Degradation of ciprofloxacin antibiotic by Homogeneous Fenton oxidation: Hybrid AHP-PROMETHEE method, optimization, biodegradability improvement and identification of oxidized by-products.

Science.gov (United States)

Salari, Marjan; Rakhshandehroo, Gholam Reza; Nikoo, Mohammad Reza

2018-09-01

The main purpose of this experimental study was to optimize Homogeneous Fenton oxidation (HFO) and identification of oxidized by-products from degradation of Ciprofloxacin (CIP) using hybrid AHP-PROMETHEE, Response Surface Methodology (RSM) and High Performance Liquid Chromatography coupled with Mass Spectrometry (HPLC-MS). At the first step, an assessment was made for performances of two catalysts (FeSO 4 ·7H 2 O and FeCl 2 ·4H 2 O) based on hybrid AHP-PROMETHEE decision making method. Then, RSM was utilized to examine and optimize the influence of different variables including initial CIP concentration, Fe 2+ concentration, [H 2 O 2 ]/[ Fe 2+ ] mole ratio and initial pH as independent variables on CIP removal, COD removal, and sludge to iron (SIR) as the response functions in a reaction time of 25 min. Weights of the mentioned responses as well as cost criteria were determined by AHP model based on pairwise comparison and then used as inputs to PROMETHEE method to develop hybrid AHP-PROMETHEE. Based on net flow results of this hybrid model, FeCl 2 ·4H 2 O was more efficient because of its less environmental stability as well as lower SIR production. Then, optimization of experiments using Central Composite Design (CCD) under RSM was performed with the FeCl 2 ·4H 2 O catalyst. Biodegradability of wastewater was determined in terms of BOD 5 /COD ratio, showing that HFO process is able to improve wastewater biodegradability from zero to 0.42. Finally, the main intermediaries of degradation and degradation pathways of CIP were investigated with (HPLC-MS). Major degradation pathways from hydroxylation of both piperazine and quinolonic rings, oxidation and cleavage of the piperazine ring, and defluorination (OH/F substitution) were suggested. Copyright © 2018 Elsevier Ltd. All rights reserved.

Oxidative degradation of toluene and limonene in air by pulsed corona technology

International Nuclear Information System (INIS)

Hoeben, W F L M; Beckers, F J C M; Pemen, A J M; Van Heesch, E J M; Kling, W L

2012-01-01

The oxidative degradation of two volatile organic compounds, i.e. toluene (fossil fuel based VOC) and limonene (biogenic VOC), has been studied. A hybrid pulsed power corona reactor with adjustable energy density has been utilized for degradation of ppm level target compounds in large air flows. The observed oxidation product range features an energy density-dependent spectrum of oxygen-functional hydrocarbons, which has been qualitatively discussed on the basis of literature studies. Typically, observed stable oxidation products for both target compounds are the biocompatible carboxylic acids acetic and formic acid. Measured degradation G-values are 23 nmol J -1 at 74% conversion of 70 ppm toluene and 181 nmol J -1 at 81% conversion of 10 ppm limonene. (paper)

Four new degradation products of doxorubicin: An application of forced degradation study and hyphenated chromatographic techniques

Directory of Open Access Journals (Sweden)

Dheeraj Kaushik

2015-10-01

Full Text Available Forced degradation study on doxorubicin (DOX was carried out under hydrolytic condition in acidic, alkaline and neutral media at varied temperatures, as well as under peroxide, thermal and photolytic conditions in accordance with International Conference on Harmonization (ICH guidelines Q1(R2. It was found extremely unstable to alkaline hydrolysis even at room temperature, unstable to acid hydrolysis at 80 °C, and to oxidation at room temperature. It degraded to four products (O-I–O-IV in oxidative condition, and to single product (A-I in acid hydrolytic condition. These products were resolved on a C8 (150 mm×4.6 mm, 5 µm column with isocratic elution using mobile phase consisting of HCOONH4 (10 mM, pH 2.5, acetonitrile and methanol (65:15:20, v/v/v. Liquid chromatography–photodiode array (LC–PDA technique was used to ascertain the purity of the products noted in LC–UV chromatogram. For their characterization, a six stage mass fragmentation (MS6 pattern of DOX was outlined through mass spectral studies in positive mode of electrospray ionization (+ESI as well as through accurate mass spectral data of DOX and the products generated through liquid chromatography–time of flight mass spectrometry (LC–MS–TOF on degraded drug solutions. Based on it, O-I–O-IV were characterized as 3-hydroxy-9-desacetyldoxorubicin-9-hydroperoxide, 1-hydroxy-9-desacetyldoxorubicin-9-hydroperoxide, 9-desacetyldoxorubicin-9-hydroperoxide and 9-desacetyldoxorubicin, respectively, whereas A-I was characterized as deglucosaminyl doxorubicin. While A-I was found to be a pharmacopoeial impurity, all oxidative products were found to be new degradation impurities. The mechanisms and pathways of degradation of doxorubicin were outlined and discussed. Keywords: Doxorubicin, TOF, Forced degradation, Liquid chromatography, Degradation product, Mass fragmentation pattern

Thermal and oxidative degradation studies of formulated C-ethers by gel-permeation chromatography

Science.gov (United States)

Jones, W. R., Jr.; Morales, W.

1982-01-01

Gel-permeation chromatography was used to analyze C-ether lubricant formulations from high-temperature bearing tests and from micro-oxidation tests. Three mu-styragel columns (one 500 and two 100 A) and a tetrahydrofuran mobile phase were found to adequately separate the C-ether degradation products. The micro-oxidation tests yielded degradation results qualitatively similar to those observed from the bearing tests. Micro-oxidation tests conducted in air yielded more degradation than did tests in nitrogen. No great differences were observed between the thermal-oxidative stabilities of the two C-ether formulations or between the catalytic degradation activities of silver and M-50 steel. C-ether formulation I did yield more degradation than did formulation II in 111- and 25-hour bearing tests, respectively.

17O NMR investigation of oxidative degradation in polymers under γ-irradiation

International Nuclear Information System (INIS)

ALAM, TODD M.; CELINA, MATHIAS C.; ASSINK, ROGER A.; CLOUGH, ROGER LEE; GILLEN, KENNETH T.

2000-01-01

The γ-irradiated-oxidation of pentacontane (C 50 H 102 ) and the polymer polyisoprene was investigated as a function of oxidation level using 17 O nuclear magnetic resonance (NMR) spectroscopy. It is demonstrated that by using 17 O labeled O 2 gas during the γ-irradiation process, details about the oxidative degradation mechanisms can be directly obtained from the analysis of the 17 O NMR spectra. Production of carboxylic acids is the primary oxygen-containing functionality during the oxidation of pentacontane, while ethers and alcohols are the dominant oxidation product observed for polyisoprene. The formation of ester species during the oxidation process is very minor for both materials, with water also being produced in significant amounts during the radiolytic oxidation of polyisoprene. The ability to focus on the oxidative component of the degradation process using 17 O NMR spectroscopy demonstrates the selectivity of this technique over more conventional approaches

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

OpenAIRE

Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

2012-01-01

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

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

Science.gov (United States)

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

2014-10-01

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

CELLULOSE DEGRADATION BY OXIDATIVE ENZYMES

Directory of Open Access Journals (Sweden)

Maria Dimarogona

2012-09-01

Full Text Available Enzymatic degradation of plant biomass has attracted intensive research interest for the production of economically viable biofuels. Here we present an overview of the recent findings on biocatalysts implicated in the oxidative cleavage of cellulose, including polysaccharide monooxygenases (PMOs or LPMOs which stands for lytic PMOs, cellobiose dehydrogenases (CDHs and members of carbohydrate-binding module family 33 (CBM33. PMOs, a novel class of enzymes previously termed GH61s, boost the efficiency of common cellulases resulting in increased hydrolysis yields while lowering the protein loading needed. They act on the crystalline part of cellulose by generating oxidized and non-oxidized chain ends. An external electron donor is required for boosting the activity of PMOs. We discuss recent findings concerning their mechanism of action and identify issues and questions to be addressed in the future.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Science.gov (United States)

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Determination of impurities and degradation products from veterinary medicinal products by HPLC method

Directory of Open Access Journals (Sweden)

Elena Gabriela Oltean

2014-06-01

Full Text Available The organic or inorganic impurities in the veterinary medicinal product can derive from starting materials, manufacturing process, incomplete purification, inappropriate storage. The acceptable levels of impurities in pharmaceuticals are estimated by comparison with standard solutions, according to the appropriate monographs. Forced degradation studies determine the stability of the method of dosage for the active compounds and for the entire finished product under excessive accelerated degradation conditions. They also provide information on degradation pathways and selectivity of analytical methods applied. The information provided by the degradation studies on the active compound and finished pharmaceutical product should demonstrate the specificity of the analytical method regarding impurities. Forced degradation studies should demonstrate that the impurities and degradation products generated do not interfere with the active compound. The current forced degradation methods consist of acid hydrolysis, basic hydrolysis, oxidation, exposure of the medicinal product to temperature and light. HPLC methods are an integral analytical instrument for the analysis of the medicinal product. The HPLC method should be able to separate, detect and quantify various specific degradation products that can appear after manufacture or storage of the medicinal product, as well as new elements appearing after synthesis. FDA and ICH guidelines recommend the enclosure of the results, including the chromatograms specific to the forced degradation-subjected medicinal product, in the documentation for marketing authorization. Using HPLC methods in forced degradation studies on medicinal products provides relevant information on the method of determination for the formulation of the medicinal product, synthesis product, packaging methods and storage.

Oxidative Degradation of Phenol containing Wastewater using Fenton Reagent, Permanganate and Ultraviolet Radiation

International Nuclear Information System (INIS)

Abd El-Rahman, N.M.; Talaat, H.A.; Sorour, M.H.

1999-01-01

Phenol containing wastewaters are generated by numerous industrial units including integrated steel mills, textile mills, plastic production, etc. The present work is targeted to explore the viable oxidation techniques for degradation of phenolic wastewater. Three modes of treatment have been adopted in this study, namely, sole oxidant mode using Fenton reagent or permanganate, UV-assisted oxidation and two consequent chemical oxidation steps. Results indicated the superiority of fenton reagent over KMnO 4 oxidation in the sole oxidant mode. On the other hand, UV-assisted KMnO 4 oxidation enables almost complete COD reduction. Dual chemical oxidation mode employing KMnO 4 oxidation followed by Fenton reagent is also an efficient oxidative degradation system

ENHANCEMENT OF RESISTANCE TO OXIDATIVE DEGRADATION OF NATURAL RUBBER THROUGH LATEX DEGRADATION

Institute of Scientific and Technical Information of China (English)

无

1998-01-01

A fully characterised natural rubber latex was subjected to mechanical degradation by stirring at intervals. The resistance to oxidative degradation of the different samples were studied by measuring the Plasticity retention indices (PRI).The results show that there is an enhancement of the PRI from 57% for the undegraded rubber to 79% for the one-hour degraded sample. Further degradation resulted in decrease of PRI as time of degradation increased. Therefore, the one-hour degraded sample is a special rubber with high oxidation resistance which is of great importance in engineering.

Supercritical water oxidation of ion exchange resins: Degradation mechanisms

Energy Technology Data Exchange (ETDEWEB)

Leybros, A.; Roubaud, A. [CEA Marcoule, DEN DTCD SPDE LFSM, F-30207 Bagnols Sur Ceze (France); Guichardon, P. [Ecole Cent Marseille, F-13451 Marseille 20 (France); Boutin, O. [Aix Marseille Univ, UMR CNRS 6181, F-13545 Aix En Provence 4 (France)

2010-07-01

Spent ion exchange resins are radioactive process wastes for which there is no satisfactory industrial treatment. Supercritical water oxidation could offer a viable treatment alternative to destroy the organic structure of resins and contain radioactivity. IER degradation experiments were carried out in a continuous supercritical water reactor. Total organic carbon degradation rates in the range of 95-98% were obtained depending on operating conditions. GC-MS chromatography analyses were carried out to determine intermediate products formed during the reaction. Around 50 species were identified for cationic and anionic resins. Degradation of poly-styrenic structure leads to the formation of low molecular weight compounds. Benzoic acid, phenol and acetic acid are the main compounds. However, other products are detected in appreciable yields such as phenolic species or heterocycles, for anionic IERs degradation. Intermediates produced by intramolecular rearrangements are also obtained. A radical degradation mechanism is proposed for each resin. In this overall mechanism, several hypotheses are foreseen, according to HOO center dot radical attack sites. (authors)

The sources, fate, and toxicity of chemical warfare agent degradation products.

Science.gov (United States)

Munro, N B; Talmage, S S; Griffin, G D; Waters, L C; Watson, A P; King, J F; Hauschild, V

1999-01-01

We include in this review an assessment of the formation, environmental fate, and mammalian and ecotoxicity of CW agent degradation products relevant to environmental and occupational health. These parent CW agents include several vesicants: sulfur mustards [undistilled sulfur mustard (H), sulfur mustard (HD), and an HD/agent T mixture (HT)]; nitrogen mustards [ethylbis(2-chloroethyl)amine (HN1), methylbis(2-chloroethyl)amine (HN2), tris(2-chloroethyl)amine (HN3)], and Lewisite; four nerve agents (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX), tabun (GA), sarin (GB), and soman (GD)); and the blood agent cyanogen chloride. The degradation processes considered here include hydrolysis, microbial degradation, oxidation, and photolysis. We also briefly address decontamination but not combustion processes. Because CW agents are generally not considered very persistent, certain degradation products of significant persistence, even those that are not particularly toxic, may indicate previous CW agent presence or that degradation has occurred. Of those products for which there are data on both environmental fate and toxicity, only a few are both environmentally persistent and highly toxic. Major degradation products estimated to be of significant persistence (weeks to years) include thiodiglycol for HD; Lewisite oxide for Lewisite; and ethyl methyl phosphonic acid, methyl phosphonic acid, and possibly S-(2-diisopropylaminoethyl) methylphosphonothioic acid (EA 2192) for VX. Methyl phosphonic acid is also the ultimate hydrolysis product of both GB and GD. The GB product, isopropyl methylphosphonic acid, and a closely related contaminant of GB, diisopropyl methylphosphonate, are also persistent. Of all of these compounds, only Lewisite oxide and EA 2192 possess high mammalian toxicity. Unlike other CW agents, sulfur mustard agents (e.g., HD) are somewhat persistent; therefore, sites or conditions involving potential HD contamination should include an

Iodate oxidation of N-Acetyl L-Cysteine: Application in drug determination and characterization of its oxidation and degradation product by mass spectrometry

International Nuclear Information System (INIS)

Siddiqui, Masom Raza; Wabaiduri, Saikh Mohammas; Alothman, Zied A; Rahman, Habibur; Alam, Sarfarah; Ali, Sajid

2014-01-01

A kinetic spectrophotometric method based on the initial rate measurement has been developed for the determination of N-acetyl L-cysteine. The developed method is based on the oxidation of N-acetyl L-cysteine with iodate. The reaction product was studied and characterized using the mass spectrometry and the structure of the product was proposed. From the mass spectrometric studies it was concluded that the oxidation of the drug resulted in the formation of a disulfide. The developed method was validated as per the guidelines of international conference on harmonization. The developed initial rate method was found to be linear in the concentration range of 1.25 - 30μg ml-1. The detection and quantitation limits were found to be 0.018 and 0.056 μG ml -1 . In the current study, the degradation product of N-acetyl L cysteine was also prepared and identified using mass spectrometry. Keywords: N- acetyl cysteine, Initial rate method, Spectrophotometry, mass spectrometry

Identification of Forced Degradation Products of Itopride by LC-PDA and LC-MS.

Science.gov (United States)

Joshi, Payal; Bhoir, Suvarna; Bhagwat, A M; Vishwanath, K; Jadhav, R K

2011-05-01

Degradation products of itopride formed under different forced conditions have been identified using LC-PDA and LC-MS techniques. Itopride was subjected to forced degradation under the conditions of hydrolysis, photolysis, oxidation, dry and wet heat, in accordance with the International Conference on Harmonization. The stress solutions were chromatographed on reversed phase C18 (250×4.6 mm, 5 μm) column with a mobile phase methanol:water (55:45, v/v) at a detection wavelength of 215 nm. Itopride degraded in acid, alkali and oxidative stress conditions. The stability indicating method was developed and validated. The degradation pathway of the drug to products II-VIII is proposed.

PEGylated single-walled carbon nanotubes activate neutrophils to increase production of hypochlorous acid, the oxidant capable of degrading nanotubes

Energy Technology Data Exchange (ETDEWEB)

Vlasova, Irina I., E-mail: irina.vlasova@yahoo.com [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Vakhrusheva, Tatyana V. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Sokolov, Alexey V.; Kostevich, Valeria A. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Research Institute for Experimental Medicine, Russian Academy of Medical Science, Saint Petersburg (Russian Federation); Gusev, Alexandr A.; Gusev, Sergey A. [Research Institute for Physico-Chemical Medicine, Federal Medico-Biological Agency, Moscow (Russian Federation); Melnikova, Viktoriya I. [Institute of Developmental Biology, Russian Academy of Science, Moscow (Russian Federation); Lobach, Anatolii S. [Institute of Problems of Chemical Physics, Russian Academy of Science, Chernogolovka (Russian Federation)

2012-10-01

Perspectives for the use of carbon nanotubes in biomedical applications depend largely on their ability to degrade in the body into products that can be easily cleared out. Carboxylated single-walled carbon nanotubes (c-SWCNTs) were shown to be degraded by oxidants generated by peroxidases in the presence of hydrogen peroxide. In the present study we demonstrated that conjugation of poly(ethylene glycol) (PEG) to c-SWCNTs does not interfere with their degradation by peroxidase/H{sub 2}O{sub 2} system or by hypochlorite. Comparison of different heme-containing proteins for their ability to degrade PEG-SWCNTs has led us to conclude that the myeloperoxidase (MPO) product hypochlorous acid (HOCl) is the major oxidant that may be responsible for biodegradation of PEG-SWCNTs in vivo. MPO is secreted mainly by neutrophils upon activation. We hypothesize that SWCNTs may enhance neutrophil activation and therefore stimulate their own biodegradation due to MPO-generated HOCl. PEG-SWCNTs at concentrations similar to those commonly used in in vivo studies were found to activate isolated human neutrophils to produce HOCl. Both PEG-SWCNTs and c-SWCNTs enhanced HOCl generation from isolated neutrophils upon serum-opsonized zymosan stimulation. Both types of nanotubes were also found to activate neutrophils in whole blood samples. Intraperitoneal injection of a low dose of PEG-SWCNTs into mice induced an increase in percentage of circulating neutrophils and activation of neutrophils and macrophages in the peritoneal cavity, suggesting the evolution of an inflammatory response. Activated neutrophils can produce high local concentrations of HOCl, thereby creating the conditions favorable for degradation of the nanotubes. -- Highlights: ► Myeloperoxidase (MPO) product hypochlorous acid is able to degrade CNTs. ► PEGylated SWCNTs stimulate isolated neutrophils to produce hypochlorous acid. ► SWCNTs are capable of activating neutrophils in blood samples. ► Activation of

Volatile profile, lipid oxidation and protein oxidation of irradiated ready-to-eat cured turkey meat products

International Nuclear Information System (INIS)

Feng, Xi; Ahn, Dong Uk

2016-01-01

Irradiation had little effects on the thiobarbituric acid reactive substances (TBARS) values in ready-to-eat (RTE) turkey meat products, while it increased protein oxidation at 4.5 kGy. The volatile profile analyses indicated that the amount of sulfur compounds increased linearly as doses increased in RTE turkey meat products. By correlation analysis, a positive correlation was found between benzene/ benzene derivatives and alcohols with lipid oxidation, while aldehydes, ketones and alkane, alkenes and alkynes were positively correlated with protein oxidation. Principle component analysis showed that irradiated meat samples can be discriminated by two categories of volatile compounds: Strecker degradation products and radiolytic degradation products. The cluster analysis of volatile data demonstrated that low-dose irradiation had minor effects on the volatile profile of turkey sausages (<1.5 kGy). However, as the doses increased, the differences between the irradiated and non-irradiated cured turkey products became significant. - Highlights: • Irradiation had little effects on lipid oxidation of ready-to-eat cured turkey. • 4.5 kGy irradiation increased protein oxidation. • Irradiated samples were isolated due to Strecker/radiolytic degradation products. • 1.5 kGy irradiation had limited effects on the volatile profile of turkey sausages. • Dimethyl disulfide can be used as a potential marker for irradiated meat products.

Combination of LC-ICP-MS, LC-MS and NMR for investigation of the oxidative degradation of selenomethionine

DEFF Research Database (Denmark)

Gammelgaard, B.; Cornett, Claus; Olsen, J.

2003-01-01

Selenomethionine (SeMet) was oxidized by heating an acidic solution with hydrogen peroxide. Samples were taken before and during the oxidation process. The oxidation products were separated by cation exchange chromatography followed by ICP-MS detection to identify the selenium containing compounds...... as well as electrospray ionization MS detection to determine the masses of the degradation products. Furthermore, the samples were analyzed by Se-77-NMR. The first appearing degradation product was selenomethionine selenoxide, which was converted via the deaminated selenoxide to methane seleninic acid...

Biodegradation of photo-oxidized lignite and characterization of the products

Science.gov (United States)

Li, Jiantao; Liu, Xiangrong; Yue, Zilin; Zhang, Yaowen

2018-01-01

Biodegradation of photo-oxidized Inner Mongolia lignite by pseudomonas aeruginosa was studied and the degradation percentage reached 56.27%, while the corresponding degradation percentage of the strain degrading raw Inner Mongolia lignite is only 23.16%. The degradation products were characterized. Proximate and ultimate analyses show that the higher oxygen content increased by photo-oxidation pretreatment maybe promoted the degradation process. Ultraviolet spectroscopy (UV) analysis of the liquid product reveals that it contains unsaturated structures and aromatic rings are the main structure units. Gas chromatography-mass spectrometry (GC-MS) analysis indicates that the main components of the ethyl acetate extracts are low molecular weight organic compounds, such as ketones, acids, hydrocarbons, esters and alcohols. Infrared spectroscopy (IR) analysis of raw lignite, photo-oxidized lignite and residual lignite demonstrates that the absorption peaks of functional groups in residual lignite disappeared or weakened obviously. Scanning electron microscopy (SEM) analysis manifests that small holes appear in photo-oxidized lignite surface, which may be promote the degradation process and this is only from the physical morphology aspects, so it can be inferred from the tests and analyses results that the more important reason of the high degradation percentage is mostly that the photo-oxidation pretreatment changes the chemical structures of lignite.

Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

Energy Technology Data Exchange (ETDEWEB)

Štengl, Václav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Grygar, Tomáš Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Bludská, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); Opluštil, František; Němec, Tomáš [Military Technical Institute of Protection Brno, Veslařská 230, 628 00 Brno (Czech Republic)

2012-12-15

Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

International Nuclear Information System (INIS)

Štengl, Václav; Grygar, Tomáš Matys; Bludská, Jana; Opluštil, František; Němec, Tomáš

2012-01-01

Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn 7 5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn 3 7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

Degradation of acrylamide by the UV/chlorine advanced oxidation process.

Science.gov (United States)

Gao, Ze-Chen; Lin, Yi-Li; Xu, Bin; Pan, Yang; Xia, Sheng-Ji; Gao, Nai-Yun; Zhang, Tian-Yang; Chen, Ming

2017-11-01

The degradation of acrylamide (AA) during UV/chlorine advanced oxidation process (AOP) was investigated in this study. The degradation of AA was negligible during UV irradiation alone. However, AA could be effectively degraded and mineralized during UV/chlorination due to the generation of hydroxyl radicals (OH). The degradation kinetics of AA during UV/chlorination fitted the pseudo-first order kinetics with the rate constant between AA and OH radicals being determined as 2.11 × 10 9  M -1  s -1 . The degradation rate and mineralization of AA during UV/chlorination were significantly promoted at acidic conditions as well as increasing chlorine dosage. The volatile degradation products of AA during UV/chlorination were identified using gas chromatography-mass spectrometry and the degradation pathways were then proposed accordingly. The formation of disinfection by-products (DBPs) in Milli-Q water and tap water during UV/chlorination of AA was also investigated. The DBPs included chloroform, dichloroacetonitrile, trichloroacetonitrile, 2,2-dichloroacetamide and 2,2,2-trichloroacetamide. Furthermore, the variations of AA degradation during UV/chlorination in different real water samples were evaluated. Copyright © 2017 Elsevier Ltd. All rights reserved.

Rapid screening of N-oxides of chemical warfare agents degradation products by ESI-tandem mass spectrometry.

Science.gov (United States)

Sridhar, L; Karthikraj, R; Lakshmi, V V S; Raju, N Prasada; Prabhakar, S

2014-08-01

Rapid detection and identification of chemical warfare agents and related precursors/degradation products in various environmental matrices is of paramount importance for verification of standards set by the chemical weapons convention (CWC). Nitrogen mustards, N,N-dialkylaminoethyl-2-chlorides, N,N-dialkylaminoethanols, N-alkyldiethanolamines, and triethanolamine, which are listed CWC scheduled chemicals, are prone to undergo N-oxidation in environmental matrices or during decontamination process. Thus, screening of the oxidized products of these compounds is also an important task in the verification process because the presence of these products reveals alleged use of nitrogen mustards or precursors of VX compounds. The N-oxides of aminoethanols and aminoethylchlorides easily produce [M + H](+) ions under electrospray ionization conditions, and their collision-induced dissociation spectra include a specific neutral loss of 48 u (OH + CH2OH) and 66 u (OH + CH2Cl), respectively. Based on this specific fragmentation, a rapid screening method was developed for screening of the N-oxides by applying neutral loss scan technique. The method was validated and the applicability of the method was demonstrated by analyzing positive and negative samples. The method was useful in the detection of N-oxides of aminoethanols and aminoethylchlorides in environmental matrices at trace levels (LOD, up to 500 ppb), even in the presence of complex masking agents, without the use of time-consuming sample preparation methods and chromatographic steps. This method is advantageous for the off-site verification program and also for participation in official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons (OPCW), the Netherlands. The structure of N-oxides can be confirmed by the MS/MS experiments on the detected peaks. A liquid chromatography-mass spectrometry (LC-MS) method was developed for the separation of isomeric N-oxides of aminoethanols and

Catalytic degradation of brominated flame retardants by copper oxide nanoparticles

Science.gov (United States)

Dror, I.; Yecheskel, Y.; Berkowitz, B.

2013-12-01

Brominated flame retardants (BFRs) have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use which may lead to contamination of water resources. In this work we present the catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) in aqueous solution. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis are compared to Fenton oxidation and to reduction by nano zero-valent iron (nZVI). The two studied BFRs are shown to degrade fully by the nCuO system within hours to days. Shorter reaction times showed differences in reaction pathways and kinetics for the two compounds. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24 h, while the TBNPA was degraded by 85% within 12 hours. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst.

Thermal oxidative degradation behaviours of flame-retardant thermotropic liquid crystal copolyester/PET blends

International Nuclear Information System (INIS)

Du Xiaohua; Zhao Chengshou; Wang Yuzhong; Zhou Qian; Deng Yi; Qu Minghai; Yang Bing

2006-01-01

The flame retardancy and the thermal oxidative degradation behaviors of the blend of poly(ethylene terephthalate) (PET) with a kind of phosphorus-containing thermotropic liquid crystal copolyester (TLCP) with high flame retardancy (limited oxygen index, 70%) have been investigated by oxygen index test (LOI), UL-94 rating and thermogravimetric analysis (TGA) in air. The results show that TLCP can dramatically improve the flame retardancy and the melt dripping behavior of PET. Moreover, the apparent activation energies of thermal oxidative degradation of the blends were evaluated using Kissinger and Flynn-Wall-Ozawa methods. It is found that addition of TLCP improve thermal stability and restrain thermal decomposition of PET in air, especially at the primary degradation stage. Py-GC/MS analysis shows that there are remarkable changes in the pyrolysis products when TLCP are blended into PET. The interaction between TLCP and PET has changed their thermal oxidative degradation mechanism

Sonocatalytic degradation of malachite green oxalate by a semiconductor metal oxide nanocatalyst.

Science.gov (United States)

Bhavani, R; Sivasamy, A

2016-12-01

Advanced Oxidation Process (AOP) technologies are considered to be better technique for the degradation or mineralization of many recalcitrant compounds and pollutants. In the present study heterogeneous sonocatalytic degradation of a model organic compound such as Malachite green oxalate (MGO) was carried out in the aqueous phase. Zinc oxide nanorods were prepared by precipitation method employing zinc acetates as precursors and were characterized by FT-IR, XRD, FE-SEM and EDAX analysis. Degradation of MGO in the aqueous phase was studied in detail under the sonocatalytic process. Effects of pH, dye concentration, oxidant concentration, kinetics and effect of electrolytes on dye degradation were carried out to check the efficiency of the sonocatalyst. Effect of energy input on the degradation processes was also investigated. The degradation of dye molecules were monitored by UV-visible spectrophotometer and Chemical Oxygen demand (COD). The dye molecules were readily degraded at above 90% in the pH range 5.0-7.0 under ultrasound with zinc oxide nanorods. The interference of electrolytes like NaCl, KCl, Na 2 CO 3 , NaHCO 3 and MgSO 4 on the degradation of dye molecules were also studied on the sonocatalytic degradation of MGO. From the kinetic studies it was observed that at lower initial concentration of dye molecules the degradation efficiency was above 90%. The rate of the reaction decreased on increasing the initial dye concentrations of the dye molecules. It was observed that the complete mineralization of dye molecules was achieved without the formation of toxic by-products. The reusability of the catalyst also showed the effective degradation of the dye molecules up to five cycles without loss of the catalytic activities. Copyright © 2015 Elsevier Inc. All rights reserved.

Particulate and gas-phase products from the atmospheric degradation of chlorpyrifos and chlorpyrifos-oxon

Science.gov (United States)

Borrás, Esther; Ródenas, Milagros; Vázquez, Mónica; Vera, Teresa; Muñoz, Amalia

2015-12-01

The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product - chlorpyrifos-oxon - are described. The photo-oxidation under the presence of NOx was studied in a large outdoor simulation chamber for both chlorpyrifos and chlorpyrifos-oxon, observing a rapid degradation (Half lifetime < 3.5 h for both compounds). Also, the photolysis reactions of both were studied. The formation of particulate matter (aerosol mass yield ranged 6-59%) and gaseous products were monitored. The chemical composition of minor products was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as 3,5,6-trichloropyridin-2-ol and ethyl 3,5,6-trichloropyridin-2-yl hydrogen phosphate. An atmospheric degradation mechanism has been amplified based on an oxidation started with OH-nucleophilic attack to Pdbnd S bond.

Degradation in Solid Oxide Cells During High Temperature Electrolysis

Energy Technology Data Exchange (ETDEWEB)

Manohar Sohal

2009-05-01

Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells. One goal of that project is to address the technical and degradation issues associated with solid oxide electrolysis cells. This report covers a variety of these degradation issues, which were discussed during a workshop on “Degradation in Solid Oxide Electrolysis Cells and Strategies for its Mitigation,” held in Phoenix, AZ on October 27, 2008. Three major degradation issues related to solid oxide electrolysis cells discussed at the workshop are: • Delamination of O2-electrode and bond layer on steam/O2-electrode side • Contaminants (Ni, Cr, Si, etc.) on reaction sites (triple-phase boundary) • Loss of electrical/ionic conductivity of electrolyte. This list is not all inclusive, but the workshop summary can be useful in providing a direction for future research related to the degradation of solid oxide electrolysis cells.

Oxidative degradation of lignin by photochemical and chemical radical generating systems

International Nuclear Information System (INIS)

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

1983-01-01

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

Conductive iron oxide minerals accelerate syntrophic cooperation in methanogenic benzoate degradation

Energy Technology Data Exchange (ETDEWEB)

Zhuang, Li; Tang, Jia; Wang, Yueqiang; Hu, Min; Zhou, Shungui, E-mail: sgzhou@soil.gd.cn

2015-08-15

Highlights: • Paddy soil contaminated with benzoate incubated with hematite and magnetite. • Iron oxides addition enhanced methanogenic benzoate degradation by 25–53%. • The facilitated syntrophy might involve direct interspecies electron transfer. • Bacillaceae, Peptococcaceae, and Methanobacterium are potentially involved. - Abstract: Recent studies have suggested that conductive iron oxide minerals can facilitate syntrophic metabolism of the methanogenic degradation of organic matter, such as ethanol, propionate and butyrate, in natural and engineered microbial ecosystems. This enhanced syntrophy involves direct interspecies electron transfer (DIET) powered by microorganisms exchanging metabolic electrons through electrically conductive minerals. Here, we evaluated the possibility that conductive iron oxides (hematite and magnetite) can stimulate the methanogenic degradation of benzoate, which is a common intermediate in the anaerobic metabolism of aromatic compounds. The results showed that 89–94% of the electrons released from benzoate oxidation were recovered in CH{sub 4} production, and acetate was identified as the only carbon-bearing intermediate during benzoate degradation. Compared with the iron-free controls, the rates of methanogenic benzoate degradation were enhanced by 25% and 53% in the presence of hematite and magnetite, respectively. This stimulatory effect probably resulted from DIET-mediated methanogenesis in which electrons transfer between syntrophic partners via conductive iron minerals. Phylogenetic analyses revealed that Bacillaceae, Peptococcaceae, and Methanobacterium are potentially involved in the functioning of syntrophic DIET. Considering the ubiquitous presence of iron minerals within soils and sediments, the findings of this study will increase the current understanding of the natural biological attenuation of aromatic hydrocarbons in anaerobic environments.

Product analysis for polyethylene degradation by radiation and thermal ageing

International Nuclear Information System (INIS)

Sugimoto, Masaki; Shimada, Akihiko; Kudoh, Hisaaki; Tamura, Kiyotoshi; Seguchi, Tadao

2013-01-01

The oxidation products in crosslinked polyethylene for cable insulation formed during thermal and radiation ageing were analyzed by FTIR-ATR. The products were composed of carboxylic acid, carboxylic ester, and carboxylic anhydride for all ageing conditions. The relative yields of carboxylic ester and carboxylic anhydride increased with an increase of temperature for radiation and thermal ageing. The carboxylic acid was the primary oxidation product and the ester and anhydride were secondary products formed by the thermally induced reactions of the carboxylic acids. The carboxylic acid could be produced by chain scission at any temperature followed by the oxidation of the free radicals formed in the polyethylene. The results of the analysis led to formulation of a new oxidation mechanism which was different from the chain reactions via peroxy radicals and peroxides. - Highlights: ► Products analysis of polyethylene degradation by radiation and thermal ageing. ► Components of carbonyl compounds produced in polyethylene by thermal and radiation oxidation were determined by FTIR. ► Carbonyl compounds comprised carboxylic acid, carboxylic ester, and carboxylic anhydride. ► Carboxylic acid was the primary oxidation product of chain scission at any oxidation temperature. ► Carboxylic ester and carboxylic anhydride are secondary products formed from carboxylic acid at higher temperature.

Lipid oxidation and vitamin D3 degradation in simulated whole milk powder as influenced by processing and storage.

Science.gov (United States)

Mahmoodani, Fatemeh; Perera, Conrad O; Abernethy, Grant; Fedrizzi, Bruno; Chen, Hong

2018-09-30

Vitamin D3 levels are known to sometimes decline in fortified products, which could be due to its degradation, although the exact mechanism is unknown. In this study, the influence of processing and storage conditions on lipid oxidation and vitamin D3 degradation were studied. Simulated whole milk powders with and without heat treatment were stored for 12 months at two different storage temperatures (20 °C and 40 °C). Stored samples without heat treatment showed higher lipid oxidation products analyzed by PV and TBARS values compared to those with heat treatment. Higher storage temperature also resulted in higher levels of lipid oxidation products. The concentration of vitamin D3 was also analyzed using UHPLC-MS/MS after PTAD derivatization in stored samples. An inverse relationship was observed between lipid oxidation products and vitamin D3 content. Finally, previtamin D3 and vitamin D3 oxidation products were quantified in stored samples using MRM analysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Degradation product characterization of therapeutic oligonucleotides using liquid chromatography mass spectrometry.

Science.gov (United States)

Elzahar, N M; Magdy, N; El-Kosasy, Amira M; Bartlett, Michael G

2018-05-01

Synthetic antisense phosphorothioate oligonucleotides (PS) have undergone rapid development as novel therapeutic agents. The increasing significance of this class of drugs requires significant investment in the development of quality control methods. The determination of the many degradation pathways of such complex molecules presents a significant challenge. However, an understanding of the potential impurities that may arise is necessary to continue to advance these powerful new therapeutics. In this study, four different antisense oligonucleotides representing several generations of oligonucleotide therapeutic agents were evaluated under various stress conditions (pH, thermal, and oxidative stress) using ion-pairing reversed-phase liquid chromatography tandem mass spectrometry (IP-RPLC-MS/MS) to provide in-depth characterization and identification of the degradation products. The oligonucleotide samples were stressed under different pH values at 45 and 90 °C. The main degradation products were observed to be losses of nucleotide moieties from the 3'- and 5'-terminus, depurination, formation of terminal phosphorothioates, and production of ribose, ribophosphorothioates (Rp), and phosphoribophosphorothioates (pRp). Moreover, the effects of different concentrations of hydrogen peroxide were studied resulting in primarily extensive desulfurization and subsequent oxidation of the phosphorothioate linkage to produce the corresponding phosphodiester. The reaction kinetics for the degradation of the oligonucleotides under the different stress conditions were studied and were found to follow pseudo-first-order kinetics. Differences in rates exist even for oligonucleotides of similar length but consisting of different sequences. Graphical abstract Identification of degradation products across several generations of oligonucleotide therapeutics using LC-MS.

Identification of major degradation products of 5-aminosalicylic acid formed in aqueous solutions and in pharmaceuticals

DEFF Research Database (Denmark)

Jensen, J.; Cornett, Claus; Olsen, C. E.

1992-01-01

of polymeric species by oxidative self-coupling of 5-ASA moieties. These results indicate that the degradation of 5-ASA follows the same mechanism as observed for the autooxidation of 4-aminophenol and 1,4-phenylenediamine. Some of the identified degradation products were found in 5-ASA......The formation of four major degradation products of 5-aminosalicylic acid (5-ASA) in buffered solutions at pH 7.0 was demonstrated by gradient HPLC analysis. The isolation and structural elucidation of the resulting degradation products showed that the degradation of 5-ASA led to the formation...

Degradation of Histamine by Lactobacillus plantarum Isolated from Miso Products.

Science.gov (United States)

Kung, Hsien-Feng; Lee, Yi-Chen; Huang, Ya-Ling; Huang, Yu-Ru; Su, Yi-Cheng; Tsai, Yung-Hsiang

2017-10-01

Histamine is a toxic chemical and is the causative agent of food poisoning. This foodborne toxin may be degraded by the oxidative deamination activity of certain microorganisms. In this study, we isolated four histamine-degrading Lactobacillus plantarum bacteria from miso products. Among them, L. plantarum D-103 exhibited 100% degradation of histamine in de Man Rogosa Sharpe (MRS) broth containing 50 ppm of histamine after 24 h of incubation at 30°C. The optimal growth, histamine oxidase, and histamine-degrading activity of L. plantarum D-103 were observed in histamine MRS broth at pH 7.0, 3% NaCl, and 30°C. It also exhibited tolerance to broad ranges of pH (4 to 10) and salt concentrations (0 to 12%) in histamine MRS broth. Therefore, the histamine-degrading L. plantarum D-103 might be used as an additive culture to prevent histamine accumulation in miso products during fermentation.

Gamma radiolytic degradation of 4-chlorophenol determination of degraded products with HPLC and GC-MS

International Nuclear Information System (INIS)

Butt, S.B.; Masood, M.N.

2007-01-01

Contamination by chlorophenols of surface water and groundwater is an emerging issue in environmental science and engineering. After their usage as pesticide, herbicide and disinfectant, these organic compounds subsequently enter the aquatic environment through a number of routes. Some of the chlorophenols are slightly biodegradable, while others are more persistent and mobile in the aquatic environment especially chlorophenols. Gamma radiolytic degradation is one of advance oxidation process that has been thought to be one of the promising treatments to deal with this problem. This radiolytic study was carried out in methanolic 4-CP (4-chlorophenol) samples. Among several factors effecting radiolytic degradation of 4-CP, dose and concentration are important that were evaluated under atmospheric conditions. A degradation yield (G -value) for 4- CP of 0.38 and 1.35 was achieved in 20 and 100 mg/dm/sup 3/ solution. It was observed that degradation yield decreases with increasing 4-CP concentration. Gamma radiolysis produce free radicals in solvent which further react with 4-CP molecules to generate different products. The identification of degradation products was proposed using HPLC and GC-MS. (author)

Computational consideration on advanced oxidation degradation of phenolic preservative, methylparaben, in water: mechanisms, kinetics, and toxicity assessments

Energy Technology Data Exchange (ETDEWEB)

Gao, Yanpeng [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); An, Taicheng, E-mail: antc99@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Fang, Hansun [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Ji, Yuemeng; Li, Guiying [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

2014-08-15

Graphical abstract: - Highlights: • Computational approach is effective to reveal the transformation mechanism of MPB. • MPB degradation was more dependent on the [{sup •} OH] than temperature during AOPs. • O{sub 2} could enhance MPB degradation, but more harmful products were formed. • The risks of MPB products in natural waters should be considered seriously. • The risks of MPB products can be overlooked in AOPs due to short half-time. - Abstract: Hydroxyl radicals ({sup •} OH) are strong oxidants that can degrade organic pollutants in advanced oxidation processes (AOPs). The mechanisms, kinetics, and toxicity assessment of the {sup •} OH-initiated oxidative degradation of the phenolic preservative, methylparaben (MPB), were systematically investigated using a computational approach, as the supplementary information for experimental data. Results showed that MPB can be initially attacked by {sup •} OH via OH-addition and H-abstraction routes. Among these routes, the {sup •} OH addition to the C atom at the ortho-position of phenolic hydroxyl group was the most significant route. However, the methyl-H-abstraction route also cannot be neglected. Further, the formed transient intermediates, OH-adduct ({sup •} MPB-OH{sub 1}) and dehydrogenated radical ({sup •} MPB(-H)α), could be easily transformed to several stable degradation products in the presence of O{sub 2} and {sup •} OH. To better understand the potential toxicity of MPB and its products to aquatic organisms, both acute and chronic toxicities were assessed computationally at three trophic levels. Both MPB and its products, particularly the OH-addition products, are harmful to aquatic organisms. Therefore, the application of AOPs to remove MPB should be carefully performed for safe water treatment.

Forced degradation studies of lansoprazole using LC-ESI HRMS and 1 H-NMR experiments: in vitro toxicity evaluation of major degradation products.

Science.gov (United States)

Shankar, G; Borkar, R M; Suresh, U; Guntuku, L; Naidu, V G M; Nagesh, N; Srinivas, R

2017-07-01

Regulatory agencies from all over the world have set up stringent guidelines with regard to drug degradation products due to their toxic effects or carcinogenicity. Lansoprazole, a proton-pump inhibitor, was subjected to forced degradation studies as per ICH guidelines Q1A (R2). The drug was found to degrade under acidic, basic, neutral hydrolysis and oxidative stress conditions, whereas it was found to be stable under thermal and photolytic conditions. The chromatographic separation of the drug and its degradation products were achieved on a Hiber Purospher, C18 (250 × 4.6 mm, 5 μ) column using 10 mM ammonium acetate and acetonitrile as a mobile phase in a gradient elution mode at a flow rate of 1.0 ml/min. The eight degradation products (DP1-8) were identified and characterized by UPLC/ESI/HRMS with in-source CID experiments combined with accurate mass measurements. DP-1, DP-2 and DP-3 were formed in acidic, DP-4 in basic, DP-5 in neutral and DP-1, DP-6, DP-7 and DP-8 were in oxidation stress condition Among eight degradation products, five were hitherto unknown degradation products. In addition, one of the major degradation products, DP-2, was isolated by using semi preparative HPLC and other two, DP-6 and DP-7 were synthesized. The cytotoxic effect of these degradation products (DP-2, DP-6 and DP-7) were tested on normal human cells such as HEK 293 (embryonic kidney cells) and RWPE-1(normal prostate epithelial cells) by MTT assay. From the results of cytotoxicity, it was found that lansoprazole as well as its degradation products (DP-2, DP-6 and DP-7) were nontoxic up to 50-μM concentrations, and the latter showed slightly higher cytotoxicity when compared with that of lansoprazole. DNA binding studies using spectroscopic techniques indicate that DP-2, DP-6 and DP-7 molecules interact with ctDNA and may bind to its surface. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Methane oxidation and degradation of organic compounds in landfill soil covers

DEFF Research Database (Denmark)

Scheutz, Charlotte; Kjeldsen, Peter

2002-01-01

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

Electrochemical degradation of clofibric acid in water by anodic oxidation

Energy Technology Data Exchange (ETDEWEB)

Sires, Ignasi [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Cabot, Pere Lluis [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Centellas, Francesc [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Garrido, Jose Antonio [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Rodriguez, Rosa Maria [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Arias, Conchita [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric [Laboratori de Ciencia i Tecnologia Electroquimica de Materials, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)]. E-mail: brillas@ub.edu

2006-10-05

Aqueous solutions containing the metabolite clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid) up to close to saturation in the pH range 2.0-12.0 have been degraded by anodic oxidation with Pt and boron-doped diamond (BDD) as anodes. The use of BDD leads to total mineralization in all media due to the efficient production of oxidant hydroxyl radical ({center_dot}OH). This procedure is then viable for the treatment of wastewaters containing this compound. The effect of pH, apparent current density, temperature and metabolite concentration on the degradation rate, consumed specific charge and mineralization current efficiency has been investigated. Comparative treatment with Pt yields poor decontamination with complete release of stable chloride ion. When BDD is used, this ion is oxidized to Cl{sub 2}. Clofibric acid is more rapidly destroyed on Pt than on BDD, indicating that it is more strongly adsorbed on the Pt surface enhancing its reaction with {center_dot}OH. Its decay kinetics always follows a pseudo-first-order reaction and the rate constant for each anode increases with increasing apparent current density, being practically independent of pH and metabolite concentration. Aromatic products such as 4-chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol are detected by gas chromatography-mass spectrometry (GC-MS) and reversed-phase chromatography. Tartronic, maleic, fumaric, formic, 2-hydroxyisobutyric, pyruvic and oxalic acids are identified as generated carboxylic acids by ion-exclusion chromatography. These acids remain stable in solution using Pt, but they are completely converted into CO{sub 2} with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed.

Electrochemical degradation of clofibric acid in water by anodic oxidation

International Nuclear Information System (INIS)

Sires, Ignasi; Cabot, Pere Lluis; Centellas, Francesc; Garrido, Jose Antonio; Rodriguez, Rosa Maria; Arias, Conchita; Brillas, Enric

2006-01-01

Aqueous solutions containing the metabolite clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid) up to close to saturation in the pH range 2.0-12.0 have been degraded by anodic oxidation with Pt and boron-doped diamond (BDD) as anodes. The use of BDD leads to total mineralization in all media due to the efficient production of oxidant hydroxyl radical (·OH). This procedure is then viable for the treatment of wastewaters containing this compound. The effect of pH, apparent current density, temperature and metabolite concentration on the degradation rate, consumed specific charge and mineralization current efficiency has been investigated. Comparative treatment with Pt yields poor decontamination with complete release of stable chloride ion. When BDD is used, this ion is oxidized to Cl 2 . Clofibric acid is more rapidly destroyed on Pt than on BDD, indicating that it is more strongly adsorbed on the Pt surface enhancing its reaction with ·OH. Its decay kinetics always follows a pseudo-first-order reaction and the rate constant for each anode increases with increasing apparent current density, being practically independent of pH and metabolite concentration. Aromatic products such as 4-chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol are detected by gas chromatography-mass spectrometry (GC-MS) and reversed-phase chromatography. Tartronic, maleic, fumaric, formic, 2-hydroxyisobutyric, pyruvic and oxalic acids are identified as generated carboxylic acids by ion-exclusion chromatography. These acids remain stable in solution using Pt, but they are completely converted into CO 2 with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed

Degradation of organophosphorus pesticide parathion methyl on nanostructured titania-iron mixed oxides

Energy Technology Data Exchange (ETDEWEB)

Henych, Jiří, E-mail: henych@iic.cas.cz [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš [Department of Material Chemistry, Institute of Inorganic Chemistry AS CR v.v.i., 25068 Řež (Czech Republic); Janoš, Pavel; Kuráň, Pavel; Štastný, Martin [Faculty of the Environment, J.E. Purkyně University, Králova Výšina 7, 400 96 Ústí nad Labem (Czech Republic)

2015-07-30

Highlights: • Ti–Fe mixed oxides were synthesized via low-temperature one-pot method. • Mixed oxides were used for degradation of parathion methyl. • Pure reference oxide samples showed no degradation ability. • Mixed oxides reached 70% degree of conversion of parathion methyl. - Abstract: Titania-iron mixed oxides with various Ti:Fe ratio were prepared by homogeneous hydrolysis of aqueous solutions of titanium(IV) oxysulphate and iron(III) sulphate with urea as a precipitating agent. The synthesized samples were characterized by X-ray diffraction, Raman and infrared spectroscopy, scanning and transmission electron microscopy, XRF analysis, specific surface area (BET) and porosity determination (BJH). These oxides were used for degradation of organophosporus pesticide parathion methyl. The highest degradation efficiency approaching <70% was found for the samples with Ti:Fe ratio 0.25:1 and 1:0.25. Contrary, parathion methyl was not degraded on the surfaces of pure oxides. In general, the highest degradation rate exhibited samples consisted of the iron or titanium oxide containing a moderate amount of the admixture. However, distinct correlations between the degradation rate and the sorbent composition were not identified.

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

Science.gov (United States)

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

2015-12-30

Sulfamethazine (SMZ) is widely used in livestock feeding and aquaculture as an antibiotic agent and growth promoter. Widespread occurrence of SMZ in surface water, groundwater, soil and sediment has been reported. In this study, degradation of SMZ by heat-activated persulfate (PS) oxidation was investigated in aqueous solution. Experimental results demonstrated that SMZ degradation followed pseudo-first-order reaction kinetics. The pseudo-first-order rate constant (kobs) was increased markedly with increasing concentration of PS and temperature. Radical scavenging tests revealed that the predominant oxidizing species was SO4·(-) with HO playing a less important role. Aniline moiety in SMZ molecule was confirmed to be the reactive site for SO4·(-) attack by comparison with substructural analogs. Nontarget natural water constituents affected SMZ removal significantly, e.g., Cl(-) and HCO3(-) improved the degradation while fulvic acid reduced it. Reaction products were enriched by solid phase extraction (SPE) and analyzed by liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-MS/MS). 6 products derived from sulfonamide S--N bond cleavage, aniline moiety oxidation and Smiles-type rearrangement were identified, and transformation pathways of SMZ oxidation were proposed. Results reveal that heat-activated PS oxidation could be an efficient approach for remediation of water contaminated by SMZ and related sulfonamides. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of forced and total degradation products of amlodipine besylate by liquid chromatography and liquid chromatography-mass spectrometry

Directory of Open Access Journals (Sweden)

Stoiljković Zora Ž.

2014-01-01

Full Text Available An isocratic, reversed-phase liquid chromatographic method was applied for the investigation of the degradation products of amlodipine besylate under the stressed conditions in solution. Amlodipine besylate stock solutions were subjected to acid and alkali hydrolysis, chemical oxidation and photodegradation as well as to the electrochemical degradation by cyclic voltammetry in 0.05 mol/L NaHCO3 on gold electrode. The total degradation of amlodipine besylate was achieved in 5 mol/L NaOH at 80°C for 6 h and the compound with molecular formula C15H16NOCl was identified as a main degradation product. Under acidic (5 mol/L HCl at 80°C for 6 h stress conditions 75.2% of amlodipine besylate degradation was recorded. Oxidative degradation in the solution of 3% H2O2-methanol 80:20 at 80°C for 6 h showed that amlodipine besylate degraded to 80.1%. After 14 days of expose in photostability chamber amlodipine besylate solution showed degradation of 32.2%. In electrochemical degradation after 9 hours of cyclization the beginning of amlodipine oxidation was shifted for 200 mV to more negative potentials, with the degradation of 66.5%. Mass spectrometry analysis confirmed the presence of dehydro amlodipine derivate with molecular formula C20H23N2O5Cl in oxidative and acidic conditions while in electrochemical degradation was detected in traces. [Projekat Ministarsva nauke Republike Srbije, br. 172013

By-products formation during degradation of isoproturon in aqueous solution. II: Chlorination.

Science.gov (United States)

Mascolo, G; Lopez, A; James, H; Fielding, M

2001-05-01

After a previous study in which the considered oxidant was ozone (Part I), a laboratory investigation has been carried out to study the degradation of the herbicide isoproturon during its reaction with another oxidant, i.e. chlorine, in aqueous solution (Part II; this paper). The specific aim was to identify the by-products formed. The effects of pH and the presence of bromide ions were studied. Reactions have been carried out at room temperature, in phosphate buffered aqueous solutions, at four pHs (6, 7, 8 and 9). By-products identification was first performed using relatively high initial reagent concentrations which were analytically convenient ([isoproturon] = 40 mg/l, [HClO + ClO-] = 160 mg Cl/l, [Br-] = 80 mg/l). In follow-up studies, the by-products identified during this preliminary step were searched for when using concentration values closer to those actually encountered at real water treatment plants ([isoproturon] = 0.4 and 0.004 mg/l, [HClO + ClO-] = 1.6 mg Cl/l, [Br-] = 0.8 and 0.008 mg/l). Under all of the studied conditions, the results showed that isoproturon is completely degraded and that it decays much faster in the presence of bromide. The pH has a negligible influence when bromide ions are absent. On the contrary, if bromide ions are present, the isoproturon decay is slower at higher pH values. High-performance liquid chromatography-mass spectrometry (HPLC-MS) analyses have led to the identification of several by-products as a result of simultaneous oxidation and substitution reactions, both occurring on the aromatic ring of the herbicide. However, the more abundant by-products are those resulting from the oxidation of the isoproturon aromatic ring. As far as halogenated by-products are concerned, the higher the bromide ion concentration the higher the ratio of brominated to chlorinated by-products. On the basis of the analytical results, a pathway for isoproturon degradation under the studied conditions is proposed.

Global Kinetic Constants for Thermal Oxidative Degradation of a Cellulosic Paper

Science.gov (United States)

Kashiwagi, Takashi; Nambu, Hidesaburo

1992-01-01

Values of global kinetic constants for pyrolysis, thermal oxidative degradation, and char oxidation of a cellulosic paper were determined by a derivative thermal gravimetric study. The study was conducted at heating rates of 0.5, 1, 1.5, 3, and 5 C/min in ambient atmospheres of nitrogen, 0.28, 1.08, 5.2 percent oxygen concentrations, and air. Sample weight loss rate, concentrations of CO, CO2, and H2O in the degradation products, and oxygen consumption were continuously measured during the experiment. Values of activation energy, preexponential factor, orders of reaction, and yields of CO, CO2, H2O, total hydrocarbons, and char for each degradation reaction were derived from the results. Heat of reaction for each reaction was determined by differential scanning calorimetry. A comparison of the calculated CO, CO2, H2O, total hydrocarbons, sample weight loss rate, and oxygen consumption was made with the measured results using the derived kinetic constants, and the accuracy of the values of kinetic constants was discussed.

Protein oxidation and degradation caused by particulate matter

Science.gov (United States)

Lai, Ching-Huang; Lee, Chun-Nin; Bai, Kuan-Jen; Yang, You-Lan; Chuang, Kai-Jen; Wu, Sheng-Ming; Chuang, Hsiao-Chi

2016-09-01

Particulate matter (PM) modulates the expression of autophagy; however, the role of selective autophagy by PM remains unclear. The objective of this study was to determine the underlying mechanisms in protein oxidation and degradation caused by PM. Human epithelial A549 cells were exposed to diesel exhaust particles (DEPs), urban dust (UD), and carbon black (CB; control particles). Cell survival and proliferation were significantly reduced by DEPs and UD in A549 cells. First, benzo(a)pyrene diolepoxide (BPDE) protein adduct was caused by DEPs at 150 μg/ml. Methionine oxidation (MetO) of human albumin proteins was induced by DEPs, UD, and CB; however, the protein repair mechanism that converts MetO back to methionine by methionine sulfoxide reductases A (MSRA) and B3 (MSRB3) was activated by DEPs and inhibited by UD, suggesting that oxidized protein was accumulating in cells. As to the degradation of oxidized proteins, proteasome and autophagy activation was induced by CB with ubiquitin accumulation, whereas proteasome and autophagy activation was induced by DEPs without ubiquitin accumulation. The results suggest that CB-induced protein degradation may be via an ubiquitin-dependent autophagy pathway, whereas DEP-induced protein degradation may be via an ubiquitin-independent autophagy pathway. A distinct proteotoxic effect may depend on the physicochemistry of PM.

Time extrapolation of radiolytic degradation product kinetics: the case of polyurethane

International Nuclear Information System (INIS)

Dannoux, A.

2007-02-01

The prediction of the environmental impact of organic materials in nuclear waste geological storage needs knowledge of radiolytic degradation mechanisms and kinetics in aerobic and anaerobic conditions. In this framework, the effect of high doses (> MGy) and the variation of dose rate have to be considered. The material studied is a polyurethane composed of polyether soft segment and aromatic hard segments. Mechanisms were built on the analysis of material submitted to irradiations of simulation (high energy electrons and gamma radiation) by FTIR spectroscopy and gaseous and liquid degradation products by gas mass spectrometry and size exclusion chromatography. The electron paramagnetic resonance study of radical process and the determination of oxygen consumption and gas formation radiolytic yields allowed us to acquire kinetic data and to estimate dose rate and high doses effects. The polyurethane radio-oxidation mainly concerns soft segments and induced cross-linkings and production by scissions of oxidised compounds (esters, alcohols, carboxylic acids). The kinetic of radical termination is rapid and the dose rate effect is limited. After 10 MGy, branching and scission reactions are in equilibrium and low molecular weight products accumulate. At last, the degradation products release in water is influenced by the oxidation rate and the temperature. After 10 MGy, the soluble fraction is stabilised at 25%. The water soluble products identified by electro-spray ionisation mass spectrometry (alcohols, aldehydes, carboxylic acids) potentially formed complexes with radionuclides. (author)

Characterization of degradation products from alkaline wet oxidation of wheat straw

DEFF Research Database (Denmark)

Klinke, H.B.; Ahring, B.K.; Schmidt, A.S.

2002-01-01

to their chemical structure, e.g. diacids (oxalic and succinic acids), furan aldehydes, phenol aldehydes, phenol ketones and phenol acids. Aromatic aldehyde formation was correlated to severe conditions with high temperatures and low pH. Apart from CO2 and water, carboxylic acids were the main degradation products...... degreesC with addition of 12 bar oxygen and 6.5 g l(-1) Na2CO3. At these conditions the hemicellulose fraction from 100 g straw consisted of soluble hemicellulose (16 g), low molecular weight carboxylic acids (11 g), monomeric phenols (0.48 g) and 2-furoic acid (0.01 g). Formic acid and acetic acid...... constituted the majority of degradation products (8.5 g). The main phenol monomers were 4-hydroxybenzaldehyde, vanillin, syringaldehyde, acetosyringone (4-hydroxy-3,5-dimethoxy-acetophenone), vanillic acid and syringic acid, occurring in 0.04-0.12 g per 100 g straw concentrations. High lignin removal from...

Oxidative degradation of chlorophenol derivatives promoted by microwaves or power ultrasound: a mechanism investigation.

Science.gov (United States)

Cravotto, Giancarlo; Binello, Arianna; Di Carlo, Stefano; Orio, Laura; Wu, Zhi-Lin; Ondruschka, Bernd

2010-03-01

Phenols are the most common pollutants in industrial wastewaters (particularly from oil refineries, resin manufacture, and coal processing). In the last two decades, it has become common knowledge that they can be effectively destroyed by nonconventional techniques such as power ultrasound (US) and/or microwave (MW) irradiation. Both techniques may strongly promote advanced oxidation processes (AOPs). The present study aimed to shed light on the effect and mechanism of US- and MW-promoted oxidative degradation of chlorophenols; 2,4-dichlorophenoxyacetic acid (2,4-D), a pesticide widespread in the environment, was chosen as the model compound. 2,4-D degradation by AOPs was carried out either under US (20 and 300 kHz) in aqueous solutions (with and without the addition of Fenton reagent) or solvent-free under MW with sodium percarbonate (SPC). All these reactions were monitored by gas chromatography-mass spectrometry (GC-MS) analysis and compared with the classical Fenton reaction in water under magnetic stirring. The same set of treatments was also applied to 2,4-dichlorophenol (2,4-DCP) and phenol, the first two products that occur a step down in the degradation sequence. Fenton and Fenton-like reagents were employed at the lowest active concentration. The effects of US and MW irradiation were investigated and compared with those of conventional treatments. Detailed mechanisms of Fenton-type reactions were suggested for 2,4-D, 2,4-DCP, and phenol, underlining the principal degradation products identified. MW-promoted degradation under solvent-free conditions with solid Fenton-like reagents (viz. SPC) is extremely efficient and mainly follows pyrolytic pathways. Power US strongly accelerates the degradation of 2,4-D in water through a rapid generation of highly reactive radicals; it does not lead to the formation of more toxic dimers. We show that US and MW enhance the oxidative degradation of 2,4-D and that a considerable saving of oxidants and cutting down of

Short-stack modeling of degradation in solid oxide fuel cells. Part I. Contact degradation

Energy Technology Data Exchange (ETDEWEB)

Gazzarri, J.I. [Department of Mechanical Engineering, University of British Columbia, 2054-6250 Applied Science Lane, Vancouver, BC V6T 1Z4 (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, ON M5S 3G8 (Canada)

2008-01-21

As the first part of a two paper series, we present a two-dimensional impedance model of a working solid oxide fuel cell (SOFC) to study the effect of contact degradation on the impedance spectrum for the purpose of non-invasive diagnosis. The two dimensional modeled geometry includes the ribbed interconnect, and is adequate to represent co- and counter-flow configurations. Simulated degradation modes include: cathode delamination, interconnect oxidation, and interconnect-cathode detachment. The simulations show differences in the way each degradation mode impacts the impedance spectrum shape, suggesting that identification is possible. In Part II, we present a sensitivity analysis of the results to input parameter variability that reveals strengths and limitations of the method, as well as describing possible interactions between input parameters and concurrent degradation modes. (author)

Short-stack modeling of degradation in solid oxide fuel cells. Part I. Contact degradation

Science.gov (United States)

Gazzarri, J. I.; Kesler, O.

As the first part of a two paper series, we present a two-dimensional impedance model of a working solid oxide fuel cell (SOFC) to study the effect of contact degradation on the impedance spectrum for the purpose of non-invasive diagnosis. The two dimensional modeled geometry includes the ribbed interconnect, and is adequate to represent co- and counter-flow configurations. Simulated degradation modes include: cathode delamination, interconnect oxidation, and interconnect-cathode detachment. The simulations show differences in the way each degradation mode impacts the impedance spectrum shape, suggesting that identification is possible. In Part II, we present a sensitivity analysis of the results to input parameter variability that reveals strengths and limitations of the method, as well as describing possible interactions between input parameters and concurrent degradation modes.

Time extrapolation of radiolytic degradation product kinetics: the case of polyurethane; Extrapolation dans le temps des cinetiques de production des produits de degradation radiolytique: application a un polyurethane

Energy Technology Data Exchange (ETDEWEB)

Dannoux, A

2007-02-15

The prediction of the environmental impact of organic materials in nuclear waste geological storage needs knowledge of radiolytic degradation mechanisms and kinetics in aerobic and anaerobic conditions. In this framework, the effect of high doses (> MGy) and the variation of dose rate have to be considered. The material studied is a polyurethane composed of polyether soft segment and aromatic hard segments. Mechanisms were built on the analysis of material submitted to irradiations of simulation (high energy electrons and gamma radiation) by FTIR spectroscopy and gaseous and liquid degradation products by gas mass spectrometry and size exclusion chromatography. The electron paramagnetic resonance study of radical process and the determination of oxygen consumption and gas formation radiolytic yields allowed us to acquire kinetic data and to estimate dose rate and high doses effects. The polyurethane radio-oxidation mainly concerns soft segments and induced cross-linkings and production by scissions of oxidised compounds (esters, alcohols, carboxylic acids). The kinetic of radical termination is rapid and the dose rate effect is limited. After 10 MGy, branching and scission reactions are in equilibrium and low molecular weight products accumulate. At last, the degradation products release in water is influenced by the oxidation rate and the temperature. After 10 MGy, the soluble fraction is stabilised at 25%. The water soluble products identified by electro-spray ionisation mass spectrometry (alcohols, aldehydes, carboxylic acids) potentially formed complexes with radionuclides. (author)

High-resolution Kendrick Mass Defect Analysis of Poly(ethylene oxide)-based Non-ionic Surfactants and Their Degradation Products.

Science.gov (United States)

Fouquet, Thierry; Shimada, Haruo; Maeno, Katsuyuki; Ito, Kanako; Ozeki, Yuka; Kitagawa, Shinya; Ohtani, Hajime; Sato, Hiroaki

2017-09-01

Matrix assisted laser desorption ionization (MALDI) high-resolution mass spectrometry (HRMS) and the recently introduced high-resolution Kendrick mass defect (HRKMD) analysis are combined to thoroughly characterize non-ionic surfactants made of a poly(ethylene oxide) (PEO) core capped by esters of fatty acids. A PEO monostearate surfactant is first analyzed as a proof of principle of the HRKMD analysis conducted with a fraction of EO as the base unit (EO/X with X being an integer) in lieu of EO for a regular KMD analysis. Data visualization is greatly enhanced and the distributions detected in the MALDI mass spectrum are assigned to a pristine (H, OH)-PEO as well as mono- and di-esterified PEO chains with palmitate and stearate end-groups in HRKMD plots computed with EO/45. The MALDI-HRMS/HRKMD analysis is then successfully applied to the more complex case of ethoxylated hydrogenated castor oil (EHCO) found to contain a large number of hydrogenated ricinoleate moieties (up to 14) in its HRKMD plot computed with EO/43, departing from the expected triglyceride structure. The exhaustiveness of the MALDI-HRMS/HRKMD strategy is validated by comparing the so-obtained fingerprints with results from alternative techniques (electrospray ionization MS, size exclusion and liquid adsorption chromatography, ion mobility spectrometry). Finally, aged non-ionic surfactants formed upon hydrolytic degradation are analyzed by MALDI-HRMS/HRKMD to easily assign the degradation products and infer the associated degradation routes. In addition to the hydrolysis of the ester groups observed for EHCO, chain scissions and new polar end-groups are observed in the HRKMD plot of PEO monostearate arising from a competitive oxidative ageing.

Degradation of natural organic matter by UV/chlorine oxidation: Molecular decomposition, formation of oxidation byproducts and cytotoxicity.

Science.gov (United States)

Wang, Wen-Long; Zhang, Xue; Wu, Qian-Yuan; Du, Ye; Hu, Hong-Ying

2017-11-01

The degradation of natural organic matters (NOMs) by the combination of UV and chlorine (UV/chlorine) was investigated in this study. UV/chlorine oxidation can effectively degrade NOMs, with the degradation of chromophores (∼80%) and fluorophores (76.4-80.8%) being more efficient than that of DOC (15.1-18.6%). This effect was attributed to the chromophores and fluorophores (double bonds, aromatic groups and phenolic groups) being preferentially degraded by UV/chlorine oxidation, particularly reactive groups with high electron donating capacity. Radical species •OH and •Cl were generated during UV/chlorine oxidation, with the contribution of •OH 1.4 times as high as that of •Cl. The degradation kinetics of different molecular weight (MW) fractions suggests that UV/chlorine oxidation degrades high MW fractions into low MW fractions, with the degradation rates of high MW fractions (>3000 Da) 4.5 times of those of medium MW fractions (1000-3000 Da). In comparison with chlorination alone, UV/chlorine oxidation did not increase the formation (30 min) and formation potential (24 h) of trihalomethanes, but instead promoted the formation and formation potential of haloacetic acids and chloral hydrate. Adsorbable organic halogen (AOX) formed from UV/chlorine oxidation of NOM were 0.8 times higher than those formed from chlorination. Cytotoxicity studies indicated that the cytotoxicity of NOM increased after both chlorination and UV/chlorine oxidation, which may be due to the formation of AOX. Copyright © 2017 Elsevier Ltd. All rights reserved.

Aqueous photodegradation of 4-tert-butylphenol: By-products, degradation pathway and theoretical calculation assessment

Energy Technology Data Exchange (ETDEWEB)

Wu, Yanlin [State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Shi, Jin; Chen, Hongche [Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China); Zhao, Jianfu [State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, Shanghai 200092 (China); Dong, Wenbo, E-mail: wbdong@fudan.edu.cn [Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China)

2016-10-01

4-tert-butylphenol (4-t-BP), an endocrine disrupting chemical, is widely distributed in natural bodies of water but is difficult to biodegrade. In this study, we focused on the transformation of 4-t-BP in photo-initiated degradation processes. The steady-state photolysis and laser flash photolysis (LFP) experiments were conducted in order to elucidate its degradation mechanism. Identification of products was performed using the GC–MS, LC-MS and theoretical calculation techniques. The oxidation pathway of 4-t-BP by hydroxyl radical (HO·) was also studied and H{sub 2}O{sub 2} was added to produce HO·. 4-tert-butylcatechol and 4-tert-butylphenol dimer were produced in 4-t-BP direct photolysis. 4-tert-butylcatechol and hydroquinone were produced by the oxidation of HO·. But the formation mechanism of 4-tert-butylcatechol in the two processes was different. The benzene ring was fractured in 4-t-BP oxidation process and 29% of TOC was degraded after 16 h irradiation. - Highlights: • Photodegradation of 4-t-BP, an endocrine disrupting chemical, has been investigated. • 3 stable byproducts were identified from photolysis and oxidation processes. • 5 transient by-products were concluded from LFP experiments. • The theoretical calculation was performed to confirm the byproducts. • 4-t-BP was degraded with increasing efficiency: 254 nm < H{sub 2}O{sub 2}/313 nm < H{sub 2}O{sub 2}/254 nm.

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

Science.gov (United States)

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.

Study on degrading graphene oxide in wastewater under different conditions for developing an efficient and economical degradation method.

Science.gov (United States)

Li, Ting; Zhang, Chao-Zhi; Gu, Chengyue

2017-12-01

With popular application of graphene and graphene oxide (GO), they have been discharged into water. Graphene and GO harm organisms. However, an efficient and economical method for removing graphene and GO in wastewater has seldom been reported. Graphene can be oxidized by hydrogen peroxide to give GO; therefore, degradation of graphene oxide is an important step in the procedure of removal of graphene from water. In this paper, GO degradation via photo-Fenton reaction under different conditions was carried out. Experimental results suggested that GO in wastewater can be efficiently and economically degraded into carbon dioxide and H 2 O when pH value is 3, concentration of H 2 O 2 and FeCl 3 are 35 mM and 5 ppm, respectively. Degradation mechanism of GO was suggested based on UV-vis absorption spectra, scanning electron microscopy, X-ray diffraction and liquid chromatography-mass spectra data of degradation intermediates. This paper suggests an efficient and economical degradation way of GO in wastewater.

Astaxanthin degradation and lipid oxidation of Pacific white shrimp oil: kinetics study and stability as affected by storage conditions

Directory of Open Access Journals (Sweden)

Sirima Takeungwongtrakul

2016-02-01

Full Text Available Abstract The kinetics of astaxanthin degradation and lipid oxidation in shrimp oil from hepatopancreas of Pacific white shrimp (Litopenaeus vannamei as affected by storage temperature were studied. When shrimp oil was incubated at different temperatures (4, 30, 45 and 60 °C for 16 h, the rate constants (k of astaxanthin degradation and lipid oxidation in shrimp oil increased with increasing temperatures (p < 0.05. Thus, astaxanthin degradation and lipid oxidation in shrimp oil were augmented at high temperature. When shrimp oils with different storage conditions (illumination, oxygen availability and temperature were stored for up to 40 days, astaxanthin contents in all samples decreased throughout storage (p < 0.05. All factors were able to enhance astaxanthin degradation during 40 days of storage. With increasing storage time, the progressive formation of primary and secondary oxidation products were found in all samples as evidenced by the increases in both peroxide values (PV and thiobarbituric acid reactive substances (TBARS (p < 0.05. Light, air and temperatures therefore had the marked effect on astaxanthin degradation and lipid oxidation in shrimp oils during the extended storage.

Gaining electricity from in situ oxidation of hydrogen produced by fermentative cellulose degradation.

Science.gov (United States)

Niessen, J; Schröder, U; Harnisch, F; Scholz, F

2005-01-01

To exploit the fermentative hydrogen generation and direct hydrogen oxidation for the generation of electric current from the degradation of cellulose. Utilizing the metabolic activity of the mesophilic anaerobe Clostridium cellulolyticum and the thermophilic Clostridium thermocellum we show that electricity generation is possible from cellulose fermentation. The current generation is based on an in situ oxidation of microbially synthesized hydrogen at platinum-poly(tetrafluoroaniline) (Pt-PTFA) composite electrodes. Current densities of 130 mA l(-1) (with 3 g cellulose per litre medium) were achieved in poised potential experiments under batch and semi-batch conditions. The presented results show that electricity generation is possible by the in situ oxidation of hydrogen, product of the anaerobic degradation of cellulose by cellulolytic bacteria. For the first time, it is shown that an insoluble complex carbohydrate like cellulose can be used for electricity generation in a microbial fuel cell. The concept represents a first step to the utilization of macromolecular biomass components for microbial electricity generation.

Oxidation of Tris (2-chloroethyl) phosphate in aqueous solution by UV-activated peroxymonosulfate: Kinetics, water matrix effects, degradation products and reaction pathways.

Science.gov (United States)

Xu, Xinxin; Chen, Jing; Qu, Ruijuan; Wang, Zunyao

2017-10-01

The feasibility of UV-activated peroxymonosulfate (PMS) technology for the degradation of Tris (2-chloroethyl) phosphate (TCEP) in an aqueous solution was investigated in this study. The conditions of [PMS] 0 : [TCEP] 0  = 20:1, T = 25 ± 2 °C and pH = 5.5 ± 0.5 cause a 94.6% removal of TCEP (1 mg L -1 ) after 30 min of Hg lamp irradiation. The effects of operating parameters (the oxidant doses, pH and presence of typical cations (Fe 3+ , Cu 2+ , Ni 2+ , NH 4 + ), anions (Cl - , HCO 3 - , NO 3 - , HPO 4 2- ) and humic acid (HA)) were evaluated. It was found that an increase of the PMS dose and the presence of Fe 3+ could accelerate the reaction, while the anions and HA inhibited the reaction. Meanwhile, TCEP removal in various water matrices was compared, and the order for TCEP removal was as follows: ultrapure water > tap water > synthetic water > secondary clarifier effluent > Jiuxiang river water. Twenty-two oxidation products were identified using an electrospray time-of-flight mass spectrometer, and the degradation pathways mainly involved radicals' addition and CO bond cleavage. Furthermore, ECOSAR analysis revealed that the intermediate products during the TCEP oxidation process were generally not harmful to three typical aquatic species. Hence, UV/PMS can be used as an efficient technology to treat TCEP-containing water and wastewaters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

Science.gov (United States)

Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

2016-11-16

Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH - or • OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

Sulphur mustard degradation on zirconium doped Ti-Fe oxides

Energy Technology Data Exchange (ETDEWEB)

Stengl, Vaclav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i 250 68 Husinec-Rez (Czech Republic); Grygar, Tomas Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR v.v.i 250 68 Husinec-Rez (Czech Republic); Oplustil, Frantisek; Nemec, Tomas [Military Technical Institute of Protection Brno Veslarska 230, 628 00 Brno (Czech Republic)

2011-09-15

Highlights: {yields} New stechiometric materials for sulphur mustard degradation. {yields} High degree of degradation, more then 95% h{sup -1}. {yields} One-pot synthesis procedure. - Abstract: Zirconium doped mixed nanodispersive oxides of Ti and Fe were prepared by homogeneous hydrolysis of sulphate salts with urea in aqueous solutions. Synthesized nanodispersive metal oxide hydroxides were characterised as the Brunauer-Emmett-Teller (BET) surface area and Barrett-Joiner-Halenda porosity (BJH), X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray (EDX) microanalysis, and acid-base titration. These oxides were taken for an experimental evaluation of their reactivity with sulphur mustard (chemical warfare agent HD or bis(2-chloroethyl)sulphide). The presence of Zr{sup 4+} dopant tends to increase both the surface area and the surface hydroxylation of the resulting doped oxides in such a manner that it can contribute to enabling the substrate adsorption at the oxide surface and thus accelerate the rate of degradation of warfare agents. The addition of Zr{sup 4+} to the hydrolysis of ferric sulphate with urea shifts the reaction route and promotes formation of goethite at the expense of ferrihydrite. We discovered that Zr{sup 4+} doped oxo-hydroxides of Ti and Fe exhibit a higher degradation activity towards sulphur mustard than any other yet reported reactive sorbents. The reaction rate constant of the slower parallel reaction of the most efficient reactive sorbents is increased with the increasing amount of surface base sites.

Different Abilities of Eight Mixed Cultures of Methane-oxidizing Bacteria to Degrade TCE

DEFF Research Database (Denmark)

Broholm, Kim; Christensen, Thomas Højlund; Jensen, Bjørn K.

1993-01-01

The ability of eight mixed cultures of methane-oxidizing bacteria to degrade trichloroethylene (TCE) was examined in laboratory batch experiments. This is one of the first reported works studying TCE degradation by mixed cultures of methane-oxidizing bacteria at 10°C, a common temperature for soils...... methanol, but only for a limited time period of about 5 days. Several explanations for the discontinued degradation of TCE are given. An experiment carried out to re-activate the methane-oxidizing bacteria after 8 days of growth on methanol by adding methane did not immediately result in degradation...... of methane and TCE. During the first 10–15 days after the addition of methane a significant degradation of methane and a minor degradation of TCE were observed. This experiment revealed that the ability of mixed cultures of methane-oxidizing bacteria to degrade TCE varied significantly even though...

Oxidative Degradation of Aminosilica Adsorbents Relevant to Postcombustion CO 2 Capture

KAUST Repository

Bollini, Praveen

2011-05-19

Coal-fired power plant flue gas exhaust typically contains 3-10% oxygen. While it is known that the monoethanolamine (MEA) oxidative degradation rate is a critical parameter affecting liquid amine absorption processes, the effect of oxygen on the stability of solid amine adsorbents remains unexplored. Here, oxidative degradation of aminosilica materials is studied under accelerated oxidizing conditions to assess the stability of different supported amine structures to oxidizing conditions. Adsorbents constructed using four different silane coupling agents are evaluated, three with a single primary, secondary, or tertiary amine at the end of a propyl surface linker, with the fourth having one secondary propylamine separated from a primary amine by an ethyl linker. Under the experimental conditions used in this study, it was found that both amine type and proximity had a significant effect on oxidative degradation rates. In particular, the supported primary and tertiary amines proved to be stable to the oxidizing conditions used, whereas the secondary amines degraded at elevated treatment temperatures. Because secondary amines are important components of many supported amine adsorbents, it is suggested that the oxidative stability of such species needs to be carefully considered in assessments of postcombustion CO2 capture processes based on supported amines. © 2011 American Chemical Society.

Oxidative Degradation of Aminosilica Adsorbents Relevant to Postcombustion CO 2 Capture

KAUST Repository

Bollini, Praveen; Choi, Sunho; Drese, Jeffrey H.; Jones, Christopher W.

2011-01-01

Coal-fired power plant flue gas exhaust typically contains 3-10% oxygen. While it is known that the monoethanolamine (MEA) oxidative degradation rate is a critical parameter affecting liquid amine absorption processes, the effect of oxygen on the stability of solid amine adsorbents remains unexplored. Here, oxidative degradation of aminosilica materials is studied under accelerated oxidizing conditions to assess the stability of different supported amine structures to oxidizing conditions. Adsorbents constructed using four different silane coupling agents are evaluated, three with a single primary, secondary, or tertiary amine at the end of a propyl surface linker, with the fourth having one secondary propylamine separated from a primary amine by an ethyl linker. Under the experimental conditions used in this study, it was found that both amine type and proximity had a significant effect on oxidative degradation rates. In particular, the supported primary and tertiary amines proved to be stable to the oxidizing conditions used, whereas the secondary amines degraded at elevated treatment temperatures. Because secondary amines are important components of many supported amine adsorbents, it is suggested that the oxidative stability of such species needs to be carefully considered in assessments of postcombustion CO2 capture processes based on supported amines. © 2011 American Chemical Society.

THE FTIR STUDIES OF PHOTO-OXIDATIVE DEGRADATION OF POLYPROPYLENE

Institute of Scientific and Technical Information of China (English)

WEN Zaiqing; HU Xingzhou; SHEN Deyan

1988-01-01

The photo-oxidative degradation process of polypropylene film containing iron ions was investigated via FTIR and absorbance substraction technique. It is shown that the iron ions play an important role in the decomposition of hydroperoxide and the increase of the degradation rate of polypropylene film. Theamorphous region of PP film undergoes degradation prior to the crystalline one.

Kinetic studies on the degradation of crystal violet by the Fenton oxidation process.

Science.gov (United States)

Wu, H; Fan, M M; Li, C F; Peng, M; Sheng, L J; Pan, Q; Song, G W

2010-01-01

The degradation of dye crystal violet (CV) by Fenton oxidation process was investigated. The UV-Vis spectrogram has shown that CV can be degraded effectively by Fenton oxidation process. Different system variables namely initial H(2)O(2) concentration, initial Fe(2 + ) concentration and reaction temperature, which have effect on the degradation of CV by Fenton oxidation process, have been studied systematically. The degradation kinetics of CV was also elucidated based on the experimental data. The degradation of CV obeys the first-order reaction kinetics. The kinetic model can be described as k=1.5 exp(-(7.5)/(RT))[H(2)O(2)](0)(0.8718)[Fe(2+)](0)(0.5062). According to the IR spectrogram, it is concluded that the benzene ring of crystal violet has been destroyed by Fenton oxidation. The result will be useful in treating dyeing wastewater containing CV by Fenton oxidation process.

Reaction kinetics and oxidation products formation in the degradation of ciprofloxacin and ibuprofen by ferrate(VI).

Science.gov (United States)

Zhou, Zhengwei; Jiang, Jia-Qian

2015-01-01

The treatment of ciprofloxacin (CIP) and ibuprofen (IBU) in test solutions by ferrate(VI) was investigated in this study. A series of jar test was performed in bench-scale at pH 6-9 and ferrate(VI) dose of 1-5 mg L(-1). Results demonstrated that ferrate(VI) removed CIP from test solutions efficiently, with above 70% of reduction under study conditions. In contrary, the removal rates of IBU were very low, less than 25% in all conditions. Raising ferrate(VI) dose improved the treatment performance, while the influence of solution pH was not significant at pH 6-9 compared with that of ferrate(VI) dose. In addition, kinetic studies of ferrate(VI) with both compounds were carried out at pH 8 and pH 9 (20 °C). Ferrate(VI) had a much higher reactivity with CIP than IBU at pH 8 and pH 9, with CIP's apparent second-order rate constants of 113.7±6.3 M(-1) s(-1) and 64.1±1.0 M(-1) s(-1), respectively. The rate constants of ferrate(VI) with IBU were less than 0.2 M(-1) s(-1) at pH 8 and pH 9. Furthermore, seven oxidation products (OPs) were formed during CIP degradation by ferrate(VI). The attack on the piperazinyl ring of the CIP by ferrate(VI) appeared to lead to the cleavage or hydroxylation of the rings, and the attack on the quinolone moiety by ferrate(VI) might lead to the cleavage of the double bond at the six-member heterocyclic ring. No OPs of IBU were detected during ferrate(VI) oxidation due to very small part of IBU was degraded by ferrate(VI). Copyright © 2014 Elsevier Ltd. All rights reserved.

The Inhibitory Effect of Natural Products on Protein Fibrillation May Be Caused by Degradation Products – A Study Using Aloin and Insulin

DEFF Research Database (Denmark)

Lobbens, Eva Stephanie; Foderà, Vito; Nyberg, Nils

2016-01-01

, high-performance liquid chromatography and transmission electron microscopy it was found that a degradation product of aloin, formed over weeks of storage, was able to significantly inhibit insulin fibrillation. The activity of the stored aloin was significantly reduced in the presence of small amounts...... of sodium azide or ascorbic acid, suggesting the active compound to be an oxidation product. A high-performance liquid chromatography method and a liquid chromatography-mass spectrometry method were developed to investigate the degradation products in the aged aloin solution. We found that the major...

RP-HPLC assay method development for Paracetamol and Lornoxicam in combination and characterization of oxidative degradation products of Lornoxicam

Directory of Open Access Journals (Sweden)

Jain Pritam S.

2013-01-01

Full Text Available A simple, specific, accurate and precise reverse phase high pressure liquid chromatographic method has been developed for the simultaneous determination of Paracetamol and Lornoxicam from tablets and to characterize degradation products of Lornoxicam by reverse phase C18 column (Inertsil ODS 3V C-18, 250 x 4.6 mm, 5 μ. The sample was analyzed using Buffer (0.02504 Molar: Methanol in the ratio of 45:55, as a mobile phase at a flow rate of 1.5 mL/min and detection at 290 nm. The retention time for Paracetamol and Lornoxicam was found to be 2.45 and 9.40 min respectively. The method can be used for estimation of combination of these drugs in tablets. The method was validated as per ICH guidelines. The linearity of developed method was achieved in the range of 249.09 - 747.29 μg/mL (r2=0.9999 for Paracetamol and 4.0125 - 12.0375 μg/mL (r2=0.9999 for Lornoxicam. Recoveries from tablets were between 98 and 102%. The method was validated with respect to linearity, accuracy, precision, robustness and forced degradation studies which further proved the stability-indicating power. During the forced degradation studies lornoxicam was observed to be labile to alkaline hydrolytic stress and oxidative stress (in the solution form. However, it was stable to the acid hydrolytic, photolytic and thermal stress (in both solid and solution form. The degraded products formed were investigated by electrospray ionization (ESI time-of-flight mass spectrometry, NMR and IR spectroscopy. A possible degradation pathway was outlined based on the results. The method was found to be sensitive with a detection limit of 0.193 μg/ml, 2.768 μg/ml and a quantitation limit of 0.638 μg/ml, 9.137 μg/ml for lornoxicam and paracetamol, respectively. Due to these attributes, the proposed method could be used for routine quality control analysis of these drugs in combined dosage forms.

Oxidative degradation of triazine- and sulfonylurea-based herbicides using Fe(VI): The case study of atrazine and iodosulfuron with kinetics and degradation products

Science.gov (United States)

The occurrence of common herbicides (Atrazine, ATZ and Iodosufuron, IDS), in waters presents potential risk to human and ecological health. The oxidative degradation of ATZ and IDS by ferrate(VI) (FeVIO42-, Fe(VI)) is studied at different pH levels where kinetically observed se...

[Studies on the degradation of paracetamol in sono-electrochemical oxidation].

Science.gov (United States)

Dai, Qi-Zhou; Ma, Wen-Jiao; Shen, Hong; Chen, Jun; Chen, Jian-Meng

2012-07-01

A novel lead dioxide electrodes co-doped with rare earth and polytetrafluoroethylene (PTFE) were prepared by the electrode position method and applied as anodes in sono-electrochemical oxidation for pharmaceutical wastewater degradation. The results showed that the APAP removal and the mineralization efficiency reached an obvious increase, which meant that the catalytic efficiency showed a significant improvement in the use of rare-earth doped electrode. The effects of process factors showed that the condition of the electrode had the best degradation efficiency with doped with Ce2O3 under electrolyte concentration of 14.2 g x L(-1), 49.58 W x cm(-2), 50 Hz, pH = 3, 71.43 mA x cm(-2). The APAP of 500 mg x L(-1) removal rate reached 92.20% and its COD and TOC values declined to 79.95% and 58.04%, the current efficiency reached 45.83% after degradation process for 2.0 h. The intermediates were monitored by the methods of GC-MS, HPLC, and IC. The main intermediates of APAP were p-benzoquinone, benzoic acid, acetic acid, maleic acid, oxalic acid, formic acid etc, and the final products were carbon dioxide and water. The goal of completely degradation of pollutant was achieved and a possible degradation way was proposed.

Oxidation of indometacin by ferrate (VI): kinetics, degradation pathways, and toxicity assessment.

Science.gov (United States)

Huang, Junlei; Wang, Yahui; Liu, Guoguang; Chen, Ping; Wang, Fengliang; Ma, Jingshuai; Li, Fuhua; Liu, Haijin; Lv, Wenying

2017-04-01

The oxidation of indometacin (IDM) by ferrate(VI) (Fe(VI)) was investigated to determine the reaction kinetics, transformation products, and changes in toxicity. The reaction between IDM and Fe(VI) followed first-order kinetics with respect to each reactant. The apparent second-order rate constants (k app ) decreased from 9.35 to 6.52 M -1  s -1 , as the pH of the solution increased from 7.0 to 10.0. The pH dependence of k app might be well explained by considering the species-specific rate constants of the reactions of IDM with Fe(VI). Detailed product studies using liquid chromatography-tandem mass spectrometry (LC-MS/MS) indicated that the oxidation products were primarily derived from the hydrolysis of amide linkages, the addition of hydroxyl groups, and electrophilic oxidation. The toxicity of the oxidation products was evaluated using the Microtox test, which indicated that transformation products exhibited less toxicity to the Vibrio fischeri bacteria. Quantitative structure-activity relationship (QSAR) analysis calculated by the ecological structure activity relationship (ECOSAR) revealed that all of the identified products exhibited lower acute and chronic toxicity than the parent pharmaceutical for fish, daphnid, and green algae. Furthermore, Fe(VI) was effective in the degradation IDM in water containing carbonate ions or fulvic acid (FA), and in lake water samples; however, higher Fe(VI) dosages would be required to completely remove IDM in lake water in contrast to deionized water.

Photo-oxidative degradation of TiO{sub 2}/polypropylene films

Energy Technology Data Exchange (ETDEWEB)

García-Montelongo, X.L. [Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico); Martínez-de la Cruz, A., E-mail: azael70@yahoo.com.mx [Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico); Vázquez-Rodríguez, S. [Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico); Torres-Martínez, Leticia M. [Facultad de Ingeniería Civil, Universidad Autónoma de Nuevo León, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico)

2014-03-01

Graphical abstract: - Highlights: • Photo-oxidative degradation of polypropylene is accelerated by TiO{sub 2} incorporation. • Weight loss, FTIR, SEM and GPC shown high degree of degradation of polypropylene. • A mechanism of the photo-degradation of polypropylene by TiO{sub 2} is proposed. - Abstract: Photo-oxidative degradation of polypropylene films with TiO{sub 2} nanoparticles incorporated was studied in a chamber of weathering with Xenon lamps as irradiation source. TiO{sub 2} powder with crystalline structure of anatase was synthesized by thermal treatments at 400 and 500 °C starting from a precursor material obtained by sol–gel method. Composites of TiO{sub 2}/polypropylene were prepared with 0.1, 0.5 and 1.0 wt% of TiO{sub 2}. The mixture of components was performed using a twin screw extruder, the resulting material was pelletized by mechanical fragmenting and then hot-pressed in order to form polypropylene films with TiO{sub 2} dispersed homogeneously. Photo-oxidative degradation process was followed by visual inspection, weight loss of films, scanning electron microscopy (SEM), infrared spectroscopy with Fourier transformed (FTIR), and gel permeation chromatography (GPC)

Theoretical and spectroscopic investigation of the oxidation and degradation of protocatechuic acid

International Nuclear Information System (INIS)

Hatzipanayioti, Despina; Karaliota, Alexandra; Kamariotaki, Mary; Aletras, Vasilios; Petropouleas, Panayiotis

2006-01-01

In this work, we report a combined experimental and theoretical study on molecular structure and spectroscopic properties of the most stable conformers of PCA. 1 H, 13 C NMR and 2D COSY NMR, ESR, IR and electronic spectroscopies were coupled with DFT theoretical calculations performed at the B3LYP/6-31G** level. The calculated geometrical parameters for the neutral protocatechuic acid PCA-H 3 , its anions, its oxidized forms and the peroxo-derivative [PCA-H-O 2 ] 2- are in line with the experimental data. The neutral catecholate is the most stable form of PCA-H 3 whilst the dianion [PCA-H] 2- presents higher energy. This anion is (experimentally) stable only under argon, reacting with dioxygen, in the presence of air. The semiquinone [PCA-H-sq(3)] - is very close in energy from [PCA-H-sq(4)] - form and an equilibrium between these two oxidized radical forms might be expected. The energetically advantageous pathway for preparation of the symmetrically delocalized [PCA-sq] 2- is to oxidize the [PCA] 3- . The occurrence of this radical dianion form was justified experimentally by ESR, IR, UV-vis and NMR spectra. The structural calculations for [PCA-H-O 2 ] 2- indicate that C 3 (and to a lesser extent C1) may undergo a nucleophilic attack from the 'co-ordinated' peroxo-group. The conditions for the non-enzymatic degradation of PCA have been established and some new products are observed: ionization of PCA-H 3 , the presence of O 2 and aprotic solvents provide the semiquinone-superoxo adduct which is then degraded to lactones, while in protic solvents, addition of H 2 O 2 and the presence of air, are essential, providing aliphatic degradation products

Determination of trace amounts of chemical warfare agent degradation products in decontamination solutions with NMR spectroscopy.

Science.gov (United States)

Koskela, Harri; Rapinoja, Marja-Leena; Kuitunen, Marja-Leena; Vanninen, Paula

2007-12-01

Decontamination solutions are used for an efficient detoxification of chemical warfare agents (CWAs). As these solutions can be composed of strong alkaline chemicals with hydrolyzing and oxidizing properties, the analysis of CWA degradation products in trace levels from these solutions imposes a challenge for any analytical technique. Here, we present results of application of nuclear magnetic resonance spectroscopy for analysis of trace amounts of CWA degradation products in several untreated decontamination solutions. Degradation products of the nerve agents sarin, soman, and VX were selectively monitored with substantially reduced interference of background signals by 1D 1H-31P heteronuclear single quantum coherence (HSQC) spectrometry. The detection limit of the chemicals was at the low part-per-million level (2-10 microg/mL) in all studied solutions. In addition, the concentration of the degradation products was obtained with sufficient confidence with external standards.

Identification of Forced Degradation Products of Itopride by LC-PDA and LC-MS

OpenAIRE

Joshi, Payal; Bhoir, Suvarna; Bhagwat, A. M.; Vishwanath, K.; Jadhav, R. K.

2011-01-01

Degradation products of itopride formed under different forced conditions have been identified using LC-PDA and LC-MS techniques. Itopride was subjected to forced degradation under the conditions of hydrolysis, photolysis, oxidation, dry and wet heat, in accordance with the International Conference on Harmonization. The stress solutions were chromatographed on reversed phase C18 (250×4.6 mm, 5 μm) column with a mobile phase methanol:water (55:45, v/v) at a detection wavelength of 215 nm. Itop...

Oxidative degradation of ion-exchange resins in acid medium. Vol. 3

International Nuclear Information System (INIS)

Eskander, S.B.; Ghattas, N.K.

1996-01-01

Volume reduction of spent ion-exchange resins used in nuclear facilities receive increasing importance due to the increase in storage cost, unstable physical and chemical properties and their relatively high specific activity (in some cases up to 1 Ci per liter). The present study is part of research program on the treatment and immobilization of radioactive spent ion-exchange resins simulate; hydrogen peroxide was used for the oxidative degradation of spent ion-exchange resins simulate in sulphuric acid medium. Five liters ring digester developed in Karlsruhe nuclear research center-(KFK)- in germany was the chosen option to perform the oxidation process. The work reported focused on the kinetics and mechanism of the oxidation process. Heating the organic resins in sulphuric acid results in its carbonization and partial oxidation of only 1.7% of the carbon added. Results show that the oxidation reaction is a relatively slow process of first order with K value in the order of 10 -4 min -1 , and the main oxidation product was carbon dioxide. The production of carbon oxide in the off gas stream increased sharply by the addition of hydrogen peroxide to the hot sulphuric acid-resin mixture. The results obtained show that more than 97% of the carbon added was oxidized to carbon dioxide and carbon monoxide. The rate constant value (K) of this reaction was calculated to be (1.69±0.13) x 10 -2 min -1 . The results of gas chromatographic analysis indicate that no significant amounts of hazardous organic materials were detected in the off-gas streams. 6 figs., 4 tabs

Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A: Kinetics, reaction pathways, and formation of brominated by-products

Energy Technology Data Exchange (ETDEWEB)

Ji, Yuefei [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Kong, Deyang [Nanjing Institute of Environmental Science, Ministry of Environmental Protection of PRC, Nanjing 210042 (China); Lu, Junhe, E-mail: jhlu@njau.edu.cn [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China); Jin, Hao; Kang, Fuxing; Yin, Xiaoming; Zhou, Quansuo [Department of Environmental Science and Engineering, Nanjing Agricultural University, Nanjing 210095 (China)

2016-08-05

Highlights: • Cobalt catalyzed peroxymonosulfate oxidation of tetrabromobisphenol A. • Phenolic moiety was the reactive site for sulfate radical attack. • Pathways include β-scission, oxidation, debromination and coupling reactions. • Brominated disinfection by-products were found during TBBPA degradation. • Humic acid inhibited TBBPA degradation but promoted DBPs formation. - Abstract: Degradation of tetrabromobisphenol A (TBBPA), a flame retardant widely spread in the environment, in Co(II) catalyzed peroxymonosulfate (PMS) oxidation process was systematically explored. The second-order-rate constant for reaction of sulfate radical (SO{sub 4}{sup ·−}) with TBBPA was determined to be 5.27 × 10{sup 10} M{sup −1} s{sup −1}. Apparently, degradation of TBBPA showed first-order kinetics to the concentrations of both Co(II) and PMS. The presence of humic acid (HA) and bicarbonate inhibited TBBPA degradation, most likely due to their competition for SO{sub 4}{sup ·−}. Degradation of TBBPA was initiated by an electron abstraction from one of the phenolic rings. Detailed transformation pathways were proposed, including β-scission of isopropyl bridge, phenolic ring oxidation, debromination and coupling reactions. Further oxidative degradation of intermediates in Co(II)/PMS process yielded brominated disinfection by-products (Br-DBPs) such as bromoform and brominated acetic acids. Evolution profile of Br-DBPs showed an initially increasing and then decreasing pattern with maximum concentrations occurring around 6–10 h. The presence of HA enhanced the formation of Br-DBPs significantly. These findings reveal potentially important, but previously unrecognized, formation of Br-DBPs during sulfate radical-based oxidation of bromide-containing organic compounds that may pose toxicological risks to human health.

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

Science.gov (United States)

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

2014-12-15

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

Electro-oxidation of the dye azure B: kinetics, mechanism, and by-products.

Science.gov (United States)

Olvera-Vargas, Hugo; Oturan, Nihal; Aravindakumar, C T; Paul, M M Sunil; Sharma, Virender K; Oturan, Mehmet A

2014-01-01

In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H₂O₂ electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals ((•)OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by (•)OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19 × 10(9) M(-1) s(-1). It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO₂ and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.

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

International Nuclear Information System (INIS)

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

1983-02-01

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

Degradation of the azo dye Acid Red 1 by anodic oxidation and indirect electrochemical processes based on Fenton's reaction chemistry. Relationship between decolorization, mineralization and products

International Nuclear Information System (INIS)

Florenza, Xavier; Solano, Aline Maria Sales; Centellas, Francesc; Martínez-Huitle, Carlos Alberto

2014-01-01

Highlights: • Degradation of Acid Red 1 by anodic oxidation, electro-Fenton and photoelectro-Fenton • Quicker and similar decolorization by electro-Fenton and photoelectro-Fenton due to oxidation with ● OH in the bulk • Almost total mineralization by photoelectro-Fenton with Pt or BDD due to fast photolysis of products by UVA light • Detection of 11 aromatic products, 15 hydroxylated compounds, 13 desulfonated derivatives and 7 carboxylic acids • Release of NH 4 + , NO 3 − and SO 4 2− ions, and generation of persistent N-products of low molecular mass - Abstract: Solutions of 236 mg dm −3 Acid Red 1 (AR1), an azo dye widely used in textile dying industries, at pH 3.0 have been comparatively treated by anodic oxidation with electrogenerated H 2 O 2 (AO-H 2 O 2 ), electro-Fenton (EF) and photoelectro-Fenton (PEF) at constant current density (j). Assays were performed with a stirred tank reactor equipped with a Pt or boron-doped diamond (BDD) anode and an air-diffusion cathode for H 2 O 2 generation from O 2 reduction. The main oxidizing agents were hydroxyl radicals produced at the anode from water oxidation in all methods and in the bulk from Fenton's reaction between generated H 2 O 2 and 0.5 mmol dm −3 Fe 2+ in EF and PEF. For each anode, higher oxidation power was found in the sequence AO-H 2 O 2 < EF < PEF. The oxidation ability of the BDD anode was always superior to that of Pt. Faster and similar decolorization efficiency was achieved in EF and PEF owing to the quicker destruction of aromatics with hydroxyl radicals produced in the bulk. The PEF process with BDD was the most potent method yielding almost total mineralization due to the additional rapid photolysis of recalcitrant intermediates like Fe(III)-carboxylate complexes under UVA irradiation. The increase in j always enhanced the decolorization and mineralization processes because of the greater production of hydroxyl radicals, but decreases the mineralization current efficiency

Dependence of transformation product formation on pH during photolytic and photocatalytic degradation of ciprofloxacin

International Nuclear Information System (INIS)

Salma, Alaa; Thoröe-Boveleth, Sven; Schmidt, Torsten C.; Tuerk, Jochen

2016-01-01

Highlights: • Identification of transformation products using an isotopically labeled surrogate. • 4 of 18 detected transformation products have been identified for the first time. • Revision of 2 molecular structures of previously reported transformation products. • PH dependence of photolytic and photocatalytic degradation of ciprofloxacin. - Abstract: Ciprofloxacin (CIP) is a broad-spectrum antibiotic with five pH dependent species in aqueous medium, which makes its degradation behavior difficult to predict. For the identification of transformation products and prediction of degradation mechanisms, a new experimental concept making use of isotopically labeled compounds together with high resolution mass spectrometry was successfully established. The utilization of deuterated ciprofloxacin (CIP-d8) facilitated the prediction of three different degradation pathways and the corresponding degradation products, four of which were identified for the first time. Moreover, two molecular structures of previously reported transformation products were revised according to the mass spectra and product ion spectra of the deuterated transformation products. Altogether, 18 transformation products have been identified during the photolytic and photocatalytic reactions at different pH values (3, 5, 7 and 9). In this work the influence of pH on both reaction kinetics and degradation mechanism was investigated for direct ultraviolet photolysis (UV-C irradiation) and photocatalysis (TiO_2/UV-C). It could be shown that the removal rates strongly depended on pH with highest removal rates at pH 9. A comparison with those at pH 3 clearly indicated that under acidic conditions ciprofloxacin cannot be easily excited by UV irradiation. We could confirm that the first reaction step for both oxidative treatment processes is mainly defluorination, followed by degradation at the piperazine ring of CIP.

Dependence of transformation product formation on pH during photolytic and photocatalytic degradation of ciprofloxacin

Energy Technology Data Exchange (ETDEWEB)

Salma, Alaa [Institut für Energie- und Umwelttechnik e. V. (IUTA, Institute of Energy and Environmental Technology), Bliersheimer Straße 58-60, 47229 Duisburg (Germany); Thoröe-Boveleth, Sven [University Hospital Aachen, Institute for Hygiene and Environmental Medicine, Pauwelsstraße 30, 52074 Aachen (Germany); Schmidt, Torsten C. [University Duisburg-Essen, Faculty of Chemistry, Instrumental Analytical Chemistry, Universitätsstraße 5, 45141 Essen (Germany); Centre for Water and Environmental Research (ZWU), University Duisburg-Essen, Universitätsstraße 2, 45141 Essen (Germany); Tuerk, Jochen, E-mail: tuerk@iuta.de [Institut für Energie- und Umwelttechnik e. V. (IUTA, Institute of Energy and Environmental Technology), Bliersheimer Straße 58-60, 47229 Duisburg (Germany); Centre for Water and Environmental Research (ZWU), University Duisburg-Essen, Universitätsstraße 2, 45141 Essen (Germany)

2016-08-05

Highlights: • Identification of transformation products using an isotopically labeled surrogate. • 4 of 18 detected transformation products have been identified for the first time. • Revision of 2 molecular structures of previously reported transformation products. • PH dependence of photolytic and photocatalytic degradation of ciprofloxacin. - Abstract: Ciprofloxacin (CIP) is a broad-spectrum antibiotic with five pH dependent species in aqueous medium, which makes its degradation behavior difficult to predict. For the identification of transformation products and prediction of degradation mechanisms, a new experimental concept making use of isotopically labeled compounds together with high resolution mass spectrometry was successfully established. The utilization of deuterated ciprofloxacin (CIP-d8) facilitated the prediction of three different degradation pathways and the corresponding degradation products, four of which were identified for the first time. Moreover, two molecular structures of previously reported transformation products were revised according to the mass spectra and product ion spectra of the deuterated transformation products. Altogether, 18 transformation products have been identified during the photolytic and photocatalytic reactions at different pH values (3, 5, 7 and 9). In this work the influence of pH on both reaction kinetics and degradation mechanism was investigated for direct ultraviolet photolysis (UV-C irradiation) and photocatalysis (TiO{sub 2}/UV-C). It could be shown that the removal rates strongly depended on pH with highest removal rates at pH 9. A comparison with those at pH 3 clearly indicated that under acidic conditions ciprofloxacin cannot be easily excited by UV irradiation. We could confirm that the first reaction step for both oxidative treatment processes is mainly defluorination, followed by degradation at the piperazine ring of CIP.

Strength degradation of oxidized graphite support column in VHTR

International Nuclear Information System (INIS)

Park, Byung Ha; No, Hee Cheon

2010-01-01

Air-ingress events caused by large pipe breaks are important accidents considered in the design of Very High Temperature Gas-Cooled Reactors (VHTRs). A main safety concern for this type of event is the possibility of core collapse following the failure of the graphite support column, which can be oxidized by ingressed air. In this study, the main target is to predict the strength of the oxidized graphite support column. Through compression tests for fresh and oxidized graphite columns, the compressive strength of IG-110 was obtained. The buckling strength of the IG-110 column is expressed using the following empirical straight-line formula: σ cr,buckling =91.34-1.01(L/r). Graphite oxidation in Zone 1 is volume reaction and that in Zone 3 is surface reaction. We notice that the ultimate strength of the graphite column oxidized in Zones 1 and 3 only depends on the slenderness ratio and bulk density. Its strength degradation oxidized in Zone 1 is expressed in the following nondimensional form: σ/σ 0 =exp(-kd), k=0.114. We found that the strength degradation of a graphite column, oxidized in Zone 3, follows the above buckling empirical formula as the slenderness of the column changes. (author)

Different spectrophotometric methods applied for the analysis of simeprevir in the presence of its oxidative degradation product: Acomparative study

Science.gov (United States)

Attia, Khalid A. M.; El-Abasawi, Nasr M.; El-Olemy, Ahmed; Serag, Ahmed

2018-02-01

Five simple spectrophotometric methods were developed for the determination of simeprevir in the presence of its oxidative degradation product namely, ratio difference, mean centering, derivative ratio using the Savitsky-Golay filters, second derivative and continuous wavelet transform. These methods are linear in the range of 2.5-40 μg/mL and validated according to the ICH guidelines. The obtained results of accuracy, repeatability and precision were found to be within the acceptable limits. The specificity of the proposed methods was tested using laboratory prepared mixtures and assessed by applying the standard addition technique. Furthermore, these methods were statistically comparable to RP-HPLC method and good results were obtained. So, they can be used for the routine analysis of simeprevir in quality-control laboratories.

Photo catalytic Degradation of Organic Dye by Sol-Gel-Derived Gallium-Doped Anatase Titanium Oxide Nanoparticles for Environmental Remediation

International Nuclear Information System (INIS)

Arghya, N.B.; Sang, W.J.; Bong-Ki, M.

2012-01-01

Photo catalytic degradation of toxic organic chemicals is considered to be the most efficient green method for surface water treatment. We have reported the sol-gel synthesis of Gadoped anatase TiO 2 nanoparticles and the photo catalytic oxidation of organic dye into nontoxic inorganic products under UV irradiation. Photodegradation experiments show very good photo catalytic activity of Ga-doped TiO 2 nanoparticles with almost 90% degradation efficiency within 3 hrs of UV irradiation, which is faster than the undoped samples. Doping levels created within the bandgap of TiO 2 act as trapping centers to suppress the photo generated electron-hole recombination for proper and timely utilization of charge carriers for the generation of strong oxidizing radicals to degrade the organic dye. Photo catalytic degradation is found to follow the pseudo-first-order kinetics with the apparent 1 st-order rate constant around 1.3 x 10 -2 min -1 . The cost-effective, sol-gel-derived TiO 2 : Ga nanoparticles can be used efficiently for light-assisted oxidation of toxic organic molecules in the surface water for environmental remediation.

Concomitant degradation of bisphenol A during ultrasonication and Fenton oxidation and production of biofertilizer from wastewater sludge.

Science.gov (United States)

Mohapatra, D P; Brar, S K; Tyagi, R D; Surampalli, R Y

2011-09-01

Degradation of bisphenol A (BPA), an endocrine disruptor, from wastewater sludge (WWS) has attracted great interest recently. In the present study, the effects of different pre-treatment methods, including ultrasonication (US), Fenton's oxidation (FO) and ferro-sonication (FS) was assessed in terms of increase in solubilization of WWS and simultaneous degradation of BPA. Among US, FO and FS pre-treatment, higher suspended solids (SS), volatile suspended solids (VSS), chemical oxygen demand (COD) and soluble organic carbon (SOC) solubilization (39.7%, 51.2%, 64.5% and 17.6%, respectively) was observed during a ferro-sonication pre-treatment process carried out for 180 min, resulting in higher degradation of BPA (82.7%). In addition, the effect of rheological parameters (viscosity and particle size) and zeta potential on the degradation of BPA in raw and different pre-treated sludges were also investigated. The results showed that a decrease in viscosity and particle size and an increase in zeta potential resulted in higher degradation of BPA. BPA degradation by laccases produced by Sinorhizobium meliloti in raw and pre-treated sludge was also determined. Higher activity of laccases (207.9 U L(-1)) was observed in ferro-sonicated pre-treated sludge (180 min ultrasonic time), resulting in higher removal of BPA (0.083 μg g(-1)), suggesting concomitant biological degradation of BPA. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrolytic Degradation of Poly (ethylene oxide)-block-Polycaprolactone Worm Micelles

OpenAIRE

Geng, Yan; Discher, Dennis E.

2005-01-01

Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly (ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by poly...

Shear and elongational rheology of photo-oxidative degraded HDPE and LLDPE

Science.gov (United States)

Wagner, Manfred Hermann; Zheng, Wang; Wang, Peng; Talamante, Sebastián Ramos; Narimissa, Esmaeil

2017-05-01

The effect of photo-oxidative degradation of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) was investigated by linear and non-linear rheological measurements. The linear-viscoelastic rheological measurements were performed at different temperatures, while the elongational viscosity was measured at 170°C and at different strain rates. The rheological data are indicative of structural changes caused by photo-oxidative degradation including formation of long-chain branches (LCB), cross-linking, and chain scission, and they revealed a cyclic and continuing competition between chain scission and LCB/gel formation. These findings are supported by additional FTIR measurements and direct measurements of the gel content of the degraded samples.

Insights into the degradation of (CF3)2CHOCH3 and its oxidative product (CF3)2CHOCHO & the formation and catalytic degradation of organic nitrates

Science.gov (United States)

Bai, Feng-Yang; Jia, Zi-Man; Pan, Xiu-Mei

2018-06-01

In this work, a systematic investigation of the atmospheric oxidation mechanism of (CF3)2CXOCH3 and their oxidative products (CF3)2CXOCHO (X = H, F) initiated by OH radical or Cl atom is performed by density functional theory. This study reveals that the introduction of NO and O2 promotes the formation of organic nitrates, which are hygroscopic and are inclined to form secondary organic aerosols (SOA) and can affect the air quality. The rate constants of the individual reactions are found to be in agreement with the experimental results. One of the intriguing findings of this work is that the peroxynitrite of (CF3)2CHOCH2OONO formed from the subsequent reactions of (CF3)2CHOCH3 is more favorable to isomerize to organic nitrate (CF3)2CHOCH2ONO2 than to dissociate into alkoxy radical (CF3)2CHOCH2O and NO2 because of the lower energy barrier of isomerization. The second significant observation is that the organic nitrate can be degraded more favorably with the presence of NH3, CH3NH2, and CH3NHCH3 than its naked decomposition reaction (CF3)2CHOCH2ONO2→(CF3)2CHOCHO + HONO. The ammonium salt, a vital part of haze, is harmful to human health and can be formed in the existence of the NH3, CH3NH2, and CH3NHCH3. In addition, the toxic substance of peroxyalkyl nitrate (CF3)2CHOC(O)ONO2 which can reduce the visibility of the atmosphere is produced as the primary subsequent oxidation product of (CF3)2CHOCHO in a NO-rich environment. The main species detected experimentally are confirmed by this study. The computational results are crucial to risk assessment and pollution prevention of the volatile organic compounds (VOCs).

Oxidative degradation of alternative gasoline oxygenates in aqueous solution by ultrasonic irradiation: Mechanistic study

Energy Technology Data Exchange (ETDEWEB)

Kim, Duk Kyung, E-mail: dkim@aum.edu [Department of Physical Science, Auburn University Montgomery, Montgomery, AL 36117 (United States); O' Shea, Kevin E., E-mail: osheak@fiu.edu [Department of Chemistry and Biochemistry, Florida International University, University Park, Miami, FL 33199 (United States); Cooper, William J. [Department of Civil and Environmental Engineering, Urban Water Research Center, University of California Irvine, Irvine, CA 92697-2175 (United States)

2012-07-15

Widespread pollution has been associated with gasoline oxygenates of branched ethers methyl tert-butyl ether (MTBE), di-isopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl ether (TAME) which enter groundwater. The contaminated plume develops rapidly and treatment for the removal/destruction of these ethers is difficult when using conventional methods. Degradation of MTBE, with biological methods and advanced oxidation processes, are rather well known; however, fewer studies have been reported for degradation of alternative oxygenates. Degradation of alternative gasoline oxygenates (DIPE, ETBE, and TAME) by ultrasonic irradiation in aqueous oxygen saturation was investigated to elucidate degradation pathways. Detailed degradation mechanisms are proposed for each gasoline oxygenate. The common major degradation pathways are proposed to involve abstraction of {alpha}-hydrogen atoms by hydroxyl radicals generated during ultrasound cavitation and low temperature pyrolytic degradation of ETBE and TAME. Even some of the products from {beta}-H abstraction overlap with those from high temperature pyrolysis, the effect of {beta}-H abstraction was not shown clearly from product study because of possible 1,5 H-transfer inside cavitating bubbles. Formation of hydrogen peroxide and organic peroxides was also determined during sonolysis. These data provide a better understanding of the degradation pathways of gasoline oxygenates by sonolysis in aqueous solutions. The approach may also serve as a model for others interested in the details of sonolysis. - Highlights: Black-Right-Pointing-Pointer Gasoline oxygenates (ETBE, TAME, DIPE) were completely degraded after 6 hours under ultrasonic irradiation in O{sub 2} saturation. Black-Right-Pointing-Pointer The major degradation pathways were proposed to involve abstraction of {alpha}-hydrogen atoms by hydroxyl radicals and low temperature pyrolytic degradation. Black-Right-Pointing-Pointer The effect of {beta

Determination of degradation products and process related impurities of asenapine maleate in asenapine sublingual tablets by UPLC

Science.gov (United States)

Kumar, Nitin; Sangeetha, D.; Kalyanraman, L.

2017-11-01

For determination of process related impurities and degradation products of asenapine maleate in asenapine sublingual Tablets, a reversed phase, stability indicating UPLC method was developed. Acetonitrile, methanol and potassium dihydrogen phosphate buffer with tetra-n- butyl ammonium hydrogen sulphate as ion pair (pH 2.2; 0.01 M) at flow rate of 0.2 ml/min were used in gradient elution mode. Separation was achieved by using acquity BEH Shield RP18 column (1.7 μm, 2.1 mm×100 mm) at 35 ºC. UV detection was performed at 228 nm. Subsequently the liquid chromatography method was validated as per ICH. The drug product was exposed to the stress conditions of acid hydrolysis, base hydrolysis, water hydrolysis, oxidative, thermal, and photolytic. In oxidative stress and thermal stress significant degradation was observed. All the degradation products were well separated from analyte peak and its impurities. Stability indicating nature of the method was proved by demonstrating the peak purity of Asenapine peak in all the stressed samples. The mass balance was found >95% for all the stress conditions. Based on method validation, the method was found specific, linear, accurate, precise, rugged and robust.

Insights into the Mechanism and Kinetics of Thermo-Oxidative Degradation of HFPE High Performance Polymer.

Science.gov (United States)

Kunnikuruvan, Sooraj; Parandekar, Priya V; Prakash, Om; Tsotsis, Thomas K; Nair, Nisanth N

2016-06-02

The growing requisite for materials having high thermo-oxidative stability makes the design and development of high performance materials an active area of research. Fluorination of the polymer backbone is a widely applied strategy to improve various properties of the polymer, most importantly the thermo-oxidative stability. Many of these fluorinated polymers are known to have thermo-oxidative stability up to 700 K. However, for space and aerospace applications, it is important to improve its thermo-oxidative stability beyond 700 K. Molecular-level details of the thermo-oxidative degradation of such polymers can provide vital information to improve the polymer. In this spirit, we have applied quantum mechanical and microkinetic analysis to scrutinize the mechanism and kinetics of the thermo-oxidative degradation of a fluorinated polymer with phenylethenyl end-cap, HFPE. This study gives an insight into the thermo-oxidative degradation of HFPE and explains most of the experimental observations on the thermo-oxidative degradation of this polymer. Thermolysis of C-CF3 bond in the dianhydride component (6FDA) of HFPE is found to be the rate-determining step of the degradation. Reaction pathways that are responsible for the experimentally observed weight loss of the polymer is also scrutinized. On the basis of these results, we propose a modification of HFPE polymer to improve its thermo-oxidative stability.

Degradation product emission from historic and modern books by headspace SPME/GC-MS: evaluation of lipid oxidation and cellulose hydrolysis.

Science.gov (United States)

Clark, Andrew J; Calvillo, Jesse L; Roosa, Mark S; Green, David B; Ganske, Jane A

2011-04-01

Volatile organic compounds emitted from a several decade series of bound periodicals (1859-1939) printed on ground wood paper, as well as historical books dating from the 1500s to early 1800s made from cotton/linen rag, were studied using an improved headspace SPME/GC-MS method. The headspace over the naturally aging books, stored upright in glass chambers, was monitored over a 24-h period, enabling the identification of a wide range of organic compounds emanating from the whole of the book. The detection of particular straight chain aldehydes, as well as characteristic alcohols, alkenes and ketones is correlated with oxidative degradation of the C(18) fatty acid constituency of paper. The relative importance of hydrolytic and oxidative chemistry involved in paper aging in books published between 1560 and 1939 was examined by comparing the relative abundances of furfural (FUR) a known cellulose hydrolysis product, and straight chain aldehydes (SCA) produced from the oxidation of fatty acids in paper. The relative abundance of furfural is shown to increase across the 379-year publication time span. A comparison of relative SCA peak areas across the series of books examined reveals that SCA emission is more important in the cotton/linen rag books than in the ground wood books.

Degradation of ultra-thin gate oxide LDD NMOSFET under GIDL stress

International Nuclear Information System (INIS)

Hu Shigang; Hao Yue; Cao Yanrong; Ma Xiaohua; Wu Xiaofeng; Chen Chi; Zhou Qingjun

2009-01-01

The degradation of device under GIDL (gate-induced drain leakage current) stress has been studied using LDD NMOSFETs with 1.4 nm gate oxides. Experimental result shows that the degradation of device parameters depends more strongly on V d than on V g . The characteristics of the GIDL current are used to analyze the damage generated during the stress. It is clearly found that the change of GIDL current before and after stress can be divided into two stages. The trapping of holes in the oxide is dominant in the first stage, but that of electrons in the oxide is dominant in the second stage. It is due to the common effects of edge direct tunneling and band-to-band tunneling. SILC (stress induced leakage current) in the NMOSFET decreases with increasing stress time under GIDL stress. The degradation characteristic of SILC also shows saturating time dependence. SILC is strongly dependent on the measured gate voltage. The higher the measured gate voltage, the less serious the degradation of the gate current. A likely mechanism is presented to explain the origin of SILC during GIDL stress.

Laser Photo-Oxidative Degradation of 4,6-Dimethyldibenzothiophene

Czech Academy of Sciences Publication Activity Database

Gondal, M.A.; Masoudi, H.M.; Pola, Josef

2008-01-01

Roč. 71, č. 9 (2008), s. 1765-1768 ISSN 0045-6535 Institutional research plan: CEZ:AV0Z40720504 Keywords : 4,6-dimethyldibenzothiophene * laser oxidative degradation * molecular oxygen Subject RIV: CC - Organic Chemistry Impact factor: 3.054, year: 2008

Self-degradation of tissue adhesive based on oxidized dextran and poly-L-lysine.

Science.gov (United States)

Matsumura, Kazuaki; Nakajima, Naoki; Sugai, Hajime; Hyon, Suong-Hyu

2014-11-26

We have developed a low-toxicity bioadhesive based on oxidized dextran and poly-L-lysine. Here, we report that the mechanical properties and degradation of this novel hydrogel bioadhesive can be controlled by changing the extent of oxidation of the dextran and the type or concentration of the anhydride species in the acylated poly-L-lysine. The dynamic moduli of the hydrogels can be controlled from 120 Pa to 20 kPa, suggesting that they would have mechanical compatibility with various tissues, and could have applications as tissue adhesives. Development of the hydrogel color from clear to brown indicates that the reaction between the dextran aldehyde groups and the poly-L-lysine amino groups may be induced by a Maillard reaction via Schiff base formation. Degradation of the aldehyde dextran may begin by reaction of the amino groups in the poly-L-lysine. The gel degradation can be ascribed to degradation of the aldehyde dextran in the hydrogel, although the aldehyde dextran itself is relatively stable in water. The oxidized dextran and poly-L-lysine, and the degraded hydrogel showed low cytotoxicities. These findings indicate that a hydrogel consisting of oxidized dextran and poly-L-lysine has low toxicity and a well-controlled degradation rate, and has potential clinical applications as a bioadhesive. Copyright © 2014 Elsevier Ltd. All rights reserved.

Enhanced degradation of chitosan by applying plasma treatment in combination with oxidizing agents for potential use as an anticancer agent.

Science.gov (United States)

Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Watthanaphanit, Anyarat; Theeramunkong, Sewan; Saito, Nagahiro; Yamashita, Kazuko; Arakawa, Ryuichi

2017-07-01

Solution plasma (SP) treatment in combination with oxidizing agents, i.e., hydrogen peroxide (H 2 O 2 ), potassium persulfate (K 2 S 2 O 8 ) and sodium nitrite (NaNO 2 ) were adopted to chitosan degradation in order to achieve fast degradation rate, low chemicals used and high yield of low-molecular-weight chitosan and chitooligosaccharide (COS). Among the studied oxidizing agents, H 2 O 2 was found to be the best choice in terms of appreciable molecular weight reduction without major change in chemical structure of the degraded products of chitosan. By the combination with SP treatment, dilute solution of H 2 O 2 (4-60mM) was required for effective degradation of chitosan. The combination of SP treatment and dilute solution of H 2 O 2 (60mM) resulted in the great reduction of molecular weight of chitosan and water-soluble chitosan was obtained as a major product. The resulting water-soluble chitosan was precipitated to obtain COS. An inhibitory effect against cervical cancer cell line (HeLa cells) of COS was also examined. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stability-indicating UPLC method for determination of Valsartan and their degradation products in active pharmaceutical ingredient and pharmaceutical dosage forms.

Science.gov (United States)

Krishnaiah, Ch; Reddy, A Raghupathi; Kumar, Ramesh; Mukkanti, K

2010-11-02

A simple, precise, accurate stability-indicating gradient reverse phase ultra-performance liquid chromatographic (RP-UPLC) method was developed for the quantitative determination of purity of Valsartan drug substance and drug products in bulk samples and pharmaceutical dosage forms in the presence of its impurities and degradation products. The method was developed using Waters Aquity BEH C18 (100 mm x 2.1 mm, 1.7 microm) column with mobile phase containing a gradient mixture of solvents A and B. The eluted compounds were monitored at 225 nm, the run time was within 9.5 min, which Valsartan and its seven impurities were well separated. Valsartan was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Valsartan was found to degrade significantly in acid and oxidative stress conditions and stable in base, hydrolytic and photolytic degradation conditions. The degradation products were well resolved from main peak and its impurities, proving the stability-indicating power of the method. The developed method was validated as per international conference on harmonization (ICH) guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. This method was also suitable for the assay determination of Valsartan in pharmaceutical dosage forms.

Photo-oxidative degradation of Chicago Sky Blue azo dye on transition metal oxide electrodes

Energy Technology Data Exchange (ETDEWEB)

Slote, J.; Luo, J.; Hepel, M. [State Univ. of New York at Potsdam, NY (United States). Dept. of Chemistry; Zhong, C.-J. [State Univ. of New York at Binghamton, NY (United States). Dept. of Chemistry

2003-07-01

Every day, an average of 128 tons of dye staffs are discharged into waste water, causing environmental harm. The authors discussed the photo-electrical method for separating the semiconductor catalyst particles from the solution and direct control of the interfacial potential as an efficient and convenient method for degrading organic dyes. Photocurrent-potential measurements were made using a standard photoelectrochemical setup. It involved a microcomputer-controlled potentiostat and a 500 watts (W) quartz halogen lamp as the illumination source. The measurement of the photocurrent represented the difference between the current under illumination and current in the dark. Three-electrode electrochemical cells were used for all experiments. The best results concerning the degradation of dyes were obtained with tungsten oxides (WO3) and molybdenum oxides (MoO3) electrodes. Confirmation that the dyes had been fully degraded was obtained by performing absorbance measurements and a high performance liquid chromatography (HPLC) analysis of the samples after degradation. The effect on the rate of decolorisation process of Chicago Sky Blue, a diazo dye, and other dyes, of pH, potential, concentration, and type of supporting electrolyte was examined. The supporting electrolyte was found to have a strong influence on the degradation of diazo dye. Illumination with visible light yielded lower degradation rates than that with ultraviolet-visible light. It appears that Chicago Sky Blue dye sensitizes the semiconductor to expand the absorption of light energy well into visible range, despite the photoelectrochemical degradation of the dye being mainly induced by the ultraviolet light. The authors proposed the mechanisms of the reactions occurring during the photodegradation process. 6 refs., 1 fig.

Reactivity of tributyl phosphate degradation products with nitric acid: Relevance to the Tomsk-7 accident

International Nuclear Information System (INIS)

Barney, G.S.; Cooper, T.D.

1995-01-01

The reaction of a degraded tributyl phosphate (TBP) solvent with nitric acid is thought to have caused the chemical explosion at the Tomsk-7 reprocessing plant at Tomsk, Russia in 1993. The estimated temperature of the organic layer was not high eneough to cause significant reaction of nitric acid with TBP or hydrocarbon diluent compounds. A more reactive organic compound was likely present in the organic layer that reacted with sufficient heat generation to raise the temperature to the point where an autocatalytic oxidation of the organic solvent was initiated. Two of the most likely reactive compounds that are present in degraded TBP solvents are n-butanol and n-butyl nitrate. The reactions of these compounds with nitric acid are the subject of this study. The objective of laboratory-scale tests was to identify chemical reactions that occur when n-butanol and n-butyl nitrate contact heated nitric acid solutions. Reaction products were identified and quantitified, the temperatures at which these reactions occur and heats of reaction were measured, and reaction variables (temperature, nitric acid concentration, organic concentration, and reaction time) were evaluated. Data showed that n-butyl nitrate is less reactive than n-butanol. An essentially complete oxidation reaction of n-butanol at 110-120 C produced four major reaction products. Mass spectrometry identified the major inorganic oxidation products for both n-butanol and n-butyl nitrate as nitric oxide and carbon dioxide. Calculated heats of reaction for n-butanol and n-butyl nitrate to form propionic acid, a major reaction product, are -1860 cal/g n-butanol and -953 cal/g n-butyl nitrate. These heats of reaction are significant and could have raised the temperature of the organic layer in the Tomsk-7 tank to the point where autocatalytic oxidation of other organic compounds present resulted in an explosion

Sequential reduction–oxidation for photocatalytic degradation of tetrabromobisphenol A: Kinetics and intermediates

International Nuclear Information System (INIS)

Guo, Yaoguang; Lou, Xiaoyi; Xiao, Dongxue; Xu, Lei; Wang, Zhaohui; Liu, Jianshe

2012-01-01

Highlights: ► Sequential photocatalytic reduction–oxidation degradation of TBBPA was firstly examined. ► Different atmospheres were found to have significant effect on debromination reaction. ► A possible sequential photocatalytic reduction–oxidation pathway was proposed. - Abstract: C-Br bond cleavage is considered as a key step to reduce their toxicities and increase degradation rates for most brominated organic pollutants. Here a sequential reduction/oxidation strategy (i.e. debromination followed by photocatalytic oxidation) for photocatalytic degradation of tetrabromobisphenol A (TBBPA), one of the most frequently used brominated flame retardants, was proposed on the basis of kinetic analysis and intermediates identification. The results demonstrated that the rates of debromination and even photodegradation of TBBPA strongly depended on the atmospheres, initial TBBPA concentrations, pH of the reaction solution, hydrogen donors, and electron acceptors. These kinetic data and byproducts identification obtained by GC–MS measurement indicated that reductive debromination reaction by photo-induced electrons dominated under N 2 -saturated condition, while oxidation reaction by photoexcited holes or hydroxyl radicals played a leading role when air was saturated. It also suggested that the reaction might be further optimized for pretreatment of TBBPA-contaminated wastewater by a two-stage reductive debromination/subsequent oxidative decomposition process in the UV-TiO 2 system by changing the reaction atmospheres.

Hydrolytic degradation of poly(ethylene oxide)-block-polycaprolactone worm micelles.

Science.gov (United States)

Geng, Yan; Discher, Dennis E

2005-09-21

Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation-induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly(ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by polycaprolactone hydrolysis, with distinct mechanism and kinetics from that which occurs in bulk material.

Pathogenic prion protein is degraded by a manganese oxide mineral found in soils

Science.gov (United States)

Russo, F.; Johnson, C.J.; McKenzie, D.; Aiken, Judd M.; Pedersen, J.A.

2009-01-01

Prions, the aetiological agents of transmissible spongiform encephalopathies, exhibit extreme resistance to degradation. Soil can retain prion infectivity in the environment for years. Reactive soil components may, however, contribute to the inactivation of prions in soil. Members of the birnessite family of manganese oxides (MnO2) rank among the strongest natural oxidants in soils. Here, we report the abiotic degradation of pathogenic prion protein (PrPTSE) by a synthetic analogue of naturally occurring birnessite minerals. Aqueous MnO2 suspensions degraded the PrPTSE as evidenced by decreased immunoreactivity and diminished ability to seed protein misfolding cyclic amplification reactions. Birnessite-mediated PrPTSE degradation increased as a solution's pH decreased, consistent with the pH-dependence of the redox potential of MnO2. Exposure to 5.6 mg MnO2 ml-1 (PrPTSE:MnO2=1 : 110) decreased PrPTSE levels by ???4 orders of magnitude. Manganese oxides may contribute to prion degradation in soil environments rich in these minerals. ?? 2009 SGM.

Photolysis of nonylphenol ethoxylates: the determination of the degradation kinetics and the intermediate products.

Science.gov (United States)

Chen, Ling; Zhou, Hai-Yun; Deng, Qin-Ying

2007-06-01

The photolysis of nonylphenol ethoxylates with an average oligomers length of ten ethoxylate units (NPEO(10)) in aqueous solution under UV, as well as the influence of humic acid (HA) on the photolysis was studied. A 125W high-pressure mercury lamp was employed as the light source. The intermediate products from the photolysis were determined by LC-MS. The results indicated that NPEO(10) underwent direct photolysis upon exposed to UV. The degradation pathway was complex. Besides the generally proposed degradation pathway of ethylene oxide (EO) side chains shortening, the oxidation of alkyl chain and EO chain led to intermediates having both a carboxylated (as well as carbonylated) ethoxylate and alkyl chain of varying lengths. The hydrogenation of benzene ring was also detected. The kinetics data showed that the first order reaction kinetics could be well used to describe the kinetics of NPEO(10) degradation. In the presence of dissolved organic matter by HA addition, the performance of NPEO(10) photodegradation was reduced. The photolysis rate decreased with increased HA concentration.

Long term performance degradation analysis and optimization of anode supported solid oxide fuel cell stacks

International Nuclear Information System (INIS)

Parhizkar, Tarannom; Roshandel, Ramin

2017-01-01

Highlights: • A degradation based optimization framework is developed. • The cost of electricity based on degradation of solid oxide fuel cells is minimized. • The effects of operating conditions on degradation mechanisms are investigated. • Results show 7.12% lower cost of electricity in comparison with base case. • Degradation based optimization is a beneficial concept for long term analysis. - Abstract: The main objective of this work is minimizing the cost of electricity of solid oxide fuel cell stacks by decelerating degradation mechanisms rate in long term operation for stationary power generation applications. The degradation mechanisms in solid oxide fuel cells are caused by microstructural changes, reactions between lanthanum strontium manganite and electrolyte, poisoning by chromium, carburization on nickel particles, formation of nickel sulfide, nickel coarsening, nickel oxidation, loss of conductivity and crack formation in the electrolyte. The rate of degradation mechanisms depends on the cell operating conditions (cell voltage and fuel utilization). In this study, the degradation based optimization framework is developed which determines optimum operating conditions to achieve a minimum cost of electricity. To show the effectiveness of the developed framework, optimization results are compared with the case that system operates at its design point. Results illustrate optimum operating conditions decrease the cost of electricity by 7.12%. The performed study indicates that degradation based optimization is a beneficial concept for long term performance degradation analysis of energy conversion systems.

Research of the degradation products of chitosan's angiogenic function

International Nuclear Information System (INIS)

Wang Jianyun; Chen Yuanwei; Ding Yulong; Shi Guoqi; Wan Changxiu

2008-01-01

Angiogenesis is of great importance in tissue engineering and has gained large attention in the past decade. But how it will be influenced by the biodegradable materials, especially their degradation products, remains unknown. Chitosan (CS) is a kind of naturally occurred polysaccharide which can be degraded in physiological environment. In order to gain some knowledge of the influences of CS degradation products on angiogenesis, the interaction of vascular endothelial cells with the degradation products was investigated in the present study. The CS degradation products were prepared by keeping CS sample in physiological saline aseptically at 37 deg. C for 120 days. Endothelial cells were co-cultured with the degradation products and the angiogenic cell behaviors, including cell proliferation, migration and tube-like structure (TLS) formation, were tested by MTT assay, cell migration quantification method (CMQM), and tube-like structure quantification method (TLSQM) respectively. Furthermore, mRNA expressions of vascular endothelial growth factor (VEGF) and matrix metallo proteinase (MMP-2) were determined by real-time reverse transcriptional polymerase chain reaction (RT-PCR). Physiological saline served as a negative control. As the results showed, the degradation products obtained from 20th to 60th day significantly inhibited the proliferation, migration, and TLS formation of endothelial cells. However, degradation products of the first 14 days and the last 30 days were found to be proangiogenic. At the molecular level, the initial results indicated that the mRNA expressions of VEGF and MMP-2 were increased by the degradation products of 7th day, but were decreased by the ones of 60th day. According to all the results, it could be concluded that the angiogenic behaviors of endothelial cells at both cellular and molecular level could be significantly stimulated or suppressed by the degradation products of CS and the influences are quite time-dependent

Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

Science.gov (United States)

Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

2014-12-01

Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

Isolation and characterization of a degradation product in leflunomide and a validated selective stability-indicating HPLC–UV method for their quantification

Directory of Open Access Journals (Sweden)

Balraj Saini

2015-06-01

Full Text Available Leflunomide (LLM is subjected to forced degradation under conditions of hydrolysis, oxidation, dry heat, and photolysis as recommended by International Conference on Harmonization guideline Q1A(R2. In total, four degradation products (I–IV were formed under different conditions. Products I, II and IV were formed in alkaline hydrolytic, acidic hydrolytic and alkaline photolytic conditions. LLM and all degradation products were optimally resolved by gradient elution over a C18 column. The major degradation product (IV formed in hydrolytic alkaline conditions was isolated through column chromatography. Based on its 1H NMR, IR and mass spectral data, it was characterized as a British Pharmacopoeial impurity B. The HPLC method was found to be linear, accurate, precise, sensitive, specific, rugged and robust for quantification of LLM as well as product IV. Finally, the method was applied to stability testing of the commercially available LLM tablets. Keywords: Leflunomide, Characterization, Forced degradation, Degradation product, HPLC–UV

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

Science.gov (United States)

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

2015-02-01

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

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

Science.gov (United States)

Kong, Xiujuan; Wu, Zihao; Ren, Ziran; Guo, Kaiheng; Hou, Shaodong; Hua, Zhechao; Li, Xuchun; Fang, Jingyun

2018-06-15

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO • ) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 10 8  M -1  s -1 and 3.6 (±0.1) × 10 7  M -1  s -1 , respectively, whereas UV photolysis and the hydroxyl radical (HO • ) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO • concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br - , whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO • was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO • oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO • . This study is the first to report the transformation pathway of a

Influence of radiolytic degradation products from organic phase

International Nuclear Information System (INIS)

Azevedo, H.L.P. de.

1980-01-01

The influence of primary and secondary degradation products from TBP - dodecane on zirconium extraction is studied. The presence of radiolytical degradation at organic phase, in systems of initial concentration of HNO 3 1 and 4M, and absorbed γ radiation doses from 0,5 to 4,5 Wh/l, lead to an increase of zirconium extraction, being the HDBP the main product of degradation responsable by this effect. The influence of secondary degradation products is significative in systems of HNO 3 1M initial concentration. The formation of precipitator in extractions of Zr in HNO 3 1M with irradiated TBP-dodecane was observed. (M.C.K.) [pt

An efficient and environment-friendly method of removing graphene oxide in wastewater and its degradation mechanisms.

Science.gov (United States)

Zhang, Chao-Zhi; Li, Ting; Yuan, Yang; Xu, Jianqiang

2016-06-01

Graphene and graphene oxide (GO) have already existed in air, water and soil due to their popular application in functional materials. However, degradation of graphene and GO in wastewater has not been reported. Degradation of GO plays a key role in the elimination of graphene and GO in wastewater due to graphene being easily oxidized to GO. In this paper, GO was completely degraded to give CO2 by Photo-Fenton. The degradation intermediates were determined by UV-vis absorption spectra, elemental analysis (EA), fourier transform infrared (FT-IR) and liquid chromatography-mass spectrometry (LC-MS). Experimental results showed that graphene oxide was completely degraded to give CO2 after 28 days. Based on UV, FT-IR, LC-MS spectra and EA data of these degradation intermediates, the degradation mechanisms of GO were supposed. This paper suggests an efficient and environment-friendly method to degrade GO and graphene. Copyright © 2016 Elsevier Ltd. All rights reserved.

Degradation of Perfluorooctanoic Acid and Perfluoroctane Sulfonate by Enzyme Catalyzed Oxidative Humification Reactions

Science.gov (United States)

Huang, Q.

2016-12-01

Poly- and perfluoroalkyl substances (PFASs) are alkyl based chemicals having multiple or all hydrogens replaced by fluorine atoms, and thus exhibit high thermal and chemical stability and other unusual characteristics. PFASs have been widely used in a wide variety of industrial and consumer products, and tend to be environmentally persistent. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) are two representative PFASs that have drawn particular attention because of their ubiquitous presence in the environment, resistance to degradation and toxicity to animals. This study examined the decomposition of PFOA and PFOS in enzyme catalyzed oxidative humification reactions (ECOHR), a class of reactions that are ubiquitous in the environment involved in natural organic humification. Reaction rates and influential factors were examined, and high-resolution mass spectrometry was used to identify possible products. Fluorides and partially fluorinated compounds were identified as likely products from PFOA and PFOS degradation, which were possibly formed via a combination of free radical decomposition, rearrangements and coupling processes. The findings suggest that PFOA and PFOS may be transformed during humification, and ECOHR can potentially be used for the remediation of these chemicals.

Effect of aerobic exercise intervention on DDT degradation and oxidative stress in rats.

Science.gov (United States)

Li, Kefeng; Zhu, Xiaohua; Wang, Yuzhan; Zheng, Shuqian; Dong, Guijun

2017-03-01

Dichlorodiphenyltrichloroethane (DDT) reportedly causes extensively acute or chronic effects to human health. Exercise can generate positive stress. We evaluated the effect of aerobic exercise on DDT degradation and oxidative stress. Male Wistar rats were randomly assigned into control (C), DDT without exercise training (D), and DDT plus exercise training (DE) groups. The rats were treated as follows: DDT exposure to D and DE groups at the first 2 weeks; aerobic exercise treatment only to the DE group from the 1st day until the rats are killed. DDT levels in excrements, muscle, liver, serum, and hearts were analyzed. Superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GSH-Px), and malondialdehyde (MDA) levels were determined. Aerobic exercise accelerated the degradation of DDT primarily to DDE due to better oxygen availability and aerobic condition and promoted the degradation of DDT. Cumulative oxidative damage of DDT and exercise led to significant decrease of SOD level. Exercise resulted in consistent increase in SOD activity. Aerobic exercise enhanced activities of CAT and GSH-Px and promoted MDA scavenging. Results suggested that exercise can accelerate adaptive responses to oxidative stress and activate antioxidant enzymes activities. Exercise can also facilitate the reduction of DDT-induced oxidative damage and promoted DDT degradation. This study strongly implicated the positive effect of exercise training on DDT-induced liver oxidative stress.

Photocatalytic degradation of phenol by iodine doped tin oxide nanoparticles under UV and sunlight irradiation

Energy Technology Data Exchange (ETDEWEB)

Al-Hamdi, Abdullah M.; Sillanpää, Mika [Laboratory of Green Chemistry, Lappeenranta University of Technology, Sammonkatu 12, 50130 Mikkeli (Finland); Dutta, Joydeep, E-mail: dutta@squ.edu.om [Chair in Nanotechnology, Water Research Center, Sultan Qaboos University, P.O. Box 17, 123 Al-Khoudh (Oman)

2015-01-05

Highlights: • A sol–gel method used to synthesize tin oxide nanoparticles. • Nanoparticles of tin oxide doped with different iodine concentrations. • Degradation studies carried up with UV–vis, TOC, HPLC and GC instruments. • 1% iodine doped tin dioxide showed maximum photodegradation efficiency. - Abstract: Iodine doped tin oxide (SnO{sub 2}:I) nanoparticles were prepared by sol–gel synthesis and their photocatalytic activities with phenol as a test contaminant were studied. In the presence of the catalysts, phenol degradation under direct sunlight was comparable to what was achieved under laboratory conditions. Photocatalytic oxidation reactions were studied by varying the catalyst loading, light intensity, illumination time, pH of the reactant and phenol concentration. Upon UV irradiation in the presence of SnO{sub 2}:I nanoparticles, phenol degrades very rapidly within 30 min, forming carboxylic acid which turns the solution acidic. Phenol degradation rate with 1% iodine doped SnO{sub 2} nanoparticles is at least an order of magnitude higher compared to the degradation achieved through undoped SnO{sub 2} nanoparticles under similar illumination conditions.

Photocatalytic degradation of phenol by iodine doped tin oxide nanoparticles under UV and sunlight irradiation

International Nuclear Information System (INIS)

Al-Hamdi, Abdullah M.; Sillanpää, Mika; Dutta, Joydeep

2015-01-01

Highlights: • A sol–gel method used to synthesize tin oxide nanoparticles. • Nanoparticles of tin oxide doped with different iodine concentrations. • Degradation studies carried up with UV–vis, TOC, HPLC and GC instruments. • 1% iodine doped tin dioxide showed maximum photodegradation efficiency. - Abstract: Iodine doped tin oxide (SnO 2 :I) nanoparticles were prepared by sol–gel synthesis and their photocatalytic activities with phenol as a test contaminant were studied. In the presence of the catalysts, phenol degradation under direct sunlight was comparable to what was achieved under laboratory conditions. Photocatalytic oxidation reactions were studied by varying the catalyst loading, light intensity, illumination time, pH of the reactant and phenol concentration. Upon UV irradiation in the presence of SnO 2 :I nanoparticles, phenol degrades very rapidly within 30 min, forming carboxylic acid which turns the solution acidic. Phenol degradation rate with 1% iodine doped SnO 2 nanoparticles is at least an order of magnitude higher compared to the degradation achieved through undoped SnO 2 nanoparticles under similar illumination conditions

Smart Methods for Linezolid Determination in the Presence of Alkaline and Oxidative Degradation Products Utilizing Their Overlapped Spectral Bands

Science.gov (United States)

Abd El-Monem Hegazy, M.; Shaaban Eissa, M.; Abd El-Sattar, O. I.; Abd El-Kawy, M. M.

2014-09-01

Linezolid (LIN) is considered the first available oxazolidinone antibacterial agent. It is susceptible to hydrolysis and oxidation. Five simple, accurate, sensitive and validated UV spectrophotometric methods were developed for LIN determination in the presence of its alkaline (ALK) and oxidative (OXD) degradation products in bulk powder and pharmaceutical formulation. Method A is a second derivative one (D2) in which LIN is determined at 240.9 nm. Method B is a pH-induced differential derivative one where LIN is determined using the fourth derivative (D4) of the difference spectra (ΔA) at 285.3 nm. Methods C, D, and E are manipulating ratio spectra, where C is the double divisor-ratio difference spectrophotometric one (DD-RD) in which LIN was determined by calculating the amplitude difference at 243.7 and 267.6 nm of the ratio spectra. Method D is the double divisor-first derivative of ratio spectra (DD-DD1) in which LIN was determined at 270.2 nm. Method E is a mean centering of ratio spectra one (MCR) in which LIN was determined at 318.0 nm. The developed methods have been validated according to ICH guidelines. The results were statistically compared to that of a reported HPLC method and there was no significant difference regarding both accuracy and precision.

Fate of CL-20 in sandy soils: Degradation products as potential markers of natural attenuation

International Nuclear Information System (INIS)

Monteil-Rivera, Fanny; Halasz, Annamaria; Manno, Dominic; Kuperman, Roman G.; Thiboutot, Sonia; Ampleman, Guy; Hawari, Jalal

2009-01-01

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH 2 =N-C(=N-NO 2 )-CH=N-CHO or its isomer N(NO 2 )=CH-CH=N-CO-CH=NH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil. - Two key intermediates of CL-20 degradation are potential markers of its natural attenuation in soil

Degradation kinetics and transformation products of chlorophene by aqueous permanganate.

Science.gov (United States)

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

2018-07-01

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

Degradation of Ultra-Thin Gate Oxide NMOSFETs under CVDT and SHE Stresses

International Nuclear Information System (INIS)

Shi-Gang, Hu; Yan-Rong, Cao; Yue, Hao; Xiao-Hua, Ma; Chi, Chen; Xiao-Feng, Wu; Qing-Jun, Zhou

2008-01-01

Degradation of device under substrate hot-electron (SHE) and constant voltage direct-tunnelling (CVDT) stresses are studied using NMOSFET with 1.4-nm gate oxides. The degradation of device parameters and the degradation of the stress induced leakage current (SILC) under these two stresses are reported. The emphasis of this paper is on SILC and breakdown of ultra-thin-gate-oxide under these two stresses. SILC increases with stress time and several soft breakdown events occur during direct-tunnelling (DT) stress. During SHE stress, SILC firstly decreases with stress time and suddenly jumps to a high level, and no soft breakdown event is observed. For DT injection, the positive hole trapped in the oxide and hole direct-tunnelling play important roles in the breakdown. For SHE injection, it is because injected hot electrons accelerate the formation of defects and these defects formed by hot electrons induce breakdown. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Mechanisms Underpinning Degradation of Protective Oxides and Thermal Barrier Coatings in High Hydrogen Content (HHC) - Fueled Turbines

Energy Technology Data Exchange (ETDEWEB)

Mumm, Daniel

2013-08-31

/thermo-chemical attack mechanisms; (iv) developing a mechanics-based analysis of the driving forces for crack growth and delamination, based on molten phase infiltration, misfit upon cooling, and loss of compliance; (v) understanding changes in TGO growth mechanisms associated with these emerging combustion product streams; and (vi) identifying degradation resistant alternative materials (including new compositions or bi-layer concepts) for use in mitigating the observed degradation modes. To address the materials stability concerns, this program integrated research thrusts aimed at: (1) Conducting tests in simulated syngas and HHC environments to evaluate materials evolution and degradation mechanisms; assessing thermally grown oxide development unique to HHC environmental exposures; carrying out high-resolution imaging and microanalysis to elucidate the evolution of surface deposits (molten phase formation and infiltration); exploring thermo-chemical instabilities; assessing thermo-mechanical drivers and thermal gradient effects on degradation; and quantitatively measuring stress evolution due to enhanced sintering and thermo-chemical instabilities induced in the coating. (2) Executing experiments to study the melting and infiltration of simulated ash deposits, and identifying reaction products and evolving phases associated with molten phase corrosion mechanisms; utilizing thermal spray techniques to fabricate test coupons with controlled microstructures to study mechanisms of instability and degradation; facilitating thermal gradient testing; and developing new materials systems for laboratory testing; (3) Correlating information on the resulting combustion environments to properly assess materials exposure conditions and guide the development of lab-scale simulations of material exposures; specification of representative syngas and high-hydrogen fuels with realistic levels of impurities and contaminants, to explore differences in heat transfer, surface degradation, and deposit

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340-400 °C.

Science.gov (United States)

Yin, Keqing; Gao, Xingbao; Sun, Yifei; Zheng, Lei; Wang, Wei

2013-11-01

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340-400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340-400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices. Copyright © 2013 Elsevier Ltd. All rights reserved.

Unravelling the Interactions between Hydrolytic and Oxidative Enzymes in Degradation of Lignocellulosic Biomass by Sporothrix carnis under Various Fermentation Conditions

Directory of Open Access Journals (Sweden)

Olusola A. Ogunyewo

2016-01-01

Full Text Available The mechanism underlying the action of lignocellulolytic enzymes in biodegradation of lignocellulosic biomass remains unclear; hence, it is crucial to investigate enzymatic interactions involved in the process. In this study, degradation of corn cob by Sporothrix carnis and involvement of lignocellulolytic enzymes in biodegradation were investigated over 240 h cultivation period. About 60% degradation of corn cob was achieved by S. carnis at the end of fermentation. The yields of hydrolytic enzymes, cellulase and xylanase, were higher than oxidative enzymes, laccase and peroxidase, over 144 h fermentation period. Maximum yields of cellulase (854.4 U/mg and xylanase (789.6 U/mg were at 96 and 144 h, respectively. Laccase and peroxidase were produced cooperatively with maximum yields of 489.06 U/mg and 585.39 U/mg at 144 h. Drastic decline in production of cellulase at 144 h (242.01 U/mg and xylanase at 192 h (192.2 U/mg indicates that they play initial roles in biodegradation of lignocellulosic biomass while laccase and peroxidase play later roles. Optimal degradation of corn cob (76.6% and production of hydrolytic and oxidative enzymes were achieved with 2.5% inoculum at pH 6.0. Results suggest synergy in interactions between the hydrolytic and oxidative enzymes which can be optimized for improved biodegradation.

Removal of organics and degradation products from industrial wastewater by a membrane bioreactor integrated with ozone or UV/H₂O₂ treatment.

Science.gov (United States)

Laera, G; Cassano, D; Lopez, A; Pinto, A; Pollice, A; Ricco, G; Mascolo, G

2012-01-17

The treatment of a pharmaceutical wastewater resulting from the production of an antibacterial drug (nalidixic acid) was investigated employing a membrane bioreactor (MBR) integrated with either ozonation or UV/H(2)O(2) process. This was achieved by placing chemical oxidation in the recirculation stream of the MBR. A conventional configuration with chemical oxidation as polishing for the MBR effluent was also tested as a reference. The synergistic effect of MBR when integrated with chemical oxidation was assessed by monitoring (i) the main wastewater characteristics, (ii) the concentration of nalidixic acid, (iii) the 48 organics identified in the raw wastewater and (iv) the 55 degradation products identified during wastewater treatment. Results showed that MBR integration with ozonation or UV/H(2)O(2) did not cause relevant drawbacks to both biological and filtration processes, with COD removal rates in the range 85-95%. Nalidixic acid passed undegraded through the MBR and was completely removed in the chemical oxidation step. Although the polishing configuration appeared to give better performances than the integrated system in removing 15 out of 48 secondary organics while similar removals were obtained for 19 other compounds. The benefit of the integrated system was however evident for the removal of the degradation products. Indeed, the integrated system allowed higher removals for 34 out of 55 degradation products while for only 4 compounds the polishing configuration gave better performance. Overall, results showed the effectiveness of the integrated treatment with both ozone and UV/H(2)O(2).

SIMULTANEOUS DEGRADATION OF SOME PHTHALATE ESTERS UNDER FENTON AND PHOTO-FENTON OXIDATION PROCESSES

Directory of Open Access Journals (Sweden)

BELDEAN-GALEA M.S.

2015-03-01

Full Text Available In this study the assessment of the degradation efficiency of five phthalates, DEP, BBP, DEHP, DINP and DIDP, found in a mixture in a liquid phase, using the Fenton and Photo Fenton oxidation processes, was conducted. It was observed that the main parameters that influence the Fenton oxidative processes of phthalates were the concentration of the oxidizing agent, H2O2, the concentration of the catalyst used, Fe2+, the pH value, UV irradiation and the reaction time. For the Fenton oxidative process, the highest degradation efficiencies were 19% for DEP, 50% for BBP, 84% for DEHP, 90% for DINP and 48% for DIDP, when the experiments were carried out using concentrations of 20 mg L-1 phthalate mixture, 100 mg L-1 H2O2, 10 mg L-1 Fe2+ at a pH value of 3, with a total reaction time of 30 minutes. For the Photo-Fenton oxidative process carried out in the same conditions as Fenton oxidative process, it was observed that after an irradiation time of 90 minutes under UV radiation the degradation efficiencies of phthalates were improved, being 22% for DEP, 71% for BBP, 97% for DEHP, 97% for DINP and 81% for DIDP.

Internal oxidation as a mechanism for steam generator tube degradation

Energy Technology Data Exchange (ETDEWEB)

Gendron, T.S. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Scott, P.M. [Framatome, Paris (France); Bruemmer, S.M. [Pacific Northwest National Laboratory, Richland, WA (United States); Thomas, L.E. [Washington State Univ., School of Mechanical and Materials Engineering, Pullman, WA (United States)

1999-12-01

Internal oxidation has been proposed as a plausible mechanism for intergranular stress-corrosion cracking (IGSCC) of alloy 600 steam generator tubing. This theory can reconcile the main thermodynamic and kinetic characteristics of the observed cracking in hydrogenated primary water. Although secondary-side IG attack or IGSCC is commonly attributed to the presence of strong, caustic or acidic solutions, more recent evidence suggests that this degradation takes place in a near neutral environment, possibly dry polluted steam. As a result, internal oxidation is also a feasible mechanism for secondary side degradation. The present paper reviews experimental work conducted in an attempt to determine the validity of this mechanism. The consequences for the expected behaviour of alloys 690 and 800 replacement materials are also described. (author)

Internal oxidation as a mechanism for steam generator tube degradation

Energy Technology Data Exchange (ETDEWEB)

Gendron, T.S. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Scott, P.M. [Framatome, Paris (France); Bruemmer, S.M. [Pacific Northwest National Lab., Richland, Washington (United States); Thomas, L.E. [Washington State Univ., School of Mechanical and Materials Engineering, Pullman, WA (United States)

1998-07-01

Internal oxidation has been proposed as a plausible mechanism for intergranular stress corrosion cracking (IGSCC) of alloy 600 steam generator tubing. This theory can reconcile the main thermodynamic and kinetic characteristics of the observed cracking in hydrogenated primary water. Although secondary side IG attack or IGSCC is commonly attributed to the presence of strong caustic or acidic solutions, more recent evidence suggests that this degradation takes place in a near-neutral environment, possibly dry polluted steam. As a result, internal oxidation is also a feasible mechanism for secondary side degradation. The present paper reviews experimental work carried out in an attempt to determine the validity of this mechanism. The consequences for the expected behaviour of alloys 690 and 800 replacement materials are also described. (author)

Internal oxidation as a mechanism for steam generator tube degradation

International Nuclear Information System (INIS)

Gendron, T.S.; Scott, P.M.; Bruemmer, S.M.; Thomas, L.E.

1998-01-01

Internal oxidation has been proposed as a plausible mechanism for intergranular stress corrosion cracking (IGSCC) of alloy 600 steam generator tubing. This theory can reconcile the main thermodynamic and kinetic characteristics of the observed cracking in hydrogenated primary water. Although secondary side IG attack or IGSCC is commonly attributed to the presence of strong caustic or acidic solutions, more recent evidence suggests that this degradation takes place in a near-neutral environment, possibly dry polluted steam. As a result, internal oxidation is also a feasible mechanism for secondary side degradation. The present paper reviews experimental work carried out in an attempt to determine the validity of this mechanism. The consequences for the expected behaviour of alloys 690 and 800 replacement materials are also described. (author)

New approach for determination of the degradation products of fenspiride hydrochloride found in oral liquid formulations.

Science.gov (United States)

Cioroiu, Bogdan I; Caba, Ioana C; Prisăcaru, Irina; Cioroiu, Mona E; Lazar, Mihai I; Niculaua, Marius

2018-05-01

Fenspiride hydrochloride (FNS) is used in treating chronic inflammatory diseases, most commonly as a liquid oral solution. FNS produces degradation products along with fenspiride N-oxide (FNO) and 1-phenylethyl-4-hydroxy-4-aminomethyl piperidine hydrochloride (PHAP). We aimed to develop and validate a chromatographic method in order to identify the main degradation products in the presence of other compounds from a liquid preparation. The method used a dual gradient using two buffer solutions: the first with pH 4.5 (buffer 1, pH 4.5-MeOH 90:10%, v/v) and the second with pH 2.9 (buffer 2, pH 2.9-acetronitrile-methanol, 65:15:10%, v/v/v). As mentioned, there was a modification of the organic mixture, starting with 10% methanol and ending with a mixture of acetonitrile-methanol (15:10%, v/v). The flow-rate was 1.5 mL/min. According to the elution program, experimental conditions started with 100% solution S1, which decreased to 0% and, simultaneously, solution S2 increased to 100% during the first 10 min and was maintained for a further 5 min. After 15 min, initial conditions were re-established. The linearity interval was 0.5-2 μg/mL and the minimum correlation coefficient was 0.999. The recovery factor was 100.47-103.17% and the limit of quantification was 0.19-0.332 μg/mL. Intra-day maximum precision was 4.08% for FNS and 2.65% for PHAP. This double-gradient mobile phase produced good specificity in relation to the degradation products of FNS and other constituents of the oral liquid formulation. Forced degradation studies revealed other related substances that were confirmed in mass balance analyses. Degradation products were confirmed in acidic, basic and oxidative media. Copyright © 2017 John Wiley & Sons, Ltd.

Sinalbin degradation products in mild yellow mustard paste

Directory of Open Access Journals (Sweden)

Paunović Dragana

2012-01-01

Full Text Available Sinalbin degradation products in mild yellow mustard paste were investigated. The analyzed material consisted of a mild yellow mustard paste condiment and ground white mustard seeds which were originally used in the mustard paste production process. The samples were extracted in a Soxhlet extraction system and analyzed by gas chromatography - mass spectrometry (GC-MS technique. The only sinalbin degradation product in ground mustard seeds was 2-(4-hydroxyphenylacetonitrile. The most abundant sinalbin degradation product in yellow mustard paste was 4-(hydroxymethylphenol. Other compounds identified in this sample were: 4-methyl phenol, 4-ethyl phenol, 4-(2-hydroxyethylphenol and 2-(4-hydroxyphenyl ethanoic acid.

Quantitative review of degradation and lifetime of solid oxide cells and stacks

DEFF Research Database (Denmark)

Skafte, Theis Løye; Hjelm, Johan; Blennow, Peter

2016-01-01

A comprehensive review of degradation and lifetime for solid oxide cells and stacks hasbeen conducted. Based on more than 50 parameters from 150 publications and 1 000 000hours of accumulated testing, this paper presents a quantitative analysis of the currentinternational status of degradation...

21 CFR 864.7320 - Fibrinogen/fibrin degradation products assay.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Fibrinogen/fibrin degradation products assay. 864.7320 Section 864.7320 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN....7320 Fibrinogen/fibrin degradation products assay. (a) Identification. A fibrinogen/fibrin degradation...

Modeling Degradation in Solid Oxide Electrolysis Cells

Energy Technology Data Exchange (ETDEWEB)

Manohar S. Sohal; Anil V. Virkar; Sergey N. Rashkeev; Michael V. Glazoff

2010-09-01

Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic no equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential, , within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, no equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

Modelling the behaviour of organic degradation products

International Nuclear Information System (INIS)

Cross, J.E.; Ewart, F.T.; Greenfield, B.F.

1989-03-01

Results are presented from recent studies at Harwell which show that the degradation products which are formed when certain organic waste materials are exposed to the alkaline conditions typical of a cementitious environment, can enhance the solubility of plutonium, even at pH values as high as 12, by significant factors. Characterisation of the degradation products has been undertaken but the solubility enhancement does not appear to be related to the concentration of any of the major organic species that have been identified in the solutions. While it has not been possible to identify by analysis the organic ligand responsible for the increased solubility of plutonium, the behaviour of D-Saccharic acid does approach the behaviour of the degradation products. The PHREEQE code has been used to simulate the solubility of plutonium in the presence of D-Saccharic acid and other model degradation products, in order to explain the solubility enhancement. The extrapolation of the experimental conditions to the repository is the major objective, but in this work the ability of a model to predict the behaviour of plutonium over a range of experimental conditions has been tested. (author)

Zinc oxide tetrapods as efficient photocatalysts for organic pollutant degradation

Science.gov (United States)

Liu, Fangzhou; Leung, Yu Hang; Djurisić, Aleksandra B.; Liao, Changzhong; Shih, Kaimin

2014-03-01

Bisphenol A (BPA) and other organic pollutants from industrial wastewater have drawn increasing concern in the past decades regarding their environmental and biological risks, and hence developing strategies of effective degradation of BPA and other organic pollutants is imperative. Metal oxide nanostructures, in particular titanium oxide (TiO2) and zinc oxide (ZnO), have been demonstrated to exhibit efficient photodegradation of various common organic dyes. ZnO tetrapods are of special interest due to their low density of native defects which consequently lead to lower recombination losses and higher photocatalytic efficiency. Tetrapods can be obtained by relatively simple and low-cost vapor phase deposition in large quantity; the micron-scale size would also be advantageous for catalyst recovery. In this study, the photodegradation of BPA with ZnO tetrapods and TiO2 nanostructures under UV illumination were compared. The concentration of BPA dissolved in DI water was analyzed by high-performance liquid chromatography (HPLC) at specified time intervals. It was observed that the photocatalytic efficiency of ZnO tetrapods eventually surpassed Degussa P25 in free-standing form, and more than 80% of BPA was degraded after 60 min. Photodegradation of other organic dye pollutants by tetrapods and P25 were also examined. The superior photocatalytic efficiency of ZnO tetrapods for degradation of BPA and other organic dye pollutants and its correlation with the material properties were discussed.

Oxidative degradation of toluene and limonene in air by pulsed corona technology

NARCIS (Netherlands)

Hoeben, W.F.L.M.; Beckers, F.J.C.M.; Pemen, A.J.M.; Heesch, van E.J.M.; Kling, W.L.

2012-01-01

The oxidative degradation of two volatile organic compounds, i.e. toluene (fossil fuel based VOC) and limonene (biogenic VOC), has been studied. A hybrid pulsed power corona reactor with adjustable energy density has been utilized for degradation of ppm level target compounds in large air flows. The

Sulfate radical degradation of acetaminophen by novel iron-copper bimetallic oxidation catalyzed by persulfate: Mechanism and degradation pathways

Science.gov (United States)

Zhang, Yuanchun; Zhang, Qian; Hong, Junming

2017-11-01

A novel iron coupled copper oxidate (Fe2O3@Cu2O) catalyst was synthesized to activate persulfate (PS) for acetaminophen (APAP) degradation. The catalysts were characterized via field-emission scanning electron microscopy and energy-dispersive X-ray spectrometry. The effects of the catalyst, PS concentration, catalyst dosage, initial pH, dissolved oxygen were analyzed for treatment optimization. Results indicated that Fe2O3@Cu2O achieved higher efficiency in APAP degradation than Fe2O3/PS and Cu2O/PS systems. The optimal removal efficiency of APAP (90%) was achieved within 40 min with 0.6 g/L PS and 0.3 g/L catalyst. To clarify the mechanism for APAP degradation, intermediates were analyzed with gas chromatography-mass spectrometry. Three possible degradation pathways were identified. During reaction, Cu(I) was found to react with Fe(III) to generate Fe(II), which is the most active phase for PS activation. Through the use of methanol and tert-butyl alcohol (TBA) as radical trappers, SO4rad - was identified as the main radical species that is generated during oxidation.

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

Energy Technology Data Exchange (ETDEWEB)

Dang, Juan; Shi, Xiangli; Zhang, Qingzhu, E-mail: zqz@sdu.edu.cn; Hu, Jingtian; Wang, Wenxing

2015-02-01

Chlorinated polycyclic aromatic hydrocarbons (ClPAHs) have become a serious environmental concern due to their widespread occurrence and dioxin-like toxicities. In this work, the mechanism of the OH-initiated atmospheric oxidation degradation of 9,10-dichlorophenanthrene (9,10-Cl{sub 2}Phe) was investigated by using high-accuracy quantum chemistry calculations. The rate constants of the crucial elementary reactions were determined by the Rice–Ramsperger–Kassel–Marcus (RRKM) theory. The theoretical results were compared with the available experimental data. The main oxidation products are a group of ring-retaining and ring-opening compounds including chlorophenanthrols, 9,10-dichlorophenanthrene-3,4-dione, dialdehydes, chlorophenanthrenequinones, nitro-9,10-Cl{sub 2}Phe and epoxides et al. The overall rate constant of the OH addition reaction is 2.35 × 10{sup −12} cm{sup 3} molecule{sup −1} s{sup −1} at 298 K and 1 atm. The atmospheric lifetime of 9,10-Cl{sub 2}Phe determined by OH radicals is about 5.05 days. This study provides a comprehensive investigation of the OH-initiated oxidation degradation of 9,10-Cl{sub 2}Phe and should contribute to clarifying its atmospheric fate. - Highlights: • We studied a comprehensive mechanism of OH-initiated degradation of 9,10-Cl{sub 2}Phe. • The atmospheric lifetime of 9,10-Cl{sub 2}Phe determined by OH radical is about 5.05 d. • The rate constants of the crucial elementary steps were evaluated. • Water plays an important role in the formation of nitro-9,10-Cl{sub 2}Phe.

Vitamin C Degradation Products and Pathways in the Human Lens*

OpenAIRE

Nemet, Ina; Monnier, Vincent M.

2011-01-01

Vitamin C and its degradation products participate in chemical modifications of proteins in vivo through non-enzymatic glycation (Maillard reaction) and formation of different products called advanced glycation end products. Vitamin C levels are particularly high in selected tissues, such as lens, brain and adrenal gland, and its degradation products can inflict substantial protein damage via formation of advanced glycation end products. However, the pathways of in vivo vitamin C degradation ...

Oxidation Degradation Study And Use Of Phenol And Amina Antioxidant Compounds In Natural Rubber Cyclical

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Arofah Megasari Siregar

2015-08-01

Full Text Available The research was conducted research into the use of commercial antioxidants Irganox 1010 wingstay to inhibit the oxidative degradation of cyclic polymers of natural rubber and polypropylene nanocomposite with commercial montmorillonite PP MMT-Clay. Proces mixing nanocomposit PPMMT using commercial compatibiliser PP-g-MA PB3200 made in an internal mixer at a temperature of 180 C for 10 minutes and 65 rpm rotor speed. Hyndered phenol antioxidant effectiveness was analyzed using Fourier Transform Infra Red FTIR. Analysis of infrared is done by measuring the broad index absorption of the carbonyl group CO at a wavelength of 1700 cm-1 and a broad index uptake hydroxyl group at a wavelength of 3400 cm-1 before and after heated in an oven temperature of 125oC with variations in exposure time. The results indicate the use of antioxidant Irganox 1010 in nanocomposite PP MMT with a stabilizing factor of 5.5. Further commercial antioxidants will be used to restrain the rate of oxidation degradation of the natural rubber products cyclical CNR.

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

Science.gov (United States)

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

2014-12-01

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

New porous titanium–niobium oxide for photocatalytic degradation of bromocresol green dye in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Chaleshtori, Maryam Zarei, E-mail: mzarei@utep.edu [Materials Research and Technology Institute (MRTI), University of Texas at El Paso, 500W. University Ave., El Paso, TX 79968 (United States); Hosseini, Mahsa; Edalatpour, Roya [Materials Research and Technology Institute (MRTI), University of Texas at El Paso, 500W. University Ave., El Paso, TX 79968 (United States); Masud, S.M. Sarif [Department of Chemistry, University of Texas at El Paso, 500W. University Ave., El Paso, TX 79968 (United States); Chianelli, Russell R., E-mail: chianell@utep.edu [Materials Research and Technology Institute (MRTI), University of Texas at El Paso, 500W. University Ave., El Paso, TX 79968 (United States)

2013-10-15

Graphical abstract: The photocatalytic activity of different porous titanium–niobium oxides was evaluated toward degradation of bromocresol green (BG) under UV light. A better catalytic activity was observed for all samples at lower pH. Catalysts have a stronger ability for degradation of BG in acid media than in alkaline media. - Highlights: • Different highly structured titanium–niobium oxides have been prepared using improved methods of synthesis. • Photo-degradation of bromocresol green dye (BG) with nanostructure titanium–niobium oxide catalysts was carried out under UV light. • The photo-catalytic activity of all catalysts was higher in lower pH. • Titanium–niobium oxide catalysts are considerably stable and reusable. - Abstract: In this study, high surface area semiconductors, non porous and porous titanium–niobium oxides derived from KTiNbO{sub 5} were synthesized, characterized and developed for their utility as photocatalysts for decontamination with sunlight. These materials were then used in the photocatalytic degradation of bromocresol green dye (BG) in aqueous solution using UV light and their catalytic activities were evaluated at various pHs. For all catalysts, the photocatalytic degradation of BG was most efficient in acidic solutions. Results show that the new porous oxides have large porous and high surface areas and high catalytic activity. A topotactic dehydration treatment greatly improves catalyst performance at various pHs. Stability and long term activity of porous materials (topo and non-topo) in photocatalysis reactions was also tested. These results suggest that the new materials can be used to efficiently purify contaminated water.

Anthocyanins degradation during storage of Hibiscus sabdariffa extract and evolution of its degradation products.

Science.gov (United States)

Sinela, André; Rawat, Nadirah; Mertz, Christian; Achir, Nawel; Fulcrand, Hélène; Dornier, Manuel

2017-01-01

Degradation parameters of two main anthocyanins from roselle extract (Hibiscus sabdariffa L.) stored at different temperatures (4-37°C) over 60days were determined. Anthocyanins and some of their degradation products were monitored and quantified using HPLC-MS and DAD. Degradation of anthocyanins followed first-order kinetics and reaction rate constants (k values), which were obtained by non-linear regression, showed that the degradation rate of delphinidin 3-O-sambubioside was higher than that of cyanidin 3-O-sambubioside with k values of 9.2·10(-7)s(-1) and 8.4·10(-7)s(-1) at 37°C respectively. The temperature dependence of the rate of anthocyanin degradation was modeled by the Arrhenius equation. Degradation of delphinidin 3-O-sambubioside (Ea=90kJmol(-1)) tended to be significantly more sensitive to an increase in temperature than cyanidin 3-O-sambubioside (Ea=80kJmol(-1)). Degradation of these anthocyanins formed scission products (gallic and protocatechuic acids respectively) and was accompanied by an increase in polymeric color index. Copyright © 2016 Elsevier Ltd. All rights reserved.

Identification of degradation products of ionic liquids in an ultrasound assisted zero-valent iron activated carbon micro-electrolysis system and their degradation mechanism.

Science.gov (United States)

Zhou, Haimei; Lv, Ping; Shen, Yuanyuan; Wang, Jianji; Fan, Jing

2013-06-15

Ionic liquids (ILs) have potential applications in many areas of chemical industry because of their unique properties. However, it has been shown that the ILs commonly used to date are toxic and not biodegradable in nature, thus development of efficient chemical methods for the degradation of ILs is imperative. In this work, degradation of imidazolium, piperidinium, pyrrolidinium and morpholinium based ILs in an ultrasound and zero-valent iron activated carbon (ZVI/AC) micro-electrolysis system was investigated, and some intermediates generated during the degradation were identified. It was found that more than 90% of 1-alkyl-3-methylimidazolium bromide ([Cnmim]Br, n = 2, 4, 6, 8, 10) could be degraded within 110 min, and three intermediates 1-alkyl-3-methyl-2,4,5-trioxoimidazolidine, 1-alkyl-3-methylurea and N-alkylformamide were detected. On the other hand, 1-butyl-1-methylpiperidinium bromide ([C4mpip]Br), 1-butyl-1-methylpyrrolidinium bromide ([C4mpyr]Br) and N-butyl-N-methylmorpholinium bromide ([C4mmor]Br) were also effectively degraded through the sequential oxidization into hydroxyl, carbonyl and carboxyl groups in different positions of the butyl side chain, and then the N-butyl side chain was broken to form the final products of N-methylpiperidinium, N-methylpyrrolidinium and N-methylmorpholinium, respectively. Based on these intermediate products, degradation pathways of these ILs were suggested. These findings may provide fundamental information on the assessment of the factors related to the environmental fate and environmental behavior of these commonly used ILs. Copyright © 2013 Elsevier Ltd. All rights reserved.

DI-(2-ETHYLHEXYL PHTHALATE OXIDATIVE DEGRADATION BY FENTON PROCESS IN SYNTHETIC AND REAL PETROCHEMICAL WASTEWATER

Directory of Open Access Journals (Sweden)

R. Esmaeli

2011-09-01

Full Text Available Di-(2-Ethylhexyl phthalate (DEHP belongs to the class of phthalate esters and is used as an additive in many products including plastics, paints and inks or as a solvent in industrial formulations. The degradation of DEHP in aqueous solution using oxidative Fenton reaction (H2O2/Fe2+ was carried out in this study. It was found that H2O2 concentration, Fe2+ concentration, and pH were the three main factors that could significantly influence the degradation rates of DEHP. The highest degradation percentage (85.6 % of DEHP was observed within 60 min at pH 3 in H2O2/Fe2+ system. The results of our study suggested that the concentration with 90 mg/L H2O2, 5 mg/L Fe2+, and 20 mg/L DEHP in the solution at pH 3 were the optimal conditions. The optimized reaction parameters were preceded for treatment of real wastewater obtained from a petrochemical plant.

Degradation of zinc oxide thin films in aqueous environment. Pt. II. Coated films

Energy Technology Data Exchange (ETDEWEB)

Rosa, L. de; Mitton, D.B.; Monetta, T.; Bellucci, F. [Naples Univ. (Italy). Dept. of Materials and Production Engineering; Springer, J. [Zentrum fuer Sonnenenergie- und Wasserstoff-Forschung Baden-Wuerttemberg (ZSW), Stuttgart (Germany)

2001-12-01

cn Part I of this research, the degradation mechanism of two different bare ZnO thin films was assessed. Degradation of the electrical properties of ZnO as well as changes in morphology were observed for both films. In the current paper, the degradation of zinc oxide thin films coated with protective acrylic paint is addressed during exposure to (i) an aqueous 3.5% NaCl solution at 85 C and (ii) a standard damp heat test at 85% R.H. and 85 C. Electrical and electrochemical techniques were employed to monitor zinc oxide degradation during exposure to the test environments. Electrochemical Impedance Spectroscopy was employed to investigate the delamination phenomena at the ZnO/coating interface and a simple equivalent circuit was developed to quantitatively measure the delamination ratio. The effect of different silane based adhesion promoters (glycidil-oxypropyl-trimethoxy-silane and aminopropyl-trimethoxy-silane) was also investigated. (orig.)

Insights into lignin degradation and its potential industrial applications.

Science.gov (United States)

Abdel-Hamid, Ahmed M; Solbiati, Jose O; Cann, Isaac K O

2013-01-01

Lignocellulose is an abundant biomass that provides an alternative source for the production of renewable fuels and chemicals. The depolymerization of the carbohydrate polymers in lignocellulosic biomass is hindered by lignin, which is recalcitrant to chemical and biological degradation due to its complex chemical structure and linkage heterogeneity. The role of fungi in delignification due to the production of extracellular oxidative enzymes has been studied more extensively than that of bacteria. The two major groups of enzymes that are involved in lignin degradation are heme peroxidases and laccases. Lignin-degrading peroxidases include lignin peroxidase (LiP), manganese peroxidase (MnP), versatile peroxidase (VP), and dye-decolorizing peroxidase (DyP). LiP, MnP, and VP are class II extracellular fungal peroxidases that belong to the plant and microbial peroxidases superfamily. LiPs are strong oxidants with high-redox potential that oxidize the major non-phenolic structures of lignin. MnP is an Mn-dependent enzyme that catalyzes the oxidation of various phenolic substrates but is not capable of oxidizing the more recalcitrant non-phenolic lignin. VP enzymes combine the catalytic activities of both MnP and LiP and are able to oxidize Mn(2+) like MnP, and non-phenolic compounds like LiP. DyPs occur in both fungi and bacteria and are members of a new superfamily of heme peroxidases called DyPs. DyP enzymes oxidize high-redox potential anthraquinone dyes and were recently reported to oxidize lignin model compounds. The second major group of lignin-degrading enzymes, laccases, are found in plants, fungi, and bacteria and belong to the multicopper oxidase superfamily. They catalyze a one-electron oxidation with the concomitant four-electron reduction of molecular oxygen to water. Fungal laccases can oxidize phenolic lignin model compounds and have higher redox potential than bacterial laccases. In the presence of redox mediators, fungal laccases can oxidize non

Oxidative degradation stability and hydrogen sulfide removal performance of dual-ligand iron chelate of Fe-EDTA/CA.

Science.gov (United States)

Miao, Xinmei; Ma, Yiwen; Chen, Zezhi; Gong, Huijuan

2017-09-05

Catalytic oxidation desulfurization using chelated iron catalyst is an effective method to remove H 2 S from various gas streams including biogas. However, the ligand of ethylenediaminetetraacetic acid (EDTA), which is usually adopted to prepare chelated iron catalyst, is liable to be oxidative degraded, and leads to the loss of desulfurization performance. In order to improve the degradation stability of the iron chelate, a series of iron chelates composed of two ligands including citric acid (CA) and EDTA were prepared and the oxidative degradation stability as well as desulfurization performance of these chelated iron catalysts were studied. Results show that the iron chelate of Fe-CA is more stable than Fe-EDTA, while for the desulfurization performance, the situation is converse. For the dual-ligand iron chelates of Fe-EDTA/CA, with the increase of mol ratio of CA to EDTA in the iron chelate solution, the oxidative degradation stability increased while the desulfurization performance decreased. The results of this work showed that Fe-EDTA/CA with a mol ratio of CA:EDTA = 1:1 presents a relative high oxidative degradation stability and an acceptable desulfurization performance with over 90% of H 2 S removal efficiency.

Identification and characterization of epoxide hydrolase activity of polycyclic aromatic hydrocarbon-degrading bacteria for biocatalytic resolution of racemic styrene oxide and styrene oxide derivatives.

Science.gov (United States)

Woo, Jung-Hee; Kwon, Tae-Hyung; Kim, Jun-Tae; Kim, Choong-Gon; Lee, Eun Yeol

2013-04-01

A novel epoxide hydrolase (EHase) from polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was identified and characterized. EHase activity was identified in four strains of PAH-degrading bacteria isolated from commercial gasoline and oil-contaminated sediment based on their growth on styrene oxide and its derivatives, such as 2,3- and 4-chlorostyrene oxides, as a sole carbon source. Gordonia sp. H37 exhibited high enantioselective hydrolysis activity for 4-chlorostyrene oxide with an enantiomeric ratio of 27. Gordonia sp. H37 preferentially hydrolyzed the (R)-enantiomer of styrene oxide derivatives resulting in the preparation of a (S)-enantiomer with enantiomeric excess greater than 99.9 %. The enantioselective EHase activity was identified and characterized in various PAH-degrading bacteria, and whole cell Gordonia sp. H37 was employed as a biocatalyst for preparing enantiopure (S)-styrene oxide derivatives.

Chromatographic determination of itopride hydrochloride in the presence of its degradation products.

Science.gov (United States)

Kaul, Neeraj; Agrawal, Himani; Maske, Pravin; Rao, Janhavi Ramchandra; Mahadik, Kakasaheb Ramoo; Kadam, Shivajirao S

2005-08-01

Two sensitive and reproducible methods are described for the quantitative determination of itopride hydrochloride (IH) in the presence of its degradation products. The first method is based on HPLC separation on a reversed phase Kromasil column [C18 (5-microm, 25 cm x 4.6 mm, ID)] at ambient temperature using a mobile phase consisting of methanol and water (70:30, v/v) adjusted to pH 4.0 with orthophosphoric acid with UV detection at 258 nm. The flow rate was 1.0 mL per min with an average operating pressure of 180 kg/cm2. The second method is based on HPTLC separation on silica gel 60 F254 using toluene:methanol:chloroform:10% ammonia (5.0:3.0:6.0:0.1, v/v/v/v) as mobile phase at 270 nm. The analysis of variance (ANOVA) and Student's t-test were applied to correlate the results of IH determination in dosage form by means of HPLC and HPTLC methods. The drug was subjected to acid and alkali hydrolysis, oxidation, dry heat, wet heat treatment, UV, and photodegradation. The proposed HPLC method was utilized to investigate the kinetics of the acidic, alkaline, and oxidative degradation processes at different temperatures and the apparent pseudo-first-order rate constant, half-life, and activation energy were calculated. In addition the pH-rate profile of degradation of IH in constant ionic strength buffer solutions in the pH range 2-11 was studied.

Photocatalytic Degradation of Malachite Green Using Nano-sized cerium-iron Oxide

Directory of Open Access Journals (Sweden)

K. L. Ameta

2014-05-01

Full Text Available Nano-sized cerium-iron oxide nanoparticles has been synthesized, characterized and explored as an efficient photocatalyst for the photocatalytic degradation of malachite green. The effects of different variables on degradation of dye were optimized such as the pH of the dye solution, dye concentration, amount of photocatalyst and light intensity. About 91% degradation of dye of 2×10-5 M concentration was observed after 2 hours at 8.5 pH and 600 Wm-2 light intensity. The reason for the high catalytic activity of the synthesized nanoparticles is ascribed to the high surface area which determines the active sites of the catalyst and accelerates the photocatalytic degradation.

ESI-MSn and LC-ESI-MS studies to characterize forced degradation products of bosentan and a validated stability-indicating LC-UV method.

Science.gov (United States)

Bansal, Gulshan; Singh, Ranjit; Saini, Balraj; Bansal, Yogita

2013-01-01

The present study reports the characterization of forced degradation products of bosentan and a validated stability-indicating HPLC method for the stability testing of bosentan tablets. The forced degradation was carried out under the conditions of hydrolysis, oxidation, dry heat and photolysis. The drug was found unstable in acid, alkali and oxidative media whereas stable to the hydrolysis in water, to dry heat and to photolysis. In total, six degradation products were formed in all conditions which were resolved in a single run on a C-18 column with gradient elution using ammonium acetate buffer (pH 4.5, 5.0mM), methanol and acetonitrile. Structures of all the degradation products were characterized through +ESI-MS(n) and LC-ESI-MS spectral data of bosentan as well as LC-ESI-MS spectral data of the products. The products II-VI were characterized as 6-amino-[2,2']bipyrimidinyl-4,5-diol, 6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-ol, 2-[6-amino-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yloxy]-ethanol, 4-tert-butyl-N-[6-(1-methoxyethoxy)-5-(2-methoxyphenoxy)-[2,2']-bipyrimidinyl-4-yl]-benzenesulfonamide and 4-tert-butyl-N-[6-hydroxy-5-(2-methoxyphenoxy)-[2,2']bipyrimidinyl-4-yl]-benzenesulfonamide, respectively. The peak of the product I was found to be due to two secondary degradation products which co-eluted and were characterized as β-hydroxyethyl p-tert-butylphenylsulfonate (Ia) and 2-[2-(2-hydroxyethoxy)-phenoxy]-ethanol (Ib). These products were formed due to hydrolysis of sulfonamide and alkylaryl ether and the diaryl ether linkages as well as dehydration of the primary alcohol group. The most probable degradation mechanisms were proposed. The HPLC method was found to be stability-indicating, linear (2-100 μg ml(-1)), accurate, precise, sensitive, specific, rugged and robust for quantitation of the drug. The method was applied to the stability testing of the commercially available bosentan tablets successfully. Copyright © 2012 Elsevier B.V. All

Characterization of Methane Degradation and Methane-Degrading Microbes in Alaska Coastal Water

Energy Technology Data Exchange (ETDEWEB)

Kirchman, David L. [Univ. of Delaware, Lewes, DE (United States)

2012-03-29

The net flux of methane from methane hydrates and other sources to the atmosphere depends on methane degradation as well as methane production and release from geological sources. The goal of this project was to examine methane-degrading archaea and organic carbon oxidizing bacteria in methane-rich and methane-poor sediments of the Beaufort Sea, Alaska. The Beaufort Sea system was sampled as part of a multi-disciplinary expedition (Methane in the Arctic Shelf or MIDAS) in September 2009. Microbial communities were examined by quantitative PCR analyses of 16S rRNA genes and key methane degradation genes (pmoA and mcrA involved in aerobic and anaerobic methane degradation, respectively), tag pyrosequencing of 16S rRNA genes to determine the taxonomic make up of microbes in these sediments, and sequencing of all microbial genes (metagenomes ). The taxonomic and functional make-up of the microbial communities varied with methane concentrations, with some data suggesting higher abundances of potential methane-oxidizing archaea in methane-rich sediments. Sequence analysis of PCR amplicons revealed that most of the mcrA genes were from the ANME-2 group of methane oxidizers. According to metagenomic data, genes involved in methane degradation and other degradation pathways changed with sediment depth along with sulfate and methane concentrations. Most importantly, sulfate reduction genes decreased with depth while the anaerobic methane degradation gene (mcrA) increased along with methane concentrations. The number of potential methane degradation genes (mcrA) was low and inconsistent with other data indicating the large impact of methane on these sediments. The data can be reconciled if a small number of potential methane-oxidizing archaea mediates a large flux of carbon in these sediments. Our study is the first to report metagenomic data from sediments dominated by ANME-2 archaea and is one of the few to examine the entire microbial assemblage potentially involved in

Properties of photocatalytically generated oxygen species produced by Ag2Se-graphene oxide heterojunction and its application for the visible-light degradation of ammonia

Science.gov (United States)

Meng, Ze-Da; Zhao, Wei; Kim, Sukyoung

2017-11-01

Reactive oxygen species (ROS) can be produced by the interactions between sunlight and light-absorbing substances in aqueous environments, and these ROS are capable of destroying various organic pollutants in wastewater. In this study, the photocatalytic degradation of ammonia in petrochemical wastewater was investigated by solar light photocatalysis. We used graphene oxide modified Ag2Se nanoparticles to enhance the activity of photochemically generated oxygen (PGO) species. There was a catastrophic decrease in the surface area and pore volume of the Ag2Se-graphene oxide (Ag2Se-G) samples because of the deposition of Ag2Se. The generation of ROS was detected by the oxidation of 1,5- diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). It was revealed that the photocurrent density and PGO effect increased with the graphene oxide modified. The experimental results indicate that this heterogeneous catalyst achieved a degradation of 88.43% under visiblelight irradiation. The NH3 degradation product was N2 and neither NO2- nor NO3- were detected.[Figure not available: see fulltext.

Oxidation of ciprofloxacin and enrofloxacin by ferrate(VI): Products identification, and toxicity evaluation

International Nuclear Information System (INIS)

Yang, Bin; Kookana, Rai S.; Williams, Mike; Ying, Guang-Guo; Du, Jun; Doan, Hai; Kumar, Anupama

2016-01-01

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters.

Oxidation of ciprofloxacin and enrofloxacin by ferrate(VI): Products identification, and toxicity evaluation

Energy Technology Data Exchange (ETDEWEB)

Yang, Bin, E-mail: Bin.Yang@csiro.au [CSIRO Land and Water, Waite Campus, PMB 2, Glen Osmond, South Australia 5064 (Australia); Kookana, Rai S.; Williams, Mike [CSIRO Land and Water, Waite Campus, PMB 2, Glen Osmond, South Australia 5064 (Australia); Ying, Guang-Guo [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Du, Jun; Doan, Hai; Kumar, Anupama [CSIRO Land and Water, Waite Campus, PMB 2, Glen Osmond, South Australia 5064 (Australia)

2016-12-15

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters.

ANALYSIS OF THE FLUX OF AN ENDOCRINE DISRUPTING DICARBOXIMIDE AND ITS DEGRADATION PRODUCTS FROM THE SOIL TO THE LOWER TROPOSPHERE

Science.gov (United States)

A method for measuring the atmospheric flux of the antiandrogenic dicarboxirnide, vinclozolin, and its degradation products was investigated. A nitric oxide laboratory chamber was modified to measure the flux of semi-volatile compounds. Pesticide application systems and soil in...

Sinalbin degradation products in mild yellow mustard paste

OpenAIRE

Paunović, Dragana; Šolević-Knudsen, Tatjana; Krivokapić, Mirjana; Zlatković, Branislav; Antić, Mališa

2012-01-01

Sinalbin degradation products in mild yellow mustard paste were investigated. The analyzed material consisted of a mild yellow mustard paste condiment and ground white mustard seeds which were originally used in the mustard paste production process. The samples were extracted in a Soxhlet extraction system and analyzed by gas chromatography - mass spectrometry (GC-MS) technique. The only sinalbin degradation product in ground mustard seeds was 2-(4-hydroxyphenyl)acetonitrile. The most a...

COMPARISON OF DIFFERENT ADVANCED OXIDATION PROCESSES DEGRADING P-CHLOROPHENOL IN AQUEOUS SOLUTION

Directory of Open Access Journals (Sweden)

H. Movahedyan ، A. M. Seid Mohammadi ، A. Assadi

2009-07-01

Full Text Available In present study, degradation of p-chlorophenol using several oxidation systems involving advanced oxidation processes such as ultraviolet/H2O2, microwave/H2O2 and both in the absence of hydrogen peroxide in batch mode by photolytic pilot plant and modified domestic microwave oven was evaluated. The oxidation rate was influenced by many factors, such as the pH value, the amount of hydrogen peroxide, irradiation time and microwave power. The optimum conditions obtained for the best degradation rate were pH=7 and H2O2 concentration of 0.05 mol/L for ultraviolet/H2O2 system and pH=10.5, H2O2 concentration of about 0.1 mol/L and microwave irradiation power of about 600W for microwave/H2O2 system at constant p-chlorophenol concentration. The degradation of p-chlorophenol by different types of oxidation processes followed first order rate decay kinetics. The rate constants were 0.137, 0.012, 0.02 and 0.004/min1 for ultraviolet/H2O2, microwave/H2O2, ultraviolet and microwave irradiation alone. Finally a comparison of the specific energy consumption showed that ultraviolet/H2O2 process reduced the energy consumption by at least 67% compared with the microwave/H2O2 process.

Degradation of fluoroquinolone antibiotics during ionizing radiation treatment and assessment of antibacterial activity, toxicity and biodegradability of the products

Science.gov (United States)

Tegze, Anna; Sági, Gyuri; Kovács, Krisztina; Homlok, Renáta; Tóth, Tünde; Mohácsi-Farkas, Csilla; Wojnárovits, László; Takács, Erzsébet

2018-06-01

This work aimed at investigating the ionizing radiation induced degradation of two fluoroquinolone antibiotics: norfloxacin and ciprofloxacin. At 0.1 mmol dm-3 concentration a low dose, 2 kGy was sufficient to degrade the initial molecules. However, despite of the high removal efficiency the degrees of both the mineralization and the oxidation were low, ∼10% and ∼25%, respectively. (The difference between the results obtained in norfloxacin and ciprofloxacin solutions was not statistically significant.) Broth microdilution tests carried out on Staphylococcus aureus evidenced removal of antibacterial activity in samples irradiated with 2 kGy. Acute toxicity determined on Vibrio fischeri bacteria showed increased toxicity at low doses indicating that the early degradation products were more toxic than the initial molecules. The results of biodegradation experiments performed in activated sludge have shown that the degradation products have become available to the metabolic processes of the microorganisms.

How do polymers degrade?

Science.gov (United States)

Lyu, Suping

2011-03-01

Materials derived from agricultural products such as cellulose, starch, polylactide, etc. are more sustainable and environmentally benign than those derived from petroleum. However, applications of these polymers are limited by their processing properties, chemical and thermal stabilities. For example, polyethylene terephthalate fabrics last for many years under normal use conditions, but polylactide fabrics cannot due to chemical degradation. There are two primary mechanisms through which these polymers degrade: via hydrolysis and via oxidation. Both of these two mechanisms are related to combined factors such as monomer chemistry, chain configuration, chain mobility, crystallinity, and permeation to water and oxygen, and product geometry. In this talk, we will discuss how these materials degrade and how the degradation depends on these factors under application conditions. Both experimental studies and mathematical modeling will be presented.

Chromium related degradation of solid oxide fuel cells; Chrom-bezogene Degradation von Festoxid-Brennstoffzellen

Energy Technology Data Exchange (ETDEWEB)

Neumann, Anita

2011-05-04

Solid Oxide Fuel Cells (SOFCs) offer a high potential for application as an auxiliary power unit (APU) for heavy goods vehicles as well as combined heat and power (CHP) systems. SOFCs are especially attractive due to their high efficiencies and the use of different fuel types. However, optimization in terms of long term stability and costs are still necessary. This work characterized the degradation of SOFCs with lanthanum strontium manganite (LSM) cathodes under chromium influence. Galvanostatic cell tests were carried out at 800 C with operation times from 250 - 3000 h and variation of the chromium source and current density. The current densities of j = 0 (A)/(cm{sup 2}), j = 0,3 (A)/(cm{sup 2}) and j = 0,5 (A)/(cm{sup 2}) were applied. The high temperature ferritic alloy Crofer22APU was used as a chromium source. Variation of the chromium source was realized by coating the Crofer22APU insert with the chromium retention layer Mn{sub 3}O{sub 4} and the cathode contact layer LCC10. Cell degradation was analyzed with regard to cell voltage, current density and area specific resistance (ASR). Microstructural alterations of the cathode as well as chromium content and distribution across the cell were investigated after completion of the cell tests. For cells with a chromium source present and operation with a nonzero current density, the course of cell degradation was divided into three phases: a run-in, weak linear degradation and strong linear degradation. A decrease of the chromium release rate by means of different coatings stretched the course of degradation along the timescale. Strong degradation, which is characterized by a significant increase in ASR as well as a decrease of current density at the operating point, was only observed when a chromium source in the setup was comb ined with operation of the cell with a non-zero current density. Operation of the cell with a chromium source but no current density caused a degradation of current density at the

Charcoal production and environmental degradation

International Nuclear Information System (INIS)

Hosier, R.H.

1993-01-01

This paper examines the environmental impacts of continued tree harvesting for charcoal production to supply the urban areas in Tanzania. Woodlands appear to recover relatively well following harvesting for charcoal production. Selective harvesting, where the high quality, low cost fuel production species and specimens are culled first from a piece of land, serves to maintain the viability of the woodlands resource while providing charcoal. This recovery period can be prolonged through any number of human induced activities, such as heavy grazing, multiple burns and extended cultivation periods. At the same time, post-harvest management techniques, such as coppice management, sprout protection and fertilization, can also improve the ability of woodlands to recover following harvesting. The environmental history of a given area determines why certain areas continue to be strong suppliers of woodfuel while others are not. For example, Shinyanga started from a low productivity base and has been degraded by successive waves of tree harvesting compounded by heavy grazing pressure. It is this multiple complex of pressures over a long period of time on land which is intrinsically of low productivity, and not the harvesting of woodlands for fuels, which has led to the environmental degradation in these areas. (author)

Photocatalytic degradation and photo-Fenton oxidation of Congo red dye pollutants in water using natural chromite—response surface optimization

Science.gov (United States)

Shaban, Mohamed; Abukhadra, Mostafa R.; Ibrahim, Suzan S.; Shahien, Mohamed. G.

2017-12-01

Refined natural Fe-chromite was characterized by XRD, FT-IR, reflected polarized microscope, XRF and UV spectrophotometer. Photocatalytic degradation and photo-Fenton oxidation of Congo red dye by Fe-chromite was investigated using 1 mL H2O2. The degradation of dye was studied as a function of illumination time, chromite mass, initial dye concentration, and pH. Fe-chromite acts as binary oxide system from chromium oxide and ferrous oxide. Thus, it exhibits photocatalytic properties under UV illumination and photo-Fenton oxidation after addition of H2O2. The degradation in the presence of H2O2 reached the equilibrium stage after 8 h (59.4%) but in the absence of H2O2 continued to 12 h (54.6%). Photocatalytic degradation results fitted well with zero, first order and second order kinetic model but it represented by second order rather than by the other models. While the photo-Fenton oxidation show medium fitting with the second order kinetic model only. The values of kinetic rate constants for the photo-Fenton oxidation were greater than those for the photocatalytic degradation. Thus, degradation of Congo red dye using chromite as catalyst is more efficient by photo-Fenton oxidation. Based on the response surface analysis, the predicted optimal conditions for maximum removal of Congo red dye by photocatalytic degradation (100%) were 12 mg/l, 0.14 g, 3, and 11 h for dye concentration, chromite mass, pH, and illumination time, respectively. Moreover, the optimum condition for photo-Fenton oxidation of dye (100%) is 13.5 mg/l, 0.10 g, 4, and 10 h, respectively.

Decomposition of clofibric acid in aqueous media by advance oxidation techniques: kinetics study and degradation pathway

International Nuclear Information System (INIS)

Syed, M.; Khan, A.M.; Khan, R.A.

2016-01-01

This study investigates the decomposition of clofibric acid (CLF) by different advanced oxidation processes (AOPs), such as UV (254 nm), VUV (185 nm), UV / TiO/sub 2/ and VUV / TiO/sub 2/. The removal efficiencies of applied AOPs were compared in the presence and absence of dissolved oxygen. The removal efficiency of the studied AOPs towards degradation of CLF were found in the order of VUV / TiO/sub 2/ + O/sub 2/ > VUV/TiO/sub 2/ + N/sub 2/ > VUV alone > UV / TiO/sub 2/ + O/sub 2/ > UV / TiO/sub 2/ +N/sub 2/ > UV alone. The decomposition kinetics of CLF was found to follow pseudo-first order rate law. VUV / TiO2 process was found to be most cheap and effective one for decomposition of CLF as compared to other applied AOPs in terms of electrical energy per order. Degradation products resulting from the degradation processes were also investigated using UPLC-MS /MS, accordingly degradation pathway was proposed. (author)

Mesoporous cerium oxide nanospheres for the visible-light driven photocatalytic degradation of dyes

Directory of Open Access Journals (Sweden)

Subas K. Muduli

2014-04-01

Full Text Available A facile, solvothermal synthesis of mesoporous cerium oxide nanospheres is reported for the purpose of the photocatalytic degradation of organic dyes and future applications in sustainable energy research. The earth-abundant, relatively affordable, mixed valence cerium oxide sample, which consists of predominantly Ce7O12, has been characterized by powder X-ray diffraction, X-ray photoelectron and UV–vis spectroscopy, and transmission electron microscopy. Together with N2 sorption experiments, the data confirms that the new cerium oxide material is mesoporous and absorbs visible light. The photocatalytic degradation of rhodamin B is investigated with a series of radical scavengers, suggesting that the mechanism of photocatalytic activity under visible-light irradiation involves predominantly hydroxyl radicals as the active species.

Effects of fungal degradation on the CuO oxidation products of lignin: A controlled laboratory study

Science.gov (United States)

Hedges, John I.; Blanchette, Robert A.; Weliky, Karen; Devol, Allan H.

1988-11-01

Duplicate samples of birch wood were degraded for 0, 4, 8 and 12 weeks by the white-rot fungus, Phlebia tremellosus, and for 12 weeks by 6 other white-rot and brown-rot fungi. P. tremellosus caused progressive weight losses and increased the H/C and O/C of the remnant wood by preferentially degrading the lignin component of the middle lamellae. This fungus increased the absolute (weight loss-corrected) yield of the vanillic acid CuO reaction product above its initial level and exponentially decreased the absolute yields of all other lignin-derived phenols. Total yields of syringyl phenols were decreased 1.5 times as fast as total vanillyl phenol yields. Within both phenol families, aldehyde precursors were degraded faster than precursors of the corresponding ketones, which were obtained in constant proportion to the total phenol yield. Although two other white-rot fungi caused similar lignin compositional trends, a fourth white-rot species, Coriolus versicolor, simultaneously eroded all cell wall components and did not concentrate polysaccharides in the remnant wood. Wood degraded by the three brown-rot fungi exhibited porous cell walls with greatly reduced integrity. The brown-rot fungi also preferentially attacked syringyl structural units, but degraded all phenol precursors at a much slower rate than the white-rotters and did not produce excess vanillic acid. Degradation by P. tremellosus linearly increased the vanillic acid/vanillin ratio, (Ad/Al)v, of the remnant birch wood throughout the 12 week degradation study and exponentially decreased the absolute yields of total vanillyl phenols, total syringyl phenols and the syringyl/vanillyl phenol ratio, S/V. At the highest (Ad/Al)v of 0.50 (12 week samples), total yields of syringyl and vanillyl phenols were decreased by 65% and 80%, respectively, with a resulting reduction of 40% in the original S/V. Many of the diagenetically related compositional trends that have been previously reported for lignins in natural

Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

Science.gov (United States)

Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

2016-01-01

Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

Rare earth oxide-doped titania nanocomposites with enhanced photocatalytic activity towards the degradation of partially hydrolysis polyacrylamide

International Nuclear Information System (INIS)

Li Jinhuan; Yang Xia; Yu Xiaodan; Xu, Leilei; Kang Wanli; Yan Wenhua; Gao Hongfeng; Liu Zhonghe; Guo Yihang

2009-01-01

Rare-earth oxide-doped titania nanocomposites (RE 3+ /TiO 2 , where RE = Eu 3+ , Pr 3+ , Gd 3+ , Nd 3+ , and Y 3+ ) were prepared by a one-step sol-gel-solvothermal method. The products exhibited anatase phase structure, mesoporosity, and interesting surface compositions with three oxygen species and two titanium species. The products were used as the photocatalysts to degrade a partially hydrolysis polyacrylamide (HPAM) under UV-light irradiation, a very useful polymer in oil recovery. For comparison, Degussa P25 and as-prepared pure TiO 2 were also tested under the same conditions. The enhanced photocatalytic activity was obtained on as-prepared Eu 3+ (Gd 3+ , Pr 3+ )/TiO 2 composites, and the reasons were explained. Finally, the degradation pathway of HPAM over the RE 3+ /TiO 2 composite was put forward based on the intermediates produced during the photocatalysis procedure.

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

Science.gov (United States)

Xiao, Liguang; Pang, Bo

2017-09-01

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

Preparation of magnetic imprinted graphene oxide composite for catalytic degradation of Congo red under dark ambient conditions.

Science.gov (United States)

Yang, Xiaochao; You, Xiaoxiao; Zhang, Bin; Guo, Chuigen; Yu, Chaosheng

2017-10-01

Magnetic imprinted N-doped P25/Fe 3 O 4 -graphene oxide (MIGNT) was prepared with methyl orange as the dummy template and pyrrole as functional monomer for catalytic degradation of Congo red (CR). Hummers method and the hydrothermal method were used to synthesize Fe 3 O 4 -GO and N-doped P25, respectively. The results of adsorption and degradation experiments showed that the adsorption capacity and catalytic degradation ability of the imprinted composite for CR were obviously higher than those of a non-imprinted one. Moreover, the effect factors on degradation efficiency of CR, such as the initial concentration of CR, catalysis time, pH of the solution and temperature, were investigated. The MIGNT was characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, a physical property measurement system and a thermal gravimetric analyzer. The degradation products of CR were detected with high performance liquid chromatography and a mass spectrometer. The MIGNT was a brand-new imprinted composite and had high degradation efficiency for CR under dark ambient conditions. The MIGNT could be recycled conveniently, due to its magnetic property, and could be used as an effective, environmentally friendly and low-cost catalytic degradation material for the treatment of water contaminated by CR.

Facile synthesis of zinc oxide nanoparticles decorated graphene oxide composite via simple solvothermal route and their photocatalytic activity on methylene blue degradation.

Science.gov (United States)

Atchudan, Raji; Edison, Thomas Nesakumar Jebakumar Immanuel; Perumal, Suguna; Karthikeyan, Dhanapalan; Lee, Yong Rok

2016-09-01

Zinc oxide nanoparticles decorated graphene oxide (ZnO@GO) composite was synthesized by simple solvothermal method where zinc oxide (ZnO) nanoparticles and graphene oxide (GO) were synthesized via simple thermal oxidation and Hummers method, respectively. The obtained materials were thoroughly characterized by various physico-chemical techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Raman spectrum shows the intensity of D to G value was close to one which confirms the obtained GO and ZnO@GO composite possesses moderate graphitization. TEM images shows the ZnO nanoparticles mean size of 15±5nm were dispersed over the wrinkled graphene layers. The photocatalytic performance of ZnO@GO composite on degradation of methylene blue (MB) is investigated and the results show that the GO plays an important role in the enhancement of photocatalytic performance. The synthesized ZnO@GO composite achieves a maximum degradation efficiency of 98.5% in a neutral solution under UV-light irradiation for 15min as compared with pure ZnO (degradation efficiency is 49% after 60min of irradiation) due to the increased light absorption, the reduced charge recombination with the introduction of GO. Moreover, the resulting ZnO@GO composite possesses excellent degradation efficiency as compared to ZnO nanoparticles alone on MB. Copyright © 2016 Elsevier B.V. All rights reserved.

Storage stability of cauliflower soup powder: The effect of lipid oxidation and protein degradation reactions.

Science.gov (United States)

Raitio, Riikka; Orlien, Vibeke; Skibsted, Leif H

2011-09-15

Soups based on cauliflower soup powders, prepared by dry mixing of ingredients and rapeseed oil, showed a decrease in quality, as evaluated by a sensory panel, during the storage of the soup powder in the dark for up to 12weeks under mildly accelerated conditions of 40°C and 75% relative humidity. Antioxidant, shown to be effective in protecting the rapeseed bulk oil, used for the powder preparation, had no effect on storage stability of the soup powder. The freshly prepared soup powder had a relatively high concentration of free radicals, as measured by electron spin resonance spectroscopy, which decreased during storage, and most remarkably during the first two weeks of storage, with only marginal increase in lipid hydroperoxides as primary lipid oxidation products, and without any increase in secondary lipid oxidation products. Analyses of volatiles by SPME-GC-MS revealed a significant increase in concentrations of 2-methyl- and 3-methyl butanals, related to Maillard reactions, together with an increase in 2-acetylpyrrole concentration. The soup powders became more brown during storage, as indicated by a decreasing Hunter L-value, in accord with non-enzymatic browning reactions. A significant increase in the concentrations of dimethyl disulfide in soup powder headspace indicated free radical-initiated protein oxidation. Protein degradation, including Maillard reactions and protein oxidation, is concluded to be more important than lipid oxidation in determining the shelf-life of dry cauliflower soup powder. Copyright © 2011 Elsevier Ltd. All rights reserved.

Graphene-modified nickel foam electrode for cathodic degradation of nitrofuranzone: Kinetics, transformation products and toxicity

Directory of Open Access Journals (Sweden)

Ya Ma

2017-12-01

Full Text Available Simple, efficient, and durable electrodes are highly demanded for practical electro­chemical process. In this study, a reduced graphene oxide modified nickel foam electrode (GR‑Ni foam was facilely prepared via one-step cyclic voltammetry electrodeposition of gra­phene oxide suspension onto the Ni foam. The electrochemical degradation of nitrofuran­zone (NFZ, a kind of typical antibiotics was studied on the GR-Ni foam cathode. The cyclic voltammetry and electrochemical impedance spectra analysis confirmed that presence of GR loading accelerated the electron transfer from the cathode surface to NFZ. With the applied cathode potential of −1.25 V (vs. Ag/AgCl, the removal efficiency of NFZ (C0 = 20 mg L−1 at the GR-Ni foam electrode reached up to 99 % within 30 min, showing a higher reaction rate constant (0.1297 min−1 than 0.0870 min−1 at the Pd-Ni foam and 0.0186 min−1 at the Ni foam electrode. It was also found that the pH, dissolved oxygen and NFZ initial concentration have slight effect on NFZ degradation at the GR-Ni foam electrode. The reactions first occurred at nitro groups (-NO2, unsaturated C=N bonds and N-N bonds to generate furan ring-containing products, and then these products were transformed into linear diamine products. The direct reduction by electrons was mainly responsible for NFZ reduction at the GR-Ni foam electrode. Even after 18 cycles, the removal efficiency of NFZ still reached up to 98 % within 1 h. In addition, the cathodic degradation process could eliminate the antibacterial activity of NFZ. The GR-Ni foam electrode would have a great potential in electrochemical process for treating wastewater containing furan antibiotics.

Degradation of low-density polyethylene in the presence of water and deuterium oxide

International Nuclear Information System (INIS)

Sedgwick, R.D.; Al-Sultan, Y.Y.; Abushihada, A.M.

1981-01-01

The degradation of low-density polyethylene in the presence of water as the degradative agent was studied at a temperature of 450 0 C and a pressure greater than 160 atm. The experimental work was conducted in an autoclave of 333-mL capacity. The results indicate the presence of paraffins, olefines, dienes, and aromatics in the degradation products. The occurrence of aromatics in the products demonstrates the importance of this degradation procedure for obtaining these valuable materials. The present work (Part 1) is believed to be the first publication to discuss the production of aromatics from polyethylenes degradation

Effects of organic degradation products on the sorption of actinides

International Nuclear Information System (INIS)

Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M.

1992-01-01

Previous work has shown that products from the chemical degradation of cellulosic matter can significantly reduce sorption of uranium(VI) and plutonium(IV) on geological materials. Uranium(IV) batch sorption experiments have now been performed to study the effect of organic degradation products in a reducing environment. Thorium(IV) sorption has also been studied since thorium is an important radioelement in its own right and has potential use as a simulant for other tetravalent actinides. Sorption onto London clay, Caithness flagstones and St. Bees sandstone was investigated. Experimental conditions were chosen to simulate both those expected close to cementitious repository (pH ∝ 11) and at the edge of the zone of migration of the alkaline plume (pH ∝ 8). Work was carried out with both authentic degradation products and with gluconate, acting as a well-characterized simulant for cellulosic degradation products. The results show that the presence of organic species can cause a reduction in sorption. This is especially so in the presence of a high concentration of gluconate ions, but the reduction is significantly less with authentic degradation products. (orig.)

Biological degradation of partially oxidated constituents of stabilized sapropel; Biologischer Abbau teiloxidierter Inhaltsstoffe stabilisierter Faulschlaemme

Energy Technology Data Exchange (ETDEWEB)

Scheminski, A.; Krull, R.; Hempel, D.C. [Technische Univ. Braunschweig (Germany). Inst. fuer Bioverfahrenstechnik

1999-07-01

Partial oxidation of sapropel with ozone destroys the cell walls of microorganisms in sludge and releases the cell constituents. Substances that are not biologically degraded because of the size or structure of their molecules are transformed into smaller, water-soluble and biologically degradable fractions by the reaction with ozone. The experiments aim to render the partially oxidated sewage sludge constituents highly biologically degradable using a minimum of oxidation agents. For the experiments described, stabilized sapropels with low biological activity are used. Hence the ozone is mainly used for the partial oxidation of recalcitrant constituents. (orig.) [German] Durch partielle Oxidation von Faulschlaemmen mit Ozon werden die Zellwaende der Mikroorganismen im Schlamm zerstoert und die Zellinhaltsstoffe freigesetzt. Dabei werden Substanzen, die aufgrund ihrer Molekuelgroesse oder -struktur biologisch nicht abgebaut werden, durch die Reaktion mit Ozon in kleinere, wasserloesliche und biologisch abbaubare Bruchstuecke ueberfuehrt. Ziel der Versuche ist es, durch den Einsatz moeglichst geringer Mengen an Oxidationsmitteln eine hohe biologische Abbaubarkeit der teiloxidierten Klaerschlamminhaltsstoffe zu erreichen. Fuer die hier vorgestellten Experimente wurden stabilisierte Faulschlaemme mit geringer biologischer Aktivitaet eingesetzt. Dadurch wird das Ozon vorwiegend zur Teiloxidation recalcitranter Inhaltsstoffe genutzt. (orig.)

Damage of polyesters by the atmospheric free radical oxidant NO3 •: a product study involving model systems

Science.gov (United States)

Goeschen, Catrin

2013-01-01

Summary Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO3 • in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed ‘hot spots’ in polyesters that are particularly vulnerable to attack by NO3 • and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions. PMID:24204400

Degradation of azo dyes by sequential Fenton's oxidation and aerobic biological treatment

International Nuclear Information System (INIS)

Tantak, Nilesh P.; Chaudhari, Sanjeev

2006-01-01

A two stage sequential Fenton's oxidation followed by aerobic biological treatment train was used to achieve decolorization and to enhance mineralization of azo dyes, viz. Reactive Black 5 (RB5), Reactive Blue 13 (RB13), and Acid Orange 7 (AO7). In the first stage, Fenton's oxidation process was used while in the second stage aerobic sequential batch reactors (SBRs) were used as biological process. Study was done to evaluate effect of pH on Fenton's oxidation process. Results reveal that pH 3 was optimum pH for achieving decolorization and dearomatization of dyes by Fenton's process. Degradation of dye was assessed by COD reduction and reduction in aromatic amines (naphthalene chromophores) which was measured by reduction in absorbance at 200 nm. More than 95% of color was removed with Fenton's oxidation process in all dyes. In overall treatment train 81.95, 85.57, and 77.83% of COD reduction was achieved in RB5, RB13, and AO7 dyes, respectively. In the Fenton's oxidation process 56, 24.5, and 80% reduction in naphthalene group was observed in RB5, RB13, and AO7, respectively, which further increased to 81.34, 68.73, and 92% after aerobic treatment. Fenton's oxidation process followed by aerobic SBRs treatment sequence seems to be viable method for achieving significant degradation of azo dye

Photo-fenton degradation of diclofenac: identification of main intermediates and degradation pathway.

Science.gov (United States)

Pérez-Estrada, Leónidas A; Malato, Sixto; Gernjak, Wolfgang; Agüera, Ana; Thurman, E Michael; Ferrer, Imma; Fernández-Alba, Amadeo R

2005-11-01

In recent years, the presence of pharmaceuticals in the aquatic environment has been of growing interest. These new contaminants are important because many of them are not degraded under the typical biological treatments applied in the wastewater treatment plants and represent a continuous input into the environment. Thus, compounds such as diclofenac are present in surface waters in all Europe and a crucial need for more enhanced technologies that can reduce its presence in the environment has become evident. In this sense, advanced oxidation processes (AOPs) represent a good choice for the treatment of hazardous nonbiodegradable pollutants. This work deals with the solar photodegradation of diclofenac, an antiinflammatory drug, in aqueous solutions by photo-Fenton reaction. A pilot-scale facility using a compound parabolic collector (CPC) reactor was used for this study. Results obtained show rapid and complete oxidation of diclofenac after 60 min, and total mineralization (disappearance of dissolved organic carbon, DOC) after 100 min of exposure to sunlight. Although diclofenac precipitates during the process at low pH, its degradation takes place in the homogeneous phase governed by a precipitation-redissolution-degradation process. Establishment of the reaction pathway was made possible by a thorough analysis of the reaction mixture identifying the main intermediate products generated. Gas chromatography-mass spectrometry (GC/ MS) and liquid chromatography coupled with time-of-flight mass spectrometry (LC/TOF-MS) were used to identify 18 intermediates, in two tentative degradation routes. The main one was based on the initial hydroxylation of the phenylacetic acid moiety in the C-4 position and subsequent formation of a quinone imine derivative that was the starting point for further multistep degradation involving hydroxylation, decarboxylation, and oxidation reactions. An alternative route was based on the transient preservation of the biphenyl amino moiety

PREVENTION OF POLYURETHANE OXIDATIVE DEGRADATION WITH PHENOLIC-ANTIOXIDANTS COVALENTLY ATTACHED TO THE HARD SEGMENTS: STRUCTURE FUNCTION RELATIONSHIPS

Science.gov (United States)

Stachelek, Stanley J; Alferiev, Ivan; Ueda, Masako; Eckels, Edward C.; Gleason, Kevin T.; Levy, Robert J

2010-01-01

Oxidative degradation of the polyurethane elastomeric (PU) components greatly reduces the efficacy of PU containing cardiovascular devices. Covalently appending the phenol-based antioxidant, 4-substituted 2,6-di-tert-butylphenol (DBP), to PU hard segments effectively reduced oxidative degradation of the PU in vivo and in vitro in prior studies by our group. In these experiments we analyze the contribution of the tethering molecule to the antioxidant capabilities of the DBP modified PU. Bromoalkylation chemistry was used to link DBP to the hard segment of the polyether polyurethane, Tecothane, via our original linker (PU-DBP), or variants containing side chains with 1 (PU-C-DBP) or 3 (PU-3C-DBP) carbons. Two additional DBP variants were fabricated in which the DBP group was appended to the alkyl chain via an oxygen atom (PU-O-DBP) or an amide linkage in the middle of the tether (PU-NHCO-DBP). All DBP variant films and unmodified control films were subject to oxidative degradation via 15 day immersion in a solution of 20% H2O2 + 0.1 M CoCl2. At the end of the oxidation protocol films were analyzed for the presence of oxidation related endpoints via scanning electron microscopy, contact angle measurements and Fourier transformation infrared spectroscopy (FTIR). All DBP containing variants resisted oxidation damage significantly better than the unmodified control PU. SEM analysis of oxidized PU-C-DBP and PU-O-DBP showed evidence of surface cracking consistent with oxidative degradation of the PU surfaces. Similarly there was a trend in increased ether cross-linking, a marker for oxidative degradation, in PU-C-DBP and PU-NHCO-DBP films. Consistent with these FTIR results, both PU-C-DBP and PU-NHCO-DBP had significant reductions in measured surface hydrophobicity as a result of oxidation. These data show for the first time that the choice of linker molecule significantly affects the efficiency of the linked phenolic antioxidant. PMID:20306526

Oxidative degradation of atenolol by heat-activated persulfate: Kinetics, degradation pathways and distribution of transformation intermediates.

Science.gov (United States)

Miao, Dong; Peng, Jianbiao; Zhou, Xiaohuan; Qian, Li; Wang, Mengjie; Zhai, Li; Gao, Shixiang

2018-05-17

Atenolol (ATL) has been widely detected in wastewater and aquatic environment. Although satisfactory removal of ATL from wastewater could be achieved, the mineralization ratio is usually low, which may result in the accumulation of its transformation products in the effluent and cause additional ecological risk to the environment. The aim of this study is to explore the effectiveness of heat activated persulfate (PS) in the removal of ATL from wastewater. Influencing factors including temperature, PS dosage, solution pH, existence of NO 3 - , Cl - , HCO 3 - and Suwannee river fulvic acid (SRFA) were examined. Complete removal of ATL was achieved within 40 min at pH 7.0 and 70 °C by using 0.5 mM PS. Inhibitive effects of HCO 3 - and FA had been observed on ATL oxidation, which was increased with the increase of their concentration. Sulfate radical (SO 4 - ) was determined as the main reactive species by quenching experiment. Eight intermediates produced in ATL degradation were identified, and four degradation pathways were proposed based on the analysis of mass spectrum and frontier electron densities. The distribution of major intermediates was influenced by reaction temperature. Hydroxylation intermediates and deamidation intermediate were the most prominent at 50 °C and 60 °C, respectively. All intermediates were completely degraded in 40 min except P134 at 70 °C. Effective removal of TOC (74.12%) was achieved with 0.5 mM PS, pH 7.0 and 70 °C after 240 min. The results proved that heat activation of PS is a promising method to remove organic pollutants in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of garlic extract on color, lipid oxidation and oxidative breakdown products in raw ground beef during refrigerated storage

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XINZHUANG ZHANG

2016-03-01

Full Text Available The study aims to investigate the effects of garlic extracts on color, lipid oxidation, and oxidative breakdown products in raw ground beef during refrigerated storage. The two treatments were:control group (C, with no addition and experiment group (D, 50 mg garlic extracts added to 100 g beef. Adding garlic extracts significant increased a* value (PA ≤ 0.05, and significant decreased TBARS and PV values (PA ≤ 0.05. The pH and –SH value of D group had a decreasing tendency (PA=0.0522 and an increasing tendency (PA=0.0636 respectively compared to C group. Garlic extracts protected phospholipids, fatty acids and polypeptides from oxidation. The results indicatethat garlic extracts have the antioxidant activity, helping maintain the meat color, inhibiting lipid oxidation and protein degradation of raw ground beef during refrigerated storage.

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

Science.gov (United States)

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

2012-03-20

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

Effects of organic degradation products on the sorption of actinides

Energy Technology Data Exchange (ETDEWEB)

Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Brownsword, M.; Linklater, C.M. (AEA Decommissioning and Radwaste, Harwell Lab. (United Kingdom))

1992-01-01

Previous work has shown that products from the chemical degradation of cellulosic matter can significantly reduce sorption of uranium(VI) and plutonium(IV) on geological materials. Uranium(IV) batch sorption experiments have now been performed to study the effect of organic degradation products in a reducing environment. Thorium(IV) sorption has also been studied since thorium is an important radioelement in its own right and has potential use as a simulant for other tetravalent actinides. Sorption onto London clay, Caithness flagstones and St. Bees sandstone was investigated. Experimental conditions were chosen to simulate both those expected close to cementitious repository (pH [proportional to] 11) and at the edge of the zone of migration of the alkaline plume (pH [proportional to] 8). Work was carried out with both authentic degradation products and with gluconate, acting as a well-characterized simulant for cellulosic degradation products. The results show that the presence of organic species can cause a reduction in sorption. This is especially so in the presence of a high concentration of gluconate ions, but the reduction is significantly less with authentic degradation products. (orig.).

Oxidation of rhizosphere sediments by Alternanthera philoxeroides : roots to quicker petroleum degradation?

International Nuclear Information System (INIS)

LaRiviere, D.; Autenrieth, R.L.; Bonner, J.

2002-01-01

Environments contaminated with organic compounds and metals can be treated using an emerging technology based on phytoremediation. The oxidation of surficial sediments through plant roots is an important feature of phytoremediation, but there is very little data available on this subject. A geochemical study conducted at the San Jacinto Wetland Research Facility (SJWRF) in Texas has shown that Alternanthera philoxeroides is a particular plant that provides oxygen to sediments. Densely vegetated areas generally exhibit redox potentials from 100 to 350 mV and are more oxidized than sparsely vegetated areas where redox potentials are often less than 0 mV. In addition, phytoremediation can accelerate bioremediation of organic compounds in surface soils by releasing enzymes and sugars that catalyze degradation or raise microbial activity. The study examined the oxidation of the rhizosphere in saturated environments such as shoreline remediation projects where oxygen is generally limited. The rate of petroleum degradation observed in studies conducted in the intertidal zone of the SJWRF is comparable to rates that have been computed for other studies, suggesting that rhizosphere has a great capacity to oxidize natural organic matter in addition to petroleum hydrocarbons. 33 refs., 2 tabs., 4 figs

Synthesis, Characterization, and Evaluation of Boron-Doped Iron Oxides for the Photocatalytic Degradation of Atrazine under Visible Light

Directory of Open Access Journals (Sweden)

Shan Hu

2012-01-01

Full Text Available Photocatalytic degradation of atrazine by boron-doped iron oxides under visible light irradiation was investigated. In this work, boron-doped goethite and hematite were successfully prepared by sol-gel method with trimethylborate as boron precursor. The powders were characterized by XRD, UV-vis diffuse reflectance spectra, and porosimetry analysis. The results showed that boron doping could influence the crystal structure, enlarge the BET surface area, improve light absorption ability, and narrow their band-gap energy. The photocatalytic activity of B-doped iron oxides was evaluated in the degradation of atrazine under the visible light irradiation, and B-doped iron oxides showed higher atrazine degradation rate than that of pristine iron oxides. Particularly, B-doped goethite exhibited better photocatalytic activity than B-doped hematite.

HPLC Separation of Vitamin E and Its Oxidation Products and Effects of Oxidized Tocotrienols on the Viability of MCF-7 Breast Cancer Cells in Vitro.

Science.gov (United States)

Drotleff, Astrid M; Büsing, Anne; Willenberg, Ina; Empl, Michael T; Steinberg, Pablo; Ternes, Waldemar

2015-10-14

Tocotrienols, a vitamin E subgroup, exert potent anticancer effects, but easily degrade due to oxidation. Eight vitamin E reference compounds, α-, β-, γ-, or δ-tocopherols or -tocotrienols, were thermally oxidized in n-hexane. The corresponding predominantly dimeric oxidation products were separated from the parent compounds by diol-modified normal-phase HPLC-UV and characterized by mass spectroscopy. The composition of test compounds, that is, α-tocotrienol, γ-tocotrienol, or palm tocotrienol-rich fraction (TRF), before and after thermal oxidation was determined by HPLC-DAD, and MCF-7 cells were treated with both nonoxidized and oxidized test compounds for 72 h. Whereas all nonoxidized test compounds (0-100 μM) led to dose-dependent decreases in cell viability, equimolar oxidized α-tocotrienol had a weaker effect, and oxidized TRF had no such effect. However, the IC50 value of oxidized γ-tocotrienol was lower (85 μM) than that of nonoxidized γ-tocotrienol (134 μM), thereby suggesting that γ-tocotrienol oxidation products are able to reduce tumor cell viability in vitro.

Thermal Treatment of Cerium Oxide and Its Properties: Adsorption Ability versus Degradation Efficiency

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Pavel Janoš

2014-01-01

Full Text Available Cerium oxide belongs to the most important heterogeneous catalysts, but its applicability as so-called reactive sorbent for the degradation of toxic chemicals was only recently discovered. For these purposes, cerium oxide is prepared by precipitation of insoluble cerium salts (carbonates with a subsequent thermal decomposition. Properties of cerium oxide prepared from the carbonate precursor are strongly affected by the temperature during the calcination. Main physicochemical properties of cerium oxide (specific surface area, crystallinity, and surface chemistry were examined in dependence on the calcination temperature. As the adsorptive properties of CeO2 are undoubtedly of great importance in the abovementioned applications, the adsorption ability was studied using an azo dye Acid Orange 7 (AO7 as a model compound. The highest sorption efficiency towards AO7 exhibited sorbents prepared at temperatures below 700°C, which was attributed mainly to the presence of hydroxyl groups on the oxide surface. A strong correlation was found between an adsorption efficiency of cerium oxides and their degradation efficiency for organophosphate pesticide parathion methyl. The >Ce–OH groups on the sorbent surface are responsible for the dye binding by the surface-complexation mechanism, and probably also for the nucleophilic cleavage of the P–O–aryl bond in the pesticide molecule.

Oxidative degradation of phenols in sono-Fenton-like systems upon high-frequency ultrasound irradiation

Science.gov (United States)

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

2017-12-01

The kinetics of oxidative degradation of phenol and chlorophenols upon acoustic cavitation in the megahertz range (1.7 MHz) is studied experimentally in model systems, and the involvement of in situ generated reactive oxygen species (ROSs) is demonstrated. The phenols subjected to high frequency ultrasound (HFUS) are ranked in terms of their rate of conversion: 2,4,6-trichlorophenol > 2,4-dichlorophenol 2-chlorophenol > 4-chlorophenol phenol. Oxidative degradation upon HFUS irradiation is most efficient at low concentrations of pollutants, due to the low steady-state concentrations of the in situ generated ROSs. A dramatic increase is observed in the efficiency of oxidation in several sonochemical oxidative systems (HFUS in combination with other chemical oxidative factors). The system with added Fe2+ (a sono-Fenton system) derives its efficiency from hydrogen peroxide generated in situ as a result of the recombination of OH radicals. The S2O8 2-/Fe2+/HFUS system has a synergetic effect on substrate oxidation that is attributed to a radical chain mechanism. In terms of the oxidation rates, degrees of conversion, and specific energy efficiencies of 4-chlorophenol oxidation based on the amount of oxidized substance per unit of expended energy the considered sonochemical oxidative systems form the series HFUS < S2O8 2-/HFUS < S2O8 2-/Fe2+/HFUS.

Serum Antioxidative Enzymes Levels and Oxidative Stress Products in Age-Related Cataract Patients

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Dong Chang

2013-01-01

Full Text Available Purpose. To investigate the activity of antioxidative enzymes and the products of oxidative stress in patients with age-related cataracts and compare the findings with those in healthy control subjects. Method. Sixty patients with age-related cataract and sixty healthy controls of matched age and gender were included in this study. Serum samples were obtained to detect the antioxidative enzymes of superoxide dismutase (SOD, catalase (CAT, and glutathione peroxidase (GSH-Px, and oxidation degradation products of malondialdehyde (MDA, 4-hydroxynonenal (4-HNE, conjugated diene (CD, advanced oxidation protein products (AOPP, protein carbonyl (PC, and 8-hydroxydeoxyguanosine (8-OHdG. Results. Serum SOD, GSH-Px, and CAT activities in cataract group were significantly decreased as compared to the control subjects (P<0.05. The levels of MDA, 4-HNE, and CD in cataract patients were significantly higher than those in the control subjects (P<0.05, P<0.01. Cataract patients had higher levels of 8-OHdG, AOPP, and PC with respect to the comparative group of normal subjects (P<0.01. And there was no statistical significance in concentration of antioxidative enzymes and oxidative stress products in patients with different subtype cataract. Conclusions. Oxidative stress is an important risk factor in the development of age-related cataract, and augmentation of the antioxidant defence systems may be of benefit to prevent or delay cataractogenesis.

Core degradation and fission product release

International Nuclear Information System (INIS)

Wright, R.W.; Hagen, S.J.L.

1992-01-01

Experiments on core degradation and melt progression in severe LWR accidents have provided reasonable understanding of the principal processes involved in the early phase of melt progression that extends through core degradation and metallic material melting and relocation. A general but not a quantitative understanding of late phase melt progression that involves ceramic material melting and relocation has also been obtained, primarily from the TMI-2 core examination. A summary is given of the current state of knowledge on core degradation and melt progression obtained from these integral experiments and of the principal remaining significant uncertainties. A summary is also given of the principal results on in-vessel fission product release obtained from these experiments. (author). 8 refs, 5 figs, 3 tabs

Degradation of solid oxide fuel cells with wood

International Nuclear Information System (INIS)

N Frank; M Saule; J Karl

2006-01-01

The Technical University of Munich investigates the degradation effects observed on SOFCs when fired with product gases from biomass gasification processes. The TUM has concentrated its research on tubular SOFCs. For this purpose tubular electrolyte-supported SOFCs have been manufactured using commercially available electrolyte tubes, anode foil and cathode paste. The tubular SOFCs were first run with hydrogen and synthetic fuels. Once stable and reproducible results were achieved, tests with product gas from four different biomass gasifiers have started. These gasifiers have been coupled to a gas cleaning device which includes sulphur and particle removal and pre-reforming. Different operation conditions of the gasifiers and the gas cleaning device have been realized and the corresponding fuel cell degradations have been analysed. (authors)

Levofloxacin oxidation by ozone and hydroxyl radicals: kinetic study, transformation products and toxicity.

Science.gov (United States)

Hamdi El Najjar, Nasma; Touffet, Arnaud; Deborde, Marie; Journel, Romain; Leitner, Nathalie Karpel Vel

2013-10-01

This work was carried out to investigate the fate of the antibiotic levofloxacin upon oxidation with ozone and hydroxyl radicals. A kinetic study was conducted at 20 °C for each oxidant. Ozonation experiments were performed using a competitive kinetic method with carbamazepin as competitor. Significant levofloxacin removal was observed during ozonation and a rate constant value of 6.0×10(4) M(-1) s(-1) was obtained at pH 7.2. An H2O2/UV system was used for the formation of hydroxyl radicals HO. The rate constant of HO was determined in the presence of a high H2O2 concentration. The kinetic expressions yielded a [Formula: see text] value of 4.5×10(9) M(-1) s(-1) at pH 6.0 and 5.2×10(9) M(-1) s(-1) at pH 7.2. These results were used to develop a model to predict the efficacy of the ozonation process and pharmaceutical removal was estimated under different ozonation conditions (i.e. oxidant concentrations and contact times). The results showed that levofloxacin was completely degraded by molecular ozone during ozonation of water and that hydroxyl radicals had no effect in real waters conditions. Moreover, LC/MS/MS and toxicity assays using Lumistox test were performed to identify ozonation transformation products. Under these conditions, four transformation products were observed and their chemical structures were proposed. The results showed an increase in toxicity during ozonation, even after degradation of all of the observed transformation products. The formation of other transformation products not identified under our experimental conditions could be responsible for the observed toxicity. These products might be ozone-resistant and more toxic to Vibrio fisheri than levofloxacin. Copyright © 2013 Elsevier Ltd. All rights reserved.

Organic contaminants degradation from the S(IV) autoxidation process catalyzed by ferrous-manganous ions: A noticeable Mn(III) oxidation process.

Science.gov (United States)

Zhang, Jiaming; Ma, Jun; Song, Haoran; Sun, Shaofang; Zhang, Zhongxiang; Yang, Tao

2018-04-15

Remarkable atrazine degradation in the S(IV) autoxidation process catalyzed by Fe 2+ -Mn 2+ (Fe 2+ /Mn 2+ /sulfite) was demonstrated in this study. Competitive kinetic experiments, alcohol inhibiting methods and electron spin resonance (ESR) experiments proved that sulfur radicals were not the major oxidation species. Mn(III) was demonstrated to be the primary active species in the Fe 2+ /Mn 2+ /sulfite process based on the comparison of oxidation selectivity. Moreover, the inhibiting effect of the Mn(III) hydrolysis and the S(IV) autoxidation in the presence of organic contaminants indicated the existence of three Mn(III) consumption routes in the Fe 2+ /Mn 2+ /sulfite process. The absence of hydroxyl radical and sulfate radical was interpreted by the competitive dynamics method. The oxidation capacity of the Fe 2+ /Mn 2+ /sulfite was independent of the initial pH (4.0-6.0) because the fast decay of S(IV) decreased initial pH below 4.0 rapidly. The rate of ATZ degradation was independent of the dissolved oxygen (DO) because that the major DO consumption process was not the rate determining step during the production of SO 5 •- . Phosphate and bicarbonate were confirmed to have greater inhibitory effects than other environmental factors because of their strong pH buffering capacity and complexing capacity for Fe 3+ . The proposed acetylation degradation pathway of ATZ showed the application of the Fe 2+ /Mn 2+ /sulfite process in the research of contaminants degradation pathways. This work investigated the characteristics of the Fe 2+ /Mn 2+ /sulfite process in the presence of organic contaminants, which might promote the development of Mn(III) oxidation technology. Copyright © 2018. Published by Elsevier Ltd.

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

International Nuclear Information System (INIS)

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

2008-01-01

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

Oxidation of the odorous compound 2,4,6-trichloroanisole by UV activated persulfate: Kinetics, products, and pathways.

Science.gov (United States)

Luo, Congwei; Jiang, Jin; Ma, Jun; Pang, Suyan; Liu, Yongze; Song, Yang; Guan, Chaoting; Li, Juan; Jin, Yixin; Wu, Daoji

2016-06-01

The transformation efficiency and products of an odorous compound 2,4,6-trichloroanisole (TCA) at the wavelength of 254 nm in the presence of persulfate were investigated for the first time. The effects of water matrix (i.e., natural organic matter (NOM), pH, carbonate/bicarbonate (HCO3(-)/CO3(2-)), and chloride ions (Cl(-))) were evaluated. The second order rate constant of TCA reacting with sulfate radical (SO4(-)) was determined to be (3.72 ± 0.10) × 10(9) M(-1) s(-1). Increasing dosage of persulfate increased the observed pseudo-first-order rate constant for TCA degradation (kobs), and the contribution of SO4(-) to TCA degradation was much higher than that of HO at each experimental condition. Degradation rate of TCA decreased with pH increasing from 4.0 to 9.0, which could be explained by the lower radical scavenging effect of dihydrogen phosphate than hydrogen phosphate in acidic condition (pH kinetic results could be described by a steady-state kinetic model. Furthermore, liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry at powerful precursor ion scan approach was used to selectively detect oxidation products of TCA. It was found that 2,4,6-trichorophenol (TCP) was the major oxidation product (i.e., the initial yield of TCP was above 90%). The second order rate constant between TCP and SO4(-) was estimated to be (4.16 ± 0.20) × 10(9) M(-1) s(-1). In addition, three products (i.e., 2,6-dichloro-1,4-benzoquinone and two aromatic ring-opening products) were detected in the reaction of TCP with SO4(-), which also appeared in the oxidation of TCA in the UV/persulfate process. A tentative pathway was proposed, where the initial one-electron oxidation of TCA by SO4(-) and further reactions (e.g., ipso-hydroxylation and aromatic ring-cleavage) of the formed cation intermediate TCA were involved. Copyright © 2016. Published by Elsevier Ltd.

Response of methane production via propionate oxidation to carboxylated multiwalled carbon nanotubes in paddy soil enrichments

Directory of Open Access Journals (Sweden)

Jianchao Zhang

2018-01-01

Full Text Available Carboxylated multiwalled carbon nanotubes (MWCNTs-COOH have become a growing concern in terms of their fate and toxicity in aqueous environments. Methane (CH4 is a major product of organic matter degradation in waterlogged environments. In this study, we determined the effect of MWCNTs-COOH on the production of CH4 from propionate oxidation in paddy soil enrichments. The results showed that the methanogenesis from propionate degradation was accelerated in the presence of MWCNTs-COOH. In addition, the rates of CH4 production and propionate degradation increased with increasing concentrations of MWCNTs-COOH. Scanning electron microscopy (SEM observations showed that the cells were intact and maintained their structure in the presence of MWCNTs-COOH. In addition, SEM and fluorescence in situ hybridization (FISH images revealed that the cells were in direct contact with the MWCNTs and formed cell-MWCNTs aggregates that contained both bacteria and archaea. On the other hand, nontoxic magnetite nanoparticles (Fe3O4 had similar effects on the CH4 production and cell integrity as the MWCNTs-COOH. Compared with no nanomaterial addition, the relative abundances of Geobacter and Methanosarcina species increased in the presence of MWCNTs-COOH. This study suggests that MWCNTs-COOH exerted positive rather than cytotoxic effects on the syntrophic oxidation of propionate in paddy soil enrichments and affected the bacterial and archaeal community structure at the test concentrations. These findings provide novel insight into the consequences of nanomaterial release into anoxic natural environments.

Mapping intermediate degradation products of poly(lactic-co-glycolic acid) in vitro.

Science.gov (United States)

Li, Jian; Nemes, Peter; Guo, Ji

2018-04-01

There is widespread interest in using absorbable polymers, such as poly(lactic-co-glycolic acid) (PLGA), as components in the design and manufacture of new-generation drug eluting stents (DES). PLGA undergoes hydrolysis to progressively degrade through intermediate chemical entities to simple organic acids that are ultimately absorbed by the human body. Understanding the composition and structure of these intermediate degradation products is critical not only to elucidate polymer degradation pathways accurately, but also to assess the safety and performance of absorbable cardiovascular implants. However, analytical approaches to determining the intermediate degradation products have yet to be established and evaluated in a standard or regulatory setting. Hence, we developed a methodology using electrospray ionization mass spectrometry to qualitatively and quantitatively describe intermediate degradation products generated in vitro from two PLGA formulations commonly used in DES. Furthermore, we assessed the temporal evolution of these degradation products using time-lapse experiments. Our data demonstrated that PLGA degradation products via heterogeneous cleavage of ester bonds are modulated by multiple intrinsic and environmental factors, including polymer chemical composition, degradants solubility in water, and polymer synthesis process. We anticipate the methodologies and outcomes presented in this work will elevate the mechanistic understanding of comprehensive degradation profiles of absorbable polymeric devices, and facilitate the design and regulation of cardiovascular implants by supporting the assessments of the associated biological response to degradation products. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1129-1137, 2018. © 2017 Wiley Periodicals, Inc.

Anodic oxidation of salicylic acid on BDD electrode: Variable effects and mechanisms of degradation

Energy Technology Data Exchange (ETDEWEB)

Rabaaoui, Nejmeddine, E-mail: chimie_tunisie@yahoo.fr [Faculte des Sciences de Sfax, Departement de Chimie, 3038 Sfax (Tunisia); Allagui, Mohamed Salah [Faculte des Sciences de Gafsa, Campus Universitaire Sidi Ahmed Zarrouk, 2112 Gafsa (Tunisia)

2012-12-15

Highlights: Black-Right-Pointing-Pointer Oxidation with BDD is a powerful electrochemical method able to mineralize. Black-Right-Pointing-Pointer SA is oxidized to aromatic compounds then CO{sub 2} and H{sub 2}O. Black-Right-Pointing-Pointer Polymeric intermediate products were formed. - Abstract: The degradation of 100 mL of solution with salicylic acid (SA) in the pH range 3.0-10.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 3 cm{sup 2} area, by applying a current of 100, 300 and 450 mA at 25 Degree-Sign C. Completed mineralization is always achieved due to the great concentration of hydroxyl radical ({center_dot}OH) generated at the BDD surface. The mineralization rate increases with increasing applied current, but decreases when drug concentration rises from 200 mg L{sup -1}. Nevertheless, the pH effect was not significant. During oxidation it was observed that catechol, 2,5-dihydroxylated benzoic acid, 2,3-dihydroxylated benzoic acid and hydroquinone were formed as aromatic intermediates. In addition, ion-exclusion chromatography allowed the detection of fumaric, maleic, oxalic and formic as the ultimate carboxylic acid.

Modeling Degradation in Solid Oxide Electrolysis Cells - Volume II

Energy Technology Data Exchange (ETDEWEB)

Manohar Motwani

2011-09-01

Idaho National Laboratory has an ongoing project to generate hydrogen from steam using solid oxide electrolysis cells (SOECs). To accomplish this, technical and degradation issues associated with the SOECs will need to be addressed. This report covers various approaches being pursued to model degradation issues in SOECs. An electrochemical model for degradation of SOECs is presented. The model is based on concepts in local thermodynamic equilibrium in systems otherwise in global thermodynamic non-equilibrium. It is shown that electronic conduction through the electrolyte, however small, must be taken into account for determining local oxygen chemical potential,, within the electrolyte. The within the electrolyte may lie out of bounds in relation to values at the electrodes in the electrolyzer mode. Under certain conditions, high pressures can develop in the electrolyte just near the oxygen electrode/electrolyte interface, leading to oxygen electrode delamination. These predictions are in accordance with the reported literature on the subject. Development of high pressures may be avoided by introducing some electronic conduction in the electrolyte. By combining equilibrium thermodynamics, non-equilibrium (diffusion) modeling, and first-principles, atomic scale calculations were performed to understand the degradation mechanisms and provide practical recommendations on how to inhibit and/or completely mitigate them.

Insulin degradation products from perfused rat kidney

International Nuclear Information System (INIS)

Duckworth, W.C.; Hamel, F.G.; Liepnieks, J.; Peavy, D.; Frank, B.; Rabkin, R.

1989-01-01

The kidney is a major site for insulin metabolism, but the enzymes involved and the products generated have not been established. To examine the products, we have perfused rat kidneys with insulin specifically iodinated on either the A14 or the B26 tyrosine. Labeled material from both the perfusate and kidney extract was examined by Sephadex G50 and high-performance liquid chromatography (HPLC). In perfusate from a filtering kidney, 22% of the insulin-sized material was not intact insulin on HPLC. With the nonfiltering kidney, 10.6% was not intact insulin. Labeled material from HPLC was sulfitolyzed and reinjected on HPLC. By use of 125 I-iodo(A14)-insulin, almost all the degradation products contained an intact A-chain. By use of 125 I-iodo(B26)-insulin, several different B-chain-cleaved products were obtained. The material extracted from the perfused kidney was different from perfusate products but similar to intracellular products from hepatocytes, suggesting that cellular metabolism by kidney and liver are similar. The major intracellular product had characteristics consistent with a cleavage between the B16 and B17 amino acids. This product and several of the perfusate products are also produced by insulin protease suggesting that this enzyme is involved in the degradation of insulin by kidney

Photolytic and photocatalytic degradation of quinclorac in ultrapure and paddy field water: identification of transformation products and pathways.

Science.gov (United States)

Pareja, Lucía; Pérez-Parada, Andrés; Agüera, Ana; Cesio, Verónica; Heinzen, Horacio; Fernández-Alba, Amadeo R

2012-05-01

Quinclorac (QNC) is an effective but rather persistent herbicide commonly used in rice production. This herbicide presents a mean persistence in the environment so its residues are considered of environmental relevance. However, few studies have been conducted to investigate its environmental behavior and degradation. In the present work, direct photolysis and TiO(2) photocatalysis of the target compound in ultrapure and paddy field water were investigated. After 10h photolysis in ultrapure water, the concentration of QNC declined 26% and 54% at 250 and 700 W m(-2), respectively. However, the amount of quinclorac in paddy field water remained almost constant under the same irradiation conditions. QNC dissipated completely after 40 min of TiO(2) photocatalysis in ultrapure water, whereas 130 min were necessary to degrade 98% of the initial concentration in paddy field water. Possible QNC photolytic and photocatalytic degradation pathways are proposed after structure elucidation of the main transformation products, through liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry and exact mass measurements. Pyridine ring hydroxylation at C-9 followed by ring opening and/or oxidative dechlorination were the key steps of QNC degradation. Copyright © 2012 Elsevier Ltd. All rights reserved.

Gas chromatography-mass spectrometry and high-performance liquid chromatographic analyses of thermal degradation products of common plastics

OpenAIRE

Pacakova, V.; Leclercq, P.A.

1991-01-01

The thermo-oxidation of five commonly used materials, namely low-density polyethylene, retarded polyethylene, paper with a polyethylene foil, a milk package and filled polypropylene, was studied. Capillary gas chromatography and gas chromatography-mass spectrometry were used to analyze the volatile degradation products, while high-performance liquid chromatography was employed to measure polycyclic aromatic hydrocarbons. The results are discussed from the point of view of toxicity of the prod...

Short stack modeling of degradation in solid oxide fuel cells. Part II. Sensitivity and interaction analysis

Science.gov (United States)

Gazzarri, J. I.; Kesler, O.

In the first part of this two-paper series, we presented a numerical model of the impedance behaviour of a solid oxide fuel cell (SOFC) aimed at simulating the change in the impedance spectrum induced by contact degradation at the interconnect-electrode, and at the electrode-electrolyte interfaces. The purpose of that investigation was to develop a non-invasive diagnostic technique to identify degradation modes in situ. In the present paper, we appraise the predictive capabilities of the proposed method in terms of its robustness to uncertainties in the input parameters, many of which are very difficult to measure independently. We applied this technique to the degradation modes simulated in Part I, in addition to anode sulfur poisoning. Electrode delamination showed the highest robustness to input parameter variations, followed by interconnect oxidation and interconnect detachment. The most sensitive degradation mode was sulfur poisoning, due to strong parameter interactions. In addition, we simulate several simultaneous two-degradation-mode scenarios, assessing the method's capabilities and limitations for the prediction of electrochemical behaviour of SOFC's undergoing multiple simultaneous degradation modes.

Short stack modeling of degradation in solid oxide fuel cells. Part II. Sensitivity and interaction analysis

Energy Technology Data Exchange (ETDEWEB)

Gazzarri, J.I. [Department of Mechanical Engineering, University of British Columbia, 2054-6250 Applied Science Lane, Vancouver, BC V6T 1Z4 (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, ON M5S 3G8 (Canada)

2008-01-21

In the first part of this two-paper series, we presented a numerical model of the impedance behaviour of a solid oxide fuel cell (SOFC) aimed at simulating the change in the impedance spectrum induced by contact degradation at the interconnect-electrode, and at the electrode-electrolyte interfaces. The purpose of that investigation was to develop a non-invasive diagnostic technique to identify degradation modes in situ. In the present paper, we appraise the predictive capabilities of the proposed method in terms of its robustness to uncertainties in the input parameters, many of which are very difficult to measure independently. We applied this technique to the degradation modes simulated in Part I, in addition to anode sulfur poisoning. Electrode delamination showed the highest robustness to input parameter variations, followed by interconnect oxidation and interconnect detachment. The most sensitive degradation mode was sulfur poisoning, due to strong parameter interactions. In addition, we simulate several simultaneous two-degradation-mode scenarios, assessing the method's capabilities and limitations for the prediction of electrochemical behaviour of SOFC's undergoing multiple simultaneous degradation modes. (author)

Functionalization of Liquid Natural Rubber via Oxidative Degradation of Natural Rubber

Directory of Open Access Journals (Sweden)

Suhawati Ibrahim

2014-12-01

Full Text Available Natural rubber (NR is a high molecular weight natural polymer and can be degraded to liquid natural rubber (LNR leaving certain functional groups at the end of chains. In this study, LNR samples prepared via oxidative degradation using H2O2 and NaNO2 as reagents were found to have different end groups depending on the pH of the reaction medium. In an acidic medium, LNR with hydroxyl terminal groups was formed as the degradation reaction was initiated by hydroxyl radicals produced from decomposition of peroxynitrite acid. In contrast, a redox reaction took place in an alkaline medium to yield LNR with carbonyl terminal groups. The mechanisms of reaction are discussed and proposed to explain the formation of different end groups when reaction carried out in acidic and alkaline media. Chain degradation in an acidic medium seems to be more effective than in an alkaline medium, and thus yields LNR with lower Mn.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption – Catalytic wet air oxidation on activated carbons

International Nuclear Information System (INIS)

Quesada-Peñate, I.; Julcour-Lebigue, C.; Jáuregui-Haza, U.J.; Wilhelm, A.M.; Delmas, H.

2012-01-01

Highlights: ► Three activated carbons (AC) compared as adsorbents and oxidation catalysts. ► Similar evolution for catalytic and adsorptive properties of AC over reuses. ► Acidic and mesoporous AC to be preferred, despite lower initial efficiency. ► Oxidative degradation of paracetamol improves biodegradability. ► Convenient hybrid adsorption–regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

Degradation of paracetamol by catalytic wet air oxidation and sequential adsorption - Catalytic wet air oxidation on activated carbons

Energy Technology Data Exchange (ETDEWEB)

Quesada-Penate, I. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Julcour-Lebigue, C., E-mail: carine.julcour@ensiacet.fr [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France); Jauregui-Haza, U. J. [Instituto Superior de Tecnologias y Ciencias Aplicadas, Ave. Salvador Allende y Luaces, Habana (Cuba); Wilhelm, A. M.; Delmas, H. [Universite de Toulouse, INPT, UPS, Laboratoire de Genie Chimique, 4, Allee Emile Monso, F-31432 Toulouse (France); CNRS, Laboratoire de Genie Chimique, F-31432 Toulouse (France)

2012-06-30

Highlights: Black-Right-Pointing-Pointer Three activated carbons (AC) compared as adsorbents and oxidation catalysts. Black-Right-Pointing-Pointer Similar evolution for catalytic and adsorptive properties of AC over reuses. Black-Right-Pointing-Pointer Acidic and mesoporous AC to be preferred, despite lower initial efficiency. Black-Right-Pointing-Pointer Oxidative degradation of paracetamol improves biodegradability. Black-Right-Pointing-Pointer Convenient hybrid adsorption-regenerative oxidation process for continuous treatment. - Abstract: The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique using an autoclave reactor and as a regenerative treatment of the carbon after adsorption in a sequential fixed bed process. Three activated carbons (ACs) from different source materials were used as catalysts: two microporous basic ACs (S23 and C1) and a meso- and micro-porous acidic one (L27). During the first CWAO experiment the adsorption capacity and catalytic performance of fresh S23 and C1 were higher than those of fresh L27 despite its higher surface area. This situation changed after AC reuse, as finally L27 gave the best results after five CWAO cycles. Respirometry tests with activated sludge revealed that in the studied conditions the use of CWAO enhanced the aerobic biodegradability of the effluent. In the ADOX process L27 also showed better oxidation performances and regeneration efficiency. This different ageing was examined through AC physico-chemical properties.

Adsorption of Poly(ethylene oxide)-Poly(lactide) Copolymers. Effects of Composition and Degradation.

Science.gov (United States)

Muller, Dries; Carlsson, Fredrik; Malmsten, Martin

2001-04-01

The effect of chemical degradation of two diblock copolymers of poly(ethylene oxide) (E) and poly(lactide) (L), E(39)L(5) and E(39)L(20), on their adsorption at silica and methylated silica was investigated with in situ ellipsometry. Steric stablization of polystyrene dispersions was investigated in relation to degradation. Hydrolysis of the poly(lactide) block of the copolymers was followed at different temperatures and pH by using HPLC to measure the occurrence of lactic acid in solution. The block copolymers were quite stable in pH-unadjusted solution at low temperature, whereas degradation was facilitated by increasing temperature or lowering of the pH. Lower degradation rates of E(39)L(20) where observed at low temperature in comparison with those of E(39)L(5), whereas the degradation rates of the copolymers were quantitatively similar at high temperature. The adsorption of the copolymers at methylated silica substrates decreased with increasing degree of degradation due to the reduction in the ability of hydrophobic block to anchor the copolymer layer at the surface. At silica the adsorption initially increased with increasing degradation, particularly for E(39)L(20) due to deposition of aggregates onto the surface. After extensive degradation the adsorption of the copolymers at both silica and methylated silica resembled that of the corresponding poly(ethylene oxide) homopolymer. Overall, it was found that the eventual reduction in adsorption occurred at a lower degree of degradation for E(39)L(5) than for E(39)L(20). Mean-field calculations showed a reduced anchoring for the block copolymers with decreasing poly(lactide) block length at hydrophobic surfaces. In accordance with this finding, it was observed that polystyrene dispersions were stabilized by E(39)L(20) or E(39)L(5) in a way that depended on both the lactide block length and the degree of degradation. Upon degradation of the hydrophobic block, stabilization of the polystyrene dispersions was

Hydroxyl radical induced degradation of salicylates in aerated aqueous solution

International Nuclear Information System (INIS)

Szabó, László; Tóth, Tünde; Homlok, Renáta; Rácz, Gergely; Takács, Erzsébet; Wojnárovits, László

2014-01-01

Ionizing radiation induced degradation of acetylsalicylic acid, its hydrolysis product salicylic acid and a salicylic acid derivative 5-sulpho-salicylic acid, was investigated in dilute aqueous solutions by UV–vis spectrophotometry, HPLC separation and diode-array or MS/MS detection, chemical oxygen demand, total organic carbon content and by Vibrio fischeri toxicity measurements. Hydroxyl radicals were shown to degrade these molecules readily, and first degradation products were hydroxylated derivatives in all cases. Due to the by-products, among them hydrogen peroxide, the toxicity first increased and then decreased with the absorbed dose. With prolonged irradiation complete mineralization was achieved. - Highlights: • In OH induced reactions of salicylates first products are hydroxylated derivatives. • With prolonged irradiation dihydroxy derivatives also form. • In aerated solutions the one-electron oxidant OH induces 3–4 oxidations. • Toxicity first increases and then decreases with dose mainly due to H 2 O 2 formation. • The toxicity in tap water is smaller than in pure water

The efficacy of an oxidation pond in mineralizing some industrial waste products with special reference to fluorene degradation: A case study

Energy Technology Data Exchange (ETDEWEB)

Ahmed, M.T.; Dewedar, A.; Mekki, L.; Diab, A.

1999-07-01

The efficacy of the oxidation pond on the outskirts of the 10th of Ramadan, the main industrial city in Egypt, was examined. Samples of wastewater collected from the inlet and the outlet were screened for some priority pollutants. Acenaphethene and fluorene were the most frequently detected polycyclic aromatic hydrocarbons, while dimethyl phthalate was the most frequently detected phthalate ester. The spectrum of pollutants, their concentrations and frequencies were similar in the inlet and the outlet, indicating an inferior mineralization capability of the pond. Several degradative bacterial strains were isolated from the pond and grown on M56 minimal media supplemented with different pollutants as the carbon source. The efficacy of pure and mixed cultures to break down fluorene, the most frequently detected pollutant was examined. Fluorene degradation was fast in the first 10 days, the followed by a slow phase. Mixed culture had a higher rate of fluorene degradation in comparison to pure cultures. High performance liquid chromatography analysis of fluorene degradation showed three degradative metabolites. But GC/MS analysis detected one compound, identified as acetamide. The present work has indicated the poor efficacy of the pond. Lack of primary treatment of industrial effluent at factory level, coupled with shock loads of toxicants that may damage the microorganisms and their degradative capabilities are presumably main factors behind such inferior performance. Moreover, the type of pollutants discharged into the pond tend to fluctuate and change depending on the rate from the factories discharge and work shifts. Such irregular feeding of persistent pollutants may have led to a wash out of specialized strains of bacteria capable to degrade such persistent pollutants.

Degradation of the fluoroquinolone enrofloxacin by electrochemical advanced oxidation processes based on hydrogen peroxide electrogeneration

International Nuclear Information System (INIS)

Guinea, Elena; Garrido, Jose Antonio; Rodriguez, Rosa Maria; Cabot, Pere-Lluis; Arias, Conchita; Centellas, Francesc; Brillas, Enric

2010-01-01

Solutions of the veterinary fluoroquinolone antibiotic enrofloxacin in 0.05 M Na 2 SO 4 of pH 3.0 have been comparatively degraded by electrochemical advanced oxidation processes such as anodic oxidation with electrogenerated H 2 O 2 (AO-H 2 O 2 ), electro-Fenton (EF), photoelectro-Fenton (PEF) and solar photoelectro-Fenton (SPEF) at constant current density. The study has been performed using an undivided stirred tank reactor of 100 ml and a batch recirculation flow plant of 2.5 l with an undivided filter-press cell coupled to a solar photoreactor, both equipped with a Pt or boron-doped diamond (BDD) anode and a carbon-polytetrafluoroethylene gas diffusion cathode to generate H 2 O 2 from O 2 reduction. In EF, PEF and SPEF, hydroxyl radical (·OH) is formed from Fenton's reaction between added catalytic Fe 2+ and generated H 2 O 2 . Almost total decontamination of enrofloxacin solutions is achieved in the stirred tank reactor by SPEF with BDD. The use of the batch recirculation flow plant showed that this process is the most efficient and can be viable for industrial application, becoming more economic and yielding higher mineralization degree with raising antibiotic content. This is feasible because organics are quickly oxidized with ·OH formed from Fenton's reaction and at BDD from water oxidation, combined with the fast photolysis of complexes of Fe(III) with generated carboxylic acids under solar irradiation. The lower intensity of UVA irradiation used in PEF with BDD causes a slower degradation. EF with BDD is less efficient since ·OH cannot destroy the most persistent Fe(III)-oxalate and Fe(III)-oxamate complexes. AO-H 2 O 2 with BDD yields the poorest mineralization because pollutants are only removed with ·OH generated at BDD. All procedures are less potent using Pt as anode due to the lower production of ·OH at its surface. Enrofloxacin decay always follows a pseudo first-order reaction. Its primary aromatic by-products and short intermediates

Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

KAUST Repository

Zhang, Tao; Li, Weiwei; Croue, Jean-Philippe

2011-01-01

The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

Catalytic ozonation of oxalate with a cerium supported palladium oxide: An efficient degradation not relying on hydroxyl radical oxidation

KAUST Repository

Zhang, Tao

2011-11-01

The cerium supported palladium oxide (PdO/CeO 2) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO 2 during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO 2 of the catalyst forming surface complexes, and 2) O 3 was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O 2), and O 2 gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO 2 in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter. © 2011 American Chemical Society.

In-Vitro gas production technique as for feed evaluation: volume of gas production and feed degradability

International Nuclear Information System (INIS)

Asih Kurniawati

2007-01-01

In-vitro gas production technique can be used to predict feed quality. The effect of molasses supplementation as a source of degradable carbohydrate to protein source red clover silage has been done using this technique. Data showed there were positive correlation between total volume gas produced and feed degradability (r = 0.96), between total volume gas produced and microbial biomass (r = 0,96). Dry matter degradability, dry matter degraded, microbial biomass production and efficiency of nitrogen utilization, highly significant (P<0,01) increased due to increasing of degradable carbohydrate. The addition of 0.3 g molasses gave the best result whereas the addition of 0.15 g and 0.225 g have better effect than 0.0625 g molasses addition and red clover only. This result suggested that In-vitro production technique can be used as tool for feed evaluation. (author)

Report: More Information Is Needed On Toxaphene Degradation Products

Science.gov (United States)

Report #2006-P-00007, Dec 16, 2005. Toxaphene in the environment changes, or degrades. The degradation products are different from the original toxaphene in chemical composition and how they appear to testing instruments, so they could go unreported.

Application of Ni-Oxide@TiO₂ Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors.

Science.gov (United States)

Lee, Seungwon; Lee, Jisuk; Nam, Kyusuk; Shin, Weon Gyu; Sohn, Youngku

2016-12-20

Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO₂ core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue) degradation under ultraviolet (UV) and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO₂ overlayer coating.

A comparative study on the radiation induced degradation of chlorinated organics and water

International Nuclear Information System (INIS)

Bekboelet, M.; Balcioglu, A.I.; Getoff, N.

1998-01-01

Complete text of publication follows. Radiation induced degradation of chlorinated benzaldehydes has been studied by the application of UV-photolysis, UV-assisted catalytic oxidation and gamma radiolysis processes. The degradation was followed in terms of the substrate removal and formation of the decomposition products such as chloride and formaldehyde. Formation of the acidic compounds were also determined by the pH decrease during irradiation periods. The below given table summarizes the obtained results in terms of photochemical G (G PH )values. The main idea of this paper was to evaluate the applied processes in relation to the end products rather and to compare the efficiency of the methods. Besides, chloride and formaldehyde formation, the substrate degradation and formation of the stable end products, were followed by HPLC analyses. Hydroxylated parent compounds chlorophenols, benzaldehyde were also detected. Formation of muconic acid through ring opening as well as the formation of lower molecular weight organic acids by decomposition such as oxalic, citric, tartaric and formic acids were observed with respect the applied oxidation process. Depending on the formed stable end products and the related probable reaction mechanisms, isomeric positions were found to be selective toward oxidative degradation

Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton

Energy Technology Data Exchange (ETDEWEB)

Flores, Nelly; Sirés, Ignasi; Garrido, José Antonio; Centellas, Francesc; Rodríguez, Rosa María; Cabot, Pere Lluís; Brillas, Enric, E-mail: brillas@ub.edu

2016-12-05

Highlights: • trans-Ferulic acid degradation by EAOPs using a stirred BDD/air-diffusion cell. • Slow substrate abatement and poor mineralization by AO-H{sub 2}O{sub 2}. • 98% Mineralization by PEF, but with rapid and similar substrate decay than by EF. • Quicker degradation by SPEF due to the more potent photolytic action of sunlight. • Reaction pathway with four primary aromatic products and three final carboxylic acids. - Abstract: Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H{sub 2}O{sub 2} (AO-H{sub 2}O{sub 2}), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing ·OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton’s reaction between cathodically generated H{sub 2}O{sub 2} and added catalytic Fe{sup 2+}. The substrate was very slowly removed by AO-H{sub 2}O{sub 2}, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with ·OH in the bulk. The AO-H{sub 2}O{sub 2} process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC–MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization

Structural insights into 2,2'-azino-Bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS)-mediated degradation of reactive blue 21 by engineered Cyathus bulleri Laccase and characterization of degradation products.

Science.gov (United States)

Kenzom, T; Srivastava, P; Mishra, S

2014-12-01

Advanced oxidation processes are currently used for the treatment of different reactive dyes which involve use of toxic catalysts. Peroxidases are reported to be effective on such dyes and require hydrogen peroxide and/or metal ions. Cyathus bulleri laccase, expressed in Pichia pastoris, catalyzes efficient degradation (78 to 85%) of reactive azo dyes (reactive black 5, reactive orange 16, and reactive red 198) in the presence of synthetic mediator ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)]. This laccase was engineered to degrade effectively reactive blue 21 (RB21), a phthalocyanine dye reported to be decolorized only by peroxidases. The 816-bp segment (toward the C terminus) of the lcc gene was subjected to random mutagenesis and enzyme variants (Lcc35, Lcc61, and Lcc62) were selected based on increased ABTS oxidizing ability. Around 78 to 95% decolorization of RB21 was observed with the ABTS-supplemented Lcc variants in 30 min. Analysis of the degradation products by mass spectrometry indicated the formation of several low-molecular-weight compounds. Mapping the mutations on the modeled structure implicated residues both near and far from the T1 Cu site that affected the catalytic efficiency of the mutant enzymes on ABTS and, in turn, the rate of oxidation of RB21. Several inactive clones were also mapped. The importance of geometry as well as electronic changes on the reactivity of laccases was indicated. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Degradation of Synthetic Dyes by Laccases – A Mini-Review

Directory of Open Access Journals (Sweden)

Legerská Barbora

2016-06-01

Full Text Available Laccases provide a promising future as a tool to be used in the field of biodegradation of synthetic dyes with different chemical structures. These enzymes are able to oxidize a wide range of phenolic substrates without the presence of additional co-factors. Laccases have been confirmed for their potential of synthetic dye degradation from wastewater and degradation products of these enzymatic reactions become less toxic than selected dyes. This study discusses the potential of laccase enzymes as agents for laccase-catalyzed degradation in terms of biodegradation efficiency of synthetic dyes, specifically: azo dyes, triphenylmethane, indigo and anthraquinone dyes. Review also summarizes the laccase-catalyzed degradation mechanisms of the selected synthetic dyes, as well as the degradation products and the toxicity of the dyes and their degradation products.

Degradation and metabolism of synthetic plastics and associated products by Pseudomonas sp.: capabilities and challenges.

Science.gov (United States)

Wilkes, R A; Aristilde, L

2017-09-01

Synthetic plastics, which are widely present in materials of everyday use, are ubiquitous and slowly-degrading polymers in environmental wastes. Of special interest are the capabilities of microorganisms to accelerate their degradation. Members of the metabolically diverse genus Pseudomonas are of particular interest due to their capabilities to degrade and metabolize synthetic plastics. Pseudomonas species isolated from environmental matrices have been identified to degrade polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polyethylene terephthalate, polyethylene succinate, polyethylene glycol and polyvinyl alcohol at varying degrees of efficiency. Here, we present a review of the current knowledge on the factors that control the ability of Pseudomonas sp. to process these different plastic polymers and their by-products. These factors include cell surface attachment within biofilms, catalytic enzymes involved in oxidation or hydrolysis of the plastic polymer, metabolic pathways responsible for uptake and assimilation of plastic fragments and chemical factors that are advantageous or inhibitory to the biodegradation process. We also highlight future research directions required in order to harness fully the capabilities of Pseudomonas sp. in bioremediation strategies towards eliminating plastic wastes. © 2017 The Society for Applied Microbiology.

Removal of nalidixic acid and its degradation products by an integrated MBR-ozonation system.

Science.gov (United States)

Pollice, A; Laera, G; Cassano, D; Diomede, S; Pinto, A; Lopez, A; Mascolo, G

2012-02-15

Chemical-biological degradation of a widely spread antibacterial (nalidixic acid) was successfully obtained by an integrated membrane bioreactor (MBR)-ozonation process. The composition of the treated solution simulated the wastewater from the production of the target pharmaceutical, featuring high salinity and a relevant concentration of sodium acetate. Aim of treatment integration was to exploit the synergistic effects of chemical oxidation and bioprocesses, by adopting the latter to remove most of the COD and the ozonation biodegradable products. Integration was achieved by placing ozonation in the recirculation stream of the bioreactor effluent. The recirculation flow rate was three-fold the MBR feed, and the performance of the integrated system was compared to the standard polishing configuration (single ozonation step after the MBR). Results showed that the introduction of the ozonation step did not cause relevant drawbacks to both biological and filtration processes. nalidixic acid passed undegraded through the MBR and was completely removed in the ozonation step. Complete degradation of most of the detected ozonation products was better achieved with the integrated MBR-ozonation process than using the sequential treatment configuration, i.e. ozone polishing after MBR, given the same ozone dosage. Copyright © 2011 Elsevier B.V. All rights reserved.

Capillary zone electrophoresis method to assay tipranavir capsules and identification of oxidation product and organic impurity by quadrupole-time of flight mass spectrometry.

Science.gov (United States)

Lago, Matheus Wagner; Friedrich, Mariane Lago; Iop, Gabrielle Dineck; de Souza, Thiago Belarmino; de Azevedo Mello, Paola; Adams, Andréa Inês Horn

2018-05-01

Tipranavir (TPV) is one of the most recently developed protease inhibitors (PI) and it is specially recommended for treatment-experienced patients who are resistant to other PI drugs. In this work, a simple and friendly environmental CZE stability-indicating method to assay TPV capsules was developed and two TPV organic impurities were identified by high resolution mass spectrometry (HRMS). The optimized analytical conditions were: background electrolyte composed of sodium borate 50mM, pH 9.0 and 5% of methanol; voltage + 28kV; hydrodynamic injection of 5s (100mbar), detection wavelength 240nm, at 25°C. The separation was achieved in a fused silica capillary with 50µm × 40cm (inner diameter × effective length), using furosemide as internal standard. All the validation parameters were met and the method was specific, even in the presence of degradation products and impurities. Oxidation was indicated as the main degradation pathway among those evaluated in this study (acidic, alkaline, thermal, photolytic and oxidative) and it showed a second order degradation kinetic, under the conditions used in this study. The main oxidation product and an organic impurity detected in the standard were characterized by Q-TOF, and both of them correspond to oxidation products of TPV. Copyright © 2018 Elsevier B.V. All rights reserved.

A Comparative Analysis of 2-(Thiocyanomethylthio-Benzothiazole Degradation Using Electro-Fenton and Anodic Oxidation on a Boron-Doped Diamond Electrode

Directory of Open Access Journals (Sweden)

Armando Vázquez

2018-01-01

Full Text Available 2-(Thiocyanomethylthio-benzothiazole (TCMTB is used as fungicide in the paper, tannery, paint, and coatings industries, and its study is important as it is considered toxic to aquatic life. In this study, a comparison of direct anodic oxidation (AO using a boron-doped diamond electrode (BDD and electro-Fenton (EF processes for TCMTB degradation in acidic chloride and sulfate media using a FM01-LC reactor was performed. The results of the electrolysis processes studied in the FM01-LC reactor showed a higher degradation of TCMTB with the anodic oxidation process than with the electro-Fenton process, reaching 81% degradation for the former process versus 47% degradation for the latter process. This difference was attributed to the decrease in H2O2 during the EF process, due to parallel oxidation of chlorides. The degradation rate and current efficiency increased as a function of volumetric flow rate, indicating that convection promotes anodic oxidation and electro-Fenton processes. The results showed that both AO and EF processes could be useful strategies for TCMTB toxicity reduction in wastewaters.

Linear equations on thermal degradation products of wood chips in alkaline glycerol

International Nuclear Information System (INIS)

Demirbas, Ayhan

2004-01-01

Wood chips of 0.3 and 2 mm depth from poplar and spruce wood samples, respectively, were degraded by using glycerol as a solvent and alkaline glycerol with and without Na 2 CO 3 and NaOH catalysts at different degradation temperatures: 440, 450, 460, 470, 480, 490 and 500 K. By products from the degradation processes of the ligno celluloses include lignin degradation products. Lignin and its degradation products have fuel values. The total degradation degree and cellulose degradation of the wood chips were determined to find the relationship, if any, between the yields of total degradation degree (YTD) and degradation temperature (T). There is a good linear relationship between YTD or the yields of cellulose degradation (YCD) and T (K). For the wood samples, the regression equations from NaOH (10%) catalytic runs for 0.3 mm x 15 mm x 15 mm chip size are: For poplar wood: (YTD=0.7250T-267.507) (YCD=0.1736T-71.707) For spruce wood: (YTD=0.2650T-105.979) (YCD=0.0707T-27.507) For Eqs., the square of the correlation coefficient (r 2 ) were 0.9841, 0.9496, 0.9839 and 0.9447, respectively

Identification of Degradation Products of Lincomycin and Iopromide by Electron Beam Irradiation

International Nuclear Information System (INIS)

Cha, Yongbyoung; Ham, Hyunsun; Myung, Seungwoon

2013-01-01

Lincomycin and Iopromide are major species among the Pharmaceuticals and Personal Care Products (PPCPs) from four major rivers in Korea. The structure characterization of six lincomycin's and two iopromide's degradation products formed under the irradiation of electron beam was performed, and the degradation efficiency as a function of the various irradiation dose and sample concentration was investigated. Electron beam (10 MeV, 0.5 mA and 5 kW) experiments for the structural characterization of the degradation products, which is fortified with lincomycin, were performed at the dose of 10 kGy. The separation of its degradation products and lincomycin was carried by C18 column (2.1 Χ 100 mm, 3.5 μm), using gradient elution with 20 mM ammonium acetate and acetonitrile. The structures of degradation products of lincomycin and iopromide were proposed by interpretation of mass spectra and chromatograms by LC/MS/MS, and also the mass fragmentation pathways of mass spectra in tandem mass spectrometry were proposed. The experiments of the degradation efficiency as a function of the irradiation dose intensity and the initial concentration of lincomycin in aqueous environment were performed, and higher dose of electron beam and lower concentration was observed the increased degradation efficiency

Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO3−δ metal oxide

International Nuclear Information System (INIS)

Leiw, Ming Yian; Guai, Guan Hong; Wang, Xiaoping; Tse, Man Siu; Ng, Chee Mang; Tan, Ooi Kiang

2013-01-01

Highlights: • Perovskite SFO prepared by high temperature and high-energy ball milling process. • SFO metal oxide shows good efficiency in degrading and mineralizing BPA. • Rapid decoloration of AO8 was achieved in the presence of SFO metal oxide. • O 2 · − is the predominant ROS for dark oxidative degradation of BPA and AO8. -- Abstract: Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment

Elaboration of nano titania-magnetic reduced graphene oxide for degradation of tartrazine dye in aqueous solution

Science.gov (United States)

Nada, Amr A.; Tantawy, Hesham R.; Elsayed, Mohamed A.; Bechelany, Mikhael; Elmowafy, Mohamed E.

2018-04-01

In this paper, magnetic nanocomposites are synthesized by loading reduced graphene oxide (RG) with two components of nanoparticles consisting of titanium dioxide (TiO2) and magnetite (Fe3O4) with varying amounts. The structural and magnetic features of the prepared composite photocatalysts were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectra (UV-vis/DRS), Raman and vibrating sample magnetometer (VSM). The resulting TiO2/magnetite reduced graphene oxide (MRGT) composite demonstrated intrinsic visible light photocatalytic activity, on degradation of tartrazine (TZ) dye from a synthetic aqueous solution. Specifically, it exhibits higher photocatalytic activity than magnetite reduced graphene oxide (MRG) and TiO2 nanoparticles. The photocatalytic degradation of TZ dye when using MRG and TiO2 for 3 h under visible light was 35% and 10% respectively, whereas for MRGT it was more than 95%. The higher photocatalytic efficiency of MRGT is due to the existence of reduced graphene oxide and magnetite which enhances the photocatalytic efficiency of the composite in visible light towards the degradation of harmful soluble azo dye (tartrazine).

Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

Science.gov (United States)

Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

2015-11-04

Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation.

Analytical aspects of the remediation of soil by wet oxidation - Characterisation of tar contaminants and their degradation products

DEFF Research Database (Denmark)

Thomsen, A.B.; Nielsen, T.; Plöger, A.

1999-01-01

Wet oxidation of tar compounds gives rise to a wide range of products. Due to the incorporation of oxygen, these products become increasingly more water soluble and the analytical strategy has to take into account the different physical/chemicalproperties of the compounds. An interplay between ga...

Structural Insights into 2,2′-Azino-Bis(3-Ethylbenzothiazoline-6-Sulfonic Acid) (ABTS)-Mediated Degradation of Reactive Blue 21 by Engineered Cyathus bulleri Laccase and Characterization of Degradation Products

Science.gov (United States)

Kenzom, T.; Srivastava, P.

2014-01-01

Advanced oxidation processes are currently used for the treatment of different reactive dyes which involve use of toxic catalysts. Peroxidases are reported to be effective on such dyes and require hydrogen peroxide and/or metal ions. Cyathus bulleri laccase, expressed in Pichia pastoris, catalyzes efficient degradation (78 to 85%) of reactive azo dyes (reactive black 5, reactive orange 16, and reactive red 198) in the presence of synthetic mediator ABTS [2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)]. This laccase was engineered to degrade effectively reactive blue 21 (RB21), a phthalocyanine dye reported to be decolorized only by peroxidases. The 816-bp segment (toward the C terminus) of the lcc gene was subjected to random mutagenesis and enzyme variants (Lcc35, Lcc61, and Lcc62) were selected based on increased ABTS oxidizing ability. Around 78 to 95% decolorization of RB21 was observed with the ABTS-supplemented Lcc variants in 30 min. Analysis of the degradation products by mass spectrometry indicated the formation of several low-molecular-weight compounds. Mapping the mutations on the modeled structure implicated residues both near and far from the T1 Cu site that affected the catalytic efficiency of the mutant enzymes on ABTS and, in turn, the rate of oxidation of RB21. Several inactive clones were also mapped. The importance of geometry as well as electronic changes on the reactivity of laccases was indicated. PMID:25261507

Phospholamban Is Downregulated by pVHL-Mediated Degradation through Oxidative Stress in Failing Heart

Directory of Open Access Journals (Sweden)

Shunichi Yokoe

2017-10-01

Full Text Available The E3 ubiquitin ligase, von Hippel–Lindau (VHL, regulates protein expression by polyubiquitination. Although the protein VHL (pVHL was reported to be involved in the heart function, the underlying mechanism is unclear. Here, we show that pVHL was upregulated in hearts from two types of genetically dilated cardiomyopathy (DCM mice models. In comparison with the wild-type mouse, both DCM mice models showed a significant reduction in the expression of phospholamban (PLN, a potent inhibitor of sarco(endoplasmic reticulum Ca2+-ATPase, and enhanced interaction between pVHL and PLN. To clarify whether pVHL is involved in PLN degradation in failing hearts, we used carbonylcyanide m-chlorophenylhydrazone (CCCP, a mitochondrial membrane potential (MMP-lowering reagent, to mimic the heart failure condition in PLN-expressing HEK293 cells and found that CCCP treatment resulted in PLN degradation and increased interaction between PLN and pVHL. However, these effects were reversed with the addition of N-acetyl-l-cysteine. Furthermore, the co-transfection of VHL and PLN in HEK293 cells decreased PLN expression under oxidative stress, whereas knockdown of VHL increased PLN expression both under normal and oxidative stress conditions. Together, we propose that oxidative stress upregulates pVHL expression to induce PLN degradation in failing hearts.

Tailoring oxides of copper-Cu_2O and CuO nanoparticles and evaluation of organic dyes degradation

International Nuclear Information System (INIS)

Raghav, Ragini; Aggarwal, Priyanka; Srivastava, Sudha

2016-01-01

We report a simple one-pot colloidal synthesis strategy tailoring cuprous or cupric nano-oxides in pure state. NaOH provided alkaline conditions (pH 12.5 -13) for nano-oxides formation, while its concentration regulated the oxidation state of the nano-oxides. The morphological, structural and optical properties of synthesized Cu_2O and CuO nanoparticles were studied by transmission electron microscopy (TEM), X-Ray diffraction (XRD) and UV-vis spectroscopy. Dye degradation capability of CuO and Cu2O nanoparticles was evaluated using four organic dyes - Malachite green, Methylene blue, Methyl orange and Methyl red. The results demonstrate effective degradation of all four dyes employing with almost comparable activity both Cu_2O and CuO nanoparticles.

The effect of natural iron oxide and oxalic acid on the photocatalytic degradation of isoproturon: a kinetics and analytical study.

Science.gov (United States)

Boucheloukh, H; Remache, W; Parrino, F; Sehili, T; Mechakra, H

2017-05-17

The photocatalytic degradation of isoproturon, a persistent toxic herbicide, was investigated in the presence of natural iron oxide and oxalic acid and under UV irradiation. The influence of the relevant parameters such as the pH and the iron oxide and oxalic acid concentrations has been studied. The presence of natural iron oxide and oxalic acid in the system effectively allow the degradation of isoproturon, whereas the presence of t-butyl alcohol adversely affects the phototransformation of the target pollutant, thus indicating that an OH radical initiated the degradation mechanism. The degradation mechanism of isoproturon was investigated by means of GC-MS analysis. Oxidation of both the terminal N-(CH 3 ) 2 and isopropyl groups is the initial process leading to N-monodemethylated (NHCH 3 ), N-formyl (N(CH 3 )CHO), and CHCH 3 OH as the main intermediates. The substitution of the isopropyl group by an OH group is also observed as a side process.

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

Science.gov (United States)

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. Copyright © 2013 Elsevier B.V. All rights reserved.

Oxidation Responsive Polymers with a Triggered Degradation via Arylboronate Self-Immolative Motifs on a Polyphosphazene Backbone.

Science.gov (United States)

Iturmendi, Aitziber; Monkowius, Uwe; Teasdale, Ian

2017-02-21

Oxidation responsive polymers with triggered degradation pathways have been prepared via attachment of self-immolative moieties onto a hydrolytically unstable polyphosphazene backbone. After controlled main-chain growth, postpolymerization functionalization allows the preparation of hydrolytically stable poly(organo)phosphazenes decorated with a phenylboronic ester caging group. In oxidative environments, triggered cleavage of the caging group is followed by self-immolation, exposing the unstable glycine-substituted polyphosphazene which subsequently undergoes to backbone degradation to low-molecular weight molecules. As well as giving mechanistic insights, detailed GPC and 1 H and 31 P NMR analysis reveal the polymers to be stable in aqueous solutions, but show a selective, fast degradation upon exposure to hydrogen peroxide containing solutions. Since the post-polymerization functionalization route allows simple access to polymer backbones with a broad range of molecular weights, the approach of using the inorganic backbone as a platform significantly expands the toolbox of polymers capable of stimuli-responsive degradation.

Thermal Degradation Kinetics Modeling of Benzophenones and Xanthones during High-Temperature Oxidation of Cyclopia genistoides (L.) Vent. Plant Material.

Science.gov (United States)

Beelders, Theresa; de Beer, Dalene; Joubert, Elizabeth

2015-06-10

Degradation of the major benzophenones, iriflophenone-3-C-glucoside-4-O-glucoside and iriflophenone-3-C-glucoside, and the major xanthones, mangiferin and isomangiferin, of Cyclopia genistoides followed first-order reaction kinetics during high-temperature oxidation of the plant material at 80 and 90 °C. Iriflophenone-3-C-glucoside-4-O-glucoside was shown to be the most thermally stable compound. Isomangiferin was the second most stable compound at 80 °C, while its degradation rate constant was influenced the most by increased temperature. Mangiferin and iriflophenone-3-C-glucoside had comparable degradation rate constants at 80 °C. The thermal degradation kinetic model was subsequently evaluated by subjecting different batches of plant material to oxidative conditions (90 °C/16 h). The model accurately predicted the individual contents of three of the compounds in aqueous extracts prepared from oxidized plant material. The impact of benzophenone and xanthone degradation was reflected in the decreased total antioxidant capacity of the aqueous extracts, as determined using the oxygen radical absorbance capacity and DPPH(•) scavenging assays.

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

Energy Technology Data Exchange (ETDEWEB)

Gui Minghui; Smuleac, Vasile [University of Kentucky, Department of Chemical and Materials Engineering (United States); Ormsbee, Lindell E. [University of Kentucky, Department of Civil Engineering (United States); Sedlak, David L. [University of California at Berkeley, Department of Civil and Environmental Engineering (United States); Bhattacharyya, Dibakar, E-mail: db@engr.uky.edu [University of Kentucky, Department of Chemical and Materials Engineering (United States)

2012-05-15

The potential for using hydroxyl radical (OH{sup Bullet }) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H{sub 2}O{sub 2} addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80-100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Moessbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H{sub 2}O{sub 2} by NP surface generated OH{sup Bullet} were investigated. Depending on the ratio of iron and H{sub 2}O{sub 2}, TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Iron oxide nanoparticle synthesis in aqueous and membrane systems for oxidative degradation of trichloroethylene from water

International Nuclear Information System (INIS)

Gui Minghui; Smuleac, Vasile; Ormsbee, Lindell E.; Sedlak, David L.; Bhattacharyya, Dibakar

2012-01-01

The potential for using hydroxyl radical (OH • ) reactions catalyzed by iron oxide nanoparticles (NPs) to remediate toxic organic compounds was investigated. Iron oxide NPs were synthesized by controlled oxidation of iron NPs prior to their use for contaminant oxidation (by H 2 O 2 addition) at near-neutral pH values. Cross-linked polyacrylic acid (PAA) functionalized polyvinylidene fluoride (PVDF) microfiltration membranes were prepared by in situ polymerization of acrylic acid inside the membrane pores. Iron and iron oxide NPs (80–100 nm) were directly synthesized in the polymer matrix of PAA/PVDF membranes, which prevented the agglomeration of particles and controlled the particle size. The conversion of iron to iron oxide in aqueous solution with air oxidation was studied based on X-ray diffraction, Mössbauer spectroscopy and BET surface area test methods. Trichloroethylene (TCE) was selected as the model contaminant because of its environmental importance. Degradations of TCE and H 2 O 2 by NP surface generated OH • were investigated. Depending on the ratio of iron and H 2 O 2 , TCE conversions as high as 100 % (with about 91 % dechlorination) were obtained. TCE dechlorination was also achieved in real groundwater samples with the reactive membranes.

Two and three way spectrophotometric-assisted multivariate determination of linezolid in the presence of its alkaline and oxidative degradation products and application to pharmaceutical formulation

Science.gov (United States)

Hegazy, Maha Abd El-Monem; Eissa, Maya Shaaban; Abd El-Sattar, Osama Ibrahim; Abd El-Kawy, Mohammad

2014-07-01

Linezolid (LIN) is determined in the presence of its alkaline (ALK) and oxidative (OXD) degradation products without preliminary separation based on ultraviolet spectrophotometry using two-way chemometric methods; principal component regression (PCR) and partial least-squares (PLS), and three-way chemometric methods; parallel factor analysis (PARAFAC) and multi-way partial least squares (N-PLS). A training set of mixtures containing LIN, ALK and OXD; was prepared in the concentration ranges of 12-18, 2.4-3.6 and 1.2-1.8 μg mL-1, respectively according to a multilevel multifactor experimental design. The multivariate calibrations were obtained by measuring the zero-order absorbance from 220 to 320 nm using the training set. The validation of the multivariate methods was realized by analyzing their synthetic mixtures. The capabilities of the chemometric analysis methods for the analysis of real samples were evaluated by determination of LIN in its pharmaceutical preparation with satisfactory results. The accuracy of the methods, evaluated through the root mean square error of prediction (RMSEP), was 0.058, 0.026, 0.101 and 0.026 for LIN using PCR, PLS, PARAFAC and N-PLS, respectively. Protolytic equilibria of LIN and its degradation products were evaluated using the corresponding absorption spectra-pH data obtained with PARAFAC. The obtained pKa values of LIN, ALK and OXD are 5.70, 8.90 and 6.15, respectively. The results obtained were statistically compared to that of a reported HPLC method, and there was no significant difference between the proposed methods and the reported method regarding both accuracy and precision.

Dark ambient degradation of Bisphenol A and Acid Orange 8 as organic pollutants by perovskite SrFeO{sub 3−δ} metal oxide

Energy Technology Data Exchange (ETDEWEB)

Leiw, Ming Yian, E-mail: LEIW0003@e.ntu.edu.sg [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); Guai, Guan Hong [GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); School of Chemical and Biomedical Engineering and Center for Advanced Bionanosystems, Nanyang Technological University, 70 Nanyang Drive, Singapore 637457 (Singapore); Wang, Xiaoping [School of Civil and Environmental Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Tse, Man Siu [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore); Ng, Chee Mang [GlobalFoundries Singapore Pte. Ltd., 60 Woodlands Industrial Park D Street 2, Singapore 738406 (Singapore); Tan, Ooi Kiang [School of Electrical and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)

2013-09-15

Highlights: • Perovskite SFO prepared by high temperature and high-energy ball milling process. • SFO metal oxide shows good efficiency in degrading and mineralizing BPA. • Rapid decoloration of AO8 was achieved in the presence of SFO metal oxide. • O{sub 2}·{sup −} is the predominant ROS for dark oxidative degradation of BPA and AO8. -- Abstract: Current advanced oxidation processes (AOPs) are chemically and energetically intensive processes, which are undesirable for cost-effective and large-scale system water treatment and wastewater recycling. This study explored the Strontium Ferrite (SFO) metal oxide on the degradation of highly concentrated organic pollutants under dark ambient condition without any external stimulants. The SFO particles with single perovskite structure were successfully synthesized with a combined high temperature and high-energy ball milling process. An endocrine disruptor, Bisphenol A (BPA) and an azo dye, Acid Orange 8 (AO8) were used as probe organic pollutants. BPA was completely degraded with 83% of mineralization in 24 h while rapid decoloration of AO8 was achieved in 60 min and complete breakdown into primary intermediates and aliphatic acids occurred in 24 h under the treatment of dispersed SFO metal oxide in water. Such efficient degradation could be attributed to the enhanced adsorption of these anionic pollutants on positively charged ball-milled SFO metal oxide surface, resulted in higher degradation activity. Preliminary degradation mechanisms of BPA and AO8 under the action of SFO metal oxide were proposed. These results showed that the SFO metal oxide could be an efficient alternative material as novel advanced oxidation technology for low cost water treatment.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

Science.gov (United States)

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Peroxymonosulfate activation and pollutants degradation over highly dispersed CuO in manganese oxide octahedral molecular sieve

Science.gov (United States)

Li, Jun; Ye, Peng; Fang, Jia; Wang, Manye; Wu, Deming; Xu, Aihua; Li, Xiaoxia

2017-11-01

Manganese oxide octahedral molecular sieves (OMS-2) supported CuO catalysts were synthesized, characterized and used in the removal of Acid Orange 7 (AO7) in aqueous solution by an oxidation process involving peroxymonosulfate (PMS). It was found that the CuO species were highly dispersed in OMS-2 with a high ratio of easily reduced surface oxygen species. The synergetic effect between CuO and OMS-2 significantly improved the dye degradation rate and catalytic stability, compared with CuO, OMS-2 and supported CuO on other materials. About 97% of the dye was removed within 15 min at neutral solution pH by using 0.2 g/L of CuO/OMS-2 and PMS. The effect of initial solution pH, PMS concentration, reaction temperature and CuO content in the composites on AO7 degradation was also investigated. Mechanism study indicated that SO4-rad radicals generated from the interaction between PMS and Mn and Cu species with different oxidation states, mainly accounted for the degradation.

Degradation of organophosphorus pesticide parathion methyl on nanostructured titania-iron mixed oxides

Czech Academy of Sciences Publication Activity Database

Henych, Jiří; Štengl, Václav; Slušná, Michaela; Matys Grygar, Tomáš; Janoš, P.; Kuráň, P.; Šťastný, M.

2015-01-01

Roč. 344, JUL (2015), s. 9-16 ISSN 0169-4332 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : Titania-iron oxides * Homogeneous hydrolysis * Degradation of organophosphates * Parathion methyl Subject RIV: CA - Inorganic Chemistry Impact factor: 3.150, year: 2015

Degradation and ecotoxicity of dye Reactive Black 5 after reductive-oxidative process : Environmental Science and Pollution Research.

Science.gov (United States)

Cuervo Lumbaque, Elisabeth; Gomes, Monike Felipe; Da Silva Carvalho, Vanessa; de Freitas, Adriane Martins; Tiburtius, Elaine Regina Lopes

2017-03-01

This research paper describes the study of a reduction-oxidation system using commercial steel wool (Fe 0 ) and H 2 O 2 for degradation of the dye Reactive Black 5 and aromatic compounds in water. The reductive process alone allowed the almost complete removal of color (97 ± 1 %) after 60 min of reaction. The decrease in spectral area (λ = 599 nm) associated with the chromophore group indicates breakage of the azo bonds. Moreover, the significant change in UV spectra can be associated with the formation of aromatic amines. Regarding the transformation products, a spectrophotometric method based on the diazotization reaction was employed to identify aromatic amines after reductive process, using sulfanilic acid as a model of aromatic amines. In addition, association with Fenton reagents improved the efficiency in the system with 93 ± 1 % degradation of intermediates formed during the reductive process. Ecotoxicological analysis revealed that the dye solution, after the reductive and oxidative processes, was not toxic to Lactuca sativa seeds. For Daphnia magna, the EC 50 (%) values observed revealed that dye solution has an EC 50 (%) = 74.1 and after reductive process, the toxicity increased (EC 50 (%) = 63.5), which might be related to the formation of aromatic amines. However, after the Fenton process, the EC 50 (%) was >100. These results demonstrated that the Fenton reaction using steel wool as an iron source was very efficient to decrease color, aromatic transformation products, and the ecotoxicity of Reactive Black 5 in solution.

Electro-Fenton and photoelectro-Fenton degradations of the drug beta-blocker propranolol using a Pt anode: Identification and evolution of oxidation products

Energy Technology Data Exchange (ETDEWEB)

Isarain-Chavez, Eloy; Cabot, Pere Lluis; Centellas, Francesc; Rodriguez, Rosa Maria; Arias, Conchita; Garrido, Jose Antonio [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric, E-mail: brillas@ub.edu [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

2011-01-30

The beta-blocker propranolol hydrochloride has been degraded by electrochemical advanced oxidation processes like electro-Fenton (EF) and photoelectro-Fenton (PEF) using a single cell with a Pt anode and an air diffusion cathode (ADE) for H{sub 2}O{sub 2} electrogeneration and a combined system containing the above Pt/ADE pair coupled in parallel to a Pt/carbon-felt (CF) cell. Organics are mainly oxidized with hydroxyl radical ({center_dot}OH) formed from Fenton's reaction between added Fe{sup 2+} and electrogenerated H{sub 2}O{sub 2}. The PEF treatment in Pt/ADE-Pt/CF system yields almost total mineralization because {center_dot}OH production is enhanced by Fe{sup 2+} regeneration from Fe{sup 3+} reduction at the CF cathode and Fe(III) complexes with generated carboxylic acids are rapidly photodecarboxylated under UVA irradiation. Lower mineralization degree is found for PEF in Pt/ADE cell due to the little influence of UVA light on Fe{sup 2+} regeneration. The homologous EF processes are much less potent as a result of the persistence of Fe(III)-carboxylate complexes. Aromatic intermediates such as 1-naphthol, 1,4-naphthoquinone and phthalic acid and generated carboxylic acids such as pyruvic, glycolic, malonic, maleic, oxamic, oxalic and formic are identified. While chloride ion remains stable, NH{sub 4}{sup +} and NO{sub 3}{sup -} ions are released to the medium. A reaction sequence for propranolol hydrochloride mineralization is proposed.

Discovery of LPMO activity on hemicelluloses shows the importance of oxidative processes in plant cell wall degradation

DEFF Research Database (Denmark)

Agger, Jane W.; Isaksen, Trine; Várnai, Anikó

2014-01-01

of LPMOs, and considering the complexity and copolymeric nature of the plant cell wall, it has been speculated that some LPMOs may act on other substrates, in particular the hemicelluloses that tether to cellulose microfibrils. We demonstrate that an LPMO from Neurospora crassa, NcLPMO9C, indeed degrades...... walls. Products generated by NcLPMO9C were analyzed using high performance anion exchange chromatography and multidimensional mass spectrometry. We show that NcLPMO9C generates oxidized products from a variety of substrates and that its product profile differs from those of hydrolytic enzymes acting...... on the same substrates. The enzyme particularly acts on the glucose backbone of xyloglucan, accepting various substitutions (xylose, galactose) in almost all positions. Because the attachment of xyloglucan to cellulose hampers depolymerization of the latter, it is possible that the beneficial effect...

COMPARISON OF METHODS FOR ETHYLHEXYL 4-METHOXYCINNAMATE ACID ESTER OXIDATION IN WATER MEDIUM

Directory of Open Access Journals (Sweden)

Waldemar Studziński

2017-07-01

Full Text Available The aim of studies was to compare an impact of oxidizing agents on degradation of ethylhexyl 4-methoxycinnamate acid (EHMC. The oxidation reaction was carried out in the presence of sodium hypochlorite, hydrogen peroxide and ozone with/without UV radiation. EHMC degradation and analysis of products were performed using gas chromatograph coupled with mass spectrometry detector. The most effective method of EHMC degradation turned out to be ozonation with participation of UV radiation. In this system, degradation proceeded the most quickly and generated formation of small amount of by-products (2-propyl-1-pentanol; 4-metoxybenzaldehyde and Z-EHMC. Under the influence of sodium hypochlorite, the numerous chloroorganic products were formed, which can cause secondary contamination of water. Application of appropriate oxidation processes can contribute to degradation of micropollutants and thus to improvement of water quality.

Degradation of chitosan hydrogel dispersed in dilute carboxylic acids by solution plasma and evaluation of anticancer activity of degraded products

Science.gov (United States)

Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Theeramunkong, Sewan; Saito, Nagahiro

2018-01-01

Chitosan is a polysaccharide that has been extensively studied in the field of biomedicine, especially its water-soluble degraded products called chitooligosaccharides (COS). In this study, COS were produced by the degradation of chitosan hydrogel dispersed in a dilute solution (i.e., 1.55 mM) of various kinds of carboxylic acids using a non-thermal plasma technology called solution plasma (SP). The degradation rates of chitosan were influenced by the type of carboxylic acids, depending on the interaction between chitosan and each carboxylic acid. After SP treatment, the water-soluble degraded products containing COS could be easily separated from the water-insoluble residue of chitosan hydrogel by centrifugation. The production yields of the COS were mostly higher than 55%. Furthermore, the obtained COS products were evaluated for their inhibitory effect as well as their selectivity against human lung cancer cells (H460) and human lung normal cells (MRC-5).

Degradation of the fluoroquinolone enrofloxacin by electrochemical advanced oxidation processes based on hydrogen peroxide electrogeneration

Energy Technology Data Exchange (ETDEWEB)

Guinea, Elena; Garrido, Jose Antonio; Rodriguez, Rosa Maria; Cabot, Pere-Lluis; Arias, Conchita; Centellas, Francesc [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain); Brillas, Enric, E-mail: brillas@ub.ed [Laboratori d' Electroquimica dels Materials i del Medi Ambient, Departament de Quimica Fisica, Facultat de Quimica, Universitat de Barcelona, Marti i Franques 1-11, 08028 Barcelona (Spain)

2010-02-15

Solutions of the veterinary fluoroquinolone antibiotic enrofloxacin in 0.05 M Na{sub 2}SO{sub 4} of pH 3.0 have been comparatively degraded by electrochemical advanced oxidation processes such as anodic oxidation with electrogenerated H{sub 2}O{sub 2} (AO-H{sub 2}O{sub 2}), electro-Fenton (EF), photoelectro-Fenton (PEF) and solar photoelectro-Fenton (SPEF) at constant current density. The study has been performed using an undivided stirred tank reactor of 100 ml and a batch recirculation flow plant of 2.5 l with an undivided filter-press cell coupled to a solar photoreactor, both equipped with a Pt or boron-doped diamond (BDD) anode and a carbon-polytetrafluoroethylene gas diffusion cathode to generate H{sub 2}O{sub 2} from O{sub 2} reduction. In EF, PEF and SPEF, hydroxyl radical (centre dotOH) is formed from Fenton's reaction between added catalytic Fe{sup 2+} and generated H{sub 2}O{sub 2}. Almost total decontamination of enrofloxacin solutions is achieved in the stirred tank reactor by SPEF with BDD. The use of the batch recirculation flow plant showed that this process is the most efficient and can be viable for industrial application, becoming more economic and yielding higher mineralization degree with raising antibiotic content. This is feasible because organics are quickly oxidized with centre dotOH formed from Fenton's reaction and at BDD from water oxidation, combined with the fast photolysis of complexes of Fe(III) with generated carboxylic acids under solar irradiation. The lower intensity of UVA irradiation used in PEF with BDD causes a slower degradation. EF with BDD is less efficient since centre dotOH cannot destroy the most persistent Fe(III)-oxalate and Fe(III)-oxamate complexes. AO-H{sub 2}O{sub 2} with BDD yields the poorest mineralization because pollutants are only removed with centre dotOH generated at BDD. All procedures are less potent using Pt as anode due to the lower production of centre dotOH at its surface. Enrofloxacin

A Bayesian approach to degradation-based burn-in optimization for display products exhibiting two-phase degradation patterns

International Nuclear Information System (INIS)

Yuan, Tao; Bae, Suk Joo; Zhu, Xiaoyan

2016-01-01

Motivated by the two-phase degradation phenomena observed in light displays (e.g., plasma display panels (PDPs), organic light emitting diodes (OLEDs)), this study proposes a new degradation-based burn-in testing plan for display products exhibiting two-phase degradation patterns. The primary focus of the burn-in test in this study is to eliminate the initial rapid degradation phase, while the major purpose of traditional burn-in tests is to detect and eliminate early failures from weak units. A hierarchical Bayesian bi-exponential model is used to capture two-phase degradation patterns of the burn-in population. Mission reliability and total cost are introduced as planning criteria. The proposed burn-in approach accounts for unit-to-unit variability within the burn-in population, and uncertainty concerning the model parameters, mainly in the hierarchical Bayesian framework. Available pre-burn-in data is conveniently incorporated into the burn-in decision-making procedure. A practical example of PDP degradation data is used to illustrate the proposed methodology. The proposed method is compared to other approaches such as the maximum likelihood method or the change-point regression. - Highlights: • We propose a degradation-based burn-in test for products with two-phase degradation. • Mission reliability and total cost are used as planning criteria. • The proposed burn-in approach is built within the hierarchical Bayesian framework. • A practical example was used to illustrate the proposed methodology.

Possible Appearance of Degradation Products of Paraquat in Crops

Energy Technology Data Exchange (ETDEWEB)

Slade, P. [Imperial Chemical Industries LTD., Jealott' s Hill Research Station, Bracknell, Berks. (United Kingdom)

1966-05-15

Chemical analysis has established that residue levels of paraquat in crops harvested after use of the chemical are at such a low level as to constitute no hazard to the consuming public. (Paraquat dichloride is 1,1'-dimethyl-4,4'-bipyridylium dichloride). There remained the possibility that toxic metabolites or other conversion products of paraquat might appear in crops. This paper is concerned with attempts to evaluate this possibility, and demonstrates that no hazard arises from the formation of degradation products. It has been shown, using paraquat labelled with {sup 14}C in the methyl groups and in the pyridine nuclei, that the chemical is not metabolically degraded in plants. However, photochemical degradation of paraquat can occur on the surface of leaves in sunlight. In vitro experiments involving ultra-violet irradiation of aqueous solutions of {sup 14}C-paraquat have shown that 4-carboxy-1-methylpyridinium chloride and methylamine hydrochloride are the only products formed in significant amount in the photochemical degradation. Paper chromatography and isotope dilution have shown that these products are formed on leaves of plants treated with {sup 14}C-paraquat (mostly after the plants are dead). Whole plant radioautography has established that 4-carboxy-1-{sup 14}C methylpyridinium chloride is not translocated at all from the dead leaves on which it is formed and certainly this compound will not appear in harvested crops. This has been confirmed in an experiment in which {sup 14}C-paraquat was used to desiccate the tops of potato plants before harvesting the tubers. All the radioactivity subsequently found in the tubers could be accounted for as paraquat (level 0.08 ppm). There was no evidence for the presence of significant amounts of other radioactive compounds in the tubers, even though chromatography of extracts of the desiccated plants showed that photochemical degradation products were formed on the leaves: these were not translocated into the

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

Science.gov (United States)

Singla, Ritu; Grieser, Franz; Ashokkumar, Muthupandian

2009-03-26

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

In Situ Hydrocarbon Degradation by Indigenous Nearshore Bacterial Populations

International Nuclear Information System (INIS)

Cherrier, J.

2005-01-01

Potential episodic hydrocarbon inputs associated with oil mining and transportation together with chronic introduction of hydrocarbons via urban runoff into the relatively pristine coastal Florida waters poses a significant threat to Florida's fragile marine environment. It is therefore important to understand the extent to which indigenous bacterial populations are able to degrade hydrocarbon compounds and also determine factors that could potentially control and promote the rate at which these compounds are broken down in situ. Previous controlled laboratory experiments carried out by our research group demonstrated that separately both photo-oxidation and cometabolism stimulate bacterial hydrocarbon degradation by natural bacterial assemblages collected from a chronically petroleum contaminated site in Bayboro Bay, Florida. Additionally, we also demonstrated that stable carbon and radiocarbon abundances of respired CO 2 could be used to trace in situ hydrocarbon degradation by indigenous bacterial populations at this same site. This current proposal had two main objectives: (a) to evaluate the cumulative impact of cometabolism and photo-oxidation on hydrocarbon degradation by natural bacterial assemblages collected the same site in Bayboro Bay, Florida and (b) to determine if in situ hydrocarbon degradation by indigenous bacterial populations this site could be traced using natural radiocarbon and stable carbon abundances of assimilated bacterial carbon. Funds were used for 2 years of full support for one ESI Ph.D. student, April Croxton. To address our first objective a series of closed system bacterial incubations were carried out using photo-oxidized petroleum and pinfish (i.e. cometabolite). Bacterial production of CO 2 was used as the indicator of hydrocarbon degradation and (delta) 13 C analysis of the resultant CO 2 was used to evaluate the source of the respired CO 2 (i.e. petroleum hydrocarbons or the pinfish cometabolite). Results from these time

Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.

Science.gov (United States)

Carlsson, Daniel O; Hua, Kai; Forsgren, Johan; Mihranyan, Albert

2014-01-30

TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery. Copyright © 2013 Elsevier B.V. All rights reserved.

Hydroxyl radical induced degradation of ibuprofen

Energy Technology Data Exchange (ETDEWEB)

Illés, Erzsébet, E-mail: erzsebet.illes@chem.u-szeged.hu [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Takács, Erzsébet [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary); Dombi, András [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Gajda-Schrantz, Krisztina [Institute of Chemistry, Research Group of Environmental Chemistry, University of Szeged, Szeged (Hungary); Department of Inorganic and Analytical Chemistry, University of Szeged, Szeged (Hungary); EMPA, Laboratory for High Performance Ceramics, Duebendorf (Switzerland); Rácz, Gergely; Gonter, Katalin; Wojnárovits, László [Institute of Isotopes, Centre for Energy Research, Hungarian Academy of Sciences, Budapest (Hungary)

2013-03-01

Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm{sup −3}. For end product characterization {sup 60}Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of {sup ·}OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation.

Hydroxyl radical induced degradation of ibuprofen

International Nuclear Information System (INIS)

Illés, Erzsébet; Takács, Erzsébet; Dombi, András; Gajda-Schrantz, Krisztina; Rácz, Gergely; Gonter, Katalin; Wojnárovits, László

2013-01-01

Pulse radiolysis experiments were used to characterize the intermediates formed from ibuprofen during electron beam irradiation in a solution of 0.1 mmol dm −3 . For end product characterization 60 Co γ-irradiation was used and the samples were evaluated either by taking their UV–vis spectra or by HPLC with UV or MS detection. The reactions of · OH resulted in hydroxycyclohexadienyl type radical intermediates. The intermediates produced in further reactions hydroxylated the derivatives of ibuprofen as final products. The hydrated electron attacked the carboxyl group. Ibuprofen degradation is more efficient under oxidative conditions than under reductive conditions. The ecotoxicity of the solution was monitored by Daphnia magna standard microbiotest and Vibrio fischeri luminescent bacteria test. The toxic effect of the aerated ibuprofen solution first increased upon irradiation indicating a higher toxicity of the first degradation products, then decreased with increasing absorbed dose. Highlights: ► In hydroxyl radical attack on the ring mainly hydroxylated products form ► The hydrated electron attacks the carboxyl group. ► Oxidative conditions are more effective in ibuprofen decomposition than reductive. ► Ecotoxicity of ibuprofen solution first increases then decreases with irradiation

Fast degradation of dyes in water using manganese-oxide-coated diatomite for environmental remediation

Science.gov (United States)

Dang, Trung-Dung; Banerjee, Arghya Narayan; Tran, Quang-Tung; Roy, Sudipta

2016-11-01

By a simple wet-chemical procedure using a permanganate in the acidic medium, diatomite coated with amorphous manganese oxide nanoparticles was synthesized. The structural, microstructural and morphological characterizations of the as-synthesized catalysts confirmed the nanostructure of MnO2 and its stabilization on the support - diatomite. The highly efficient and rapid degradation of methylene blue and methyl orange over synthesized MnO2 coated Diatomite has been carried out. The results revealed considerably faster degradation of the dyes against the previously reported data. The proposed mechanism of the dye-degradation is considered to be a combinatorial effect of chemical, physicochemical and physical processes. Therefore, the fabricated catalysts have potential application in waste water treatment, and pollution degradation for environmental remediation.

Thermal oxidative degradation kinetics of agricultural residues using distributed activation energy model and global kinetic model.

Science.gov (United States)

Ren, Xiu'e; Chen, Jianbiao; Li, Gang; Wang, Yanhong; Lang, Xuemei; Fan, Shuanshi

2018-08-01

The study concerned the thermal oxidative degradation kinetics of agricultural residues, peanut shell (PS) and sunflower shell (SS). The thermal behaviors were evaluated via thermogravimetric analysis and the kinetic parameters were determined by using distributed activation energy model (DAEM) and global kinetic model (GKM). Results showed that thermal oxidative decomposition of two samples processed in three zones; the ignition, burnout, and comprehensive combustibility between two agricultural residues were of great difference; and the combustion performance could be improved by boosting heating rate. The activation energy ranges calculated by the DAEM for the thermal oxidative degradation of PS and SS were 88.94-145.30 kJ mol -1 and 94.86-169.18 kJ mol -1 , respectively. The activation energy obtained by the GKM for the oxidative decomposition of hemicellulose and cellulose was obviously lower than that for the lignin oxidation at identical heating rate. To some degree, the determined kinetic parameters could acceptably simulate experimental data. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effects of cellulosic degradation products on uranium sorption in the geosphere

International Nuclear Information System (INIS)

Baston, G.M.N.; Berry, J.A.; Bond, K.A.; Boult, K.A.; Brownsword, M.; Linklater, C.M.

1994-01-01

The current design concept for intermediate- and some low-level radioactive waste disposal in the UK involves emplacement in a cementitious repository deep underground. The movement of radionuclides away from such a repository through the host rock formation towards the biosphere is expected to be retarded to a significant degree by sorption processes. One major issue being studied is the effect on uranium sorption of degradation products arising from organic waste matter, especially cellulosic materials. The sorption of uranium could be reduced by degradation products, either because of complexation, or through the organic materials competing for sorption sites. Because of the complexity of authentic degradation products, work has also been carried out using gluconate and iso-saccharinate as well-characterised simulants. In the presence of high concentrations of either the authentic or simulated degradation products, significant reductions in uranium sorption have been observed. However, in the presence of lower concentrations of these organic materials, such as would be present in the repository, sorption was reduced at most by only a small margin and, in some cases, the results suggested a slight increase. ((orig.))

Effects of cellulosic degradation products on uranium sorption in the geosphere

Energy Technology Data Exchange (ETDEWEB)

Baston, G.M.N. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom)); Berry, J.A. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom)); Bond, K.A. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom)); Boult, K.A. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom)); Brownsword, M. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom)); Linklater, C.M. (AEA Technology, Harwell, Didcot, Oxon OX11 0RA (United Kingdom))

1994-10-01

The current design concept for intermediate- and some low-level radioactive waste disposal in the UK involves emplacement in a cementitious repository deep underground. The movement of radionuclides away from such a repository through the host rock formation towards the biosphere is expected to be retarded to a significant degree by sorption processes. One major issue being studied is the effect on uranium sorption of degradation products arising from organic waste matter, especially cellulosic materials. The sorption of uranium could be reduced by degradation products, either because of complexation, or through the organic materials competing for sorption sites. Because of the complexity of authentic degradation products, work has also been carried out using gluconate and iso-saccharinate as well-characterised simulants. In the presence of high concentrations of either the authentic or simulated degradation products, significant reductions in uranium sorption have been observed. However, in the presence of lower concentrations of these organic materials, such as would be present in the repository, sorption was reduced at most by only a small margin and, in some cases, the results suggested a slight increase. ((orig.))

Application of Ni-Oxide@TiO2 Core-Shell Structures to Photocatalytic Mixed Dye Degradation, CO Oxidation, and Supercapacitors

Directory of Open Access Journals (Sweden)

Seungwon Lee

2016-12-01

Full Text Available Performing diverse application tests on synthesized metal oxides is critical for identifying suitable application areas based on the material performances. In the present study, Ni-oxide@TiO2 core-shell materials were synthesized and applied to photocatalytic mixed dye (methyl orange + rhodamine + methylene blue degradation under ultraviolet (UV and visible lights, CO oxidation, and supercapacitors. Their physicochemical properties were examined by field-emission scanning electron microscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, and UV-visible absorption spectroscopy. It was shown that their performances were highly dependent on the morphology, thermal treatment procedure, and TiO2 overlayer coating.

Structural characterisation of degradation products formed upon di-n-butyl phthalate radiolysis by high-performance liquid chromatography electro-spray tandem mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Tintaru, A.; Charles, L. [Univ Aix Marseille 1, CNRS, Lab Chim Provence Spectrometries Appl Chim Struct, UMR 6264, F-13397 Marseille (France); Univ Aix Marseille 2, CNRS, Lab Chim Provence Spectrometries Appl Chim Struct, UMR 6264, F-13397 Marseille (France); Labed, V. [CEA Marcoule, DTCD SPDE L2ED, F-30207 Bagnols Sur Ceze (France)

2010-07-01

Complete text of publication follows: Structural characterisation of 15 degradation products, formed upon di-n-butyl phthalate (DBP) radiolysis, has been achieved using a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) coupling. The dissociation behaviour of protonated DBP was first established to be further used to characterise structural deviation in the degradation products. Based on accurate mass measurements, compounds shown by HPLC-MS analysis were all found to be DBP oxidation products, amongst which various sets of isomers could be distinguished. Collision-induced dissociation experiments performed on each electro-sprayed molecule first allowed unambiguous definition of the location of the additional oxygen atoms; that is, in the alkyl branch or on the aromatic ring. Although location of the oxygen atom in the alkyl branches could not always be precisely determined, relative abundances of some product ions allowed oxygenated functions to be identified

ANALYTICAL METHOD DEVELOPMENT FOR ALACHLOR ESA AND OTHER ACETANILIDE HERBICIDE DEGRADATION PRODUCTS

Science.gov (United States)

In 1998, USEPA published a Drinking Water Contaminant Candidate List (CCL) of 50 chemicals and 10 microorganisms. "Alachlor ESA and other acetanilide herbicide degradation products" is listed on the the 1998 CCL. Acetanilide degradation products are generally more water soluble...

Degradation Mechanism of Poly(Ether-Urethane) Estane Induced by High Energy Radiation (III) : Radiolytic Gases and Water Soluble Products

International Nuclear Information System (INIS)

Dannoux, A.

2006-01-01

Within the framework of nuclear waste management, there is interest in the prediction of long-term behaviour of organic materials subjected to high energy radiation. Once organic waste has been stored, gases and low molecular products might be generated from materials irradiated by radionuclides. Long-term behaviour of organic material in nuclear waste has several common concerns with radiation ageing of polymers. But a more detailed description of the chemical evolution is needed for nuclear waste management. In a first approach, an extensive work on radiation ageing is used to identify the different processes encountered during the degradation of a polyurethane, including oxidation dose rate-effects and influence of dose on the oxidation mechanism. In a second approach, a study is performed to identify and quantify gases and possible production of water soluble chemical complexing agents which might enhance radionuclides migration away from the repository. In this work, we present results concerning the production of radiolytic gases and the formation of water soluble oligomers reached with leaching tests Films were made from a poly(ether-urethane) synthesized from methylene bis(p-phenyl isocyanate) (MDI) and poly(tetramethylene glycol) (PTMG) with 1,4 butanediol (BD) and were irradiated by high-energy electron beam to cover a wide doses range and by γ rays to determine the formation/consumption yields of gases. They were measured by mass spectrometry and gas-chromatography/mass spectrometry (GC/MS). The migration of water soluble oligomers in water was reached by measuring the weight loss versus leaching time. The identification of oligomers was performed by using a mass spectrometry with an electrospray ionisation interface (ESI-MS-MS). The analysis of radiolytic gases indicates the formation of H 2 , CO 2 and CO with respective radiolytic yields of 1, 0.5 and 0.3 molecule/100 eV. The consumption of O 2 is evaluated to 6 molecules/100 eV. For absorbed doses

Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction

Energy Technology Data Exchange (ETDEWEB)

Lv Tian [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Pan Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Liu Xinjuan; Lu Ting; Zhu Guang; Sun Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China)

2011-10-13

Highlights: > ZnO-reduced graphene oxide composite is synthesized via microwave assisted reaction. > The method allows a facile, safe and rapid reaction in aqueous media. > A high dye degradation efficiency is achieved under UV light irradiation. - Abstract: A quick and facile microwave-assisted reaction is used to synthesize ZnO-reduced graphene oxide (RGO) hybrid composites by reducing graphite oxide dispersion with zinc nitrate using a microwave synthesis system. Their photocatalytic performance in degradation of methylene blue is investigated and the results show that the RGO plays an important role in the enhancement of photocatalytic performance and the ZnO-RGO composite with 1.1 wt. % RGO achieves a maximum degradation efficiency of 88% in a neutral solution under UV light irradiation for 260 min as compared with pure ZnO (68%) due to the increased light absorption, the reduced charge recombination with the introduction of RGO.

On-Site Enzyme Production by Trichoderma asperellum for the Degradation of Duckweed

DEFF Research Database (Denmark)

Bech, Lasse; Herbst, Florian-Alexander; Grell, Morten Nedergaard

2015-01-01

The on-site production of cell wall degrading enzymes is an important strategy for the development of sustainable bio-refinery processes. This study concerns the optimization of production of plant cell wall-degrading enzymes produced by Trichoderma asperellum. A comparative secretome analysis...

Photocatalytic degradation of tetracycline by Ti-MCM-41 prepared at room temperature and biotoxicity of degradation products

Science.gov (United States)

Zhou, Kefu; Xie, Xiao-Dan; Chang, Chang-Tang

2017-09-01

Ti-doped MCM-41 with different Si/Ti molar ratios was prepared at room temperature to degrade tetracycline antibiotics in aqueous solution. The Ti was doped into the skeleton structure of MCM-41. The photocatalytic activity of Ti-doped MCM-41 was investigated. The optimal catalyst had Si/Ti molar ratio of 25 and over 99% removal of oxytetracycline in 150 min, and the removal could maintain 98% after 5 reuses. Ions and soluble organic matters in natural water affected the degradation reaction when Ti-doped MCM-41 was used to treat simulated wastewater of chicken farms. The degradation products of oxytetracycline, tetracycline and chlortetracycline were detected by Escherichia coli DH5α and HPLC-MS/MS. No intermediate product with higher toxicity was detected.

Pathways for degradation of plastic polymers floating in the marine environment.

Science.gov (United States)

Gewert, Berit; Plassmann, Merle M; MacLeod, Matthew

2015-09-01

Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon-carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to precede biodegradation. When heteroatoms are present in the main chain of a polymer, degradation proceeds by photo-oxidation, hydrolysis, and biodegradation. Degradation of plastic polymers can lead to low molecular weight polymer fragments, like monomers and oligomers, and formation of new end groups, especially carboxylic acids.

Formaldehyde production from isoprene oxidation across NOx regimes

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2016-03-01

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

Azo dyes degradation using TiO2-Pt/graphene oxide and TiO2-Pt/reduced graphene oxide photocatalysts under UV and natural sunlight irradiation

Science.gov (United States)

Rosu, Marcela-Corina; Coros, Maria; Pogacean, Florina; Magerusan, Lidia; Socaci, Crina; Turza, Alexandru; Pruneanu, Stela

2017-08-01

The photocatalytic degradation of azo dyes with different structures (amaranth, sunset yellow and tartrazine) using TiO2-Pt nanoparticles (TPt), TiO2-Pt/graphene oxide (TPt-GO) and TiO2-Pt/reduced graphene oxide (TPt-rGO) composites were investigated in the presence of UV and natural sunlight irradiation. The composites were prepared by a combined chemical-thermal method and characterized by Transmission Electron Microscopy (TEM), X-ray powder diffraction (XRD), Infrared (FTIR) and UV-Vis spectroscopy. The modification of TiO2-Pt with graphene oxide shifted its optical absorption edge towards the visible region and increased its photocatalytic activity under UV and natural sunlight irradiation. The efficiency of catalysts on azo dyes degradation (in similar conditions) reached high values (above 99%) under sunlight conditions, proving the remarkable photocatalytic activities of obtained composites. TPt-GO nanocomposite exhibited higher photoactivity than TPt or TPt-rGO, demonstrating degradation efficiencies of 99.56% for amaranth, 99.15% for sunset yellow and 96.23% for tartrazine. The dye photodegradation process follows a pseudo-first-order kinetic with respect to the Langmuir-Hinshelwood reaction mechanism. A direct dependence between azo dyes degradation rate and chemical structure of dyes has been observed.

Oxidation Kinetics and Strength Degradation of Carbon Fibers in a Cracked Ceramic Matrix Composite

Science.gov (United States)

Halbig, Michael C.

2003-01-01

Experimental results and oxidation modeling will be presented to discuss carbon fiber susceptibility to oxidation, the oxidation kinetics regimes and composite strength degradation and failure due to oxidation. Thermogravimetric Analysis (TGA) was used to study the oxidation rates of carbon fiber and of a pyro-carbon interphase. The analysis was used to separately obtain activation energies for the carbon constituents within a C/SiC composite. TGA was also conducted on C/SiC composite material to study carbon oxidation and crack closure as a function of temperature. In order to more closely match applications conditions C/SiC tensile coupons were also tested under stressed oxidation conditions. The stressed oxidation tests show that C/SiC is much more susceptible to oxidation when the material is under an applied load where the cracks are open and allow for oxygen ingress. The results help correlate carbon oxidation with composite strength reduction and failure.

Reduced graphene oxide-CdS nanocomposite with enhanced photocatalytic 4-Nitrophenol degradation

Science.gov (United States)

Chakraborty, Koushik; Ibrahim, Sk; Das, Poulomi; Ghosh, Surajit; Pal, Tanusri

2017-05-01

We report the photocatalytic activity of reduced graphene oxide cadmium sulfide (RGO-CdS) composite towards the degradation of 4-Nitrophenol (4-NP) under simulated solar light illumination. The solution processable RGO-CdS composite was synthesized by one pot single step low cost solvothermal process, where the reduction of graphene oxide (GO), synthesis and attachment of CdS onto RGO sheets were done simultaneously. The structural and morphological characterization of the RGO-CdS composite and the reduction of GO was confirmed by X-ray diffractometry, TEM imaging and Fourier transform infrared spectroscopy respectively. The photocatalytic efficiency of RGO-CdS composite is 2.6 times higher in compare to controlled CdS. In RGO-CdS composite the photo induced electrons transfer from CdS nanorod to RGO sheets, which reduces the recombination probability of photo generated electron-hole in the CdS. These well separated photoinduced charges enhanced the photocatalytic activity of the RGO-CdS composite. Our study establishes the RGO-CdS composite as a potential photocatalyst for the degradation of organic water pollutant.

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

Science.gov (United States)

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.

Solid-phase photocatalytic degradation of polyethylene film with manganese oxide OMS-2

Science.gov (United States)

Liu, Guanglong; Liao, Shuijiao; Zhu, Duanwei; Cui, Jingzhen; Zhou, Wenbing

2011-01-01

Solid-phase photocatalytic degradation of polyethylene (PE) film with cryptomelane-type manganese oxide (OMS-2) as photocatalyst was investigated in the ambient air under ultraviolet and visible light irradiation. The properties of the composite films were compared with those of the pure PE film through performing weight loss monitoring, IR spectroscopy, scanning electron microscopic (SEM) and X-ray photoelectron spectroscopy (XPS). The photoinduced degradation of PE-OMS-2 composite films was higher than that of the pure films, while there has been little change under the visible light irradiation. The weight loss of PE-OMS-2 (1.0 wt%) composite films steadily decreased and reached 16.5% in 288 h under UV light irradiation. Through SEM observation there were some cavities on the surface of composite films, but few change except some surface chalking phenomenon occurred in pure PE film. The degradation rate with ultraviolet irradiation is controllable by adjusting the content of OMS-2 particles in PE plastic. Finally, the mechanism of photocatalytic degradation of the composite films was briefly discussed.

Oxidative degradation property of the proton-exchange membranes based on fluorinated polymer using radiation-induced grafting

International Nuclear Information System (INIS)

Mitani, N.; Muto, F.; Fujii, K.; Sato, Y.; Kakigi, T.; Matsuura, A.; Li Jingye; Miura, T.; Oshima, A.; Washio, M.

2006-01-01

To grow popularity of polymer electrolyte fuel cells (PEFCs), it is important that the life-time of FC will be evaluated. In the PEFCs operation, the oxygenated water would be produced by fuel gases crossover reaction. Moreover, the metal ions such as Fe 2+ would dissolve from piping and humidification bubblers in FC systems. As the results, the dissolved metal ions catalyze with oxygenated water, and then active oxidative radicals such as hydroxy and hydroperoxy radicals are induced by Fenton reaction. The oxidative radicals have considered one of the reasons of deterioration of FC performance. In our previous study, the partial-fluorinated sulfonic acid membranes based on crosslinked PTFE (sulfonated RX-PTFE) have been fabricated by pre EB-grafting method. In this study, in order to evaluate the chemical durability exerted on the PEFC performance of sulfonated RX-PTFE, we carried out the accelerated degradation test by Fenton reaction. The test conditions were 6 vol% H 2 O 2 with 5 ppm Fe 2+ solution at 60 degree C. The properties of sulfonated RX-PTFE before and after degradation tests were measured by means of X-ray photoelectron spectroscopy (XPS) and other methods. According to oxidative degradation test, the sulfonated RX-PTFE with higher crosslinking density of main chain became hard to deteriorate. On the contrary, the higher grafting yields became easy to degrade. It is suggested that the oxidative degradation would be greatly influenced to the grafted chain length and crosslinking density of main chain. From XPS after Fenton treated sulfonated RX-PTFE, the signal of S 2p and S 2s was disappeared. And also, by TGA and TG-MS analysis, it was found that the reduction of grafted chains was taken place. Furthermore, the crosslinked PTFE chains may be degraded through the reduction of grafted chain. The PEFC operation tests of sulfonated RX-PTFE before and after degradation tests were carried out. When the weight loss of sulfonated RX-PTFE was almost the same

Accelerated thermal and radiation-oxidation combined degradation of electric cable insulation materials

International Nuclear Information System (INIS)

Yagi, Toshiaki; Seguchi, Tadao; Yoshida, Kenzo

1986-03-01

For the development of accelerated testing methodology to estimate the life time of electric cable, which is installed in radiation field such as a nuclear reactor containment vessel, radiation and thermal combined degradation of cable insulation and jacketing materials was studied. The materials were two types of formulated polyethylene, ethylene-propylene rubber, Hypalon, and Neoprene. With Co-60 γ-rays the materials were irradiated up to 0.5 MGy under vacuum and in oxygen under pressure, then exposed to thermal aging at elevated temperature in oxygen. The degradation was investigated by the tensile test, gelfraction, and swelling measurements. The thermal degradation rate for each sample increases with increase of oxygen concentration, i.e. oxygen pressure, during the aging, and tends to saturate above 0.2 MPa of oxygen pressure. Then, the effects of irradiation and the temperature on the thermal degradation rate were investigated at the oxygen pressure of 0.2 MPa in the temperature range from 110 deg C to 150 deg C. For all of samples irradiated in oxygen, the following thermal degradation rate was accelerated by several times comparing with unirradiated samples, while the rate of thermal degradation for the sample except Neoprene irradiated under vacuum was nearly equal to that of unirradiated one. By the analysis of thermal degradation rate against temperature using Arrhenius equation, it was found that the activation energy tends to decrease for the samples irradiated in oxidation condition. (author)

Application of zinc oxide fiber in the photocatalytic degradation of methyl orange

International Nuclear Information System (INIS)

Gerchman, D.; Alves, A.K.; Berutti, F.A.; Bergmann, C.P.

2011-01-01

In this work, zinc oxide fibers were obtained by electrospinning using polyvinylbutyral and zinc nitrate as precursors. After the synthesis, the material was heat treated at different temperatures to evaluate the effect of microstructure on its photocatalytic activity. The fibers obtained after heat treatment were characterized for morphology, phases, crystallinity and photocatalytic activity. The photocatalysis reaction was accompanied by the degradation of methyl orange in the presence of zinc oxide under UV illumination. It was observed that the crystallinity of zincite is a fundamental factor for the control of the photocatalytic activity of this material. (author)

Degradation of cellulose at the wet-dry interface. II. Study of oxidation reactions and effect of antioxidants.

Science.gov (United States)

Jeong, Myung-Joon; Dupont, Anne-Laurence; de la Rie, E René

2014-01-30

To better understand the degradation of cellulose upon the formation of a tideline at the wet-dry interface when paper is suspended in water, the production of chemical species involved in oxidation reactions was studied. The quantitation of hydroperoxides and hydroxyl radicals was carried out in reverse phase chromatography using triphenylphosphine and terephthalic acid, respectively, as chemical probes. Both reactive oxygen species were found in the tideline immediately after its formation, in the range of micromoles and nanomoles per gram of paper, respectively. The results indicate that hydroxyl radicals form for the most part in paper before the tideline experiment, whereas hydroperoxides appear to be produced primarily during tideline formation. Iron sulfate impregnation of the paper raised the production of hydroperoxides. After hygrothermal aging in sealed vials the hydroxyl radical content in paper increased significantly. When aged together in the same vial, tideline samples strongly influenced the degradation of samples from other areas of the paper (multi-sample aging). Different types of antioxidants were added to the paper before the tideline experiment to investigate their effect on the oxidation reactions taking place. In samples treated with iron sulfate or artificially aged, the addition of Irgafos 168 (tris(2,4-ditert-butylphenyl) phosphate) and Tinuvin 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate) reduced the concentration of hydroperoxides and hydroxyl radicals, respectively. Tinuvin 292 was also found to considerably lower the rate of cellulose chain scission reactions during hygrothermal aging of the paper. Copyright © 2013 Elsevier Ltd. All rights reserved.

A comparative genomic analysis of the oxidative enzymes potentially involved in lignin degradation by Agaricus bisporus

Science.gov (United States)

Harshavardhan Doddapaneni; Venkataramanan Subramanian; Bolei Fu; Dan Cullen

2013-01-01

The oxidative enzymatic machinery for degradation of organic substrates in Agaricus bisporus (Ab) is at the core of the carbon recycling mechanisms in this fungus. To date, 156 genes have been tentatively identified as part of this oxidative enzymatic machinery, which includes 26 peroxidase encoding genes, nine copper radical oxidase [including three...

Radiation-induced oxidative degradation of poly(vinyl chloride)

International Nuclear Information System (INIS)

Hegazy, E.S.A.; Seguchi, T.; Machi, S.

1981-01-01

Gas evolution and oxygen consumption in the γ-irradiation of PVC were studied. The gas evolution and the oxidative degradation are retarded by the presence of plasticizers and stabilizers. The G(HCl) and G(H 2 ) are 8 and 0.24 for the irradiation of pure PVC under vacuum and 0.02 and 0.14 for that of plasticized PVC, respectively. Gas evolution increases in the presence of oxygen, specially for the pure PVC. The G(-O 2 ) values for the pure and plasticized PVC are 30 and 12, respectively. The dependence of gas evolution and oxygen consumption on the oxygen pressure is more pronounced for the plasticized PVC than pure PVC because the oxygen diffusion is controlled

Reliability demonstration methodology for products with Gamma Process by optimal accelerated degradation testing

International Nuclear Information System (INIS)

Zhang, Chunhua; Lu, Xiang; Tan, Yuanyuan; Wang, Yashun

2015-01-01

For products with high reliability and long lifetime, accelerated degradation testing (ADT) may be adopted during product development phase to verify whether its reliability satisfies the predetermined level within feasible test duration. The actual degradation from engineering is usually a strictly monotonic process, such as fatigue crack growth, wear, and erosion. However, the method for reliability demonstration by ADT with monotonic degradation process has not been investigated so far. This paper proposes a reliability demonstration methodology by ADT for this kind of product. We first apply Gamma process to describe the monotonic degradation. Next, we present a reliability demonstration method by converting the required reliability level into allowable cumulative degradation in ADT and comparing the actual accumulative degradation with the allowable level. Further, we suggest an analytical optimal ADT design method for more efficient reliability demonstration by minimizing the asymptotic variance of decision variable in reliability demonstration under the constraints of sample size, test duration, test cost, and predetermined decision risks. The method is validated and illustrated with example on reliability demonstration of alloy product, and is applied to demonstrate the wear reliability within long service duration of spherical plain bearing in the end. - Highlights: • We present a reliability demonstration method by ADT for products with monotonic degradation process, which may be applied to verify reliability with long service life for products with monotonic degradation process within feasible test duration. • We suggest an analytical optimal ADT design method for more efficient reliability demonstration, which differs from the existed optimal ADT design for more accurate reliability estimation by different objective function and different constraints. • The methods are applied to demonstrate the wear reliability within long service duration of

Study of the degradation of organic molecules complexing radionuclides by using Advanced Oxidation Processes

International Nuclear Information System (INIS)

Rekab, K.

2014-01-01

This research thesis reports the study of the application of two AOPs (Advanced Oxidation Processes) to degrade and mineralise organic molecules which are complexing radio-elements, and thus to allow their concentrations by trapping on mineral matrices. EDTA (ethylene diamine tetraacetic acid) is chosen as reference organic complexing agent for preliminary tests performed with inactive cobalt 59 before addressing actual nuclear effluents with active cobalt 60. The author first presents the industrial context (existing nuclear wastes, notably liquid effluents and their processing) and proposes an overview of the state of the art on adsorption and precipitation of cobalt (natural and radioactive isotope). Then, the author presents the characteristics of the various studied oxides, the photochemical reactor used to perform tests, experimental techniques and operational modes. Results are then presented regarding various issues: adsorption of EDTA and the Co-EDTA complex, and cobalt precipitation; determination of the lamp photon flow by chemical actinometry and by using the Keitz method; efficiency of different processes (UV, UV/TiO 2 , UV/H 2 O 2 ) to degrade EDTA and to degrade the Co-EDTA complex; processing of a nuclear effluent coming from La Hague pools with determination of decontamination factors

Phenol oxidation with hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Ramiez Cortina, R.C.; Hernadez Perez, I. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico); Ortiz Lozoya, C.E. [Univ. Autonoma Metropolitana - Azcapotzalco, Div. de CBI, Dept. de Energia, Azcapotzalco (Mexico)]|[Inst. Mexicano del Petroleo (Mexico); Alonso Gutierrez, M.S. [Inst. National Polytechnique, ENSCT, Lab. of Chimie Agro-Industrielle, Toulouse (France)

2003-07-01

In this work the process application of advanced oxidation is investigated with hydrogen peroxide, for the phenol destruction. The experiments were carried out in a glass reactor of 750 mL. Three phenol concentrations were studied (2000, 1000 and 500 ppm) being oxidized with H{sub 2}O{sub 2} (1, 2 and 3 M). The tests of oxidation had a reaction time of 48 h at ambient temperature and pressure. The phenol degradation was determined as COD at different reaction times and intermediate oxidation products were analyzed by chromatography. The results of this study show that it is possible to degrade phenol (1000 ppm) until 90% with H{sub 2}O{sub 2} 2M. Being achieved the best efficiency with a good molar relationship of H{sub 2}O{sub 2}/phenol. Intends a reaction outline in the degradation of the phenol. (orig.)

Degradation products of irradiated haloperidol: implications for the development of an implantible delivery system

Energy Technology Data Exchange (ETDEWEB)

Booker, J

1988-01-01

Haloperidol was chosen as a model compound to determine whether the degradation products created by sterilizing dose of gamma radiation would contaminate an implantible delivery device and be hazardous to the health of the person using it. Acrolein, chlorobenzene, and several other products were identified among the degradation products. They were quantitated and evaluated as being potentially dangerous. It is recommended that the development protocol for a radiation-sterilized, implantible drug include the identification and evaluation of the degradation products.

Degradation products of irradiated haloperidol: implications for the development of an implantible delivery system

International Nuclear Information System (INIS)

Booker, J.

1988-01-01

Haloperidol was chosen as a model compound to determine whether the degradation products created by sterilizing dose of gamma radiation would contaminate an implantible delivery device and be hazardous to the health of the person using it. Acrolein, chlorobenzene, and several other products were identified among the degradation products. They were quantitated and evaluated as being potentially dangerous. It is recommended that the development protocol for a radiation-sterilized, implantible drug include the identification and evaluation of the degradation products. (author)

Electrochemical AC impedance model of a solid oxide fuel cell and its application to diagnosis of multiple degradation modes

Energy Technology Data Exchange (ETDEWEB)

Gazzarri, J.I.; Kesler, O. [Department of Mechanical Engineering, University of British Columbia, 2054-6250 Applied Science Lane, Vancouver, BC V6T 1Z4 (Canada)

2007-05-01

A finite element model of the impact of diverse degradation mechanisms on the impedance spectrum of a solid oxide fuel cell is presented as a tool for degradation mode identification. Among the degradation mechanisms that cause electrode active area loss, the attention is focused on electrode delamination and uniformly distributed surface area loss, which were found to cause distinct and specific changes in the impedance spectrum. Degradation mechanisms resulting in uniformly distributed reactive surface area loss include sintering, sulphur poisoning, and possibly incipient coke formation at the anode, and chromium deposition at the cathode. Parametric studies reveal the extent and limits of applicability of the model and detectability of the different degradation modes, as well as the influence of different cell geometries on the change in impedance behaviour resulting from the loss of active area. It is expected that this technique could form the basis of a useful diagnostic tool for both solid oxide fuel cell developers and users. (author)

Degradation of carbamazepine using hydrodynamic cavitation combined with advanced oxidation processes.

Science.gov (United States)

Thanekar, Pooja; Panda, Mihir; Gogate, Parag R

2018-01-01

Degradation of carbamazepine (CBZ), a widely detected recalcitrant pharmaceutical in sewage treatment plant (STP) effluent, has been studied in the present work using combination of hydrodynamic cavitation (HC) and advanced oxidation processes (AOPs). Due to its recalcitrant nature, it cannot be removed effectively by the conventional wastewater treatment plants (WWTPs) which make CBZ a pharmaceutical of very high environmental relevance and impact as well as stressing the need for developing new treatment schemes. In the present study, the effect of inlet pressure (3-5bar) and operating pH (3-11) on the extent of degradation have been initially studied with an objective of maximizing the degradation using HC alone. The established optimum conditions as pressure of 4bar and pH of 4 resulted in maximum degradation of CBZ as 38.7%. The combined approaches of HC with ultraviolet irradiation (HC+UV), hydrogen peroxide (HC+H 2 O 2 ), ozone (HC+O 3 ) as well as combination of HC, H 2 O 2 and O 3 (HC+H 2 O 2 +O 3 ) have been investigated under optimized pressure and operating pH. It was observed that a significant increase in the extent of degradation is obtained for the combined operations of HC+H 2 O 2 +O 3 , HC+O 3 , HC+H 2 O 2 , and HC+UV with the actual extent of degradation being 100%, 91.4%, 58.3% and 52.9% respectively. Kinetic analysis revealed that degradation of CBZ fitted into first order kinetics model for all the approaches. The processes were also compared on the basis of cavitational yield and also in terms of total treatment cost. Overall, it has been demonstrated that combined process of HC, H 2 O 2 and O 3 can be effectively used for treatment of wastewater containing CBZ. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, Characterization, and Use of Novel Bimetal Oxide Catalyst for Photoassisted Degradation of Malachite Green Dye

Directory of Open Access Journals (Sweden)

K. L. Ameta

2014-01-01

Full Text Available This work reports a simple, novel, and cost effective synthesis of nanobimetal oxide catalyst using cerium and cadmium nitrates as metal precursors. The cerium-cadmium oxide nanophotocatalyst was synthesized by coprecipitation method and characterized by X-ray powder diffraction method to analyze the particle size. XRD study reveals a high degree of crystallinity and 28.43 nm particle size. The photocatalytic efficiency of the synthesized nanobimetal catalyst was examined by using it for the photocatalytic degradation of malachite green dye. Experiments were conducted to study the effect of various parameters, such as the pH of the dye solution, concentration of dye, amount of catalyst, and light intensity on the rate of dye degradation. The progress of the dye degradation was monitored spectrophotometrically by taking the optical density of the dye solution at regular intervals. Experimental results indicate that the dye degrades best at pH 8.0 with light intensity 600 Wm−2 and catalyst loading 0.03 g/50 mL of dye solution. The rate constant for the reaction was 7.67 × 10−4 s−1.

TBP degradation products. Separation and gas-chromatographic determination

International Nuclear Information System (INIS)

Kuada, T.A.; Alem, C.M.; Matsuda, H.T.; Araujo, B.F. de; Araujo, J.A de.

1991-11-01

A separation method for di butylphosphate, mono butylphosphate and phosphoric acid as degradation products in organic and aqueous streams of the process containing variable amounts of actinides and fission products is described. The products were separated by extraction and after methylation the final determination was carried out by gas chromatography. TPP was used as internal standard and 5 to 500 mg/L concentration range was determined with 1 to 10% deviation depending on the concentration of organo phosphates. (author)

Oxidative stability of fatty acid alkyl esters: a review.

Directory of Open Access Journals (Sweden)

Michal Angelovič

2015-12-01

Full Text Available The purpose of this study was to investigate and to process the current literary knowledge of the physico-chemical properties of vegetable oil raw used for biodiesel production in terms of its qualitative stability. An object of investigation was oxidative stability of biodiesel. In the study, we focused on the qualitative physico-chemical properties of vegetable oils used for biodiesel production, oxidative degradation and its mechanisms, oxidation of lipids, mechanisms of autooxidation, effectivennes of different synthetic antioxidants in relation to oxidative stability of biodiesel and methods of oxidative stability determination. Knowledge of the physical and chemical properties of vegetable oil as raw material and the factors affecting these properties is critical for the production of quality biodiesel and its sustainability. According to the source of oilseed, variations in the chemical composition of the vegetable oil are expressed by variations in the molar ratio among different fatty acids in the structure. The relative ratio of fatty acids present in the raw material is kept relatively constant after the transesterification reaction. The quality of biodiesel physico-chemical properties is influenced by the chain length and the level of unsaturation of the produced fatty acid alkyl esters. A biodiesel is thermodynamically stable. Its instability primarily occurs from contact of oxygen present in the ambient air that is referred to as oxidative instability. For biodiesel is oxidation stability a general term. It is necessary to distinguish ‘storage stability' and ‘thermal stability', in relation to oxidative degradation, which may occur during extended periods of storage, transportation and end use. Fuel instability problems can be of two related types, short-term oxidative instability and long-term storage instability. Storage instability is defined in terms of solid formation, which can plug nozzles, filters, and degrade engine

Estimation of physicochemical properties of 2-ethylhexyl-4-methoxycinnamate (EHMC) degradation products and their toxicological evaluation.

Science.gov (United States)

Gackowska, Alicja; Studziński, Waldemar; Kudlek, Edyta; Dudziak, Mariusz; Gaca, Jerzy

2018-06-01

The organic UV filters, commonly used in personal protection products, are of concern because of their potential risk to aquatic ecosystems and living organisms. One of UV filters is ethylhexyl-4-methoxycinnamate (EHMC) acid. Studies have shown that, in the presence of oxidizing and chlorinating factors, EHMC forms a series of products with different properties than the substrate. In this study, the toxicities of EHMC and its transformation/degradation products formed under the influence of NaOCl/UV and H 2 O 2 /UV systems in the water medium were tested using Microtox® bioassay and by observation of mortality of juvenile crustaceans Daphnia magna and Artemia Salina. We have observed that oxidation and chlorination products of EHMC show significantly higher toxicity than EHMC alone. The toxicity of chemicals is related to their physicochemical characteristic such as lipophilicity and substituent groups. With the increase in lipophilicity of products, expressed as log K OW , the toxicity (EC 50 ) increases. On the basis of physicochemical properties such as vapour pressure (VP), solubility (S), octanol-water partition coefficient (K OW ), bioconcentration factor (BCF) and half-lives, the overall persistence (P OV ) and long-range transport potential (LRTP) of all the products and EHMC were calculated. It was shown that the most persistent and traveling on the long distances in environment are methoxyphenol chloroderivatives, then methoxybenzene chloroderivatives, EHMC chloroderivatives, methoxybenzaldehyde chloroderivatives and methoxycinnamate acid chloroderivatives. These compounds are also characterised by high toxicity.

Degradation of 2,4-dichlorophenoxyacetic acid in water by ozone-hydrogen peroxide process

Institute of Scientific and Technical Information of China (English)

YU Ying-hui; MA Jun; HOU Yan-jun

2006-01-01

This study reports an investigation into the degradation of 2,4-dichlorophenoxyacetic acid in bubble contactor column by O3/H2O2 process, which is widely used as a principal advanced oxidation process. The degradation of 2,4-dichlorophenoxyacetic acid was studied under different H2O2/O3 molar ratio and pH value. Meanwhile, TOC removal was investigated both in distilled water and tap water. The influences of ozone transfer and consumed hydrogen peroxide were also discussed. The degradation products and oxidation intermediates were identified by GC-MS and LC-MS. A possible reaction mechanism was thus proposed.

Efficient heterogeneous and environmentally friendly degradation of nerve agents on a tungsten-based POM

International Nuclear Information System (INIS)

Mizrahi, Dana M.; Saphier, Sigal; Columbus, Ishay

2010-01-01

Common (chemical warfare agent) CWA decontaminants exhibit harsh and corrosive characteristics, and are harmful to the environment. In the course of our quest for active sorbents as efficient decontaminants, Keggin-type polyoxometalate (POM) (NH 4 ) 3 PW 12 O 40 was tested for oxidative degradation of CWAs. Although oxidation did not take place, sarin (GB) and VX were smoothly decontaminated to non-toxic products within 1 and 10 days, respectively. Degradation was carried out directly on the powder, eliminating the need for solvents. Mustard gas (HD), whose degradation is highly dependent on oxidation, was not decontaminated by this POM. Solid state MAS NMR ( 31 P and 13 C) was utilized both for POM characterization and for decontamination studies monitoring.

Microbial degradation of coconut coir dust for biomass production

Energy Technology Data Exchange (ETDEWEB)

Uyenco, F.R.; Ochoa, J.A.K.

Several species of white-rot fungi were studied for its ability to degrade the lignocellulose components of coir dust at optimum conditions. The most effective fungi was Phanerochaeta chrysosporium UPCC 4003. This organism degraded the lignocellulose complex of coir dust at a rate of about 25 percent in 4 weeks. The degradation process was carried on with minimal nitrogen concentration, coconut water supplementation and moisture levels between 85-90 percent. Shake flask cultures of the degraded coir dust using cellulolytic fungi were not effective. In fermentor cultures with Chaetomium cellulolyticum UPCC 3934, supplemented coir dust was converted into a microbial biomass product (MBP) with 15.58 percent lignin, 19.20 percent cellulose and 18.87 percent protein. More work is being done on the utilization of coir dust on a low technology.

Mechanistic studies of the alkaline degradation of cellulose in cement

International Nuclear Information System (INIS)

Greenfield, B.F.; Robertson, G.P.; Spindler, M.W.; Harrison, W.N.; Somers, P.J.

1993-07-01

The alkaline degradation of cellulose-based materials under conditions simulating those of a deep underground radioactive waste repository has been investigated. A number of key degradation products, of which 2-C-(hydroxymethyl)-3-deoxy-D-pentonic acid (isosaccharinic acid) is the most important, have been synthesised, and the solubilities of their plutonium complexes have been determined. Analysis of leachates of anaerobically degraded cellulose has shown concentrations of organic acids which are broadly consistent with the enhanced plutonium solubilities found in these leachates. Reaction mechanisms have been identified that can lead to isosaccharinic acid production by non-oxidative transformations, which may be catalysed by some divalent cations. (Author)

Oxidative degradation of polybenzimidazole membranes as electrolytes for high temperature proton exchange membrane fuel cells

DEFF Research Database (Denmark)

Liao, J.H.; Li, Qingfeng; Rudbeck, H.C.

2011-01-01

the oxidative degradation of the polymer membrane was studied under the Fenton test conditions by the weight loss, intrinsic viscosity, size exclusion chromatography, scanning electron microscopy and Fourier transform infrared spectroscopy. During the Fenton test, significant weight losses depending...... on the initial molecular weight of the polymer were observed. At the same time, viscosity and SEC measurements revealed a steady decrease in molecular weight. The degradation of acid doped PBI membranes under Fenton test conditions is proposed to start by the attack of hydroxyl radicals at the carbon atom......Polybenzimidazole membranes imbibed with acid are emerging as a suitable electrolyte material for high-temperature polymer electrolyte fuel cells. The oxidative stability of polybenzimidazole has been identified as an important issue for the long-term durability of such cells. In this paper...

Effects of accelerated degradation on metal supported thin film-based solid oxide fuel cell

DEFF Research Database (Denmark)

Reolon, R. P.; Sanna, S.; Xu, Yu

2018-01-01

A thin film-based solid oxide fuel cell is deposited on a Ni-based metal porous support by pulsed laser deposition with a multi-scale-graded microstructure design. The fuel cell, around 1 μm in thickness, is composed of a stabilized-zirconia/doped-ceria bi-layered dense electrolyte and nanostruct......A thin film-based solid oxide fuel cell is deposited on a Ni-based metal porous support by pulsed laser deposition with a multi-scale-graded microstructure design. The fuel cell, around 1 μm in thickness, is composed of a stabilized-zirconia/doped-ceria bi-layered dense electrolyte......, electrochemical performances are steady, indicating the stability of the cell. Under electrical load, a progressive degradation is activated. Post-test analysis reveals both mechanical and chemical degradation of the cell. Cracks and delamination of the thin films promote a significant nickel diffusion and new...

Stability and oxidation products of hydrolysable tannins in basic conditions detected by HPLC/DAD-ESI/QTOF/MS.

Science.gov (United States)

Tuominen, Anu; Sundman, Terhi

2013-01-01

Hydrolysable tannins occur in plants that are used for food or medicine by humans or herbivores. Basic conditions can alter the structures of tannins, that is, the oxidation of phenolic groups can lead to the formation of toxic quinones. Previously, these labile quinones and other oxidation products have been studied with colorimetric or electron paramagnetic resonance methods, which give limited information about products. To study the stability and oxidation products of hydrolysable tannins in basic conditions using HPLC with a diode-array detector (DAD) combined with electrospray ionisation (ESI) and quadrupole time-of-flight (QTOF) MS. Three galloyl glucoses, four galloyl derivatives with different polyols and three ellagitannins were purified from plants. The incubation reactions of tannins were monitored by HPLC/DAD at five pH values and in reduced oxygen conditions. Reaction products were identified based on UV spectra and mass spectral fragmentation obtained with the high-resolution HPLC/DAD-ESI/QTOF/MS. The use of a base-resistant HPLC column enabled injections without the sample pre-treatment and thus detection of short-lived products. Hydrolysable tannins were unstable in basic conditions and half-lives were mostly less than 10 min at pH 10. Degradation rates were faster at pH 11 but slower at milder pH. The HPLC analyses revealed that various products were formed and identified to be the result of hydrolysis, deprotonation and oxidation. Interestingly, the main hydrolysis product was ellagic acid; it was also formed from galloyl glucoses that do not contain oxidatively coupled galloyl groups in their initial structures. HPLD/DAD-ESI/QTOF/MS was an efficient method for the identification of polyphenol oxidation products and showed how different pH conditions determine the fate of hydrolysable tannins. Copyright © 2013 John Wiley & Sons, Ltd.

Degradation Studies of Polyolefins Incorporating Transparent Nanoparticulate Zinc Oxide UV Stabilizers

International Nuclear Information System (INIS)

Ammala, A.; Hill, A.J.; Meakin, P.; Pas, S.J.; Turney, T.W.

2002-01-01

Coated and dispersed nanoparticulate zinc oxide is shown to improve ultra violet (UV) stability of polypropylene and high-density polyethylene without changing its characteristic absorption spectrum in the visible region (400-800-nm). The performance of these nanoparticulate UV stabilizers is compared to conventional hindered amine light stabilizers (HALS). QUV accelerated weathering is used to simulate long-term exposure. Positron annihilation lifetime spectroscopy (PALS) is used to provide an indication of physical and chemical changes due to accelerated weathering and is shown to have potential for detecting changes well before other techniques. Visual observation, optical microscopy, carbonyl index, yellowness index and PALS indicate that nanoparticulate zinc oxide gives superior resistance to UV degradation compared to organic HALS at appropriate loading levels

Lipid oxidation. Part 2. Oxidation products of olive oil methyl esters.

Science.gov (United States)

Pokorný, J; Tài, P; Parízková, H; Smidrkalová, E; El-Tarras, M F; Janícek, G

1976-01-01

Olive oil was converted into methyl esters which were autoxidized at 60 degrees C. The composition of oxidized products was determined by the comparison of infrared spectra and NMR spectra of the original and acetylated samples, the sample reduced with potassium iodide and the acetylated reduced sample. Oxidized products were separated by preparative thin layer chromatography on silica gel and characterized by selective detection and by infrared spectrometry of the fractions. The oxidation products consisted of hydroperoxido butyl oleate, substituted hydroperoxides, mono- and disubstituted monomeric derivatives and a small amount of oligomers.

Multiple Syntrophic Interactions in a Terephthalate-Degrading Methanogenic Consortium

Energy Technology Data Exchange (ETDEWEB)

Lykidis, Athanasios; Chen, Chia-Lung; Tringe, Susannah G.; McHardy, Alice C.; Copeland, Alex 5; Kyrpides, Nikos C.; Hugenholtz, Philip; Liu, Wen-Tso

2010-08-05

Terephthalate (TA) is one of the top 50 chemicals produced worldwide. Its production results in a TA-containing wastewater that is treated by anaerobic processes through a poorly understood methanogenic syntrophy. Using metagenomics, we characterized the methanogenic consortium tinside a hyper-mesophilic (i.e., between mesophilic and thermophilic), TA-degrading bioreactor. We identified genes belonging to dominant Pelotomaculum species presumably involved in TA degradation through decarboxylation, dearomatization, and modified ?-oxidation to H{sub 2}/CO{sub 2} and acetate. These intermediates are converted to CH{sub 4}/CO{sub 2} by three novel hyper-mesophilic methanogens. Additional secondary syntrophic interactions were predicted in Thermotogae, Syntrophus and candidate phyla OP5 and WWE1 populations. The OP5 encodes genes capable of anaerobic autotrophic butyrate production and Thermotogae, Syntrophus and WWE1 have the genetic potential to oxidize butyrate to COsub 2}/H{sub 2} and acetate. These observations suggest that the TA-degrading consortium consists of additional syntrophic interactions beyond the standard H{sub 2}-producing syntroph ? methanogen partnership that may serve to improve community stability.

Production of oceanic nitrous oxide by ammonia-oxidizing archaea

Directory of Open Access Journals (Sweden)

C. R. Löscher

2012-07-01

Full Text Available The recent finding that microbial ammonia oxidation in the ocean is performed by archaea to a greater extent than by bacteria has drastically changed the view on oceanic nitrification. The numerical dominance of archaeal ammonia-oxidizers (AOA over their bacterial counterparts (AOB in large parts of the ocean leads to the hypothesis that AOA rather than AOB could be the key organisms for the oceanic production of the strong greenhouse gas nitrous oxide (N₂O that occurs as a by-product of nitrification. Very recently, enrichment cultures of marine ammonia-oxidizing archaea have been reported to produce N₂O.

Here, we demonstrate that archaeal ammonia monooxygenase genes (amoA were detectable throughout the water column of the eastern tropical North Atlantic (ETNA and eastern tropical South Pacific (ETSP Oceans. Particularly in the ETNA, comparable patterns of abundance and expression of archaeal amoA genes and N₂O co-occurred in the oxygen minimum, whereas the abundances of bacterial amoA genes were negligible. Moreover, selective inhibition of archaea in seawater incubations from the ETNA decreased the N₂O production significantly. In studies with the only cultivated marine archaeal ammonia-oxidizer Nitrosopumilus maritimus SCM1, we provide the first direct evidence for N₂O production in a pure culture of AOA, excluding the involvement of other microorganisms as possibly present in enrichments. N. maritimus showed high N₂O production rates under low oxygen concentrations comparable to concentrations existing in the oxycline of the ETNA, whereas the N₂O production from two AOB cultures was comparably low under similar conditions. Based on our findings, we hypothesize that the production of N₂O in tropical ocean areas results mainly from archaeal nitrification and will be affected by the predicted decrease in dissolved

An integrated (electro- and bio-oxidation) approach for remediation of industrial wastewater containing azo-dyes: Understanding the degradation mechanism and toxicity assessment

International Nuclear Information System (INIS)

Aravind, Priyadharshini; Selvaraj, Hosimin; Ferro, Sergio; Sundaram, Maruthamuthu

2016-01-01

Highlights: • Firstly, the mediated electro-oxidation allows rapid discoloration of the effluent. • Cost effective sunlight-mediated removal of bio-toxic active chlorine species. • Electrochemical pretreatment enhances the biodegradability of textile wastewater. • About 90% COD removal was achieved by a subsequent biodegradation. • By-products from degradation of dyes have shown to be ecofriendly and non-toxic. - Abstract: A hybrid approach for the remediation of recalcitrant dye wastewater is proposed. The chlorine-mediated electrochemical oxidation of real textile effluents and synthetic samples (using Ti/IrO_2-RuO_2-TiO_2 anodes), lead to discoloration by 92% and 89%, respectively, in 100 min, without significant mineralization. The remediation was obtained through biodegradation, after removing the residual bio-toxic active chlorine species via sunlight exposition. Results show that the electrochemical discoloration enhances the effluent biodegradability with about 90% COD removal employing acclimatized naphthalene-degrading bacterial consortia, within 144 h. Based on results obtained through FT-IR and GC–MS, it is likely that azo group stripping and oxidative cleavage of dyes occur due to the nucleophilic attack of active chlorine species during electro-oxidation. This leads to generation of aromatic intermediates which are further desulfonated, deaminated or oxidized only at their functional groups. These aromatic intermediates were mineralized into simpler organic acids and aldehydes by bacterial consortia. Phyto-toxicity trials on Vigna radiata confirmed the toxic nature of the untreated dye solutions. An increase in root and shoot development was observed with the electrochemically treated solutions, the same was higher in case of bio-treated solutions. Overall, obtained results confirm the capability of the proposed hybrid oxidation scheme for the remediation of textile wastewater.

Nitrous Oxide Production by Abundant Benthic Macrofauna

DEFF Research Database (Denmark)

Stief, Peter; Schramm, Andreas

of the short-term metabolic induction of gut denitrification is the preferential production of nitrous oxide rather than dinitrogen. On a large scale, gut denitrification in, for instance, Chironomus plumosus larvae can increase the overall nitrous oxide emission of lake sediment by a factor of eight. We...... screened more than 20 macrofauna species for nitrous oxide production and identified filter-feeders and deposit-feeders that occur ubiquitously and at high abundance (e.g., chironomids, ephemeropterans, snails, and mussels) as the most important emitters of nitrous oxide. In contrast, predatory species...... that do not ingest large quantities of microorganisms produced insignificant amounts of nitrous oxide. Ephemera danica, a very abundant mayfly larva, was monitored monthly in a nitrate-polluted stream. Nitrous oxide production by this filter-feeder was highly dependent on nitrate availability...

[Control on products of NDMA degradation by UV/O3].

Science.gov (United States)

Xu, Bing-bing; Chen, Zhong-lin; Qi, Fei; Yang, Lei; Huang, Lu-xi

2008-12-01

Comparison experiments of two advanced oxidation processes, UV/O3 and UV/H2O2, were carried out to evaluate their degradation effect of N-nitrosodimethylamine (NDMA) and controlling effect of dimethylamine (DMA) formation. The results showed that UV/H2O2 could enhance NDMA degradation, but could not control on the formation of DMA. UV/O3 was not only effective for NDMA degradation, but also was good at controlling on DMA formation. Furthermore, factors affecting the formation of DMA during degradation of NDMA by UV/O3 were studied. The formation of DMA decreased with O3 dosage increasing and DMA was 0.98 mg x L(-1) with 7.7 mg x L(-1) NDMA and 6.64 mg x L(-1) O3 dose. Solution pH had obvious effect on controlling of DMA formation during degradation of NDMA by UV/O3 . The formation of DMA lightly increased with pH increasing from acid to neutral but dramatically decreased in basic aqueous solution. The formation of DMA was only 0.3 mg x L(-1) when the initial concentration of NDMA was 7.7 mg x L(-1) under pH = 11.0 condition. UV/O3 had better controlling of DMA formation with lesser initial concentration of NDMA.

Comparison of CORA and MELCOR core degradation simulation and the MELCOR oxidation model

International Nuclear Information System (INIS)

Wang, Jun; Corradini, Michael L.; Fu, Wen; Haskin, Troy; Tian, Wenxi; Zhang, Yapei; Su, Guanghui; Qiu, Suizheng

2014-01-01

Highlights: • Oxidation model of MELCOR is analyzed and the improving suggestion is provided. • MELCOR core degradation calculating results are compared with CORA experiment. • Flow rate of argon and steam, the generating rate of hydrogen is calculated and compared. • Temperature spatial variation and temperature history is calculated and presented. - Abstract: MELCOR is widely used and sufficiently trusted for severe accident analysis. However, the occurrence of Fukushima has increased the focus on severe accident codes and their use. A MELCOR core degradation calculation was conducted at the University of Wisconsin–Madison under the help of Sandia. The calculation results were checked by comparing with a past CORA experiment. MELCOR calculation results included the flow rate of argon and steam, the generation rate of hydrogen. Through this work, the performance of MELCOR COR package was reviewed in detail. This paper compares the hydrogen generation rates predicted by MELCOR to the CORA test data. While agreement is reasonable it could be improved. Additionally, the MELCOR zirconium oxidation model was analyzed

Comparison of CORA and MELCOR core degradation simulation and the MELCOR oxidation model

Energy Technology Data Exchange (ETDEWEB)

Wang, Jun [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China); Corradini, Michael L., E-mail: corradini@engr.wisc.edu [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Fu, Wen [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Haskin, Troy [College of Engineering, The University of Wisconsin-Madison, Madison, WI 53706 (United States); Tian, Wenxi; Zhang, Yapei; Su, Guanghui; Qiu, Suizheng [State Key Laboratory of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049 (China)

2014-09-15

Highlights: • Oxidation model of MELCOR is analyzed and the improving suggestion is provided. • MELCOR core degradation calculating results are compared with CORA experiment. • Flow rate of argon and steam, the generating rate of hydrogen is calculated and compared. • Temperature spatial variation and temperature history is calculated and presented. - Abstract: MELCOR is widely used and sufficiently trusted for severe accident analysis. However, the occurrence of Fukushima has increased the focus on severe accident codes and their use. A MELCOR core degradation calculation was conducted at the University of Wisconsin–Madison under the help of Sandia. The calculation results were checked by comparing with a past CORA experiment. MELCOR calculation results included the flow rate of argon and steam, the generation rate of hydrogen. Through this work, the performance of MELCOR COR package was reviewed in detail. This paper compares the hydrogen generation rates predicted by MELCOR to the CORA test data. While agreement is reasonable it could be improved. Additionally, the MELCOR zirconium oxidation model was analyzed.

Environmental degradation of oxidation resistant and thermal barrier coatings for fuel-flexible gas turbine applications

Science.gov (United States)

Mohan, Prabhakar

The development of thermal barrier coatings (TBCs) has been undoubtedly the most critical advancement in materials technology for modern gas turbine engines. TBCs are widely used in gas turbine engines for both power-generation and propulsion applications. Metallic oxidation-resistant coatings (ORCs) are also widely employed as a stand-alone protective coating or bond coat for TBCs in many high-temperature applications. Among the widely studied durability issues in these high-temperature protective coatings, one critical challenge that received greater attention in recent years is their resistance to high-temperature degradation due to corrosive deposits arising from fuel impurities and CMAS (calcium-magnesium-alumino-silicate) sand deposits from air ingestion. The presence of vanadium, sulfur, phosphorus, sodium and calcium impurities in alternative fuels warrants a clear understanding of high-temperature materials degradation for the development of fuel-flexible gas turbine engines. Degradation due to CMAS is a critical problem for gas turbine components operating in a dust-laden environment. In this study, high-temperature degradation due to aggressive deposits such as V2O5, P2O 5, Na2SO4, NaVO3, CaSO4 and a laboratory-synthesized CMAS sand for free-standing air plasma sprayed (APS) yttria stabilized zirconia (YSZ), the topcoat of the TBC system, and APS CoNiCrAlY, the bond coat of the TBC system or a stand-alone ORC, is examined. Phase transformations and microstructural development were examined by using x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. This study demonstrated that the V2O5 melt degrades the APS YSZ through the formation of ZrV2O7 and YVO 4 at temperatures below 747°C and above 747°C, respectively. Formation of YVO4 leads to the depletion of the Y2O 3 stabilizer and the deleterious transformation of the YSZ to the monoclinic ZrO2 phase. The investigation on the YSZ degradation by Na 2SO4 and a Na2SO4 + V2

Analysis of the Precursors, Simulants and Degradation Products of Chemical Warfare Agents.

Science.gov (United States)

Witkiewicz, Zygfryd; Neffe, Slawomir; Sliwka, Ewa; Quagliano, Javier

2018-09-03

Recent advances in analysis of precursors, simulants and degradation products of chemical warfare agents (CWA) are reviewed. Fast and reliable analysis of precursors, simulants and CWA degradation products is extremely important at a time, when more and more terrorist groups and radical non-state organizations use or plan to use chemical weapons to achieve their own psychological, political and military goals. The review covers the open source literature analysis after the time, when the chemical weapons convention had come into force (1997). The authors stated that during last 15 years increased number of laboratories are focused not only on trace analysis of CWA (mostly nerve and blister agents) in environmental and biological samples, but the growing number of research are devoted to instrumental analysis of precursors and degradation products of these substances. The identification of low-level concentration of CWA degradation products is often more important and difficult than the original CWA, because of lower level of concentration and a very large number of compounds present in environmental and biological samples. Many of them are hydrolysis products and are present in samples in the ionic form. For this reason, two or three instrumental methods are used to perform a reliable analysis of these substances.

Identification and in vitro cytotoxicity of ochratoxin A degradation products formed during coffee roasting.

Science.gov (United States)

Cramer, Benedikt; Königs, Maika; Humpf, Hans-Ulrich

2008-07-23

The mycotoxin ochratoxin A is degraded by up to 90% during coffee roasting. In order to investigate this degradation, model heating experiments with ochratoxin A were carried out, and the reaction products were analyzed by HPLC-DAD and HPLC-MS/MS. Two ochratoxin A degradation products were identified, and their structure and absolute configuration were determined. As degradation reactions, the isomerization to 14-(R)-ochratoxin A and the decarboxylation to 14-decarboxy-ochratoxin A were identified. Subsequently, an analytical method for the determination of these compounds in roasted coffee was developed. Quantification was carried out by HPLC-MS/MS and the use of stable isotope dilution analysis. By using this method for the analysis of 15 coffee samples from the German market, it could be shown that, during coffee roasting, the ochratoxin A diastereomer 14-(R)-ochratoxin A was formed in amounts of up to 25.6% relative to ochratoxin A. The decarboxylation product was formed only in traces. For toxicity evaluations, first preliminary cell culture assays were performed with the two new substances. Both degradation products exhibited higher IC50 values and caused apoptotic effects with higher concentrations than ochratoxin A in cultured human kidney epithelial cells. Thus, these cell culture data suggest that the degradation products are less cytotoxic than ochratoxin A.

Identification and ecotoxicity of degradation products of chloroacetamide herbicides from UV-treatment of water

DEFF Research Database (Denmark)

Souissi, Yasmine; Bouchonnet, Stéphane; Bourcier, Sophie

2013-01-01

The widespread occurrence of chlorinated herbicides and their degradation products in the aquatic environment raises health and environmental concerns. As a consequence pesticides, and to a lesser degree their degradation products, are monitored by authorities both in surface waters and drinking...... waters. In this study the formation of degradation products from ultraviolet (UV) treatment of the three chloroacetamide herbicides acetochlor, alachlor and metolachlor and their biological effects were investigated. UV treatment is mainly used for disinfection in water and wastewater treatments. First...

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

Science.gov (United States)

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

2014-04-01

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

Degradation study of pesticides by direct photolysis - Structural characterization and potential toxicity of photo products

International Nuclear Information System (INIS)

Rifai, A.

2013-01-01

Pesticides belong to the large family of organic pollutants. In general, they are intended to fight against crop pests. Distribution of pesticides in nature creates pollution in DIFFERENT compartments of the biosphere (water, soil and air) and can induce acute toxic effects on human beings of the terrestrial and aquatic living biomass. It is now shown that some pesticides are endocrine disruptors and are particularly carcinogenic and mutagenic effects in humans. Pesticides can undergo various processes of transformation in the natural life cycle (biodegradation, volatilization, solar radiation ...) or following applied in the sectors of natural water purification and treatment stations sewage treatment. The presence of degradation products of pesticides in our environment is even more alarming that their structures and potential toxicities generally unknown. Molecules belonging to two families of pesticides were selected for this study: herbicides, represented by metolachlor, and fungicides represented by procymidone, pyrimethanil and boscalid. The first part of the thesis focused on the development of an analytical strategy to characterize the structures of compounds from degradation by photolysis of pesticides. The second part focused on estimating the toxicity of degradation products using a test database in silico. Identification of degradation products was achieved through two complementary analysis techniques: the gas chromatography coupled to a mass spectrometer ''multi-stage'' (GC-MSn) and liquid chromatography coupled to a tandem mass spectrometer (LC-MS/MS). The estimation of the toxicity of the degradation products was performed using the TEST program QSAR recently developed to try to predict the toxicity of molecules. The strategy of the structural elucidation of degradation products of pesticides studied is based on studying of the mechanisms of fragmentation of parent molecules of the degradation products. The molar mass of parent

Characterization of kerogen from Messel shale based on multistage alkaline permanganate degradation

Energy Technology Data Exchange (ETDEWEB)

Vitorovic, D.; Ambles, A.; Bajc, S.; Cvetkovic, O.

1988-07-01

A 17-step alkaline permanganate degradation of kerogen from Messel shale (F.R.G.) was carried out. A very high total yield of oxidation products was obtained (91.7% based on original kerogen). Detailed g.c.-m.s. analyses of ether-soluble acids, soluble products of further controlled permanganate degradation of precipitated acids and acids from aqueous solutions, served as a basis for the quantitative estimation of the participation of various types of products and for comparison with other kerogens. Taking into account the slight aliphatic nature of the acidic oxidation products (53.4%), the existence of an aliphatic cross-linked nucleus in the Messel shale kerogen is postulated. However, on the basis of high participation of both aromatic (21.2%), and alkane-polycarboxylic (20.2%) and cyloalkanoic (5.2%) acids, a high proportion of alicyclic, heterocyclic and aromatic structural elements in the structure of this kerogen was demonstrated. The most interesting finding was the isolation and identification, in significant amounts, of a series of monocarboxylic mono- and bicyclic cycloalkanoic acids. A small quantity of isoprenoid acids was found in the oxidation products. A homogeneous structure of the Messel shale kerogen is suggested. 17 refs., 9 figs., 4 tabs.

Identification of thermal degradation products of polymers by capillary gas chromatography

NARCIS (Netherlands)

Pacakova, V.; Borecka, M.; Leclercq, P.A.; Kaiser, R.E.

1981-01-01

Samples of polyethylene, polypropylene, polystyrene and five styrene copolymers were thermally degraded in a quartz tubular reactor at 5100e in an inert atmosphere. The degradation products were separated on-line on capillary coltmlS coated with squalane, OV-17 and SE-30 as stationary phases. The

Efficient heterogeneous and environmentally friendly degradation of nerve agents on a tungsten-based POM

Energy Technology Data Exchange (ETDEWEB)

Mizrahi, Dana M., E-mail: danami@iibr.gov.il [Department of Organic Chemistry, Israel Institute for Biological Research, P.O. Box 19, Ness Ziona 74100 (Israel); Saphier, Sigal; Columbus, Ishay [Department of Organic Chemistry, Israel Institute for Biological Research, P.O. Box 19, Ness Ziona 74100 (Israel)

2010-07-15

Common (chemical warfare agent) CWA decontaminants exhibit harsh and corrosive characteristics, and are harmful to the environment. In the course of our quest for active sorbents as efficient decontaminants, Keggin-type polyoxometalate (POM) (NH{sub 4}){sub 3}PW{sub 12}O{sub 40} was tested for oxidative degradation of CWAs. Although oxidation did not take place, sarin (GB) and VX were smoothly decontaminated to non-toxic products within 1 and 10 days, respectively. Degradation was carried out directly on the powder, eliminating the need for solvents. Mustard gas (HD), whose degradation is highly dependent on oxidation, was not decontaminated by this POM. Solid state MAS NMR ({sup 31}P and {sup 13}C) was utilized both for POM characterization and for decontamination studies monitoring.

Comparison of AOPs Efficiencies on Phenolic Compounds Degradation

Directory of Open Access Journals (Sweden)

Lourdes Hurtado

2016-01-01

Full Text Available In this work, a comparison of the performances of different AOPs in the phenol and 4-chlorophenol (4-CP degradation at lab and pilot scale is presented. It was found that, in the degradation of phenol, the performance of a coupled electro-oxidation/ozonation process is superior to that observed by a photo-Fenton process. Phenol removal rate was determined to be 0.83 mg L−1 min−1 for the coupled process while the removal rate for photo-Fenton process was only 0.52 mg L−1 min−1. Regarding 4-CP degradation, the complete disappearance of the molecule was achieved and the efficiency decreasing order was as follows: coupled electro-oxidation/ozonation > electro-Fenton-like process > photo-Fenton process > heterogeneous photocatalysis. Total organic carbon was completely removed by the coupled electro-oxidation/ozonation process. Also, it was found that oxalic acid is the most recalcitrant by-product and limits the mineralization degree attained by the technologies not applying ozone. In addition, an analysis on the energy consumption per removed gram of TOC was conducted and it was concluded that the less energy consumption is achieved by the coupled electro-oxidation/ozonation process.

Derivative spectrophotometry for the determination of faropenem in the presence of degradation products: an application for kinetic studies.

Science.gov (United States)

Cielecka-Piontek, Judyta

2013-07-01

A simple and selective derivative spectrophotometric method was developed for the quantitative determination of faropenem in pure form and in pharmaceutical dosage. The method is based on the zero-crossing effect of first-derivative spectrophotometry (λ = 324 nm), which eliminates the overlapping effect caused by the excipients present in the pharmaceutical preparation, as well as degradation products, formed during hydrolysis, oxidation, photolysis, and thermolysis. The method was linear in the concentration range 2.5-300 μg/mL (r = 0.9989) at λ = 341 nm; the limits of detection and quantitation were 0.16 and 0.46 μg/mL, respectively. The method had good precision (relative standard deviation from 0.68 to 2.13%). Recovery of faropenem ranged from 97.9 to 101.3%. The first-order rate constants of the degradation of faropenem in pure form and in pharmaceutical dosage were determined by using first-derivative spectrophotometry. A statistical comparison of the validation results and the observed rate constants for faropenem degradation with these obtained with the high-performance liquid chromatography method demonstrated that both were compatible.

Organochlorine Pesticides and Degradation Products in Soil around ...

African Journals Online (AJOL)

The levels and compositions of organochlorine pesticides and degradation products in soil samples collected from a former formulation plant in Morogoro municipality, Tanzania, were determined. Extraction was performed by pressurized fluid extraction using n-hexane:acetone (75:25) mixture. Clean-up of extracts was ...

Clay minerals and metal oxides strongly influence the structure of alkane-degrading microbial communities during soil maturation.

Science.gov (United States)

Steinbach, Annelie; Schulz, Stefanie; Giebler, Julia; Schulz, Stephan; Pronk, Geertje J; Kögel-Knabner, Ingrid; Harms, Hauke; Wick, Lukas Y; Schloter, Michael

2015-07-01

Clay minerals, charcoal and metal oxides are essential parts of the soil matrix and strongly influence the formation of biogeochemical interfaces in soil. We investigated the role of these parental materials for the development of functional microbial guilds using the example of alkane-degrading bacteria harbouring the alkane monooxygenase gene (alkB) in artificial mixtures composed of different minerals and charcoal, sterile manure and a microbial inoculum extracted from an agricultural soil. We followed changes in abundance and community structure of alkane-degrading microbial communities after 3 and 12 months of soil maturation and in response to a subsequent 2-week plant litter addition. During maturation we observed an overall increasing divergence in community composition. The impact of metal oxides on alkane-degrading community structure increased during soil maturation, whereas the charcoal impact decreased from 3 to 12 months. Among the clay minerals illite influenced the community structure of alkB-harbouring bacteria significantly, but not montmorillonite. The litter application induced strong community shifts in soils, maturated for 12 months, towards functional guilds typical for younger maturation stages pointing to a resilience of the alkane-degradation function potentially fostered by an extant 'seed bank'.

Radiation degradation of aromatic pollutants exit in wastewater and ph dependence

International Nuclear Information System (INIS)

Takriti, S.

2002-12-01

The effect of gamma radiation on the degradation of phenol (hydroxybenzene), resorcinol (1,3 dihydroxybenzen) and hydroquinone (1,4 dihydroxybenzen) exit in waste water was investigated. The concentrations of these pollutants as well as the irradiated solution ph were studied. The results showed that the phenol is very resistance against the radiation doses comparing the other phenol compounds. Phenol was also a product of radiolysis of resorcinol and hydroquinone. On the other hand, the acid phase of the irradiation sample increased the degradation rate of pollutants. Spectrophotometer (UV-VIS) and chromatography (HPLC) were used to monitor the analysis of the radiation product solution. The results illustrated the existing of many substances such as organic alcohol, aldehyde, ketone and acidic functional groups as a final radiation products. The degradation of benzene, monochlorobenzene (CB) and 1,2 dichlorobenzene (1,2 DCB) exit in waste water by gamma irradiation was investigated. The effect of the irradiated solution composition was studied. The results showed that the benzene is very resistance against the radiation doses comparing to other chlorobenzene. However, the existence of oxidizing substances in the irradiation phase leads to increase the degradation rate of pollutants. The dechlorination of CB and 1,2 DCB that is a result of the hydrated electron reaction with studied compounds was observed. Chromatography (HPLC) and spectrophotometer (UV-VIS) were used to monitor the analysis of the radiation product solution. The results illustrated the existing of many species as a final radiation product. On the other, the irradiation phase containing scavengers such as methanol and ethanol requires large doses to decompose the pollutants, while the oxidizing phase accelerates the degradation. (author)

Relationship between gas production and starch degradation in feed samples

NARCIS (Netherlands)

Chai, W.Z.; Gelder, van A.H.; Cone, J.W.

2004-01-01

An investigation was completed of the possibilities to estimate starch fermentation in rumen fluid using the gas production technique by incubating the total sample. Gas production from six starchy feed ingredients and eight maize silage samples were recorded and related to starch degradation

Epoxidation of the methamphetamine pyrolysis product, trans-phenylpropene, to trans-phenylpropylene oxide by CYP enzymes and stereoselective glutathione adduct formation

International Nuclear Information System (INIS)

Sanga, Madhu; Younis, Islam R.; Tirumalai, Padma S.; Bland, Tina M.; Banaszewska, Monica; Konat, Gregory W.; Tracy, Timothy S.; Gannett, Peter M.; Callery, Patrick S.

2006-01-01

Pyrolytic products of smoked methamphetamine hydrochloride are well established. Among the various degradation products formed, trans-phenylpropene (trans-β-methylstyrene) is structurally similar to styrene analogues known to be bioactivated by CYP enzymes. In human liver microsomes, trans-phenylpropene was converted to the epoxide trans-phenylpropylene oxide (trans-2-methyl-3-phenyloxirane) and cinnamyl alcohol. Incubation of trans-phenylpropene with microsomes in the presence of enzyme-specific P450 enzyme inhibitors indicated the involvement of CYP2E1, CYP1A2, and CYP3A4 enzymes. Both (R,R)-phenylpropylene oxide and (S,S)-phenylpropylene oxide were formed in human liver microsomal preparations. Enantiomers of trans-phenylpropylene oxide were stereoselectively and regioselectively conjugated in a Phase II drug metabolism reaction catalyzed by human liver cytosolic enzymes consisting of conjugation with glutathione. The structure of the phenylpropylene oxide-glutathione adduct is consistent with nucleophilic ring-opening by attack at the benzylic carbon. Exposure of cultured C6 glial cells to (S,S)-phenylpropylene oxide produced a cytotoxic response in a concentration-dependent manner based on cell degeneration and death

Conversion of waste polystyrene through catalytic degradation into valuable products

Energy Technology Data Exchange (ETDEWEB)

Shah, Jasmin; Jan, Muhammad Rasul; Adnan [University of Peshawar, Peshawar (Pakistan)

2014-08-15

Waste expanded polystyrene (EPS) represents a source of valuable chemical products like styrene and other aromatics. The catalytic degradation was carried out in a batch reactor with a mixture of polystyrene (PS) and catalyst at 450 .deg. C for 30 min in case of Mg and at 400 .deg. C for 2 h both for MgO and MgCO{sub 3} catalysts. At optimum degradation conditions, EPS was degraded into 82.20±3.80 wt%, 91.60±0.20 wt% and 81.80±0.53 wt% liquid with Mg, MgO and MgCO{sub 3} catalysts, respectively. The liquid products obtained were separated into different fractions by fractional distillation. The liquid fractions obtained with three catalysts were compared, and characterized using GC-MS. Maximum conversion of EPS into styrene monomer (66.6 wt%) was achieved with Mg catalyst, and an increase in selectivity of compounds was also observed. The major fraction at 145 .deg. C showed the properties of styrene monomer. The results showed that among the catalysts used, Mg was found to be the most effective catalyst for selective conversion into styrene monomer as value added product.

Degradation in steam of 60 cm-long B{sub 4}C control rods

Energy Technology Data Exchange (ETDEWEB)

Dominguez, C., E-mail: christina.dominguez@irsn.fr; Drouan, D.

2014-08-01

In the framework of nuclear reactor core meltdown accident studies, the degradation of boron carbide control rod segments exposed to argon/steam atmospheres was investigated up to about 2000 °C in IRSN laboratories. The sequence of the phenomena involved in the degradation has been found to take place as expected. Nevertheless, the ZrO{sub 2} oxide layer formed on the outer surface of the guide tube was very protective, significantly delaying and limiting the guide tube failure and therefore the boron carbide pellet oxidation. Contrary to what was expected, the presence of the control rod decreases the hydrogen release instead of increasing it by additional oxidation of boron compounds. Boron contents up to 20 wt.% were measured in metallic mixtures formed during degradation. It was observed that these metallic melts are able to attack the surrounding fuel rods, which could have consequences on fuel degradation and fission product release kinetics during severe accidents.

Transparent conducting oxides and production thereof

Science.gov (United States)

Gessert, Timothy A.; Yoshida, Yuki; Coutts, Timothy J.

2014-06-10

Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber. The method may also comprise depositing a metal oxide on the target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

An integrated (electro- and bio-oxidation) approach for remediation of industrial wastewater containing azo-dyes: Understanding the degradation mechanism and toxicity assessment

Energy Technology Data Exchange (ETDEWEB)

Aravind, Priyadharshini, E-mail: priya.bdu07@gmail.com [Corrosion and Materials Protection Division (CMPD), CSIR—Central electrochemical research institute (CECRI), Karaikudi 630 003 (India); Selvaraj, Hosimin [Corrosion and Materials Protection Division (CMPD), CSIR—Central electrochemical research institute (CECRI), Karaikudi 630 003 (India); Ferro, Sergio [Ecas4 Australia, Unit 8, 1 London Road, Mile End, South Australia 5031 (Australia); Sundaram, Maruthamuthu [Corrosion and Materials Protection Division (CMPD), CSIR—Central electrochemical research institute (CECRI), Karaikudi 630 003 (India)

2016-11-15

Highlights: • Firstly, the mediated electro-oxidation allows rapid discoloration of the effluent. • Cost effective sunlight-mediated removal of bio-toxic active chlorine species. • Electrochemical pretreatment enhances the biodegradability of textile wastewater. • About 90% COD removal was achieved by a subsequent biodegradation. • By-products from degradation of dyes have shown to be ecofriendly and non-toxic. - Abstract: A hybrid approach for the remediation of recalcitrant dye wastewater is proposed. The chlorine-mediated electrochemical oxidation of real textile effluents and synthetic samples (using Ti/IrO{sub 2}-RuO{sub 2}-TiO{sub 2} anodes), lead to discoloration by 92% and 89%, respectively, in 100 min, without significant mineralization. The remediation was obtained through biodegradation, after removing the residual bio-toxic active chlorine species via sunlight exposition. Results show that the electrochemical discoloration enhances the effluent biodegradability with about 90% COD removal employing acclimatized naphthalene-degrading bacterial consortia, within 144 h. Based on results obtained through FT-IR and GC–MS, it is likely that azo group stripping and oxidative cleavage of dyes occur due to the nucleophilic attack of active chlorine species during electro-oxidation. This leads to generation of aromatic intermediates which are further desulfonated, deaminated or oxidized only at their functional groups. These aromatic intermediates were mineralized into simpler organic acids and aldehydes by bacterial consortia. Phyto-toxicity trials on Vigna radiata confirmed the toxic nature of the untreated dye solutions. An increase in root and shoot development was observed with the electrochemically treated solutions, the same was higher in case of bio-treated solutions. Overall, obtained results confirm the capability of the proposed hybrid oxidation scheme for the remediation of textile wastewater.

Hemoglobin fructation promotes heme degradation through the generation of endogenous reactive oxygen species

Science.gov (United States)

Goodarzi, M.; Moosavi-Movahedi, A. A.; Habibi-Rezaei, M.; Shourian, M.; Ghourchian, H.; Ahmad, F.; Farhadi, M.; Saboury, A. A.; Sheibani, N.

2014-09-01

Protein glycation is a cascade of nonenzymatic reactions between reducing sugars and amino groups of proteins. It is referred to as fructation when the reducing monosaccharide is fructose. Some potential mechanisms have been suggested for the generation of reactive oxygen species (ROS) by protein glycation reactions in the presence of glucose. In this state, glucose autoxidation, ketoamine, and oxidative advance glycation end products (AGEs) formation are considered as major sources of ROS and perhaps heme degradation during hemoglobin glycation. However, whether fructose mediated glycation produces ROS and heme degradation is unknown. Here we report that ROS (H2O2) production occurred during hemoglobin fructation in vitro using chemiluminescence methods. The enhanced heme exposure and degradation were determined using UV-Vis and fluorescence spectrophotometry. Following accumulation of ROS, heme degradation products were accumulated reaching a plateau along with the detected ROS. Thus, fructose may make a significant contribution to the production of ROS, glycation of proteins, and heme degradation during diabetes.

Synthesis and application of multiple rods gold-zinc oxide nano structures in the photo catalytic degradation of methyl orange

International Nuclear Information System (INIS)

Arab Chamjangali, M.; Bagherian, G.; Bahramian, B.; Fahimi Rad, B.

2015-01-01

Zinc oxide and gold-zinc oxide (Au-Zn O) nano structures with multiple rods (multi pods) morphology were successfully prepared. Au-Zn O nano structures were synthesized via a simple precipitation route method in the presence of oligo aniline-coated gold nanoparticles. The Au-Zn O catalyst obtained was applied for the degradation of methyl orange in an aqueous solution under UV irradiation Effects of the operational parameters such as the solution p H, amount of photocatalyst, and dye concentration on the photo catalytic degradation and decolorisation of methyl orange were studied. Detailed studies including kinetic study and regeneration of catalyst were carried out on the optimal conditions for the photodegradation of methyl orange by Au-Zn O multi pods in aqueous solution. Effect of foreign species on the photodegradation of methyl orange was also studied. An enhancement of the photo catalytic activities for photodegradation of methyl orange was observed when the gold nanoparticles were loaded on the zinc oxide multi pods. The proposed catalyst was applied for the degradation of methyl orange in synthetic wastewater samples with satisfactory results.

Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

International Nuclear Information System (INIS)

Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T.

2017-01-01

Highlights: • AuNPs on PDMAEMA brushes immobilized reduced graphene oxide was used as catalyst. • A novel highly efficient, reusable heterogeneous catalyst for dyes degradation. • Rhodamine B, Methyl Orange and Eosin Y was used for study. • Apparent rate constant observed was 21.8, 26.2, and 8.7 (×10 −3 s −1 ) respectively. - Abstract: In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (k app ), which is found to be 21.8, 26.2, and 8.7 (×10 −3 s −1 ), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

Energy Technology Data Exchange (ETDEWEB)

Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T., E-mail: dhnaraj_masram27@rediffmail.com

2017-02-28

Highlights: • AuNPs on PDMAEMA brushes immobilized reduced graphene oxide was used as catalyst. • A novel highly efficient, reusable heterogeneous catalyst for dyes degradation. • Rhodamine B, Methyl Orange and Eosin Y was used for study. • Apparent rate constant observed was 21.8, 26.2, and 8.7 (×10{sup −3} s{sup −1}) respectively. - Abstract: In the present work, we report gold nanoparticles (AuNPs) on poly (dimethylaminoethyl methacrylate) (PDMAEMA) brushes immobilized reduced graphene oxide (Au/PDMAEMA/RGO) as catalyst for degradation kinetic studies of Rhodamine B (RB), Methyl Orange (MO) and Eosine Y (EY) dyes, having an excellent catalytic activity, as evident by the apparent rate constant (k{sub app}), which is found to be 21.8, 26.2, and 8.7 (×10{sup −3} s{sup −1}), for RB, MO and EY respectively. Au/PDMAEMA/RGO catalyst is easy to use, highly efficient, recyclable, which make it suitable for applications in waste water management. Foremost, synthesis of PDMAEMA brushes on graphene oxide is accomplished by Atom transfer radical polymerization method (ATRP), whereas AuNPs are synthesized by simple chemical reduction method.

Diclofenac and 2‐anilinophenylacetate degradation by combined activity of biogenic manganese oxides and silver

Science.gov (United States)

Meerburg, Francis; Hennebel, Tom; Vanhaecke, Lynn; Verstraete, Willy; Boon, Nico

2012-01-01

Summary The occurrence of a range of recalcitrant organic micropollutants in our aquatic environment has led to the development of various tertiary wastewater treatment methods. In this study, biogenic manganese oxides (Bio‐MnOx), biogenic silver nanoparticles (Bio‐Ag0) and ionic silver were used for the oxidative removal of the frequently encountered drug diclofenac and its dechlorinated form, 2‐anilinophenylacetate (APA). Diclofenac was rapidly degraded during ongoing manganese oxidation by Pseudomonas putida MnB6. Furthermore, whereas preoxidized Bio‐MnOx, Bio‐Ag0 and Ag+ separately did not show any removal capacity for diclofenac, an enhanced removal occurred when Bio‐MnOx and silver species were combined. Similar results were obtained for APA. Finally, a slow removal of diclofenac but more rapid APA degradation was observed when silver was added to manganese‐free P. putida biomass. Combining these results, three mechanisms of diclofenac and APA removal could be distinguished: (i) a co‐metabolic removal during active Mn2+ oxidation by P. putida; (ii) a synergistic interaction between preoxidized Bio‐MnOx and silver species; and (iii) a (bio)chemical process by biomass enriched with silver catalysts. This paper demonstrates the use of P. putida for water treatment purposes and is the first report of the application of silver combined with biogenic manganese for the removal of organic water contaminants. PMID:22221449

Degradation of sulfamethoxazole by UV, UV/H2O2 and UV/persulfate (PDS): Formation of oxidation products and effect of bicarbonate.

Science.gov (United States)

Yang, Yi; Lu, Xinglin; Jiang, Jin; Ma, Jun; Liu, Guanqi; Cao, Ying; Liu, Weili; Li, Juan; Pang, Suyan; Kong, Xiujuan; Luo, Congwei

2017-07-01

The frequent detection of sulfamethoxazole (SMX) in wastewater and surface waters gives rise of concerns about their ecotoxicological effects and potential risks to induce antibacterial resistant genes. UV/hydrogen peroxide (UV/H 2 O 2 ) and UV/persulfate (UV/PDS) advanced oxidation processes have been demonstrated to be effective for the elimination of SMX, but there is still a need for a deeper understanding of product formations. In this study, we identified and compared the transformation products of SMX in UV, UV/H 2 O 2 and UV/PDS processes. Because of the electrophilic nature of SO 4 - , the second-order rate constant for the reaction of sulfate radical (SO 4 - ) with the anionic form of SMX was higher than that with the neutral form, while hydroxyl radical (OH) exhibited comparable reactivity to both forms. The direct photolysis of SMX predominately occurred through cleavage of the NS bond, rearrangement of the isoxazole ring, and hydroxylation mechanisms. Hydroxylation was the dominant pathway for the reaction of OH with SMX. SO 4 - favored attack on NH 2 group of SMX to generate a nitro derivative and dimeric products. The presence of bicarbonate in UV/H 2 O 2 inhibited the formation of hydroxylated products, but promoted the formation of the nitro derivative and the dimeric products. In UV/PDS, bicarbonate increased the formation of the nitro derivative and the dimeric products, but decreased the formation of the hydroxylated dimeric products. The different effect of bicarbonate on transformation products in UV/H 2 O 2 vs. UV/PDS suggested that carbonate radical (CO 3 - ) oxidized SMX through the electron transfer mechanism similar to SO 4 - but with less oxidation capacity. Additionally, SO 4 - and CO 3 - exhibited higher reactivity to the oxazole ring than the isoxazole ring of SMX. Ecotoxicity of transformation products was estimated by ECOSAR program based on the quantitative structure-activity relationship analysis as well as by experiments using

Spectroscopic evidence for intermediate species formed during aniline polymerization and polyaniline degradation.

Science.gov (United States)

Planes, G A; Rodríguez, J L; Miras, M C; García, G; Pastor, E; Barbero, C A

2010-09-21

Spectroscopic methods are used to investigate the formation of low molecular mass intermediates during aniline (ANI) oxidation and polyaniline (PANI) degradation. Studying ANI anodic oxidation by in situ Fourier transform infrared spectroscopy (FTIRS) it is possible to obtain, for the first time, spectroscopic evidence for ANI dimers produced by head-to-tail (4-aminodiphenylamine, 4ADA) and tail-to-tail (benzidine, BZ) coupling of ANI cation radicals. The 4ADA dimer is adsorbed on the electrode surface during polymerization, as proved by cyclic voltammetry of thin PANI films and its infrared spectrum. This method also allows, with the help of computational simulations, to assign characteristic vibration frequencies for the different oxidation states of PANI. The presence of 4ADA retained inside thin polymer layers is established too. On the other hand, FTIRS demonstrates that the electrochemically promoted degradation of PANI renders p-benzoquinone as its main product. This compound, retained inside the film, is apparent in the cyclic voltammogram in the same potential region previously observed for 4ADA dimer. Therefore, applying in situ FTIRS is possible to distinguish between different chemical species (4ADA or p-benzoquinone) which give rise to voltammetric peaks in the same potential region. Indophenol and CO(2) are also detected by FTIRS during ANI oxidation and polymer degradation. The formation of CO(2) during degradation is confirmed by differential electrochemical mass spectroscopy. To the best of our knowledge, this is the first evidence of the oxidation of a conducting polymer to CO(2) by electrochemical means. The relevance of the production of different intermediate species towards PANI fabrication and applications is discussed.

Identification of the Products of Oxidation of Quercetin by Air Oxygenat Ambient Temperature

Directory of Open Access Journals (Sweden)

Viktor A Utsal

2007-03-01

Full Text Available Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH ∼ 8-10 at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic and 2,4,6-trihydroxybenzoic (phloroglucinic acids, as well as the decarboxylation product of the latter – 1,3,5-trihydroxybenzene (phloroglucinol. In accordance with the literature data, this process involves the cleavage of the γ-pyrone fragment (ring C of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxybenzoic acid (depside. However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4 %. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol, but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin, or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.

Wet oxidative degradation of cellulosic wastes 5- chemical and thermal properties of the final waste forms

International Nuclear Information System (INIS)

Eskander, S.B.; Saleh, H.M.

2002-01-01

In this study, the residual solution arising from the wet oxidative degradation of solid organic cellulosic materials, as one of the component of radioactive solid wastes, using hydrogen peroxide as oxidant. Were incorporated into ordinary Portland cement matrix. Leaching as well as thermal characterizations of the final solidified waste forms were evaluated to meet the final disposal requirements. Factors, such as the amount of the residual solution incorporated, types of leachant. Release of different radionuclides and freezing-thaw treatment, that may affect the leaching characterization. Were studied systematically from the data obtained, it was found that the final solid waste from containing 35% residual solution in tap water is higher than that in ground water or sea water. Based on the data obtained from thermal analysis, it could be concluded that incorporating the residual solution form the wet oxidative degradation of cellulosic materials has no negative effect on the hydration of cement materials and consequently on the thermal stability of the final solid waste from during the disposal process

Identification of intermediates and assessment of ecotoxicity in the oxidation products generated during the ozonation of clofibric acid.

Science.gov (United States)

Rosal, Roberto; Gonzalo, María S; Boltes, Karina; Letón, Pedro; Vaquero, Juan J; García-Calvo, E

2009-12-30

The degradation of an aqueous solution of clofibric acid was investigated during catalytic and non-catalytic ozonation. The catalyst, TiO(2), enhanced the production of hydroxyl radicals from ozone and raised the fraction or clofibric acid degraded by hydroxyl radicals. The rate constant for the reaction of clofibric acid and hydroxyl radicals was not affected by the presence of the catalyst. The toxicity of the oxidation products obtained during the reaction was assessed by means of Vibrio fischeri and Daphnia magna tests in order to evaluate the potential formation of toxic by-products. The results showed that the ozonation was enhanced by the presence of TiO(2,) the clofibric acid being removed completely after 15 min at pH 5. The evolution of dissolved organic carbon, specific ultraviolet absorption at 254 nm and the concentration of carboxylic acids monitored the degradation process. The formation of 4-chlorophenol, hydroquinone, 4-chlorocatechol, 2-hydroxyisobutyric acid and three non-aromatic compounds identified as a product of the ring-opening reaction was assessed by exact mass measurements performed by liquid chromatography coupled to time-of-flight mass spectrometry (LC-TOF-MS). The bioassays showed a significant increase in toxicity during the initial stages of ozonation following a toxicity pattern closely related to the formation of ring-opening by-products.

Modelling sulfamethoxazole degradation under different redox conditions

Science.gov (United States)

Sanchez-Vila, X.; Rodriguez-Escales, P.

2015-12-01

Sulfamethoxazole (SMX) is a low adsorptive, polar, sulfonamide antibiotic, widely present in aquatic environments. Degradation of SMX in subsurface porous media is spatially and temporally variable, depending on various environmental factors such as in situ redox potential, availability of nutrients, local soil characteristics, and temperature. It has been reported that SMX is better degraded under anoxic conditions and by co-metabolism processes. In this work, we first develop a conceptual model of degradation of SMX under different redox conditions (denitrification and iron reducing conditions), and second, we construct a mathematical model that allows reproducing different experiments of SMX degradation reported in the literature. The conceptual model focuses on the molecular behavior and contemplates the formation of different metabolites. The model was validated using the experimental data from Barbieri et al. (2012) and Mohatt et al. (2011). It adequately reproduces the reversible degradation of SMX under the presence of nitrite as an intermediate product of denitrification. In those experiments degradation was mediated by the transient formation of a diazonium cation, which was considered responsible of the substitution of the amine radical by a nitro radical, forming the 4-nitro-SMX. The formation of this metabolite is a reversible process, so that once the concentration of nitrite was back to zero due to further advancement of denitrification, the concentration of SMX was fully recovered. The forward reaction, formation of 4-nitro SMX, was modeled considering a kinetic of second order, whereas the backward reaction, dissociation of 4-nitro-SMX back to the original compound, could be modeled with a first order degradation reaction. Regarding the iron conditions, SMX was degraded due to the oxidation of iron (Fe2+), which was previously oxidized from goethite due to the degradation of a pool of labile organic carbon. As the oxidation of iron occurred on the

Kinetics of Phenol Degradation in Aqueous Solution Oxidized under Low Frequency Ultrasonic Irradiation

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Marwan Marwan

2014-06-01

Full Text Available Phenol is categorized as a refractory pollutant and its presence in water stream is strictly limited according to the government regulation. The present study investigated the degra-dation of phenol in aqueous solution by the effect of ultrasound. The process took place in a 500 ml glass reactor equipped with magnetic stirring and irradiated by low frequency (28 kHz ultrasound from a horn type probe. Ultrasonic irradiation was found to enhance oxidation rates at ambient conditions, compared to other approaches. Optimum conditions were observed at a stirring speed of 400 rpm and temperature of 30 C in acidic solution. It was revealed that the phenol degradation was the first order kinetics with respect to phenol. A low value of the activation energy 6.04 kcal/mol suggested that diffusional steps were rate determining during the phenol decomposition. It also confirmed that phenol was mostly degraded in the film region and less occurred in the bulk solution.

Application of electrochemical advanced oxidation processes with a boron-doped diamond anode to degrade acidic solutions of Reactive Blue 15 (Turqueoise Blue) dye

International Nuclear Information System (INIS)

Solano, Aline Maria Sales; Martínez-Huitle, Carlos Alberto; Garcia-Segura, Sergi; El-Ghenymy, Abdellatif

2016-01-01

Highlights: • Degradation of Reactive Blue 15 solution at pH 3.0 by electrochemical oxidation, electro-Fenton and photoelectro-Fenton. • Hard destruction of the dye and its products by BDD(·OH) and much more rapidly by ·OH. • 94% mineralization by the most powerful photoelectro-Fenton at 66.7 mA cm"−"2, with acetic acid accumulation. • 25 aromatics and heteroaromatics, 30 hydroxylated derivatives and 4 carboxylic acids as products. • Release of Cl"−, SO_4"2"− and pre-eminently NO_3"− during dye mineralization. - Abstract: The degradation of the copper-phthalocyanine dye Reactive Blue 15 dye in sulfate medium has been comparatively studied by electrochemical oxidation with electrogenerated H_2O_2 (EO-H_2O_2), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments with 100 cm"3 solutions of 0.203 mmol dm"−"3 dye were performed with a stirred tank reactor containing a boron-doped diamond (BDD) anode and an air-diffusion cathode for continuous H_2O_2 production. Experimental conditions of pH 3.0 and 0.50 mmol dm"−"3 Fe"2"+ as catalyst were found optimal for the EF process by the predominant oxidation with hydroxyl radicals formed in the bulk from Fenton’s reaction between added Fe"2"+ and generated H_2O_2. The kinetics of Reactive Blue 15 abatement was followed by reversed-phase HPLC and always obeyed a pseudo-first-order reaction. The decolorization rate in EO-H_2O_2 was much lower than dye decay due to the formation of large quantities of colored intermediates under the action of hydroxyl radicals generated at the BDD anode from water oxidation. In contrast, the color and dye removals were much more rapid in EF and PEF by the most efficient oxidation of hydroxyl radicals produced from Fenton’s reaction. PEF was the most powerful treatment owing to the photolytic action of UVA irradiation, yielding 94% mineralization after 360 min at 66.7 mA cm"−"2. The effect of current density over the performance of all methods was examined. LC

Analysis of deltamethrin's degradation products by irradiation

International Nuclear Information System (INIS)