the paper are entitled (1) In Situ electrolysis was explored to achieve enhanced yields of iron-oxidizing bacteria, (2)Structure/function studies were performed on redox-active biomolecules from Thiobacillus ferrooxidans, (3) Novel redox-active biomolecules were demonstrated in other iron autotrophs, and (4) New probes of metalloprotein electron-transfer reactions were synthesized and characterized.

  14. Nitric oxide as an antioxidant

    SciTech Connect

    Kanner, J.; Harel, S.; Granit, R. )

    1991-08-15

    Benzoate monohydroxy compounds, and in particular salicylate, were produced during interaction of ferrous complexes with hydrogen peroxide (Fenton reaction) in a N2 environment. These reactions were inhibited when Fe complexes were flushed, prior to the addition in the model system, by nitric oxide. Methionine oxidation to ethylene by Fenton reagents was also inhibited by nitric oxide. Myoglobin in several forms such as metmyoglobin, oxymyoglobin, and nitric oxide-myoglobin were interacted with an equimolar concentration of hydrogen peroxide. Spectra changes in the visible region and the changes in membrane (microsomes) lipid peroxidation by the accumulation of thiobarbituric acid-reactive substances (TBA-RS) were determined. The results showed that metmyoglobin and oxymyoglobin were activated by H2O2 to ferryl myoglobin, which initiates membrane lipid peroxidation; but not nitric oxide-myoglobin, which, during interaction with H2O2, did not form ferryl but metmyoglobin which only poorly affected lipid peroxidation. It is assumed that nitric oxide, liganded to ferrous complexes, acts to prevent the prooxidative reaction of these complexes with H2O2.

  15. Oxidative Stress Markers in Sputum

    PubMed Central

    Antus, Balazs

    2016-01-01

    Although oxidative stress is thought to play a pivotal role in the pathogenesis of inflammatory airway diseases, its assessment in clinical practice remains elusive. In recent years, it has been conceptualized that oxidative stress markers in sputum should be employed to monitor oxidative processes in patients with asthma, chronic obstructive pulmonary disease (COPD), or cystic fibrosis (CF). In this review, the use of sputum-based oxidative markers was explored and potential clinical applications were considered. Among lipid peroxidation-derived products, 8-isoprostane and malondialdehyde have been the most frequently investigated, while nitrosothiols and nitrotyrosine may serve as markers of nitrosative stress. Several studies have showed higher levels of these products in patients with asthma, COPD, or CF compared to healthy subjects. Marker concentrations could be further increased during exacerbations and decreased along with recovery of these diseases. Measurement of oxidized guanine species and antioxidant enzymes in the sputum could be other approaches for assessing oxidative stress in pulmonary patients. Collectively, even though there are promising findings in this field, further clinical studies using more established detection techniques are needed to clearly show the benefit of these measurements in the follow-up of patients with inflammatory airway diseases. PMID:26885248

  16. Lipid oxidation in the skin.

    PubMed

    Niki, Etsuo

    2015-01-01

    Skin is the largest organ of the body and exerts several physiological functions such as a protective barrier against moisture loss and noxious agents including ultraviolet irradiation. Oxidation of skin may impair such functions and induce skin disorders including photoaging and skin cancer. Skin surface lipids, a mixture of sebaceous and epidermal lipids, have unique species and fatty acid profile. The major unsaturated lipids are squalene, sebaleic aicd, linoleic acid, and cholesterol. Singlet oxygen and ozone as well as free radicals and enzymes are important oxidants for skin lipids. Squalene is the major target for singlet oxygen, giving rise to twelve regio-isomeric squalene hydroperoxides. Ultraviolet radiation activates lipoxygenase and cyclooxygenase, inducing specific enzymatic oxidation of lipids. Free radical mediated lipid peroxidation gives multiple oxidation products. Lipid oxidation products produced by these mechanisms are observed in human skin and induce various skin diseases, but in contrast to plasma and other tissues, identification and quantitative measurement of lipid oxidation products in skin are scarce and should be the subjects of future studies. PMID:25312699

  17. Accelerated oxidation processes is biodiesel

    SciTech Connect

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

    1999-12-01

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

  18. Effect of matrix components on UV/H2O2 and UV/S2O8(2-) advanced oxidation processes for trace organic degradation in reverse osmosis brines from municipal wastewater reuse facilities.

    PubMed

    Yang, Yi; Pignatello, Joseph J; Ma, Jun; Mitch, William A

    2016-02-01

    When reverse osmosis brines from potable wastewater reuse plants are discharged to poorly-flushed estuaries, the concentrated organic contaminants are a concern for receiving water ecosystems. UV/hydrogen peroxide (UV/H2O2) and UV/persulfate [Formula: see text] advanced oxidation processes (AOPs) may reduce contaminant burdens prior to discharge, but the effects of the high levels of halide, carbonate and effluent organic matter (EfOM) normally present in these brines are unclear. On the one hand, these substances may reduce process efficiency by scavenging reactive oxygen species (ROS), hydroxyl (OH) and sulfate [Formula: see text] radicals. On the other, the daughter radicals generated by halide and carbonate scavenging may themselves degrade organics, offsetting the effect of ROS scavenging. UV/H2O2 and [Formula: see text] AOPs were compared for degradation of five pharmaceuticals spiked into brines obtained from two reuse facilities and the RO influent from one of them. For UV/H2O2, EfOM scavenged ∼75% of the OH, reducing the degradation efficiency of the target contaminants to a similar extent; halide and carbonate scavenging and the reactivities of associated daughter radicals were less important. For [Formula: see text] , anions (mostly Cl(-)) scavenged ∼93% of the SO4(-). Because daughter radicals of Cl(-) contributed to contaminant degradation, the reduction in contaminant degradation efficiency was only ∼75-80%, with the reduction driven by daughter radical scavenging by EfOM. Conversion of [Formula: see text] to more selective halogen and carbonate radicals resulted in a wider range of degradation efficiencies among the contaminants. For both AOPs, 250 mJ/cm(2) average fluence achieved significant removal of four pharmaceuticals, with significantly better performance by [Formula: see text] treatment for some constituents. Accounting for the lower brine flowrates, the energy output to achieve this fluence in brines is comparable to that often applied to RO permeates. However, much higher fluence was required for the least reactive pharmaceutical. Comparing AOP application to the RO influent or brine, equal or greater removal was achieved for brine treatment for comparable energy input. AOP treatment of brines could be applied to reduce, but not eliminate, contaminant burdens prior to discharge. PMID:26657355

  19. 21 CFR 172.260 - Oxidized polyethylene.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Oxidized polyethylene. 172.260 Section 172.260... CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... polyethylene is the basic resin produced by the mild air oxidation of polyethylene. The polyethylene used...

  20. 21 CFR 172.260 - Oxidized polyethylene.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Oxidized polyethylene. 172.260 Section 172.260... CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... polyethylene is the basic resin produced by the mild air oxidation of polyethylene. The polyethylene used...

  1. 21 CFR 177.1620 - Polyethylene, oxidized.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Polyethylene, oxidized. 177.1620 Section 177.1620... Contact Surfaces § 177.1620 Polyethylene, oxidized. Oxidized polyethylene identified in paragraph (a) of... following prescribed conditions: (a) Oxidized polyethylene is the basic resin produced by the mild...

  2. 21 CFR 172.260 - Oxidized polyethylene.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Oxidized polyethylene. 172.260 Section 172.260... CONSUMPTION Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may... polyethylene is the basic resin produced by the mild air oxidation of polyethylene. The polyethylene used...

  3. 21 CFR 172.260 - Oxidized polyethylene.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Oxidized polyethylene. 172.260 Section 172.260 Food... Coatings, Films and Related Substances § 172.260 Oxidized polyethylene. Oxidized polyethylene may be safely used as a component of food, subject to the following restrictions: (a) Oxidized polyethylene is...

  4. 21 CFR 172.260 - Oxidized polyethylene.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Oxidized polyethylene. 172.260 Section 172.260... § 172.260 Oxidized polyethylene. Oxidized polyethylene may be safely used as a component of food, subject to the following restrictions: (a) Oxidized polyethylene is the basic resin produced by the...

  5. 49 CFR 173.337 - Nitric oxide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Nitric oxide. 173.337 Section 173.337... SHIPMENTS AND PACKAGINGS Gases; Preparation and Packaging 173.337 Nitric oxide. (a) Nitric oxide must be... valve and valve seat that will not deteriorate in contact with nitric oxide. Cylinders or valves may...

  6. Metal oxide nanostructures with hierarchical morphology

    DOEpatents

    Ren, Zhifeng (Newton, MA); Lao, Jing Yu (Saline, MI); Banerjee, Debasish (Ann Arbor, MI)

    2007-11-13

    The present invention relates generally to metal oxide materials with varied symmetrical nanostructure morphologies. In particular, the present invention provides metal oxide materials comprising one or more metallic oxides with three-dimensionally ordered nanostructural morphologies, including hierarchical morphologies. The present invention also provides methods for producing such metal oxide materials.

  7. Radiation-induced cationic polymerization of limonene oxide,. cap alpha. -pinene oxide, and. beta. -pinene oxide

    SciTech Connect

    Aikins, J.A.; Williams, F.

    1984-01-01

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

  8. Oxidative coupling of methane over sodium promoted praseodymium oxide

    SciTech Connect

    Gaffney, A.M.; Jones, C.A.; Leonard, J.J.; Sofranko, J.A. )

    1988-12-01

    Unpromoted and alkali-promoted lanthanide oxides were evaluated in the oxidative coupling of methane to higher hydrocarbons. Methane conversion was carried out catalytically and in a redox mode by cycling methane and air independently over the lanthanide oxides. The sodium-promoted nonstoichiometric oxide, 4% Na on Pr{sub 6}O{sub 11}, was most active and selective, giving in the redox mode 21% methane conversion and 76% C{sub 2}{sup +} selectivity at 800 C and 1.4. WHSV (weight hourly space velocity, g CH{sub 4}/g cat. hr). At comparable conversion catalytic methane conversion had a C{sub 2}{sup +} selectivity of 64%. This selectivity deficit with respect to redox is attributed to an additional destructive route of the methyl radical, namely the reaction with molecular oxygen to yield a methylperoxy intermediate. Process variable studies support a mechanism whereby methane is activated at the metal oxide surface to form a methyl radical and in the gas phase C{sub 2}{sup +} hydrocarbon building occurs.

  9. Nitrous oxide production and methane oxidation by different ammonia-oxidizing bacteria

    SciTech Connect

    Jiang, Q.Q.; Bakken, L.R.

    1999-06-01

    Ammonia-oxidizing bacteria (AOB) are thought to contribute significantly to N{sub 2}O production and methane oxidation in soils. Most knowledge derives from experiments with Nitrosomonas europaea, which appears to be of minor importance in most soils compared to Nitrosospira spp. The authors have conducted a comparative study of levels of aerobic N{sub 2}O production in six phylogenetically different Nitrosospira strains newly isolated from soils and in two N. europaea and Nitrosospira multiformis type strains. The fraction of oxidized ammonium released as N{sub 2}O during aerobic growth was remarkably constant for all the Nitrosospira strains, irrespective of the substrate supply (urea versus ammonium), the pH, or substrate limitation. N. europaea and Nitrosospira multiformis released similar fractions of N{sub 2}O when they were supplied with ample amounts of substrates, but the fractions rose sharply when they were restricted by a low pH or substrate limitation. Phosphate buffer doubled the N{sub 2}O release for all types of AOB. No detectable oxidation of atmospheric methane was detected. Calculations based on detection limits as well as data in the literature on CH{sub 4} oxidation by AOB bacteria prove that none of the tested strains contribute significantly to the oxidation of atmospheric CH{sub 4} in soils.

  10. Oxidation state of Mn in the Mn oxide produced by Leptothrix discophora SS-1

    NASA Astrophysics Data System (ADS)

    Adams, Lee F.; Ghiorse, William C.

    1988-08-01

    Leptothrix discophora SS-1 excretes at least one Mn 2+-oxidizing protein that, in association with acidic exopolymers, catalyzes a rapid oxidation of Mn 2+. Iodometric titration of Mn oxide product showed that the oxidation state of Mn increased with age of the oxide from 3.32 in samples 11 hours old to 3.62 in samples formed over a period of 30 days. Electron diffraction of 90-day old samples showed evidence of poorly crystalline Mn(IV) oxides. Simultaneous measurement of oxygen consumption and Mn oxide formation during 15 min reaction periods indicated that the initial Mn product possessed an average oxidation state no greater than 3.6. Results suggest that the Mn 2+-oxidizing system of Leptothrix discophora SS-1 first generates Mn oxide with an average oxidation state close to Mn(III). Aging increases this oxidation state to give the mixed Mn(III, IV) oxide product observed in older samples.

  11. Opportunities for functional oxides in yttrium oxide-titanium oxide-zirconium oxide system: Applications for novel thermal barrier coatings

    NASA Astrophysics Data System (ADS)

    Francillon, Wesley

    This dissertation is an investigation of materials and processed under consideration for next generation thermal structural oxides with potential applications as thermal barrier coatings; wherein, high temperature stability and mechanical properties affect durability. Two notable next generation materials systems under investigation are pyrochlore and co-doped zirconia oxides. The motivation for this work is based on current limitations of the currently used thermal barrier material of yttria stabilized zirconia (YSZ) deposited by the plasma spray processes. The rapid quenching associated with the plasma spray process, results in a metastable structure that is a non-transformable tetragonal structure in the yttria partially stabilized zirconia system rather than the equilibrium anticipated two phase mixture of cubic and monoclinic phases. It has been shown that this metastable structure offers enhanced toughness and thus durability during thermomechanical cycling from the operating temperatures in excess of 1000C to ambient. However, the metastable oxides are susceptible to partitioning at temperatures greater than 1200C, thus resulting in a transformation of the tetragonal phase oxides. Transformations of the tetragonal prime phase into the parent cubic and tetragonal prime phase result in coating degradation. Several of the emerging oxides are based on rare earth additions to zirconia. However, there is limited information of the high temperature stability of these oxide coatings and more notably these compositions exhibit limited toughness for durable performance. A potential ternary composition based on the YSZ system that offers the ability to tailor the phase structure is based YO1.5-TiO2 -ZrO2. The ternary of YO1.5-TiO2-ZrO 2 has the current TBC composition of seven molar percent yttria stabilized zirconia, pyrochlore phase oxide and zirconia doped with yttria and titania additions (Ti-YSZ). The Ti-YSZ phase field is of interest because at equilibrium it is a single tetragonal phase. Thus, compositions are of single phase tetragonal phase, theoretically, should not undergo high temperature partitioning. Single Tetragonal phase oxides of Ti-YSZ also offer the possibility of enhanced toughness and higher temperature stability akin to those observed in yttria partially stabilized zirconia. Many pyrochlore oxides are under review because they have shown to have lower thermal conductivity than YSZ oxides. This study focused on chemically synthesizing homogeneous starting material compositions in a metastable state (preferably amorphous), following its evolution according to the phase hierarchy under conditions of kinetic constraints. The current equilibrium diagram of YO1.5-TiO2-ZrO 2 is based on theoretical calculations. One of the contributions of this work is the redefined phase fields in YO1.5-TiO2-ZrO 2 based on our experimental results. Investigated compositions were based on tie lines of Y2-xTi2ZrxO7+x/2 and Y2Ti2-yZryO7 representing substitution of Zr4+ for Y3+ and Zr4+ for Ti4+ respectively. More notably, we observed extended metastable phases in pyrochlore and fluorite oxides at low temperature. The significance of this result is that it offers a larger compositional range for investing pyrochlore oxides with associated high temperature phase stability for TBC applications. In tetragonal oxides, our results showed that Ti-YSZ results have slower partitioning kinetics in comparison to YSZ at high temperature. This study also emphasized the deposition of advanced ceramic coatings by plasma spray for tetragonal and pyrochlore systems, compositionally complex functional oxides that may potentially have lower thermal conductivity values compared to current YSZ oxides. Next generation thermal barrier coatings require powders with high chemical purity, chemical homogeneity, controlled particle size/shape and pertinent phase state. Thermal spray offers an avenue to create novel materials and deposits directly from the precursor and compositionally controlled powder feedstock. This study contributed to investigating an unexplored field that offers a variety of opportunities in materials synthesis that would not be possible by conventional methods. Understanding processing-microstructure-property correlations is of considerable importance in thermal spray of functional oxide materials. This thesis demonstrated by radio-frequency thermal spray that the complex pyrochlore oxide Y 2Ti2O7 could be deposited by directly injecting molecularly mixed precursors to form oxide coatings. Structural analysis revealed the metastable fluorite phase; however, with thermal treatments at relatively low temperature of 700°C the pyrochlore phase was obtained. For Ti-YSZ coatings, the tetragonal phase oxides were obtained with unique microstructures, however, the tetragonal prime destabilized at 1200°C. This dissertation explored novel oxide compositions through detailed structural analysis. The approach presented a comprehensive and integrated investigation as it pertains to phase evolution of oxides in powder feedstock to coating characteristics (phase/properties).

  12. Transparent conducting oxides and production thereof

    SciTech Connect

    Gessert, Timothy A; Yoshida, Yuki; Coutts, Timothy J

    2014-05-27

    Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target (110) doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber (100). The method may also comprise depositing a metal oxide on the target (110) to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

  13. Transparent conducting oxides and production thereof

    SciTech Connect

    Gessert, Timothy A.; Yoshida, Yuki; Coutts, Timothy J.

    2014-06-10

    Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber. The method may also comprise depositing a metal oxide on the target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

  14. Method for plating with metal oxides

    DOEpatents

    Silver, Gary L.; Martin, Frank S.

    1994-08-23

    A method of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate.

  15. Method for plating with metal oxides

    DOEpatents

    Silver, G.L.; Martin, F.S.

    1994-08-23

    A method is disclosed of plating hydrous metal oxides on at least one substrate, which method is indifferent to the electrochemical properties of the substrate, and comprises reacting metallic ions in aqueous solution with an appropriate oxidizing agent such as sodium hypochlorite or calcium sulfite with oxygen under suitable conditions of pH and concentration such that oxidation and precipitation of metal oxide are sufficiently slow to allow satisfactory plating of metal oxide on the substrate. 1 fig.

  16. Supercapacitors with graphene oxide separators and reduced graphite oxide electrodes

    NASA Astrophysics Data System (ADS)

    Shulga, Y. M.; Baskakov, S. A.; Baskakova, Y. V.; Volfkovich, Y. M.; Shulga, N. Y.; Skryleva, E. A.; Parkhomenko, Y. N.; Belay, K. G.; Gutsev, G. L.; Rychagov, A. Y.; Sosenkin, V. E.; Kovalev, I. D.

    2015-04-01

    A supercapacitor (SC) with electrodes fabricated from graphite oxide reduced by a microwave exfoliation (MEGO) method and the separator made from the graphite oxide paper (GOP) formed after precipitation of water suspension of graphene oxide was designed for the first time. The specific capacitance of this SC exceeded 200 F/g. The specific area of our MEGO is 2400 m2/g when measured using the standard contact porosimetry method, whereas it is several times smaller (?600 m2/g) when measured by using the Brunauer-Emmett-Teller method based on the low-temperature nitrogen adsorption. By using the angle resolved X-ray photoelectron spectroscopy we found that surface layers of the GOP separator contain smaller oxygen concentration than the bulk layers.

  17. Anomalous oxidation states in oxide multilayers for fuel cell applications

    SciTech Connect

    Perkins, James; Fearn, Sarah; Cook, S. N.; Srinivasan, R.; Rouleau, Christopher M; Christen, Hans M; West, G. D.; Morris, R. J. H.; Fraser, H. L.; Skinner, Stephen; Kilner, John; McComb, David

    2010-01-01

    Significant interest has been directed towards interface enhanced ionic conductivity. Advanced analytical techniques including electron microscopy (TEM/STEM), electron energy loss spectroscopy (EELS), and secondary ion mass spectrometry (SIMS) have been used to characterize CeO2/Ce0.85Sm0.15O2 multilayer thin films grown by pulsed laser deposition. High quality growth is observed, but ionic conductivity measured by impedance spectroscopy and 18O tracer experiments is consistent with bulk materials. EELS analysis reveals the unusual situation of layers containing only Ce(IV) adjacent to layers containing both Ce(III) and Ce(IV). Post oxygen annealing induced oxygen diffusion and mixed oxidation states in both layers, but only in the vicinity of low angle grain boundaries perpendicular to the layers. The implications of this remarkable metastability of Ce oxidation states on the design of novel electrolytes for solid oxide fuel cells is discussed.

  18. Oxidation of Octopus vulgaris hemocyanin by nitrogen oxides

    SciTech Connect

    Salvato, B.; Giacometti, G.M.; Beltramini, M.; Zilio, F.; Giacometti, G.; Magliozzo, R.S.; Peisach, J.

    1989-01-24

    The reaction of Octopus vulgaris hemocyanin with nitrite was studied under a variety of conditions in which the green half-met derivative is formed. Analytical evidence shows that the amount of chemically detectable nitrite in various samples of the derivative is not proportional to the cupric copper detected by EPR. The kinetics of oxidation of hemocyanin as a function of protein concentration and pH, in the presence of nitrite and ascorbate, is consistent with a scheme in which NO/sub 2/ is the reactive oxidant. We suggest that the green half-methemocyanin contains a metal center with one cuprous and one cupric copper without an exogenous nitrogen oxide ligand.

  19. Highly oxidized graphene nanosheets via the oxidization of detonation carbon

    NASA Astrophysics Data System (ADS)

    Nepal, A.; Chiu, G.; Xie, J.; Singh, G. P.; Ploscariu, N.; Klankowski, S.; Sung, T.; Li, J.; Flanders, B. N.; Hohn, K. L.; Sorensen, C. M.

    2015-08-01

    A unique approach was developed to produce highly oxygenated graphene nanosheets (OGNs) by solution-based oxidation of the pristine graphene nanosheets (GNs) prepared via a controlled detonation of acetylene with oxygen. The produced OGNs are about 250 nm in size and are hydrophilic in nature. The C/O ratio was dramatically reduced from 49:1 in the pristine GNs to about 1:1 in OGNs, as determined by X-ray photoelectron spectroscopy. This C/O in OGNs is the least ever found in all oxidized graphitic materials that have been reported. Thus, the OGNs produced from the detonated GNs with such high degree of oxidation herein yield a novel and promising material for future applications.

  20. A Study of Oxides for Solid Oxide Cells

    NASA Astrophysics Data System (ADS)

    Comets, Olivier

    As the world energy consumption increases, it is a question of global health to increase energy production efficiency and to reduce CO2 emissions. In that respect, solid oxide cells are solid state devices that convert directly fuel into electricity, or vice versa. In fact, when run in fuel cell mode, such devices produce electricity with efficiency up to twice that of current natural gas power plants. However, systems equipped with them have only seen limited commercialization owing to issues of cost, durability, and performance. In this thesis, three different aspects of solid oxide cells are studied. First, the effects of stress on the properties of mixed ionic electronic conducting oxides are considered. Such oxides can be used as electrode materials, where they are often subject to large stresses, which can, in turn, affect their performance. Hence, understanding the relationship between stress and properties in such materials is crucial. Non-stoichiometry in strontium substituted lanthanum cobaltite is found to increase under tension and to decrease under compression. Then, degradation taking place when the cell is run in electrolysis mode is discussed. A high current allows for a high production rate of hydrogen gas. However, this can also lead to oxygen bubble nucleating in the electrolyte and subsequent degradation of the cell. The analysis conducted here shows that such nucleation phenomenon can be avoided by keeping the overpotential at the oxygen electrode below a critical value. Finally, the growth and coarsening of catalyst nanoparticles at the surface of an oxide is studied. Scientists have developed new oxides for anodes in which a catalyst material is dissolved and exsolves under operating conditions. As the performance of the cell is controlled by the surface area of the catalyst phase, understanding the kinetics of the growth is critical to predict the performance of the cell. An approach is developed to study the growth of one particle, in the limiting case where only bulk transport is allowed.

  1. Fast Ferrous Heme-NO Oxidation in Nitric Oxide Synthases

    PubMed Central

    Tejero, Jess; Santolini, Jrme; Stuehr, Dennis J.

    2009-01-01

    During catalysis, the heme in nitric oxide synthase (NOS) binds NO before releasing it to the environment. Oxidation of the NOS ferrous heme-NO complex by O2 is key for catalytic cycling, but the mechanism is unclear. We utilized stopped-flow methods to study reaction of O2 with ferrous heme-NO complexes of the inducible and neuronal NOS enzymes. We found that the reaction does not involve heme-NO dissociation, but instead proceeds by a rapid, direct reaction of O2 with the ferrous heme-NO complex. This behavior is novel and may distinguish heme-thiolate enzymes like NOS from related heme proteins. PMID:19691141

  2. Solid oxide electrochemical reactor science.

    SciTech Connect

    Sullivan, Neal P.; Stechel, Ellen Beth; Moyer, Connor J.; Ambrosini, Andrea; Key, Robert J.

    2010-09-01

    Solid-oxide electrochemical cells are an exciting new technology. Development of solid-oxide cells (SOCs) has advanced considerable in recent years and continues to progress rapidly. This thesis studies several aspects of SOCs and contributes useful information to their continued development. This LDRD involved a collaboration between Sandia and the Colorado School of Mines (CSM) ins solid-oxide electrochemical reactors targeted at solid oxide electrolyzer cells (SOEC), which are the reverse of solid-oxide fuel cells (SOFC). SOECs complement Sandia's efforts in thermochemical production of alternative fuels. An SOEC technology would co-electrolyze carbon dioxide (CO{sub 2}) with steam at temperatures around 800 C to form synthesis gas (H{sub 2} and CO), which forms the building blocks for a petrochemical substitutes that can be used to power vehicles or in distributed energy platforms. The effort described here concentrates on research concerning catalytic chemistry, charge-transfer chemistry, and optimal cell-architecture. technical scope included computational modeling, materials development, and experimental evaluation. The project engaged the Colorado Fuel Cell Center at CSM through the support of a graduate student (Connor Moyer) at CSM and his advisors (Profs. Robert Kee and Neal Sullivan) in collaboration with Sandia.

  3. Cadmium stress: an oxidative challenge.

    PubMed

    Cuypers, Ann; Plusquin, Michelle; Remans, Tony; Jozefczak, Marijke; Keunen, Els; Gielen, Heidi; Opdenakker, Kelly; Nair, Ambily Ravindran; Munters, Elke; Artois, Tom J; Nawrot, Tim; Vangronsveld, Jaco; Smeets, Karen

    2010-10-01

    At the cellular level, cadmium (Cd) induces both damaging and repair processes in which the cellular redox status plays a crucial role. Being not redox-active, Cd is unable to generate reactive oxygen species (ROS) directly, but Cd-induced oxidative stress is a common phenomenon observed in multiple studies. The current review gives an overview on Cd-induced ROS production and anti-oxidative defense in organisms under different Cd regimes. Moreover, the Cd-induced oxidative challenge is discussed with a focus on damage and signaling as downstream responses. Gathering these data, it was clear that oxidative stress related responses are affected during Cd stress, but the apparent discrepancies observed in between the different studies points towards the necessity to increase our knowledge on the spatial and temporal ROS signature under Cd stress. This information is essential in order to reveal the exact role of Cd-induced oxidative stress in the modulation of downstream responses under a diverse array of conditions. PMID:20361350

  4. [Behavioral effects of oxidative stress].

    PubMed

    Saginadze, N; Sakandelidze, R; Mitagvariya, N

    2015-03-01

    It is known that oxidative stress is involved in the development of many pathological processes, but at the same time it became clear that it can play a significant role in processes of physiological adaptation. There are suggestions that oxidative stress can make a significant contribution to the disorders of learning and memory processes. This assumption served as a basis of this study, in which we tried to reveal the effects of low and high-level oxidative stress on behavior of rats in a multi-way maze. As an experimental model of oxidative stress, induced by hydrogen peroxide (H2O2) we used oral administration of 0.1 and 0.2% aqueous solution of H2O2. It was found that animals treated with 0.1% hydrogen peroxide, significantly increased their behavioral activity and in the stage of "automatic behavior" they passed all the maze twice as fast as animals from the control group. But in case of 0.2% H2O2 locomotor activity of animals decreased sharply and for maze passing they spent in average 4-fold more time in comparison with the control group. In our opinion, the first dose of stress was within the range of hormetic mechanism's stimulation, but increased dose, led to its inhibition, which is a classic manifestation of hormetic effects of oxidative stress. PMID:25879564

  5. Oxidation of low cobalt alloys

    NASA Technical Reports Server (NTRS)

    Barrett, C. A.

    1982-01-01

    Four high temperature alloys: U-700, Mar M-247, Waspaloy and PM/HIP U-700 were modified with various cobalt levels ranging from 0 percent to their nominal commercial levels. The alloys were then tested in cyclic oxidation in static air at temperatures ranging from 1000 to 1150 C at times from 500 to 100 1 hour cycles. Specific weight change with time and X-ray diffraction analyses of the oxidized samples were used to evaluate the alloys. The alloys tend to be either Al2O3/aluminate spinel or Cr2O3/chromite spinel formers depending on the Cr/Al ratio in the alloy. Waspaloy with a ratio of 15:1 is a strong Cr2O3 former while this U-700 with a ratio of 3.33:1 tends to form mostly Cr2O3 while Mar M-247 with a ratio of 1.53:1 is a strong Al2O3 former. The best cyclic oxidation resistance is associated with the Al2O3 formers. The cobalt levels appear to have little effect on the oxidation resistance of the Al2O3/aluminate spinel formers while any tendency to form Cr2O3 is accelerated with increased cobalt levels and leads to increased oxidation attack.

  6. Space flight and oxidative stress

    NASA Technical Reports Server (NTRS)

    Stein, T. P.

    2002-01-01

    Space flight is associated with an increase in oxidative stress after return to 1g. The effect is more pronounced after long-duration space flight. The effects lasts for several weeks after landing. In humans there is increased lipid peroxidation in erythrocyte membranes, reduction in some blood antioxidants, and increased urinary excretion of 8-iso-prostaglandin F(2alpha) and 8-oxo-7,8 dihydro-2 deoxyguanosine. Isoprostane 8-iso-prostaglandin F(2alpha) and 8-oxo-7,8 dihydro-2 deoxyguanosine are markers for oxidative damage to lipids and DNA, respectively. The changes have been attributed to a combination of the energy deficiency that occurs during flight and substrate competition for amino acids occurring between repleting muscle and other tissues during the recovery phase. The observations in humans have been complemented by rodent studies. Most rodent studies showed increased production of lipid peroxidation products postflight and decreased antioxidant enzyme activity postflight. The rodent observations were attributed to the stress associated with reentry into Earth's gravity. Decreasing the imbalance between the production of endogenous oxidant defenses and oxidant production by increasing the supply of dietary antioxidants may lessen the severity of the postflight increase in oxidative stress.

  7. Cardiopulmonary Bypass and Oxidative Stress

    PubMed Central

    Zakkar, Mustafa; Guida, Gustavo; Suleiman, M-Saadeh; Angelini, Gianni D.

    2015-01-01

    The development of the cardiopulmonary bypass (CPB) revolutionized cardiac surgery and contributed immensely to improved patients outcomes. CPB is associated with the activation of different coagulation, proinflammatory, survival cascades and altered redox state. Haemolysis, ischaemia, and perfusion injury and neutrophils activation during CPB play a pivotal role in oxidative stress and the associated activation of proinflammatory and proapoptotic signalling pathways which can affect the function and recovery of multiple organs such as the myocardium, lungs, and kidneys and influence clinical outcomes. The administration of agents with antioxidant properties during surgery either intravenously or in the cardioplegia solution may reduce ROS burst and oxidative stress during CPB. Alternatively, the use of modified circuits such as minibypass can modify both proinflammatory responses and oxidative stress. PMID:25722792

  8. Cellulose degradation by oxidative enzymes

    PubMed Central

    Dimarogona, Maria; Topakas, Evangelos; Christakopoulos, Paul

    2012-01-01

    Enzymatic degradation of plant biomass has attracted intensive research interest for the production of economically viable biofuels. Here we present an overview of the recent findings on biocatalysts implicated in the oxidative cleavage of cellulose, including polysaccharide monooxygenases (PMOs or LPMOs which stands for lytic PMOs), cellobiose dehydrogenases (CDHs) and members of carbohydrate-binding module family 33 (CBM33). PMOs, a novel class of enzymes previously termed GH61s, boost the efficiency of common cellulases resulting in increased hydrolysis yields while lowering the protein loading needed. They act on the crystalline part of cellulose by generating oxidized and non-oxidized chain ends. An external electron donor is required for boosting the activity of PMOs. We discuss recent findings concerning their mechanism of action and identify issues and questions to be addressed in the future. PMID:24688656

  9. Fundamentals of metal oxide catalysis

    NASA Astrophysics Data System (ADS)

    Nair, Hari

    The properties of metal oxide catalysts and hence, catalytic activity are highly dependent on the composition and structure of these oxides. This dissertation has 3 parts -- all directed towards understanding relationships between structure, composition and activity in metal oxide catalysts. The first part of this dissertation focuses on supported metal oxide catalysts of tungsten, vanadium and molybdenum. Mechanisms are proposed for ethanol oxidative dehydrogenation which is used to probe the acidity and reducibility of these oxide catalysts. These studies are then used to develop a novel method to quantify active redox sites and determine the nature of the active site on these catalysts -- our results show that the intrinsic redox turn-over frequency is independent of the nature of the metal oxide and its loading and that the actual rate obtained over an oxide is only a function of the number of removable oxygen atoms linking the metal to the support. The extension of Ultraviolet-visible Diffuse Reflectance Spectroscopy (UV-vis DRS) to the study of active oxide domains in binary oxide catalysts is demonstrated for distinguishing between interacting and non-interacting domains in binary MoO x-WOx catalysts on alumina. We show also how the rigorous analysis of pre-edge features, absorption white-line intensity and the full width at half maximum of the white-line in X-ray Absorption Spectra provide determinants for metal atom coordination and domain size in supported metal oxide catalysts. The second part of this work looks at effects of structure variations on the activity of polyoxometalate catalysts that are promising for the production of Methacrylic Acid from Isobutane. The use of these catalysts is limited by structural changes that impact their performance -- an "activation" period is required before the catalysts become active for methacrylic acid production and structural changes also lead to degradation of the catalyst, which are also seen during thermal degradation. The affect of reaction conditions on the lifetime of these catalysts is investigated. The structural changes occurring in these catalysts are studied during thermal degradation at the bulk-scale (using UV-vis DRS, XAS and X-ray Diffraction) and at the atomic-scale (using High-Resolution Transmission Electron Microscopy). These studies show that the actual mechanism of structural reorganization occurs through a twinning process which eventually leads to MoO3, which is inactive for methacrylic acid production. This gives new insight into how to make these catalysts commercially attractive. Finally, the design and fabrication of a micro-reactor to perform complete spectroscopic and reactive characterization of supported metal oxide catalysts is presented; we aim to integrate semiconductor microfabrication technology with conventional spectroscopic tools to create cost-effective, simple and flexible tools for catalytic studies.

  10. Aromatic-radical oxidation kinetics

    SciTech Connect

    Not Available

    1992-01-01

    Research progress in three areas is described. Progress achieved in the extensive experimental investigation of the oxidation and pyrolysis of cyclopentadiene is summarized first. The mechanistic implications of the experimental work are also discussed. An overview is given of the successful research effort devoted to modelling flow reactor toluene and benzene oxidation data. As mentioned above, one of the ultimate goals of this research is to develop a comprehensive, detailed chemical kinetic model of aromatics oxidation. The success already achieved in this effort augurs well for reaching the broader goal. The toluene/benzene model, however, does have a number of shortcomings which suggest the need for further experiments. A description is given of attempts to predict the laminar flame speeds of toluene and benzene. The difficulties encountered and the solutions found highlight the need of an examination of certain chemical steps that impact most the energy release of a burning aromatic fuel.

  11. Graphite Oxidation Thermodynamics/Reactions

    SciTech Connect

    Propp, W.A.

    1998-09-01

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

  12. [Oxidative stress on idiopathic osteonecrosis].

    PubMed

    Matsumoto, Tadami; Kitamura, Kenji; Ichiseki, Touru; Kaneuji, Ayumi; Sugimori, Tanzo

    2007-06-01

    The increasing incidence of steroid-induced osteonecrosis of the femoral head is a recent and emerging problem. In-depth pathogenesis, however, has not been well understood. We focused on oxidative stress, which was reported to be involved in many diseases, and conducted animal studies to investigate it. Our results from the rabbit model of steroid-induced osteonecrosis demonstrated that administration of steroids caused oxidative damage in bones, and the administration of glutathione reduced the incidence of osteonecrosis. We were also the first to have successfully induced osteonecrosis in rats by administering buthionine sulfoximine (BSO) . The results indicated the involvement of oxidative stress in the development of osteonecrosis and may contribute to elucidating the underlying mechanisms and prevention of the pathogenesis of steroid-induced osteonecrosis. PMID:17548928

  13. Silicon oxidation in fluoride solutions

    NASA Technical Reports Server (NTRS)

    Sancier, K. M.; Kapur, V.

    1980-01-01

    Silicon is produced in a NaF, Na2SiF6, and Na matrix when SiF4 is reduced by metallic sodium. Hydrogen is evolved during acid leaching to separate the silicon from the accompanying reaction products, NaF and Na2SiF6. The hydrogen evolution reaction was studied under conditions simulating leaching conditions by making suspensions of the dry silicon powder in aqueous fluoride solutions. The mechanism for the hydrogen evolution is discussed in terms of spontaneous oxidation of silicon resulting from the cooperative effects of (1) elemental sodium in the silicon that reacts with water to remove a protective silica layer, leaving clean reactive silicon, and (2) fluoride in solution that complexes with the oxidized silicon in solution and retards formation of a protective hydrous oxide gel.

  14. Patterning by area selective oxidation

    DOEpatents

    Nam, Chang-Yong; Kamcev, Jovan; Black, Charles T.; Grubbs, Robert

    2015-12-29

    Technologies are described for methods for producing a pattern of a material on a substrate. The methods may comprise receiving a patterned block copolymer on a substrate. The patterned block copolymer may include a first polymer block domain and a second polymer block domain. The method may comprise exposing the patterned block copolymer to a light effective to oxidize the first polymer block domain in the patterned block copolymer. The method may comprise applying a precursor to the block copolymer. The precursor may infuse into the oxidized first polymer block domain and generate the material. The method may comprise applying a removal agent to the block copolymer. The removal agent may be effective to remove the first polymer block domain and the second polymer block domain from the substrate, and may not be effective to remove the material in the oxidized first polymer block domain.

  15. OXIDATION OF NITROPYRIN TO 6-CHOLORPICOLINIC ACID BY THE AMMONIA-OXIDIZING BACTERIUM NOSTROSOMAS EUROPAEA

    EPA Science Inventory

    Suspensions of Nitrosomonas europaea catalyzed the oxidation of the commercial nitrification inhibitor nitrapyrin [2-chloro-6-(trichloromethyl)-pyridine]. apid oxidation of nitrapyrin (at a concentration of 10 uM) required the concomitant oxidation of ammonia, hydroxylamine, or h...

  16. Adaptive oxide electronics: A review

    NASA Astrophysics Data System (ADS)

    Ha, Sieu D.; Ramanathan, Shriram

    2011-10-01

    Novel information processing techniques are being actively explored to overcome fundamental limitations associated with CMOS scaling. A new paradigm of adaptive electronic devices is emerging that may reshape the frontiers of electronics and enable new modalities. Creating systems that can learn and adapt to various inputs has generally been a complex algorithm problem in information science, albeit with wide-ranging and powerful applications from medical diagnosis to control systems. Recent work in oxide electronics suggests that it may be plausible to implement such systems at the device level, thereby drastically increasing computational density and power efficiency and expanding the potential for electronics beyond Boolean computation. Intriguing possibilities of adaptive electronics include fabrication of devices that mimic human brain functionality: the strengthening and weakening of synapses emulated by electrically, magnetically, thermally, or optically tunable properties of materials.In this review, we detail materials and device physics studies on functional metal oxides that may be utilized for adaptive electronics. It has been shown that properties, such as resistivity, polarization, and magnetization, of many oxides can be modified electrically in a non-volatile manner, suggesting that these materials respond to electrical stimulus similarly as a neural synapse. We discuss what device characteristics will likely be relevant for integration into adaptive platforms and then survey a variety of oxides with respect to these properties, such as, but not limited to, TaOx, SrTiO3, and Bi4-xLaxTi3O12. The physical mechanisms in each case are detailed and analyzed within the framework of adaptive electronics. We then review theoretically formulated and current experimentally realized adaptive devices with functional oxides, such as self-programmable logic and neuromorphic circuits. Finally, we speculate on what advances in materials physics and engineering may be needed to realize the full potential of adaptive oxide electronics.

  17. Method for hot pressing beryllium oxide articles

    DOEpatents

    Ballard, Ambrose H.; Godfrey, Jr., Thomas G.; Mowery, Erb H.

    1988-01-01

    The hot pressing of beryllium oxide powder into high density compacts with little or no density gradients is achieved by employing a homogeneous blend of beryllium oxide powder with a lithium oxide sintering agent. The lithium oxide sintering agent is uniformly dispersed throughout the beryllium oxide powder by mixing lithium hydroxide in an aqueous solution with beryllium oxide powder. The lithium hydroxide is converted in situ to lithium carbonate by contacting or flooding the beryllium oxide-lithium hydroxide blend with a stream of carbon dioxide. The lithium carbonate is converted to lithium oxide while remaining fixed to the beryllium oxide particles during the hot pressing step to assure uniform density throughout the compact.

  18. Catalyst for Oxidation of Volatile Organic Compounds

    NASA Technical Reports Server (NTRS)

    Wood, George M. (Inventor); Upchurch, Billy T. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Kielin, Erik J. (Inventor); Brown, Kenneth G. (Inventor); Schyryer, Jacqueline L. (Inventor); DAmbrosia, Christine M. (Inventor)

    2000-01-01

    Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

  19. Initial oxidation of polycrystalline Permalloy surface

    NASA Astrophysics Data System (ADS)

    Salou, M.; Lescop, B.; Rioual, S.; Lebon, A.; Youssef, J. Ben; Rouvellou, B.

    2008-09-01

    X-ray photoelectron spectroscopy (XPS) and work-function measurements were used in combination to investigate the initial steps of Permalloy (Ni 80Fe 20) oxidation at room temperature. They showed that, after oxygen saturation, the surface is covered by nickel oxide (NiO), nickel hydroxide (Ni(OH) 2) and iron oxides (Fe xO y), and there is no preferential oxidation. Iron oxidation proceeds through the formation of FeO (Fe 2+) followed with Fe 2O 3 growth (Fe 3+). The oxidation is governed by a dissociative Langmuir-type oxidation: the sticking coefficient is decreasing over oxygen exposure. Oxidation continues by oxygen dissolution into the first layers to form a nano-oxide of about 8 in thickness.

  20. Oxidative Stress in Atopic Dermatitis

    PubMed Central

    Ji, Hongxiu; Li, Xiao-Kang

    2016-01-01

    Atopic dermatitis (AD) is a chronic pruritic skin disorder affecting many people especially young children. It is a disease caused by the combination of genetic predisposition, immune dysregulation, and skin barrier defect. In recent years, emerging evidence suggests oxidative stress may play an important role in many skin diseases and skin aging, possibly including AD. In this review, we give an update on scientific progress linking oxidative stress to AD and discuss future treatment strategies for better disease control and improved quality of life for AD patients. PMID:27006746

  1. Solid oxide fuel cell generator

    DOEpatents

    Draper, R.; George, R.A.; Shockling, L.A.

    1993-04-06

    A solid oxide fuel cell generator has a pair of spaced apart tubesheets in a housing. At least two intermediate barrier walls are between the tubesheets and define a generator chamber between two intermediate buffer chambers. An array of fuel cells have tubes with open ends engaging the tubesheets. Tubular, axially elongated electrochemical cells are supported on the tubes in the generator chamber. Fuel gas and oxidant gas are preheated in the intermediate chambers by the gases flowing on the other side of the tubes. Gas leakage around the tubes through the tubesheets is permitted. The buffer chambers reentrain the leaked fuel gas for reintroduction to the generator chamber.

  2. Oxidative calcium release from catechol.

    PubMed

    Riley, Patrick A; Stratford, Michael R L

    2015-04-01

    Oxidation of 4-methylcatechol previously exposed to aqueous calcium chloride was shown by ion chromatography to be associated with release of calcium ions. The catechol was oxidised to the corresponding orthoquinone by the use of tyrosinase from Agaricus bisporus. The oxidative release of calcium from the catechol is ascribed to the diminution of the available hydroxyl functions able to act as chelating groups. Our results suggest that the redox status of melanin may regulate calcium binding and influence calcium levels in pigmented cells. PMID:25740160

  3. Oxidative Reactions with Nonaqueous Enzymes

    SciTech Connect

    Jonathan S. Dordick; Douglas Clark; Brian H Davison; Alexander Klibanov

    2001-12-30

    The objective of this work is to demonstrate a proof-of-concept of enzymatic oxidative processing in nonaqueous media using alkene epoxidation and phenolic polymerization as relevant targets. This project will provide both the fundamental and applied investigations necessary to initiate the implementation of oxidative biocatalysts as commercially relevant alternatives to chemical processing in general, and to phenolic polymerizations and alkene epoxidation specifically. Thus, this work will address the Bioprocessing Solicitation Area to: (1) makes major improvements to phenolic polymerization and alkene epoxidation technologies; (2) is expected to be cost competitive with competing conventional processes; and (3) produces higher yields with less waste.

  4. Solid oxide fuel cell generator

    DOEpatents

    Draper, Robert (Churchill Boro, PA); George, Raymond A. (Pittsburgh, PA); Shockling, Larry A. (Plum Borough, PA)

    1993-01-01

    A solid oxide fuel cell generator has a pair of spaced apart tubesheets in a housing. At least two intermediate barrier walls are between the tubesheets and define a generator chamber between two intermediate buffer chambers. An array of fuel cells have tubes with open ends engaging the tubesheets. Tubular, axially elongated electrochemical cells are supported on the tubes in the generator chamber. Fuel gas and oxidant gas are preheated in the intermediate chambers by the gases flowing on the other side of the tubes. Gas leakage around the tubes through the tubesheets is permitted. The buffer chambers reentrain the leaked fuel gas for reintroduction to the generator chamber.

  5. Aromatic-radical oxidation chemistry

    SciTech Connect

    Glassman, I.; Brezinsky, K.

    1993-12-01

    The research effort has focussed on discovering an explanation for the anomalously high CO{sub 2} concentrations observed early in the reaction sequence of the oxidation of cyclopentadiene. To explain this observation, a number of plausible mechanisms have been developed which now await experimental verification. One experimental technique for verifying mechanisms is to probe the reacting system by perturbing the radical concentrations. Two forms of chemical perturbation of the oxidation of cyclopentadiene were begun during this past year--the addition of NO{sub 2} and CO to the reacting mixture.

  6. Ultrafast graphene oxide humidity sensors.

    PubMed

    Borini, Stefano; White, Richard; Wei, Di; Astley, Michael; Haque, Samiul; Spigone, Elisabetta; Harris, Nadine; Kivioja, Jani; Ryhänen, Tapani

    2013-12-23

    Sensors allow an electronic device to become a gateway between the digital and physical worlds, and sensor materials with unprecedented performance can create new applications and new avenues for user interaction. Graphene oxide can be exploited in humidity and temperature sensors with a number of convenient features such as flexibility, transparency and suitability for large-scale manufacturing. Here we show that the two-dimensional nature of graphene oxide and its superpermeability to water combine to enable humidity sensors with unprecedented response speed (∼30 ms response and recovery times). This opens the door to various applications, such as touchless user interfaces, which we demonstrate with a 'whistling' recognition analysis. PMID:24206232

  7. Oxidative stress and immunotoxicity induced by graphene oxide in zebrafish.

    PubMed

    Chen, Minjie; Yin, Junfa; Liang, Yong; Yuan, Shaopeng; Wang, Fengbang; Song, Maoyong; Wang, Hailin

    2016-05-01

    Graphene oxide (GO) has been extensively explored as a promising nanomaterial for applications in biology because of its unique properties. Therefore, systematic investigation of GO toxicity is essential to determine its fate in the environment and potential adverse effects. In this study, acute toxicity, oxidative stress and immunotoxicity of GO were investigated in zebrafish. No obvious acute toxicity was observed when zebrafish were exposed to 1, 5, 10 or 50mg/L GO for 14 days. However, a number of cellular alterations were detected by histological analysis of the liver and intestine, including vacuolation, loose arrangement of cells, histolysis and disintegration of cell boundaries. As evidence for oxidative stress, malondialdehyde levels and superoxide dismutase and catalase activities were increased and glutathione content was decreased in the liver after treatment with GO. GO treatment induced an immune response in zebrafish, as demonstrated by increased expression of tumor necrosis factor α, interleukin-1 β, and interleukin-6 in the spleen. Our findings demonstrated that GO administration in an aquatic system can cause oxidative stress and immune toxicity in adult zebrafish. To our knowledge, this is the first report of immune toxicity of GO in zebrafish. PMID:26921726

  8. Diabetes, oxidative stress, nitric oxide and mitochondria function.

    PubMed

    Friederich, Malou; Hansell, Peter; Palm, Fredrik

    2009-05-01

    The role of altered mitochondria function has recently emerged as an important mechanism for the development of diabetic complications. Altered mitochondria function has also been implicated in the ageing process, defective insulin secretion, hypertension, arteriosclerosis, ischemia-reperfusion injury and apoptosis. Normally, the mitochondria are associated with ATP production using primarily pyruvate as the substrate, but recent reports indicate that tissue specific preferences exist. Also, the mitochondria are a substantial source of superoxide production, preferentially during states of elevated intracellular glucose concentrations. The mitochondria function is regulated by several factors including nitric oxide, oxidative stress, mammalian target of rapamycin, ADP and P(i) availability, which result in a complex regulation of ATP production and oxygen consumption, but also superoxide generation. These factors seem to be tissue specific, which warrants a more diverse mechanistic model applying to that specific tissue or cell type. This review presents the basic functions of the mitochondria and focuses on the complex interplay between oxidative stress, nitric oxide and uncoupling proteins in regulating mitochondria function with special focus on diabetes-induced alterations occurring on the mitochondria level. PMID:19442097

  9. Hydrous metal oxide catalysts for oxidation of hydrocarbons

    SciTech Connect

    Miller, J.E.; Dosch, R.G.; McLaughlin, L.I.

    1993-07-01

    This report describes work performed at Sandia under a CRADA with Shell Development of Houston, Texas aimed at developing hydrous metal oxide (HMO) catalysts for oxidation of hydrocarbons. Autoxidation as well as selective oxidation of 1-octene was studied in the presence of HMO catalysts based on known oxidation catalysts. The desired reactions were the conversion of olefin to epoxides, alcohols, and ketones, HMOs seem to inhibit autoxidation reactions, perhaps by reacting with peroxides or radicals. Attempts to use HMOs and metal loaded HMOs as epoxidation catalysts were unsuccessful, although their utility for this reaction was not entirely ruled out. Likewise, alcohol formation from olefins in the presence of HMO catalysts was not achieved. However, this work led to the discovery that acidified HMOs can lead to carbocation reactions of hydrocarbons such as cracking. An HMO catalyst containing Rh and Cu that promotes the reaction of {alpha}-olefins with oxygen to form methyl ketones was identified. Although the activity of the catalyst is relatively low and isomerization reactions of the olefin simultaneously occur, results indicate that these problems may be addressed by eliminating mass transfer limitations. Other suggestions for improving the catalyst are also made. 57 refs.

  10. IRON OXIDE NANOPARTICLE-INDUCED OXIDATIVE STRESS AND INFLAMMATION

    EPA Science Inventory

    1. Nanoparticle Physicochemical Characterizations
    2. We first focused on creating NP systems that could be used to test our hypotheses and assessing their stability in aqueous media. The iron oxide NP systems were not stable in cell culture medium o...

    3. SELECTIVE OXIDATION IN SUPERCRITICAL CARBON DIOXIDE USING CLEAN OXIDANTS

      EPA Science Inventory

      We have systematically investigated heterogeneous catalytic oxidation of different substrates in supercritical carbon dioxide (SC-CO2). Three types of catagysts: a metal complex, 0.5% platinum g-alumina and 0.5% palladium g-alumina were used at a pressure of 200 bar, temperatures...

    4. Nanoscale oxidation of Cu100: oxide morphology and surface reactivity.

      PubMed

      Lampimki, M; Lahtonen, K; Hirsimki, M; Valden, M

      2007-01-21

      Surface oxidation of Cu(100) in O(2) has been investigated in situ by x-ray photoelectron spectroscopy, x-ray induced Auger electron spectroscopy (XAES), and scanning tunneling microscopy (STM) as a function of surface temperature (T(S)=303-423 K) and O(2) pressure (p(O(2) )=3.7 x 10(-2)-213 mbars). Morphology of the oxide on the surface and in the near surface layers is characterized by utilizing STM and the inelastic electron background of the XAES O KLL signal. Analysis of the peak shape of the XAES Cu LMM facilitates the quantification of Cu, Cu(2)O, and CuO surface concentrations. The authors conclude that the surface oxidation of Cu(100) proceeds in three distinct steps: (1) Dissociative adsorption of O(2) and the onset of Cu-(2 square root 2 x square root 2)R45 degrees -O (theta(O)=0.5 ML) surface reconstruction, (2) initial formation of Cu(2)O and the appearance of 1.8 A high elongated islands that also adopt the Cu-(2 square root 2 x square root 2)R45 degrees -O structure, and (3) formation of highly corrugated Cu-O islands which together with the surface reconstruction strongly enhance the reactivity of the surface towards further oxide formation. Both Cu(2)O and CuO formations are enhanced by increased surface temperature, but no pressure dependence can be seen. PMID:17249892

    5. Oxidative stress inhibition and oxidant activity by fibrous clays.

      PubMed

      Cervini-Silva, Javiera; Nieto-Camacho, Antonio; Gómez-Vidales, Virginia

      2015-09-01

      Fibrous clays (sepiolite, palygorskite) are produced at 1.2m tonnes per year and have a wide range of industrial applications needing to replace long-fibre length asbestos. However, information on the beneficial effects of fibrous clays on health remains scarce. This paper reports on the effect of sepiolite (Vallecas, Spain) and palygorskite (Torrejón El Rubio, Spain) on cell damage via oxidative stress (determined as the progress of lipid peroxidation, LP). The extent of LP was assessed using the Thiobarbituric Acid Reactive Substances assay. The oxidant activity by fibrous clays was quantified using Electron-Paramagnetic Resonance. Sepiolite and palygorskite inhibited LP, whereby corresponding IC50 values were 6557±1024 and 4250±289μgmL(-1). As evidenced by dose-response experiments LP inhibition by palygorskite was surface-controlled. Fibrous clay surfaces did not stabilize HO species, except for suspensions containing 5000μgmL(-1). A strong oxidant (or weak anti-oxidant) activity favours the inhibition of LP by fibrous clays. PMID:26071933

    6. Facile Access to Graphene Oxide from Ferro-Induced Oxidation

      PubMed Central

      Yu, Chao; Wang, Cai-Feng; Chen, Su

      2016-01-01

      Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers’ method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials. PMID:26818784

    7. Graphene oxide and H2 production from bioelectrochemical graphite oxidation

      NASA Astrophysics Data System (ADS)

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

      2015-11-01

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

    8. Graphene oxide and H2 production from bioelectrochemical graphite oxidation

      PubMed Central

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

      2015-01-01

      Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES. PMID:26573014

    9. Facile Access to Graphene Oxide from Ferro-Induced Oxidation.

      PubMed

      Yu, Chao; Wang, Cai-Feng; Chen, Su

      2016-01-01

      Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers' method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials. PMID:26818784

    10. Facile Access to Graphene Oxide from Ferro-Induced Oxidation

      NASA Astrophysics Data System (ADS)

      Yu, Chao; Wang, Cai-Feng; Chen, Su

      2016-01-01

      Methods allowing the oxidation of graphite to graphene oxide (GO) are vital important for the production of graphene from GO. This oxidation reaction has mainly relied on strong acid strategy for 174 years, which circumvents issues associated with toxicity of reagent and product, complex post-treatment, high cost and waste generation. Here, we report a green route for performing this oxidization reaction via a ferro-induced strategy, with use of water, potassium ferrate (Fe(VI)) and hydrogen peroxide (H2O2) as reagents, to produce about 65% yield of GO (vs. 40% for Hummers’ method, the most commonly used concentrated acid strategy) and non-toxic by-products. Moreover, GO produced from this new method shows equivalent performance to those reported previously. This H2SO4-free strategy makes it possible to process graphite into GO in a safe, low-cost, time-saving, energy-efficient and eco-friendly pathway, opening a promising avenue for the large-scale production of GO and GO-based materials.

    11. Oxidation mechanisms for alloys in single-oxidant gases

      SciTech Connect

      Whittle, D.P.

      1981-03-01

      Scales formed on alloys invariably contain the alloy constituents in a ratio different from that in the alloy, owing to the differing thermodynamic tendencies of the alloy components to react with the oxidant and to differences in diffusion rates in scale and alloy phases. This complex interrelationship between transport rates and the thermodynamics of the alloy-oxidant system can be analyzed using multicomponent diffusion theory when transport-controlled growth of single or multi-layered scales occurs. In particular, the superimposition of the diffusion data on an isothermal section of the appropriate phase diagram indicates the likely morphologies of the reaction products, including the sequence of phases found in the scale, the occurrence of internal oxidation and the development of an irregular metal/scale interface. The scale morphologies on alloys are also time-dependent: there is an initial transient stage, a steady state period, and a final breakdown, the latter often related to mechanical influences such as scale adherence, spallation, thermal or mechanical stresses and void formation. Mechanical influences have a more devastating effect in alloy oxidation due to the changes in alloy surface composition during the steady state period.

    12. Volatilization of oxides during oxidation of some superalloys at 1200 C

      NASA Technical Reports Server (NTRS)

      Zaplatynsky, I.

      1977-01-01

      Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541 chromium was found to be the main metallic element in the oxide scales.