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Sample records for heat-activated persulfate oxidation

  1. Heat-activated persulfate oxidation of methyl- and ethyl-parabens: Effect, kinetics, and mechanism.

    PubMed

    Chen, Yiqun; Deng, Pinya; Xie, Pengchao; Shang, Ran; Wang, Zongping; Wang, Songlin

    2017-02-01

    We evaluated the degradation of methylparaben (MeP) and ethylparaben (EtP), two representative parabens, using the heat-activated persulfate system in a laboratory. Both sulfate and hydroxyl radicals contributed to the removal of the two parabens. The degradations of both MeP and EtP were improved by increasing the heating temperature or persulfate dose in accordance with a pseudo-first-order reaction model. The oxidation efficiency of parabens was found to be pH-dependent; decreasing in the order pH 5.0 > 7.0 > 9.0. The presence of chloride, bicarbonate, or humic acid was found to inhibit the degradation of the two parabens to some extent because of competition for the reactive radicals, with humic acid having the most serious effect. Dealkylation of the methyl unit, decarboxylation of the carboxylic group, and subsequent hydrolysis are proposed to be involved in the degradation pathway of MeP. The results suggest that the heat-activated persulfate system might be efficiently applied in the treatment of paraben-containing water samples. This was also supported by the results of applying this system to treat a real water sample containing both MeP and EtP.

  2. Transport and Application of Heat-Activated Persulfate for In-situ Chemical Oxidation of Residual Trichloroethylene

    NASA Astrophysics Data System (ADS)

    Quig, L.; Johnson, G. R.

    2015-12-01

    characterizing the overall transport behavior and application of persulfate/heat-activated persulfate in a natural porous media for the ISCO of residual nonaqueous phase liquid, this work aids in improving the implementation of persulfate ISCO systems.

  3. Oxidation of bisphenol A in water by heat-activated persulfate.

    PubMed

    Potakis, Nikolaos; Frontistis, Zacharias; Antonopoulou, Maria; Konstantinou, Ioannis; Mantzavinos, Dionissios

    2016-05-27

    The heat-activated persulfate oxidation of bisphenol A (BPA), a representative endocrine disrupting compound, was investigated with respect to the effect of several process variables on degradation rates. The activation temperature appears to be the single most important parameter, i.e. a temperature increase from 40 to 70 °C results in an 80-fold rate increase. Regarding initial BPA concentration, the reaction follows a pseudo-first order rate expression, where the kinetic constant decreases from 11.5 10(-2) to 3.5 10(-2) min(-1) when BPA concentration increases from 110 to 440 μg/L. Reactions in actual water matrices, such as bottled water and secondary treated wastewater, are slower than in pure water since various organic/inorganic water constituents compete with BPA for being oxidized by the reactive oxidizing species; this was confirmed with experiments in pure water spiked with humic acid or bicarbonate. Interestingly though, the presence of chloride seems to promote BPA degradation. Furthermore, degradation is favored at near-neutral pH and increased sodium persulfate (SPS) concentrations. Experiments at an increased BPA concentration of 20 mg/L were performed to identify transformation by-products (TBPs), as well as assess the mineralization and toxicity of the treated samples. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) revealed the formation of eleven TBPs of BPA and plausible pathways including hydroxylation, oxidation, cleavage and oligomerization reactions are proposed. Mineralization occurs slower than BPA degradation, while the toxicity to marine bacteria Vibrio fischeri increases during the early stages of the reaction but it progressively decreases thereafter.

  4. Degradation of ethyl paraben by heat-activated persulfate oxidation: statistical evaluation of operating factors and transformation pathways.

    PubMed

    Frontistis, Zacharias; Antonopoulou, Maria; Konstantinou, Ioannis; Mantzavinos, Dionissios

    2017-01-01

    A factorial design methodology was implemented to evaluate the importance of ethyl paraben (EP) concentration (500-1500 μg/L), sodium persulfate concentration (400-500 mg/L), temperature (40-60 °C), reaction time (2-30 min), water matrix (pure water or secondary treated wastewater), and initial solution pH (3-9) on EP removal by heat-activated persulfate oxidation. All individual effects, except the solution pH, were statistically significant and so were the second-order interactions of ethyl paraben concentration with temperature or the reaction time. The influence of the water matrix was crucial, and the efficiency of the process was lower in secondary treated wastewater due to the presence of natural organic matter and inorganic salts that compete with ethyl paraben for the reactive oxygen species. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to identify major transformation by-products (TBPs); 13 compounds were detected as TBPs of EP. Degradation occurred through (i) hydroxylation, (ii) dealkylation, and (iii) oligomerization reactions leading to TBPs with ether and biphenyl structures. Oligomerization reactions were found to be the dominant pathway during the first steps of the reaction. The toxicity of 500 μg/L EP in secondary treated wastewater was tested against marine bacteria Vibrio fischeri; toxicity increased during the first minutes due to the production of several TBPs, but it consistently decreased thereafter.

  5. Impact of activation methods on persulfate oxidation of methyl tert-butyl ether.

    PubMed

    Deng, Dayi; Peng, Libin; Guan, Mengyun; Kang, Yuan

    2014-01-15

    To provide guidance on the selection of proper persulfate processes for the remediation of MTBE contaminated groundwater, MTBE aqueous solutions were treated with three common field persulfate processes including heat activated persulfate, Fe(III)-EDTA activated persulfate and alkaline persulfate, respectively. The results were compared with MTBE oxidation by Fenton's reagent and persulfate alone at 25°C. The impact of the activating conditions on the fate of MTBE and its daughter products was investigated. Heat activation at 40°C offered the most rapid removal of MTBE and its daughter products, while Fe(III)-EDTA activation showed higher efficiency of MTBE removal but low removal efficiency of its daughter products. On the other hand, alkaline persulfate showed slower kinetics for the removal of MTBE and less accumulation of the daughter products. Furthermore, tert-butyl alcohol and acetone were observed as the main purgeable daughter products along with a small amount of tert-butyl formate in persulfate oxidation of MTBE, while tert-butyl formate, tert-butyl alcohol and acetone were the main products in Fenton oxidation. Mechanistic analysis suggests that degradation of MTBE by persulfate most likely happens via non-oxygen demand pathways, different from the dominant oxygen demand degradation pathways observed in Fenton oxidation.

  6. 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.

  7. Water temperature significantly impacts the formation of iodinated haloacetamides during persulfate oxidation.

    PubMed

    Chu, Wenhai; Hu, Jianglin; Bond, Tom; Gao, Naiyun; Xu, Bin; Yin, Daqiang

    2016-07-01

    The use of persulfate oxidation processes is receiving increasing interest for the removal of aquatic contaminants. However, it is unknown whether its application in the presence of iodide has the potential to directly form iodinated DBPs. This study investigated formation of six chlorinated, brominated and iodinated di-haloacetamides (DHAcAms) during persulfate oxidation in the presence of bromide and iodide. Formation of the same DHAcAms during chlorination was monitored for comparison. Persulfate oxidation of natural water formed diiodoacetamide (DIAcAm), and heat-activated persulfate, at 45 °C and 55 °C, generated bromoiodoacetamide (BIAcAm) and dibromoacetamide (DBAcAm), besides DIAcAm. At an ambient iodide concentration of 0.3 μM, total DHAcAms increased slightly from 0.43 to 0.57 nM as the water temperature increased from 4 °C to 35 °C, respectively (only DIAcAm detected), then significantly increased to 1.6 nM at 55 °C (DIAcAm, BIAcAm and DBAcAm detected). Equivalent total DHAcAm concentrations in the presence of 3.0 μM iodide were 0.5, 0.91 and 2.1 nM, respectively. Total DHAcAms formed during chlorination, predominantly dichloroacetamide (DCAcAm) and bromochloroacetamide (BCAcAm), were always significantly higher than that during persulfate oxidation. However, an integrated risk assessment showed the toxicity resulting from the DHAcAms was higher during persulfate oxidation than chlorination. An increase in water temperature from 25 °C to 55 °C significantly increased the integrated toxic risk values for both persulfate oxidation and chlorination. Use of persulfate oxidation should be weighed against the formation of high-toxicity iodinated HAcAms in waters with high ambient iodide concentrations.

  8. 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.

  9. Homogeneous and Heterogeneous Photocatalytic Water Oxidation by Persulfate.

    PubMed

    Fukuzumi, Shunichi; Jung, Jieun; Yamada, Yusuke; Kojima, Takahiko; Nam, Wonwoo

    2016-04-20

    Photocatalytic water oxidation by persulfate (Na2 S2 O8 ) with [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a photocatalyst provides a standard protocol to study the catalytic reactivity of water oxidation catalysts. The yield of evolved oxygen per persulfate is regarded as a good index for the catalytic reactivity because the oxidation of bpy of [Ru(bpy)3 ](2+) and organic ligands of catalysts competes with the catalytic water oxidation. A variety of metal complexes act as catalysts in the photocatalytic water oxidation by persulfate with [Ru(bpy)3 ](2+) as a photocatalyst. Herein, the catalytic mechanisms are discussed for homogeneous water oxidation catalysis. Some metal complexes are converted to metal oxide or hydroxide nanoparticles during the photocatalytic water oxidation by persulfate, acting as precursors for the actual catalysts. The catalytic reactivity of various metal oxides is compared based on the yield of evolved oxygen and turnover frequency. A heteropolynuclear cyanide complex is the best catalyst reported so far for the photocatalytic water oxidation by persulfate and [Ru(bpy)3 ](2+) , affording 100 % yield of O2 per persulfate.

  10. Oxidation of atrazine by photoactivated potassium persulfate in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Khandarkhaeva, M. S.; Aseev, D. G.; Sizykh, M. R.; Batoeva, A. A.

    2016-11-01

    General laws of the photochemical oxidation of atrazine by inorganic peroxo compounds under the impact of solar radiation are studied. It is found that almost complete conversion of atrazine can be achieved via photochemical oxidation with persulfate after 120 min, but no deep mineralization is observed. The effect an aqueous matrix has on the processes of atrazine degradation in combined oxidation systems is considered.

  11. Intensification of sonochemical degradation of ammonium perfluorooctanoate by persulfate oxidant.

    PubMed

    Hao, Feifei; Guo, Weilin; Wang, Anqi; Leng, Yanqiu; Li, Helian

    2014-03-01

    Ammonium perfluorooctanoate (APFO) is an emerging environmental pollutant attracting significant attention due to its global distribution, high persistence, and bioaccumulation properties. The decomposition of APFO in aqueous solution with a combination of persulfate oxidant and ultrasonic irradiation was investigated. The effects of operating parameters, such as ultrasonic power, persulfate concentration, APFO concentration, and initial media pH on APFO degradation were discussed. In the absence of persulfate, 35.5% of initial APFO in 46.4 μmol/L solution under ultrasound irradiation, was decomposed rapidly after 120 min with the defluorination ratio reaching 6.73%. In contrast, when 10 mmol/L persulfate was used, 51.2% of initial APFO (46.4 μmol/L) was decomposed and the defluorination ratio reached 11.15% within 120 min reaction time. Enhancement of the decomposition of APFO can be explained by acceleration of substrate decarboxylation, induced by sulfate radical anions formed from the persulfate during ultrasonic irradiation. The SO4(-•)/APFO reactions at the bubble-water interface appear to be the primary pathway for the sonochemical degradation of the perfluorinated surfactants.

  12. Ultrasound assisted, thermally activated persulfate oxidation of coal tar DNAPLs.

    PubMed

    Peng, Libin; Wang, Li; Hu, Xingting; Wu, Peihui; Wang, Xueqing; Huang, Chumei; Wang, Xiangyang; Deng, Dayi

    2016-11-15

    The feasibility of ultrasound assisted, thermally activated persulfate for effective oxidation of twenty 2-6 ringed coal tar PAHs in a biphasic tar/water system and a triphasic tar/soil/water system were investigated and established. The results indicate that ultrasonic assistance, persulfate and elevated reaction temperature are all required to achieve effective oxidation of coal tar PAHs, while the heating needed can be provided by ultrasonic induced heating as well. Further kinetic analysis reveals that the oxidation of individual PAH in the biphasic tar/water system follows the first-order kinetics, and individual PAH oxidation rate is primary determined by the mass transfer coefficients, tar/water interfacial areas, the aqueous solubility of individual PAH and its concentration in coal tar. Based on the kinetic analysis and experimental results, the contributions of ultrasound, persulfate and elevated reaction temperature to PAHs oxidation were characterized, and the effects of ultrasonic intensity and oxidant dosage on PAHs oxidation efficiency were investigated. In addition, the results indicate that individual PAH degradability is closely related to its reactivity as well, and the high reactivity of 4-6 ringed PAHs substantially improves their degradability.

  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 (50°C) 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.

  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.

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

    EPA Science Inventory

    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 ...

  16. Oxidative degradation of propachlor by ferrous and copper ion activated persulfate.

    PubMed

    Liu, C S; Shih, K; Sun, C X; Wang, F

    2012-02-01

    The process of in situ chemical oxidation (ISCO) by persulfate (S(2)O(8)(2-)) can be accelerated by metal ion activation, which more effectively degrades subsurface pollutants by enhancing sulfate radical (SO(4)(-)) generation. This study compared the results of propachlor degradation by Cu(2+) and Fe(2+) activated persulfate and revealed differing degradation kinetics and mechanisms between the two types of activation system. The activation of persulfate by Fe(2+) ions generally resulted in rapid degradation in the early stage, but was accompanied by a dramatic decrease in efficiency due to the rapid depletion of Fe(2+) by the sulfate radicals generated. In contrast, the Cu(2+) activated persulfate had a longer lasting degradation effect and a proportionally greater degradation enhancement at elevated Cu(2+) concentrations. An optimal Fe(2+) concentration should be sought to activate the persulfate, as a high Fe(2+) concentration of 2.5mM or above, as was used in this study, may inhibit propachlor degradation due to the competitive consumption of sulfate radicals by the excess Fe(2+) ions. Higher temperatures (55°C compared with 30°C) resulted in enhanced metal activation, particularly with the Cu(2+) activated system. Furthermore, acidic conditions were found to be more favorable for propachlor degradation by metal activated persulfate. The ecotoxicity of degraded propachlor samples, which was indicated by average well color development (AWCD) for its microbial community activity, was confirmed to be decreased during the degradation processes with these two ions activated persulfate.

  17. Combined remediation of pyrene-contaminated soil with a coupled system of persulfate oxidation and phytoremediation with ryegrass.

    PubMed

    Chen, Xiao; Li, Hongbing; Liu, Xiaoyan; Zhang, Xinying; Liang, Xia; He, Chiquan; Cao, Liya

    2016-10-01

    The in situ chemical oxidation technology (ISCO) and phytoremediation for PAHs have been studied respectively, but few focus on the feasibility of combining persulfate with ryegrass. This literature revealed the effect of persulfate oxidation on the growth of ryegrass and the removal ratios of pyrene in the couple system of persulfate oxidation and phytoremediation. The results demonstrated that half of pyrene in test soil was oxidized by persulfate in 7 days and then the residual pyrene concentration was decreased to a lower level by ryegrass in the following 2 months in oxidation treatment and drip washing and plants (OWP) and oxidation treatment and drip washing and plants and fertilization (OWFP) treatment. Ryegrass could grow well after persulfate oxidation with the oxidized soil washed by water. Ryegrass in OWP and OWFP treatments had higher ratios of overground and underground biomass. However, the seeds of ryegrass cannot germinate when drip washing was omitted. Pyrene together with residual persulfate changed soil enzyme activities. Drip washing and the growth of ryegrass made soil enzyme activities tend to returned to normal levels. Persulfate oxidation and phytoremediation were compatible to make contributions to the dissipation of pyrene. Persulfate oxidation activated by heat had higher removal efficiency of PAHs and phytoremediation could further decrease the pyrene concentration in spiked soil.

  18. Activated Persulfate Oxidation of Perfluorooctanoic Acid (PFOA) in Groundwater under Acidic Conditions

    PubMed Central

    Yin, Penghua; Hu, Zhihao; Song, Xin; Liu, Jianguo; Lin, Na

    2016-01-01

    Perfluorooctanoic acid (PFOA) is an emerging contaminant of concern due to its toxicity for human health and ecosystems. However, successful degradation of PFOA in aqueous solutions with a cost-effective method remains a challenge, especially for groundwater. In this study, the degradation of PFOA using activated persulfate under mild conditions was investigated. The impact of different factors on persulfate activity, including pH, temperature (25 °C–50 °C), persulfate dosage and reaction time, was evaluated under different experimental conditions. Contrary to the traditional alkaline-activated persulfate oxidation, it was found that PFOA can be effectively degraded using activated persulfate under acidic conditions, with the degradation kinetics following the pseudo-first-order decay model. Higher temperature, higher persulfate dosage and increased reaction time generally result in higher PFOA degradation efficiency. Experimental results show that a PFOA degradation efficiency of 89.9% can be achieved by activated persulfate at pH of 2.0, with the reaction temperature of 50 °C, molar ratio of PFOA to persulfate as 1:100, and a reaction time of 100 h. The corresponding defluorination ratio under these conditions was 23.9%, indicating that not all PFOA decomposed via fluorine removal. The electron paramagnetic resonance spectrometer analysis results indicate that both SO4−• and •OH contribute to the decomposition of PFOA. It is proposed that PFOA degradation occurs via a decarboxylation reaction triggered by SO4−•, followed by a HF elimination process aided by •OH, which produces one-CF2-unit-shortened perfluoroalkyl carboxylic acids (PFCAs, Cn−1F2n−1COOH). The decarboxylation and HF elimination processes would repeat and eventually lead to the complete mineralization all PFCAs. PMID:27322298

  19. 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

  20. 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 ...

  1. Spectrophotometric determination of persulfate by oxidative decolorization of azo dyes for wastewater treatment.

    PubMed

    Ding, Yaobin; Zhu, Lihua; Yan, Jingchun; Xiang, Qingqing; Tang, Heqing

    2011-11-01

    Persulfate can efficiently decolorize azo dyes through oxidizing these compounds, which enabled us to develop a method of rapid spectrophotometric determination of persulfate for monitoring the wastewater treatment on the basis of the oxidation decolorization of azo dyes. Four azo dyes with different molecular structures were investigated as probes, and the influences of operation parameters including reaction time, solution pH, initial dye concentration, and initial concentration of activator Fe(2+) were checked on the determination of persulfate. Under optimum conditions, the decolorization degree of the dyes responded linearly with persulfate concentration for all the four azo dyes, and the linear range and detection limit were found to be 2.0-150 μmol L(-1) and 0.62 μmol L(-1) for rhodamine B, 2.0-100 μmol L(-1) and 0.42 μmol L(-1) for methylene blue, 4.0-150 μmol L(-1) and 0.50 μmol L(-1) for methyl violet, and 20-150 μmol L(-1) and 8.1 μmol L(-1) for orange II. A persulfate treatment of a spiked wastewater sample was satisfactorily monitored with the new method.

  2. 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,...

  3. 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 ε(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.

  4. Degradation kinetics and mechanism of aniline by heat-assisted persulfate oxidation.

    PubMed

    Xie, Xiaofang; Zhang, Yongqing; Huang, Weilin; Huang, Shaobing

    2012-01-01

    Oxidation of aniline by persulfate in aqueous solutions was investigated and the reaction kinetic rates under different temperature, persulfate concentration and pH conditions were examined in batch experiments. The results showed that, the aniline degradation followed pseudo first-order reaction model. Aniline degradation rate increased with increasing temperature or persulfate concentration. In the pH range of 3 to 11, a low aniline degradation rate was obtained at strong acid system (pH 3), while a high degradation rate was achieved at strong alkalinity (pH 11). Maximum aniline degradation occurred at pH 7 when the solution was in a weak level of acid and alkalinity (pH 5, 7 and 9). Produced intermediates during the oxidation process were identified using liquid chromatography-mass spectrometry technology. And nitrobenzene, 4-4'-diaminodiphenyl and 1-hydroxy-1,2-diphenylhydrazine have been identified as the major intermediates of aniline oxidation by persulfate and the degradation mechanism of aniline was also tentatively proposed.

  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. 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

    2014-09-02

    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.

  7. Enhanced dewaterability of sewage sludge in the presence of Fe(II)-activated persulfate oxidation.

    PubMed

    Zhen, Guangyin; Lu, Xueqin; Zhao, Youcai; Chai, Xiaoli; Niu, Dongjie

    2012-07-01

    The potential benefits of Fe(II)-activated persulfate oxidation on sludge dewatering and its mechanisms were investigated in this study. Capillary suction time (CST) was used to evaluate sludge dewaterability. Both extracellular polymeric substances (EPS) and viscosity were determined in an attempt to explain the observed changes in sludge dewaterability. The optimal conditions to give preferable dewaterability characteristics were found to be persulfate (S(2)O(8)(2-)) 1.2 mmol/gVSS, Fe(II) 1.5 mmol/gVSS, and pH 3.0-8.5, which demonstrated a very high CST reduction efficiency (88.8% reduction within 1 min). It was further observed that both soluble EPS and viscosity played relatively negative roles in sludge dewatering, whereas no correlation was established between sludge dewaterability and bound EPS. Three-dimensional excitation-emission matrix (EEM) fluorescence spectra also revealed that soluble EPS of sludge were degraded and sludge flocs were ruptured by persulfate oxidation, which caused the release of water in the intracellular pace and subsequent improvement of its dewaterability.

  8. 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.

  9. Effect of anions on the oxidation of organic compounds with ultrasonically activated persulfate

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    The effect of anions typically present in natural and waste waters on the oxidation of the azo dye methyl orange with persulfate activated with high-frequency ultrasound was studied. At a chloride concentration of 1 mmol/L, the rate constant of substrate oxidation increased 1.5-fold, but further increase in the chloride content retarded the process. The addition of nitrates, carbonates, and hydrogen carbonates to the solution inhibited the process (NO 3 - < HCO 3 - ~ CO 3 2- ). These tendencies were in good agreement with the results obtained on a real water matrix of the natural surface water from Lake Baikal.

  10. 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.

  11. 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.

  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. Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate

    NASA Astrophysics Data System (ADS)

    Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

    2016-04-01

    Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0–100 mg/g total solids (TS)) and persulfate (0–1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0–100 mg/g TS) and hydrogen peroxide (HP) (0–1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000.

  14. Role of oxidants in enhancing dewaterability of anaerobically digested sludge through Fe (II) activated oxidation processes: hydrogen peroxide versus persulfate

    PubMed Central

    Song, Kang; Zhou, Xu; Liu, Yiqi; Gong, Yanyan; Zhou, Beibei; Wang, Dongbo; Wang, Qilin

    2016-01-01

    Improving dewaterability of sludge is important for the disposal of sludge in wastewater treatment plants (WWTPs). This study, for the first time, investigated the Fe(II) activated oxidization processes in improving anaerobically digested sludge (ADS) dewaterability. The combination of Fe(II) (0–100 mg/g total solids (TS)) and persulfate (0–1,000 mg/g TS) under neutral pH as well as the combination of Fe(II) (0–100 mg/g TS) and hydrogen peroxide (HP) (0–1,000 mg/g TS) under pH 3.0 were used to examine and compare their effect on the ADS dewaterability enhancement. The highest ADS dewaterability enhancement was attained at 25 mg Fe(II)/g TS and 50 mg HP/g TS, when the CST (CST: the capillary suction time, a sludge dewaterability indicator) was reduced by 95%. In contrast, the highest CST reduction in Fe(II)-persulfate conditioning was 90%, which was obtained at 50 mg Fe(II)/g TS and 250 mg persulfate/g TS. The results showed that Fe(II)-HP conditioning was comparable with Fe(II)-persulfate conditioning in terms of highest CST reduction. Economic analysis suggested that the Fe(II)-HP conditioning was more promising for improving ADS dewaterability compared with Fe(II)-persulfate conditioning, with the saving being up to $65,000 per year in a WWTP with a population equivalent of 100,000. PMID:27109500

  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 H2O2–persulfate binary mixtur...

  16. Ferrous-activated persulfate oxidation of arsenic(III) and diuron in aquatic system.

    PubMed

    Zhou, Lei; Zheng, Wei; Ji, Yuefei; Zhang, Jinfeng; Zeng, Chao; Zhang, Ya; Wang, Qi; Yang, Xi

    2013-12-15

    In situ chemical oxidation (ISCO) can be an effective technology for the remediation of soil and groundwater polluted by organic and inorganic contaminants. This study investigated the oxidation of arsenic(III) (As(III)) and diuron using ferrous activated persulfate-based ISCO. The results indicated that Fe(II)/persulfate oxidation could be an effective method to oxidize As(III) and diuron. Effects of pH, S2O8(2-) and Fe(II) amounts on the destruction of As(III) and diuron were examined in batch experiments. Acidic conditions favored the removal of As(III) and diuron. Four chelating agents, citric acid (CA), Na2S2O3, diethylene triamine pentaacetic acid (DTPA) and ethylene diamine tetraacetic acid disodium (EDTA-Na2) were used in attempt to maintain the quantity of ferrous ion in solution. In our experiments, CA and Na2S2O3 were found to be more effective than DTPA and EDTA-Na2. Our results also revealed a widely practical prospect of inorganic chelating agent Na2S2O3. Hydroxyl and sulfate radical were determined to play key roles in the oxidation process by using ethanol and tertiary butanol as molecular probes. Oxidation of As(III) yielded As(V) via the electron-transfer reaction. In the oxidation process of diuron, a stepwise nucleophilic substitution of chlorine by hydroxyl and a stepwise oxidation process of the methyl on the dimethylurea group by hydroxyl and sulfate radical were proposed.

  17. Polyaniline/cellulose fiber composite prepared using persulfate as oxidant for Cr(VI)-detoxification.

    PubMed

    Liu, Xiangyao; Zhou, Wanpeng; Qian, Xueren; Shen, Jing; An, Xianhui

    2013-01-30

    Cellulose fibers were engineered by in situ oxidative polymerization of aniline using ammonium persulfate as oxidant/initiator. The polyaniline/cellulose fiber composite was used for the treatment of Cr(VI)-contaminated water, and its effect was evaluated. Under the conditions studied, the composite exhibited very high water detoxification efficiency, as a result of reduction of Cr(VI) to Cr(III) in combination with adsorption of the Cr(III) onto the cellulosic substrate. Cellulose fibers used in the study served two purposes simultaneously, i.e., carrier of polyaniline and the adsorbent for Cr(III). The complexation of polyaniline with cellulose fibers provided synergistic effects on Cr(VI)-detoxification.

  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 6 nm 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 100 mg/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.

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

    PubMed

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

    2017-03-20

    The widespread occurrence of organophosphorus pesticides (OPPs) in the environment poses risks to both ecologic system as well as human health. This study investigated the oxidation kinetics of chlorpyrifos (CP), one of the typical OPPs, by thermoactivated persulfate (PS) oxidation process, and evaluated the influence of key kinetic factors, such as PS concentrations, pH, temperature, bicarbonate, and chloride ions. The reaction pathways and mechanisms were also proposed based on products identification by LC-MS techniques. Our results revealed that increasing initial PS concentration and temperature favored the decomposition of CP, whereas the oxidation efficiency was not affected by pH change ranging from 3 to 11. Bicarbonate was found to play a detrimental role on CP removal rates, while chloride showed no effect. The oxidation pathways including initial oxidation of P=S bond to P=O, dechlorination, dealkylation, and the dechlorination-hydroxylation were proposed, and the detailed underlying mechanisms were also discussed. Molecular orbital (MO) calculations indicated that P=S bond was the most favored oxidation site of the molecule. The toxicity of reaction solution was believed to increase due to the formation of products with P=O structures. This work demonstrates that OPPs can readily react with SO4(·-) and provides important information for further research on the oxidation of these contaminants.

  1. 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.

  2. 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.

  3. 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 (k(obs)) 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.

  4. Mechanism of base activation of persulfate.

    PubMed

    Furman, Olha S; Teel, Amy L; Watts, Richard J

    2010-08-15

    Base is the most commonly used activator of persulfate for the treatment of contaminated groundwater by in situ chemical oxidation (ISCO). A mechanism for the base activation of persulfate is proposed involving the base-catalyzed hydrolysis of persulfate to hydroperoxide anion and sulfate followed by the reduction of another persulfate molecule by hydroperoxide. Reduction by hydroperoxide decomposes persulfate into sulfate radical and sulfate anion, and hydroperoxide is oxidized to superoxide. The base-catalyzed hydrolysis of persulfate was supported by kinetic analyses of persulfate decomposition at various base:persulfate molar ratios and an increased rate of persulfate decomposition in D(2)O vs H(2)O. Stoichiometric analyses confirmed that hydroperoxide reacts with persulfate in a 1:1 molar ratio. Addition of hydroperoxide to basic persulfate systems resulted in rapid decomposition of the hydroperoxide and persulfate and decomposition of the superoxide probe hexachloroethane. The presence of superoxide was confirmed with scavenging by Cu(II). Electron spin resonance spectroscopy confirmed the generation of sulfate radical, hydroxyl radical, and superoxide. The results of this research are consistent with the widespread reactivity reported for base-activated persulfate when it is used for ISCO.

  5. Enhanced dewaterability of sewage sludge with zero-valent iron-activated persulfate oxidation system.

    PubMed

    Hu, Lingling; Liao, Yu; He, Chun; Pan, Wenqi; Liu, Shangkun; Yang, Yichang; Li, Shuzhen; Sun, Lianpeng

    2015-01-01

    The potential benefits of zero-valent iron-activated persulfate (Na2S2O8) oxidation in enhanced dewaterability of sludge, along with the associated mechanisms were investigated in this study. The sludge dewaterability was evaluated in terms of specific resistance to filtration (SRF) and water content. Based on these indexes, it was observed that ZVI-S2O8(2) oxidation effectively improved sludge dewaterability. The optimal conditions to give preferable dewaterability were found when the molar ratio of ZVI/S2O8(2-) was 5:1 and pH value was 3.0. The most important mechanism was proposed to be the degradation of extracellular polymeric substances (EPS) incorporated in sludge flocs and rupture of microbial cells. Three-dimensional excitation-emission matrix fluorescence spectra revealed that the powerful SO4- and ·OH generated from ZVI-S2O8(2-) system destroyed the particular functional groups of fluorescing substances (aromatic protein-like and tryptophan protein-like substances), resulting in the release of bound water and the subsequent enhancement of dewaterability. Therefore, ZVI/S2O8(2-) oxidation is an alternative approach showing great potential to be applied in sludge treatment plants.

  6. Novel insights into enhanced dewaterability of waste activated sludge by Fe(II)-activated persulfate oxidation.

    PubMed

    Zhen, Guangyin; Lu, Xueqin; Li, Yuyou; Zhao, Youcai; Wang, Baoying; Song, Yu; Chai, Xiaoli; Niu, Dongjie; Cao, Xianyan

    2012-09-01

    The potential of Fe(II)-activated persulfate (S(2)O(8)(2-)) oxidation on enhancing the dewaterability of sludge flocs from 3-full scale wastewater treatment plants (WWTPs) were investigated. Normalized capillary suction time (CST) was applied to evaluate sludge dewaterability. Both extracellular polymeric substances (EPS) and metabolic activity of microorganisms were determined to explore the responsible mechanism. Fe(II)-S(2)O(8)(2-) oxidation effectively improved sludge dewaterability. The most important mechanisms were proposed to be the degradation of EPS incorporated in sludge flocs and rupture of microbial cells. Three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy confirmed that the powerful SO(4)(-) from Fe(II)-S(2)O(8)(2-) system destroyed the particular functional groups of fluorescing substances (i.e., aromatic protein-, tryptophan protein-, humic- and fulvic-like substances) in EPS and caused cleavage of linkages in the polymeric backbone and simultaneous destruction of microbial cells, resulting in the release of EPS-bound water, intracellular materials and water of hydration inside cells, and subsequent enhancement of dewaterability.

  7. Zero-valent iron-activated persulfate oxidation of a commercial alkyl phenol polyethoxylate.

    PubMed

    Temiz, Kubra; Olmez-Hanci, Tugba; Arslan-Alaton, Idil

    2016-01-01

    Aqueous Triton X-45 (TX-45; 20 mg/L; original total organic carbon (TOC) = 14 mg/L), a representative, commercially important alkylphenol polyethoxylate, was subjected to persulfate (PS) oxidation activated with zero-valent iron (ZVI) nanoparticles. After optimization of the ZVI/PS treatment combination (1 g/L ZVI; 2.5 mM PS at pH5) in terms of pH (3-9), ZVI (0.5-5 g/L) and PS (0.5-5.0 mM) concentrations, TX-45 could be efficiently (>90%) degraded within short treatment periods (<60 min) accompanied with significant (>40%) TOC removals. The degree of PS consumption and Fe release was also followed during the experiments and a positive correlation existed between enhanced TX-45 removals and ZVI-activated PS consumption rates accompanied with a parallel Fe release. Acute toxicity tests were conducted using two different bioassays to examine the toxicological safety of the ZVI/PS oxidation system. Acute toxicity profiles significantly decreased from an original value of 66% relative inhibition to 21% and from 16% relative inhibition to non-toxic values according to Vibrio fischeri and Pseudokirchneriella subcapitata bioassays, respectively. The photobacterium V. fischeri appeared to be more sensitive to TX-45 and its degradation products than the microalgae P. subcapitata.

  8. 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 radOH radical, SO4rad - 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.

  9. Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature.

    PubMed

    Yang, Shiying; Yang, Xin; Shao, Xueting; Niu, Rui; Wang, Leilei

    2011-02-15

    Persulfate (PS) oxidative degradation of azo dye acid orange 7 (AO7) in an aqueous solution was studied in the presence of suspended granular activated carbon (GAC) at ambient temperature (e.g., 25°C). It was observed that there existed a remarkable synergistic effect in the GAC/PS combined system. Higher PS concentration and GAC dosage resulted in higher AO7 degrading rates. Near-neutral was the optimal initial pH. Adsorption had an adverse effect on AO7 degradation. AO7 had not only a good decolorization, but a good mineralization. The decomposition of PS followed a first-order kinetics behavior both in the presence and in the absence of AO7. Radical mechanism was studied and three radical scavengers (methanol (MA), tert-butanol (TBA), phenol) were used to determine the kind of major active species taking part in the degradation of AO7 and the location of degradation reaction. It was assumed that the degradation of AO7 did not occur in the liquid phase, but in the porous bulk and boundary layer on the external surface of GAC. SO(4)(-•) or HO•, generated on or near the surface of GAC, played a major role in the AO7 degradation. Finally, the recovery performance of GAC was studied through the GAC reuse experiments.

  10. 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.

  11. Oxidation of atrazine in aqueous media by solar- enhanced Fenton-like process involving persulfate and ferrous ion.

    PubMed

    Khandarkhaeva, Marina; Batoeva, Agniya; Aseev, Denis; Sizykh, Marina; Tsydenova, Oyuna

    2017-03-01

    The oxidation of s-triazines (using atrazine (ATZ) as a model compound) by a solar-enhanced Fenton-like process involving persulfate and ferrous ion was studied. A flow-through tubular photoreactor was employed for the experiments. The solar-enhanced oxidative system involving ferrous ion and persulfate (Solar/S2O8(2-)/Fe(2+)) showed the highest ATZ degradation efficiency when compared with other treatments (unactivated S2O8(2-), Solar - sunlight only, S2O8(2-)/Fe(2+), Solar/S2O8(2-)). Complete degradation of ATZ and 20% reduction in total organic carbon (TOC) content were observed after 30min of the treatment. The in situ generated (•)ОН and SO4(-•) radicals were shown to be involved in ATZ oxidation using the radical scavengers methanol and tert-butyl alcohol. Furthermore, iron compounds were shown to act not only as catalysts but also as photo-sensitizers, as the introduction of ferrous ion into the reaction mixture led to an increased absorbance of the solution and expansion of the absorption spectrum into the longer wavelength spectral region.

  12. Oxidation of Benzene by Persulfate in the Presence of Fe(III)- and Mn(IV)-Containing Oxides: Stoichiometric Efficiency and Transformation Products.

    PubMed

    Liu, Haizhou; Bruton, Thomas A; Li, Wei; Buren, Jean Van; Prasse, Carsten; Doyle, Fiona M; Sedlak, David L

    2016-01-19

    Sulfate radical (SO4(•-)) is a strong, short-lived oxidant that is produced when persulfate (S2O8(2-)) reacts with transition metal oxides during in situ chemical oxidation (ISCO) of contaminated groundwater. Although engineers are aware of the ability of transition metal oxides to activate persulfate, the operation of ISCO remediation systems is hampered by an inadequate understanding of the factors that control SO4(•-) production and the overall efficiency of the process. To address these shortcomings, we assessed the stoichiometric efficiency and products of transition metal-catalyzed persulfate oxidation of benzene with pure iron- and manganese-containing minerals, clays, and aquifer solids. For most metal-containing solids, the stoichiometric efficiency, as determined by the loss of benzene relative to the loss of persulfate, approached the theoretical maximum. Rates of production of SO4(•-) or hydroxyl radical (HO(•)) generated from radical chain reactions were affected by the concentration of benzene, with rates of S2O8(2-) decomposition increasing as the benzene concentration increased. Under conditions selected to minimize the loss of initial transformation products through reaction with radicals, the production of phenol only accounted for 30%-60% of the benzene lost in the presence of O2. The remaining products included a ring-cleavage product that appeared to contain an α,β-unsaturated aldehyde functional group. In the absence of O2, the concentration of the ring-cleavage product increased relative to phenol. The formation of the ring-cleavage product warrants further studies of its toxicity and persistence in the subsurface.

  13. Enhanced Reactant-Contaminant Contact through the Use of Persulfate In Situ Chemical Oxidation (ISCO)

    DTIC Science & Technology

    2011-02-01

    Figure 6.3.2.2. The permeameter column and sample holder ring were made of polyvinyl chloride (PVC). The sample holder ring was fitted tightly with an O...D 698 Optimum water content, % 18.7 ASTM D 698 Column Materials Polyvinyl chloride (PVC) pipe (ASTM D 3034) with a 10.2-cm inner diameter was...and electron spin resonance spectroscopy. In addition, the effect of activated persulfate formulations on the permeability and morphology of

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

    PubMed

    Mora, Verónica C; Madueño, Laura; Peluffo, Marina; Rosso, Janina A; Del Panno, María 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 140 mg/kgDRY SOIL of phenanthrene were treated with different persulfate (PS) concentrations 0.86-41.7 g/kgDRY SOIL and incubated for 28 days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28 days 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.

  15. Selective oxidative degradation of toluene for the recovery of surfactant by an electro/Fe²⁺/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.

  16. Persulfate activation by naturally occurring trace minerals.

    PubMed

    Teel, Amy L; Ahmad, Mushtaque; Watts, Richard J

    2011-11-30

    The potential for 13 naturally occurring minerals to mediate the decomposition of persulfate and generate a range of reactive oxygen species was investigated to provide fundamental information on activation mechanisms when persulfate is used for in situ chemical oxidation (ISCO). Only four of the minerals (cobaltite, ilmenite, pyrite, and siderite) promoted the decomposition of persulfate more rapidly than persulfate-deionized water control systems. The other nine minerals decomposed persulfate at the same rate or more slowly than the control systems. Mineral-mediated persulfate activation was conducted with the addition of one of three probe compounds to detect the generation of reactive oxygen species: anisole (sulfate+hydroxyl radical), nitrobenzene (hydroxyl radical), and hexachloroethane (reductants and nucleophiles). The reduced mineral pyrite promoted rapid generation of sulfate+hydroxyl radical. However, the remainder of the minerals provided minimal potential for the generation of reactive oxygen species. The results of this research demonstrate that the majority of naturally occurring trace minerals do not activate persulfate to generate reactive oxygen species, and other mechanisms of activation are necessary to promote contaminant destruction in the subsurface during persulfate ISCO.

  17. Innovative combination of electrolysis and Fe(II)-activated persulfate oxidation for improving the dewaterability of waste activated sludge.

    PubMed

    Zhen, Guang-Yin; Lu, Xue-Qin; Li, Yu-You; Zhao, You-Cai

    2013-05-01

    The feasibility of electrolysis integrated with Fe(II)-activated persulfate (S2O8(2-)) oxidation to improve waste activated sludge (WAS) dewaterability was evaluated. The physicochemical properties (sludge volume (SV), total suspended solids (TSS) and volatile suspended solids (VSS)) and extracellular polymeric substances (EPS), including slime EPS, loosely bound EPS (LB-EPS) and tightly bound EPS (TB-EPS) were characterized to identify their exact roles in sludge dewatering. While dewaterability negatively corresponded to LB-EPS, TB-EPS, protein (PN) and polysaccharide (PS) in LB-EPS and TB-EPS, it was independent of SV, TSS, VSS, slime EPS and PN/PS. Further study through scanning electron microscope (SEM) verified the entrapment of bacterial cells by TB-EPS, protecting them against electrolysis disruption. Comparatively, electrolysis integrated with S2O8(2-)/Fe(II) oxidation was able to effectively disrupt the protective barrier and crack the entrapped cells, releasing the water inside EPS and cells. Therefore, the destruction of both TB-EPS and cells is the fundamental reason for the enhanced dewaterability.

  18. Advanced treatment of effluents from an industrial park wastewater treatment plant by ferrous ion activated persulfate oxidation process.

    PubMed

    Zhu, Songmei; Zhou, Zhen; Jiang, Haitao; Ye, Jianfeng; Ren, Jiamin; Gu, Lingyun; Wang, Luochun

    The advanced oxidation technology, ferrous ion (Fe(II)) activated persulfate (PS) producing sulfate radicals, was used for the advanced treatment of effluent from an integrated wastewater treatment plant in a papermaking industrial park. Separate and interactive effects of PS dosage, Fe(II)/PS ratio and initial pH on chemical oxygen demand (COD) removal were analyzed by the response surface methodology (RSM). The results showed that Fe(II)-PS system was effective in COD removal from the secondary effluent. PS dosage was the most dominant factor with positive influence on COD removal, followed by initial pH value. The optimum conditions with COD removal of 54.4% were obtained at PS/COD of 2.2, initial pH of 6.47 and Fe(II)/PS of 1.89. UV-visible spectrum analysis showed that after RSM optimization, Fe(II)-PS system effectively degraded large organic molecules into small ones, and decreased humification degree of the effluent. Three-dimensional fluorescence analysis demonstrated that aromatic protein and fulvic substances were fully decomposed by the Fe(II)-PS treatment.

  19. Removal of dinitrotoluenes in wastewater by sono-activated persulfate.

    PubMed

    Chen, Wen-Shing; Su, Yi-Chang

    2012-07-01

    Oxidative degradation of dinitrotoluenes (DNTs) in wastewater was performed using persulfate anions combined with ultrasonic irradiation, wherein a synergistic effect is observed. The batch-wise experiments were carried out to elucidate the influence of various operating parameters on sono-activated persulfate oxidation, including ultrasonic power intensity, persulfate anion concentration, reaction temperature and acidity of wastewater. It is noteworthy that the nitrotoluene contaminants could be almost completely eliminated by virtue of sono-activated persulfate oxidation, wherein sulfate radicals serve as principal oxidants, of which amounts are significantly enhanced via addition of sodium sulfate. Based on the results given by gas chromatograph-mass spectrometer (GC-MS), it is postulated that the methyl group of DNTs preliminarily underwent oxidation pathway into dinitrobenzoic acid, followed by decarboxylation to form 1,3-dinitrobenzene (DNB). In sum, the sono-activated persulfate oxidation is a promising method for treatment of nitrotoluenes in wastewater.

  20. 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...

  1. 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...

  2. 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.

  3. 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.

  4. Hg0 absorption in potassium persulfate solution*

    PubMed Central

    Ye, Qun-feng; Wang, Cheng-yun; Wang, Da-hui; Sun, Guan; Xu, Xin-hua

    2006-01-01

    The aqueous phase oxidation of gaseous elemental mercury (Hg0) by potassium persulfate (KPS) catalyzed by Ag+ was investigated using a glass bubble column reactor. Concentration of gaseous mercury and potassium persulfate were measured by cold vapor atom absorption (CVAA) and ion chromatograph (IC), respectively. The effects of pH value, concentration of potassium persulfate and silver nitrate (SN), temperature, Hg0 concentration in the reactor inlet and tertiary butanol (TBA), free radical scavenger, on the removal efficiency of Hg0 were studied. The results showed that the removal efficiency of Hg0 increased with increasing concentration of potassium persulfate and silver nitrate, while temperature and TBA were negatively effective. Furthermore, the removal efficiency of Hg0 was much better in neutral solution than in both acidic and alkaline solution. But the influence of pH was almost eliminated by adding AgNO3. High Hg0 concentration has positive effect. The possible reaction mechanism of gaseous mercury was also discussed. PMID:16615172

  5. 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.

  6. Occupational non-immediate type allergic asthma due to ammonium persulfate.

    PubMed

    Polychronakis, Ioannis; Thanasias, Efthimios; Raulf-Heimsoth, Monika; Merget, Rolf

    2013-01-01

    While numerous cases of immediate-type occupational asthma due to persulfates with positive skin prick test reactions to ammonium persulfate are well documented, few non-immediate type reactions have been described in the literature. We report the case of an atopic worker who developed work-related asthmatic symptoms shortly after he began his job in persulfate production. The diagnosis of asthma was corroborated by methacholine testing. The patient showed a positive patch test reaction to ammonium persulfate, while skin prick test was negative. He presented an isolated late symptomatic airway obstruction after a cumulative dose of 0.6 mg ammonium persulfate administered by a dosimeter method. An immunologic mechanism was demonstrated by a significant increase in exhaled nitric oxide and the number of eosinophils in induced sputum. These findings suggest that isolated late bronchial reactions to persulfates are mediated by eosinophilic inflammatory responses.

  7. 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 et al., 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 (254 nm wavelength, 40 W 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 0.04 mM-0.31 mM 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 = 11.76 mM; [SPS]0 = 1.26 mM; temperature (29 ± 3 °C). 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.

  8. 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...

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Final report on the safety assessment of Ammonium, Potassium, and Sodium Persulfate.

    PubMed

    Pang, S; Fiume, M Z

    2001-01-01

    Ammonium, Potassium, and Sodium Persulfate are inorganic salts used as oxidizing agents in hair bleaches and hair-coloring preparations. Persulfates are contained in hair lighteners at concentrations up to 60%, in bleaches and lighteners at up to 22% and 16%, respectively, and in off-the-scalp products used to highlight hair strands at up to 25%. They are used in professional product bleaches and lighteners at similar concentrations. Much of the available safety test data are for Ammonium Persulfate, but these data are considered applicable to the other salts as well. Acute dermal, oral, and inhalation toxicity studies are available, but only the latter are remarkable, with gross lesions observed in the lungs, liver, stomach, and spleen. In short-term and subchronic feeding studies the results were mixed; some studies found no evidence of toxicity and others found local damage to the mucous membrane in the gastrointestinal tract, but no other systemic effects. Short-term inhalation toxicity was observed when rats were exposed to aerosolized Ammonium Persulfate at concentrations of 4 mg/m3 and greater. Ammonium Persulfate (as a moistened powder) was not an irritant to intact rabbit skin, but was sensitizing (in a saline solution) to the guinea pig. It was slightly irritating to rabbit eyes. Ammonium Persulfate was negative in the Ames test and the chromosomal aberration test. No significant evidence of tumor promotion or carcinogenicity was observed in studies of rats receiving topical applications of Ammonium Persulfate. The persulfates were reported to cause both delayed-type and immediate skin reactions, including irritant dermatitis, allergic eczematous dermatitis, localized contact urticaria, generalized urticaria, rhinitis, asthma, and syncope. The most common causes of allergic dermatitis in hairdressers are the active ingredients in hair dyes, and Ammonium Persulfate has been identified as a frequent allergen. A sensitization study that also examined the

  14. In-situ Activation of Persulfate by Iron Filings and Degradation of 1,4-dioxane

    PubMed Central

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

    2015-01-01

    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

  15. Persulfate based pretreatment to enhance the enzymatic digestibility of rice straw.

    PubMed

    Ahmed, Muhammad Ajaz; Seo, Yeong Hwan; Terán-Hilares, Ruly; Rehman, Muhammad Saif U R; Han, Jong-In

    2016-12-01

    Oxidation induced by potassium persulfate was evaluated as an economic substitute for the Fenton-like reaction for the purpose of rice straw pretreatment in terms of temperature (80-140°C), potassium persulfate concentration (5-100mM) and process time (0.5-3h), an optimal pretreatment condition was identified: 120°C for 2 h with 75mM potassium persulfate concentration and yielded 91% enzymatic digestibility using 25.2FPU/g of biomass. Crystallinity index, SEM and SEM-EDS analyses revealed that biomass was indeed disrupted and components like silica were exposed. All this suggested that this persulfate-based pretreatment method, which is distinctively advantageous in terms of effectiveness and economics, can indeed be a competitive option.

  16. 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 = 0.00053•Iv + 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

  17. 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.

  18. 78 FR 40695 - Persulfates From the People's Republic of China: Final Results of Expedited Third Sunset Review...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-07-08

    ... the order are persulfates, including ammonium, potassium, and sodium persulfates. The chemical formula... . Potassium persulfates are currently classifiable under subheading 2833.40.10 of the Harmonized...

  19. Removal of 2-MIB and geosmin by electrogenerated persulfate: Performance, mechanism and pathways.

    PubMed

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Gao, Naiyun

    2017-02-01

    In this study, the degradation of 2-methylisoborneol (2-MIB) and geosmin (GSM) was evaluated by electrochemical oxidation (EO) using boron-doped diamond (BDD) electrode. Both 2-MIB and GSM could be degraded efficiently in sulfate electrolyte compared to inert nitrate or perchlorate electrolytes, implying that in-situ generated persulfate may be responsible for contaminants degradation. The observed linear relationship between 2-MIB (GSM) degradation rates and persulfate generation rates further proved that the in-situ generated persulfate enhanced 2-MIB (GSM) degradation. Moreover, a divided electrolytic cell was employed to investigate the effect of cathodic reactions on contaminants degradation and persulfate generation, and results confirmed that both anodic and cathodic reactions participated in 2-MIB (GSM) degradation. High current density and low solution pH were found to be favorable for 2-MIB and GSM degradation. The degradation intermediates were identified and the possible pathways of 2-MIB and GSM degradation were proposed. This study indicated that the EO process with BDD anode could be considered as a potential alternative for the removal of 2-MIB and GSM.

  20. Decolorization of an azo dye Orange G in microbial fuel cells using Fe(II)-EDTA catalyzed persulfate.

    PubMed

    Niu, Cheng-Gang; Wang, Ying; Zhang, Xue-Gang; Zeng, Guang-Ming; Huang, Da-Wei; Ruan, Min; Li, Xiang-Wei

    2012-12-01

    This study constructed a microbial fuel cell (MFC) using Fe(II)-EDTA catalyzed persulfate as the cathode solutions to decolorize Orange G (OG) and harvest electricity simultaneously. Chelated Fe(2+) could activate persulfate to generate sulfate free radicals (SO(4)(-)) which with high oxidation potential (E(0)=2.6 V) can degrade azo dyes. The influence of some important factors such as pH value of cathode solutions, dosages of K(2)S(2)O(8), Fe(2+) and EDTA were investigated in a two-chamber microbial fuel cell. Under an optimal condition, the maximum power density achieved 91.1 mW m(-2), the OG removal rate was 97.4% and the K(2)S(2)O(8) remaining rate was 47.3% after 12 h. The OG degradation by Fe(II)-EDTA catalyzed persulfate was found to follow the second-order kinetic model.

  1. Specific immunoglobulin E in patients with immediate persulfate hypersensitivity.

    PubMed

    Aalto-Korte, Kristiina; Mäkinen-Kiljunen, Soili

    2003-07-01

    Persulfate salts may cause contact urticaria, allergic and irritant contact dermatitis, rhinitis and asthma. The mechanism of the immediate reactions has been unclear. Positive prick test, skin application and nasal and bronchial provocations identify immediate allergy. There is only 1 previous report of specific binding of immunoglobulin E (IgE) to ammonium persulfate demonstrated by radioallergosorbent test (RAST). In the present study, fresh 2% ammonium and potassium persulfate solutions were used for prick testing. Patients with positive prick tests were further evaluated with open skin application, immunospot and RAST. Prick testing with persulfate salts was performed in a total of 138 patients. 7 patients had a positive reaction to at least 1 persulfate salt. 6 of the patients had had skin symptoms, urticaria, eczema or angioedema, because of contact with hair bleaches. Open application on healthy skin was performed in 4 patients, and 3 out of them had urticarial reactions. The sera of 5 patients were investigated with immunospot and RAST. On immunospot, specific binding of IgE to human serum albumin (HSA)-conjugated ammonium and potassium persulfate was found in 2 patients. 1 immunospot-positive patient also had a positive RAST to ammonium persulfate-HSA conjugate. The mechanism of immediate hypersensitivity to persulfates thus seems to be IgE-mediated at least in some patients.

  2. Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation

    NASA Astrophysics Data System (ADS)

    Li, Xianghui; Guo, Weilin; Liu, Zhonghua; Wang, Ruiqin; Liu, Hua

    2016-04-01

    Fe-based metal-organic frameworks (MOFs) including MIL-101(Fe), MIL-100(Fe), MIL-53(Fe), and MIL-88B(Fe) prepared via a facile solvothermal process were introduced as both adsorbents and catalysts to generate powerful radicals from persulfate for acid orange 7 (AO7) removal in aqueous solution. Various catalysts were described and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray photoelectron spectra. Because of the high specific surface area of the materials, we studied the adsorption isotherms of the four MILs by the fitting of Langmuir adsorption isotherm. Meanwhile, the catalytic activities in persulfate oxidation system were investigated. The results showed that the sequence of the materials ability in the combination of adsorption and degradation was MIL-101(Fe) > MIL-100(Fe) > MIL-53(Fe) > MIL-88B(Fe), which had a close connection with the activity of metal ion in active site of the catalysts and their different cages in size. Moreover, the reactive species in MILs/persulfate system were identified as sulfate radicals and hydroxyl radicals. The reaction mechanism for persulfate activation over MILs was also studied.

  3. A novel conditioning process for enhancing dewaterability of waste activated sludge by combination of zero-valent iron and persulfate.

    PubMed

    Zhou, Xu; Wang, Qilin; Jiang, Guangming; Liu, Peng; Yuan, Zhiguo

    2015-06-01

    Improvement of sludge dewaterability is crucial for reducing the costs of sludge disposal in wastewater treatment plants. This study presents a novel conditioning method for improving waste activated sludge dewaterability by combination of persulfate and zero-valent iron. The combination of zero-valent iron (0-30g/L) and persulfate (0-6g/L) under neutral pH substantially enhanced the sludge dewaterability due to the advanced oxidization reactions. The highest enhancement of sludge dewaterability was achieved at 4g persulfate/L and 15g zero-valent iron/L, with which the capillary suction time was reduced by over 50%. The release of soluble chemical oxygen demand during the conditioning process implied the decomposition of sludge structure and microorganisms, which facilitated the improvement of dewaterability due to the release of bound water that was included in sludge structure and microorganism. Economic analysis showed that the proposed conditioning process with persulfate and ZVI is more economically favorable for improving WAS dewaterability than classical Fenton reagent.

  4. Decolorization of Methylene Blue by Persulfate Activated with FeO Magnetic Particles.

    PubMed

    Hung, Chang-Mao; Chen, Chiu-Wen; Liu, Yi-Yuan; Dong, Cheng-Di

    2016-08-01

    In this study, the degradation of methylene blue (MB) was conducted to evaluate the feasibility of using persulfate oxidation activated with iron oxide (FeO) magnetic particles. The results demonstrated that the decolorization rate of MB increased with increasing FeO concentration, exhibiting maximum efficiency at pH0 3.0. The kinetics of MB was studied in the binary FeO catalyst and persulfate oxidation system. The surface properties of FeO before and after reaction was analyzed using cyclic voltammogram (CV), three-dimensional excitation-emission fluorescence matrix (EEFM) spectroscopy, zeta potential, particle size distribution measurements, X-ray diffraction (XRD) and environmental scanning electron microscopy-energy dispersive X-ray spectrometry (ESEM-EDS). The CV data indicated that a reversible redox reaction holds the key to explaining the significant activity of the catalyst. EEFM was used to evaluate the catalyst yield of FeO by fluorescence intensity plots with excitation/emission at 220/300 nm and 260/300 nm. The XRD and ESEM-EDS results confirmed the presence of FeO in the catalyst.

  5. Rate of phosphoantimonylmolybdenum blue complex formation in acidic persulfate digested sample matrix for total dissolved phosphorus determination: importance of post-digestion pH adjustment.

    PubMed

    Huang, Xiao-Lan; Zhang, Jia-Zhong

    2008-10-19

    Acidic persulfate oxidation is one of the most common procedures used to digest dissolved organic phosphorus compounds in water samples for total dissolved phosphorus determination. It has been reported that the rates of phosphoantimonylmolybdenum blue complex formation were significantly reduced in the digested sample matrix. This study revealed that the intermediate products of persulfate oxidation, not the slight change in pH, cause the slowdown of color formation. This effect can be remedied by adjusting digested samples pH to a near neural to decompose the intermediate products. No disturbing effects of chlorine on the phosphoantimonylmolybdenum blue formation in seawater were observed. It is noted that the modification of mixed reagent recipe cannot provide near neutral pH for the decomposition of the intermediate products of persulfate oxidation. This study provides experimental evidence not only to support the recommendation made in APHA standard methods that the pH of the digested sample must be adjusted to within a narrow range of sample, but also to improve the understanding of role of residue from persulfate decomposition on the subsequent phosphoantimonylmolybdenum blue formation.

  6. Recovery of gold from waste electrical and electronic equipment (WEEE) using ammonium persulfate.

    PubMed

    Alzate, Andrea; López, Maria Esperanza; Serna, Claudia

    2016-11-01

    This paper presents a novel methodology to recover gold from waste electrical and electronic equipment (WEEE) using ammonium persulfate ((NH4)2S2O8). Gold was recovered as a fine coating using substrate oxidation without shredding or grinding process. The WEEE sample was characterized giving values of Au: 1.05g/kg, Fe: 86.00g/kg, Ni: 73.64g/kg, Cu: 26.65g/kg. The effect of (NH4)2S2O8 concentration (0.22-1.10M), oxygen (0.0-1.4L/min) and L/S ratio (10-30mL/g) on the main responses (substrate oxidation and Au recovery) was investigated implementing response surface methodology with numerical optimization. A quadratic model was developed and quantities greater than 98% of Au were recovered. The findings presented suggest that, optimized quantities of ammonium persulfate in aqueous highly oxygenated media could be used to extract superficial gold from WEEE.

  7. Scientists Design Heat-Activated Penis Implant

    MedlinePlus

    ... implant, Le used a heat-activated exoskeleton of nitinol, a metal known for its elasticity. A urologist could do a simplified operation to insert the nitinol implant, which would remain flaccid at body temperature ...

  8. Preparation of Mg-vermiculite nanoparticles using potassium persulfate treatment.

    PubMed

    Matĕjka, Vlastimil; Supová-Krístková, Monika; Kratosvá, Gabriela; Valásková, Marta

    2006-08-01

    Delamination/exfoliation process of the Mg-vermiculite (Letovice, Czech Republic), particles with size less than 5 microm, was studied after potassium persulfate treatment and compared with known method utilized hydrogen peroxide treatment. X-ray powder diffraction (XRPD) patterns showed that treatment of Mg-vermiculite with different molar concentration of potassium persulfate: c = 0.02, 0.04, and 0.08 mol x dm(-3) at the temperature 60 degrees C for 2 hr caused reduction of relative intensity (I(rel.)) of the basal 001 diffraction to the 15%, 9%, and 4%, respectively, compared to intensity of 001 diffraction of untreated Mg-vermiculite (I(rel.) = 100%). On the other hand I(rel.) of the 001 diffraction of Mg-vermiculite after treatment with 30% and 50% (c = 9.8 and 17.4 mol x dm(-3)) hydrogen peroxide at the 60 degrees C for 2 hr decreased only to I(rel.) = 36% and 32%, respectively. Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) verified effect of potassium persulfate treatment on structure degradation which is connected with higher degree of delamination/exfoliation of the particles and their cracking into nano-sized particles.

  9. Kinetics and Mechanism of Ultrasonic Activation of Persulfate: An in Situ EPR Spin Trapping Study.

    PubMed

    Wei, Zongsu; Villamena, Frederick A; Weavers, Linda K

    2017-03-21

    Ultrasound (US) was shown to activate persulfate (PS) providing an alternative activation method to base or heat as an in situ chemical oxidation (ISCO) method. The kinetics and mechanism of ultrasonic activation of PS were examined in aqueous solution using an in situ electron paramagnetic resonance (EPR) spin trapping technique and radical trapping with probe compounds. Using the spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), hydroxyl radical ((•)OH) and sulfate radical anion (SO4(•-)) were measured from ultrasonic activation of persulfate (US-PS). The yield of (•)OH was up to 1 order of magnitude greater than that of SO4(•-). The comparatively high (•)OH yield was attributed to the hydrolysis of SO4(•-) in the warm interfacial region of cavitation bubbles formed from US. Using steady-state approximations, the dissociation rate of PS in cavitating bubble systems was determined to be 3 orders of magnitude greater than control experiments without sonication at ambient temperature. From calculations of the interfacial volume surrounding cavitation bubbles and using the Arrhenius equation, an effective mean temperature of 340 K at the bubble-water interface was estimated. Comparative studies using the probe compounds tert-butyl alcohol and nitrobenzene verified the bubble-water interface as the location for PS activation by high temperature with (•)OH contributing a minor role in activating PS to SO4(•-). The mechanisms unveiled in this study provide a basis for optimizing US-PS as an ISCO technology.

  10. 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

  11. Promoted degradation of perfluorooctanic acid by persulfate when adding activated carbon.

    PubMed

    Lee, Yu-Chi; Lo, Shang-Lien; Kuo, Jeff; Huang, Chin-Pao

    2013-10-15

    Treatment of persistent perfluorooctanoic acid (PFOA) in water using persulfate (PS) oxidation typically requires an elevated temperature or UV irradiation, which is energy-consuming. Under relatively low temperatures of 25-45°C, activated carbon (AC) activated PS oxidation of PFOA was evaluated for its potential of practical applications. With presence of AC in PS oxidation, PFOA removal efficiency at 25°C reached 682% with a high defluorination efficiency of 549% after 12h and few intermediates of short-chain perfluorinated carboxylic acids (PFCAs) were found. The removal and defluorination rates with the combined AC/PS system were approximately 12 and 19 times higher than those of the PS-only system, respectively. Activated carbon not only removes PFOA through adsorption, but also activates PS to form sulfate radicals that accelerate the decomposition and mineralization of PFOA. The activation energy for PS oxidation of PFOA was reduced from 668 to 261kJ/mol by the catalytic effect of AC, which implies a lower reaction temperature and a shorter reaction time would suffice. A 2-cycle schematic reaction mechanism was used to describe PS oxidation of PFOA with the generation of various intermediates and end-products.

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

    EPA Science Inventory

    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(H2O2)-persulfate binary mixture. Thermal activation (60◦C) resulted in t...

  13. 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.

  14. Effect of persulfate and persulfate/H₂O₂ on biodegradability of an anaerobic stabilized landfill leachate.

    PubMed

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

    2015-10-01

    The current study investigated the effects of S2O8(2-) and S2O8(2-)/H2O2 oxidation processes on the biodegradable characteristics of an anaerobic stabilized leachate. Total COD removal efficiency was found to be 46% after S2O8(2-) oxidation (using 4.2 g S2O8(2-)/1g COD0, at pH 7, for 60 min reaction time and at 350 rpm shaking speed), and improved to 81% following S2O8(2-)/H2O2 oxidation process (using 5.88 g S2O8(2-) dosage, 8.63 g H2O2 dosage, at pH 11 and for 120 min reaction time at 350 rpm). Biodegradability in terms of BOD5/COD ratio of the leachate enhanced from 0.09 to 0.1 and to 0.17 following S2O8(2-) and S2O8(2-)/H2O2 oxidation processes, respectively. The fractions of COD were determined before and after each oxidation processes (S2O8(2-) and S2O8(2-)/H2O2). The fraction of biodegradable COD(bi) increased from 36% in raw leachate to 57% and 68% after applying S2O8(2-) and S2O8(2-)/H2O2 oxidation, respectively. As for soluble COD(s), its removal efficiency was 39% and 78% following S2O8(2-) and S2O8(2-)/H2O2 oxidation, respectively. The maximum removal for particulate COD was 94% and was obtained after 120 min of S2O8(2-)/H2O2 oxidation. As a conclusion, S2O8(2-)/H2O2 oxidation could be an efficient method for improving the biodegradability of anaerobic stabilized leachate.

  15. [Advanced Treatment of Effluent from Industrial Park Wastewater Treatment Plant by Ferrous Ion Activated Sodium Persulfate].

    PubMed

    Zhu, Song-mei; Zhou, Zhen; Gu, Ling-yun; Jiang, Hai-tao; Ren, Jia-min; Wang, Luo-chun

    2016-01-15

    Fe(II) activated sodium persulfate (PS) technology was used for advanced treatment of effluent from industrial park wastewater treatment plant. Separate and combined effects of PS/COD, Fe(II)/PS and pH on COD and TOC removal were analyzed by the response surface methodology. Variations of organic substances before and after Fe(II)-PS oxidation were characterized by UV-Vis spectrometry, gel chromatography and three-dimensional fluorescence. PS/COD and Fe(II)/PS had significant effect on COD removal, while all the three factors had significant effect on TOC removal. The combined effect of PS/COD and pH had significant effect on COD removal. COD and TOC removal efficiencies reached 50.7% and 60.6% under optimized conditions of PS/COD 3.47, Fe(II)/PS 3.32 and pH 6.5. Fe(II)-PS oxidation converted macromolecular organic substances to small ones, and reduced contents of protein-, humic- and fulvic-like substances.

  16. Non-photochemical production of singlet oxygen via activation of persulfate by carbon nanotubes.

    PubMed

    Cheng, Xin; Guo, Hongguang; Zhang, Yongli; Wu, Xiao; Liu, Yang

    2017-02-08

    The reaction between persulfate (PS) and carbon nanotubes (CNTs) for the degradation of 2,4-dichlorophenol (2,4-DCP) was investigated. It was demonstrated that CNTs could efficiently activate PS for the degradation of 2,4-DCP. Results suggested that the neither hydroxyl radical (OH) nor sulfate radical (SO4(-)) was produced therein. For the first time, the generation of singlet oxygen ((1)O2) was proved by several methods including electron paramagnetic resonance spectrometry (EPR) and liquid chromatography mass spectrometry measurements. Moreover, the generation of the superoxide radical as a precursor of the singlet oxygen was also confirmed by using certain scavengers and EPR measurement, in which the presence of molecular oxygen was not required as a precursor of (1)O2. The efficient generation of (1)O2 using the PS/CNTs system without any light irradiation can be employed for the selective oxidation of aqueous organic compounds under neutral conditions with the mineralization and toxicity evaluated. A kinetic model was developed to theoretically evaluate the adsorption and oxidation of 2,4-DCP on the CNTs. Accordingly, a catalytic mechanism was proposed involving the formation of a dioxirane intermediate between PS and CNTs, and the subsequent decomposition of this intermediate into (1)O2.

  17. 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.

  18. UV/persulfate preoxidation to improve coagulation efficiency of Microcystis aeruginosa.

    PubMed

    Chen, Yiqun; Xie, Pengchao; Wang, Zongping; Shang, Ran; Wang, Songlin

    2017-01-15

    The performance of UV-activated persulfate (UV/PS) technology as preoxidation process to enhance Microcystis aeruginosa removal by subsequent coagulation-sedimentation was firstly evaluated. The results demonstrate that UV/PS preoxidation could successfully promote coagulation of algae cells through the effective neutralization of zeta potential, which was caused by the changes of cell morphology, size distribution and surface properties after simultaneous UV irradiation and formed reactive species (i.e. SO4(-) and HO) oxidation. Since excessive oxidation would cause cell rupture along with the release of organics, which could deteriorate coagulation efficiency, optimal PS dose (60mg/L) and UV dose (375mJ/cm(2)) were proposed to exist in this study. The concentrations of extracellular algal organic matter (AOM) sharply increased by 48.2% during the preoxidation period, while gradually decreased in the following coagulation and sedimentation. Most of the concerned disinfection by-products (DBPs) monotonically decreased or followed fluctuant reduction with increasing PS doses, whereas the trichloromethane, trichloroacetic acid and dichloroacetonitrile persistently increased, which was inferred to be related to the variation of AOM. This study suggests that UV/PS might be a potential pretreatment process to assist coagulation on the removal of algae.

  19. Degradation of carbon tetrachloride in aqueous solution in the thermally activated persulfate system.

    PubMed

    Xu, Minhui; Gu, Xiaogang; Lu, Shuguang; Qiu, Zhaofu; Sui, Qian; Miao, Zhouwei; Zang, Xueke; Wu, Xiaoliang

    2015-04-09

    Thermal activation of persulfate (PS) has been identified to be effective in the destruction of organic pollutants. The feasibility of carbon tetrachloride (CT) degradation in the thermally activated PS system was evaluated. The experimental results showed that CT could be readily degraded at 50 °C with a PS concentration of 0.5M, and CT degradation and PS consumption followed the pseudo-first order kinetic model. Superoxide radical anion (O2(*-)) was the predominant radical species responsible for CT degradation and the split of CCl was proposed as the possible reaction pathways for CT degradation. The process of CT degradation was accelerated by higher PS dose and lower initial CT concentration. No obvious effect of the initial pH on the degradation of CT was observed in the thermally activated PS system. Cl(*-), HCO3(*-), and humic acid (HA) had negative effects on CT degradation. In addition, the degradation of CT in the thermally activated PS system could be significantly promoted by the solvents addition to the solution. In conclusion, the thermally activated PS process is a promising option in in-situ chemical oxidation/reduction remediation for degrading highly oxidized organic contaminants such as CT that is widely detected in contaminated sites.

  20. Colloidal photonic glass for electro-optic display stabilized with potassium persulfate (KPS) in polar solvent

    NASA Astrophysics Data System (ADS)

    Lee, Hye-Young; Kim, Young-Seok; Yi, Gi-Ra

    2016-04-01

    We introduced carbon-shell with potassium persulfate structure to modify the repulsive force between particles and minimize scattered light. The reflected structural color varied from blue to red and showed high color purity with high cycle stability.

  1. Silver-catalyzed PuO sub 2 dissolution with persulfate

    SciTech Connect

    Fisher, F D; Barney, G S; Cooper, T D; Duchsherer, M J

    1991-06-01

    This report consists of 14 slides and associated narrative for a presentation to be given at the 15th Annual Actinide Separations Conference on silver-catalyzed PuO{sub 2} dissolution with persulfate. (JL)

  2. 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.

  3. [Degradation of Acid Orange 7 with Persulfate Activated by Silver Loaded Granular Activated Carbon].

    PubMed

    Wang, Zhong-ming; Huang, Tian-yin; Chen, Jia-bin; Li, Wen-wei; Zhang, Li-ming

    2015-11-01

    Granular activated carbon with silver loaded as activator (Ag/GAC) was prepared using impregnation method. N2 adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were adopted to characterize the Ag/GAC, showing that silver was successfully loaded on granular activated carbon. The oxidation degradation of acid orange 7 (AO7) by the Ag/GAC activated by persulfate (PS) was investigated at ambient temperature. The influences of factors such as Ag loading, PS or Ag/GAC dosages and initial pH on the degradation of AO7 were evaluated. The results demonstrated that the degradation rate of AO7 could reach more than 95.0% after 180 min when the Ag loading content, PS/AO7 molar ratio, the Ag/GAC dosage were 12.7 mg x g(-1), 120: 1, 1.0 g x L(-1), respectively. The initial pH had significant effect on the AO7 degradation, with pH 5.0 as the optimal pH for the degradation of AO7. The possible degradation pathway was proposed for the AO7 degradation by using UV-visible spectroscopy and gas chromatography-mass spectrometry (GG/MS). The azo bond and naphthalene ring in the AO7 were destroyed during the degradation, with phthalic acid and acetophenone as the main degradation products.

  4. Activated carbon fiber for heterogeneous activation of persulfate: implication for the decolorization of azo dye.

    PubMed

    Chen, Jiabin; Hong, Wei; Huang, Tianyin; Zhang, Liming; Li, Wenwei; Wang, Ying

    2016-09-01

    Activated carbon fiber (ACF) was used as a green catalyst to activate persulfate (PS) for oxidative decolorization of azo dye. ACF demonstrated a higher activity than activated carbon (AC) to activate PS to decolorize Orange G (OG). The decolorization efficiency of OG increased as ACF loading, PS dosage, and temperature increased. OG decolorization followed a pseudo first-order kinetics, and the activation energy was 40.902 kJ/mol. pH had no apparent effect on OG decolorization. Radical quenching experiments with various radical scavengers (e.g., alcohols, phenol) showed that radical-induced decolorization of OG took place on the surface of ACF, and both SO4 (·-) and HO· were responsible for OG decolorization. The impact of inorganic salts was also evaluated because they are important compositions of dye wastewater. Cl(-) and SO4 (2-) exhibited a promoting effect on OG decolorization, and the accelerating rate increased with elevating dosage of ions. Addition of Cl(-) and SO4 (2-) could increase the adsorption of OG on ACF surface, thus favorable for OG decolorization caused by the surface-bound SO4 (·-) and HO·. Conversely, HCO3 (-) and humic acid (HA) slightly inhibited OG decolorization. The azo band and naphthalene ring on OG were remarkably destructed to other intermediates and finally mineralized to CO2 and H2O.

  5. 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

  6. Flow injection chemiluminescence determination of vitamin B12 using on-line UV-persulfate photooxidation and charge coupled device detection.

    PubMed

    Murillo Pulgarín, José A; García Bermejo, Luisa F; Sánchez García, M Nieves

    2011-01-01

    A sensitive chemiluminescence method for vitamin B(12) using a charge-coupled device (CCD) photodetector combined with on-line UV-persulfate oxidation in a simple continuous flow system has been developed. The principle for the determination of vitamin B(12) is based on the enhancive effect of cobalt (II) on the chemiluminescence reaction between luminol and percarbonate in alkaline medium. In addition, percarbonate has been investigated and proposed as a powerful source of hydrogen peroxide as oxidant agent in this chemiluminescence reaction. The digestion of vitamin B(12) to release the cobalt (II) is reached by UV irradiation treatment in a persulfate medium. The CCD detector, directly connected to the flow cell, is used with the continuous flow manifold to obtain the full spectral characteristics of cobalt (II) catalyzed luminol-percarbonate reaction. The vitamin B(12) oxidation process and chemical conditions for the chemiluminescence reaction were investigated and optimized. The increment of the emission intensity was proportional to the concentration of vitamin B(12) , giving a second-order calibration graph over the cobalt (II) concentration range from 10 to 5000 μg L(-1)(r(2) = 0.9985) with a detection limit of 9.3 μg L(-1). The proposed method was applied to the determination of vitamin B(12) in different kinds of pharmaceuticals.

  7. Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion.

    PubMed

    Jiang, Xiaoxuan; Wu, Yanlin; Wang, Peng; Li, Hongjing; Dong, Wenbo

    2013-07-01

    Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO4(-·)), which was generated by the activation of persulfate (S2O8(2-)) with ferrous ion (Fe(2+)). S2O8(2-) was activated by Fe(2+) to produce SO4(-·), and iron powder (Fe(0)) was used as a slow-releasing source of dissolved Fe(2+). The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S2O8(2-) or Fe(2+) concentrations and then decreased with excess Fe(2+) concentration. The adding mode of Fe(2+) had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97% with sequential addition of Fe(2+), while complete degradation was observed with continuous diffusion of Fe(2+), and the latter achieved higher TOC removal rate. When Fe(0) was employed as a slow-releasing source of dissolved Fe(2+), 100% of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85%) was obtained within 2 h. In the Fe(0)-S2O8(2-) system, Fe(0) as the activator of S2O8(2-) could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe(0)-S2O8(2-) system has perspective for future works.

  8. Degradation of trimethoprim by gamma irradiation in the presence of persulfate

    NASA Astrophysics Data System (ADS)

    Zhang, Zhonglei; Yang, Qi; Wang, Jianlong

    2016-10-01

    The degradation and mineralization of trimethoprim (TMP) by gamma irradiation was investigated in the presence of persulfate (PS). The TMP was degraded at initial concentration of 20 mg/L in aqueous solution with addition of 0, 0.5, 1, 1.5, 2 mM persulfate respectively. The effect of pH values (6.5, 7.5 and 8.5) on TMP degradation was also determined. The experimental results showed that the degradation and mineralization of TMP could be significantly enhanced by persulfate at acidic condition (pH=6.5). Several intermediate products generated during gamma irradiation process through hydroxylation, demethylation and cleavage were identified using liquid chromatography with tandem mass spectrometry (HPLC-MS). The degradation pathway of TMP was tentatively proposed based on the identification of intermediate products.

  9. Phenol abatement using persulfate activated by nZVI, H2O2 and NaOH and development of a kinetic model for alkaline activation.

    PubMed

    Lominchar, Miguel A; Rodríguez, Sergio; Lorenzo, David; Santos, Noelia; Romero, Arturo; Santos, Aurora

    2017-02-24

    Three persulfate (PS) activation methods (nanoparticles of zero-valent iron (nZVI), hydrogen peroxide and alkali) were compared using phenol as target pollutant. Firstly, four experiments were conducted at 25°C in a batch way using the same initial phenol and oxidant concentrations (10 mM and 420 mM, respectively), being the molar ratio activator/PS fixed to 0.005 with nZVI (mass ratio 0.0011 nZVI/PS), to 2 using hydrogen peroxide and to 2 and 4 with NaOH. Phenol and PS conversions and aromatic byproducts profiles during 168 h reaction time were measured and compared, as well as mineralization and ecotoxicity of the samples. It was found that both phenol and aromatic byproducts (catechol and hydroquinone) totally disappeared using PS activated by alkali before 24 h, while a significant amount of aromatic intermediates was obtained with nZVI and H2O2. Additional runs were carried out using shorter times (0-2 h) to discriminate the oxidation route and the kinetic model of phenol abatement by using PS activated by alkali. Different initial concentrations of phenol (5-15 mM), PS (210 and 420 mM) and molar ratio NaOH/PS (2 and 4) were employed. The kinetic model obtained predicts accurately the evolution of phenol, persulfate, hydroquinone and catechol.

  10. Ultra-sustainable Fe78Si9B13 metallic glass as a catalyst for activation of persulfate on methylene blue degradation under UV-Vis light

    NASA Astrophysics Data System (ADS)

    Jia, Zhe; Duan, Xiaoguang; Zhang, Wenchang; Wang, Weimin; Sun, Hongqi; Wang, Shaobin; Zhang, Lai-Chang

    2016-12-01

    Stability and reusability are important characteristics of advanced catalysts for wastewater treatment. In this work, for the first time, sulfate radicals (SO4•‑) with a high oxidative potential (Eo = 2.5–3.1 V) were successfully activated from persulfate by a Fe78Si9B13 metallic glass. This alloy exhibited a superior surface stability and reusability while activating persulfate as indicated by it being used for 30 times while maintaining an acceptable methylene blue (MB) degradation rate. The produced SiO2 layer on the ribbon surface expanded strongly from the fresh use to the 20th use, providing stable protection of the buried Fe. MB degradation and kinetic study revealed 100% of the dye degradation with a kinetic rate k = 0.640 within 20 min under rational parameter control. The dominant reactive species for dye molecule decomposition in the first 10 min of the reaction was hydroxyl radicals (•OH, Eo = 2.7 V) and in the last 10 min was sulfate radicals (SO4•‑), respectively. Empirical operating variables for dye degradation in this work were under catalyst dosage 0.5 g/L, light irradiation 7.7 μW/cm2, and persulfate concentration 1.0 mmol/L. The amorphous Fe78Si9B13 alloy in this work will open a new gate for wastewater remediation.

  11. Ultra-sustainable Fe78Si9B13 metallic glass as a catalyst for activation of persulfate on methylene blue degradation under UV-Vis light

    PubMed Central

    Jia, Zhe; Duan, Xiaoguang; Zhang, Wenchang; Wang, Weimin; Sun, Hongqi; Wang, Shaobin; Zhang, Lai-Chang

    2016-01-01

    Stability and reusability are important characteristics of advanced catalysts for wastewater treatment. In this work, for the first time, sulfate radicals (SO4∙−) with a high oxidative potential (Eo = 2.5–3.1 V) were successfully activated from persulfate by a Fe78Si9B13 metallic glass. This alloy exhibited a superior surface stability and reusability while activating persulfate as indicated by it being used for 30 times while maintaining an acceptable methylene blue (MB) degradation rate. The produced SiO2 layer on the ribbon surface expanded strongly from the fresh use to the 20th use, providing stable protection of the buried Fe. MB degradation and kinetic study revealed 100% of the dye degradation with a kinetic rate k = 0.640 within 20 min under rational parameter control. The dominant reactive species for dye molecule decomposition in the first 10 min of the reaction was hydroxyl radicals (∙OH, Eo = 2.7 V) and in the last 10 min was sulfate radicals (SO4∙−), respectively. Empirical operating variables for dye degradation in this work were under catalyst dosage 0.5 g/L, light irradiation 7.7 μW/cm2, and persulfate concentration 1.0 mmol/L. The amorphous Fe78Si9B13 alloy in this work will open a new gate for wastewater remediation. PMID:27922099

  12. Ultra-sustainable Fe78Si9B13 metallic glass as a catalyst for activation of persulfate on methylene blue degradation under UV-Vis light.

    PubMed

    Jia, Zhe; Duan, Xiaoguang; Zhang, Wenchang; Wang, Weimin; Sun, Hongqi; Wang, Shaobin; Zhang, Lai-Chang

    2016-12-06

    Stability and reusability are important characteristics of advanced catalysts for wastewater treatment. In this work, for the first time, sulfate radicals (SO4∙(-)) with a high oxidative potential (E(o) = 2.5-3.1 V) were successfully activated from persulfate by a Fe78Si9B13 metallic glass. This alloy exhibited a superior surface stability and reusability while activating persulfate as indicated by it being used for 30 times while maintaining an acceptable methylene blue (MB) degradation rate. The produced SiO2 layer on the ribbon surface expanded strongly from the fresh use to the 20(th) use, providing stable protection of the buried Fe. MB degradation and kinetic study revealed 100% of the dye degradation with a kinetic rate k = 0.640 within 20 min under rational parameter control. The dominant reactive species for dye molecule decomposition in the first 10 min of the reaction was hydroxyl radicals (∙OH, E(o) = 2.7 V) and in the last 10 min was sulfate radicals (SO4∙(-)), respectively. Empirical operating variables for dye degradation in this work were under catalyst dosage 0.5 g/L, light irradiation 7.7 μW/cm(2), and persulfate concentration 1.0 mmol/L. The amorphous Fe78Si9B13 alloy in this work will open a new gate for wastewater remediation.

  13. On the Efect of the Oxidative Reagents on the Conductivity of Polyaniline/MMT Nanocomposites

    NASA Astrophysics Data System (ADS)

    Garcia-Bernabé, A.; Gil-Agustí, M.; Ortega, G.; Llovera, P.; Almarza, A.; Vázquez, S.; Amantia, D.; Aubouy, L.

    2010-06-01

    The synthesis of polyaniline has been reported using three different oxidative reagents: ammonium persulfate, potassium iodate and potassium iodate+sodium hypochlorite. This polyaniline has been used to prepare several nanocomposites with different percentage of Montmorillonite. The DC conductivity of the nanocomposites was determined by impedance spectroscopy. The oxidative reagent that gives higher conductivity is ammonium persulfate. The temperature dependence of the conductivity was studied.

  14. Activation of persulfates by natural magnetic pyrrhotite for water disinfection: Efficiency, mechanisms, and stability.

    PubMed

    Xia, Dehua; Li, Yan; Huang, Guocheng; Yin, Ran; An, Taicheng; Li, Guiying; Zhao, Huijun; Lu, Anhuai; Wong, Po Keung

    2017-04-01

    This study introduces natural occurring magnetic pyrrhotite (NP) as an environmentally friendly, easy available, and cost-effective alternative catalyst to activate persulfate (PS) of controlling microbial water contaminants. The E. coli K-12 inactivation kinetics observed in batch experiments was well described with first-order reaction. The optimum inactivation rate (k = 0.47 log/min) attained at a NP dose of 1 g/L and a PS dose of 1 mM, corresponding to total inactivation of 7 log10 cfu/mL cells within 15 min. Measured k increased > 2-fold when temperature increased from 20 to 50 °C; and > 4-fold when pH decreased from 9 to 3. Aerobic conditions were more beneficial to cell inactivation than anaerobic conditions due to more reactive oxygen species (ROS) generated. ROS responsible for the inactivation were identified to be SO4(-) > OH > H2O2 based on a positive scavenging test and in situ ROS determination. In situ characterization suggested that PS effectively bind to NP surface was likely to form charge transfer complex (≡Fe(II)⋯O3SOOSO3(-)), which mediated ROS generation and E. coli K-12 oxidation. The increased cell-envelope lesions consequently aggravated intracellular protein depletion and genome damage to cause definite bacterial death. The NP still maintained good physiochemical structure and stable activity even after 4 cycle. Moreover, NP/PS system also exhibited good E. coli K-12 inactivation efficiency in authentic water matrices like surface water and effluents of secondary wastewater.

  15. Biochar supported nanoscale zerovalent iron composite used as persulfate activator for removing trichloroethylene.

    PubMed

    Yan, Jingchun; Han, Lu; Gao, Weiguo; Xue, Song; Chen, Mengfang

    2015-01-01

    Biochar (BC) supported nanoscale zerovalent iron (nZVI) composite was synthesized and used as an activator for persulfate to enhance the trichloroethylene (TCE) removal in aqueous solutions. The degradation efficiency of TCE (0.15mmolL(-1)) was 99.4% in the presence of nZVI/BC (4.5mmolL(-1), nZVI to BC mass ratio was 1:5) and persulfate (4.5mmolL(-1)) within 5min, which was significantly higher than that (56.6%) in nZVI-persulfate system under the same conditions. Owing to large specific surface area and oxygen-containing functional groups of BC, nZVI/BC enhanced the SO4(-) generation and accelerated TCE degradation. On the basis of the characterization and analysis data, possible activation mechanisms of the Fe(2+)/Fe(3+) (Fe(II)/Fe(III)) redox action and the electron-transfer mediator of the BC oxygen functional groups promoting the generation of SO4(-) in nZVI/BC-persulfate system were clarified.

  16. 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).

  17. Achieving synergy between chemical oxidation and stabilization in a contaminated soil.

    PubMed

    Srivastava, Vipul J; Hudson, Jeffrey Michael; Cassidy, Daniel P

    2016-07-01

    Eight in situ solidification/stabilization (ISS) amendments were tested to promote in situ chemical oxidation (ISCO) with activated persulfate (PS) in a contaminated soil. A 3% (by weight) dose of all ISS amendments selected for this study completely activated a 1.5% dose of PS within 3 h by raising temperatures above 30 °C (heat activation) and/or increasing pH above 10.5 (alkaline activation). Heat is released by the reaction of CaO with water, and pH increases because this reaction produces Ca(OH)2. Heat activation is preferred because it generates 2 mol of oxidizing radicals per mole of PS, whereas alkaline activation releases only 1. The relative contribution of heat vs. alkaline activation increased with CaO content of the ISS amendment, which was reflected by enhanced contaminant oxidation with increasing CaO content, and was confirmed by comparing to controls promoting purely heat or alkaline (NaOH) activation. The test soil was contaminated with benzene, toluene, ethylbenzene, and xylenes (BTEX) and polycyclic aromatic hydrocarbons (PAH), particularly naphthalene (NAP). ISS-activated PS oxidized between 47% and 84% of the BTEX & NAP, and between 13% and 33% of the higher molecular weight PAH. ISS-activated PS reduced the leachability of BTEX & NAP by 76%-91% and of the 17 PAH by 83%-96%. Combined ISCO/ISS reduced contaminant leachability far than ISCO or ISS treatments alone, demonstrating the synergy that is possible with combined remedies.

  18. 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…

  19. 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.

  20. 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.

  1. Persulfate-assisted photodegradation of diethylstilbestrol using monoclinic BiVO4 under visible-light irradiation.

    PubMed

    Liu, Yang; Zhang, Yongli; Guo, Hongguang; Cheng, Xin; Liu, Hongwei; Tang, Weihong

    2017-02-01

    In this study, the photosynergistic performance of BiVO4 with persulfate (PS) is demonstrated under visible light irradiation for the first time. Diethylstilbestrol (DES) was selected as a reluctant compound, and factors including dosages of PS and catalyst, solution pHs, initial concertration of DES, and inorganic anions were evaluated. The morphology and chemical state of bismuth vanadate (BiVO4) was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive spectrometer (EDS), and ultraviolet-visible (UV-Vis) diffuse reflectance spectroscopy (DRS). It was found that the degradation of DES was promoted in either acid or alkaline solutions. The increase of PS and BiVO4 dosages was beneficial to the reactions, while incremental concentration of DES showed the inhibiting effect. By scavenging hVB(+), Cl(-) was able to make the promotion, differentiated from the exsiting HCO- 3. Moreover, the photocatalytic mechanism for the BiVO4/PS/vis-light system was proposed by using several probe compounds (isopropanol, tert-butanol, and 1,4-benzoquinone), which consists of h+ VB/e- CB generation and recombination on the surface of BiVO4 as well as free radical oxidation in the solutions. The study provides a distinctive method to treat organic contaminants using visible light in the aqueous environment.

  2. 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.

  3. Degradation of trichloroethene by siderite-catalyzed hydrogen peroxide and persulfate: Investigation of reaction mechanisms and degradation products

    PubMed Central

    Yan, Ni; Liu, Fei; Xue, Qiang; Brusseau, Mark L.; Liu, Yali; Wang, Junjie

    2015-01-01

    A binary catalytic system, siderite-catalyzed hydrogen peroxide (H2O2) coupled with persulfate (S2O82−), was investigated for the remediation of trichloroethene (TCE) contamination. Batch experiments were conducted to investigate reaction mechanisms, oxidant decomposition rates, and degradation products. By using high performance liquid chromatography (HPLC) coupled with electron paramagnetic resonance (EPR), we identified four radicals (hydroxyl (HO·), sulfate (SO4−·), hydroperoxyl (HO2·), and superoxide (O2−·)) in the siderite-catalyzed H2O2-S2O82− system. In the absence of S2O82− (i.e., siderite-catalyzed H2O2), a majority of H2O2 was decomposed in the first hour of the experiment, resulting in the waste of HO·. The addition of S2O82− moderated the H2O2 decomposition rate, producing a more sustainable release of hydroxyl radicals that improved the treatment efficiency. Furthermore, the heat released by H2O2 decomposition accelerated the activation of S2O82−, and the resultant SO4−· was the primary oxidative agent during the first two hours of the reaction. Dichloroacetic acid was firstly detected by ion chromatography (IC). The results of this study indicate a new insight to the reaction mechanism for the catalytic binary H2O2-S2O82− oxidant system, and the delineation of radicals and the discovery of the chlorinated byproduct provide useful information for efficient treatment of chlorinated-solvent contamination in groundwater. PMID:26236152

  4. Degradation of trichloroethene by siderite-catalyzed hydrogen peroxide and persulfate: Investigation of reaction mechanisms and degradation products.

    PubMed

    Yan, Ni; Liu, Fei; Xue, Qiang; Brusseau, Mark L; Liu, Yali; Wang, Junjie

    2015-08-15

    A binary catalytic system, siderite-catalyzed hydrogen peroxide (H2O2) coupled with persulfate (S2O8(2-)), was investigated for the remediation of trichloroethene (TCE) contamination. Batch experiments were conducted to investigate reaction mechanisms, oxidant decomposition rates, and degradation products. By using high performance liquid chromatography (HPLC) coupled with electron paramagnetic resonance (EPR), we identified four radicals (hydroxyl (HO·), sulfate (SO4(-)·), hydroperoxyl (HO2·), and superoxide (O2(-)·)) in the siderite-catalyzed H2O2-S2O8(2-) system. In the absence of S2O8(2-) (i.e., siderite-catalyzed H2O2), a majority of H2O2 was decomposed in the first hour of the experiment, resulting in the waste of HO·. The addition of S2O8(2-) moderated the H2O2 decomposition rate, producing a more sustainable release of hydroxyl radicals that improved the treatment efficiency. Furthermore, the heat released by H2O2 decomposition accelerated the activation of S2O8(2-), and the resultant SO4(-)· was the primary oxidative agent during the first two hours of the reaction. Dichloroacetic acid was firstly detected by ion chromatography (IC). The results of this study indicate a new insight to the reaction mechanism for the catalytic binary H2O2-S2O8(2-) oxidant system, and the delineation of radicals and the discovery of the chlorinated byproduct provide useful information for efficient treatment of chlorinated-solvent contamination in groundwater.

  5. Allergic contact cheilitis due to effervescent dental cleanser: combined responsibilities of the allergen persulfate and prosthesis porosity.

    PubMed

    Le Coz, C J; Bezard, M

    1999-11-01

    A 55-year-old man with a dental prosthesis for 3 years had had a chronic relapsing cheilitis for more than 1 year. He was patch tested with the European standard series, his own topicals, and the dental cleanser at 10% pet. A relevant positive reaction ++ was found to the cleansing agent, which contained 20% potassium persulfate. The breakdown of the test confirmed sensitivity to this agent and to ammonium persulfate, both positive (++) at 2.5% pet. The patient was free of symptoms after he had avoided the cleanser. Subsequent chemical investigations performed with a fragment of a used dental prosthesis revealed strong adsorption of persulfate, both on the resin and on the dental tartar. Cleansing agents, adsorbed on tartar and porous resins of worn dental prostheses, should be considered as potential sensitizers and consequently patch tested on such patients with chronic cheilitis.

  6. 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 (4.2 ± 0.6) × 10(8) M(-1)s(-1) and (7.6 ± 0.6) × 10(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 2 mM 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.

  7. Metal-free catalysis of persulfate activation and organic-pollutant degradation by nitrogen-doped graphene and aminated graphene.

    PubMed

    Chen, Hao; Carroll, Kenneth C

    2016-08-01

    We evaluated three types of functionalized, graphene-based materials for activating persulfate (PS) and removing (i.e., sorption and oxidation) sulfamethoxazole (SMX) as a model emerging contaminant. Although advanced oxidative water treatment requires PS activation, activation requires energy or chemical inputs, and toxic substances are contained in many catalysts. Graphene-based materials were examined herein as an alternative to metal-based catalysts. Results show that nitrogen-doped graphene (N-GP) and aminated graphene (NH2-GP) can effectively activate PS. Overall, PS activation by graphene oxide was not observed in this study. N-GP (50 mg L(-1)) can rapidly activate PS (1 mM) to remove >99.9% SMX within 3 h, and NH2-GP (50 mg L(-1)) activated PS (1 mM) can also remove 50% SMX within 10 h. SMX sorption and total removal was greater for N-GP, which suggests oxidation was enhanced by increasing proximity to PS activation sites. Increasing pH enhanced the N-GP catalytic ability, and >99.9% SMX removal time decreased from 3 h to 1 h when pH increased from 3 to 9. However, the PS catalytic ability was inhibited at pH 9 for NH2-GP. Increases in ionic strength (100 mM NaCl or Na2SO4) and addition of radical scavengers (500 mM ethanol) both had negligible impacts on SMX removal. With bicarbonate addition (100 mM), while the catalytic ability of N-GP remained unaltered, NH2-GP catalytic ability was inhibited completely. Humic acid (250 mg L(-1)) was partially effective in inhibiting SMX removal in both N-GP and NH2-GP systems. These results have implications for elucidating oxidant catalysis mechanisms, and they quantify the ability of functionalization of graphene with hetero-atom doping to effectively catalyze PS for water treatment of organic pollutants including emerging contaminants.

  8. 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.

  9. 76 FR 35402 - Persulfates From the People's Republic of China: Notice of Correction to the Final Results of the...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-06-17

    ... International Trade Administration Persulfates From the People's Republic of China: Notice of Correction to the...; telephone: (202) 482-8173. SUPPLEMENTARY INFORMATION: Correction On May 17, 2011, the Department of Commerce... the PRC is A-570-847. Pursuant to section 751(h) of the Tariff Act of 1930, as amended (``the...

  10. Comparative evaluation of iodoacids removal by UV/persulfate and UV/H2O2 processes.

    PubMed

    Xiao, Yongjun; Zhang, Lifeng; Zhang, Wei; Lim, Kok-Yong; Webster, Richard D; Lim, Teik-Thye

    2016-10-01

    To develop a cost-effective method for post-formation mitigation of iodinated disinfection by-products, degradation of iodoacids by UV, UV/PS (persulfate), and UV/H2O2 was extensively investigated in this study. UV direct photolysis of 4 iodoacids followed first-order kinetics with rate constants in the range of 2.43 × 10(-4)-3.02 × 10(-3) cm(2) kJ(-1). The derived quantum yields (Ф254) of the 4 iodoacids range from 0.13 to 0.34, respectively. A quantitative structure-activity relationship (QSAR) model was subsequently established and applied to predict the direct photolysis rates of 6 other structurally similar iodoacids whose standards are commercially unavailable. At a UV dose of 140 mJ cm(-2) which is typically applied for disinfection of drinking water, the removal percentages of 4 iodoacids were only between 3.35% and 34.7%. Thus, ICH2CO2H (IAA), the most photo-recalcitrant species, was selected as the target compound for removal in the UV/PS and UV/H2O2 processes. The IAA degradation rates decreased with increasing pH from 3 to 11 in both processes. Humic acid (HA) and HCO3(-) had inhibitory effects on IAA degradation in both processes. Cl(-) adversely affected the IAA degradation in the UV/PS process but had no effect in the UV/H2O2 process. Generally, in the deionized (DI) water, surface water, treated drinking water, and secondary effluent, UV/PS process is more effective than UV/H2O2 process for IAA removal, based on the same molar ratio of oxidant: IAA. SO4(-) generated in the UV/PS process yields a greater mineralization of IAA than HO in the UV/H2O2 process. IO3(-) was the predominant end-product in the UV/PS process, while I(-) was the major end-product in the UV/H2O2 process. The respective contributions of UV, HO, and SO4(-) for IAA removal in the UV/PS process were 7.8%, 14.7%, and 77.5%, respectively, at a specific condition (1.5 μM IAA, 60 μM oxidant, and pH 7). Compared to UV/H2O2 process, UV/PS was also observed as more cost

  11. Pretreatment of shale gas drilling flowback fluid (SGDF) by the microscale Fe(0)/persulfate/O3 process (mFe(0)/PS/O3).

    PubMed

    Zhang, Heng; Xiong, Zhaokun; Ji, Fangzhou; Lai, Bo; Yang, Ping

    2017-06-01

    Shale gas drilling flowback fluid (SGDF) generated during shale gas extraction is of great concern due to its high total dissolved solid, radioactive elements and organic matter. To remove the toxic and refractory pollutants in SGDF and improve its biodegradability, a microsacle Fe(0)/Persulfate/O3 process (mFe(0)/PS/O3) was developed to pretreat this wastewater obtained from a shale gas well in southwestern China. First, effects of mFe(0) dosage, O3 flow rate, PS dosage, pH values on the treatment efficiency of mFe(0)/PS/O3 process were investigated through single-factor experiments. Afterward, the optimal conditions (i.e., pH = 6.7, mFe(0) dosage = 6.74 g/L, PS = 16.89 mmol/L, O3 flow rate = 0.73 L/min) were obtained by using response surface methodology (RSM). Under the optimal conditions, high COD removal (75.3%) and BOD5/COD ratio (0.49) were obtained after 120 min treatment. Moreover, compared with control experiments (i.e., mFe(0), O3, PS, mFe(0)/O3, mFe(0)/PS, O3/PS), mFe(0)/PS/O3 system exerted better performance for pollutants removal in SGDF due to strong synergistic effect between mFe(0), PS and O3. In addition, the decomposition or transformation of the organic pollutants in SGDF was analyzed by using GC-MS. Finally, the reaction mechanism of the mFe(0)/PS/O3 process was proposed according to the analysis results of SEM-EDS and XRD. It can be concluded that high-efficient mFe(0)/PS/O3 process was mainly resulted from the combination effect of direct oxidation by ozone and persulfate, heterogeneous and homogeneous catalytic oxidation, Fenton-like reaction and adsorption. Therefore, mFe(0)/PS/O3 process was proven to be an effective method for pretreatment of SGDF prior to biological treatment.

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

    PubMed

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

    2013-11-06

    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 6.3395×10(4) g/mol and 1.69283×10(5) g/mol, respectively, with polydispersity index of 2.7.

  13. 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.

  14. Persistence of Asthmatic Response after Ammonium Persulfate-Induced Occupational Asthma in Mice

    PubMed Central

    Ollé-Monge, Marta; Muñoz, Xavier; Vanoirbeek, Jeroen A. J.; Gómez-Ollés, Susana; Morell, Ferran; Cruz, María-Jesus

    2014-01-01

    Introduction Since persulfate salts are an important cause of occupational asthma (OA), we aimed to study the persistence of respiratory symptoms after a single exposure to ammonium persulfate (AP) in AP-sensitized mice. Material and Methods BALB/c mice received dermal applications of AP or dimethylsulfoxide (DMSO) on days 1 and 8. On day 15, they received a single nasal instillation of AP or saline. Airway hyperresponsiveness (AHR) was assessed using methacholine provocation, while pulmonary inflammation was evaluated in bronchoalveolar lavage (BAL), and total serum immunoglobulin E (IgE), IgG1 and IgG2a were measured in blood at 1, 4, 8, 24 hours and 4, 8, 15 days after the single exposure to the causal agent. Histological studies of lungs were assessed. Results AP-treated mice showed a sustained increase in AHR, lasting up to 4 days after the challenge. There was a significant increase in the percentage of neutrophils 8 hours after the challenge, which persisted for 24 hours in AP-treated mice. The extent of airway inflammation was also seen in the histological analysis of the lungs from challenged mice. Slight increases in total serum IgE 4 days after the challenge were found, while IgG gradually increased further 4 to 15 days after the AP challenge in AP-sensitized mice. Conclusions In AP-sensitized mice, an Ig-independent response is induced after AP challenge. AHR appears immediately, but airway neutrophil inflammation appears later. This response decreases in time; at early stages only respiratory and inflammatory responses decrease, but later on immunological response decreases as well. PMID:25303285

  15. Heat-activated Plasmonic Chemical Sensors for Harsh Environments

    SciTech Connect

    Carpenter, Michael; Oh, Sang-Hyun

    2015-12-01

    A passive plasmonics based chemical sensing system to be used in harsh operating environments was investigated and developed within this program. The initial proposed technology was based on combining technologies developed at the SUNY Polytechnic Institute Colleges of Nanoscale Science and Engineering (CNSE) and at the University of Minnesota (UM). Specifically, a passive wireless technique developed at UM was to utilize a heat-activated plasmonic design to passively harvest the thermal energy from within a combustion emission stream and convert this into a narrowly focused light source. This plasmonic device was based on a bullseye design patterned into a gold film using focused ion beam methods (FIB). Critical to the design was the use of thermal stabilizing under and overlayers surrounding the gold film. These stabilizing layers were based on both atomic layer deposited films as well as metal laminate layers developed by United Technologies Aerospace Systems (UTAS). While the bullseye design was never able to be thermally stabilized for operating temperatures of 500oC or higher, an alternative energy harvesting design was developed by CNSE within this program. With this new development, plasmonic sensing results are presented where thermal energy is harvested using lithographically patterned Au nanorods, replacing the need for an external incident light source. Gas sensing results using the harvested thermal energy are in good agreement with sensing experiments, which used an external incident light source. Principal Component Analysis (PCA) was used to reduce the wavelength parameter space from 665 variables down to 4 variables with similar levels of demonstrated selectivity. The method was further improved by patterning rods which harvested energy in the near infrared, which led to a factor of 10 decrease in data acquisition times as well as demonstrated selectivity with a reduced wavelength data set. The combination of a plasmonic-based energy harvesting

  16. The effects of post-persulfate-digestion procedures on total phosphorus analysis in water.

    PubMed

    Zhou, Meifang; Struve, David M

    2004-11-01

    There are differences between the EPA Method 365 and the APHA-AWWA-WEF's Standard Method 4500 with respect to the post-digestion treatment procedures of the persulfate-digested water. The effects on total phosphorus analysis of different post-digestion treatment procedures, such as neutralization and reacidification, and shaking/settling, were investigated in this study using the total phosphorus measurements of water samples from the Everglades Round Robin (ERR) study and comparing the results with the ERR study. The effects of the insoluble particles or phosphorus adsorption/precipitation on/with Al and Fe hydroxides in different post-digestion treatment procedures adequately accounted for the differences between the most probable value and the higher or lower total phosphorus measurements reported in the ERR study. Based on the results of this investigation we recommend that a clearly defined set of digestion and post-digestion treatment procedures be adopted as the standard for total phosphorus analysis using the ascorbic acid method.

  17. 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.

  18. Degradation of diclofenac by UV-activated persulfate process: Kinetic studies, degradation pathways and toxicity assessments.

    PubMed

    Lu, Xian; Shao, Yisheng; Gao, Naiyun; Chen, Juxiang; Zhang, Yansen; Xiang, Huiming; Guo, Youluo

    2017-03-21

    Diclofenac (DCF) is the frequently detected non-steroidal pharmaceuticals in the aquatic environment. In this study, the degradation of DCF was evaluated by UV-254nm activated persulfate (UV/PS). The degradation of DCF followed the pseudo first-order kinetics pattern. The degradation rate constant (kobs) was accelerated by UV/PS compared to UV alone and PS alone. Increasing the initial PS dosage or solution pH significantly enhanced the degradation efficiency. Presence of various natural water constituents had different effects on DCF degradation, with an enhancement or inhibition in the presence of inorganic anions (HCO3(-) or Cl(-)) and a significant inhibition in the presence of NOM. In addition, preliminary degradation mechanisms and major products were elucidated using LC-MS/MS. Hydroxylation, decarbonylation, ring-opening and cyclation reaction involving the attack of SO4(•)(-) or other substances, were the main degradation mechanism. TOC analyzer and Microtox bioassay were employed to evaluate the mineralization and cytotoxicity of solutions treated by UV/PS at different times, respectively. Limited elimination of TOC (32%) was observed during the mineralization of DCF. More toxic degradation products and their related intermediate species were formed, and the UV/PS process was suitable for removing the toxicity. Of note, longer degradation time may be considered for the final toxicity removal.

  19. 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.

  20. Comparison of the effectiveness of soil heating prior or during in situ chemical oxidation (ISCO) of aged PAH-contaminated soils.

    PubMed

    Ranc, Bérénice; Faure, Pierre; Croze, Véronique; Lorgeoux, Catherine; Simonnot, Marie-Odile

    2017-03-15

    Thermal treatments prior or during chemical oxidation of aged polycyclic aromatic hydrocarbon (PAH)-contaminated soils have already shown their ability to increase oxidation effectiveness. However, they were never compared on the same soil. Furthermore, oxygenated polycyclic aromatic hydrocarbons (O-PACs), by-products of PAH oxidation which may be more toxic and mobile than the parent PAHs, were very little monitored. In this study, two aged PAH-contaminated soils were heated prior (60 or 90 °C under Ar for 1 week) or during oxidation (60 °C for 1 week) with permanganate and persulfate, and 11 O-PACs were monitored in addition to the 16 US Environmental Protection Agency (US EPA) PAHs. Oxidant doses were based on the stoichiometric oxidant demand of the extractable organic fraction of soils by using organic solvents, which is more representative of the actual contamination than only the 16 US EPA PAHs. Higher temperatures actually resulted in more pollutant degradation. Two treatments were about three times more effective than the others: soil heating to 60 °C during persulfate oxidation and soil preheating to 90 °C followed by permanganate oxidation. The results of this study showed that persulfate effectiveness was largely due to its thermal activation, whereas permanganate was more sensitive to PAH availability than persulfate. The technical feasibility of these two treatments will soon be field-tested in the unsaturated zone of one of the studied aged PAH-contaminated soils.

  1. 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.

  2. 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.

  3. Photochemical oxidation of persistent cyanide-related compounds

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

  4. [Influences of pH and complexing agents on degradation of reactive brilliant blue KN-R by ferrous activated persulfate].

    PubMed

    Zhang, Cheng; Wan, Jin-Quan; Ma, Yong-Wen; Wang, Yan; Huang, Ming-Zhi; Lan, Ming

    2012-03-01

    The influences of pH and complexing agents on degradation of reactive brilliant blue KN-R by ferrous activated persulfate were investigated, and finally the complexed and the uncomplexed system were compared. Because the lower the pH the more quickly will be the dissociation of S2O8(2-) to the SO4(-*) and the ORP of the dominant radical SO4(-*) in the acidic condition is higher than the dominant radical *OH in the alkaline condition, KN-R degradation rates in acidic condition are far outweigh in the neutral and alkaline conditions. When pH value was 3, the residual rate of KN-R was 17.0% within 3 hours by EDTA system with the lowest PS consumption rate 32.3%, so EDTA was the best complexing agent choice in acidic condition. When pH value was 7, the residual rates of KN-R were 11.3%, 12.4% within 3 days by EDTA, citric acid system with the PS residual rates 28.9%, 28.0% respectively, so EDTA, citric acid were the better choices in the neutral condition. When pH value was 10, glucose acid, citric acid, EDTA and tartaric acid systems all had the similar KN-R degradation rates and PS residual rates, so all could acted as the complexing agents, when the system contained trace amounts of ferrous, the addition of complexing agent would greatly improve the degradation rate of pollutant, from original 52.5% to 79.3% of 3 d, so PS is suitable for in situ chemical oxidation (ISCO).

  5. Enhanced reactivity of microscale Fe/Cu bimetallic particles (mFe/Cu) with persulfate (PS) for p-nitrophenol (PNP) removal in aqueous solution.

    PubMed

    Ji, Qingqing; Li, Jun; Xiong, Zhaokun; Lai, Bo

    2017-04-01

    In this study, batch experiments were conducted to examine the enhanced reactivity of microscale Fe/Cu bimetallic particles (mFe/Cu) with persulfate (PS) for p-nitrophenol (PNP) removal in aqueous solution. The key operating parameters (i.e., theoretical Cu mass loadings (TMLCu), mFe/Cu dosage, PS dose, initial pH and temperature) were optimized by the batch experiments, respectively. The experimental data were followed well the pseudo-first-order kinetic model. Result reveals that refractory PNP (500 mg L(-1)) was effectively degraded by mFe/Cu-PS system with removal of 98.4% and kobs of 1.91 min(-1) after only 3 min treatment under the optimal operating conditions. Moreover, compared with control experiments (i.e., mFe/Cu, microscale Fe(0) with PS (mFe(0)-PS), and PS alone), mFe/Cu-PS system exerted better performance for PNP removal due to the strong synergistic effect between PS and mFe/Cu. According to the analysis results of degradation kinetics of PNP, COD (chemical oxygen demand) removal, UV-vis absorption spectra and the intermediates formed, the results reveal that the PNP removal by mFe/Cu-PS system was mainly attributed to reduction accompanied slight oxidation. And based on the analysis of surface characteristics of mFe/Cu particles, it is further demonstrated that PS could enhance the reactivity of mFe/Cu through rapid corrosion of iron surface and decrease of surface passivation of mFe/Cu surface when the low molar ratio of PS to mFe/Cu (i.e., 1:43) was used in this study. These results also illustrates mFe/Cu-PS can be as a high efficient pretreatment technology for the removal of toxic refractory PNP from wastewater.

  6. 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...

  7. Adiabatic polymerization of acrylamide in water under the effect of the potassium persulfate-sodium metabisulfite-copper sulfate system

    SciTech Connect

    Kurenkov, V.F.; Baiburdov, T.A.; Stupen'kova, L.L.

    1988-04-10

    Since adiabatic polymerization of acrylamide (AA) has been studied very little and the information on the effect of copper ions on polymerization of AA prepared in dilute aqueous solutions is very limited, the features of adiabatic polymerization of AA in concentrated aqueous solutions in the presence of the potassium persulfate-sodium metabisulfite-copper sulfate redox initiating system were investigated in this study. The empirical equation for the overall rate of adiabatic polymerization of acrylamide in concentrated aqueous solutions was found, and the effective total activation energy, which decreases with an increase in the concentration of CuSO/sub 4/, was determined. An increase in the molecular weight of the polymer with an increase in the concentration of the monomer and a decrease in the concentration of the components of the initiating system was demonstrated.

  8. 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

    2015-09-30

    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.

  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. 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

  12. 13-week inhalation toxicity study (including 6- and 13-week recovery periods) with ammonium persulfate dust in albino rats.

    PubMed

    Signorin, J; Ulrich, C E; Butt, M T; D'Amato, E A

    2001-11-01

    The subchronic inhalation toxicity of ammonium persulfate was characterized using Sprague-Dawley rats (20/sex/group) at respirable dust concentrations of 0, 5.0, 10.3, and 25 mg/m(3). Whole-body exposures were conducted 6 h/day, 5 days/wk for 13 wk. Gravimetric airborne test material samples were taken daily and particle size samples were taken weekly from each exposure chamber for analysis. Ten animals/sex/group were necropsied after 13 wk of exposure, and 5 animals/sex/group were held for 6- and 13-wk recovery periods. Animals were observed for clinical signs. Effects on body weight, food consumption, clinical chemistry and hematology, ophthalmologic parameters, organ weights, gross lesions, and histopathology were evaluated. There were no exposure-related deaths during the study. Rales and increased respiration rate were noted in both males and females in the 25 mg/m(3) group, and in a few animals in the 10.3 mg/m(3) group. The incidence of these clinical signs decreased to zero during the first few weeks of the recovery period. Body weights for both males and females in the 25 mg/m(3) group were significantly depressed during most of the exposure period compared to the control group. By the end of the recovery period, body weights for the exposed animals were similar to the control group values. Lung weights were elevated in the 25 mg/m(3) group after 13 wk of exposure, but were similar to controls at 6 wk postexposure. Irritation of the trachea and bronchi/bronchiole was noted microscopically after 13 wk of exposure to 25 mg/m(3). These lesions had recovered by 6 wk postexposure. Based on the results of this study, the no-observed-adverse-effect level (NOAEL) was 10.3 mg/m(3), while the no-observed-effect level (NOEL) for exposure of rats to a dust aerosol of ammonium persulfate was 5.0 mg/m(3).

  13. 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

  14. 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.

  15. Heat-activated heat-pump development and potential application of Stirling-engine technology

    NASA Astrophysics Data System (ADS)

    Fairchild, P. D.; West, C. D.

    1982-06-01

    Presented is a brief overview of the heat-activated heat pump technology development program being carried out with emphasis on the Stirling engine technology projects. The major projects are reviewed as they were formulated and carried out under the previous product development guidelines. The revised technology development focus and current status of those major hardware projects are discussed. The key issues involved in applying Stirling engine technology to heat pump equipment are assessed. The approach and planned future activities to address those issues are described. Also included are brief descriptions of two projects in this area supported by the Gas Research Institute.

  16. Degradation of MDEA in aqueous solution in the thermally activated persulfate system.

    PubMed

    Li, Yong-Tao; Yue, Dong; Wang, Bing; Ren, Hong-Yang

    2017-03-01

    The feasibility of methyldiethanolamine (MDEA) degradation in thermally activated PS system was evaluated. Effects of the PS concentration, pH, activation temperature and reaction time on MDEA degradation were investigated. Simultaneity, the thermodynamic analysis and degradation process were also performed. Several findings were made in this study including the following: the degradation rates of MDEA in thermally activated PS systems were higher than other systems. MDEA could be readily degraded at 40°C with a PS concentration of 25.2 mM, the process of MDEA degradation was accelerated by higher PS dose and reaction temperature, and MDEA degradation and PS consumption followed the pseudo-first-order kinetic model. The thermodynamic analysis showed that the activation process followed an endothermic path of the positive value of [Formula: see text] and spontaneous with the negative value of [Formula: see text], high temperature was favorable to the degradation of MDEA with the apparent activation energy of 87.11 KJ/mol. Combined FT-IR with GC-MS analysis techniques, MDEA could be oxidative degraded after the C-N bond broken to small molecules of organic acids, alcohols or nitro compounds until oxidized to CO2 and H2O. In conclusion, the thermally activated PS process is a promising option for degrading MDEA effluent liquor.

  17. Inducible Transposition of a Heat-Activated Retrotransposon in Tissue Culture.

    PubMed

    Masuta, Yukari; Nozawa, Kosuke; Takagi, Hiroki; Yaegashi, Hiroki; Tanaka, Keisuke; Ito, Tasuku; Saito, Hideyuki; Kobayashi, Hisato; Matsunaga, Wataru; Masuda, Seiji; Kato, Atsushi; Ito, Hidetaka

    2016-12-23

    A transposition of a heat-activated retrotransposon named ONSEN required compromise of a small RNA-mediated epigenetic regulation that includes RNA-directed DNA methylation (RdDM) machinery after heat treatment. In the current study, we analyzed the transcriptional and transpositional activation of ONSEN to better understand the underlying molecular mechanism involved in the maintenance and/or induction of transposon activation in plant tissue culture. We found the transposition of heat-primed ONSEN during tissue culture independently of RdDM mutation. The heat activation of ONSEN transcripts was not significantly up-regulated in tissue culture compared with that in heat-stressed seedlings, indicating that the transposition of ONSEN was regulated independently of the transcript level. RdDM-related genes were up-regulated by heat stress in both tissue culture and seedlings. The level of DNA methylation of ONSEN did not show any change in tissue culture, and the amount of ONSEN-derived small RNAs was not affected by heat stress. The results indicated that the transposition of ONSEN was regulated by an alternative mechanism in addition to the RdDM-mediated epigenetic regulation in tissue culture. We applied the tissue culture-induced transposition of ONSEN to Japanese radish, an important breeding species of the family Brassicaceae. Several new insertions were detected in a regenerated plant derived from heat-stressed tissues and its self-fertilized progeny, revealing the possibility of molecular breeding without genetic modification.

  18. 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.

  19. 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

  20. Toward elucidating the heat activation mechanism of the TRPV1 channel gating by molecular dynamics simulation.

    PubMed

    Wen, Han; Qin, Feng; Zheng, Wenjun

    2016-12-01

    As a key cellular sensor, the TRPV1 cation channel undergoes a gating transition from a closed state to an open state in response to various physical and chemical stimuli including noxious heat. Despite years of study, the heat activation mechanism of TRPV1 gating remains enigmatic at the molecular level. Toward elucidating the structural and energetic basis of TRPV1 gating, we have performed molecular dynamics (MD) simulations (with cumulative simulation time of 3 μs), starting from the high-resolution closed and open structures of TRPV1 solved by cryo-electron microscopy. In the closed-state simulations at 30°C, we observed a stably closed channel constricted at the lower gate (near residue I679), while the upper gate (near residues G643 and M644) is dynamic and undergoes flickery opening/closing. In the open-state simulations at 60°C, we found higher conformational variation consistent with a large entropy increase required for the heat activation, and both the lower and upper gates are dynamic with transient opening/closing. Through ensemble-based structural analyses of the closed state versus the open state, we revealed pronounced closed-to-open conformational changes involving the membrane proximal domain (MPD) linker, the outer pore, and the TRP helix, which are accompanied by breaking/forming of a network of closed/open-state specific hydrogen bonds. By comparing the closed-state simulations at 30°C and 60°C, we observed heat-activated conformational changes in the MPD linker, the outer pore, and the TRP helix that resemble the closed-to-open conformational changes, along with partial formation of the open-state specific hydrogen bonds. Some of the residues involved in the above key hydrogen bonds were validated by previous mutational studies. Taken together, our MD simulations have offered rich structural and dynamic details beyond the static structures of TRPV1, and promising targets for future mutagenesis and functional studies of the TRPV1 channel

  1. The effects of heat activation on Bacillus spore germination, with nutrients or under high pressure, with or without various germination proteins.

    PubMed

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

    2015-04-01

    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 75 °C heat activation times: 15 min for l-valine germination via the GerA GR and 4 h for germination with the L-asparagine-glucose-fructose-K(+) 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.

  2. Remediation of PAH-contaminated sediments by chemical oxidation.

    PubMed

    Ferrarese, Elisa; Andreottola, Gianni; Oprea, Irina Aura

    2008-03-21

    The aim of this experimental investigation was to assess the feasibility of using chemical oxidation to degrade sorbed polycyclic aromatic hydrocarbons (PAHs) in case of old date sediment contamination. For this purpose several bench scale laboratory tests were performed, with the following liquid reactants: hydrogen peroxide, modified Fenton's reagent, activated sodium persulfate, potassium permanganate, as well as a combination of potassium permanganate and hydrogen peroxide, and a combination of activated sodium persulfate and hydrogen peroxide. The main target of the study was to find out what liquid oxidant was more effective in reducing the pollutant content and to assess the optimal reactant doses. The initial total PAH concentration in sediment samples was about 2800mg/kgSS (light PAHs about 1600mg/kgSS, heavy PAHs about 1200mg/kgSS) and a 95% degradation was required to meet the remediation goals. Based on the results of this study, chemical oxidation proved to be an effective remediation technology, amenably applicable for the ex situ remediation of the sediments of concern. Different reactants resulted however in different removal efficiencies. The best remediation performances were achieved with the use of modified Fenton's reagent, hydrogen peroxide and potassium permanganate, with oxidant dosages about 100mmols per 30g sediment sample. In all these cases the residual heavy PAH concentration in the treated samples was below 100mg/kgSS. The optimal oxidant dosages determined in this study were quite high, as sorbed PAH mineralization requires very vigorous oxidation conditions, especially for soils and sediments with high organic matter content. The results indicated that the optimal oxidant dose must be carefully determined under site-specific conditions. In fact, if the oxidation conditions are not strong enough, the reactants cannot be able to attack the most recalcitrant compounds, while also too high oxidant doses can result in a decrease in the

  3. 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.

  4. Evaluation of a Stochastic Inactivation Model for Heat-Activated Spores of Bacillus spp. ▿

    PubMed Central

    Corradini, Maria G.; Normand, Mark D.; Eisenberg, Murray; Peleg, Micha

    2010-01-01

    Heat activates the dormant spores of certain Bacillus spp., which is reflected in the “activation shoulder” in their survival curves. At the same time, heat also inactivates the already active and just activated spores, as well as those still dormant. A stochastic model based on progressively changing probabilities of activation and inactivation can describe this phenomenon. The model is presented in a fully probabilistic discrete form for individual and small groups of spores and as a semicontinuous deterministic model for large spore populations. The same underlying algorithm applies to both isothermal and dynamic heat treatments. Its construction does not require the assumption of the activation and inactivation kinetics or knowledge of their biophysical and biochemical mechanisms. A simplified version of the semicontinuous model was used to simulate survival curves with the activation shoulder that are reminiscent of experimental curves reported in the literature. The model is not intended to replace current models to predict dynamic inactivation but only to offer a conceptual alternative to their interpretation. Nevertheless, by linking the survival curve's shape to probabilities of events at the individual spore level, the model explains, and can be used to simulate, the irregular activation and survival patterns of individual and small groups of spores, which might be involved in food poisoning and spoilage. PMID:20453137

  5. Optimizing COD removal from greywater by photoelectro-persulfate process using Box-Behnken design: assessment of effluent quality and electrical energy consumption.

    PubMed

    Ahmadi, Mehdi; Ghanbari, Farshid

    2016-10-01

    Greywater (GW) is a potential source for water reuse in various applications. However, GW treatment is still a vital issue in water reuse in cases of environmental standards and risk to public health. This study investigates optimization and modeling of a hybrid process for COD removal from GW. Persulfate (PS) was simultaneously activated by electrogenerated ferrous ion (EC) and UV to generate sulfate radical. Photoelectro-persulfate (PEPS) was optimized by Box-Behnken design and the effects of four variables (pH, PS dosage, current density, and electrolysis time) were evaluated on COD removal. The results and several coefficients showed that the obtained model was acceptable for predicting the COD removal. Moreover, under optimum conditions (pH = 6.9, PS = 8.8 mM, current density = 2.0 mA/cm(2), and 49.3 min electrolysis time), BOD5, turbidity, TSS, phosphate, and UV254 were effectively removed and COD and BOD5 values reached to discharge standards. Different configurations of the processes were assessed for COD removal. The order of COD removal efficiency followed: PS < Fe(II) < UV/PS ≤ Fe(II)/PS < Fe(II)/PS/UV < electrocoagulation ≤ electrocoagulation/UV < electro-PS < PEPS. The monitoring PS concentration during 60 min reaction time in the aforesaid processes indicated that PEPS could remarkably activate PS. The solution pH was also monitored and related results revealed that the presence of PS during the 10 min first time decreased pH value while production of hydroxide ion at cathode increased pH significantly. Finally, the contribution of electrochemical process in the electrical energy consumption was far less than that of photolysis process in hybrid PEPS process.

  6. Development and demonstration of a Stirling/Rankine heat activated heat pump. Phase 3B: Engine technology development testing

    NASA Astrophysics Data System (ADS)

    1984-11-01

    The results of the Phase 3B Stirling/Rankine Heat Activated Heat Pump product development program are given. Results of the Phase 2 program indicated deficiencies in the performance of the free-piston Stirling engine and mismatching of the dynamic characteristics of the engine and the compressor. These deficiencies were further investigated during in-depth diagnostic testing of the engine/compressor unit in the Phase 3B and indicated appropriate engine/compressor matching criteria.

  7. A novel approach for determining total titanium from titanium dioxide nanoparticles suspended in water and biosolids by digestion with ammonium persulfate.

    PubMed

    Khosravi, Kambiz; Hoque, M Ehsanul; Dimock, Brian; Hintelmann, Holger; Metcalfe, Chris D

    2012-02-03

    Titanium dioxide (i.e. TiO(2)) in nano-form is a constituent of many nanomaterials that are used in sunscreens, cosmetics, industrial products and in biomedical applications. Quantification of TiO(2) nanoparticles in various matrixes is a topic of great interest for researchers studying the potential health and environmental impacts of nanoparticles. However, analysis of TiO(2) as Ti(4+) is difficult because current digestion techniques require use of strong acids that may be a health and safety risk in the laboratory. To overcome this problem, we developed a new method to digest TiO(2) nanoparticles using ammonium persulfate as a fusing reagent. The digestion technique requires short times to completion and optimally requires only 1 g of fusing reagent. The fusion method showed >95% recovery of Ti(4+) from 6 μg mL(-1) aqueous suspensions prepared from 10 μg mL(-1) suspension of different forms of TiO(2,) including anatase, rutile and mixed nanosized crystals, and amorphous particles. These recoveries were greater than open hot-plate digestion with a tri-acid solution and comparable to microwave digestion with a tri-acid solution. Cations and anions commonly found in natural waters showed no significant interferences when added to samples in amounts of 10 ng to 110 mg, which is a much broader range of these ions than expected in environmental samples. Using ICP-MS for analysis, the method detection limit (MDL) was determined to be 0.06 ng mL(-1), and the limit of quantification (LOQ) was 0.20 ng mL(-1). Analysis of samples of untreated and treated wastewater and biosolids collected from wastewater treatment plants yielded concentrations of TiO(2) of 1.8 and 1.6 ng mL(-1) for the wastewater samples, respectively, and 317.4 ng mg(-1) dry weights for the biosolids. The reactions between persulfate ions and TiO(2) were evaluated using stoichiometric methods and FTIR and XRD analysis. A formula for the fusing reaction is proposed that involves the formation of sulfate

  8. Distortion behavior of heat-activated acrylic denture-base resin in conventional and long, low-temperature processing methods.

    PubMed

    Kawara, M; Komiyama, O; Kimoto, S; Kobayashi, N; Kobayashi, K; Nemoto, K

    1998-06-01

    There have been many reports on fatal distortion of heat-activated acrylic denture-base resin which is still widely used in the field of removable prosthodontics. However, these reports have failed to report quantitatively on polymerization and thermal shrinkage factors. In the present study, we attempted to verify that the shrinkage of heat-activated acrylic denture-base resin was caused mainly by thermal contraction after processing. Furthermore, we examined the degree of distortion resulting from long, low-temperature processing, and compared the results with that of the conventional method. The strain gauge and thermo-couple were embedded in a specimen at the time of resin packing. The measurement started from the beginning of processing and continued until the specimen was bench-cooled and immediately before and after it was de-flasked, as well as during seven-day immersion in water at 37 degrees C. The resin expanded when processed by the conventional method. Meanwhile, mild shrinkage, possibly polymerization shrinkage, was observed when the resin was processed by the low-temperature method. This suggested that polymerization shrinkage was compensated for by thermal expansion during processing by the conventional method. Moreover, the shrinkage strains in the period from the completion of processing to immediately after de-flasking, in both the conventional and low-temperature methods, were identical to the theoretical value of thermal shrinkage which we obtained by multiplying the linear coefficients of thermal expansion by temperature differences. The shrinkage strain in the specimen processed by the low-temperature method, measured from the end of processing to immediately after de-flasking, averaged 64% of that in the specimen processed by the conventional method. The results revealed quantitatively that the shrinkage of heat-activated acrylic denture-base resin was mainly thermal shrinkage, and demonstrated the advantage of the low-temperature method in

  9. Nanoscale zero-valent iron/persulfate enhanced upflow anaerobic sludge blanket reactor for dye removal: Insight into microbial metabolism and microbial community

    PubMed Central

    Pan, Fei; Zhong, Xiaohan; Xia, Dongsheng; Yin, Xianze; Li, Fan; Zhao, Dongye; Ji, Haodong; Liu, Wen

    2017-01-01

    This study investigated the efficiency of nanoscale zero-valent iron combined with persulfate (NZVI/PS) for enhanced degradation of brilliant red X-3B in an upflow anaerobic sludge blanket (UASB) reactor, and examined the effects of NZVI/PS on anaerobic microbial communities during the treatment process. The addition of NZVI (0.5 g/L) greatly enhanced the decolourization rate of X-3B from 63.8% to 98.4%. The Biolog EcoPlateTM technique was utilized to examine microbial metabolism in the reactor, and the Illumina MiSeq high-throughput sequencing revealed 22 phyla and 88 genera of the bacteria. The largest genera (Lactococcus) decreased from 33.03% to 7.94%, while the Akkermansia genera increased from 1.69% to 20.23% according to the abundance in the presence of 0.2 g/L NZVI during the biological treatment process. Meanwhile, three strains were isolated from the sludge in the UASB reactors and identified by 16 S rRNA analysis. The distribution of three strains was consistent with the results from the Illumina MiSeq high throughput sequencing. The X-ray photoelectron spectroscopy results indicated that Fe(0) was transformed into Fe(II)/Fe(III) during the treatment process, which are beneficial for the microorganism growth, and thus promoting their metabolic processes and microbial community. PMID:28300176

  10. Nanoscale zero-valent iron/persulfate enhanced upflow anaerobic sludge blanket reactor for dye removal: Insight into microbial metabolism and microbial community.

    PubMed

    Pan, Fei; Zhong, Xiaohan; Xia, Dongsheng; Yin, Xianze; Li, Fan; Zhao, Dongye; Ji, Haodong; Liu, Wen

    2017-03-16

    This study investigated the efficiency of nanoscale zero-valent iron combined with persulfate (NZVI/PS) for enhanced degradation of brilliant red X-3B in an upflow anaerobic sludge blanket (UASB) reactor, and examined the effects of NZVI/PS on anaerobic microbial communities during the treatment process. The addition of NZVI (0.5 g/L) greatly enhanced the decolourization rate of X-3B from 63.8% to 98.4%. The Biolog EcoPlate(TM) technique was utilized to examine microbial metabolism in the reactor, and the Illumina MiSeq high-throughput sequencing revealed 22 phyla and 88 genera of the bacteria. The largest genera (Lactococcus) decreased from 33.03% to 7.94%, while the Akkermansia genera increased from 1.69% to 20.23% according to the abundance in the presence of 0.2 g/L NZVI during the biological treatment process. Meanwhile, three strains were isolated from the sludge in the UASB reactors and identified by 16 S rRNA analysis. The distribution of three strains was consistent with the results from the Illumina MiSeq high throughput sequencing. The X-ray photoelectron spectroscopy results indicated that Fe(0) was transformed into Fe(II)/Fe(III) during the treatment process, which are beneficial for the microorganism growth, and thus promoting their metabolic processes and microbial community.

  11. Nanoscale zero-valent iron/persulfate enhanced upflow anaerobic sludge blanket reactor for dye removal: Insight into microbial metabolism and microbial community

    NASA Astrophysics Data System (ADS)

    Pan, Fei; Zhong, Xiaohan; Xia, Dongsheng; Yin, Xianze; Li, Fan; Zhao, Dongye; Ji, Haodong; Liu, Wen

    2017-03-01

    This study investigated the efficiency of nanoscale zero-valent iron combined with persulfate (NZVI/PS) for enhanced degradation of brilliant red X-3B in an upflow anaerobic sludge blanket (UASB) reactor, and examined the effects of NZVI/PS on anaerobic microbial communities during the treatment process. The addition of NZVI (0.5 g/L) greatly enhanced the decolourization rate of X-3B from 63.8% to 98.4%. The Biolog EcoPlateTM technique was utilized to examine microbial metabolism in the reactor, and the Illumina MiSeq high-throughput sequencing revealed 22 phyla and 88 genera of the bacteria. The largest genera (Lactococcus) decreased from 33.03% to 7.94%, while the Akkermansia genera increased from 1.69% to 20.23% according to the abundance in the presence of 0.2 g/L NZVI during the biological treatment process. Meanwhile, three strains were isolated from the sludge in the UASB reactors and identified by 16 S rRNA analysis. The distribution of three strains was consistent with the results from the Illumina MiSeq high throughput sequencing. The X-ray photoelectron spectroscopy results indicated that Fe(0) was transformed into Fe(II)/Fe(III) during the treatment process, which are beneficial for the microorganism growth, and thus promoting their metabolic processes and microbial community.

  12. 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.

  13. 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.

  14. 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.

  15. Degradation of ciprofloxacin by 280 nm ultraviolet-activated persulfate: Degradation pathway and intermediate impact on proteome of Escherichia coli.

    PubMed

    Ye, Jin-Shao; Liu, Juan; Ou, Hua-Se; Wang, Lin-Lin

    2016-12-01

    In this study, the degradation of ciprofloxacin (CIP) was explored using ultraviolet activated persulfate (UV/PS) with 280 nm ultraviolet light-emitting diodes (UV-LEDs), and the toxicological assessment of degrading intermediates was performed using iTRAQ labeling quantitative proteomic technology. The quantitative mass spectrum results showed that 280 nm UV/PS treatment had a high transformation efficiency of CIP ([CIP] = 3 μM, [S2O8(2-)] = 210 μM, apparent rate constants 0.2413 min(-1)). The high resolution mass spectrum analyses demonstrated that the primary intermediates included C15H16FN3O3 (m/z 306.1248) and C17H18FN3O4 (m/z 348.1354). The former one was formed by the cleavage of piperazine ring, while the later one was generated by the addition of a hydroxyl on the quinolone backbone. The toxicological assessment demonstrated that 56 and 110 proteins had significant up regulations and down regulations, respectively, in the Escherichia coli exposed to degraded CIP compared to untreated CIP. The majority of up-regulated proteins, such as GapA, SodC, were associated with primary metabolic process rather than responses to stress and toxic substance, inferring that the moderate UV/PS treatment can reduce the antibacterial activity of CIP by incomplete mineralization. Consequently, these results provided a novel insight into the application of UV-LED/PS treatment as a promising removal methodology for quinolones.

  16. Persulfate initiated ultra-low cross-linked poly(N-isopropylacrylamide) microgels possess an unusual inverted cross-linking structure.

    PubMed

    Virtanen, O L J; Mourran, A; Pinard, P T; Richtering, W

    2016-05-07

    Cross-linking density and distribution are decisive for the mechanical and other properties of stimuli-sensitive poly(N-isopropylacrylamide) microgels. Here we investigate the structure of ultra-low cross-linked microgels by static light scattering and scanning force microscopy, and show that they have an inverted cross-linking structure with respect to conventional microgels, contrary to what has been assumed previously. The conventional microgels have the largest polymer volume fraction in the core from where the particle density decays radially outwards, whereas ultra-low cross-linked particles have the highest polymer volume fraction close to the surface. On a solid substrate these particles form buckled shapes at high surface coverage, as shown by scanning force micrographs. The special structure of ultra-low cross-linked microgels is attributed to cross-linking of the particle surface, which is exposed to hydrogen abstraction by radicals generated from persulfate initiators during and after polymerization. The particle core, which is less accessible to the diffusion of radicals, has consequently a lower polymer volume fraction in the swollen state. By systematic variation of the cross-linker concentration it is shown that the cross-linking contribution from peroxide under typical synthesis conditions is weaker than that from the use of 1 mol% N,N'-methylenebisacrylamide. Soft deformable hydrogel particles are of interest because they emulate biological tissues, and understanding the underlying synthesis principle enables tailoring the microgel structure for biomimetic applications. Deformability of microgels is usually controlled by the amount of added cross-linker; here we however highlight an alternative approach through structural softness.

  17. Enhanced Photoelectrocatalytic Decomplexation of Cu-EDTA and Cu Recovery by Persulfate Activated by UV and Cathodic Reduction.

    PubMed

    Zeng, Huabin; Liu, Shanshan; Chai, Buyu; Cao, Di; Wang, Yan; Zhao, Xu

    2016-06-21

    In order to enhance Cu-EDTA decomplexation and copper cathodic recovery via the photoelectrocatalytic (PEC) process, S2O8(2-) was introduced into the PEC system with a TiO2/Ti photoanode. At a current density of 0.2 mA/cm(2) and initial solution pH of 3.0, the decomplexation ratio of Cu complexes was increased from 47.5% in the PEC process to 98.4% with 5 mM S2O8(2-) addition into the PEC process (PEC/S2O8(2-)). Correspondently, recovery percentage of Cu was increased to 98.3% from 47.4% within 60 min. It was observed that nearly no copper recovery occurred within the initial reaction period of 10 min. Combined with the analysis of ESR and electrochemical LSV curves, it was concluded that activation of S2O8(2-) into SO4(·-) radicals by cathodic reduction occurred, which was prior to the reduction of liberated Cu(2+) ions. UV irradiation of S2O8(2-) also led to the production of SO4(·-). The generated SO4(·-) radicals enhanced the oxidation of Cu-EDTA. After the consumption of S2O8(2-), the Cu recovery via cathodic reduction proceeded quickly. Acidification induced by the transformation of SO4(·-) to OH· favored the copper cathodic recovery. The combined PEC/S2O8(2-) process was also efficient for the TOC removal from a real electroplating wastewater with the Cu recovery efficiency higher than 80%.

  18. 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 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. 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 (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/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.

  19. A pulsed electron beam synthesis of PEDOT conducting polymers by using sulfate radicals as oxidizing species

    NASA Astrophysics Data System (ADS)

    Coletta, Cecilia; Cui, Zhenpeng; Dazzi, Alexandre; Guigner, Jean-Michel; Néron, Stéphane; Marignier, Jean-Louis; Remita, Samy

    2016-09-01

    In this study, an original radiolytic method, based on pulsed electron beam irradiation, is used for the synthesis of conducting PEDOT in an aqueous solution containing EDOT monomers in the presence of potassium persulfate, K2S2O8, at 0 °C. At this low temperature, EDOT monomers are not chemically oxidized by S2O82- anions, initiating PEDOT polymerization, but are rather oxidized by sulfate radicals, SO4•-, which are radiolytically generated by the reaction of solvated electrons, produced by water radiolysis, with persulfate anions. Successfully, as demonstrated by UV-vis absorption spectrophotometry and ATR-FTIR spectroscopy, irradiating the aqueous solution, by using a series of accumulated electron pulses, enables complete EDOT oxidation and quantitative in situ PEDOT polymerization through a step-by-step oxidation mechanism. The morphology of PEDOT polymers, mixed with unreacted K2S2O8 salt, is characterized by Cryo-TEM microscopy in aqueous solution and by SEM after deposition. Successfully, in the absence of any washing step, high resolution AFM microscopy, coupled with infrared nanospectroscopy, is used to discriminate between the organic polymers and the inorganic salt and to probe the local chemical composition of PEDOT nanostructures. The results demonstrate that PEDOT polymers form globular self-assembled nanostructures which preferentially adsorb onto unreacted K2S2O8 solid nanoplates. The present results first demonstrate the efficiency of sulfate radicals as oxidizing species for the preparation of nanostructured PEDOT polymers and second highlight the promising potentiality of electron accelerators in the field of conducting polymers synthesis.

  20. Graphene-assisted room-temperature synthesis of 2D nanostructured hybrid electrode materials: dramatic acceleration of the formation rate of 2D metal oxide nanoplates induced by reduced graphene oxide nanosheets.

    PubMed

    Sung, Da-Young; Gunjakar, Jayavant L; Kim, Tae Woo; Kim, In Young; Lee, Yu Ri; Hwang, Seong-Ju

    2013-05-27

    A new prompt room temperature synthetic route to 2D nanostructured metal oxide-graphene-hybrid electrode materials can be developed by the application of colloidal reduced graphene oxide (RGO) nanosheets as an efficient reaction accelerator for the synthesis of δ-MnO2 2D nanoplates. Whereas the synthesis of the 2D nanostructured δ-MnO2 at room temperature requires treating divalent manganese compounds with persulfate ions for at least 24 h, the addition of RGO nanosheet causes a dramatic shortening of synthesis time to 1 h, underscoring its effectiveness for the promotion of the formation of 2D nanostructured metal oxide. To the best of our knowledge, this is the first example of the accelerated synthesis of 2D nanostructured hybrid material induced by the RGO nanosheets. The observed acceleration of nanoplate formation upon the addition of RGO nanosheets is attributable to the enhancement of the oxidizing power of persulfate ions, the increase of the solubility of precursor MnCO3, and the promoted crystal growth of δ-MnO2 2D nanoplates. The resulting hybridization between RGO nanosheets and δ-MnO2 nanoplates is quite powerful not only in increasing the surface area of manganese oxide nanoplate but also in enhancing its electrochemical activity. Of prime importance is that the present δ-MnO2 -RGO nanocomposites show much superior electrode performance over most of 2D nanostructured manganate systems including a similar porous assembly of RGO and layered MnO2 nanosheets. This result underscores that the present RGO-assisted solution-based synthesis can provide a prompt and scalable method to produce nanostructured hybrid electrode materials.

  1. Gas-Phase Oxidation via Ion/Ion Reactions: Pathways and Applications

    NASA Astrophysics Data System (ADS)

    Pilo, Alice L.; Zhao, Feifei; McLuckey, Scott A.

    2017-01-01

    Here, we provide an overview of pathways available upon the gas-phase oxidation of peptides and DNA via ion/ion reactions and explore potential applications of these chemistries. The oxidation of thioethers (i.e., methionine residues and S-alkyl cysteine residues), disulfide bonds, S-nitrosylated cysteine residues, and DNA to the [M+H+O]+ derivative via ion/ion reactions with periodate and peroxymono-sulfate anions is demonstrated. The oxidation of neutral basic sites to various oxidized structures, including the [M+H+O]+, [M-H]+, and [M-H-NH3]+ species, via ion/ion reactions is illustrated and the oxidation characteristics of two different oxidizing reagents, periodate and persulfate anions, are compared. Lastly, the highly efficient generation of molecular radical cations via ion/ion reactions with sulfate radical anion is summarized. Activation of the newly generated molecular radical peptide cations results in losses of various neutral side chains, several of which generate dehydroalanine residues that can be used to localize the amino acid from which the dehydroalanine was generated. The chemistries presented herein result in a diverse range of structures that can be used for a variety of applications, including the identification and localization of S-alkyl cysteine residues, the oxidative cleavage of disulfide bonds, and the generation of molecular radical cations from even-electron doubly protonated peptides.

  2. Removal of PCBs in contaminated soils by means of chemical reduction and advanced oxidation processes.

    PubMed

    Rybnikova, V; Usman, M; Hanna, K

    2016-09-01

    Although the chemical reduction and advanced oxidation processes have been widely used individually, very few studies have assessed the combined reduction/oxidation approach for soil remediation. In the present study, experiments were performed in spiked sand and historically contaminated soil by using four synthetic nanoparticles (Fe(0), Fe/Ni, Fe3O4, Fe3 - x Ni x O4). These nanoparticles were tested firstly for reductive transformation of polychlorinated biphenyls (PCBs) and then employed as catalysts to promote chemical oxidation reactions (H2O2 or persulfate). Obtained results indicated that bimetallic nanoparticles Fe/Ni showed the highest efficiency in reduction of PCB28 and PCB118 in spiked sand (97 and 79 %, respectively), whereas magnetite (Fe3O4) exhibited a high catalytic stability during the combined reduction/oxidation approach. In chemical oxidation, persulfate showed higher PCB degradation extent than hydrogen peroxide. As expected, the degradation efficiency was found to be limited in historically contaminated soil, where only Fe(0) and Fe/Ni particles exhibited reductive capability towards PCBs (13 and 18 %). In oxidation step, the highest degradation extents were obtained in presence of Fe(0) and Fe/Ni (18-19 %). The increase in particle and oxidant doses improved the efficiency of treatment, but overall degradation extents did not exceed 30 %, suggesting that only a small part of PCBs in soil was available for reaction with catalyst and/or oxidant. The use of organic solvent or cyclodextrin to improve the PCB availability in soil did not enhance degradation efficiency, underscoring the strong impact of soil matrix. Moreover, a better PCB degradation was observed in sand spiked with extractable organic matter separated from contaminated soil. In contrast to fractions with higher particle size (250-500 and <500 μm), no PCB degradation was observed in the finest fraction (≤250 μm) having higher organic matter content. These findings

  3. 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.

  4. 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 ...

  5. 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.

  6. Degradation of acid red 97 dye in aqueous medium using wet oxidation and electro-Fenton techniques.

    PubMed

    Kayan, Berkant; Gözmen, Belgin; Demirel, Muhammet; Gizir, A Murat

    2010-05-15

    Degradation of the acid red 97 dye using wet oxidation, by different oxidants, and electro-Fenton systems was investigated in this study. The oxidation effect of different oxidants such as molecular oxygen, periodate, persulfate, bromate, and hydrogen peroxide in wet oxidation system was compared. Mineralization of AR97 with periodate appeared more effective when compared with that of the other oxidants at equal initial concentration. When 5 mM of periodate was used, at the first minute of the oxidative treatment, the decolorization percentage of AR97 solution at 150 and 200 degrees C reached 88 and 98%, respectively. The total organic carbon removal efficiency at these temperatures also reached 60 and 80%. The degradation of AR97 was also studied by electro-Fenton process. The optimal current value and Fe(2+) concentration were found to be 300 mA and 0.2 mM, respectively. The results showed that electro-Fenton process can lead to 70 and 95% mineralization of the dye solution after 3 and 5h giving carboxylic acids and inorganic ions as final end-products before mineralization. The products obtained from degradation were identified by GC/MS as 1,2-naphthalenediol, 1,1'-biphenyl-4-amino-4-ol, 2-naphthalenol diazonium, 2-naphthalenol, 2,3-dihydroxy-1,4-naphthalenedion, phthalic anhydride, 1,2-benzenedicarboxylic acid, phthaldehyde, 3-hydroxy-1,2-benzenedicarboxylic acid, 4-amino-benzoic acid, and 2-formyl-benzoic acid.

  7. 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

    2012-08-09

    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.

  8. Improved Understanding of In Situ Chemical Oxidation Contaminant Oxidation Kinetics

    DTIC Science & Technology

    2007-12-01

    activated persulfate and found fairly rapid degradation of TNT, RDX, HMX, and 4- nitrophenol . The kinetics generally are first-order and the effect of...pH 7, and phosphate buffer concentrations between 50 - 100 mM. 14 7. Determining K" for Activated Hydrogen Peroxide4 An exhaustive literature...spectra of substituted benzenes. Bull. Chem. Soc. Jpn., 47, 2563-2572. 53. Kobayashi, T., Nagakura, S., 1975. Photoelectron spectra of nitrophenols

  9. The Effect of Artificial Aging on The Bond Strength of Heat-activated Acrylic Resin to Surface-treated Nickel-chromium-beryllium Alloy

    PubMed Central

    Al Jabbari, Youssef S.; Zinelis, Spiros; Al Taweel, Sara M.; Nagy, William W.

    2016-01-01

    Purpose The debonding load of heat-activated polymethylmethacrylate (PMMA) denture base resin material to a nickel-chromium-beryllium (Ni-Cr-Be) alloy conditioned by three different surface treatments and utilizing two different commercial bonding systems was investigated. Materials and Methods Denture resin (Lucitone-199) was bonded to Ni-Cr-Be alloy specimens treated with Metal Primer II, the Rocatec system with opaquer and the Rocatec system without opaquer. Denture base resin specimens bonded to non-treated sandblasted Ni-Cr-Be alloy were used as controls. Twenty samples for each treatment condition (80 specimens) were tested. The 80 specimens were divided into two categories, thermocycled and non-thermocycled, containing four groups of ten specimens each. The non-thermocycled specimens were tested after 48 hours’ storage in room temperature water. The thermocycled specimens were tested after 2,000 cycles in 4°C and 55°C water baths. The debonding load was calculated in Newtons (N), and collected data were subjected by non parametric test Kruskal-Wallis One Way Analysis of Variance on Ranks and Dunn’s post hoc test at the α = 0.05. Results The Metal Primer II and Rocatec system without opaquer groups produced significantly higher bond strengths (119.9 and 67.6 N), respectively, than did the sandblasted and Rocatec system with opaquer groups, where the bond strengths were 2.6 N and 0 N, respectively. The Metal Primer II was significantly different from all other groups (P<0.05). The bond strengths of all groups were significantly decreased (P<0.05) after thermocycling. Conclusions Although thermocycling had a detrimental effect on the debonding load of all surface treatments tested, the Metal Primer II system provided higher values among all bonding systems tested, before and after thermocycling. PMID:27335613

  10. Effects of hydrogen peroxide pretreatment and heat activation of silane on the shear bond strength of fiber-reinforced composite posts to resin cement

    PubMed Central

    Shin, Tae-Bong; Lee, Joo-Hee; Ahn, Kang-Min; Kim, Tae-Hyung

    2016-01-01

    PURPOSE To evaluate the effects of hydrogen peroxide pretreatment and heat activation of silane on the shear bond strength of fiber-reinforced composite posts to resin cement. MATERIALS AND METHODS The specimens were prepared to evaluate the bond strength of epoxy resin-based fiber posts (D.T. Light-Post) to dual-curing resin cement (RelyX U200). The specimens were divided into four groups (n=18) according to different surface treatments: group 1, no treatment; group 2, silanization; group 3, silanization after hydrogen peroxide etching; group 4, silanization with warm drying at 80℃ after hydrogen peroxide etching. After storage of the specimens in distilled water at 37℃ for 24 hours, the shear bond strength (in MPa) between the fiber post and resin cement was measured using a universal testing machine. The fractured surface of the fiber post was examined using scanning electron microscopy. Data were analyzed using one-way ANOVA and post-hoc analysis with Tukey's HSD test (α=0.05). RESULTS Silanization of the fiber post (Group 2) significantly increased the bond strength in comparison with the non treated control (Group 1) (P<.05). Heat drying after silanization also significantly increased the bond strength (Group 3 and 4) (P<.05). However, no effect was determined for hydrogen peroxide etching before applying silane agent (Group 2 and 3) (P>.05). CONCLUSION Fiber post silanization and subsequent heat treatment (80℃) with warm air blower can be beneficial in clinical post cementation. However, hydrogen peroxide etching prior to silanization was not effective in this study. PMID:27141252

  11. A high-threshold heat-activated channel in cultured rat dorsal root ganglion neurons resembles TRPV2 and is blocked by gadolinium.

    PubMed

    Leffler, Andreas; Linte, Ramona Madalina; Nau, Carla; Reeh, Peter; Babes, Alexandru

    2007-07-01

    Heat-activated ion channels from the vanilloid-type TRP group (TRPV1-4) seem to be central for heat-sensitivity of nociceptive sensory neurons. Displaying a high-threshold (> 52 degrees C) for activation, TRPV2 was proposed to act as a sensor for intense noxious heat in mammalian sensory neurons. However, although TRPV2 is expressed in a distinct population of thinly myelinated primary afferents, a widespread expression in a variety of neuronal and non-neuronal tissues suggests a more diverse physiological role of TRPV2. In its role as a heat-sensor, TRPV2 has not been thoroughly characterized in terms of biophysical and pharmacological properties. In the present study, we demonstrate that the features of heterologously expressed rat TRPV2 closely resemble those of high-threshold heat-evoked currents in medium- and large-sized capsaicin-insensitive rat dorsal root ganglion (DRG) neurons. Both in TRPV2-expressing human embryonic kidney (HEK)293t cells and in DRGs, high-threshold heat-currents were sensitized by repeated activation and by the TRPV1-3 agonist, 2-aminoethoxydiphenyl borate (2-APB). In addition to a previously described block by ruthenium red, we identified the trivalent cations, lanthanum (La(3+)) and gadolinium (Gd(3+)) as potent blockers of TRPV2. Thus, we present a new pharmacological tool to distinguish between heat responses of TRPV2 and the closely related capsaicin-receptor, TRPV1, which is strongly sensitized by trivalent cations. We demonstrate that self-sensitization of heat-evoked currents through TRPV2 does not require extracellular calcium and that TRPV2 can be activated in cell-free membrane patches in the outside-out configuration. Taken together our results provide new evidence for a role of TRPV2 in mediating high-threshold heat responses in a subpopulation of mammalian sensory neurons.

  12. 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.

  13. Dopamine-melanin film deposition depends on the used oxidant and buffer solution.

    PubMed

    Bernsmann, Falk; Ball, Vincent; Addiego, Frédéric; Ponche, Arnaud; Michel, Marc; Gracio, José Joaquin de Almeida; Toniazzo, Valérie; Ruch, David

    2011-03-15

    The deposition of "polydopamine" films, from an aqueous solution containing dopamine or other catecholamines, constitutes a new and versatile way to functionalize solid-liquid interfaces. Indeed such films can be deposited on almost all kinds of materials. Their deposition kinetics does not depend markedly on the surface chemistry of the substrate, and the films can reach thickness of a few tens of nanometers in a single reaction step. Up to now, even if a lot is known about the oxidation mechanism of dopamine in solution, only little information is available to describe the deposition mechanism on surfaces either by oxidation in solution or by electrodeposition. The deposition kinetics of melanin was only investigated from dopamine solutions using oxygen or ammonium persulfate as an oxidant and from a tris(hydroxymethyl) aminomethane (Tris) containing buffer solutions at pH 8.5. Many other oxidants could be used, and the buffer agent containing a primary amine group may influence the deposition process. Herein we show that the deposition kinetics of melanin from dopamine containing buffers at pH 8.5 can be markedly modified using Cu(2+) instead of O2 as an oxidant: the deposition kinetics remains linear up to thicknesses of more than 70 nm, whereas the film growth stops at 45 ± 5 nm in the presence of 02. In addition, the films prepared from Cu(2+) containing solutions display an absorption spectrum with defined peaks at 320 and 370 nm, which are absent in the spectra of films prepared in oxygenated solutions. The replacement of Tris buffer by phosphate buffer also has a marked effect on the melanin deposition kinetics.

  14. Oxidative conversion as a means of detecting precursors to perfluoroalkyl acids in urban runoff.

    PubMed

    Houtz, Erika F; Sedlak, David L

    2012-09-04

    A new method was developed to quantify concentrations of difficult-to-measure and unidentified precursors of perfluoroalkyl carboxylic (PFCA) and sulfonic (PFSA) acids in urban runoff. Samples were exposed to hydroxyl radicals generated by thermolysis of persulfate under basic pH conditions and perfluoroalkyl acid (PFAA) precursors were transformed to PFCAs of related perfluorinated chain length. By comparing PFCA concentrations before and after oxidation, the concentrations of total PFAA precursors were inferred. Analysis of 33 urban runoff samples collected from locations around the San Francisco Bay, CA indicated that PFOS (2.6-26 ng/L), PFOA (2.1-16 ng/L), and PFHxA (0.9-9.7 ng/L) were the predominant perfluorinated compounds detected prior to sample treatment. Following oxidative treatment, the total concentrations of PFCAs with 5-12 membered perfluoroalkyl chains increased by a median of 69%, or between 2.8 and 56 ng/L. Precursors that produced PFHxA and PFPeA upon oxidation were more prevalent in runoff samples than those that produced PFOA, despite lower concentrations of their corresponding perfluorinated acids prior to oxidation. Direct measurements of several common precursors to PFOS and PFOA (e.g., perfluorooctanesulfonamide and 8:2 fluorotelomer sulfonate) accounted for less than 25% of the observed increase in PFOA, which increased by a median value of 37%. Exposure of urban runoff to sunlight, advanced oxidation processes, or microbes could result in modest, but measurable, increases in concentrations of PFCAs and PFSAs.

  15. 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.

  16. 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.

  17. Sulfate radical-advanced oxidation process (SR-AOP) for simultaneous removal of refractory organic contaminants and ammonia in landfill leachate.

    PubMed

    Deng, Yang; Ezyske, Casey M

    2011-11-15

    Typically, a mature landfill leachate contains high levels of non-biodegradable organics and ammonia nitrogen. Simultaneous removal of the both persistent leachate pollutants is a significant challenge. This paper reports the first scientific study to apply a sulfate radical (SO(4)(·-)) - based advanced oxidation process (SR-AOP) to treat a mature leachate, with an emphasis of concurrent removal of refractory organics and ammonia. In this study, all the experiments were run in a batch reactor with temperature control. In the thermal persulfate oxidation (TPO) process, persulfate (S(2)O(8)(2-)) was activated by heat to produce powerful oxidants, SO(4)(·-) (E(o) = 2.6 V). Three factors affecting the removal efficiencies of chemical oxygen demand (COD) and ammonia nitrogen were investigated, including initial solution pH (3-8.3), temperature (27-50 °C), and chemical dose (S(2)O(8)(2-):12COD(0) = 0.25-2.0). Typically, acidic pH (3-4), higher temperature, and higher dose favored the removal of COD and ammonia. At S(2)O(8)(2-):12COD(0) = 2 and 50 °C, the COD removal rates were 79% and 91% at pH 8.3 (no pH adjustment) and 4, respectively; and the ammonia nitrogen removal reached 100% at pH 8.3 or 4. SR-AOP appears to be more advantageous over hydroxyl radical (OH∙)-based advanced oxidation processes (HR-AOPs) because OH∙ almost does not oxidize ammonia. Furthermore, compared with Fenton treatment of the same batch leachate sample, the TPO could achieve a higher COD removal at an identical chemical dose. For example, COD removal was 40% at H(2)O(2):2.125COD(0) = 2 during Fenton treatment (pH 3), but 91% at S(2)O(8)(2-):12COD(0) = 2 during TPO (pH 4). These findings demonstrate that SR-AOP is a promising landfill leachate treatment method.

  18. [Nitric oxide].

    PubMed

    Rovira, I

    1995-01-01

    Nitric oxide was identified as the relaxing factor derived from the endothelium in 1987. Nitric oxide synthesis allows the vascular system to maintain a state of vasodilation, thereby regulating arterial pressure. Nitric oxide is also found in platelets, where it inhibits adhesion and aggregation; in the immune system, where it is responsible for the cytotoxic action of macrophages; and in the nervous system, where it acts as neurotransmitter. A deficit in endogenous synthesis of nitric oxide contributes to such conditions as essential arterial hypertension, pulmonary hypertension and heart disease. An excess of nitrous oxide induced by endotoxins and cytokinins, meanwhile, is believed to be responsible for hypotension in septic shock and for hyperdynamic circulatory state in cirrhosis of the liver. Nitric oxide has also been implicated in the rejection of transplanted organs and in cell damage after reperfusion. Inhaled nitrous oxide gas reduces pulmonary hypertension without triggering systemic hypotension in both experimental and clinical conditions. It also produces selective vasodilation when used to ventilate specific pulmonary areas, thereby improving the ventilation/perfusion ratio and, hence, oxygenation. Nitric oxide inhalation is effective in pulmonary hypertension-coincident with chronic obstructive lung disease, in persistent neonatal pulmonary hypertension and in pulmonary hypertension with congenital or acquired heart disease. Likewise, it reduces intrapulmonary shunt in acute respiratory failure and improves gas exchange. Under experimental conditions nitric oxide acts as a bronchodilator, although it seems to be less effective for this purpose in clinical use.(ABSTRACT TRUNCATED AT 250 WORDS)

  19. Liquid chromatography, chemical oxidation, and online carbon isotope dilution mass spectrometry as a universal quantification system for nonvolatile organic compounds.

    PubMed

    Díaz, Sergio Cueto; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo; Alonso, J Ignacio García

    2013-02-05

    A procedure for the universal detection and quantification of polar organic compounds separated by liquid chromatography (LC) based on postcolumn carbon isotope dilution mass spectrometry (IDMS) was developed. The eluent from the LC column is mixed online with a continuous flow of (13)C-enriched sodium bicarbonate, and the sodium persulfate oxidation reaction in acidic media is employed to achieve isotope equilibration. All carbon-containing compounds eluting from the column are oxidized to (12)CO(2) and (13)CO(2), respectively, and the carbon dioxide is separated from the aqueous phase using a gas-permeable membrane. The gaseous carbon dioxide is then carried to the mass spectrometer for isotope ratio measurements. Different water-soluble organic compounds were evaluated using a flow injection configuration to assess the efficiency of the oxidation process. Most water-soluble organic compounds tested showed quantitative oxidation. However, chemical structures involving conjugated C═N double bounds and guanidinium-like structures were found to be resistant to the oxidation and were further studied. For this purpose, (13)C(1)-labeled creatine (with the isotopic label in the guanidinium group) was employed as model compound. Specific conditions for the quantitative oxidation of these compounds required lower flow rates and the addition of metallic catalysts. This novel approach was tested as a universal detection and quantification system for LC. A simple standard mixture of four amino acids was separated under 100% aqueous conditions and quantified without the need for specific standards with good accuracy and precision using potassium hydrogen phthalate as internal standard. The main field of application of the developed method is for the purity assessment of organic standards with direct traceability to the International System of Units (SI).

  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

  1. A case of chemical scalp burns after hair highlights: experimental evidence of oxidative injuries.

    PubMed

    Bertani, Roberta; Sgarbossa, Paolo; Pendolino, Flavio; Facchin, Giangiacomo; Snenghi, Rossella

    2016-12-01

    Hair highlights are quite common procedures carried out in hair salons by using a mixture of a lightening powder containing persulfates with a suspension containing hydrogen peroxide: a representative case of chemical scalp burns is described as a consequence of this treatment. The aim of the paper is to demonstrate the strict relationship between the scalp damage and the commercial products used in a case of hair highlighting. The results of some chemical analyses have been reported, showing, in particular, that the chemical reactivity of the mixture changes in the time, thus strongly suggesting that the procedure for the application of the mixture is critical for the occurrence of possible accidents. The presence in the powder of chemical compounds bearing aliphatic chains as surfactants explains the appearance of dramatic symptoms after days due to a slow dissolution of the oxidant compounds in the stratum corneum of skin with no effect in reducing injury of palliative treatments. Safety suggestions and recommendations for producers and workers are also included.

  2. Iron Oxides

    SciTech Connect

    Qafoku, Nikolla; Amonette, James E.

    2016-09-19

    Abstract: Fe oxides are common clay-sized oxide, oxyhydroxide and hydroxide soil minerals. They are compounds of Fe, O, and H that have structures based on close-packed arrays of O. The octahedral and tetrahedral cavities within these arrays are filled with either Fe3+ or Fe2+ to form Fe(O/OH)6, FeO6, or FeO4 structural units. All of the naturally occurring Fe oxide minerals usually undergo some degree of isomorphous substitution of other metal ions for Fe in their structures. Relatively simple techniques may be used to identify Fe oxides in the field based on their typical colors and magnetic properties. In the laboratory, a variety of instrumental techniques can be used to confirm phase identity and to quantify amount. Of these, X-ray diffraction, infrared spectroscopy, electron microscopy, thermal analysis, and Mössbauer spectroscopy are the most commonly used techniques. As oxides, the functional groups on their surfaces may have positive, negative, or no charge depending on pH and on the concentration and nature of other ions in the contact solution. A net positive surface charge usually is observed in soils because Fe oxides have a point-of-zero-charge in the neutral or slightly basic pHs. The functional groups on the surface form complexes with cations and anions from the aqueous phase. Their sorption and electron-buffering properties significantly affect the geochemical cycles of almost all elements having agronomic or environmental significance.

  3. Spectrophotometric detection of iodide and chromic (III) in urine after oxidation to iodine and chromate (VI).

    PubMed

    Paul, Buddha D; Jacobs, Aaron

    2005-10-01

    Tests for oxidizing adulterants in urine are a continuing challenge to the drug-testing program. Iodine was found to destroy morphine and 6-acetylmorphine almost immediately. The effects were less evident on 11 -nor-delta9-tetrahydrocannabinol-9-carboxylic acid (THC-acid). When the urine solution was tested for iodine by a chromogenic substrate, 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS), no iodine was detected. Masking drug and adulterant simultaneously made iodine a preferred oxidizing adulterant for drug abusers. In this study, the reduced iodide was oxidized by sodium nitrite to iodine. The excess nitrite was decomposed by sulfamic acid and the iodine was detected by ABTS. Linearity was 12.7 to 635 mg/L (0.1 to 5 mmol/L, y = 0.9966x + 0.0016, R2 = 1.0000). Precisions (coefficient of variation) were within +/- 4.1% and quantitative accuracies were within 97% of expected values (n=5). Chromate, iodate, periodate, and persulfate interfered with the method. To alleviate the problem, the positive specimens were tested again by an iodine-specific method. After oxidation, the samples were treated with sodium azide and ammonium thiocyanate. In presence of thiocyanate, the azide reduced iodine to iodide almost immediately, and the solutions showed negative response to ABTS. The results were compared with that of a control group tested without thiocyanate. When iodine was present, the ratios of thiocyanate to control were less than 6%. Chromate was also found to destroy THC-acid in urine, and during storage most of the chromate changed to chromic (III). In this study, chromic was oxidized to chromate by hydrogen peroxide and sodium hydroxide and detected by 1,5-diphenylcarbazide. Linearity was 5.2 to 156 mg/L (0.1 to 3.0 mmol/L, y = 1.0285x - 0.0034, R2 = 0.9998). Precisions were within +/- 8.5% and quantitative accuracies were within 92% of expected values (n=5). The test was not interfered by other oxidizing agents. Both iodide and chromic oxidation

  4. 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

  5. Oxide Thermoelectrics

    SciTech Connect

    Singh, David J

    2008-01-01

    Thermoelectricity in oxides, especially NaxCoO2 and related materials, is discussed from the point of view of first principles calculations and Boltzmann transport theory. The electronic structure of this material is exceptional in that it has a combination of very narrow bands and strong hybridization between metal d states and ligand p states. As shown within the framework of conventional Boltzmann transport theory, this leads to high Seebeck coefficients even at metallic carrier densities. This suggests a strategy of searching for other narrow band oxides that can be doped metallic with mobile carriers. Some possible avenues for finding such materials are suggested.

  6. Oxidation catalyst

    DOEpatents

    Ceyer, Sylvia T.; Lahr, David L.

    2010-11-09

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

  7. 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.

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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...

  13. Morphological effects of single-layer graphene oxide in the formation of covalently bonded polypyrrole composites using intermediate diisocyanate chemistry

    NASA Astrophysics Data System (ADS)

    Whitby, Raymond L. D.; Korobeinyk, Alina; Mikhalovsky, Sergey V.; Fukuda, Takahiro; Maekawa, Toru

    2011-10-01

    Single-layer graphene oxide (SLGO) possesses carboxylic and hydroxyl groups suitable for reactions with aliphatic or aromatic diisocyanate molecules. TEM analysis reveals that aliphatic diisocyanate molecules caused SLGO to scroll into star-like formations, whereas aromatic diisocyanate molecules retained SGLO in a flat-sheet morphology. TGA confirms the stabilisation of the formed urea and urethane groups on SLGO, but the onset of sheet pyrolysis occurs at a lower temperature due to isocyanate reactions with anhydride and epoxide groups embedded in the sheet. Pendant isocyanate groups act as bridging units to facilitate the attachment of pyrrole molecules, which are then used as anchor sites for the covalent polymerisation of pyrrole to polypyrrole (PPy). The use of FeCl3 as the polymerisation catalyst generated both covalent and free PPy, but also iron hydroxide nanoparticles were observed decorating the SLGO surface. When using ammonium persulfate as a catalyst and dodecylbenzenesulfonate as a dopant, free PPy could be removed under treatment with solvents to leave a purely covalent system. Discrete regions of SLGO were observed decorated with nanoparticles of PPy along the edge or across the surface of individual sheets. It was found that the flexibility of the SLGO sheet and the type of diisocyanate used directly affected the electrical resistance of the final composite.

  14. 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.

  15. 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.

  16. 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

  17. Modification of the surface chemistry of single- and multi-walled carbon nanotubes by HNO3 and H2SO4 hydrothermal oxidation for application in direct contact membrane distillation.

    PubMed

    Morales-Torres, Sergio; Silva, Tânia L S; Pastrana-Martínez, Luisa M; Brandão, Ana T S C; Figueiredo, José L; Silva, Adrián M T

    2014-06-28

    A specific methodology based on nitric acid hydrothermal oxidation was used to control the surface chemistry of multi-walled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes (CNTs) with different lengths, and this methodology was adapted to the use of sulphuric acid containing ammonium persulfate as an oxidizing agent. The amount of oxygen-containing surface groups depends on the number and length of the graphene layers of the CNTs, thicker and shorter CNTs having more reactive sites for surface functionalization. In particular, the oxidation of MWCNTs was more pronounced than that of short SWCNTs and less surface groups were introduced into long SWCNTs, regardless of the acid used at any fixed concentration. It was also possible to tailor the surface chemistry of both SWCNTs and MWCNTs by using the adopted methodologies, and the amount of both oxygen- and sulphur-containing functional groups was correlated with the concentration of each oxidizing agent used. Mathematical functions that allow precise control of the amount and type of the surface groups introduced into carbon nanotubes were obtained. Buckypapers were also prepared over a polytetrafluoroethylene commercial membrane. These membranes were tested in direct contact membrane distillation and, under salinity conditions, the membrane prepared using oxidized MWCNTs (instead of SWCNTs) was the most efficient, the permeate flux of the commercial membrane significantly increasing in the presence of these CNTs, while completely rejecting chloride ions. In addition, the permeate flux was precisely correlated with the amount of oxygenated functional surface groups (as well as with the pH of point of zero charge) of the oxidized MWCNTs.

  18. Effects of oxidizing adulterants on detection of 11-nor-delta9-THC-9-carboxylic acid in urine.

    PubMed

    Paul, Buddha D; Jacobs, Aaron

    2002-10-01

    Bleach, nitrite, chromate, and hydrogen peroxide-peroxidase are effective urine adulterants used by the illicit drug users to conceal marijuana-positive results. Methods for detecting nitrite and chromate are available. Effects of other oxidizing agents that could possibly be used as adulterants and are difficult to detect or measure are presented in this report. Urine samples containing 40 ng/mL of 11-nor-delta9-THC-9-carboxylic acid (THC-acid) were treated with 10 mmol/L of commonly available oxidizing agents. Effects of horseradish peroxidase of activity 10 unit/mL and extracts from 2.5 g of red radish (Raphanus sativus, Radicula group), horseradish (Armoracia rusticana), Japanese radish (Raphanus sativus, Daikon group), and black mustard seeds (Brassica nigra), all with 10 mmol/L of hydrogen peroxide, were also examined. After 5 min, 16 h and 48 h of exposure at room temperature (23 degrees C) the specimens were tested by a gas chromatographic-mass spectrometric method for THC-acid. A control group treated with sodium hydrosulfite to reduce the oxidants, was also tested to investigate the effect of oxidizing agents on THC-acid in the extraction method. THC-acid was lost completely in the extraction method when treated with chromate, nitrite, oxone, and hydrogen peroxide/ferrous ammonium sulfate (Fenton's reagent). Some losses were also observed with persulfate and periodate (up to 25%). These oxidants, and other oxidizing agents like permanganate, periodate, peroxidase, and extracts from red radish, horseradish, Japanese radish and black mustard seeds destroyed most of the THC-acid (> 94%) within 48 h of exposure. Chlorate, perchlorate, iodate, and oxychloride under these conditions showed little or no effect. Complete loss was observed when THC-acid was exposed to 50 mmol/L of oxychloride for 48 h. Several oxidizing adulterants that are difficult to test by the present urine adulterant testing methods showed considerable effects on the destruction of THC

  19. Spore heat-activation requirements and germination responses correlate with sequences of germinant receptors and with the presence of a specific spoVA2mob operon in food-borne strains of Bacillus subtilis.

    PubMed

    Krawczyk, Antonina O; de Jong, Anne; Omony, Jimmy; Holsappel, Siger; Wells-Bennik, Marjon H J; Kuipers, Oscar P; Eijlander, Robyn T

    2017-01-27

    Spore heat resistance, germination and outgrowth are problematic bacterial properties compromising food safety and quality. Large inter-strain variation in these properties makes prediction and control of spore behavior challenging. High-level heat resistance and slow germination of spores of some natural B. subtilis isolates, encountered in foods, have been attributed to the occurrence of the spoVA(2mob) operon carried on the Tn1546 transposon. In this study, we further investigate the correlation between the presence of this operon in high-level heat resistant spores and their germination efficiencies before and after exposure to various sub-lethal heat treatments (heat-activation, HA), which are known to significantly improve spore responses to nutrient germinants. We show that high-level heat resistant spores harboring spoVA(2mob) required higher HA temperatures for efficient germination than spores lacking spoVA(2mob) The optimal spore HA requirements additionally depended on the nutrients used to trigger germination, L-alanine (L-Ala) or a mixture of L-asparagine, D-glucose, D-fructose and K(+) (AGFK). The distinct HA requirements of these two spore germination pathways are likely related to differences in properties of specific germinant receptors. Moreover, spores that germinated inefficiently in AGFK contained specific changes in sequences of the GerB and GerK germinant receptors, which are involved in this germination response. In contrast, no relation was found between transcription levels of main germination genes and spore germination phenotypes. The findings presented in this study have great implications for practices in the food industry, where heat treatments are commonly used to inactivate pathogenic and spoilage microbes, including bacterial spore-formers.

  20. Fatty Acid Oxidation Disorders

    MedlinePlus

    ... other health conditions > Fatty acid oxidation disorders Fatty acid oxidation disorders E-mail to a friend Please ... these disorders, go to genetests.org . What fatty acid oxidation disorders are tested for in newborn screening? ...

  1. 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

  2. Oxidation at Surfaces of Uranium Oxide Particles

    NASA Astrophysics Data System (ADS)

    Schueneman, Richard; Burgraff, Larry

    2001-04-01

    Uranium dioxide (UO2 (S)) is unstable in an oxidizing environment and oxidizes until covered with a layer of uranium trioxide (UO3 (C)). During the oxidation process, uranium cations change from U+4 to U+6 and the oxide crystal structure changes from face centered cubic to orthorhombic. Seven UO2(S) samples were prepared by pressing UO2 (S) powder into a tungsten screen and then subjected to five different temperatures and three partial pressures of oxygen. UO2 (S) oxidation was monitored with in situ photoluminescence (PL) spectroscopy. Quantitative oxidation data was obtained with secondary ion mass spectrometry (SIMS) and x-ray photoelectron spectroscopy (XPS). The in situ PL spectra did not identify UO3 (C) forming on the sample surfaces however, a new PL signature not associated with uranyl was observed. SIMS and XPS data from oxidized UO2 (S) samples indicated that at low temperatures, surface oxidation is kinetically limited and at high temperatures, surface oxidation is limited by diffusion. A model for the oxidation rate to UO3 (C) was not developed due to the temperature dependant oxidation process and high vacuum reduction of amorphous UO3 (A) present on the UO2 (S) sample surfaces prior to oxidation. A PL emission spectra intensity reduction was noticed on a UO3 (C) sample at room temperature under high vacuum. A reduction and re-oxidation of three additional UO3 (C) samples identified a kinetically irreversible reduction process for UO3(C) under high vacuum. A SIMS surface scan was performed on a fourth UO3(C) sample before and after exposure to ultra-high vacuum (10-8 torr) and the results suggest the reduction of UO3(C) to lower oxides (U3O8, U3O7 and UO2) at room temperature.

  3. 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.

  4. 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.

  5. 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

  6. Photo-oxidation catalysts

    DOEpatents

    Pitts, J. Roland; Liu, Ping; Smith, R. Davis

    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.

  7. The enzymatic oxidation of graphene oxide.

    PubMed

    Kotchey, Gregg P; Allen, Brett L; Vedala, Harindra; Yanamala, Naveena; Kapralov, Alexander A; Tyurina, Yulia Y; Klein-Seetharaman, Judith; Kagan, Valerian E; Star, Alexander

    2011-03-22

    Two-dimensional graphitic carbon is a new material with many emerging applications, and studying its chemical properties is an important goal. Here, we reported a new phenomenon--the enzymatic oxidation of a single layer of graphitic carbon by horseradish peroxidase (HRP). In the presence of low concentrations of hydrogen peroxide (∼40 μM), HRP catalyzed the oxidation of graphene oxide, which resulted in the formation of holes on its basal plane. During the same period of analysis, HRP failed to oxidize chemically reduced graphene oxide (RGO). The enzymatic oxidation was characterized by Raman, ultraviolet-visible, electron paramagnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, atomic force microscopy, sodium dodecyl sulfate-polyacrylamide gel electrophoresis, and gas chromatography-mass spectrometry. Computational docking studies indicated that HRP was preferentially bound to the basal plane rather than the edge for both graphene oxide and RGO. Owing to the more dynamic nature of HRP on graphene oxide, the heme active site of HRP was in closer proximity to graphene oxide compared to RGO, thereby facilitating the oxidation of the basal plane of graphene oxide. We also studied the electronic properties of the reduced intermediate product, holey reduced graphene oxide (hRGO), using field-effect transistor (FET) measurements. While RGO exhibited a V-shaped transfer characteristic similar to a single layer of graphene that was attributed to its zero band gap, hRGO demonstrated a p-type semiconducting behavior with a positive shift in the Dirac points. This p-type behavior rendered hRGO, which can be conceptualized as interconnected graphene nanoribbons, as a potentially attractive material for FET sensors.

  8. Oxidative stress and myocarditis.

    PubMed

    Tada, Yuko; Suzuki, Jun-Ichi

    2016-01-01

    Reactive oxygen species (ROS) such as superoxide anion and hydrogen peroxide are produced highly in myocarditis. ROS, which not only act as effectors for pathogen killing but also mediate signal transduction in the stress responsive pathways, are closely related with both innate and adaptive immunity. On the other hand, oxidative stress overwhelming the capacity of anti-oxidative system generated in severe inflammation has been suggested to damage tissues and exacerbate inflammation. Oxidative stress worsens the autoimmunological process of myocarditis, and suppression of the anti-oxidative system and long-lasting oxidative stress could be one of the pathological mechanisms of cardiac remodeling leading to inflammatory cardiomyopathy. Oxidative stress is considered to be one of the promising treatment targets of myocarditis. Evidences of anti-oxidative treatments in myocarditis have not been fully established. Basic strategies of anti-oxidative treatments include inhibition of ROS production, activation of anti-oxidative enzymes and elimination of generated free radicals. ROS are produced by mitochondrial respiratory chain reactions and enzymes including NADPH oxidases, cyclooxygenase, and xanthine oxidase. Other systems involved in inflammation and stress response, such as NF-κB, Nrf2/Keap1, and neurohumoral factors also influence oxidative stress in myocarditis. The efficacy of anti-oxidative treatments could also depend on the etiology and the phases of myocarditis. We review in this article the pathological significance of ROS and oxidative stress, and the potential anti-oxidative treatments in myocarditis.

  9. Oxidative Stress, Nitric Oxide, and Diabetes

    PubMed Central

    Pitocco, Dario; Zaccardi, Francesco; Di Stasio, Enrico; Romitelli, Federica; Santini, Stefano A.; Zuppi, Cecilia; Ghirlanda, Giovanni

    2010-01-01

    In the recent decades, oxidative stress has become focus of interest in most biomedical disciplines and many types of clinical research. Increasing evidence from research on several diseases show that oxidative stress is associated with the pathogenesis of diabetes, obesity, cancer, ageing, inflammation, neurodegenerative disorders, hypertension, apoptosis, cardiovascular diseases, and heart failure. Based on this research, the emerging concept is that oxidative stress is the “final common pathway”, through which risk factors of several diseases exert their deleterious effects. Oxidative stress causes a complex dysregulation of cell metabolism and cell-cell homeostasis. In this review, we discuss the role of oxidative stress in the pathogenesis of insulin resistance and beta-cell dysfunction. These are the two most relevant mechanisms in the pathophysiology of type 2 diabetes, and in the pathogenesis of diabetic vascular complications, the leading cause of death in diabetic patients. PMID:20703435

  10. Oxidative stress, nitric oxide, and diabetes.

    PubMed

    Pitocco, Dario; Zaccardi, Francesco; Di Stasio, Enrico; Romitelli, Federica; Santini, Stefano A; Zuppi, Cecilia; Ghirlanda, Giovanni

    2010-01-01

    In the recent decades, oxidative stress has become focus of interest in most biomedical disciplines and many types of clinical research. Increasing evidence from research on several diseases show that oxidative stress is associated with the pathogenesis of diabetes, obesity, cancer, ageing, inflammation, neurodegenerative disorders, hypertension, apoptosis, cardiovascular diseases, and heart failure. Based on this research, the emerging concept is that oxidative stress is the "final common pathway", through which risk factors of several diseases exert their deleterious effects. Oxidative stress causes a complex dysregulation of cell metabolism and cell-cell homeostasis. In this review, we discuss the role of oxidative stress in the pathogenesis of insulin resistance and beta-cell dysfunction. These are the two most relevant mechanisms in the pathophysiology of type 2 diabetes, and in the pathogenesis of diabetic vascular complications, the leading cause of death in diabetic patients.

  11. Zinc oxide overdose

    MedlinePlus

    Zinc oxide is an ingredient in many products. Some of these are certain creams and ointments used ... prevent or treat minor skin burns and irritation. Zinc oxide overdose occurs when someone eats one of ...

  12. 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.

  13. 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

  14. Electrolytic oxidation of anthracite

    USGS Publications Warehouse

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

    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.

  15. 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.

  16. Studies in zirconium oxidation

    NASA Technical Reports Server (NTRS)

    Draley, J. E.; Drunen, C. J.; Levitan, J.

    1968-01-01

    Study provides insight into the oxidation mechanism of zirconium by combining electrical measurements with oxidation data. The measurement of electrical potential across growing scale on zirconium and the determination of conventional weight-change oxidation data were carried out at 550, 700, and 800 degrees C.

  17. Rhodium oxides in unusual oxidation states

    NASA Astrophysics Data System (ADS)

    Reisner, Barbara Alice

    Mixed valence RhIII/RhIV oxides have been proposed as a promising class of candidate compounds for superconductivity. Unfortunately, it is difficult to stabilize rhodates with a formal oxidation state approaching RhIV, as other techniques used for the synthesis of rhodium. oxides favor the most commonly observed formal oxidation state, RhIII. One technique which has been used to stabilize metal oxides in high formal oxidation states is crystallization from molten hydroxides. This thesis explores the use of molten hydroxides to enhance the reactivity of rhodium oxides in order to synthesize rhodates with high formal oxidation states. K0.5RhO2, Rb0.2RhO2, and CsxRhO2 were synthesized from pure alkali metal hydroxides. All crystallized with a previously unobserved polytype in the alkali metal rhodate system. Due to the low activity of dissolved oxygen species in LiOH and NaOH, LiRhO2 and NaRhO2 cannot be crystallized. The formal oxidation state of rhodium in AxRhO2 (A = K, Rb, Cs) is a function of the alkali metal hydroxide used to synthesize these oxides. These materials exhibit remarkable stability for layered metal oxides containing the heavier alkali metals, but all phases are susceptible to intercalation by water. The synthesis, structural characterization, magnetic susceptibility, and reactivity of these oxides are reported. Sr2RhO4 and a new rhodate were crystallized from a KOH-Sr(OH)2 flux. The synthesis and characterization of these materials is reported. Efforts to substitute platinum for rhodium in Sr 2RhO4 are also discussed. Mixed alkali metal-alkaline earth metal hydroxide fluxes were used to crystallize LiSr3RhO6, and NaSr3RhO 6. The synthesis of LiSr3RhO6 and NaSr3RhO 6 represents the first example of the stabilization of a rhodium oxide with a formal oxidation state approaching RhV. X-ray diffraction, electron beam microprobe analysis, thermogravimetric analysis, potentiometric titrations, X-ray photoelectron spectroscopy, and magnetic susceptibility

  18. Oxidation state in chondrites

    NASA Technical Reports Server (NTRS)

    Rubin, Alan E.; Fegley, Bruce; Brett, Robin

    1988-01-01

    An evaluation is made of extant data on chondrite oxidation states and intrinsic O fugacities. A variety of oxidation states are exhibited by the chondritic meteorites; petrologic and chemical data may be used to arrange the major chondrite groups in order of oxidation state. The intrinsic O fugacity measurements on chondrite whole-rock samples are noted to display a corresponding ordering of oxidation states. Metamorphosed chondrites and igneous meteorites that were substantially altered by metamorphic reactions, outgassing, and igneous processes may preserve information on the oxidation state and size of their parent bodies.

  19. Oxidative DNA modifications.

    PubMed

    Poulsen, Henrik E

    2005-07-01

    Oxidative DNA modifications are frequent in mammalian DNA and have been suggested an important mechanism in carcinogenesis, diabetes and ageing. The foundations for this suggestion are: Evidence for the importance of oxidative DNA modifications in cancer development is: high levels of oxidative lesions in cancer tissue; highly conserved and specific DNA repair systems targeting oxidative lesions; high levels of oxidative DNA lesions in oxidative DNA repair knock-out animals; defective repair of oxidative lesions in cancer-prone progeria syndromes; reduced cancer incidence in populations with high dietary antioxidant intake; and increased oxidative stress to DNA in tobacco smokers. Conflicting evidence for a relation between oxidative stress to DNA and cancer is: disagreement about the true levels and occurrence of the oxidative lesions in vivo; failure to identify the localization of oxidative lesions in important genes, e.g. tumor suppressor and oncogenes; lack of evidence that the oxidative lesions induce mutations in vivo; no cancer development in animals knocked-out for specific DNA repair enzymes in spite of high tissue levels of oxidative lesions; and unchanged cancer rates after antioxidant interventions in large clinical controlled and randomized trials. The rate of DNA oxidation has been estimated from urinary excretion of repair products and it is evident that if these lesions were not repaired, a large part of DNA would be oxidized to a degree not compatible with living. The methodologies by which oxidative DNA modifications are measured cover a wide and different range, advantages and disadvantages will be presented. One particular problem is artificial oxidation, and methods to prevent such artifacts will be presented together with results from a large interlaboratory standardization program. The methodology by which the lesions can be measured is complicated and prone to artifacts during DNA isolation, digestion, derivatization and maybe even during

  20. A Microscale Oxidation Puzzle

    NASA Astrophysics Data System (ADS)

    Pelter, Michael W.; Macudzinski, Rebecca M.; Passarelli, Mary Ellen

    2000-11-01

    We have adapted oxidation of an alcohol with sodium hypochlorite solution to a "puzzle" approach by using a diol as the substrate for oxidation. The diols under investigation have both a primary and a secondary hydroxyl group. There are three possible outcomes to the reaction: (i) only the primary alcohol is oxidized to the aldehyde (or carboxylic acid); (ii) only the secondary alcohol is oxidized to the ketone; or (iii) both alcohols are oxidized. The assignment is to perform the reaction and determine the structure of the product through interpretation of the IR spectrum. Examples using two commercially available diols are shown.

  1. Partial oxidation catalyst

    DOEpatents

    Krumpelt, Michael; Ahmed, Shabbir; Kumar, Romesh; Doshi, Rajiv

    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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Oxidizer Scoping Studies

    SciTech Connect

    Chancellor, Christopher John

    2016-11-07

    The purpose of this report is to present the results of the acceptable knowledge (AK) review of oxidizers present in active waste streams, provide a technical analysis of the oxidizers, and report the results of the scoping study testing. This report will determine the fastest burning oxidizer to be used in the development of a Test Plan for Preparation and Testing of Sorbents Mixed with Oxidizer found in Transuranic Waste (DWT-TP-001). The companion report, DWT-RPT-002, Sorbent Scoping Studies, contains similar information for sorbents identified during the AK review of TRU waste streams. The results of the oxidizer and sorbent scoping studies will be used to inform the QL1 test plan. The QL1 test results will support the development of a basis of knowledge document that will evaluate oxidizing chemicals and sorbents in TRU waste and provide guidance for treatment.

  8. OXIDATION OF TRANSURANIC ELEMENTS

    DOEpatents

    Moore, R.L.

    1959-02-17

    A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

  9. 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.

  10. Mixed oxide solid solutions

    DOEpatents

    Magno, Scott; Wang, Ruiping; Derouane, Eric

    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.

  11. 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.

  12. 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.

  13. 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.

  14. 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)

  15. CYTOTOXIC PHOSPHOLIPID OXIDATION PRODUCTS

    PubMed Central

    Chen, Rui; Yang, Lili; McIntyre, Thomas M.

    2008-01-01

    Phospholipid oxidation products accumulate in the necrotic core of atherosclerotic lesions, in apoptotic cells, and circulate in oxidized LDL. Phospholipid oxidation generates toxic products, but little is known about which specific products are cytotoxic, their receptors, or the mechanism(s) that induces cell death. We find the most common phospholipid oxidation product of oxidized LDL, phosphatidylcholine with esterified sn-2 azelaic acid, induced apoptosis at low micromolar concentrations. The synthetic ether phospholipid hexadecyl azelaoyl phosphatidylcholine (HAzPC) was rapidly internalized, and over-expression of PLA2g7 (PAF acetylhydrolase) that specifically hydrolyzes such oxidized phospholipids suppressed apoptosis. Internalized HAzPC associated with mitochondria, and cytochrome C and apoptosis-inducing factor escaped from mitochondria to the cytoplasm and nucleus, respectively, in cells exposed to HAzPC. Isolated mitochondria exposed to HAzPC rapidly swelled, and released cytochrome C and apoptosis-inducing factor. Other phospholipid oxidation products induced swelling, but HAzPC was the most effective and was twice as effective as its diacyl homolog. Cytoplasmic cytochrome C completes the apoptosome, and activated caspase 9 and 3 were present in cells exposed to HAzPC. Irreversible inhibition of caspase 9 blocked downstream caspase 3 activation, and prevented apoptosis. Mitochondrial damage initiated this apoptotic cascade because over-expression of Bcl-XL, an anti-apoptotic protein localized to mitochondria, blocked cytochrome C escape, and apoptosis. Thus, exogenous phospholipid oxidation products target intracellular mitochondria to activate the intrinsic apoptotic cascade. PMID:17597068

  16. 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.

  17. Stabilized chromium oxide film

    DOEpatents

    Garwin, Edward L.; Nyaiesh, Ali R.

    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.

  18. 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.

  19. Oxide dispersion strengthened superalloy

    NASA Technical Reports Server (NTRS)

    Glasgow, T. K.; Kim, Y. G.; Curwick, L. R.; Merrick, H. F.

    1981-01-01

    MA6000E alloy is strengthened at high temperatures by dispersion of yttrium oxide. Strength properties are about twice those of conventional nickel base alloys. Good thermal fatigue, intermediate temperature strength, and good oxidation resistance give alloy unique combination of benefits. Application in aircraft gas turbine is improved.

  20. Death from Nitrous Oxide.

    PubMed

    Bäckström, Björn; Johansson, Bengt; Eriksson, Anders

    2015-11-01

    Nitrous oxide is an inflammable gas that gives no smell or taste. It has a history of abuse as long as its clinical use, and deaths, although rare, have been reported. We describe two cases of accidental deaths related to voluntary inhalation of nitrous oxide, both found dead with a gas mask covering the face. In an attempt to find an explanation to why the victims did not react properly to oncoming hypoxia, we performed experiments where a test person was allowed to breath in a closed system, with or without nitrous oxide added. Vital signs and gas concentrations as well as subjective symptoms were recorded. The experiments indicated that the explanation to the fact that neither of the descendents had reacted to oncoming hypoxia and hypercapnia was due to the inhalation of nitrous oxide. This study raises the question whether nitrous oxide really should be easily, commercially available.

  1. Crystalline oxides on silicon.

    PubMed

    Reiner, James W; Kolpak, Alexie M; Segal, Yaron; Garrity, Kevin F; Ismail-Beigi, Sohrab; Ahn, Charles H; Walker, Fred J

    2010-07-20

    This review outlines developments in the growth of crystalline oxides on the ubiquitous silicon semiconductor platform. The overall goal of this endeavor is the integration of multifunctional complex oxides with advanced semiconductor technology. Oxide epitaxy in materials systems achieved through conventional deposition techniques is described first, followed by a description of the science and technology of using atomic layer-by-layer deposition with molecular beam epitaxy (MBE) to systematically construct the oxide-silicon interface. An interdisciplinary approach involving MBE, advanced real-space structural characterization, and first-principles theory has led to a detailed understanding of the process by which the interface between crystalline oxides and silicon forms, the resulting structure of the interface, and the link between structure and functionality. Potential applications in electronics and photonics are also discussed.

  2. 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.

  3. 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 μg/mL did not exhibit toxicity to human fibroblast cells, and the dose of more than 50 μg/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.

  4. 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

  5. Highly oxidized graphene oxide and methods for production thereof

    DOEpatents

    Tour, James M.; Kosynkin, Dmitry V.

    2016-08-30

    A highly oxidized form of graphene oxide and methods for production thereof are described in various embodiments of the present disclosure. In general, the methods include mixing a graphite source with a solution containing at least one oxidant and at least one protecting agent and then oxidizing the graphite source with the at least one oxidant in the presence of the at least one protecting agent to form the graphene oxide. Graphene oxide synthesized by the presently described methods is of a high structural quality that is more oxidized and maintains a higher proportion of aromatic rings and aromatic domains than does graphene oxide prepared in the absence of at least one protecting agent. Methods for reduction of graphene oxide into chemically converted graphene are also disclosed herein. The chemically converted graphene of the present disclosure is significantly more electrically conductive than is chemically converted graphene prepared from other sources of graphene oxide.

  6. 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.

  7. Biologically inspired oxidation catalysis.

    PubMed

    Que, Lawrence; Tolman, William B

    2008-09-18

    The development of processes for selective hydrocarbon oxidation is a goal that has long been pursued. An additional challenge is to make such processes environmentally friendly, for example by using non-toxic reagents and energy-efficient catalytic methods. Excellent examples are naturally occurring iron- or copper-containing metalloenzymes, and extensive studies have revealed the key chemical principles that underlie their efficacy as catalysts for aerobic oxidations. Important inroads have been made in applying this knowledge to the development of synthetic catalysts that model enzyme function. Such biologically inspired hydrocarbon oxidation catalysts hold great promise for wide-ranging synthetic applications.

  8. Oxidative acylation using thioacids

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.

    1997-01-01

    Several important prebiotic reactions, including the coupling of amino acids into polypeptides by the formation of amide linkages, involve acylation. Theae reactions present a challenge to the understanding of prebiotic synthesis. Condensation reactions relying on dehydrating agents are either inefficient in aqueous solution or require strongly acidic conditions and high temperatures. Activated amino acids such as thioester derivatives have therefore been suggested as likely substrates for prebiotic peptide synthesis. Here we propose a closely related route to amide bond formation involving oxidative acylation by thioacids. We find that phenylalanine, leucine and phenylphosphate are acylated efficiently in aqueous solution by thioacetic acid and an oxidizing agent. From a prebiotic point of view, oxidative acylation has the advantage of proceeding efficiently in solution and under mild conditions. We anticipate that oxidative acylation should prove to be a general method for activating carboxylic acids, including amino acids.

  9. Oxidative Tritium Decontamination System

    DOEpatents

    Gentile, Charles A. , Guttadora, Gregory L. , Parker, John J.

    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.

  10. 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.

  11. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides. (auth)

  12. Metal atom oxidation laser

    DOEpatents

    Jensen, R.J.; Rice, W.W.; Beattie, W.H.

    1975-10-28

    A chemical laser which operates by formation of metal or carbon atoms and reaction of such atoms with a gaseous oxidizer in an optical resonant cavity is described. The lasing species are diatomic or polyatomic in nature and are readily produced by exchange or other abstraction reactions between the metal or carbon atoms and the oxidizer. The lasing molecules may be metal or carbon monohalides or monoxides.

  13. ADVANCED OXIDATION PROCESS

    SciTech Connect

    Dr. Colin P. Horwitz; Dr. Terrence J. Collins

    2003-11-04

    The removal of recalcitrant sulfur species, dibenzothiophene and its derivatives, from automotive fuels is an integral component in the development of cleaner burning and more efficient automobile engines. Oxidative desulfurization (ODS) wherein the dibenzothiophene derivative is converted to its corresponding sulfoxide and sulfone is an attractive approach to sulfur removal because the oxidized species are easily extracted or precipitated and filtered from the hydrocarbon phase. Fe-TAML{reg_sign} activators of hydrogen peroxide (TAML is Tetra-Amido-Macrocyclic-Ligand) catalytically convert dibenzothiophene and its derivatives rapidly and effectively at moderate temperatures (50-60 C) and ambient pressure to the corresponding sulfoxides and sulfones. The oxidation process can be performed in both aqueous systems containing alcohols such as methanol, ethanol, or t-butanol, and in a two-phase hydrocarbon/aqueous system containing tert-butanol or acetonitrile. In the biphasic system, essentially complete conversion of the DBT to its oxidized products can be achieved using slightly longer reaction times than in homogeneous solution. Among the key features of the technology are the mild reaction conditions, the very high selectivity where no over oxidation of the sulfur compounds occurs, the near stoichiometric use of hydrogen peroxide, the apparent lack of degradation of sensitive fuel components, and the ease of separation of oxidized products.

  14. 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.…

  15. 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

  16. Antibacterial activity of graphite, graphite oxide, graphene oxide, and reduced graphene oxide: membrane and oxidative stress.

    PubMed

    Liu, Shaobin; Zeng, Tingying Helen; Hofmann, Mario; Burcombe, Ehdi; Wei, Jun; Jiang, Rongrong; Kong, Jing; Chen, Yuan

    2011-09-27

    Health and environmental impacts of graphene-based materials need to be thoroughly evaluated before their potential applications. Graphene has strong cytotoxicity toward bacteria. To better understand its antimicrobial mechanism, we compared the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO), and reduced graphene oxide (rGO)) toward a bacterial model-Escherichia coli. Under similar concentration and incubation conditions, GO dispersion shows the highest antibacterial activity, sequentially followed by rGO, Gt, and GtO. Scanning electron microscope (SEM) and dynamic light scattering analyses show that GO aggregates have the smallest average size among the four types of materials. SEM images display that the direct contacts with graphene nanosheets disrupt cell membrane. No superoxide anion (O(2)(•-)) induced reactive oxygen species (ROS) production is detected. However, the four types of materials can oxidize glutathione, which serves as redox state mediator in bacteria. Conductive rGO and Gt have higher oxidation capacities than insulating GO and GtO. Results suggest that antimicrobial actions are contributed by both membrane and oxidation stress. We propose that a three-step antimicrobial mechanism, previously used for carbon nanotubes, is applicable to graphene-based materials. It includes initial cell deposition on graphene-based materials, membrane stress caused by direct contact with sharp nanosheets, and the ensuing superoxide anion-independent oxidation. We envision that physicochemical properties of graphene-based materials, such as density of functional groups, size, and conductivity, can be precisely tailored to either reducing their health and environmental risks or increasing their application potentials.

  17. Antioxidants and protein oxidation.

    PubMed

    Griffiths, H R

    2000-11-01

    Proteins are susceptible to oxidation by reactive oxygen species, where the type of damage induced is characteristic of the denaturing species. The induction of protein carbonyls is a widely applied biomarker, arising from primary oxidative insult. However, when applied to complex biological and pathological conditions it can be subject to interference from lipid, carbohydrate and DNA oxidation products. More recently, interest has focused on the analysis of specific protein bound oxidised amino acids. Of the 22 amino acids, aromatic and sulphydryl containing residues have been regarded as being particularly susceptible to oxidative modification, with L-DOPA from tyrosine, ortho-tyrosine from phenylalanine; sulphoxides and disulphides from methionine and cysteine respectively; and kynurenines from tryptophan. Latterly, the identification of valine and leucine hydroxides, reduced from hydroperoxide intermediates, has been described and applied. In order to examine the nature of oxidative damage and protective efficacy of antioxidants the markers must be thoroughly evaluated for dosimetry in vitro following damage by specific radical species. Antioxidant protection against formation of the biomarker should be demonstrated in vitro. Quantification of biomarkers in proteins from normal subjects should be within the limits of detection of any analytical procedure. Further to this, the techniques for isolation and hydrolysis of specific proteins should demonstrate that in vitro oxidation is minimised. There is a need for the development of standards for quality assurance material to standardise procedures between laboratories. At present, antioxidant effects on protein oxidation in vivo are limited to animal studies, where dietary antioxidants have been reported to reduce dityrosine formation during rat exercise training. Two studies on humans have been reported last year. The further application of these methods to human studies is indicated, where the quality of the

  18. 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.

  19. 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.

  20. 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.

  1. Erythropoietin and oxidative stress.

    PubMed

    Maiese, Kenneth; Chong, Zhao Zhong; Hou, Jinling; Shang, Yan Chen

    2008-05-01

    Unmitigated oxidative stress can lead to diminished cellular longevity, accelerated aging, and accumulated toxic effects for an organism. Current investigations further suggest the significant disadvantages that can occur with cellular oxidative stress that can lead to clinical disability in a number of disorders, such as myocardial infarction, dementia, stroke, and diabetes. New therapeutic strategies are therefore sought that can be directed toward ameliorating the toxic effects of oxidative stress. Here we discuss the exciting potential of the growth factor and cytokine erythropoietin for the treatment of diseases such as cardiac ischemia, vascular injury, neurodegeneration, and diabetes through the modulation of cellular oxidative stress. Erythropoietin controls a variety of signal transduction pathways during oxidative stress that can involve Janus-tyrosine kinase 2, protein kinase B, signal transducer and activator of transcription pathways, Wnt proteins, mammalian forkhead transcription factors, caspases, and nuclear factor kappaB. Yet, the biological effects of erythropoietin may not always be beneficial and may be poor tolerated in a number of clinical scenarios, necessitating further basic and clinical investigations that emphasize the elucidation of the signal transduction pathways controlled by erythropoietin to direct both successful and safe clinical care.

  2. 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.

  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. 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.

  5. Oxidative Tritium Decontamination System

    SciTech Connect

    Charles A. Gentile; John J. Parker; Gregory L. Guttadora; Lloyd P. Ciebiera

    2002-02-11

    The Princeton Plasma Physics Laboratory, Tritium Systems Group has developed and fabricated an Oxidative Tritium Decontamination System (OTDS), which is designed to reduce tritium surface contamination on various components and items. The system is configured to introduce gaseous ozone into a reaction chamber containing tritiated items that require a reduction in tritium surface contamination. Tritium surface contamination (on components and items in the reaction chamber) is removed by chemically reacting elemental tritium to tritium oxide via oxidation, while purging the reaction chamber effluent to a gas holding tank or negative pressure HVAC system. Implementing specific concentrations of ozone along with catalytic parameters, the system is able to significantly reduce surface tritium contamination on an assortment of expendable and non-expendable items. This paper will present the results of various experimentation involving employment of this system.

  6. 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 inflammatory–proliferative response. Repetitive cycles of hypoxia and reoxygenation associated with changes in synovial perfusion are postulated to activate hypoxia-inducible factor-1α and nuclear factor-κB, 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

  7. 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.

  8. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    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.

  9. 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.

  10. 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.

  11. Methanol partial oxidation reformer

    DOEpatents

    Ahmed, Shabbir; Kumar, Romesh; Krumpelt, Michael

    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.

  12. 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.

  13. 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.

  14. Molecular water oxidation catalyst

    DOEpatents

    Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

    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.

  15. Krypton oxides under pressure.

    PubMed

    Zaleski-Ejgierd, Patryk; Lata, Pawel M

    2016-02-02

    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.

  16. 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}.

  17. Bacterial nitric oxide synthases.

    PubMed

    Crane, Brian R; Sudhamsu, Jawahar; Patel, Bhumit A

    2010-01-01

    Nitric oxide synthases (NOSs) are multidomain metalloproteins first identified in mammals as being responsible for the synthesis of the wide-spread signaling and protective agent nitric oxide (NO). Over the past 10 years, prokaryotic proteins that are homologous to animal NOSs have been identified and characterized, both in terms of enzymology and biological function. Despite some interesting differences in cofactor utilization and redox partners, the bacterial enzymes are in many ways similar to their mammalian NOS (mNOS) counterparts and, as such, have provided insight into the structural and catalytic properties of the NOS family. In particular, spectroscopic studies of thermostable bacterial NOSs have revealed key oxyheme intermediates involved in the oxidation of substrate L-arginine (Arg) to product NO. The biological functions of some bacterial NOSs have only more recently come to light. These studies disclose new roles for NO in biology, such as taking part in toxin biosynthesis, protection against oxidative stress, and regulation of recovery from radiation damage.

  18. 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.

  19. Conformations of organophosphine oxides

    DOE PAGES

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P.; ...

    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

  20. Highly oxidized superconductors

    DOEpatents

    Morris, Donald E.

    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.

  1. 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.

  2. 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

  3. Doped zinc oxide microspheres

    DOEpatents

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    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.

  4. 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.

  5. Nitric oxide neurotoxicity.

    PubMed

    Dawson, V L; Dawson, T M

    1996-06-01

    Derangements in glutamate neurotransmission have been implicated in several neurodegenerative disorders including, stroke, epilepsy, Huntington's disease, Alzheimer's disease, and amyotrophic lateral sclerosis (ALS). Activation of the N-methyl-D-aspartate (NMDA) receptor subtype of glutamate receptors results in the influx of calcium which binds calmodulin and activates neuronal nitric oxide synthase (nNOS), to convent L-arginine to citrulline and nitric oxide (NO). NO has many roles in the central nervous system as a messenger molecule, however, when generated in excess NO can be neurotoxic. Excess NO is in part responsible for glutamate neurotoxicity in primary neuronal cell culture and in animal models of stroke. It is likely that most of the neurotoxic actions of NO are mediated by peroxynitrite (ONOO-), the reaction product from NO and superoxide anion. In pathologic conditions, peroxynitrite and oxygen free radicals can be generated in excess of a cell antioxidant capacity resulting in severe damage to cellular constituents including proteins, DNA and lipids. The inherent biochemical and physiological characteristics of the brain, including high lipid concentrations and energy requirements, make it particularly susceptible to free radical and oxidant mediated insult. Increasing evidence indicates that many neurologic disorders may have components of free radical and oxidative stress induced injury.

  6. Oxidative stress in myopia.

    PubMed

    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.

  7. 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

  8. Mercuric oxide poisoning

    MedlinePlus

    ... oxide may be found in some: Button batteries (batteries containing mercury are no longer sold in the United States) Disinfectants Fungicides There have been reports of inorganic mercury poisoning from the use of skin-lightening creams. Note: This list may ...

  9. Metal Oxide Reduction Linked to Anaerobic Methane Oxidation.

    PubMed

    Oni, Oluwatobi E; Friedrich, Michael W

    2017-02-01

    Microbial methanotrophy is important in mitigating methane emissions to the atmosphere. Geochemical evidence suggests the occurrence of anaerobic methane oxidation with metal oxides in natural environments. A study has now identified, for the first time, novel freshwater archaea of the order Methanosarcinales that can oxidize methane with Fe(III) and Mn(IV) minerals as electron acceptors.

  10. 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.

  11. Protein oxidation and peroxidation

    PubMed Central

    Davies, Michael J.

    2016-01-01

    Proteins are major targets for radicals and two-electron oxidants in biological systems due to their abundance and high rate constants for reaction. With highly reactive radicals damage occurs at multiple side-chain and backbone sites. Less reactive species show greater selectivity with regard to the residues targeted and their spatial location. Modification can result in increased side-chain hydrophilicity, side-chain and backbone fragmentation, aggregation via covalent cross-linking or hydrophobic interactions, protein unfolding and altered conformation, altered interactions with biological partners and modified turnover. In the presence of O2, high yields of peroxyl radicals and peroxides (protein peroxidation) are formed; the latter account for up to 70% of the initial oxidant flux. Protein peroxides can oxidize both proteins and other targets. One-electron reduction results in additional radicals and chain reactions with alcohols and carbonyls as major products; the latter are commonly used markers of protein damage. Direct oxidation of cysteine (and less commonly) methionine residues is a major reaction; this is typically faster than with H2O2, and results in altered protein activity and function. Unlike H2O2, which is rapidly removed by protective enzymes, protein peroxides are only slowly removed, and catabolism is a major fate. Although turnover of modified proteins by proteasomal and lysosomal enzymes, and other proteases (e.g. mitochondrial Lon), can be efficient, protein hydroperoxides inhibit these pathways and this may contribute to the accumulation of modified proteins in cells. Available evidence supports an association between protein oxidation and multiple human pathologies, but whether this link is causal remains to be established. PMID:27026395

  12. 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)

  13. 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.

  14. 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.

  15. 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.

  16. Oxygen sensitive, refractory oxide composition

    DOEpatents

    Holcombe, Jr., Cressie E.; Smith, Douglas D.

    1976-01-01

    Oxide compositions containing niobium pentoxide and an oxide selected from the group consisting of hafnia, titania, and zirconia have electrical conductivity characteristics which vary greatly depending on the oxygen content.

  17. 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

  18. Current Toxicology of Ethylene Oxide,

    DTIC Science & Technology

    1982-12-01

    carcinogenicity are presented. The overall toxicological implications and a recommendation on the use of ethylene oxide are briefly discussed. (U...wer exposed to ethylene oxide vapour. A single exposure of the male rats to vapour at 100 ppm for 4 hours resulted in reproduction A abnormalities...oxide causes leukemia. It should be noted also that ethylene oxide in the presence of water produces ethylene glycol. Subchronic and chronic exposures

  19. Nitric oxide scavengers differentially inhibit ammonia oxidation in ammonia-oxidizing archaea and bacteria.

    PubMed

    Sauder, Laura A; Ross, Ashley A; Neufeld, Josh D

    2016-04-01

    Differential inhibitors are important for measuring the relative contributions of microbial groups, such as ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA), to biogeochemical processes in environmental samples. In particular, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO) represents a nitric oxide scavenger used for the specific inhibition of AOA, implicating nitric oxide as an intermediate of thaumarchaeotal ammonia oxidation. This study investigated four alternative nitric oxide scavengers for their ability to differentially inhibit AOA and AOB in comparison to PTIO. Caffeic acid, curcumin, methylene blue hydrate and trolox were tested onNitrosopumilus maritimus, two unpublished AOA representatives (AOA-6f and AOA-G6) as well as the AOB representative Nitrosomonas europaea All four scavengers inhibited ammonia oxidation by AOA at lower concentrations than for AOB. In particular, differential inhibition of AOA and AOB by caffeic acid (100 μM) and methylene blue hydrate (3 μM) was comparable to carboxy-PTIO (100 μM) in pure and enrichment culture incubations. However, when added to aquarium sponge biofilm microcosms, both scavengers were unable to inhibit ammonia oxidation consistently, likely due to degradation of the inhibitors themselves. This study provides evidence that a variety of nitric oxide scavengers result in differential inhibition of ammonia oxidation in AOA and AOB, and provides support to the proposed role of nitric oxide as a key intermediate in the thaumarchaeotal ammonia oxidation pathway.

  20. Catalytic oxidation of dimethyl ether

    SciTech Connect

    Zelenay, Piotr; Wu, Gang; Johnston, Christina M.; Li, Qing

    2016-05-10

    A composition for oxidizing dimethyl ether includes an alloy supported on carbon, the alloy being of platinum, ruthenium, and palladium. A process for oxidizing dimethyl ether involves exposing dimethyl ether to a carbon-supported alloy of platinum, ruthenium, and palladium under conditions sufficient to electrochemically oxidize the dimethyl ether.

  1. Doped palladium containing oxidation catalysts

    SciTech Connect

    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.

  2. Oxidative generation of guanine radicals by carbonate radicals and their reactions with nitrogen dioxide to form site specific 5-guanidino-4-nitroimidazole lesions in oligodeoxynucleotides.

    PubMed

    Joffe, Avrum; Mock, Steven; Yun, Byeong Hwa; Kolbanovskiy, Alexander; Geacintov, Nicholas E; Shafirovich, Vladimir

    2003-08-01

    A simple photochemical approach is described for synthesizing site specific, stable 5-guanidino-4-nitroimidazole (NIm) adducts in single- and double-stranded oligodeoxynucleotides containing single and multiple guanine residues. The DNA sequences employed, 5'-d(ACC CG(1)C G(2)TC CG(3)C G(4)CC) and 5'-d(ACC CG(1)C G(2)TC C), were a portion of exon 5 of the p53 tumor suppressor gene, including the codons 157 (G(2)) and 158 (G(3)) mutation hot spots in the former sequence with four Gs and the codon 157 (G(2)) mutation hot spot in the latter sequence with two Gs. The nitration of oligodeoxynucleotides was initiated by the selective photodissociation of persulfate anions to sulfate radicals induced by UV laser pulses (308 nm). In aqueous solutions, of bicarbonate and nitrite anions, the sulfate radicals generate carbonate anion radicals and nitrogen dioxide radicals by one electron oxidation of the respective anions. The guanine residue in the oligodeoxynucleotide is oxidized by the carbonate anion radical to form the neutral guanine radical. While the nitrogen dioxide radicals do not react with any of the intact DNA bases, they readily combine with the guanine radicals at either the C8 or the C5 positions. The C8 addition generates the well-known 8-nitroguanine (8-nitro-G) lesions, whereas the C5 attack produces unstable adducts, which rapidly decompose to NIm lesions. The maximum yields of the nitro products (NIm + 8-nitro-G) were typically in the range of 20-40%, depending on the number of guanine residues in the sequence. The ratio of the NIm to 8-nitro-G lesions gradually decreases from 3.4 in the model compound, 2',3',5'-tri-O-acetylguanosine, to 2.1-2.6 in the single-stranded oligodeoxynucleotides and to 0.8-1.1 in the duplexes. The adduct of the 5'-d(ACC CG(1)C G(2)TC C) oligodeoxynucleotide containing the NIm lesion in codon 157 (G(2)) was isolated in HPLC-pure form. The integrity of this adduct was established by a detailed analysis of exonuclease digestion

  3. Metal oxide-based transparent conducting oxides

    NASA Astrophysics Data System (ADS)

    Gillispie, Meagen Anne

    Transparent conducting oxides (TCOs) are important materials widely used for transparent contacts in flat panel displays, light emitting diodes, and solar cells. While Sn-doped In2O3 (ITO) continues to be the TCO of choice, the increasing cost of raw In has resulted in an increasing interest in developing In-free alternatives to ITO. In this work, two metal oxide systems were investigated for their viability as In-free TCO materials. First, Nb- or Ta-doped anatase TiO2 was selected due to the recent reports of high conductivity in pulse laser deposited (PLD) films. Thin films doped with either 15 mol% Nb or 20 mol% Ta were deposited on glass and SrTiO3 (STO) substrates using RF magnetron sputtering techniques. In all cases, maximum conductivity was achieved when the films crystallized in the anatase structure of TiO2. Films sputtered on STO possessed similar electrical and optical properties as PLD films on STO, yet at a much lower deposition temperature while films deposited on glass had much lower conductivity, due to dramatically reduced mobility. Two-dimensional x-ray diffraction analysis showed that doped TiO2 films sputter deposited on STO were biaxially textured along the (004) direction. This texturing was not observed in films deposited on glass, which were composed of randomly-oriented crystalline anatase. Biaxial texturing in the film helps to reduce grain boundary resistance, thereby increasing carrier mobility and further enhancing conductivity. The Cu-based delafossite system (CuBO2, B is a 3+ metal cation) was selected as the second TCO material system due to its natural p-type conductivity, a rarity among existing TCOs. Study of this system was two-pronged: (1) application of codoping techniques to achieve bipolar conductivity; and (2) investigate stability of mixed B cation delafossites. CuAlO2 and CuGaO2 were both codoped with varying ratios of donors and acceptors in an attempt to achieve bipolar conductivity. Very little change in the electrical

  4. Oxides Heterostructures for Nanoelectronics

    SciTech Connect

    C Dubourdieu; I Gelard; O Salicio; G Saint-Girons; B Vilquin; G Hollinger

    2011-12-31

    We summarise in this paper the work of two groups focusing on the synthesis and characterisation of functional oxide for nanoelectronic applications. In the first section, we discuss the growth by liquid-injection MOCVD of oxides heterostructures. Interface engineering for the minimisation of silicate formation during the growth of polycrystalline SrTiO{sub 3} on Si is first presented. It is realised via the change of reactant flow or chemical nature at the Si surface. We then report on the epitaxy on oxide substrates of manganites films and superlattices and on their magnetic and electrical properties. La{sub 0.7}Sr{sub 0.3}MnO{sub 3} and La{sub 0.8}MnO{sub 3-{delta}} as well as multiferroic hexagonal ReMnO{sub 3} manganites are considered. We show that the film thickness and related strain may be used to tune the properties. Finally, we demonstrate the growth of MgO nanowires by CVD at a moderate temperature of 600 C, using gold as a catalyst. In the second section, we discuss the growth of epitaxial oxide heterostructures by MBE. First, the direct epitaxy of SrTiO{sub 3} on Si is considered. Issues and control of the SrTiO{sub 3}/Si interface are discussed. An abrupt interface is achieved. We show that SrTiO{sub 3} on Si can be used as a buffer layer for the epitaxy of various perovskite oxides such as LaAlO{sub 3} or La{sub 0.7}Sr0.3MnO{sub 3}. La{sub 0.7}Sr{sub 0.3}MnO{sub 3} films are ferromagnetic and metallic at room temperature. The epitaxial growth of complex oxides on Si wafers opens up the route to the integration of a wide variety of functionalities in nanoelectronics. Finally, we discuss the monolithic integration of III-V compounds such as InP on Si using epitaxial SrTiO{sub 3} buffer layers for the future integration of optics on Si.

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

    SciTech Connect

    Ekerdt, J.G.

    1992-02-03

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

  6. Iron oxide surfaces

    NASA Astrophysics Data System (ADS)

    Parkinson, Gareth S.

    2016-03-01

    The current status of knowledge regarding the surfaces of the iron oxides, magnetite (Fe3O4), maghemite (γ-Fe2O3), haematite (α-Fe2O3), and wüstite (Fe1-xO) is reviewed. The paper starts with a summary of applications where iron oxide surfaces play a major role, including corrosion, catalysis, spintronics, magnetic nanoparticles (MNPs), biomedicine, photoelectrochemical water splitting and groundwater remediation. The bulk structure and properties are then briefly presented; each compound is based on a close-packed anion lattice, with a different distribution and oxidation state of the Fe cations in interstitial sites. The bulk defect chemistry is dominated by cation vacancies and interstitials (not oxygen vacancies) and this provides the context to understand iron oxide surfaces, which represent the front line in reduction and oxidation processes. Fe diffuses in and out from the bulk in response to the O2 chemical potential, forming sometimes complex intermediate phases at the surface. For example, α-Fe2O3 adopts Fe3O4-like surfaces in reducing conditions, and Fe3O4 adopts Fe1-xO-like structures in further reducing conditions still. It is argued that known bulk defect structures are an excellent starting point in building models for iron oxide surfaces. The atomic-scale structure of the low-index surfaces of iron oxides is the major focus of this review. Fe3O4 is the most studied iron oxide in surface science, primarily because its stability range corresponds nicely to the ultra-high vacuum environment. It is also an electrical conductor, which makes it straightforward to study with the most commonly used surface science methods such as photoemission spectroscopies (XPS, UPS) and scanning tunneling microscopy (STM). The impact of the surfaces on the measurement of bulk properties such as magnetism, the Verwey transition and the (predicted) half-metallicity is discussed. The best understood iron oxide surface at present is probably Fe3O4(100); the structure is

  7. 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

  8. Oxidative stress & male infertility.

    PubMed

    Makker, Kartikeya; Agarwal, Ashok; Sharma, Rakesh

    2009-04-01

    The male factor is considered a major contributory factor to infertility. Apart from the conventional causes for male infertility such as varicocoele, cryptorchidism, infections, obstructive lesions, cystic fibrosis, trauma, and tumours, a new and important cause has been identified: oxidative stress. Oxidative stress is a result of the imbalance between reactive oxygen species (ROS) and antioxidants in the body. It is a powerful mechanism that can lead to sperm damage, deformity and eventually, male infertility. This review discusses the physiological need for ROS and their role in normal sperm function. It also highlights the mechanism of production and the pathophysiology of ROS in relation to the male reproductive system and enumerate the benefits of incorporating antioxidants in clinical and experimental settings.

  9. 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.

  10. Controlled CO preferential oxidation

    DOEpatents

    Meltser, Mark A.; Hoch, Martin M.

    1997-01-01

    Method for controlling the supply of air to a PROX 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 therebetween 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.

  11. Infrared transparent conductive oxides

    NASA Astrophysics Data System (ADS)

    Johnson, Linda F.; Moran, Mark B.

    2001-09-01

    A novel class of complex metal oxides that have potential as transparent conducting oxides (TCOs) for the electromagnetic-interference (EMI) shielding on IR-seeker windows and missile domes has been identified. These complex metal oxides exhibit the rhombohedral (R3m) crystalline structure of naturally occurring delafossite, CuFeO2. The general chemical formula is ABO2 where A is a monovalent metal (Me+1 such as Cu, Ag, Au, Pt or Pd, and B is a trivalent metal (Me3+) such as Al,Ti,Cr,Co,Fe,Ni,Cs,Rh,Ga,Sn,In,Y,La,Pr,Nd,Sm or Eu. By adjusting the oxygen content, the conductivity can be varied over a wide range so that the delafossites behave as insulators, semiconductors or metals. This paper presents results for films of p-type CuxAlyOz and n-type CuxCryOz deposited by reactive magnetron co-sputtering from high-purity-metal targets. Films have been deposited using conventional RF- and DC-power supplies, and a new asymmetric-bipolar-pulsed- DC-power supply. Similar to the high-temperature-copper- oxide superconductors, the presence of Cu-O bonds is critical for the unique properties. Fourier transform infrared (FTIR) and electron spectroscopy for chemical analysis (ESCA) are used to understand the relationship between the optoelectornic properties and the molecular structure of the films. For example, FTIR absorption bands at 1470 and 1395cm-1 are present only in CuxAlyOz films that exhibit enhanced electrical conductivity. When these bands are absent, the CuxAlyOz films have high values of resistivity. In addition to the 1470 and 1395cm-1 bands observed in CuxAlyOz films, another pair of bands at 1040 and 970cm-1 is present in CuxCryOz films.

  12. 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.

  13. Oxidative Stress in Malaria

    PubMed Central

    Percário, Sandro; Moreira, Danilo R.; Gomes, Bruno A. Q.; Ferreira, Michelli E. S.; Gonçalves, 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

  14. Inorganic Halogen Oxidizer Research

    DTIC Science & Technology

    1975-02-26

    KEY WORDS (Continue on reverse aide il necesxary and identity by block number) Synthesis, Novel Oxidizers, Perchlorates, Fluorination , Halogen...C. J. Schack, R. D. Wilson, and E. C. Curtis, 5th European Fluorine Symposium, Avie.nore, Scotland (September 1974) 20. "New Energetic Halogen...elimination lasers. For NF-, no evidence for protonation was found at tempera- tures as low as -78 C. Furthermore, attempts to fluorinate NH. AsF

  15. Deactivation of Oxidation Catalysts

    DTIC Science & Technology

    1991-05-01

    the fresh catalyst . The loss in chromium may be related to the formation of volatile chromium oxychlorde which vaporizes from the catalyst . It is...CeO2 only marginally improved the thtrmal stability. The addition of 2% water vapor inhibited the oxidation of ethanol for all three copper catalysts ...original activity. Field tests of a copper chromite catalyst on process gas containing H2S, methyl mercaptan, n-aldehydes, and furfural showed

  16. CVD and Oxidative Stress

    PubMed Central

    Cervantes Gracia, Karla; Llanas-Cornejo, Daniel; Husi, Holger

    2017-01-01

    Nowadays, it is known that oxidative stress plays at least two roles within the cell, the generation of cellular damage and the involvement in several signaling pathways in its balanced normal state. So far, a substantial amount of time and effort has been expended in the search for a clear link between cardiovascular disease (CVD) and the effects of oxidative stress. Here, we present an overview of the different sources and types of reactive oxygen species in CVD, highlight the relationship between CVD and oxidative stress and discuss the most prominent molecules that play an important role in CVD pathophysiology. Details are given regarding common pharmacological treatments used for cardiovascular distress and how some of them are acting upon ROS-related pathways and molecules. Novel therapies, recently proposed ROS biomarkers, as well as future challenges in the field are addressed. It is apparent that the search for a better understanding of how ROS are contributing to the pathophysiology of CVD is far from over, and new approaches and more suitable biomarkers are needed for the latter to be accomplished. PMID:28230726

  17. Designing topologicality using oxides

    NASA Astrophysics Data System (ADS)

    Pardo, Victor

    In this talk we will describe a series of ab intio calculations carried out on different oxide-based systems and their nanostructures that show emerging non-trivial topological properties or nodal Fermi surfaces. We will show that various well-known oxide structures with the appropriate filling host Dirac points at the Fermi level that could eventually respond to spin-orbit coupling. In particular, we will focus on the results obtained in rutile multilayers, perovskite bilayers grown along the polar (111) direction and corundum-based multilayers. Topologically non-trivial phases occur in various limits of spin-orbit coupling strength and on-site Coulomb repulsion, using different fillings of the d-shell for various 3d and 5d elements in the active layers. The different systems will be discussed and compared to try to understand the key ingredients that lead to non-trivial topological properties in oxides and how these can be enhanced or tuned. We acknowledge support of the MINECO through the Ramon y Cajal Program and Project No. MAT2013-44673-R and Xunta de Galicia through Project No. EM2013/037.

  18. The oxidation of landscapes

    NASA Astrophysics Data System (ADS)

    Rempe, D.; Hahm, W. J.; Dietrich, W. E.

    2015-12-01

    At the base of the critical zone, fresh rock is transformed through chemical alteration of minerals and fracturing. The resulting hydrologically dynamic weathered bedrock zone strongly influences how mass is routed throughout a landscape. Studies of weathering in a variety of lithologies and climates have documented the role of oxygen in driving the onset of weathering. Porosity is generated through processes such as the formation of sulfuric acid via oxidative pyrite dissolution and strain via iron oxidation in biotite. The transport of meteoric oxygen is therefore a mechanism that links the topographic surface to weathering processes at depth. Here, we present an alternative to the theory that the advance of an oxidation front is driven by downward advection and diffusion of meteoric fluid. We present field data and theory that suggest that the slow drainage of groundwater within fresh bedrock drives the displacement of unreactive pore fluid from low-porosity fresh bedrock. This drainage, and the subsequent introduction of meteoric fluid to fresh rock, is a hillslope scale process driven by channel incision. The resulting distribution of weathered rock across the landscape is thus controlled by the fresh bedrock porosity and permeability and the rate of channel incision.

  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. Molecular theory of graphene oxide.

    PubMed

    Sheka, Elena F; Popova, Nadezhda A

    2013-08-28

    Applied to graphene oxide, the molecular theory of graphene considers its oxide as a final product in the succession of polyderivatives related to a series of oxidation reactions involving different oxidants. The graphene oxide structure is created in the course of a stepwise computational synthesis of polyoxides of the (5,5) nanographene molecule governed by an algorithm that takes into account the molecule's natural radicalization due to the correlation of its odd electrons, the extremely strong influence of the structure on properties, and a sharp response of the molecule behavior on small actions of external factors. Taking these together, the theory has allowed for a clear, transparent and understandable explanation of the hot points of graphene oxide chemistry and suggesting reliable models of both chemically produced and chemically reduced graphene oxides.

  1. 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 1 week 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.

  2. 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.

  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. 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.

  5. The 2016 oxide electronic materials and oxide interfaces roadmap

    NASA Astrophysics Data System (ADS)

    Lorenz, M.; Ramachandra Rao, M. S.; Venkatesan, T.; Fortunato, E.; Barquinha, P.; Branquinho, R.; Salgueiro, D.; Martins, R.; Carlos, E.; Liu, A.; Shan, F. K.; Grundmann, M.; Boschker, H.; Mukherjee, J.; Priyadarshini, M.; DasGupta, N.; Rogers, D. J.; Teherani, F. H.; Sandana, E. V.; Bove, P.; Rietwyk, K.; Zaban, A.; Veziridis, A.; Weidenkaff, A.; Muralidhar, M.; Murakami, M.; Abel, S.; Fompeyrine, J.; Zuniga-Perez, J.; Ramesh, R.; Spaldin, N. A.; Ostanin, S.; Borisov, V.; Mertig, I.; Lazenka, V.; Srinivasan, G.; Prellier, W.; Uchida, M.; Kawasaki, M.; Pentcheva, R.; Gegenwart, P.; Miletto Granozio, F.; Fontcuberta, J.; Pryds, N.

    2016-11-01

    Oxide electronic materials provide a plethora of possible applications and offer ample opportunity for scientists to probe into some of the exciting and intriguing phenomena exhibited by oxide systems and oxide interfaces. In addition to the already diverse spectrum of properties, the nanoscale form of oxides provides a new dimension of hitherto unknown phenomena due to the increased surface-to-volume ratio. Oxide electronic materials are becoming increasingly important in a wide range of applications including transparent electronics, optoelectronics, magnetoelectronics, photonics, spintronics, thermoelectrics, piezoelectrics, power harvesting, hydrogen storage and environmental waste management. Synthesis and fabrication of these materials, as well as processing into particular device structures to suit a specific application is still a challenge. Further, characterization of these materials to understand the tunability of their properties and the novel properties that evolve due to their nanostructured nature is another facet of the challenge. The research related to the oxide electronic field is at an impressionable stage, and this has motivated us to contribute with a roadmap on ‘oxide electronic materials and oxide interfaces’. This roadmap envisages the potential applications of oxide materials in cutting edge technologies and focuses on the necessary advances required to implement these materials, including both conventional and novel techniques for the synthesis, characterization, processing and fabrication of nanostructured oxides and oxide-based devices. The contents of this roadmap will highlight the functional and correlated properties of oxides in bulk, nano, thin film, multilayer and heterostructure forms, as well as the theoretical considerations behind both present and future applications in many technologically important areas as pointed out by Venkatesan. The contributions in this roadmap span several thematic groups which are represented by

  6. Au/metal oxides for low temperature CO oxidation

    SciTech Connect

    Srinivas, G.; Wright, J.; Bai, C.S.; Cook, R.

    1996-12-31

    Oxidation of carbon monoxide is important for several operations including fuel cells and carbon dioxide lasers. Room temperature CO oxidation has been investigated on a series of Au/metal oxide catalysts at conditions typical of spacecraft atmospheres; CO = 50 ppm, CO{sub 2} = 7,000 ppm, H{sub 2}O = 40% (RH) at 25{degrees}C, balance = air, and gas hourly space velocities of 7,000-60,000 hr{sup -1}. The addition of Au increases the room temperature CO oxidation activity of the metal oxides dramatically. All the Au/metal oxides deactivate during the CO oxidation reaction, especially in the presence of CO{sub 2} in the feed. The stability of the Au/metal oxide catalysts decreases in the following order: TiO{sub 2} > Fe{sub 2}O{sub 3} > NiO > Co{sub 3}O{sub 4}. The stability appears to decrease with an increase in the basicity of the metal oxides. In situ FTIR of CO adsorption on Au/TiO{sub 2} at 25{degrees}C indicates the formation of adsorbed CO, carboxylate, and carbonate species on the catalyst surface.

  7. 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.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

  8. 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

  9. Oxidation of sulfites on vanadium-molybdenum oxides

    NASA Astrophysics Data System (ADS)

    Matrosova, O. V.; Vishnetskaya, M. V.

    2014-01-01

    The low temperature emission of 1O2 singlet oxygen from xV2O5 · yMoO3 binary oxides is investigated by means of flash desorption. Conditions for the generation of 1O2 on their surfaces are determined, along with the correlation between the amount of 1O2 and the degree of NaHSO3 conversion in the oxidation reaction. It is shown that on the surface of oxides there are oxygen species that upon decomposition produce 1O2 involved in the oxidation of HSO{3/-}.

  10. Silicon-Based Oxide/Silicon/Oxide Resonant Tunneling

    DTIC Science & Technology

    1998-03-01

    approximately 0.5 eV in the limit of high Ge content where only thin layers can be grown without lattice relaxation. Silicon germanium and its alloys...FINAL REPORT FOR SILICON -BASED OXIDE/ SILICON /OXIDE RESONANT TUNNELING CONTRACT NO. F49620-95-C-0001 1 December 1994 - 31 March 1998 Prepared For...RSSilicon-Based Oxide/ Silicon /Oxide Re sonant Tunneling 61102F L Aurkaft-n2305/CS Dr Seabaugh 7. MORMIG VIGNIIIO;NAME(S) 1 GRISS(ES) Pf~fOMING ORGANIZATION

  11. 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.

  12. 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.

  13. 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.

  14. Oxidative stress and ageing.

    PubMed

    Birch-Machin, M A; Bowman, A

    2016-10-01

    Oxidative stress is the resultant damage due to redox imbalances (increase in destructive free radicals [reactive oxygen species (ROS)] and reduction in antioxidant protection/pathways) and is linked to ageing in many tissues including skin. In ageing skin there are bioenergetic differences between keratinocytes and fibroblasts which provide a potential ageing biomarker. The differences in skin bioenergy are part of the mitochondrial theory of ageing which remains one of the most widely accepted ageing theories describing subsequent increasing free radical generation. Mitochondria are the major source of cellular oxidative stress and form part of the vicious cycle theory of ageing. External and internal sources of oxidative stress include UVR/IR, pollution (environment), lifestyle (exercise and diet), alcohol and smoking all of which may potentially impact on skin although many exogenous actives and endogenous antioxidant defence systems have been described to help abrogate the increased stress. This also links to differences in skin cell types in terms of the UVR action spectrum for nuclear and mitochondrial DNA damage (the latter a previously described UVR biomarker in skin). Recent work associates bioenergy production and oxidative stress with pigment production thereby providing another additional potential avenue for targeted anti-ageing intervention in skin. This new data supporting the detrimental effects of the numerous wavelengths of UVR may aid in the development of cosmetic/sunscreen design to reduce the effects of photoageing. Recently, complex II of the mitochondrial electron transport chain appears to be more important than previously thought in the generation of free radicals (suggested predominantly by non-human studies). We investigated the relationship between complex II and ageing using human skin as a model tissue. The rate of complex II activity per unit of mitochondria was determined in fibroblasts and keratinocytes cultured from skin covering

  15. Electrolytic oxide reduction system

    DOEpatents

    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).

  16. Oxidative sulfonation of benzene

    SciTech Connect

    Kashnikova, L.V.; Golodov, V.A.; Vozdvizhenskii, V.F.; Levintova, T.D.

    1988-02-10

    The oxidative sulfonation of benzene with sulfur dioxide was studied in the presence of copper(II) chloride. The relation of the reaction rate to the amount of sulfur dioxide absorbed and the relation of the initial reaction rate to the benzene concentration is shown. With rise in benzene concentration, the initial reaction rate rose linearly and the amount of SO/sub 2/ absorbed remained practically constant. A mechanism was proposed that included the stage of the successive formation of an intermediate containing Cu(II) with benzene and sulfur dioxide and its subsequent redox breakdown to the final products as a result of attack by a Cu(II) benzene complex.

  17. 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.

  18. Oxidative stress in cyanobacteria.

    PubMed

    Latifi, Amel; Ruiz, Marion; Zhang, Cheng-Cai

    2009-03-01

    Reactive oxygen species (ROS) are byproducts of aerobic metabolism and potent agents that cause oxidative damage. In oxygenic photosynthetic organisms such as cyanobacteria, ROS are inevitably generated by photosynthetic electron transport, especially when the intensity of light-driven electron transport outpaces the rate of electron consumption during CO(2) fixation. Because cyanobacteria in their natural habitat are often exposed to changing external conditions, such as drastic fluctuations of light intensities, their ability to perceive ROS and to rapidly initiate antioxidant defences is crucial for their survival. This review summarizes recent findings and outlines important perspectives in this field.

  19. PREPARATION OF REFRACTORY OXIDE MICROSPHERE

    DOEpatents

    Haws, C.C. Jr.

    1963-09-24

    A method is described of preparing thorium oxide in the form of fused spherical particles about 1 to 2 microns in diameter. A combustible organic solution of thorium nitrate containing additive metal values is dispersed into a reflected, oxygen-fed flame at a temperature above the melting point of the resulting oxide. The metal additive is aluminum at a proportion such as to provide 1 to 10 weight per cent aluminum oxide in the product, silicon at the same proportion, or beryllium at a proportion of 12 to 25 weight per cent beryllium oxide in the product. A minor proportion of uranium values may also be provided in the solution. The metal additive lowers the oxide melting point and allows fusion and sphere formation in conventional equipment. The product particles are suitable for use in thorium oxide slurries for nuclear reactors. (AEC)

  20. Computer Simulation Of Cyclic Oxidation

    NASA Technical Reports Server (NTRS)

    Probst, H. B.; Lowell, C. E.

    1990-01-01

    Computer model developed to simulate cyclic oxidation of metals. With relatively few input parameters, kinetics of cyclic oxidation simulated for wide variety of temperatures, durations of cycles, and total numbers of cycles. Program written in BASICA and run on any IBM-compatible microcomputer. Used in variety of ways to aid experimental research. In minutes, effects of duration of cycle and/or number of cycles on oxidation kinetics of material surveyed.

  1. Nanoporous silicon oxide memory.

    PubMed

    Wang, Gunuk; Yang, Yang; Lee, Jae-Hwang; Abramova, Vera; Fei, Huilong; Ruan, Gedeng; Thomas, Edwin L; Tour, James M

    2014-08-13

    Oxide-based two-terminal resistive random access memory (RRAM) is considered one of the most promising candidates for next-generation nonvolatile memory. We introduce here a new RRAM memory structure employing a nanoporous (NP) silicon oxide (SiOx) material which enables unipolar switching through its internal vertical nanogap. Through the control of the stochastic filament formation at low voltage, the NP SiOx memory exhibited an extremely low electroforming voltage (∼ 1.6 V) and outstanding performance metrics. These include multibit storage ability (up to 9-bits), a high ON-OFF ratio (up to 10(7) A), a long high-temperature lifetime (≥ 10(4) s at 100 °C), excellent cycling endurance (≥ 10(5)), sub-50 ns switching speeds, and low power consumption (∼ 6 × 10(-5) W/bit). Also provided is the room temperature processability for versatile fabrication without any compliance current being needed during electroforming or switching operations. Taken together, these metrics in NP SiOx RRAM provide a route toward easily accessed nonvolatile memory applications.

  2. Magnetoexcitons in cuprous oxide

    NASA Astrophysics Data System (ADS)

    Schweiner, Frank; Main, Jörg; Wunner, Günter; Freitag, Marcel; Heckötter, Julian; Uihlein, Christoph; Aßmann, Marc; Fröhlich, Dietmar; Bayer, Manfred

    2017-01-01

    Two of the most striking experimental findings when investigating exciton spectra in cuprous oxide using high-resolution spectroscopy are the observability and the fine structure splitting of F excitons reported by J. Thewes et al. [Phys. Rev. Lett. 115, 027402 (2015), 10.1103/PhysRevLett.115.027402]. These findings show that it is indispensable to account for the complex valence band structure and the cubic symmetry of the solid in the theory of excitons. This is all the more important for magnetoexcitons, where the external magnetic field reduces the symmetry of the system even further. We present the theory of excitons in Cu2O in an external magnetic field and especially discuss the dependence of the spectra on the direction of the external magnetic field, which cannot be understood from a simple hydrogenlike model. Using high-resolution spectroscopy, we also present the corresponding experimental spectra for cuprous oxide in Faraday configuration. The theoretical results and experimental spectra are in excellent agreement as regards not only the energies but also the relative oscillator strengths. Furthermore, this comparison allows for the determination of the fourth Luttinger parameter κ of this semiconductor.

  3. Pristine graphite oxide.

    PubMed

    Dimiev, Ayrat; Kosynkin, Dmitry V; Alemany, Lawrence B; Chaguine, Pavel; Tour, James M

    2012-02-08

    Graphite oxide (GO) is a lamellar substance with an ambiguous structure due to material complexity. Recently published GO-related studies employ only one out of several existing models to interpret the experimental data. Because the models are different, this leads to confusion in understanding the nature of the observed phenomena. Lessening the structural ambiguity would lead to further developments in functionalization and use of GO. Here, we show that the structure and properties of GO depend significantly on the quenching and purification procedures, rather than, as is commonly thought, on the type of graphite used or oxidation protocol. We introduce a new purification protocol that produces a product that we refer to as pristine GO (pGO) in contrast to the commonly known material that we will refer to as conventional GO (cGO). We explain the differences between pGO and cGO by transformations caused by reaction with water. We produce ultraviolet-visible spectroscopic, Fourier transform infrared spectroscopic, solid-state nuclear magnetic resonance spectroscopic, thermogravimetric, and scanning electron microscopic analytical evidence for the structure of pGO. This work provides a new explanation for the acidity of GO solutions and allows us to add critical details to existing GO models.

  4. 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.

  5. 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.

  6. Zinc oxide varistors and/or resistors

    DOEpatents

    Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

    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.

  7. The chemistry of graphene oxide.

    PubMed

    Dreyer, Daniel R; Park, Sungjin; Bielawski, Christopher W; Ruoff, Rodney S

    2010-01-01

    The chemistry of graphene oxide is discussed in this critical review. Particular emphasis is directed toward the synthesis of graphene oxide, as well as its structure. Graphene oxide as a substrate for a variety of chemical transformations, including its reduction to graphene-like materials, is also discussed. This review will be of value to synthetic chemists interested in this emerging field of materials science, as well as those investigating applications of graphene who would find a more thorough treatment of the chemistry of graphene oxide useful in understanding the scope and limitations of current approaches which utilize this material (91 references).

  8. 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.

  9. Continuous lengths of oxide superconductors

    DOEpatents

    Kroeger, Donald M.; List, III, Frederick A.

    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.

  10. Magnetic frustration of graphite oxide

    NASA Astrophysics Data System (ADS)

    Lee, Dongwook; Seo, Jiwon

    2017-03-01

    Delocalized π electrons in aromatic ring structures generally induce diamagnetism. In graphite oxide, however, π electrons develop ferromagnetism due to the unique structure of the material. The π electrons are only mobile in the graphitic regions of graphite oxide, which are dispersed and surrounded by sp3-hybridized carbon atoms. The spin-glass behavior of graphite oxide is corroborated by the frequency dependence of its AC susceptibility. The magnetic susceptibility data exhibit a negative Curie temperature, field irreversibility, and slow relaxation. The overall results indicate that magnetic moments in graphite oxide slowly interact and develop magnetic frustration.

  11. Magnetic frustration of graphite oxide

    PubMed Central

    Lee, Dongwook; Seo, Jiwon

    2017-01-01

    Delocalized π electrons in aromatic ring structures generally induce diamagnetism. In graphite oxide, however, π electrons develop ferromagnetism due to the unique structure of the material. The π electrons are only mobile in the graphitic regions of graphite oxide, which are dispersed and surrounded by sp3-hybridized carbon atoms. The spin-glass behavior of graphite oxide is corroborated by the frequency dependence of its AC susceptibility. The magnetic susceptibility data exhibit a negative Curie temperature, field irreversibility, and slow relaxation. The overall results indicate that magnetic moments in graphite oxide slowly interact and develop magnetic frustration. PMID:28327606

  12. Semiconductor-oxide heterostructured nanowires using postgrowth oxidation.

    PubMed

    Wallentin, Jesper; Ek, Martin; Vainorious, Neimantas; Mergenthaler, Kilian; Samuelson, Lars; Pistol, Mats-Erik; Reine Wallenberg, L; Borgström, Magnus T

    2013-01-01

    Semiconductor-oxide heterointerfaces have several electron volts high-charge carrier potential barriers, which may enable devices utilizing quantum confinement at room temperature. While a single heterointerface is easily formed by oxide deposition on a crystalline semiconductor, as in MOS transistors, the amorphous structure of most oxides inhibits epitaxy of a second semiconductor layer. Here, we overcome this limitation by separating epitaxy from oxidation, using postgrowth oxidation of AlP segments to create axial and core-shell semiconductor-oxide heterostructured nanowires. Complete epitaxial AlP-InP nanowire structures were first grown in an oxygen-free environment. Subsequent exposure to air converted the AlP segments into amorphous aluminum oxide segments, leaving isolated InP segments in an oxide matrix. InP quantum dots formed on the nanowire sidewalls exhibit room temperature photoluminescence with small line widths (down to 15 meV) and high intensity. This optical performance, together with the control of heterostructure segment length, diameter, and position, opens up for optoelectrical applications at room temperature.

  13. 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...

  14. EDITORIAL: Oxide semiconductors

    NASA Astrophysics Data System (ADS)

    Kawasaki, M.; Makino, T.

    2005-04-01

    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

  15. 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

  16. Liquid-phase oxidation of cyclohexanone over cerium oxide catalyst

    SciTech Connect

    Shen, H.C. ); Weng, H.S. )

    1990-05-01

    Catalytic oxidation of cyclohexanone in the liquid phase with glacial acetic acid as the solvent over cerium oxide was studied between 5 and 15 atm and 98 and 118 {degrees} C in a batch reactor. The products were adipic acid, glutaric acid, succinic acid, caprolactone, carbon oxides, etc. The reaction undergoes a short induction period prior to a rapid reaction regime. In both regimes, the reaction is independent of oxygen pressure when the system pressure is above 10 atm. The induction period is inversely proportional to both of the catalyst weight and cyclohexanone concentration.During the rapid reaction regime, the reaction rate was found to be proportional to the 0.5 power of the catalyst weight and to the 1.5 power of the cyclohexanone concentration. Reaction mechanisms and rate expressions are proposed. The carbon oxides produced in this study were much lower than those previously reported. The cerium oxide catalyst is stable during the reaction.

  17. Room Temperature Chemical Oxidation of Delafossite-Type Oxides

    NASA Astrophysics Data System (ADS)

    Trari, M.; Töpfer, J.; Doumerc, J. P.; Pouchard, M.; Ammar, A.; Hagenmuller, P.

    1994-07-01

    Examination of the delafossite-type structure of CuLaO 2 and CuYO 2 suggests that there is room enough to accomodate intercalated oxide ions and the charge compensation resulting simply from the oxidation of an equivalent amount of Cu + into Cu 2+. Reaction with hypohalites in an aqueous solution leads to color change. Evidence of the formation of Cu 2+ is given by TGA, iodometric titration, and magnetic (static and EPR) measurements. The obtained La and Y compounds seem to behave in a different way: whereas CuLaO 2+ x appears as a single phase, CuYO 2+ x corresponds to a two-phase mixture, with respectively low and high x values, the latter being isostructural with the thermally oxidized compound recently reported by Cava et al. Comparison is stressed between the oxides obtained by oxidation at room and those obtained at higher temperatures.

  18. Operation of staged membrane oxidation reactor systems

    SciTech Connect

    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.

  19. 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.

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

    PubMed

    Andueza, Aitor; García-Garzón, Antonia; Ruiz de Galarreta, Marina; Ansorena, Eduardo; Iraburu, María J; López-Zabalza, María J; Martínez-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.

  1. 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.

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

    NASA Astrophysics Data System (ADS)

    Maciel, Elisabete; da Silva, Raquel Nunes; Simões, Cláudia; Domingues, Pedro; Domingues, M. Rosário 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.

  3. Structural characterization of oxidized glycerophosphatidylserine: evidence of polar head oxidation.

    PubMed

    Maciel, Elisabete; da Silva, Raquel Nunes; Simões, Cláudia; Domingues, Pedro; Domingues, M Rosário 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. 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.

  5. 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 (C(n)DMPO) and alkyl diethyl (C(n)DEPO) 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.

  6. 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.

  7. Biological water oxidation.

    PubMed

    Cox, Nicholas; Pantazis, Dimitrios A; Neese, Frank; Lubitz, Wolfgang

    2013-07-16

    Photosystem II (PSII), a multisubunit pigment-protein supercomplex found in cyanobacteria, algae, and plants, catalyzes a unique reaction in nature: the light-driven oxidation of water. Remarkable recent advances in the structural analysis of PSII now give a detailed picture of the static supercomplex on the molecular level. These data provide a solid foundation for future functional studies, in particular the mechanism of water oxidation and oxygen release. The catalytic core of the PSII is a tetramanganese-calcium cluster (Mn₄O₅Ca), commonly referred to as the oxygen-evolving complex (OEC). The function of the OEC rests on its ability to cycle through five metastable states (Si, i = 0-4), transiently storing four oxidizing equivalents, and in so doing, facilitates the four electron water splitting reaction. While the latest crystallographic model of PSII gives an atomic picture of the OEC, the exact connectivity within the inorganic core and the S-state(s) that the X-ray model represents remain uncertain. In this Account, we describe our joint experimental and theoretical efforts to eliminate these ambiguities by combining the X-ray data with spectroscopic constraints and introducing computational modeling. We are developing quantum chemical methods to predict electron paramagnetic resonance (EPR) parameters for transition metal clusters, especially focusing on spin-projection approaches combined with density functional theory (DFT) calculations. We aim to resolve the geometric and electronic structures of all S-states, correlating their structural features with spectroscopic observations to elucidate reactivity. The sequence of manganese oxidations and concomitant charge compensation events via proton transfer allow us to rationalize the multielectron S-state cycle. EPR spectroscopy combined with theoretical calculations provides a unique window into the tetramangenese complex, in particular its protonation states and metal ligand sphere evolution, far

  8. 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.

  9. 21 CFR 184.1545 - Nitrous oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Nitrous oxide. 184.1545 Section 184.1545 Food and... Substances Affirmed as GRAS § 184.1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No.... Nitrous oxide is manufactured by the thermal decomposition of ammonium nitrate. Higher oxides of...

  10. 21 CFR 184.1545 - Nitrous oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Nitrous oxide. 184.1545 Section 184.1545 Food and... Substances Affirmed as GRAS § 184.1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No.... Nitrous oxide is manufactured by the thermal decomposition of ammonium nitrate. Higher oxides of...

  11. 21 CFR 184.1545 - Nitrous oxide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Nitrous oxide. 184.1545 Section 184.1545 Food and... Substances Affirmed as GRAS § 184.1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No.... Nitrous oxide is manufactured by the thermal decomposition of ammonium nitrate. Higher oxides of...

  12. 21 CFR 184.1545 - Nitrous oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Nitrous oxide. 184.1545 Section 184.1545 Food and... Substances Affirmed as GRAS § 184.1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No.... Nitrous oxide is manufactured by the thermal decomposition of ammonium nitrate. Higher oxides of...

  13. 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.

  14. Ceramic oxide powders and the formation thereof

    DOEpatents

    Katz, Joseph L.; Hung, Cheng-Hung

    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.

  15. 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.

  16. 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.

  17. Complex oxides: Intricate disorder

    SciTech Connect

    Uberuaga, Blas Pedro

    2016-02-29

    In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore, how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought4.

  18. Complex oxides: Intricate disorder

    DOE PAGES

    Uberuaga, Blas Pedro

    2016-02-29

    In this study, complex oxides such as pyrochlores have a myriad of potential technological applications, including as fast ion conductors and radiation-tolerant nuclear waste forms. They are also of interest for their catalytic and spin ice properties. Many of these functional properties are enabled by the atomic structure of the cation sublattices. Pyrochlores (A2B2O7) contain two different cations (A and B), typically a 3+ rare earth and a 4+ transition metal such as Hf, Zr, or Ti. The large variety of chemistries that can form pyrochlores leads to a rich space in which to search for exotic new materials. Furthermore,more » how cations order or disorder on their respective sublattices for a given chemical composition influences the functional properties of the oxide. For example, oxygen ionic conductivity is directly correlated with the level of cation disorder — the swapping of A and B cations1. Further, the resistance of these materials against amorphization has also been connected with the ability of the cations to disorder2, 3. These correlations between cation structure and functionality have spurred great interest in the structure of the cation sublattice under irradiation, with significant focus on the disordering mechanisms and disordered structure. Previous studies have found that, upon irradiation, pyrochlores often undergo an order-to-disorder transformation, in which the resulting structure is, from a diffraction point of view, indistinguishable from fluorite (AO2) (ref. 3). Shamblin et al. now reveal that the structure of disordered pyrochlore is more complicated than previously thought4.« less

  19. Bilirubin oxidation in brain.

    PubMed

    Hansen, T W

    2000-01-01

    Bilirubin is a product of heme catabolism which by virtue of its lipid solubility can cross the blood-brain barrier and enter the brain. Neonatal jaundice is a common transitional phenomenon which is due to the combination of increased heme catabolism and rate limitations as far as hepatic conjugation and biliary excretion of bilirubin. In the great majority of cases this is an innocuous condition, which is even posited to have some beneficial effects due to the ability of bilirubin to quench free oxygen radicals. However, because bilirubin is neurotoxic, hyperbilirubinemia in the newborn may exceptionally result in death in the neonatal period, or survival with severe neurological sequelae (kernicterus). Bilirubin enters the brain through an intact blood-brain barrier. Clearance of bilirubin from brain partly involves retro-transfer through the blood-brain barrier, and possibly also through the brain-CSF barrier into CSF. Work in our lab during the past 5 years has substantiated earlier work which had suggested that bilirubin may also be metabolized in brain. The responsible enzyme is found on the inner mitochondrial membrane, and oxidizes bilirubin at a rate of 100-300 pmol bilirubin/mg protein/minute. The enzyme activity is lower in the newborn compared with the mature animal, and is also lower in neurons compared with glia. Studies of different rat strains have documented genetic variability. The enzyme is cytochrome-c-dependent, but has as yet not been unequivocally identified. The rate of oxidation of bilirubin is such that this enzyme probably contributes meaningfully to the clearance of bilirubin from brain.

  20. In-Situ Chemical Oxidation

    DTIC Science & Technology

    2006-08-01

    chlorophenols). Aliphatic alcohols, aldehydes, and organic acids generally react so slowly that the reaction rates are of little interest. However, formic ...may produce reac- tion byproducts that include dichloroacetaldehyde and dichloroacetic acid , compounds with lower toxicity. Similarly, oxidation of...phenolic compounds may pro- duce an assortment of carboxylic acids (Huling et al., 1998) that are nontoxic. Oxidation of these byproducts to CO2

  1. Nitrous oxide and perioperative outcomes.

    PubMed

    Ko, Hanjo; Kaye, Alan David; Urman, Richard D

    2014-06-01

    There is emerging evidence related to the effects of nitrous oxide on important perioperative patient outcomes. Proposed mechanisms include metabolic effects linked to elevated homocysteine levels and endothelial dysfunction, inhibition of deoxyribonucleic acid and protein formation, and depression of chemotactic migration by monocytes. Newer large studies point to possible risks associated with the use of nitrous oxide, although data are often equivocal and inconclusive. Cardiovascular outcomes such as stroke or myocardial infarction were shown to be unchanged in previous studies, but the more recent Evaluation of Nitrous Oxide in the Gas Mixture for Anesthesia I trial shows possible associations between nitrous oxide and increased cardiovascular and pulmonary complications. There are also possible effects on postoperative wound infections and neuropsychological function, although the multifactorial nature of these complications should be considered. Teratogenicity linked to nitrous oxide use has not been firmly established. The use of nitrous oxide for routine anesthetic care may be associated with significant costs if complications such as nausea, vomiting, and wound infections are taken into consideration. Overall, definitive data regarding the effect of nitrous oxide on major perioperative outcomes are lacking. There are ongoing prospective studies that may further elucidate its role. The use of nitrous oxide in daily practice should be individualized to each patient's medical conditions and risk factors.

  2. 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.

  3. Inhibiting Wet Oxidation of Ammonia

    NASA Technical Reports Server (NTRS)

    Onisko, D. B. L.

    1985-01-01

    Simple modification of wet-oxidation process for treating organicwaste reduces loss of fixed nitrogen, potentially valuable byproduct of process. Addition of sufficient sulfuric acid to maintain reaction pH below 3 greatly reduces oxidation of ammonia to free nitrogen. No equipment modification required.

  4. The oxidation of carbonized binders

    SciTech Connect

    Prokushin, V.N.; Fedoseev, S.D.; Kleimenov, V.V.; Kovaneva, M.A.; Marochkin, E.P.; Smyslov, V.I.; Trapeznikov, N.M.

    1983-01-01

    The oxidation by air of carbonized binders used in the production of carbonaceous materials has been studied by the derivatographic method. The effective activation energies of the process have been calculated. Of the materials investigated, the greatest oxidative resistance was possessed by coke obtained from medium-temperature hard-coal pitch.

  5. 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.

  6. Magnesium reduction of uranium oxide

    SciTech Connect

    Elliott, G.R.B.

    1985-08-13

    A method and apparatus are provided for reducing uranium oxide with magnesium to form uranium metal. The reduction is carried out in a molten-salt solution of density greater than 3.4 grams per cubic centimeter, thereby allowing the uranium product to sink and the magnesium oxide byproduct to float, consequently allowing separation of product and byproduct.

  7. 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

  8. Oxidative stress in Parkinson's disease.

    PubMed

    Nikam, Shashikant; Nikam, Padmaja; Ahaley, S K; Sontakke, Ajit V

    2009-01-01

    Oxidative stress contributes to the cascade, leading to dopamine cell degeneration in Parkinson's disease. However, oxidative stress is intimately linked to other components of the degenerative process, such as mitochondrial dysfunction, excitotoxicity, nitric oxide toxicity and inflammation. It is therefore difficult to determine whether oxidative stress leads to or is a consequence of, these events. Oxidative stress was assessed by estimating lipid peroxidation product in the form of thiobarbituric acid reactive substances, nitric oxide in the form of nitrite & nitrate. Enzymatic antioxidants in the form of superoxide dismutase, glutathione peroxidase, catalase, ceruloplasmin and non enzymatic antioxidant vitamins e.g. vitamin E and C in either serum or plasma or erythrocyte in 40 patients of Parkinson's disease in the age group 40-80 years. Trace elements e.g. copper, zinc and selenium were also estimated. Plasma thiobarbituric acid reactive substances and nitric oxide levels were Significantly high but superoxide dismutase, glutathione peroxidase, catalase, ceruloplasmin, vitamin-E, vitamin-C, copper, zinc and selenium levels were significantly low in Parkinson's disease when compared with control subjects. Present study showed that elevated oxidative stress may be playing a role in dopaminergic neuronal loss in substentia nigra pars compacta and involved in pathogenesis of the Parkinson's disease.

  9. Water oxidation: High five iron

    NASA Astrophysics Data System (ADS)

    Lloret-Fillol, Julio; Costas, Miquel

    2016-03-01

    The oxidation of water is essential to the sustainable production of fuels using sunlight or electricity, but designing active, stable and earth-abundant catalysts for the reaction is challenging. Now, a complex containing five iron atoms is shown to efficiently oxidize water by mimicking key features of the oxygen-evolving complex in green plants.

  10. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    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.

  11. Detection of nitric oxide pollution

    NASA Technical Reports Server (NTRS)

    Chackerian, C., Jr.; Weisbach, M. F.

    1973-01-01

    Studies of absorption spectra enhancement of certain atomic and molecular species inserter in dye-laser cavities have indicated that nitric oxide can be determined at low concentrations. Absorption coefficient of small amounts of nitric oxide in intra-laser-cavity absorption cell containing helium is enhanced by more than two orders of magnitude.

  12. Photodetachment of Lanthanide Oxide Anions

    NASA Astrophysics Data System (ADS)

    Covington, A. M.; Emmons, E. D.; Kraus, R. G.; Thompson, J. S.; Calabrese, D.; Davis, V. T.

    2007-06-01

    Laser photodetached electron spectroscopy (LPES) has been used to study the structure and collision properties of lanthanide oxide anions including LaOn^- and CeOn^-. Preliminary photoelectron spectra from these anions will be presented along with ion beam production data from these and other lanthanide oxide anions.

  13. 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...

  14. 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.

  15. Transparent metal oxide nanowire transistors

    NASA Astrophysics Data System (ADS)

    Chen, Di; Liu, Zhe; Liang, Bo; Wang, Xianfu; Shen, Guozhen

    2012-05-01

    With the features of high mobility, a high electric on/off ratio and excellent transparency, metal oxide nanowires are excellent candidates for transparent thin-film transistors, which is one of the key technologies to realize transparent electronics. This article provides a comprehensive review of the state-of-the-art research activities that focus on transparent metal oxide nanowire transistors. It begins with the brief introduction to the synthetic methods for high quality metal oxide nanowires, and the typical nanowire transfer and printing techniques with emphasis on the simple contact printing methodology. High performance transparent transistors built on both single nanowires and nanowire thin films are then highlighted. The final section deals with the applications of transparent metal oxide nanowire transistors in the field of transparent displays and concludes with an outlook on the current perspectives and future directions of transparent metal oxide nanowire transistors.

  16. Transparent metal oxide nanowire transistors.

    PubMed

    Chen, Di; Liu, Zhe; Liang, Bo; Wang, Xianfu; Shen, Guozhen

    2012-05-21

    With the features of high mobility, a high electric on/off ratio and excellent transparency, metal oxide nanowires are excellent candidates for transparent thin-film transistors, which is one of the key technologies to realize transparent electronics. This article provides a comprehensive review of the state-of-the-art research activities that focus on transparent metal oxide nanowire transistors. It begins with the brief introduction to the synthetic methods for high quality metal oxide nanowires, and the typical nanowire transfer and printing techniques with emphasis on the simple contact printing methodology. High performance transparent transistors built on both single nanowires and nanowire thin films are then highlighted. The final section deals with the applications of transparent metal oxide nanowire transistors in the field of transparent displays and concludes with an outlook on the current perspectives and future directions of transparent metal oxide nanowire transistors.

  17. 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

  18. 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.

  19. 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.

  20. Oxidation of Inconel alloy MA754 at low oxidation potential

    SciTech Connect

    Braski, D.N.; Goodell, P.D.; Cathcart, J.V.; Kane, R.H.

    1983-01-01

    It has been known for some time that the addition of small oxide particles to an 80 Ni-20 Cr alloy not only increases its elevated-temperature strength, but also markedly improves its resistance to oxidation. The mechanism by which the oxide dispersoid enhances the oxidation resistance was studied. Initial experiments were performed using inconel alloy MA754, which is nominally: 78 Ni, 20 Cr, 0.05 C, 0.3 Al, 0.5 Ti, 1.0 Fe, and 0.6 Y/sub 2/O/sub 3/ (wt %). Small disks (3 mm diam x 0.38 mm thick) were cut from MA754 plate stock and prepared with two different surface conditions. The first was prepared by mechanically polishing one side of a disk through 0.5 ..mu..m diamond on a syntron polisher while the second used an additional sulfuric acid-methanol electropolishing treatment to remove the cold-worked surface layer. Disks having both surface treatments were oxidized in a radiantly heated furnace for 30 s at 1000/sup 0/C. Three different environments were investigated: hydrogen with nominal dew points of 0/sup 0/C, -25/sup 0/C, and -55/sup 0/C. The oxide particles and films were examined in TEM by using extraction replicas (carbon) and by backpolishing to the oxide/metal interface. The particles were analyzed by EDS and SAD. Preliminary results are given.

  1. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

    PubMed

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-07-20

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation.

  2. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts

    PubMed Central

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  3. 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)...

  4. 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)...

  5. 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)...

  6. 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.

  7. Treatment of Fatty Acid Oxidation Disorders

    MedlinePlus

    ... of fatty acid oxidation disorders Treatment of fatty acid oxidation disorders E-mail to a friend Please ... page It's been added to your dashboard . Fatty acid oxidation disorders are rare health conditions that affect ...

  8. Ethanol oxidation on metal oxide-supported platinum catalysts

    SciTech Connect

    L. M. Petkovic 090468; Sergey N. Rashkeev; D. M. Ginosar

    2009-09-01

    Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbon monoxide exhaust emissions. However, on Ethanol is a renewable fuel that can be used as an additive to gasoline (or its substitute) with the advantage of octane enhancement and reduced carbon monoxide exhaust emissions. However, on the standard three-way catalysts, the conversion of unburned ethanol is low because both ethanol and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles trap and accumulate oxygen at their surface and perimeter sites and play the role of “stoves” that burn ethanol molecules and their partially oxidized derivatives to the “final” products. The ?-Al2O3 surfaces provided higher mobility of the fragments of ethanol molecules than the SiO2 surface and hence increased the supply rate of these objects to the Pt particles. This will in turn produce a higher conversion rate of unburned ethanol.and some of its partially oxidized derivatives are highly resistant to oxidation. A combination of first-principles density-functional theory (DFT) based calculations and in-situ diffuse reflectance infrared spectroscopy (DRIFTS) analysis was applied to uncover some of the fundamental phenomena associated with ethanol oxidation on Pt containing catalysts. In particular, the objective was to analyze the role of the oxide (i.e., ?-Al2O3 or SiO2) substrate on the ethanol oxidation activity. The results showed that Pt nanoparticles

  9. The oxidation of Octopus vulgaris hemocyanin by nitrogen oxides.

    PubMed

    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 NO2 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.

  10. 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.

  11. 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.

  12. Mechanism of bacterial pyrite oxidation.

    PubMed

    Silverman, M P

    1967-10-01

    The oxidation by Ferrobacillus ferrooxidans of untreated pyrite (FeS(2)) as well as HCl-pretreated pyrite (from which most of the acid-soluble iron species were removed) was studied manometrically. Oxygen uptake was linear during bacterial oxidation of untreated pyrite, whereas with HCl-pretreated pyrite both a decrease in oxygen uptake at 2 hr and nonlinear oxygen consumption were observed. Ferric sulfate added to HCl-pretreated pyrite restored approximately two-thirds of the decrease in total bacterial oxygen uptake and caused oxygen uptake to revert to nearly linear kinetics. Ferric sulfate also oxidized pyrite in the absence of bacteria and O(2); recovery of ferric and ferrous ions was in excellent agreement with the reaction Fe(2)(SO(4))(3) + FeS(2) = 3FeSO(4) + 2S, but the elemental sulfur produced was negligible. Neither H(2)S nor S(2)O(3) (2-) was a product of the reaction. It is probable that two mechanisms of bacterial pyrite oxidation operate concurrently: the direct contact mechanism which requires physical contact between bacteria and pyrite particles for biological pyrite oxidation, and the indirect contact mechanism according to which the bacteria oxidize ferrous ions to the ferric state, thereby regenerating the ferric ions required for chemical oxidation of pyrite.

  13. The oxidation of Fe(111)

    NASA Astrophysics Data System (ADS)

    Davies, Robert; Edwards, Dyfan; Gräfe, Joachim; Gilbert, Lee; Davies, Philip; Hutchings, Graham; Bowker, Michael

    2011-09-01

    The oxidation of Fe(111) was studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and scanning tunnelling microscopy (STM). Oxidation of the crystal was found to be a very fast process, even at 200 K, and the Auger O signal saturation level is reached within ~ 50 × 10 - 6 mbar s. Annealing the oxidised surface at 773 K causes a significant decline in apparent surface oxygen concentration and produces a clear (6 × 6) LEED pattern, whereas after oxidation at ambient temperature no pattern was observed. STM results indicate that the oxygen signal was reduced due to the nucleation of large, but sparsely distributed oxide islands, leaving mainly the smooth (6 × 6) structure between the islands. The reactivity of the (6 × 6) layer towards methanol was investigated using temperature programmed desorption (TPD), which showed mainly decomposition to CO and CO 2, due to the production of formate intermediates on the surface. Interestingly, this removes the (6 × 6) structure by reduction, but it can be reformed from the sink of oxygen present in the large oxide islands simply by annealing at 773 K for a few minutes. The (6 × 6) appears to be a relatively stable, pseudo-oxide phase, that may be useful as a model oxide surface.

  14. 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.

  15. Growth of nitrite-oxidizing bacteria by aerobic hydrogen oxidation.

    PubMed

    Koch, Hanna; Galushko, Alexander; Albertsen, Mads; Schintlmeister, Arno; Gruber-Dorninger, Christiane; Lücker, Sebastian; Pelletier, Eric; Le Paslier, Denis; Spieck, Eva; Richter, Andreas; Nielsen, Per H; Wagner, Michael; Daims, Holger

    2014-08-29

    The bacterial oxidation of nitrite to nitrate is a key process of the biogeochemical nitrogen cycle. Nitrite-oxidizing bacteria are considered a highly specialized functional group, which depends on the supply of nitrite from other microorganisms and whose distribution strictly correlates with nitrification in the environment and in wastewater treatment plants. On the basis of genomics, physiological experiments, and single-cell analyses, we show that Nitrospira moscoviensis, which represents a widely distributed lineage of nitrite-oxidizing bacteria, has the genetic inventory to utilize hydrogen (H2) as an alternative energy source for aerobic respiration and grows on H2 without nitrite. CO2 fixation occurred with H2 as the sole electron donor. Our results demonstrate a chemolithoautotrophic lifestyle of nitrite-oxidizing bacteria outside the nitrogen cycle, suggesting greater ecological flexibility than previously assumed.

  16. Alumina composites for oxide/oxide fibrous monoliths

    SciTech Connect

    Cruse, T. A.; Polzin, B. J.; Picciolo, J. J.; Singh, D.; Tsaliagos, R. N.; Goretta, K. C.

    2000-03-01

    Most work on ceramic fibrous monoliths (FMs) has focused on the Si{sub 3}N{sub 4}/BN system. In an effort to develop oxidation-resistant FMs, several oxide systems have recently been examined. Zirconia-toughened alumina and alumina/mullite appear to be good candidates for the cell phase of FMs. These composites offer higher strength and toughness than pure alumina and good high-temperature stability. By combining these oxides, possibly with a weaker high-temperature oxide as the cell-boundary phase, it should be possible to product a strong, resilient FM that exhibits graceful failure. Several material combinations have been examined. Results on FM fabrication and microstructural development are presented.

  17. 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.

  18. 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.

  19. Oxide Deposition By PECVD

    NASA Astrophysics Data System (ADS)

    Ibbotson, Dale E.; Hsieh, Julian J.; Flamm, Daniel L.; Mucha, J. A.

    1989-03-01

    We have studied the chemical and physical properties of silicon oxide films plasma deposited from TEOS (tetraethoxysilane), to gain an understanding of the origins of (1) step coverage and (2) film stability. TEOS was diluted in helium/oxygen mixtures and deposited as a function of discharge frequency (150 kHz and 14 MHz) and 02 flow in a parallel plate reactor. The typical deposition conditions were 1 torr total pressure, 320°C substrate temperature, 1 -9% TEOS, 1 -80% 02, and -0.1 W/cm2 discharge power. Films deposited at high frequency with excess oxygen were generally oxygen-rich, chemically unstable and hygroscopic, while films deposited at low frequency were stable to moisture and slightly deficient in oxygen. However, coverage profiles of high frequency films showed an unusual degree of directionality, which could be used to advantage for the coating of high aspect ratio features. We suggest that a judicious combination of high and low frequency discharges may improve film properties while maintaining directional step coverage. Isotopic labeling experiments were performed using 1802 to gain insight into the origins of the oxygen that is contained in these PECVD films. Complete isotopic scrambling was not observed. Film composition data suggest that there is one tenacious Si-0 bond which remains with the silicon from the original TEOS molecule during the reaction to form Si02.

  20. Photocatalytic oxidation of sulfamethazine.

    PubMed

    Kaniou, S; Pitarakis, K; Barlagianni, I; Poulios, I

    2005-07-01

    The photocatalytic degradation of sulfamethazine (SMT), a sulfonamide drug, has been investigated in aqueous heterogeneous solutions containing n-type oxide semiconductors as photocatalysts. The disappearance of the organic molecule follows approximately a pseudo-first-order kinetics according to the Langmuir-Hinshelwood model. It was observed that, with TiO2 P-25 and ZnO as photocatalysts, quantitative degradation of the organic molecule occurs after 4 h. During this time the desulfurization of the substrate is complete, while only 30% of the nitrogen in the organic compound was recovered in the form of nitrate and ammonium ions, indicating that various other nitrogen-containing organic compounds remain in the solution. The addition of H2O2 leads, in the case of TiO2 P-25, to a twofold increase on the reaction rate, while a negative effect has been observed in the presence of ZnO. The initial apparent photonic efficiency (zeta0) of the photooxidation and the mineralization under various experimental conditions have been calculated.

  1. Superflexibility of graphene oxide

    PubMed Central

    Poulin, Philippe; Jalili, Rouhollah; Neri, Wilfrid; Nallet, Frédéric; Colin, Annie; Wallace, Gordon; Zakri, Cécile

    2016-01-01

    Graphene oxide (GO), the main precursor of graphene-based materials made by solution processing, is known to be very stiff. Indeed, it has a Young’s modulus comparable to steel, on the order of 300 GPa. Despite its very high stiffness, we show here that GO is superflexible. We quantitatively measure the GO bending rigidity by characterizing the flattening of thermal undulations in response to shear forces in solution. Characterizations are performed by the combination of synchrotron X-ray diffraction at small angles and in situ rheology (rheo-SAXS) experiments using the high X-ray flux of a synchrotron source. The bending modulus is found to be 1 kT, which is about two orders of magnitude lower than the bending rigidity of neat graphene. This superflexibility compares with the fluidity of self-assembled liquid bilayers. This behavior is discussed by considering the mechanisms at play in bending and stretching deformations of atomic monolayers. The superflexibility of GO is a unique feature to develop bendable electronics after reduction, films, coatings, and fibers. This unique combination of properties of GO allows for flexibility in processing and fabrication coupled with a robustness in the fabricated structure. PMID:27647890

  2. 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.

  3. Oxidative desulfurization: kinetic modelling.

    PubMed

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  4. Nitrous oxide availability.

    PubMed

    Murray, M J; Murray, W J

    1980-04-01

    Nitrous oxide (N2O) is marketed as an inhalation anesthetic and as a food ingredient (e.g., whipping cream propellant). In the human, inhalation has been associated with "highs," peripheral nerve damage, mitotic poisoning of bone marrow, psychosis, and mental impairment. Exposure to hypoxemic mixtures has resulted in death. The commercial N2O sources specifically studied were aerosol whipping cream containers (three brands) and 6.5-cm cylinders, or chargers (two brands). The gas content and N2O concentrations of these devices were measured. The aerosol cans, when not shaken, will dispense at least 3 liters of 87 to 90% N2O. Charger misuse may occur when they are substituted for identically designed carbon dioxide (CO2) chargers of a seltzer bottle; 4.3 to 5.0 liters of 93 to 98% N2O is expelled at a controllable rate. The toxicity of these inexpensive N2O products, their high potential for misuse, and the absence of labeling (chargers) argue that their distribution be discontinued.

  5. Nitric oxide enhancement strategies

    PubMed Central

    Bryan, Nathan S

    2015-01-01

    It is becoming increasingly clear that many diseases are characterized or associated with perturbations in nitric oxide (NO) production/signaling. Therapeutics or strategies designed to restore normal NO homeostasis will likely have broad application and utility. This highly complex and multistep pathway for NO production and subsequent target activation provides many steps in the endogenous pathway that may be useful targets for drug development for cardiovascular disease, antimicrobial, cancer, wound healing, etc. This article will summarize known strategies that are currently available or in development for enhancing NO production or availability in the human body. Each strategy will be discussed including exogenous sources of NO, use of precursors to promote NO production and downstream pathways affected by NO production with advantages and disadvantages highlighted for each. Development of NO-based therapeutics is and will continue to be a major focus of biotech, academia as well as pharmaceutical companies. Application of safe and effective strategies will certainly transform health and disease. PMID:28031863

  6. 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.

  7. Peroxisomes, oxidative stress, and inflammation

    PubMed Central

    Terlecky, Stanley R; Terlecky, Laura J; Giordano, Courtney R

    2012-01-01

    Peroxisomes are intracellular organelles mediating a wide variety of biosynthetic and biodegradative reactions. Included among these are the metabolism of hydrogen peroxide and other reactive species, molecules whose levels help define the oxidative state of cells. Loss of oxidative equilibrium in cells of tissues and organs potentiates inflammatory responses which can ultimately trigger human disease. The goal of this article is to review evidence for connections between peroxisome function, oxidative stress, and inflammation in the context of human health and degenerative disease. Dysregulated points in this nexus are identified and potential remedial approaches are presented. PMID:22649571

  8. Nitric oxide and cardiovascular system.

    PubMed

    Cengel, Atiye; Sahinarslan, Asife

    2006-12-01

    Endothelium has many important functions including the control of blood-tissue permeability and vascular tonus, regulation of vascular surface properties for homeostasis and inflammation. Nitric oxide is the chief molecule in regulation of endothelial functions. Nitric oxide deficiency, which is also known as endothelial dysfunction, is the first step for the occurrence of many disease states in cardiovascular system including heart failure, hypertension, dyslipidemia, insulin resistance, diabetes mellitus, hyperhomocysteinemia and smoking. This review deals with the importance of nitric oxide for cardiovascular system. It also includes the latest improvements in the diagnosis and treatment of endothelial dysfunction.

  9. High-temperature oxide thermoelectrics

    NASA Astrophysics Data System (ADS)

    Terasaki, Ichiro

    2011-09-01

    We have evaluated the power factor of transition metal oxides at high temperatures using the Heikes formula and the Ioffe-Regel conductivity. The evaluated power factor is found to be nearly independent of carrier concentration in a wide range of doping, and explains the experimental data for cobalt oxides well. This suggests that the same power factor can be obtained with a thermopower larger than 2kB/e, and also suggests a reasonably high value of the dimensionless figure of merit ZT. We propose an oxide thermoelectric power generator by using materials having a thermopower larger than 300 μV/K.

  10. 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.

  11. Process for removing sulfur oxide and nitrogen oxide

    SciTech Connect

    Bhattacharyya, A

    1989-05-16

    This patent describes a process for reducing at least one of (1) the sulfur oxide content of a sulfur oxide-containing gas and (2) the nitrogen oxide content of a nitrogen oxide-containing gs which includes contacting the gas with a material at conditions to reduce at least one of (1) the sulfur oxide content of the gas and (2) the nitrogen oxide of the gas, the improvement comprising utilizing as at least a portion of the material the spinel/clay composition produced in accordance with the process comprising: (a) combining (1) an acidic, aluminum-containing composition in which the aluminum is present in a positively charged species, and (2) a basic alkaline earth metal-containing composition to form a gel mixture; and (b) mixing the gel with kaolin clay to form a co-gel mixture; and (c) calcinating the co-gel mixture to form the alkaline earth metal, aluminum-containing spinel composition, in a kaolin clay matrix.

  12. 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.

  13. Metal-Catalyzed Oxidation and Photo-oxidation of Glucagon.

    PubMed

    Zhang, Jian

    2016-08-01

    The oxidation of glucagon by the H2O2/Cu(2+) system and by simulated sunlight was studied using HPLC-MS methodologies. It was found that copper ion-catalyzed oxidation is much faster in the residue 1-12 region than in photo-oxidation, but it is slower than photo-oxidation in the residue 18-29 region. This difference is due to the unique feature of the primary sequence of glucagon. The residue 1-12 region contains His-1 and Asp-9 that can bind to Cu(2+) ions and catalyze the oxidation of His-1 and Tyr-10, while the residue 18-29 region lacks these charged residues near the liable Met-27 and Trp-25 and hence no catalysis by the neighboring groups occurs. Fragment (residue 13-17) was more stable than the other regions of the peptide toward photo-oxidation because it contains only one oxidizable residue, Tyr-13. These findings may help explain the mechanism of action of glucagon and provide some hints for the development of effective anti-diabetic drug molecules and stable glucagon formulations.

  14. Nitric oxide and oxidative stress in placental explant cultures.

    PubMed

    Goncalves, Juvic M; Casart, Ysabel C; Camejo, María I

    2016-01-01

    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.

  15. 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).

  16. Catastrophic Oxidation of Copper: A Brief Review

    NASA Astrophysics Data System (ADS)

    Belousov, V. V.; Klimashin, A. A.

    2012-10-01

    A brief review of the current understanding of copper accelerated oxidation in the presence of low-melting oxides (Bi2O3, MoO3, and V2O5) is given. Special attention is paid to the kinetics, thermodynamics, and mechanisms of accelerated oxidation of copper. The mechanisms of two stages (fast and superfast) of the copper accelerated oxidation are considered. It is shown that the fast oxidation of copper occurs by a diffusion mechanism. Oxygen diffusion along the liquid channels in the oxide scale is the rate-limiting step in the overall mechanism. The superfast oxidation of copper occurs by a fluxing mechanism. Realization of the particular mechanism depends on the mass ratio of low-melting oxide to the metal. The mass ratios of low-melting oxide to the metal and the oxygen partial pressures for superfast oxidation of copper are established. A model of the fast oxidation of copper is discussed.

  17. Non-conventional halide oxidation pathways : oxidation by imidazole triplet and surface specific oxidation by ozone

    NASA Astrophysics Data System (ADS)

    Ammann, Markus; Corral-Arroyo, Pablo; Aellig, Raphael; Orlando, Fabrizio; Lee, Ming-Tao; Artiglia, Luca

    2016-04-01

    Oxidation of halide ions (chloride, bromide, iodide) are the starting point of halogen release mechanisms out of sea water, marine aerosol or other halide containing continental aerosols. Slow oxidation of chloride and bromide by ozone in the bulk aqueous phase is of limited relevance. Faster surface specific oxidation has been suggested based on heterogeneous kinetics experiments. We provide first insight into very efficient bromide oxidation by ozone at the aqueous solution - air interface by surface sensitive X-ray photoelectron spectroscopy indicating significant build-up of an oxidized intermediate at the surface within millisecond time scales. The second source of oxidants in the condensed we have considered is the absorption of light by triplet forming photosensitizers at wavelengths longer than needed for direct photolysis and radical formation. We have performed coated wall flow tube experiments with mixtures of citric acid (CA) and imidazole-2-carboxaldehyde (IC) to represent secondary organic material rich marine aerosol. The halide ions bromide and iodide have been observed to act as efficient electron donors leading to their oxidation, HO2 formation and finally release of molecular halogen compounds. The photosensitization of imidazole-2-carboxaldehyde (IC) involves a well-known mechanism where the triplet excited state of IC is reduced by citric acid to a reduced ketyl radical that reacts with halide ions. A competition kinetics approach has been used to evaluate the rate limiting steps and to assess the significance of this source of halogens to the gas phase.

  18. 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.

  19. 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

  20. FLUORINATION OF OXIDIC NUCLEAR FUEL

    DOEpatents

    Mecham, W.J.; Gabor, J.D.

    1963-07-23

    A process of volatilizing fissionable material away from fission products, present together in neutron-bombarded uranium oxide, by reaction with an oxygen-fluorine mixture at 350 to 500 deg C is described. (AEC)

  1. Neurotoxicity of manganese oxide nanomaterials

    NASA Astrophysics Data System (ADS)

    Stefanescu, Diana M.; Khoshnan, Ali; Patterson, Paul H.; Hering, Janet G.

    2009-11-01

    Manganese (Mn) toxicity in humans has been observed as manganism, a disease that resembles Parkinson's disease. The mechanism of Mn toxicity and the chemical forms that may be responsible for its neurotoxicity are not well understood. We examined the toxicity of Mn oxide nanomaterials in a neuronal precursor cell model, using the MTS assay to evaluate mitochondrial function in living cells and the LDH assay to quantify the release of the enzyme lactate dehydrogenase as a result of damage to the cell membrane. Both assays show that the toxicity of Mn is dependent on the type of Mn oxide nanomaterial and its concentration as well as on the state of cell differentiation. Following exposure to Mn oxide nanomaterials, reactive oxygen species (ROS) are generated, and flow cytometry experiments suggest that cell death occurred through apoptosis. During exposure to Mn oxide nanomaterials, increased levels of the transcription factor NF-κB (which mediates the cellular inflammatory response) were observed.

  2. 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...

  3. 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...

  4. Oxidative stress and hypertension.

    PubMed

    Harrison, David G; Gongora, Maria Carolina

    2009-05-01

    This review has summarized some of the data supporting a role of ROS and oxidant stress in the genesis of hypertension. There is evidence that hypertensive stimuli, such as high salt and angiotensin II, promote the production of ROS in the brain, the kidney, and the vasculature and that each of these sites contributes either to hypertension or to the untoward sequelae of this disease. Although the NADPH oxidase in these various organs is a predominant source, other enzymes likely contribute to ROS production and signaling in these tissues. A major clinical challenge is that the routinely used antioxidants are ineffective in preventing or treating cardiovascular disease and hypertension. This is likely because these drugs are either ineffective or act in a non-targeted fashion, such that they remove not only injurious ROS Fig. 5. Proposed role of T cells in the genesis of hypertension and the role of the NADPH oxidase in multiple cells/organs in modulating this effect. In this scenario, angiotensin II stimulates an NADPH oxidase in the CVOs of the brain, increasing sympathetic outflow. Sympathetic nerve terminals in lymph nodes activate T cells, and angiotensin II also directly activates T cells. These stimuli also activate expression of homing signals in the vessel and likely the kidney, which attract T cells to these organs. T cells release cytokines that stimulate the vessel and kidney NADPH oxidases, promoting vasoconstriction and sodium retention. SFO, subfornical organ. 630 Harrison & Gongora but also those involved in normal cell signaling. A potentially important and relatively new direction is the concept that inflammatory cells such as T cells contribute to hypertension. Future studies are needed to understand the interaction of T cells with the CNS, the kidney, and the vasculature and how this might be interrupted to provide therapeutic benefit.

  5. 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.

  6. Oxidation protection coatings for polymers

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Sovey, J. S.; Banks, B. A. (Inventor)

    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.

  7. 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.

  8. Stochastic modeling of carbon oxidation

    SciTech Connect

    Chen, W.Y,; Kulkarni, A.; Milum, J.L.; Fan, L.T.

    1999-12-01

    Recent studies of carbon oxidation by scanning tunneling microscopy indicate that measured rates of carbon oxidation can be affected by randomly distributed defects in the carbon structure, which vary in size. Nevertheless, the impact of this observation on the analysis or modeling of the oxidation rate has not been critically assessed. This work focuses on the stochastic analysis of the dynamics of carbon clusters' conversions during the oxidation of a carbon sheet. According to the classic model of Nagle and Strickland-Constable (NSC), two classes of carbon clusters are involved in three types of reactions: gasification of basal-carbon clusters, gasification of edge-carbon clusters, and conversion of the edge-carbon clusters to the basal-carbon clusters due to the thermal annealing. To accommodate the dilution of basal clusters, however, the NSC model is modified for the later stage of oxidation in this work. Master equations governing the numbers of three classes of carbon clusters, basal, edge and gasified, are formulated from stochastic population balance. The stochastic pathways of three different classes of carbon during oxidation, that is, their means and the fluctuations around these means, have been numerically simulated independently by the algorithm derived from the master equations, as well as by an event-driven Monte Carlo algorithm. Both algorithms have given rise to identical results.

  9. 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.

  10. 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

  11. The metabolomics of oxidative stress.

    PubMed

    Noctor, Graham; Lelarge-Trouverie, Caroline; Mhamdi, Amna

    2015-04-01

    Oxidative stress resulting from increased availability of reactive oxygen species (ROS) is a key component of many responses of plants to challenging environmental conditions. The consequences for plant metabolism are complex and manifold. We review data on small compounds involved in oxidative stress, including ROS themselves and antioxidants and redox buffers in the membrane and soluble phases, and we discuss the wider consequences for plant primary and secondary metabolism. While metabolomics has been exploited in many studies on stress, there have been relatively few non-targeted studies focused on how metabolite signatures respond specifically to oxidative stress. As part of the discussion, we present results and reanalyze published datasets on metabolite profiles in catalase-deficient plants, which can be considered to be model oxidative stress systems. We emphasize the roles of ROS-triggered changes in metabolites as potential oxidative signals, and discuss responses that might be useful as markers for oxidative stress. Particular attention is paid to lipid-derived compounds, the status of antioxidants and antioxidant breakdown products, altered metabolism of amino acids, and the roles of phytohormone pathways.

  12. Catalytic Chemistry on Oxide Nanostructures

    SciTech Connect

    Asthagiri, Aravind; Dixon, David A.; Dohnalek, Zdenek; Kay, Bruce D.; Rodriquez, Jose A.; Rousseau, Roger J.; Stacchiola, Dario; Weaver, Jason F.

    2016-05-29

    Metal oxides represent one of the most important and widely employed materials in catalysis. Extreme variability of their chemistry provides a unique opportunity to tune their properties and to utilize them for the design of highly active and selective catalysts. For bulk oxides, this can be achieved by varying their stoichiometry, phase, exposed surface facets, defect, dopant densities and numerous other ways. Further, distinct properties from those of bulk oxides can be attained by restricting the oxide dimensionality and preparing them in the form of ultrathin films and nanoclusters as discussed throughout this book. In this chapter we focus on demonstrating such unique catalytic properties brought by the oxide nanoscaling. In the highlighted studies planar models are carefully designed to achieve minimal dispersion of structural motifs and to attain detailed mechanistic understanding of targeted chemical transformations. Detailed level of morphological and structural characterization necessary to achieve this goal is accomplished by employing both high-resolution imaging via scanning probe methods and ensemble-averaged surface sensitive spectroscopic methods. Three prototypical examples illustrating different properties of nanoscaled oxides in different classes of reactions are selected.

  13. NMR spectroscopy for assessing lipid oxidation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Although lipid oxidation involves a variety of chemical reactions to produce numerous substances, most of traditional methods assessing lipid oxidation measure only one kind of oxidation product. For this reason, in general, one indicator of oxidation is not enough to accurately describe the oxidati...

  14. 21 CFR 184.1545 - Nitrous oxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Nitrous oxide. 184.1545 Section 184.1545 Food and....1545 Nitrous oxide. (a) Nitrous oxide (empirical formula N2O, CAS Reg. No. 10024-97-2) is also known as... slightly sweet smell. It does not burn but will support combustion. Nitrous oxide is manufactured by...

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. Metal oxide nanostructures with hierarchical morphology

    SciTech Connect

    Ren, Zhifeng; Lao, Jing Yu; Banerjee, Debasish

    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.

  2. Solid State Cooling with Advanced Oxide Materials

    DTIC Science & Technology

    2014-06-03

    Properties and Response of Epitaxial Oxide Thin Films for Advanced Devices, Workshop on Oxide Electronics (Sept. 2011, Napa , CA) [Invited] 19. L. W. Martin...Properties and Response of Epitaxial Oxide Thin Films for Advanced Devices, Workshop on Oxide Electronics (Sept. 2011, Napa , CA) [Invited] 19. L. W

  3. The oxidation of metals and alloys

    NASA Technical Reports Server (NTRS)

    Scheil, Erich

    1952-01-01

    This paper reviews the various types of oxidation processes occurring with pure metals and gives explanations for the varying time-temperature-oxidation rate relations that exist for copper, tungsten, zinc, cadmium, and tantalum. The effect of shape and crystal structure on oxidation is discussed. Principles derived are applied to the oxidation of alloys.

  4. 49 CFR 173.337 - Nitric oxide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 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...

  5. 49 CFR 173.337 - Nitric oxide.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 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. 49 CFR 173.337 - Nitric oxide.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 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...

  7. 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...

  8. Thin film hydrous metal oxide catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  9. 21 CFR 73.2250 - Iron oxides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Iron oxides. 73.2250 Section 73.2250 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2250 Iron oxides. (a) Identity. The color additives iron oxides consist of any one or any combination of synthetically prepared iron oxides, including...

  10. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... space of an ethylene oxide cargo tank for a period of 30 days under the condition of paragraph (e)...

  11. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... space of an ethylene oxide cargo tank for a period of 30 days under the condition of paragraph (e)...

  12. 46 CFR 154.1725 - Ethylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Ethylene oxide. 154.1725 Section 154.1725 Shipping COAST....1725 Ethylene oxide. (a) A vessel carrying ethylene oxide must: (1) Have cargo piping, vent piping, and... space of an ethylene oxide cargo tank for a period of 30 days under the condition of paragraph (e)...

  13. Novel biomarker pipeline to probe the oxidation sites and oxidation degrees of hemoglobin in bovine erythrocytes exposed to oxidative stress.

    PubMed

    Zong, Wansong; Wang, Xiaoning; Yang, Chuanxi; Du, Yonggang; Sun, Weijun; Xu, Zhenzhen

    2016-06-01

    Research on biomarkers for protein oxidation might give insight into the mechanistic mode of oxidative stress. In the work present here, a novel pipeline was established to probe the oxidation mechanism of bovine hemoglobin (Hb) with its oxidation products serving as the biomarkers. Reactive oxygen species generated by irradiation were used to mimic oxidative stress conditions to oxidize Hb in bovine erythrocytes. After Hb extraction and digestion, oxidized peptides in the tryptic fragments were assigned by comparison with the extracted ion chromatography spectra of native peptide from the control sample. Subsequent tandem mass spectrometry analysis of these peptides proved that oxidation was limited to partially exposed amino acid residues (α-Phe36 , β-Met1 , β-Trp14 , for instance) in Hb. Quantitation analysis on these oxidized peptides showed that oxidation degrees of target sites had positive correlations with the extended oxidation dose and the oxidation processes were also controlled by residues types. Compared with the conventional protein carbonyl assay, the identified oxidized products were feasibility biomarkers for Hb oxidation, indicating that the proposed biomarker pipeline was suitable to provide specific and valid information for protein oxidation. Copyright © 2015 John Wiley & Sons, Ltd.

  14. 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.

  15. 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.

  16. Autoimmunity and oxidatively modified autoantigens

    PubMed Central

    Kurien, Biji T.; Scofield, R. Hal

    2008-01-01

    Oxidative damage mediated by reactive oxygen species results in the generation of deleterious by-products. The oxidation process itself and the proteins modified by these molecules are important mediators of cell toxicity and disease pathogenesis. Aldehydic products, mainly the 4-hydroxy-2-alkenals, form adducts with proteins and make them highly immunogenic. Proteins modified in this manner have been shown to induce pathogenic antibodies in a variety of diseases including systemic lupus erythematosus (SLE), alcoholic liver disease, diabetes mellitus (DM) and rheumatoid arthritis (RA). 8-oxodeoxyguanine (oxidatively modified DNA) and low density lipoproteins (LDL) occur in SLE, a disease in which premature atherosclerosis is a serious problem. In addition, immunization with 4-hydroxy-2-nonenal (HNE) modified 60 kD Ro autoantigen induces an accelerated epitope spreading in an animal model of SLE. Advanced glycation end product (AGE) pentosidine and AGE modified IgG have been shown to correlate with RA disease activity. Oxidatively modified glutamic acid decarboxylase is important in type 1 DM, while autoantibodies against oxidized LDL are prevalent in Behcet’s disease. The fragmentation of scleroderma specific autoantigens occurs as a result of oxidative modification and is thought to be responsible for the production of autoantibodies through the release of cryptic epitopes. The administration of antioxidants is a viable untried alternative for preventing or ameliorating autoimmune disease, particularly on account of the overwhelming evidence for the involvement of oxidative damage in autoimmunity. However, this should be viewed in the light of disappointing results obtained with the use of antioxidants in cardiovascular disease. PMID:18625446

  17. Microbial Formation of Manganese Oxides

    PubMed Central

    Greene, Anthony C.; Madgwick, John C.

    1991-01-01

    Microbial manganese oxidation was demonstrated at high Mn2+ concentrations (5 g/liter) in bacterial cultures in the presence of a microalga. The structure of the oxide produced varied depending on the bacterial strain and mode of culture. A nonaxenic, acid-tolerant microalga, a Chlamydomonas sp., was found to mediate formation of manganite (γ-MnOOH). Bacteria isolated from associations with crude cultures of this alga grown in aerated bioreactors formed disordered γ-MnO2 from Mn2+ at concentrations of 5 g/liter over 1 month, yielding 3.3 g of a semipure oxide per liter. All algal-bacterial cultures removed Mn2+ from solution, but only those with the highest removal rates formed an insoluble oxide. While the alga was an essential component of the reaction, a Pseudomonas sp. was found to be primarily responsible for the formation of a manganese precipitate. Medium components—algal biomass and urea—showed optima at 5.7 and 10 g/liters, respectively. The scaled-up culture (50 times) gave a yield of 22.3 g (53 mg/liter/day from a 15-liter culture) of semipure disordered γ-MnO2, identified by X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy, and had a manganese oxide O/Mn ratio of 1.92. The Mn(IV) content in the oxide was low (30.5%) compared with that of mined or chemically formed γ-MnO2 (ca. 50%). The shortfall in the bacterial oxide manganese content was due to biological and inorganic contaminants. FTIR spectroscopy, transmission electron microscopy, and electron diffraction studies have identified manganite as a likely intermediate product in the formation of disordered γ-MnO2. PMID:16348459

  18. 21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59...

  19. 21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59...

  20. 21 CFR 172.808 - Copolymer condensates of ethylene oxide and propylene oxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Copolymer condensates of ethylene oxide and... ethylene oxide and propylene oxide. Copolymer condensates of ethylene oxide and propylene oxide may be... percent aqueous solution. (2) α-Hydro-omega-hydroxy-poly (oxy-ethylene)poly(oxypropylene)-(53-59...