WorldWideScience

Sample records for benzoapyrene oxidative degradation

  1. Bacillus subtilis is a Potential Degrader of Pyrene and Benzo[a]pyrene

    Directory of Open Access Journals (Sweden)

    Lynette Ekunwe

    2005-08-01

    Full Text Available Polycyclic Aromatic Hydrocarbons (PAHs are a group of compounds that pose many health threats to human and animal life. They occur in nature as a result of incomplete combustion of organic matter, as well as from many anthropogenic sources including cigarette smoke and automobile exhaust. PAHs have been reported to cause liver damage, red blood cell damage and a variety of cancers. Because of this, methods to reduce the amount of PAHs in the environment are continuously being sought. The purpose of this study was to find soil bacteria capable of degrading high molecular weight PAHs, such as pyrene (Pyr and benzo[a]pyrene (BaP, which contain more than three benzene rings and so persist in the environment. Bacillus subtilis, identified by fatty acid methyl ester (FAME analysis, was isolated from PAH contaminated soil. Because it grew in the presence of 33μg/ml each of pyrene, 1-AP and 1-HP, its biodegradation capabilities were assessed. It was found that after a four-day incubation period at 30oC in 20μg/ml pyrene or benzo[a]pyrene, B. subtilis was able to transform approximately 40% and 50% pyrene and benzo[a]pyrene, respectively. This is the first report implicating B. subtilis in PAH degradation. Whether or not the intermediates resulting from the transformation are more toxic than their parent compounds, and whether B. subtilis is capable of mineralizing pyrene or benzo[a]pyrene to carbon dioxide and water, remains to be evaluated.

  2. Monitoring of radiolytic degradation of benzo(a)pyrene using γ-rays in aqueous media by HPLC

    International Nuclear Information System (INIS)

    Butt, S. Bilal; Qureshi, Rashid N.; Ahmed, Shafaat

    2005-01-01

    Poly nuclear aromatic hydrocarbons (PAHs) are generated in the environment by various industrial processes and anthropogenic activities. These compounds are quite stable and persist in the environment due to the aromatic bonding within the rings. Benzo(a)pyrene (B(a)P) is a potential carcinogenic and conditions for its degradation have been optimized by investigating γ-ray dose intensity, its concentration effect and the influence of surfactant presence. HPLC has been used to monitor the degree of degradation of B(a)P under the optimum conditions

  3. Nucleoside adducts from the in vitro reaction of benzo[a]pyrene-7,8-dihydrodiol 9,10-oxide or benzo[a]pyrene 4,5-oxide with nucleic acids.

    Science.gov (United States)

    Jennette, K W; Jeffrey, A M; Blobstein, S H; Beland, F A; Harvey, R G; Weinstein, I B

    1977-03-08

    The covalent binding of benzo[a]pyrene 4,5-oxide and benzo[a]pyrene-7,8-dihydrodiol 9,10-oxide isomer I and isomer II to nucleic acids in aqueous acetone solution has been investigated. Benzo[a]pyrene 4,5-oxide reacted preferentially with guanosine residues. On the other hand, benzo[a]pyrene-7,8-dihydrodiol 9,10-oxide isomer I and II reacted extensively with guanosine, adenosine, and cytidine residues. Time course studies showed that the reactivity of isomer I or isomer II with homopolyribonucleotides followed the order poly(G) greater than poly(A) greater than poly(C). Alkaline or enzymatic hydrolysis of the modified nucleic acids and subsequent chromatography on Sephadex LH-20 columns yielded benzo[a]pyrene-nucleotide adducts. These were enzymatically converted to the corresponding nucleosides which were resolved into several distinct components by high-pressure liquid chromatography. Evidence was obtained for the presence of multiple nucleoside adducts of guanosine, adenosine, cytidine, deoxyguanosine, deoxyadenosine, and deoxycytidine. The HPLC profiles of adducts formed with isomer I were different from the corresponding profiles of adducts formed with isomer II. Structural aspects of these nucleoside adducts are discussed.

  4. Preliminary evidence of the role of hydrogen peroxide in the degradation of benzo[a]pyrene by a non-white rot fungus Fusarium solani

    International Nuclear Information System (INIS)

    Veignie, Etienne; Rafin, Catherine; Woisel, Patrice; Cazier, Fabrice

    2004-01-01

    In order to study the enzymatic mechanisms involved in the successive steps of BaP degradation by a Deuteromycete fungus Fusarium solani, we developed an indirect approach by using inhibitors of enzymes. We used either specific inhibitors of peroxidases (i.e. salicylhydroxamic acid) and of cytochrome P-450 (i.e. piperonyl butoxyde) or inhibitors of both enzymes (i.e. potassium cyanide). Surprisingly, no expected decrease of BaP degradation was observed with most inhibitors tested. On the contrary, more BaP was degraded. Only butylated hydroxytoluene, which acts as a free radical scavenger, inhibited BaP degradation. The inhibition of these enzymes, which use H 2 O 2 as a cosubstrat, might have resulted in an increase of hydrogen peroxide availability in the fungal cultures. This enhancement could induce formation of reactive oxygen species (ROS) which might be the agents that initiate benzo[a]pyrene oxidation. This study proposed a hypothetic alternative metabolic pathway involved in PAH metabolism by Fusarium solani. - An alternative metabolic pathway was demonstrated

  5. Removal of pyrene and benzo(a)pyrene micropollutant from water via adsorption by green synthesized iron oxide nanoparticles

    Science.gov (United States)

    Hassan, Saad S. M.; Abdel-Shafy, Hussein I.; Mansour, Mona S. M.

    2018-03-01

    Polycyclic aromatic hydrocarbons (PAHs) in water are classified as organic micropollutants, which are carcinogenic even in very low concentration (ppb). In this study the green synthesized iron oxide nanoparticles (IONPs) were green synthesized at room temperature by using pomegranate peel extract. The green synthesized IONPs were used for adsorbing benzo(a)pyrene and pyrene (PAHs) from water. Factors affecting the adsorption were investigated. These factors are: nanoparticles dose, pH, temperature, and initial concentration of PAHs. The overall results showed that the maximum adsorption capacities of IONPs towards pyrene and benzo(a)pyrene were 2.8 and 0.029 mg g-1, respectively. The thermodynamic study indicated an exothermic adsorption process of pyrene and benzo(a)pyrene. The kinetic and isotherm studies were carried out. The obtained data revealed that the adsorption process follows a pseudo-second order mechanism and obeys Langmuir isotherm model. In addition, the IONPs proved to be a potential candidate for the adsorption of pyrene and benzo(a)pyrene even after five cycles of use and regeneration. The investigation was extended using semi-pilot plant to remove the studied PAHs from artificially contaminated water. The results showed that the IONPs was capable to remove the pyrene and benzo (a) pyrene at the rate of 98.5 and 99%, respectively. It also can be used as disinfectant.

  6. 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.

  7. 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.

  8. Combined effects of inhaled plutonium oxide and benzo[a]pyrene on lung carcinogenesis in rats

    International Nuclear Information System (INIS)

    Metivier, H.; Masse, R.; Wahrendorf, J.; Lafuma, J.

    1986-01-01

    This study describes the effect of two intratracheal instillations (5 mg each) of benzo[a]pyrene (BP) on lung carcinogenesis in rats that had previously inhaled three levels of 239 PuO 2 . The BP does not modify survival in the high-level 239 PuO 2 -exposed rats, but markedly reduces survival in the two other groups. Median survival time with BP alone is shorter (666 days) than for the control group (838 days). Tumor incidence was increased by BP exposure, and the tumors were usually fatal, whereas tumors observed after 239 PuO 2 inhalation alone were usually not fatal. Statistical analysis of these data poses a problem because of the need to compare incidental and fatal tumors. 22 refs., 5 figs., 7 tabs

  9. Advanced Oxidation Degradation of Diclofenac

    Energy Technology Data Exchange (ETDEWEB)

    Cooper, William J., E-mail: wcooper@uci.edu [Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, CA 92697 (United States); Song Weihua, E-mail: wsong@fudan.edu.cn [Department of Environmental Science & Engineering, Fudan University, Shanghai 200433 (China)

    2012-07-01

    Advanced oxidation/reduction processes (AO/RPs), utilize free radical reactions to directly degrade chemical contaminants as an alternative to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and the model compound (2, 6-dichloraniline) with the two major AO/RP radicals; the hydroxyl radical (•OH) and hydrated electron (e{sup -}{sub aq}). The bimolecular reaction rate constants (M{sup -1} s{sup -1}) for diclofenac for •OH was (9.29 ± 0.11) x 10{sup 9}, and, for e- aq was (1.53 ± 0.03) x10{sup 9}. Preliminary degradation mechanisms are suggested based on product analysis using {sup 60}Co γ-irradiation and LC-MS for reaction by-product identification. The toxicity of products was evaluated using the Vibrio fischeri luminescent bacteria method. (author)

  10. Advanced Oxidation Degradation of Diclofenac

    International Nuclear Information System (INIS)

    Cooper, William J.; Song Weihua

    2012-01-01

    Advanced oxidation/reduction processes (AO/RPs), utilize free radical reactions to directly degrade chemical contaminants as an alternative to traditional water treatment. This study reports the absolute rate constants for reaction of diclofenac sodium and the model compound (2, 6-dichloraniline) with the two major AO/RP radicals; the hydroxyl radical (•OH) and hydrated electron (e - aq ). The bimolecular reaction rate constants (M -1 s -1 ) for diclofenac for •OH was (9.29 ± 0.11) x 10 9 , and, for e- aq was (1.53 ± 0.03) x10 9 . Preliminary degradation mechanisms are suggested based on product analysis using 60 Co γ-irradiation and LC-MS for reaction by-product identification. The toxicity of products was evaluated using the Vibrio fischeri luminescent bacteria method. (author)

  11. Formation of quinones by one-electron oxidation in the metabolism of benzo[a]pyrene and 6-fluorobenzo[a]pyrene

    International Nuclear Information System (INIS)

    Cavalieri, E.; Wong, A.; Cremonesi, P.; Warner, C.; Rogan, E.

    1986-01-01

    Metabolic activation of polycyclic aromatic hydrocarbons (PAH), as well as other chemical carcinogens, occurs by two major pathways: One-electron oxidation and two-electron oxidation, or monooxygenation. One-electron oxidation generates radical cations or radicals, depending on the molecule in which the oxidation occurs, whereas two-electron oxidation produces oxygenated metabolites. Radical cations of PAH are ultimate electrophilic metabolites capable of binding to cellular macromolecules to initiate the tumor process. In this paper the authors will provide evidence that one-electron oxidation is involved not only in PAH carcinogenesis, but also in the formation of certain metabolites. Metabolism of benzo[a]pyrene (BP) by cytochrome P-450 monooxygenase yields three classes of products: phenols, dihydrodiols and the quinones, 1,6-, 3,6- and 6,12- dione

  12. Oxidative degradation of alkylphenols by horseradish peroxidase.

    Science.gov (United States)

    Sakuyama, Hisae; Endo, Yasushi; Fujimoto, Kenshiro; Hatana, Yasuhiko

    2003-01-01

    Alkylphenols such as bisphenol A (2,2-bis(4-hydroxyphenyl)propane; BPA), p-nonylphenol (p-NP), and p-octylphenol (p-OP) that are known as endocrine disrupters were oxidized by horseradish (Armoracia rusticana) peroxidase (HRP) with H2O2. The optimal pHs for BPA, p-NP, and p-OP were 8.0, 7.0, and 5.0, respectively. The optimal temperature for BPA was 20 degrees C. Although BPA was rapidly degraded by HRP, its degradation depended on the concentration of HRP. Most of the oxidation products of BPA were polymers, although some 4-isopropenylphenol was produced. When male Japanese medaka (Oryzias latipes) were exposed to BPA, vitellogenin in the blood increased. However, no increased vitellogenin was observed in medaka exposed to HRP-oxidized BPA. The enzymatic oxidation of BPA using HRP was able to eliminate its estrogen-like activity.

  13. Short-term exposure to benzo[a]pyrene causes oxidative damage and affects haemolymph steroid levels in female crab Portunus trituberculatus

    International Nuclear Information System (INIS)

    Wen, Jianmin; Pan, Luqing

    2016-01-01

    Concern has increased regarding the adverse effects of polycyclic aromatic hydrocarbons (PAHs) on reproduction. However, limited information is available on the effects of PAHs in crustacean. In order to determine whether benzo[a]pyrene (B[a]P) could cause reproductive toxicity on the swimming crab Portunus trituberculatus, sexually mature female crabs were exposed to environmentally relevant concentrations of B[a]P (0, 0.1, 0.5 and 2.5 μg/L) for 10 days. B[a]P treatments resulted in high accumulation in ovary, and induced oxidative stress in a dose-dependent manner on ovary of crab. Furthermore, the haemolymph estradiol (E_2) and testosterone (T) levels were significantly decreased. Histological investigation also revealed the reproductive toxicity caused by B[a]P. The results demonstrated that waterborne exposure to B[a]P caused oxidative damage and disrupted sex steroids in female crab P. trituberculatus, ultimately resulting in histological alternation. - Highlights: • Waterborne exposure to B[a]P resulted in high accumulation in crab ovary. • The haemolymph 17β-estradiol and testosterone levels were significantly decreased by B[a]P exposure. • B[a]P induced oxidative damage in crab ovary. • B[a]P exposure caused histopathological alterations in crab ovary. - B[a]P disrupted sex steroids, caused oxidative damage and histological alternation in female crab P. trituberculatus.

  14. 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.

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

    Institute of Scientific and Technical Information of China (English)

    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.

  16. Reduced cytochrome P4501A activity and recovery from oxidative stress during subchronic benzo[a]pyrene and benzo[e]pyrene treatment of rainbow trout

    International Nuclear Information System (INIS)

    Curtis, Lawrence R.; Garzon, Claudia B.; Arkoosh, Mary; Collier, Tracy; Myers, Mark S.; Buzitis, Jon; Hahn, Mark E.

    2011-01-01

    This study assessed the role of aryl hydrocarbon receptor (AHR) affinity, and cytochrome P4501A (CYP1A) protein and activity in polyaromatic hydrocarbon (PAH)-induced oxidative stress. In the 1-100 nM concentration range benzo[a]pyrene (BaP) but not benzo[e]pyrene (BeP) competitively displaced 2 nM [ 3 H]2, 3, 7, 8-tetrachloro-dibenzo-p-dioxin from rainbow trout AHR2α. Based on appearance of fluorescent aromatic compounds in bile over 3, 7, 14, 28 or 50 days of feeding 3 μg of BaP or BeP/g fish/day, rainbow trout liver readily excreted these polyaromatic hydrocarbons (PAHs) and their metabolites at near steady state rates. CYP1A proteins catalyzed more than 98% of ethoxyresorufin-O-deethylase (EROD) activity in rainbow trout hepatic microsomes. EROD activity of hepatic microsomes initially increased and then decreased to control activities after 50 days of feeding both PAHs. Immunohistochemistry of liver confirmed CYP1A protein increased in fish fed both PAHs after 3 days and remained elevated for up to 28 days. Neither BaP nor BeP increased hepatic DNA adduct concentrations at any time up to 50 days of feeding these PAHs. Comet assays of blood cells demonstrated marked DNA damage after 14 days of feeding both PAHs that was not significant after 50 days. There was a strong positive correlation between hepatic EROD activity and DNA damage in blood cells over time for both PAHs. Neither CYP1A protein nor 3-nitrotyrosine (a biomarker for oxidative stress) immunostaining in trunk kidney were significantly altered by BaP or BeP after 3, 7, 14, or 28 days. There was no clear association between AHR2α affinity and BaP and BeP-induced oxidative stress. - Highlights: → No direct association between aryl hydrocarbon receptor affinity and polyaromatic hydrocarbon induced oxidative stress. → There was a strong correlation between cytochrome P4501A activity and oxidative stress as measured with the comet assay. → There was no correlation between cytochrome P4501A

  17. 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.

  18. 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.

  19. DNA oxidation and DNA repair in gills of zebra mussels exposed to cadmium and benzo(a)pyrene.

    Science.gov (United States)

    Michel, Cécile; Vincent-Hubert, Françoise

    2015-11-01

    Freshwater bivalve molluscs are considered as effective indicators of environmental pollution. The comet assay allows the detection of DNA damage such as DNA strand breaks and alkali-labile sites. The main oxidative lesion, 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodG), which is a pre-mutagenic lesion, can be detected by the comet assay coupled with the hOGG1 DNA repair enzyme. With this modified assay we recently observed that BaP induced 8-oxodG lesions and with the modified comet-Fpg assay we observed that Cd induced oxidative DNA damage. The aim of this study was to determine the stability of DNA lesions in Cd and BaP exposed zebra mussels using the comet-hOGG1 assay. Mussels were exposed for 24 h to these two chemicals and then placed in clean water for 6 days. We observed that BaP (7, 12 and 18 µg/L) induced an increase of DNA strand break levels as soon as 6 h of exposure and that the two highest concentrations of BaP induced a low level of hOGG1-sensitive sites. After 2 days of depuration, BaP induced DNA lesions returned to the basal level, indicating an effective DNA repair. Cd (3, 32 and 81 µg/L) induced an increase of the DNA strand break levels and a low level of hOGG1-sensitive sites. This study revealed that BaP-induced DNA lesions are repaired more efficiently than Cd-induced DNA lesions. As the level of hOGG1 sensitive sites was increased in Cd and BaP exposed mussels, it seems that these chemicals induce 8-oxo-dG.

  20. 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...

  1. Metal oxide semiconductors for dye degradation

    International Nuclear Information System (INIS)

    Adhikari, Sangeeta; Sarkar, Debasish

    2015-01-01

    Highlights: • Hydrothermal synthesis of monoclinic and hexagonal WO 3 nanostructures. • Nanocuboid and nanofiber growth using different structure directing agents. • WO 3 –ZnO nanocomposites for dye degradation under UV and visible light. • High photocatalytic efficiency is achieved by 10 wt% monoclinic WO 3 . • WO 3 assists to trap hole in UV and arrests electron in visible light irradiation. - Abstract: Organic contaminants are a growing threat to the environment that widely demands their degradation by high efficient photocatalysts. Thus, the proposed research work primely focuses on the efficient degradation of methyl orange using designed WO 3 –ZnO photocatalysts under both UV and visible light irradiation. Two different sets of WO 3 nanostructures namely, monoclinic WO 3 (m-WO 3 ) and hexagonal WO 3 (h-WO 3 ) synthesizes in presence of a different structure directing agents. A specific dispersion technique allows the intimate contact of as-synthesized WO 3 and ultra-violet active commercial ZnO photocatalyst in different weight variations. ZnO nanocrystal in presence of an optimum 10 wt% m-WO 3 shows a high degree of photocatalytic activity under both UV and visible light irradiation compared to counterpart h-WO 3 . Symmetrical monoclinic WO 3 assists to trap hole in UV, but electron arresting mechanism predominates in visible irradiation. Coupling of monoclinic nanocuboid WO 3 with ZnO proves to be a promising photocatalyst in both wavelengths.

  2. 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.

  3. 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)

  4. 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.

  5. Metal oxide semiconductors for dye degradation

    Energy Technology Data Exchange (ETDEWEB)

    Adhikari, Sangeeta; Sarkar, Debasish, E-mail: dsarkar@nitrkl.ac.in

    2015-12-15

    Highlights: • Hydrothermal synthesis of monoclinic and hexagonal WO{sub 3} nanostructures. • Nanocuboid and nanofiber growth using different structure directing agents. • WO{sub 3}–ZnO nanocomposites for dye degradation under UV and visible light. • High photocatalytic efficiency is achieved by 10 wt% monoclinic WO{sub 3}. • WO{sub 3} assists to trap hole in UV and arrests electron in visible light irradiation. - Abstract: Organic contaminants are a growing threat to the environment that widely demands their degradation by high efficient photocatalysts. Thus, the proposed research work primely focuses on the efficient degradation of methyl orange using designed WO{sub 3}–ZnO photocatalysts under both UV and visible light irradiation. Two different sets of WO{sub 3} nanostructures namely, monoclinic WO{sub 3} (m-WO{sub 3}) and hexagonal WO{sub 3} (h-WO{sub 3}) synthesizes in presence of a different structure directing agents. A specific dispersion technique allows the intimate contact of as-synthesized WO{sub 3} and ultra-violet active commercial ZnO photocatalyst in different weight variations. ZnO nanocrystal in presence of an optimum 10 wt% m-WO{sub 3} shows a high degree of photocatalytic activity under both UV and visible light irradiation compared to counterpart h-WO{sub 3}. Symmetrical monoclinic WO{sub 3} assists to trap hole in UV, but electron arresting mechanism predominates in visible irradiation. Coupling of monoclinic nanocuboid WO{sub 3} with ZnO proves to be a promising photocatalyst in both wavelengths.

  6. Synergetic effect of alkaline earth metal oxides and iron oxides on the degradation of hexachlorobenzene and its degradation pathway.

    Science.gov (United States)

    Su, Guijin; Liu, Yexuan; Huang, Linyan; Shi, Yali; Zhang, Aiqian; Zhang, Lixia; Liu, Wenbin; Gao, Lirong; Zheng, Minghui

    2013-01-01

    The degradation of hexachlorobenzene (HCB) was carried out over physical mixtures of a series of alkaline earth metal oxides (MO: M=Mg, Ca, Sr, Ba) and iron oxides with different crystal types (Fe(x)O(y):Fe(2)O(3) or Fe(3)O(4)) at 300°C. These physical mixtures all showed a synergetic effect toward the degradation of HCB. A range of degradation products were identified by various methods, including tri- to penta-chlorobenzenes by gas chromatography/mass spectrometry (GC-MS), tri- to penta-chlorophenols, tetrachlorocatechol (TCC) and tetrachlorohydroquinone (TCHQ) by GC-MS after derivatization, and formic and acetic acids by ion chromatography. Two degradation pathways, hydrodechlorination and oxidative degradation, appear to occur competitively. However, more sequential chlorinated benzene and phenol congeners were formed over mixed MO/Fe(3)O(4) than over mixed MO/Fe(2)O(3) under the same conditions. The oxidative reaction dominated over mixed MO/Fe(2)O(3) and was promoted as the major reaction by the synergetic effect, while both the oxidative and hydrodechlorination reactions were important over mixed MO/Fe(3)O(4), and both pathways are remarkably promoted by the synergetic effect. The enhanced hydrodechlorination may be attributed to free electrons generated by the transformation of Fe(3)O(4) into Fe(2)O(3), and hydrogen provided by water adsorbed on the MO. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. 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

  8. 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)

  9. 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.

  10. 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.

  11. 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.

  12. 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)

  13. 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)

  14. 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)

  15. 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.

  16. 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)

  17. 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.

  18. Chlorophyll catalyse the photo-transformation of carcinogenic benzo[a]pyrene in water

    Science.gov (United States)

    Luo, Lijuan; Lai, Xueying; Chen, Baowei; Lin, Li; Fang, Ling; Tam, Nora F. Y.; Luan, Tiangang

    2015-01-01

    Algal blooms cause great damage to water quality and aquaculture. However, this study showed that dead algal cells and chlorophyll could accelerate the photo-transformation of benzo[a]pyrene (BaP), a ubiquitous and persistent pollutant with potently mutagenic and carcinogenic toxicities, under visible light irradiation. Chlorophyll was found to be the major active substance in dead algal cells, and generated a high level of singlet oxygen to catalyse the photo-transformation of BaP. According to various BaP metabolites formed, the degradation mechanism was proposed as that chlorophyll in dead algal cells photo-oxidized BaP to quinones via photocatalytic generation of singlet oxygen. The results provided a good insight into the role of chlorophyll in the photo-transformation of organic contaminants and could be a possible remediation strategy of organic pollutants in natural environment. PMID:26239357

  19. 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

  20. 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.

  1. Copper-mediated oxidative degradation of catecholamines and oxidative damage of protein

    Energy Technology Data Exchange (ETDEWEB)

    Goncalves, P.R.; Harria, M.I.N.; Felix, J.M.; Hoffmann, M.E. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Biologia

    1997-12-31

    Full text. Degradative oxidation of catecholamines has been a matter of large interest in recent years due to the evidences associating their autoxidation with the etiology of neurotoxic and cardiotoxic processes. In this work we present data on the degradative oxidation of catecholamines of physiological importance: isoproterenol (IP), epinephrine (EP), norepinephrine (NEP), deoxyepinephrine (DEP) and dopamine (DA). The degradative oxidation of the catecholamines was followed by measurement of spectral changes and oxygen consumption by neutral aqueous solutions. The data show that Cu{sup 2+} strongly accelerated the rate of catecholamine oxidation, following the decreasing order; EP>DEP>IP>NEP>DA. The production of superoxide anion radical during catecholamine oxidation was very slow, even in the presence of Cu{sup 2+}. The ability of IP to induce damages on bovine serum albumin (BSA) was determined by measuring the formation of carbonyl-groups in the protein, detected by reduction with tritiated Na BH{sub 4}. The incubation of BSA with IP (50-500{mu}M), in the presence of 100{mu}M Cu{sup 2+} leaded to an increased and dose dependent {sup 3} H-incorporation by the oxidized protein. The production of oxidative damage by IP/Cu{sup 2+} was accompanied by marked BSA fragmentation, detected by SDS-polyacrylamide gel dependent (25-400{mu}M IP) des appearance of the original BSA band and appearance of smaller fragments spread in the gel, when incubation has been done in the presence of 100{mu}M Cu{sup 2+}. These results suggest that copper-catalysed oxidative degradation of proteins induced by catecholamines might be critically involved in the toxic action of these molecules

  2. 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

  3. Oxidative degradation of triclosan by potassium permanganate: Kinetics, degradation products, reaction mechanism, and toxicity evaluation.

    Science.gov (United States)

    Chen, Jing; Qu, Ruijuan; Pan, Xiaoxue; Wang, Zunyao

    2016-10-15

    In this study, we systematically investigated the potential applicability of potassium permanganate for removal of triclosan (TCS) in water treatment. A series of kinetic experiments were carried out to study the influence of various factors, including the pH, oxidant doses, temperature, and presence of typical anions (Cl(-), SO4(2-), NO3(-)), humic acid (HA), and fulvic acid (FA) on triclosan removal. The optimal reaction conditions were: pH = 8.0, [TCS]0:[KMnO4]0 = 1:2.5, and T = 25 °C, where 20 mg/L of TCS could be completely degraded in 120 s. However, the rate of TCS (20 μg/L) oxidation by KMnO4 ([TCS]0:[KMnO4]0 = 1:2.5) was 1.64 × 10(-3) mg L(-1)·h(-1), lower than that at an initial concentration of 20 mg/L (2.24 × 10(3) mg L(-1)·h(-1)). A total of eleven products were detected by liquid chromatography-quadrupole-time-of-flight-mass spectrometry (LC-Q-TOF-MS) analysis, including phenol and its derivatives, benzoquinone, an organic acid, and aldehyde. Two main reaction pathways involving CO bond cleavage (-C(8)O(7)-) and benzene ring opening (in the less chlorinated benzene ring) were proposed, and were further confirmed based on frontier electron density calculations and point charges. Furthermore, the changes in the toxicity of the reaction solution during TCS oxidation by KMnO4 were evaluated by using both the luminescent bacteria Photobacterium phosphoreum and the water flea Daphnia magna. The toxicity of 20 mg/L triclosan to D. magna and P. phosphoreum after 60 min was reduced by 95.2% and 43.0%, respectively. Phenol and 1,4-benzoquinone, the two representative degradation products formed during permanganate oxidation, would yield low concentrations of DBPs (STHMFP, 20.99-278.97 μg/mg; SHAAFP, 7.86 × 10(-4)-45.77 μg/mg) after chlorination and chloramination. Overall, KMnO4 can be used as an effective oxidizing agent for TCS removal in water and wastewater treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. 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.

  5. 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...

  6. 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

  7. Degradation of dyestuff materials by fenton oxidation, Part 4

    International Nuclear Information System (INIS)

    Shahrour, Kh.; Hachem, Ch.; Karabet, F.

    2008-01-01

    The oxidative degradation of various kinds of dyes (Azo carmine B, Tartrazine, Calcon, Methyle Orange, and Coomassie Brilliant Blue G 250, Methylene Blue, Bismark Brown Y(G) and Black 5) have been studied using Fenton's reagent (Fe 2+ and H 2 O 2 ). Many experiments were carried out on Azo carmine B as a model with initial concentration of 10 -4 to investigate the process's optimal conditions, pH, H 2 O 2 dosage, Fe 2+ dosage , temperature. The optimal conditions found were: pH=3, [H 2 O 2 ]=3 x 10 -3 M, [Fe 2+ ]=10 -4 M, t=60 Centigrade. under these contritions it was observed that Azo carmine B can be degraded at high extent (96.46%) after 50 min, however, the mineralization reached only (31.2%) in term of TOC and (41.1%) in term of COD. Results show that dyes are decomposed in two-stage reaction. In the first stage (Fe 2= /H 2 O 2 ) dyes decomposes rapidly within 0.5-5 min and the reaction obeys the pseudo-first-order. In the second stage (Fe 3+ /H 2 O 2 ) the dye decomposition is somewhat less rapidly, and the reaction follows the first order rate kinetic with respect to the dye concentration. (author)

  8. 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...

  9. 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.

  10. 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.

  11. Gene expression of heat shock protein 70, interleukin-1β and tumor necrosis factor α as tools to identify immunotoxic effects on Xenopus laevis: A dose–response study with benzo[a]pyrene and its degradation products

    International Nuclear Information System (INIS)

    Martini, Federica; Fernández, Carlos; Tarazona, José V.; Pablos, M. Victoria

    2012-01-01

    The exposure to benzo[a]pyrene (B[a]P) results in an alteration of immune function in mammals and fish, and the analysis of cytokine mRNA levels has been suggested for predicting the immunomodulatory potential of chemicals. To obtain evidence of the innate immune responses to B[a]P in Xenopus laevis, the present study monitored the mRNA expression of interleukin 1-β (IL-1β), tumor necrosis factor α (TNF-α) and heat shock protein 70 (HSP70) in a laboratorial exposure. Tadpoles exposed to 8.36, 14.64, 89.06 and 309.47 μg/L of B[a]P,were used for detecting hsp70, IL-1β and TNF-α mRNA induction. A dose–response increase in the expression of hsp70 and IL-1β mRNA was found. The results of this study confirmed the use of hsp70 and IL-1β, but not TNF-α, as sensitive indicators of immunotoxic effect of B[a]P in X. laevis. Further research would be required for the validation of these endpoints. - Highlights: ► We study innate immune responses to benzo[a]pyrene in Xenopus laevis. ► mRNA expression of three typical proinflammatory proteins was monitored. ► Heat shock protein 70 mRNA induction showed a concentration/response/time relationship. ► Interleukin 1-β also showed a clear concentration/response relationship. ► Interleukin 1-β and heat shock protein 70 are useful indicators of immunotoxic effects. - The present study analyzed the use of cytokine mRNA levels as an earlier tool for predicting immunotoxicological risks to Xenopus laevis in a dose–response pattern.

  12. 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.

  13. 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.

  14. The oxidative degradation by pyrolusite of p-nitrophenol wastewater ...

    African Journals Online (AJOL)

    aminophenol was degraded into H2O and CO2 finally. The degradation mechanism of wastewater from pretreatment by pyrolusite has been further investigated based on previous work. International Journal of Engineering, Science and Technology, Vol.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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%.

  20. Degradation of triketone herbicides, mesotrione and sulcotrione, using advanced oxidation processes

    International Nuclear Information System (INIS)

    Jović, Milica; Manojlović, Dragan; Stanković, Dalibor; Dojčinović, Biljana; Obradović, Bratislav; Gašić, Uroš; Roglić, Goran

    2013-01-01

    Highlights: • Thirteen products are identified during all degradations for both pesticides. • In all degradations same products and mechanism was observed for both pesticides. • Dominant mechanism for all degradations starts with attack on the carbonyl group. • Only in ozone and DBD degradation one product is formed in radical reaction. • Only in Fenton degradation opening of benzene ring occurs. -- Abstract: Degradation of two triketone herbicides, mesotrione and sulcotrione, was studied using four different advanced oxidation processes (AOPs): ozonization, dielectric barrier discharge (DBD reactor), photocatalysis and Fenton reagent, in order to find differences in mechanism of degradation. Degradation products were identified by high performance liquid chromatography (HPLC–DAD) and UHPLC–Orbitrap–MS analyses. A simple mechanism of degradation for different AOP was proposed. Thirteen products were identified during all degradations for both pesticides. It was assumed that the oxidation mechanisms in the all four technologies were not based only on the production and use of the hydroxyl radical, but they also included other kinds of oxidation mechanisms specific for each technology. Similarity was observed between degradation mechanism of ozonation and DBD. The greatest difference in the products was found in Fenton degradation which included the opening of benzene ring. When degraded with same AOP pesticides gave at the end of treatment the same products. Global toxicity and COD value of samples was determined after all degradations. Real water sample was used to study influence of organic matter on pesticide degradation. These results could lead to accurate estimates of the overall effects of triketone herbicides on environmental ecosystems and also contributed to the development of improved removal processes

  1. 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.

  2. 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

  3. 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...

  4. 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...

  5. 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

  6. 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.

  7. Degradation of polyethylene induced by plasma in oxidizing atmospheres

    International Nuclear Information System (INIS)

    Colin, E.; Olayo, M.G.; Cruz, G.J.

    2002-01-01

    The garbage of polyethylene is not easily degradable in normal environmental conditions . The indiscriminate use of this polymer and the enormous quantity of garbage which is generated carries a damage to the environment due to its long life as waste. The objective of this work is to study the conditions in which can be carried out the degradation of polyethylene. A form of accelerating the degradation is exposing it to plasma with reactive atmospheres. In this work a study of surface modification of polyethylene by plasmas with discharges of direct current of oxygen and nitrogen is presented. (Author)

  8. Degradation of phenolic compounds by using advanced oxidation processes

    Energy Technology Data Exchange (ETDEWEB)

    Rodriguez, M. [Univ. de los Andes, Escuela Basica de Ingenieria, La Hechicera, Merida (Venezuela); Hincapie, M. [Dept. de Ingenieria Sanitaria y Ambiental, Univ. de Antioquia, Medellin (Colombia); Curco, D.; Contreras, S.; Gimenez, J.; Esplugas, S. [Dept. de Ingenieria Quimica, Facultad de Quimica, Univ. de Barcelona, Barcelona (Spain)

    2003-07-01

    A new empirical kinetic equation [r = k{sub 1}c - k{sub 2} (c{sub 0} - c)] is proposed for the photocatalytic degradation of phenolic compounds. This equation considers the influence of the intermediates in the degradation of the pollutant. The correct formulation of the contaminant mass balance in the experimental device that operates in recycle mode was done. The proposed empirical kinetic equation fitted quite well with the experimental results obtained in the TiO{sub 2}-photocatalytic degradation of phenol. (orig.)

  9. 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.

  10. 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.

  11. 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.

  12. The degradation of lining of rotary furnaces in the production of zinc oxide

    Czech Academy of Sciences Publication Activity Database

    Luptáková, Natália; Pešlová, F.; Anisimov, E.

    2014-01-01

    Roč. 21, č. 3 (2014), s. 116-121 ISSN 1335-0803 Institutional support: RVO:68081723 Keywords : zinc oxide * the production of zinc oxide * zinc slag * refractories * the degradation of rotary furnace linings Subject RIV: JG - Metallurgy http://ojs.mateng.sk/index.php/Mateng/article/view/133/194

  13. 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...

  14. 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

  15. 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.

  16. 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.

  17. Materials Degradation During the Stressed Oxidation of CMCs

    Data.gov (United States)

    National Aeronautics and Space Administration — The objective of the proposed research is to quantitatively characterize and understand the effect of oxidation of composite constituents on the initiation and...

  18. effects of ethylene oxide resterilisation and in-vitro degradation

    African Journals Online (AJOL)

    2013-06-01

    Jun 1, 2013 ... Subjects: Two composite meshes were used in the study: One mesh is ... Ethylene oxide gas sterilisation was performed ... were completed for control and resterilisation specimens. .... lowers in-hospital care expenses.

  19. 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.

  20. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  1. 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)

  2. Interface strength and degradation of adhesively bonded porous aluminum oxides

    DEFF Research Database (Denmark)

    T. Abrahami, Shoshan; M. M. de Kok, John; Gudla, Visweswara Chakravarthy

    2017-01-01

    For more than six decades, chromic acid anodizing has been the main step in the surface treatment of aluminum for adhesivelybonded aircraft structures. Soon this process, known for producing a readily adherent oxide with an excellent corrosion resistance,will be banned by strict international....... The relationship between the anodizing conditions insulfuric and mixtures of sulfuric and phosphoric acid electrolytes and the formation and durability of bonding under variousenvironmental conditions was investigated. Scanning electron microscopy was used to characterize the oxide features. Selectedspecimens were...... studied with transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy to measureresin concentration within structurally different porous anodic oxide layers as a function of depth. Results show that there are twocritical morphological aspects for strong and durable bonding. First...

  3. 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.)

  4. 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.

  5. 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)

  6. 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)

  7. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Henych, Jiří; Janos, P.; Skoumal, M.

    2016-01-01

    Roč. 236, č. 2016 (2016), s. 239-258 ISSN 0179-5953 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : chemical warfare agent * metal nanoparticle * unique surface- chemistry * mesoporous manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 3.930, year: 2016

  8. Neutron induced degradation in nitrided pyrogenic field oxide MOS capacitors

    Science.gov (United States)

    Vaidya, S. J.; Sharma, D. K.; Shaikh, A. M.; Chandorkar, A. N.

    2002-09-01

    Neutron induced oxide charge trapping and generation of interface states in MOS capacitors with pyrogenic and nitrided pyrogenic field oxides have been studied. In order to assess the damage due to neutrons alone, it is necessary to account for the damage produced by the accompanying gamma rays from neutron radiation. This is done by measuring the intensity of gamma radiation accompanying neutrons at different neutron fluences at the irradiation position. MOS capacitor structures were subjected to neutron radiation in a swimming pool type of reactor. Other samples from the same batch were then subjected to an equivalent dose of gamma radiation from a Co 60 source. The difference in the damage observed was used to characterize the damage caused by neutrons. It is observed that neutrons, though uncharged, are capable of causing ionization damage. This damage is found to be significant when the radiation is performed under biased conditions. Nitridation in different ambients is found to improve the radiation performance of pyrogenic field oxides with respect to positive charge build up as well as interface state generation. Pyrogenic oxide nitrided in N 2O is found to be the best oxynitride as damage due to neutrons is the least.

  9. Interface strength and degradation of adhesively bonded porous aluminum oxides

    NARCIS (Netherlands)

    Abrahami, S.T.; de Kok, John M.M.; Gudla, Visweswara C.; Ambat, Rajan; Terryn, H.A.; Mol, J.M.C.

    2017-01-01

    For more than six decades, chromic acid anodizing has been the main step in the surface treatment of aluminum for adhesively bonded aircraft structures. Soon this process, known for producing a readily adherent oxide with an excellent corrosion resistance, will be banned by strict international

  10. Oxidative degradation of pentachlorophenol by permanganate for ISCO application.

    Science.gov (United States)

    Matta, Roger; Chiron, Serge

    2018-03-01

    Potassium permanganate (KMnO 4 ) has been an effective technology for the in situ chemical oxidation (ISCO) of many organic compounds including chlorinated alkanes and alkenes, but it has rarely been applied for oxidizing aromatic organochlorines. This study confirms the ability of permanganate to oxidize an aromatic chlorinated compound, pentachlorophenol (PCP), in an efficient manner at neutral pH. The rate of the reaction between KMnO 4 and PCP was calculated and the results indicated that the reaction between PCP and permanganate is relatively fast with a second-order rate constant k″ ∼ 30 M -1  s -1 . Besides the kinetic aspect, the authors identified the main reaction by-products, and proposed a possible reaction mechanism scheme. The general pathway shows the formation of chlorinated intermediates, and ultimately, the complete mineralization to chloride, water, and CO 2 confirmed by total organic carbon and chloride measurement in solution. Flow-through column experiments, consisting of flushing a PCP-contaminated sandy or natural soil with oxidant, showed the good ability of permanganate to eliminate the pollutant. After 24 h of treatment, 77% and 56% of PCP abatement were obtained for sandy and natural soil, respectively. These findings show the high potential of permanganate for the in situ remediation of aromatic organochlorine contaminated soils.

  11. Sulphur mustard degradation on zirconium doped Ti-Fe oxides

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Matys Grygar, Tomáš; Opluštil, F.; Němec, T.

    2011-01-01

    Roč. 192, č. 3 (2011), s. 1491-1504 ISSN 0304-3894 Institutional research plan: CEZ:AV0Z40320502 Keywords : warfare agents * nanodispersive oxides * homogeneous hydrolysis * urea Subject RIV: CA - Inorganic Chemistry Impact factor: 4.173, year: 2011

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. Neutron induced degradation in nitrided pyrogenic field oxide MOS capacitors

    CERN Document Server

    Vaidya, S J; Shaikh, A M; Chandorkar, A N

    2002-01-01

    Neutron induced oxide charge trapping and generation of interface states in MOS capacitors with pyrogenic and nitrided pyrogenic field oxides have been studied. In order to assess the damage due to neutrons alone, it is necessary to account for the damage produced by the accompanying gamma rays from neutron radiation. This is done by measuring the intensity of gamma radiation accompanying neutrons at different neutron fluences at the irradiation position. MOS capacitor structures were subjected to neutron radiation in a swimming pool type of reactor. Other samples from the same batch were then subjected to an equivalent dose of gamma radiation from a Co sup 6 sup 0 source. The difference in the damage observed was used to characterize the damage caused by neutrons. It is observed that neutrons, though uncharged, are capable of causing ionization damage. This damage is found to be significant when the radiation is performed under biased conditions. Nitridation in different ambients is found to improve the radi...

  18. Oxidative degradation of Boltysh shale by alkaline potassium permanganate

    Energy Technology Data Exchange (ETDEWEB)

    Pobul, I Ya; Fomina, A S

    1974-01-01

    This reaction proceeded in stages at 47 to 48/sup 0/C with a 3 percent solution of potassium permanganate in a 1 percent alkaline solution. The products were separated into groups and identified by gas-liquid chromatography. Small amounts of monocarboxylic acids were identified, with normal and branched chains, from acetic to lauric acid. Dicarboxylic acids were mainly of normal structure, or methyl substituted, from succinic to hexadecanedicarboxylic acid. No tricarboxylic acids were detected. For products of primary oxidation insoluble in acid media, a high content of C/sub 10/-C/sub 16/ acids was characteristic, and for the final degree of oxidation C/sub 11/-C/sub 18/ acids. The organic portion of shale consists of structural units, differing in mass and in stability to alkaline permanganate.

  19. 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)

  20. 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.

  1. Amoxicillin Oxidative Degradation Synthesized by Nano Zero Valent Iron

    Directory of Open Access Journals (Sweden)

    AR Yazdanbakhsh

    2016-03-01

    Full Text Available Introduction: Amoxicillin is one of the most important groups of pharmaceuticals that benefits humans and animals. However, antibiotics excertion in wastewaters and environment have emerged as a serious risk to the biotic environment, and their toxic effects can harm the organisms. Iron-based metallic nanoparticles have received special attention in regard with remediation of groundwater contaminants. In the typical nZVI-based bimetallic particle system, Fe acts as the reducing agent. Thus, the present study aimed to evaluate the synthesis and characteristics of nZVI in regard with degrading AMX. Methods: In this study, nZVI nanoparticles were synthesized using the liquid-phase reduction method by EDTA as a stabilizer material. Structure and properties of nanoparticles were characterized by BET, SEM, XRD and EDX analysis. A multi-variate analysis was applied using a response surface methodology (RSM in order to develop a quadratic model as a functional relationship between AMX removal efficiency and independent variables ( initial pH values, dosage of nZVI, contact time and amoxicillin concentration. The four independent variables of solution pH (2–10, AMX concentration (5-45mg/l, contact time (5-85 min and nanoparticles dose (0.25 – 1.25 g were transformed to the coded values. Results: The study results demonstrated that more than 69 % of AMX was removed by nZVI. The optimal AMX removal conditions using nZVI were found as 1.25 g of nZVI, pH 4, contact time of 80 min and concentration of 30 mg/l. Conclusions: The ability of nZVI in degradation of AMX revealed that these materials can serve as a potential nano material with respect to the environmental remediation.

  2. 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

  3. Review of oxidative degradations of certain heterocyclic polymers

    Science.gov (United States)

    Mayo, F. R.

    1971-01-01

    The curing and decompositions of polyphenylenes and several nitrogen-containing condensation polymers, particularly polybenzimidazoles and pyrones, are reviewed critically. It is concluded that the condensations are usually imperfect and incomplete and that in most of the published work the late stages of the condensation are complicated by the beginnings of the charring and carbonization processes. Most discussions of mechanisms in this range are highly speculative and of little value. The most promising fields for further research are at lower temperatures, where slow oxidation processes deserve study, and at higher temperatures, where it may be possible to influence carbonization processes to obtain better products.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. Thermal oxidative degradation of wood modified with aminophenylborates

    Directory of Open Access Journals (Sweden)

    Klyachenkova Olga

    2016-01-01

    Full Text Available Comparative thermal analysis in the presence of oxygen was carried out for samples of native pine wood and wood samples modified with aminophenylborates. Significant decrease in the amount of heat released during thermal decomposition of the modified samples was established, which is due to the increase of carbonaceous residues on the surface. Reduction of heat release during decomposition of the modified samples may be explained by the lower yield of combustible volatile products as well as by thin film of boron oxide, formed on the surface of the modified wood, that partially reflects heat flow. Produced upon the modifier decomposition water vapor and inert nitrogen oxides dilute gaseous mixture near the wood surface and isolate it from oxygen. This enhances fire-resistance of wood modified with mono- and diethanolamine(N→Bphenylborates. Hydroxyl group at the sixth carbon atom of the glucopyranose ring of cellulose participates in reactions of cellulose modification, which prevents formation of flammable levoglucosan and, consequently, improves the fire-resistance of the modified wood.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. In vitro investigations of α-amylase mediated hydrolysis of cyclodextrins in the presence of ibuprofen, flurbiprofen, or benzo[a]pyrene

    DEFF Research Database (Denmark)

    Riisager, Ludmilla Lumholdt; Holm, R.; Jørgensen, E. B.

    2012-01-01

    -γ-cyclodextrins have different biopharmaceutical behaviours than the other evaluated cyclodextrins. The rate of degradation was affected by the addition of the inclusion complex forming additives flurbiprofen, ibuprofen and benzo[a]pyrene. This effect between the degradation dynamics and the included additives...

  14. 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

  15. Enhanced sulfamethoxazole degradation through ammonia oxidizing bacteria co-metabolism and fate of transformation products.

    Science.gov (United States)

    Kassotaki, Elissavet; Buttiglieri, Gianluigi; Ferrando-Climent, Laura; Rodriguez-Roda, Ignasi; Pijuan, Maite

    2016-05-01

    The occurrence of the widely-used antibiotic sulfamethoxazole (SFX) in wastewaters and surface waters has been reported in a large number of studies. However, the results obtained up-to-date have pointed out disparities in its removal. This manuscript explores the enhanced biodegradation potential of an enriched culture of Ammonia Oxidizing Bacteria (AOB) towards SFX. Several sets of batch tests were conducted to establish a link between SFX degradation and specific ammonia oxidation rate. The occurrence, degradation and generation of SFX and some of its transformation products (4-Nitro SFX, Desamino-SFX and N(4)-Acetyl-SFX) was also monitored. A clear link between the degradation of SFX and the nitrification rate was found, resulting in an increased SFX removal at higher specific ammonia oxidation rates. Moreover, experiments conducted under the presence of allylthiourea (ATU) did not present any removal of SFX, suggesting a connection between the AMO enzyme and SFX degradation. Long term experiments (up to 10 weeks) were also conducted adding two different concentrations (10 and 100 μg/L) of SFX in the influent of a partial nitrification sequencing batch reactor, resulting in up to 98% removal. Finally, the formation of transformation products during SFX degradation represented up to 32%, being 4-Nitro-SFX the most abundant. Copyright © 2016 Elsevier Ltd. All rights reserved.

  16. 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.

  17. 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)

  18. 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.

  19. TiO₂-Based Photocatalytic Geopolymers for Nitric Oxide Degradation.

    Science.gov (United States)

    Strini, Alberto; Roviello, Giuseppina; Ricciotti, Laura; Ferone, Claudio; Messina, Francesco; Schiavi, Luca; Corsaro, Davide; Cioffi, Raffaele

    2016-06-24

    This study presents an experimental overview for the development of photocatalytic materials based on geopolymer binders as catalyst support matrices. Particularly, geopolymer matrices obtained from different solid precursors (fly ash and metakaolin), composite systems (siloxane-hybrid, foamed hybrid), and curing temperatures (room temperature and 60 °C) were investigated for the same photocatalyst content (i.e., 3% TiO₂ by weight of paste). The geopolymer matrices were previously designed for different applications, ranging from insulating (foam) to structural materials. The photocatalytic activity was evaluated as NO degradation in air, and the results were compared with an ordinary Portland cement reference. The studied matrices demonstrated highly variable photocatalytic performance depending on both matrix constituents and the curing temperature, with promising activity revealed by the geopolymers based on fly ash and metakaolin. Furthermore, microstructural features and titania dispersion in the matrices were assessed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analyses. Particularly, EDS analyses of sample sections indicated segregation effects of titania in the surface layer, with consequent enhancement or depletion of the catalyst concentration in the active sample region, suggesting non-negligible transport phenomena during the curing process. The described results demonstrated that geopolymer binders can be interesting catalyst support matrices for the development of photocatalytic materials and indicated a large potential for the exploitation of their peculiar features.

  20. 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

  1. 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

  2. Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

    Czech Academy of Sciences Publication Activity Database

    Štengl, Václav; Henych, Jiří; Matys Grygar, Tomáš; Pérez, Raul

    2015-01-01

    Roč. 61, JAN (2015), s. 259-269 ISSN 0025-5408 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : Nanostructured oxides * Stoichiometric degradation * Trimethyl phosphate Subject RIV: CA - Inorganic Chemistry Impact factor: 2.435, year: 2015

  3. 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.

  4. 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.

  5. 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.

  6. 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)

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.)

  13. Pulse radiolysis studies concerning oxidative degradation processes in linear polymers

    International Nuclear Information System (INIS)

    Schnabel, Wolfram

    1986-01-01

    On the basis of pulse radiolysis experiments carried out with various polymers in dilute solution three modes of action of molecular oxygen, 0 2 , can be discriminated with respect to main-chain scission: (a) 0 2 acts as a promoter, (b) 0 2 acts as an inhibitor, and (c) 0 2 acts as a fixing agent for main-chain breaks. The promoting mode of action (a) is due to the inhibition of simultaneously occurring intermolecular crosslinking (DNA, polymethylvinylketone) and/or to the combination of peroxyl radicals with the subsequent formation of readily decomposing oxyl radicals (polyethylene oxide, polyacrylamide, polyvinylpyrrolidone, polyribouridylic acid, polyriboadenylic acid, polyribocytidylic acid). The inhibiting mode of action (b) pertains to the reaction of 0 2 with macroradicals that otherwise undergo main-chain rupture (amylose polymethylmethacrylate). Fixing of main-chain ruptures (mode c) becomes important, if macroradicals generated by a very fast rupture of bonds in the main-chain, are prone to recombine quickly. This mode of action was evidenced in the case of polybutenesulfone where main-chain scission involves the extrusion of small segments of the chain. (author)

  14. 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.

  15. 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)

  16. 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

  17. Preliminary screening oxidative degradation methyl orange using ozone/ persulfate

    Science.gov (United States)

    Aqilah Razali, Nur; Zulzikrami Azner Abidin, Che; An, Ong Soon; Ridwan, Fahmi Muhammad; Haqi Ibrahim, Abdul; Nasuha Sabri, Siti; Huan Kow, Su

    2018-03-01

    The present study focusing on the performances of advanced oxidation process by using ozonation method towards Methyl Orange based on the efficiency of colour removal and Chemical Oxygen Demand (COD) removal. Factorial design with response surface methodology (RSM) was used to evaluate the interaction between operational conditions, such as pH, initial concentration, contact time and persulfate dosage to obtain the optimum range conditions using a semi-batch reactor. The range of independent variables investigated were pH (3-11), initial concentration (100-500mg/L), contact time (10-50min) and persulfate dosage (20-100mM) while the response variables were colour removal and COD removal of Methyl Orange. The experimental results and statistical analysis showed all the parameters were significant. Thus, from this findings, optimization of operational conditions that had been suggested from the ozone/persulfate RSM analysis were (pH 3, 100 mg/L, 50min, 60mM) that would be produced 99% Colour Removal and 80% COD Removal and help in promoting an efficient ozonation process. The effect list data that showed the most contributed effects to increase the percentages of colour removal were pH and persulfate dosage whereas the contact time and initial concentration had the highest positive effects on the COD removal. Other than that, the interaction between pH, contact time and persulfate dosage were found to be the most influencing interaction. Therefore the least influencing interaction was interaction between persulfate dosage and pH. In this study, the correlation coefficient value R2 for colour removal and COD removal of Methyl Orange were R2= 0.9976 and R2= 0.9924 which suggested a good fit of the first-order regression model with the experimental data.

  18. 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.

  19. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

  1. 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

  2. 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.

  3. 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.

  4. Benzo[a]pyrene co-metabolism in the presence of plant root extracts and exudates: Implications for phytoremediation

    Energy Technology Data Exchange (ETDEWEB)

    Rentz, Jeremy A [Civil and Environmental Engineering, University of Iowa, Iowa City, IA 52242 (United States); Alvarez, Pedro J.J. [Civil and Environmental Engineering, Rice University, Houston, TX 77251 (United States); Schnoor, Jerald L [Civil and Environmental Engineering, University of Iowa, Iowa City, IA 52242 (United States)

    2005-08-15

    Benzo[a]pyrene, a high molecular weight (HMW) polycyclic aromatic hydrocarbon (PAH) was removed from solution by Sphingomonas yanoikuyae JAR02 while growing on root products as a primary carbon and energy source. Plant root extracts of osage orange (Maclura pomifera), hybrid willow (Salix albaxmatsudana), or kou (Cordia subcordata), or plant root exudates of white mulberry (Morus alba) supported 15-20% benzo[a]pyrene removal over 24 h that was similar to a succinate grown culture and an unfed acetonitrile control. No differences were observed between the different root products tested. Mineralization of {sup 14}C-7-benzo[a]pyrene by S. yanoikuyae JAR02 yielded 0.2 to 0.3% {sup 14}CO{sub 2} when grown with plant root products. Collectively, these observations were consistent with field observations of enhanced phytoremediation of HMW PAH and corroborated the hypothesis that co-metabolism may be a plant/microbe interaction important to rhizoremediation. However, degradation and mineralization was much less for root product-exposed cultures than salicylate-induced cultures, and suggested the rhizosphere may not be an optimal environment for HMW PAH degradation by Sphingomonas yanoikuyae JAR02. - Bacterial benzo[a]pyrene cometabolism, a plant-microbe interaction affecting polycyclic aromatic hydrocarbon phytoremediation was demonstrated with Sphingomonas yanoikuyae JAR02 that utilized plant root extracts and exudates as primary substrates.

  5. Benzo[a]pyrene co-metabolism in the presence of plant root extracts and exudates: Implications for phytoremediation

    International Nuclear Information System (INIS)

    Rentz, Jeremy A.; Alvarez, Pedro J.J.; Schnoor, Jerald L.

    2005-01-01

    Benzo[a]pyrene, a high molecular weight (HMW) polycyclic aromatic hydrocarbon (PAH) was removed from solution by Sphingomonas yanoikuyae JAR02 while growing on root products as a primary carbon and energy source. Plant root extracts of osage orange (Maclura pomifera), hybrid willow (Salix albaxmatsudana), or kou (Cordia subcordata), or plant root exudates of white mulberry (Morus alba) supported 15-20% benzo[a]pyrene removal over 24 h that was similar to a succinate grown culture and an unfed acetonitrile control. No differences were observed between the different root products tested. Mineralization of 14 C-7-benzo[a]pyrene by S. yanoikuyae JAR02 yielded 0.2 to 0.3% 14 CO 2 when grown with plant root products. Collectively, these observations were consistent with field observations of enhanced phytoremediation of HMW PAH and corroborated the hypothesis that co-metabolism may be a plant/microbe interaction important to rhizoremediation. However, degradation and mineralization was much less for root product-exposed cultures than salicylate-induced cultures, and suggested the rhizosphere may not be an optimal environment for HMW PAH degradation by Sphingomonas yanoikuyae JAR02. - Bacterial benzo[a]pyrene cometabolism, a plant-microbe interaction affecting polycyclic aromatic hydrocarbon phytoremediation was demonstrated with Sphingomonas yanoikuyae JAR02 that utilized plant root extracts and exudates as primary substrates

  6. 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.

  7. The degradation of lining of rotary furnaces in the production of zinc oxide

    OpenAIRE

    Natália Luptáková; Evgeniy Anisimov; Františka Pešlová

    2014-01-01

    This paper is closely connected with the complex problem of degradation relating to the refractories of rotary furnace linings in the production of zinc oxide. Zinc oxide can be produced by variety of ways, but the most common method of production which is used in Europe is indirect, i.e. pyrolytic combustion of zinc. This method is also called "French process" of manufacturing ZnO. But this mentioned method of preparation leads to the creation of the enormous amount of zinc slag including ch...

  8. 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)

  9. 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...

  10. 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...

  11. Synthesis of Nickel Oxide Nanoparticles Using Gelatine as a Green Template for Photocatalytic Degradation of Dye

    OpenAIRE

    JAY YANG LEE

    2018-01-01

    Nickel oxide (NiO) nanoparticles were synthesized through sol-gel method with an environmentally friendly templating agent, which is gelatin. The synthesized NiO were characterized to determine the chemical and physical properties of the nanoparticles. The optimum synthesis parameters were used in photocatalytic degradation of Reactive Black 5 and Acid Yellow 25 dye to determine the catalytic activity of the nanoparticles.

  12. On the degradability of printing and dyeing wastewater by wet air oxidation.

    Science.gov (United States)

    Hu, X; Lei, L; Chen, G; Yue, P L

    2001-06-01

    A modified first-order kinetics model was used to study the wet air oxidation of printing and dyeing wastewater. The model simulations are in good agreement with experimental data. The results indicate that a certain fraction of organic pollutants in the printing and dyeing wastewater could not be removed even at elevated temperature and prolonged reaction time. The ratio of degradable organic matter is found independent of temperature and can be improved by using a catalyst.

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

    OpenAIRE

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

    2017-01-01

    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. Main methods: 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 trea...

  14. 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.

  15. The degradation of lining of rotary furnaces in the production of zinc oxide

    Directory of Open Access Journals (Sweden)

    Natália Luptáková

    2014-06-01

    Full Text Available This paper is closely connected with the complex problem of degradation relating to the refractories of rotary furnace linings in the production of zinc oxide. Zinc oxide can be produced by variety of ways, but the most common method of production which is used in Europe is indirect, i.e. pyrolytic combustion of zinc. This method is also called "French process" of manufacturing ZnO. But this mentioned method of preparation leads to the creation of the enormous amount of zinc slag including chemical complexes of elements Fe, Zn and Al. The mechanism of degradation of the lining leads to slag rests and it is closely connected with the mutual interaction of the aggressive agents with the components of the lining. This process creates a new undesired surface layer which increased the overall thickness of zinc slag. Stuck slag has the influence on rapid degradation of the linings and moreover it also decreases the production quality of ZnO. Analysis results introduced in this paper are significant information for minimizing of degradation of rotary furnaces.  

  16. 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.

  17. Protein oxidation and degradation during proliferative senescence of human MRC-5 fibroblasts.

    Science.gov (United States)

    Sitte, N; Merker, K; von Zglinicki, T; Grune, T

    2000-03-01

    One of the highlights of age-related changes of cellular metabolism is the accumulation of oxidized proteins. The aging process on a cellular level can be treated either as the ongoing proliferation until a certain number of cell divisions is reached (the Hayflick limit) or as the aging of nondividing cells, that is, the age-related changes in cells without proliferation. The present investigation was undertaken to reveal the changes in protein turnover, proteasome activity, and protein oxidation status during proliferative senescence. We were able to demonstrate that the activity of the cytosolic proteasomal system declines dramatically during the proliferative senescence of human MRC-5 fibroblasts. Regardless of the loss in activity, it could be demonstrated that there are no changes in the transcription and translation of proteasomal subunits. This decline in proteasome activity was accompanied by an increased concentration of oxidized proteins. Cells at higher proliferation stages were no longer able to respond with increased degradation of endogenous [(35)S]-Met-radiolabeled proteins after hydrogen peroxide- or quinone-induced oxidative stress. It could be demonstrated that oxidized proteins in senescent human MRC-5 fibroblasts are not as quickly removed as they are in young cells. Therefore, our study demonstrates that the accumulation of oxidized proteins and decline in protein turnover and activity of the proteasomal system are not only a process of postmitotic aging but also occur during proliferative senescence and result in an increased half-life of oxidized proteins.

  18. [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.

  19. Controlled Defects of Zinc Oxide Nanorods for Efficient Visible Light Photocatalytic Degradation of Phenol

    Directory of Open Access Journals (Sweden)

    Jamal Al-Sabahi

    2016-03-01

    Full Text Available Environmental pollution from human and industrial activities has received much attention as it adversely affects human health and bio-diversity. In this work we report efficient visible light photocatalytic degradation of phenol using supported zinc oxide (ZnO nanorods and explore the role of surface defects in ZnO on the visible light photocatalytic activity. ZnO nanorods were synthesized on glass substrates using a microwave-assisted hydrothermal process, while the surface defect states were controlled by annealing the nanorods at various temperatures and were characterized by photoluminescence and X-ray photoelectron spectroscopy. High performance liquid chromatography (HPLC was used for the evaluation of phenol photocatalytic degradation. ZnO nanorods with high surface defects exhibited maximum visible light photocatalytic activity, showing 50% degradation of 10 ppm phenol aqueous solution within 2.5 h, with a degradation rate almost four times higher than that of nanorods with lower surface defects. The mineralization process of phenol during degradation was also investigated, and it showed the evolution of different photocatalytic byproducts, such as benzoquinone, catechol, resorcinol and carboxylic acids, at different stages. The results from this study suggest that the presence of surface defects in ZnO nanorods is crucial for its efficient visible light photocatalytic activity, which is otherwise only active in the ultraviolet region.

  20. 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.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. A validated stability-indicating RP-HPLC method for levofloxacin in the presence of degradation products, its process related impurities and identification of oxidative degradant.

    Science.gov (United States)

    Lalitha Devi, M; Chandrasekhar, K B

    2009-12-05

    The objective of current study was to develop a validated specific stability indicating reversed-phase liquid chromatographic method for the quantitative determination of levofloxacin as well as its related substances determination in bulk samples, pharmaceutical dosage forms in the presence of degradation products and its process related impurities. Forced degradation studies were performed on bulk sample of levofloxacin as per ICH prescribed stress conditions using acid, base, oxidative, water hydrolysis, thermal stress and photolytic degradation to show the stability indicating power of the method. Significant degradation was observed during oxidative stress and the degradation product formed was identified by LCMS/MS, slight degradation in acidic stress and no degradation was observed in other stress conditions. The chromatographic method was optimized using the samples generated from forced degradation studies and the impurity spiked solution. Good resolution between the peaks corresponds to process related impurities and degradation products from the analyte were achieved on ACE C18 column using the mobile phase consists a mixture of 0.5% (v/v) triethyl amine in sodium dihydrogen orthophosphate dihydrate (25 mM; pH 6.0) and methanol using a simple linear gradient. The detection was carried out at 294 nm. The limit of detection and the limit of quantitation for the levofloxacin and its process related impurities were established. The stressed test solutions were assayed against the qualified working standard of levofloxacin and the mass balance in each case was in between 99.4 and 99.8% indicating that the developed LC method was stability indicating. Validation of the developed LC method was carried out as per ICH requirements. The developed LC method was found to be suitable to check the quality of bulk samples of levofloxacin at the time of batch release and also during its stability studies (long term and accelerated stability).

  9. 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

  10. A stability indicating HPLC method for determination of mebeverine in the presence of its degradation products and kinetic study of its degradation in oxidative condition.

    Science.gov (United States)

    Souri, E; Aghdami, A Negahban; Adib, N

    2014-01-01

    An HPLC method for determination of mebeverine hydrochloride (MH) in the presence of its degradation products was developed. The degradation of MH was studied under hydrolysis, oxidative and photolysis stress conditions. Under alkaline, acidic and oxidative conditions, degradation of MH was observed. The separation was performed using a Symmetry C18 column and a mixture of 50 mM KH2PO4, acetonitrile and tetrahydrfuran (THF) (63:35:2; v/v/v) as the mobile phase. No interference peaks from degradation products in acidic, alkaline and oxidative conditions were observed. The linearity, accuracy and precision of the method were studied. The method was linear over the range of 1-100 μg/ml MH (r(2)>0.999) and the CV values for intra-day and inter-day variations were in the range of 1.0-1.8%. The limit of quantification (LOQ) and the limit of detection (LOD) of the method were 1.0 and 0.2 μg/ml, respectively. Determination of MH in pharmaceutical dosage forms was performed using the developed method. Furthermore the kinetics of the degradation of MH in the presence of hydrogen peroxide was investigated. The proposed method could be a suitable method for routine quality control studies of mebeverine dosage forms.

  11. 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)

  12. Heme degrading protein HemS is involved in oxidative stress response of Bartonella henselae.

    Directory of Open Access Journals (Sweden)

    MaFeng Liu

    Full Text Available Bartonellae are hemotropic bacteria, agents of emerging zoonoses. These bacteria are heme auxotroph Alphaproteobacteria which must import heme for supporting their growth, as they cannot synthesize it. Therefore, Bartonella genome encodes for a complete heme uptake system allowing the transportation of this compound across the outer membrane, the periplasm and the inner membranes. Heme has been proposed to be used as an iron source for Bartonella since these bacteria do not synthesize a complete system required for iron Fe³⁺ uptake. Similarly to other bacteria which use heme as an iron source, Bartonellae must transport this compound into the cytoplasm and degrade it to allow the release of iron from the tetrapyrrole ring. For Bartonella, the gene cluster devoted to the synthesis of the complete heme uptake system also contains a gene encoding for a polypeptide that shares homologies with heme trafficking or degrading enzymes. Using complementation of an E. coli mutant strain impaired in heme degradation, we demonstrated that HemS from Bartonella henselae expressed in E. coli allows the release of iron from heme. Purified HemS from B. henselae binds heme and can degrade it in the presence of a suitable electron donor, ascorbate or NADPH-cytochrome P450 reductase. Knocking down the expression of HemS in B. henselae reduces its ability to face H₂O₂ induced oxidative stress.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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...

  20. Isolation of oxidative degradation products of atorvastatin with supercritical fluid chromatography.

    Science.gov (United States)

    Klobčar, Slavko; Prosen, Helena

    2015-12-01

    The isolation of four oxidative degradation products of atorvastatin using preparative high-performance liquid chromatography applying at least two chromatographic steps is known from the literature. In this paper it is shown that the same four impurities could be isolated from similarly prepared mixtures in only one step using supercritical fluid chromatography. The methods for separation were developed and optimized. The preparation of the mixtures was altered in such a way as to enhance the concentration of desired impurities. Appropriate solvents were applied for collection of separated impurities in order to prevent degradation. The structures of the isolated impurities were confirmed and their purity determined. The preparative supercritical fluid chromatography has proven to be superior to preparative HPLC regarding achieved purity of standards applying fewer chromatographic as well as isolation steps. Copyright © 2015 John Wiley & Sons, Ltd.

  1. 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.

  2. Determination of Polybutadiene Unsaturation Content in Thermal and Thermo-Oxidative Degradation Processes by NMR

    Directory of Open Access Journals (Sweden)

    Farshid Ziaee

    2013-01-01

    Full Text Available The unsaturation content of various polybutadiene (PBD types of 1,4-cis, 1,4-trans and 1,2-vinyl isomers with different molecular weights was investigated. An important parameter for unsaturation content of polybutadiene would be the determination of olefnic and aliphatic contents for three types of isomers. For this purpose, proton and carbon nuclear magnetic resonance spectroscopy methods were employed for determination of 1,4-cis, 1,4-trans and 1,2-vinyl contents. A change of adjustable parameter of NMR software was made for accurate integrals giving better results. The accuracy in calculation of low molecular weight PBD, surface area of chain end group decreased in aliphatic region. Furthermore, the changing of unsaturation content versus time was considered for 1,2-PBD and 1,4-PBD in thermal degradation conditions at 250°C. NMR results showed that during heating, the unsaturation content decreased for 1,2-PBD and was not changed for 1,4-PBD. In fact, the basic factor responsible for changing of unsaturation content in thermal degradation of PBD may be due to the presence of 1,2-vinyl isomer. Finally, changing in unsaturation content versus time was observed for 1,2-PBD and 1,4-PBD in thermo-oxidative degradation conditions at 100°C. The NMR results showed that at extended time, the unsaturation content decreased for 1,4-PBD and was not changed for 1,2-PBD. Moreover, the basic factor for changes in unsaturation content in thermo-oxidative degradation of PBD is due to the presence of 1,4-cis and 1,4-trans isomers.

  3. 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

  4. Degradation of the corrosion resistance of anodic oxide films through immersion in the anodising electrolyte

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Rubio, M. [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, 28049-Madrid (Spain); Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Ocon, P., E-mail: pilar.ocon@uam.e [Departamento de Quimica-Fisica Aplicada, Universidad Autonoma de Madrid, 28049-Madrid (Spain); Curioni, M.; Thompson, G.E.; Skeldon, P. [Corrosion and Protection Center, School of Materials, The University of Manchester, M60 1QD England (United Kingdom); Lavia, A. [Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Garcia, I. [Department of Surface Technologies, Engineering of Materials and Processes, Airbus Spain, Av. John Lennon s/n 28906-Getafe (Spain); Department of Corrosion and Protection, National Center for Metallurgical Research CENIM-CSIC, Av. Gregorio del Amo 8, 28040-Madrid (Spain)

    2010-07-15

    The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.

  5. Degradation of the corrosion resistance of anodic oxide films through immersion in the anodising electrolyte

    International Nuclear Information System (INIS)

    Garcia-Rubio, M.; Ocon, P.; Curioni, M.; Thompson, G.E.; Skeldon, P.; Lavia, A.; Garcia, I.

    2010-01-01

    The deterioration of AA2024, AA6061 and AA7475 anodised in an environmentally-compliant tartaric acid/sulphuric acid electrolyte has been examined as a function of the immersion time in the electrolyte after termination of anodising. By transmission electron microscopy and scanning electron microscopy, degradation of the porous oxide film was qualitatively observed on AA2024. Electrochemical impedance spectroscopy revealed that AA2024 and AA7075 were more sensitive to prolonged immersion in the anodising electrolyte compared with AA6061, due to increased barrier layer thinning rates and increased susceptibility to localized corrosion. Salt spray tests confirmed the previous, indicating decay of anticorrosion performance for AA2024 and AA7075.

  6. 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.

  7. 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.

  8. 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.

  9. 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)

  10. Thickness-dependent photocatalytic performance of graphite oxide for degrading organic pollutants under visible light.

    Science.gov (United States)

    Oh, Junghoon; Chang, Yun Hee; Kim, Yong-Hyun; Park, Sungjin

    2016-04-28

    Photocatalysts use sustainable solar light energy to trigger various catalytic reactions. Metal-free nanomaterials have been suggested as cost-effective and environmentally friendly photocatalysts. In this work, we propose thickness-controlled graphite oxide (GO) as a metal-free photocatalyst, which is produced by exfoliating thick GO particles via stirring and sonication. All GO samples exhibit photocatalytic activity for degrading an organic pollutant, rhodamine B under visible light, and the thickest sample shows the best catalytic performance. UV-vis-NIR diffuse reflectance absorption spectra indicate that thicker GO samples absorb more vis-NIR light than thinner ones. Density-functional theory calculations show that GO has a much smaller band gap than that of single-layer graphene oxide, and thus suggest that the largely-reduced band gap is responsible for this trend of light absorption.

  11. Gold nanoworms immobilized graphene oxide polymer brush nanohybrid for catalytic degradation studies of organic dyes

    Science.gov (United States)

    Mogha, Navin Kumar; Gosain, Saransh; Masram, Dhanraj T.

    2017-02-01

    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 (kapp), 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.

  12. 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

  13. 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.

  14. Molecular characterization of kerogens by mild selective chemical degradation - ruthenium tetroxide oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Boucher, R.J.; Standen, G.; Eglinton, G. (University of Bristol, Bristol (UK). Organic Geochemistry Unit)

    1991-06-01

    Molecular characterization of two kerogen isolates (Messel and Kimmeridge Clay), two kerogen-rich shales (green River and Maoming) and a coal, (Loy Yang) was undertaken using selective chemical degradation with ruthenium tetroxide (RuO{sub 4}). The RuO{sub 4} oxidation gave extracts which were soluble in dichloromethane and contained series of straight chain monocarboxylic acids, {alpha},{omega}-dicarboxylic acids, branched mono- and dicarboxylic acids, isoprenoid and cyclic acids. Straight chain carboxylic acids were predominant (65-87% of quantified chromatogram components for the range of sedimentary organic matter studied), reflecting the major content of polymethylene chains in these kerogens. This mild, oxidative technique serves to differentiate kerogens at a molecular level, thereby supplementing existing conventional chemical, pyrolytic, n.m.r. and other techniques. 39 refs., 3 figs., 5 tabs.

  15. 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...

  16. 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.

  17. Enhanced Phospholipase A2 Group 3 Expression by Oxidative Stress Decreases the Insulin-Degrading Enzyme

    Science.gov (United States)

    Yui, Daishi; Nishida, Yoichiro; Nishina, Tomoko; Mogushi, Kaoru; Tajiri, Mio; Ishibashi, Satoru; Ajioka, Itsuki; Ishikawa, Kinya; Mizusawa, Hidehiro; Murayama, Shigeo; Yokota, Takanori

    2015-01-01

    Oxidative stress has a ubiquitous role in neurodegenerative diseases and oxidative damage in specific regions of the brain is associated with selective neurodegeneration. We previously reported that Alzheimer disease (AD) model mice showed decreased insulin-degrading enzyme (IDE) levels in the cerebrum and accelerated phenotypic features of AD when crossbred with alpha-tocopherol transfer protein knockout (Ttpa -/-) mice. To further investigate the role of chronic oxidative stress in AD pathophysiology, we performed DNA microarray analysis using young and aged wild-type mice and aged Ttpa -/- mice. Among the genes whose expression changed dramatically was Phospholipase A2 group 3 (Pla2g3); Pla2g3 was identified because of its expression profile of cerebral specific up-regulation by chronic oxidative stress in silico and in aged Ttpa -/- mice. Immunohistochemical studies also demonstrated that human astrocytic Pla2g3 expression was significantly increased in human AD brains compared with control brains. Moreover, transfection of HEK293 cells with human Pla2g3 decreased endogenous IDE expression in a dose-dependent manner. Our findings show a key role of Pla2g3 on the reduction of IDE, and suggest that cerebrum specific increase of Pla2g3 is involved in the initiation and/or progression of AD. PMID:26637123

  18. Enhanced Phospholipase A2 Group 3 Expression by Oxidative Stress Decreases the Insulin-Degrading Enzyme.

    Directory of Open Access Journals (Sweden)

    Daishi Yui

    Full Text Available Oxidative stress has a ubiquitous role in neurodegenerative diseases and oxidative damage in specific regions of the brain is associated with selective neurodegeneration. We previously reported that Alzheimer disease (AD model mice showed decreased insulin-degrading enzyme (IDE levels in the cerebrum and accelerated phenotypic features of AD when crossbred with alpha-tocopherol transfer protein knockout (Ttpa-/- mice. To further investigate the role of chronic oxidative stress in AD pathophysiology, we performed DNA microarray analysis using young and aged wild-type mice and aged Ttpa-/- mice. Among the genes whose expression changed dramatically was Phospholipase A2 group 3 (Pla2g3; Pla2g3 was identified because of its expression profile of cerebral specific up-regulation by chronic oxidative stress in silico and in aged Ttpa-/- mice. Immunohistochemical studies also demonstrated that human astrocytic Pla2g3 expression was significantly increased in human AD brains compared with control brains. Moreover, transfection of HEK293 cells with human Pla2g3 decreased endogenous IDE expression in a dose-dependent manner. Our findings show a key role of Pla2g3 on the reduction of IDE, and suggest that cerebrum specific increase of Pla2g3 is involved in the initiation and/or progression of AD.

  19. 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.

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

    Directory of Open Access Journals (Sweden)

    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.

  1. Contribution of Polyphenol Oxidation, Chlorophyll and Vitamin C Degradation to the Blackening of Piper nigrum L.

    Science.gov (United States)

    Gu, Fenglin; Huang, Feifei; Wu, Guiping; Zhu, Hongying

    2018-02-09

    Black pepper ( Piper nigrum L.) is the most widely used spice in the world. Blackening is considered to be beneficial and important in the processing of black pepper because it contributes to its color and flavor. The purpose of this paper is to investigate polyphenol oxidation as well as the chlorophyll and vitamin C (VC) degradation in the blackening of Piper nigrum L. Black pepper was produced by four methods, and changes in polyphenols, chlorophyll and VC were studied by high performance liquid chromatography (HPLC) and ultraviolet-visible and visible (UV-Vis) spectrophotometry. The results show that polyphenol oxidase activity significantly decreased during the preparation of black pepper, and the concentrations of phenolic compounds, VC, and chlorophyll a and b also significantly decreased. Polyphenol oxidation and chlorophyll and VC degradation contribute to the blackening. A crude extract of phenolic compounds from black pepper was prepared by the system solvent method. The greater the polarity of the extraction solvent, the higher the extraction rates of the phenolic compounds and the total phenol content. Pepper phenolic compounds were analyzed by HPLC analysis.

  2. Contribution of Polyphenol Oxidation, Chlorophyll and Vitamin C Degradation to the Blackening of Piper nigrum L.

    Directory of Open Access Journals (Sweden)

    Fenglin Gu

    2018-02-01

    Full Text Available Black pepper (Piper nigrum L. is the most widely used spice in the world. Blackening is considered to be beneficial and important in the processing of black pepper because it contributes to its color and flavor. The purpose of this paper is to investigate polyphenol oxidation as well as the chlorophyll and vitamin C (VC degradation in the blackening of Piper nigrum L. Black pepper was produced by four methods, and changes in polyphenols, chlorophyll and VC were studied by high performance liquid chromatography (HPLC and ultraviolet-visible and visible (UV-Vis spectrophotometry. The results show that polyphenol oxidase activity significantly decreased during the preparation of black pepper, and the concentrations of phenolic compounds, VC, and chlorophyll a and b also significantly decreased. Polyphenol oxidation and chlorophyll and VC degradation contribute to the blackening. A crude extract of phenolic compounds from black pepper was prepared by the system solvent method. The greater the polarity of the extraction solvent, the higher the extraction rates of the phenolic compounds and the total phenol content. Pepper phenolic compounds were analyzed by HPLC analysis.

  3. 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.

  4. EFFECT OF NATURAL IRON OXIDE, HYDROGEN PEROXIDE, AND OXALIC ACID ON PHOTOCHEMICAL DEGRADATION OF 2-CHLOROPHENOL

    Directory of Open Access Journals (Sweden)

    W REMACHE

    2014-07-01

    Full Text Available The voluntary or accidental release of chemical compounds in the environment is a major cause of pollution of natural waters. Most of chlorophenols are toxic and hardly biodegradable and are difficult to remove from the environment. Therefore, it is important to find innovative and economical methods for the safe and complete destruction. The objective of this work is to test the activity photocatalytic of natural iron oxide (NIO in the photodegradation of 2-chlorophenol (2-CP. The analysis chromatographic with HPLC of solutions exposed under UV irradiation revealed that the degradation of 2-CP was negligible under the condition of using only natural iron oxide. The effect of wavelength on photoreactivity of NIO was also investigated in this process: at high wavelength thus at low energy the efficiency of degradation is important. We have also investigated the activation of NIO by hydrogen peroxide and oxalic acid, The results showed that the photodegradation of 2-CP under UVA irradiation could be enhanced greatly in the presence of oxalate. 2-CP was completly removed after 240 minutes of irradiation when the concentration of oxalic acid is equal to 2.10-3 M. The use of 2.0 % of isopropanol as a scavenger confirmed the intervention of hydroxyl radicals in the photodegradation of 2-CP.

  5. Photoelectrocatalytic degradation of oxalic acid by spray deposited nanocrystalline zinc oxide thin films

    International Nuclear Information System (INIS)

    Shinde, S.S.; Shinde, P.S.; Sapkal, R.T.; Oh, Y.W.; Haranath, D.; Bhosale, C.H.; Rajpure, K.Y.

    2012-01-01

    Highlights: ► Influence of substrate temperature onto the physico-chemical properties. ► Photochemical, structural, luminescent, optoelectrical and thermal properties. ► The kinetics of oxalic acid degradation with reaction mechanism. ► Extent of mineralization by COD and TOC. - Abstract: The high quality nano-crystalline zinc oxide thin films are deposited onto corning glasses by spray pyrolysis technique. The influence of reaction temperature onto their photoelectrochemical, structural, morphological, optoelectronic, luminescence and thermal properties has been investigated. The structural characteristics studied by X-ray diffractometry has complemented by resistivity measurements and UV–Vis spectroscopy. The photoelectrochemical activity shows enhancement in short circuit current (I sc = 0.357 mA) and open circuit voltage (V oc = 0.48 V). Direct band gap calculated by considering R and T values of ZnO thin films increases from 3.14–3.21 eV exhibiting a slight blue shift in band edge. Three characteristic luminescence peaks having near band-edge, blue and green emission are observed in the photoluminescence spectra. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant in films. Photocatalytic degradation of oxalic acid followed with reaction mechanism by using zinc oxide photoelectrode under solar illumination has been investigated.

  6. 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

  7. 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.

  8. Kinetics of Phenol Degradation in Aqueous Solution Oxidized under Low Frequency Ultrasonic Irradiation

    Directory of Open Access Journals (Sweden)

    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.

  9. 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.

  10. 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.

  11. 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.

  12. Oxidative stress induces caveolin 1 degradation and impairs caveolae functions in skeletal muscle cells.

    Directory of Open Access Journals (Sweden)

    Alexis Mougeolle

    Full Text Available Increased level of oxidative stress, a major actor of cellular aging, impairs the regenerative capacity of skeletal muscle and leads to the reduction in the number and size of muscle fibers causing sarcopenia. Caveolin 1 is the major component of caveolae, small membrane invaginations involved in signaling and endocytic trafficking. Their role has recently expanded to mechanosensing and to the regulation of oxidative stress-induced pathways. Here, we increased the amount of reactive oxidative species in myoblasts by addition of hydrogen peroxide (H2O2 at non-toxic concentrations. The expression level of caveolin 1 was significantly decreased as early as 10 min after 500 μM H2O2 treatment. This reduction was not observed in the presence of a proteasome inhibitor, suggesting that caveolin 1 was rapidly degraded by the proteasome. In spite of caveolin 1 decrease, caveolae were still able to assemble at the plasma membrane. Their functions however were significantly perturbed by oxidative stress. Endocytosis of a ceramide analog monitored by flow cytometry was significantly diminished after H2O2 treatment, indicating that oxidative stress impaired its selective internalization via caveolae. The contribution of caveolae to the plasma membrane reservoir has been monitored after osmotic cell swelling. H2O2 treatment increased membrane fragility revealing that treated cells were more sensitive to an acute mechanical stress. Altogether, our results indicate that H2O2 decreased caveolin 1 expression and impaired caveolae functions. These data give new insights on age-related deficiencies in skeletal muscle.

  13. Enhanced degradation of paracetamol by UV-C supported photo-Fenton process over Fenton oxidation.

    Science.gov (United States)

    Manu, B; Mahamood, S

    2011-01-01

    For the treatment of paracetamol in water, the UV-C Fenton oxidation process and classic Fenton oxidation have been found to be the most effective. Paracetamol reduction and chemical oxygen demand (COD) removal are measured as the objective functions to be maximized. The experimental conditions of the degradation of paracetamol are optimized by the Fenton process. Influent pH 3, initial H(2)O(2) dosage 60 mg/L, [H(2)O(2)]/[Fe(2+)] ratio 60 : 1 are the optimum conditions observed for 20 mg/L initial paracetamol concentration. At the optimum conditions, for 20 mg/L of initial paracetamol concentration, 82% paracetamol reduction and 68% COD removal by Fenton oxidation, and 91% paracetamol reduction and 82% COD removal by UV-C Fenton process are observed in a 120 min reaction time. By HPLC analysis, 100% removal of paracetamol is observed at the above optimum conditions for the Fenton process in 240 min and for the UV-C photo-Fenton process in 120 min. The methods are effective and they may be used in the paracetamol industry.

  14. 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.

  15. Comparison of Five Advanced Oxidation Processes for Degradation of Pesticide in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Augustine Chioma Affam

    2018-01-01

    Full Text Available The study compared the technical efficiency and economic cost of five advanced oxidation processes (Fenton, UV photo-Fenton, solar photo-Fenton, UV/TiO2/H2O2 and FeGAC/H2O2 for degradation of the pesticides chlorpyrifos cypermethrin and chlorothalonil in aqueous solution. The highest degradation in terms of COD and TOC removals and improvement of the biodegradability (BOD5/COD ratio index (BI were observed to be (i Fenton - 69.03% (COD, 55.61% (TOC, and 0.35 (BI; (ii UV photo-Fenton -78.56% (COD, 63.76% (TOC and 0.38 (BI;  (iii solar photo-Fenton - 74.19% (COD, 58.32% (TOC and 0.36 (BI; (iv UV/TiO2/H2O2 - 53.62% (COD, 21.54% (TOC, and 0.26 (BI; and  (v the most technical efficient and cost effective process was FeGAC/H2O2. At an optimum condition (FeGAC 5 g/L, H2O2 100 mg/L, and reaction time of 60 min at pH 3, the COD and TOC removal efficiency were 96.19 and 85.60%, respectively, and the biodegradation index was 0.40. The degradation rate constant and cost were 0.0246 min-1 and $0.74/kg TOC, respectively. The FeGAC/H2O2 process is the most technically efficient and cost effective for pretreatment of the pesticide wastewater before biological treatment. Copyright © 2018 BCREC Group. All rights reserved Received: 26th July 2017; Revised: 26nd September 2017; Accepted: 27th September 2017; Available online: 22nd January 2018; Published regularly: 2nd April 2018 How to Cite: Affam, A.C., Chaudhuri, M., Kutty, S.R.M. (2018. Comparison of Five Advanced Oxidation Processes for Degradation of Pesticide in Aqueous Solution. Bulletin of Chemical Reaction Engineering & Catalysis, 13 (1: 179-186 (doi:10.9767/bcrec.13.1.1394.179-186

  16. 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.

  17. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    International Nuclear Information System (INIS)

    Pura, Jarosław; Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna; Laskowski, Zbigniew; Gierej, Maciej

    2016-01-01

    Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800–900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic “cauliflower-shape protrusions”. The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires’ surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires’ preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better

  18. Investigation of the degradation mechanism of catalytic wires during oxidation of ammonia process

    Energy Technology Data Exchange (ETDEWEB)

    Pura, Jarosław, E-mail: jaroslawpura@gmail.com [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Wieciński, Piotr; Kwaśniak, Piotr; Zwolińska, Marta; Garbacz, Halina; Zdunek, Joanna [Faculty of Material Science and Engineering, Warsaw University of Technology, Wołoska 141, 02-507 Warsaw (Poland); Laskowski, Zbigniew; Gierej, Maciej [Precious Metal Mint, Weteranów 95, 05-250 Radzymin (Poland)

    2016-12-01

    Highlights: • Degradation mechanisms of precious metal catalytic gauzes is proposed. • Significant change of gauzes morphology and chemical composition was observed. • Samples were analyzed using SEM, EDS and micro-XCT techniques. - Abstract: The most common catalysts for the ammonia oxidation process are 80 μm diameter platinum-rhodium wires knitted or woven into the form of a gauze. In an aggressive environment and under extreme conditions (temperature 800–900 °C, intensive gas flow, high pressure) precious elements are drained from the surface of the wires. Part of this separated material quickly decomposes on the surface in the form of characteristic “cauliflower-shape protrusions”. The rest of the platinum is captured by palladium-nickel catalytic-capture gauzes located beneath. In our investigation we focused on the effects of the degradation of gauzes from one industrial catalytic system. The aim of the study was to compare the degree and the mechanism of degradation of gauzes from a different part of the reactor. The study covered PtRh7 catalytic and PdNi5 catalytic-capture gauzes. X-ray computer microtomography investigation revealed that despite strong differences in morphology, each Pt-Rh wire has a similar specific surface area. This indicates that the oxidation process and morphological changes of the wires occur in a self-regulating balance, resulting in the value of the specific surface area of the catalyst. Microtomography analysis of Pd-Ni wires revealed strong redevelopment of the wires’ surface, which is related to the platinum capture phenomenon. Scanning electron microscope observations also revealed the nanostructure in the cauliflower-shape protrusions and large grains in the wires’ preserved cores. The high temperature in the reactor and the long-term nature of the process do not favor the occurrence of the nanostructure in this type of material. Further and detailed analysis of this phenomena will provide a better

  19. Bacterial growth and substrate degradation by BTX-oxidizing culture in response to salt stress.

    Science.gov (United States)

    Lee, Chi-Yuan; Lin, Ching-Hsing

    2006-01-01

    Interactions between microbial growth and substrate degradation are important in determining the performance of trickle-bed bioreactors (TBB), especially when salt is added to reduce biomass formation in order to alleviate media clogging. This study was aimed at quantifying salinity effects on bacterial growth and substrate degradation, and at acquiring kinetic information in order to improve the design and operation of TBB. Experiment works began by cultivating a mixed culture in a chemostat reactor receiving artificial influent containing a mixture of benzene, toluene, and xylene (BTX), followed by using the enrichment culture to degrade the individual BTX substrates under a particular salinity, which ranged 0-50 g l(-1) in batch mode. Then, the measured concentrations of biomass and residual substrate versus time were analyzed with the microbial kinetics; moreover, the obtained microbial kinetic constants under various salinities were modeled using noncompetitive inhibition kinetics. For the three substrates the observed bacterial yields appeared to be decreased from 0.51-0.74 to 0.20-0.22 mg mg(-1) and the maximum specific rate of substrate utilization, q, declined from 0.25-0.42 to 0.07-0.11 h(-1), as the salinity increased from 0 to 50 NaCl g l(-1). The NaCl acted as noncompetitive inhibitor, where the modeling inhibitions of the coefficients, K ( T(S)), were 22.7-29.7 g l(-1) for substrate degradation and K ( T(mu)), 13.0-19.0 g l(-1), for biomass formation. The calculated ratios for the bacterial maintenance rate, m (S), to q, further indicated that the percentage energy spent on maintenance increased from 19-24 to 86-91% as salinity level increased from 0 to 50 g l(-1). These results revealed that the bacterial growth was more inhibited than substrate degradation by the BTX oxidizers under the tested salinity levels. The findings from this study demonstrate the potential of applying NaCl salt to control excessive biomass formation in biotrickling filters.

  20. 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.

  1. 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

  2. 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

  3. Reusability Performance of Zinc Oxide Nanoparticles for Photocatalytic Degradation of POME

    Science.gov (United States)

    Zarifah Zainuri, Nur; Hanis Hayati Hairom, Nur; Abu Bakar Sidik, Dilaelyana; Misdan, Nurasyikin; Yusof, Norhaniza; Wahab Mohammad, Abdul

    2018-03-01

    Performance and reusability of different zinc oxide nanoparticles (ZnO-PVP and ZnO-PEG) for photocatalytic degradation of palm-mill oil effluent (POME) has been studied. The nanoparticles properties were characterised with fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The TEM results show that ZnO-PEG nanoparticles exhibit the smaller size than ZnO-PVP with less agglomeration. It was found that ZnO-PEG shows better effectiveness than ZnO-PVP in reducing turbidity, colour and increasing the dissolved oxygen (DO). By using two types of reusability methods: (a) oven drying (b) hot water rinsing, the oven drying method portrayed the most efficient route for POME treatment. This research would be a solution to the palm oil industry for photocatalyst recovering as well as reduction of the chemical usage in order to meet the development of advanced and greener technologies.

  4. Degradation of Solid Oxide Electrolysis Cells Operated at High Current Densities

    DEFF Research Database (Denmark)

    Tao, Youkun; Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

    2014-01-01

    In this work the durability of solid oxide cells for co-electrolysis of steam and carbon dioxide (45 % H2O + 45 % CO2 + 10 % H2) at high current densities was investigated. The tested cells are Ni-YSZ electrode supported, with a YSZ electrolyte and either a LSM-YSZ or LSCF-CGO oxygen electrode....... A current density of -1.5 and -2.0 A/cm2 was applied to the cell and the gas conversion was 45 % and 60 %, respectively. The cells were operated for a period of up to 700 hours. The electrochemical analysis revealed significant performance degradation for the ohmic process, oxygen ion interfacial transfer...

  5. Degradation of phthalate in aqueous solution by advanced oxidation process, photo-fenton

    International Nuclear Information System (INIS)

    Trabelsi, S.; Bellakhal, N.; Oturan, N.; Oturan, M.A.

    2009-01-01

    A photochemical method for degradation of persistent organic pollutants present in liquid effluents from the plastic industry and in the leaching described. This method, called P hoto-Fenton i nvolves the generation of radicals hydroxyl coupling between the Fenton reaction and photochemistry, OH radicals. Thus formed react with very high speeds, organic substances pollutants leading to their oxidation to total mineralization. In this study, we applied the process photo-Fenton treatment Plasticizers, Phthalates. For this, optimization of experimental parameters (namely the relationship between the concentrations of hydrogen peroxide and iron concentration catalyst) was performed. Under optimal conditions and determined the kinetics mineralization of phthalic anhydride by OH was studied. The overall results confirm the effectiveness of photo-Fenton process for the decontamination of liquid effluents responsible for persistent organic pollutants (Pop's).

  6. Oxidative degradation of tetramethylammonium hydroxide (TMAH) by UV/persulfate and associated acute toxicity assessment.

    Science.gov (United States)

    Huang, Jingting; Wang, Kai-Sung; Liang, Chenju

    2017-07-29

    Tetramethylammonium hydroxide (TMAH) is widely used in high-tech industries as a developing agent. Ultraviolet (UV) light-activated persulfate (PS, S 2 O 8 2- ) can be used to generate strongly oxidative sulfate radicals, and it also exhibits the potential to treat TMAH-containing wastewater. This study initially investigated the effect of S 2 O 8 2- concentration and UV strength on the UV/S 2 O 8 2- process for the degradation of TMAH in a batch reactor. The results suggested that 15 watts (W) of UV-activated S 2 O 8 2- at concentrations of 10 or 50 mM resulted in pseudo-first-order TMAH degradation rate constants of 3.1-4.2 × 10 -2 min -1 , which was adopted for determining the hydraulic retention time (HRT) in a continuous stirred tank reactor (CSTR). The operating conditions (15 W UV/10 mM S 2 O 8 2- ) with a HRT of 129 min resulted in stable residual concentrations of S 2 O 8 2- and TMAH at approximately 2.6 mM and 20 mg L -1 in effluent, respectively. Several TMAH degradation intermediates including trimethylamine, dimethylamine, and methylamine were also detected. The effluent was adjusted to a neutral pH and evaluated for its biological acute toxicity using Cyprinus carpio as a bioassay organism. The "bio-acute toxicity unit" (TU a ) was determined to be 1.41, which indicated that the effluent was acceptable for being discharged into an aquatic ecosystem.

  7. Degradation of solid oxide fuel cell metallic interconnects in fuels containing sulfur

    Energy Technology Data Exchange (ETDEWEB)

    Ziomek-Moroz, M.; Hawk, Jeffrey A.

    2005-01-01

    Hydrogen is the main fuel for all types of fuel cells except direct methanol fuel cells. Hydrogen can be generated from all manner of fossil fuels, including coal, natural gas, diesel, gasoline, other hydrocarbons, and oxygenates (e.g., methanol, ethanol, butanol, etc.). Impurities in the fuel can cause significant performance problems and sulfur, in particular, can decrease the cell performance of fuel cells, including solid oxide fuel cells (SOFC). In the SOFC, the high (800-1000°C) operating temperature yields advantages (e.g., internal fuel reforming) and disadvantages (e.g., material selection and degradation problems). Significant progress in reducing the operating temperature of the SOFC from ~1000 ºC to ~750 ºC may allow less expensive metallic materials to be used for interconnects and as balance of plant (BOP) materials. This paper provides insight on the material performance of nickel, ferritic steels, and nickel-based alloys in fuels containing sulfur, primarily in the form of H2S, and seeks to quantify the extent of possible degradation due to sulfur in the gas stream.

  8. Comparative study of photocatalytic oxidation on the degradation of formaldehyde and fuzzy mathematics evaluation of filters

    Science.gov (United States)

    Yu, Huili; Zhang, Jieting

    2012-04-01

    In this study, formaldehyde, one of the major volatile organic compounds, is chosen as the target pollutant. The polytetrafluoroethylene (PTFE) filter, a low cost and commonly used material in industry, is employed as the substrate for nano TiO2 photocatalyst coating at room temperature, which has been scarcely used compared to ceramics or glass beads. Furthermore, a specific experimental set-up that is similar to actual air purification system is developed for the testing. The degradation mechanisms of photolysis reaction, adsorption and photocatalytic oxidation reaction on volatile organic compounds are present respectively. The influences of three aspects mentioned above are compared by a serial of experimental data. The high efficiency of volatile organic compounds on the degradation of formaldehyde is assured. Furthermore, the purification characteristics of three kinds of activated carbon filters and PTFE filter with nano TiO2 are evaluated with the method of fuzzy mathematics. In the end, the result shows that the filter with nano TiO2 has the optimal comprehensive performances.

  9. Degradation of cytotoxic agent in soap and detergent wastewater by advanced oxidation processes

    International Nuclear Information System (INIS)

    Iqbal, M.; Bhatti, I.A.; Nisar, J.

    2017-01-01

    Wastewater from soap and detergent industries is a source of high pollution and contamination for water sheds. In present investigation, cytotoxic profiling was documented from Faisalabad, Sargodha and Gujranwala cities, Pakistan, followed by advanced oxidation processes (AOPs) treatments (UV and gamma radiation). The cytotoxicity was evaluated by Allium cepa, haemolytic and brine shrimp bioassays. Independent variables such as gamma radiation absorbed dose, H2O2, TiO2 concentrations, reaction time, pH and shaking speed were optimized using statistical techniques. The raw soap and detergent wastewater showed cytotoxicity up to high extent. At optimized conditions, > 94% degradation was achieved both in case of UV (exposure time 100 min, TiO2 concentration 5.93 g/L, H2O2 4.39%, pH 6.50 and shaking speed 110 rpm) and gamma radiation (12.69 kGy absorbed dose in the presence of 4.65% H2O2) treated samples and water quality parameters (WQP) also improved significantly. The cytotoxicity reduced sharply as a result of AOPs treatment at optimized conditions. From the results, it is evident that AOPs under investigation could be used for the degradation and cytotoxicity reduction of soap and detergent wastewater. (author)

  10. 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.

  11. 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.

  12. Effect of communities of ammonia-oxidizing bacteria on degradation of 17-alpha-ethynylestradiol by nitrifying activated sludge

    Energy Technology Data Exchange (ETDEWEB)

    Limpiyakorn, T.; Sermwaraphan, P.; Kurisu, F.

    2009-07-01

    An endocrine disrupting compound, 17-alpha-ethynylestradiol (EE2), is a synthetic estrogen used as a key ingredient in oral contraceptives pill. this persistent organic pollutant, no biodegradable by most microorganisms, is discharged via municipal waste streams to natural receiving waters. Recently, it was found that ammonia-oxidizing bacteria (AOB) in nitrifying activated sludge (NAS) enriched with high ammonium loads can degrade EE2 via co-metabolism during ammonia oxidation. (Author)

  13. Degradation of Acetaminophen and Its Transformation Products in Aqueous Solutions by Using an Electrochemical Oxidation Cell with Stainless Steel Electrodes

    Directory of Open Access Journals (Sweden)

    Miguel Ángel López Zavala

    2016-09-01

    Full Text Available In this study, a novel electrochemical oxidation cell using stainless steel electrodes was found to be effective in oxidizing acetaminophen and its transformation products in short reaction times. Aqueous solutions of 10 mg/L-acetaminophen were prepared at pH 3, 5, 7, and 9. These solutions were electrochemically treated at direct current (DC densities of 5.7 mA/cm2, 7.6 mA/cm2, and 9.5 mA/cm2. The pharmaceutical and its intermediates/oxidation products were determined by using high pressure liquid chromatography (HPLC. The results showed that electrochemical oxidation processes occurred in the cell. Acetaminophen degradation rate constants increased proportionally with the increase of current intensity. High current densities accelerated the degradation of acetaminophen; however, this effect diminished remarkably at pH values greater than 5. At pH 3 and 9.5 mA/cm2, the fastest degradation of acetaminophen and its intermediates/oxidation products was achieved. To minimize the wear down of the electrodes, a current density ramp is recommended, first applying 9.5 mA/cm2 during 2.5 min or 7.6 mA/cm2 during 7.5 min and then continuing the electrochemical oxidation process at 5.7 mA/cm2. This strategy will hasten the acetaminophen oxidation, extend the electrode’s life, and shorten the reaction time needed to degrade the pharmaceutical and its intermediates/oxidation products. DC densities up to 9.5 mA/cm2 can be supplied by photovoltaic cells.

  14. Rapid Surface Oxidation as a Source of Surface Degradation Factor for Bi 2 Se 3

    KAUST Repository

    Kong, Desheng

    2011-06-28

    Bismuth selenide (Bi2Se3) is a topological insulator with metallic surface states (SS) residing in a large bulk bandgap. In experiments, synthesized Bi2Se3 is often heavily n-type doped due to selenium vacancies. Furthermore, it is discovered from experiments on bulk single crystals that Bi2Se3 gets additional n-type doping after exposure to the atmosphere, thereby reducing the relative contribution of SS in total conductivity. In this article, transport measurements on Bi2Se3 nanoribbons provide additional evidence of such environmental doping process. Systematic surface composition analyses by X-ray photoelectron spectroscopy reveal fast formation and continuous growth of native oxide on Bi2Se3 under ambient conditions. In addition to n-type doping at the surface, such surface oxidation is likely the material origin of the degradation of topological SS. Appropriate surface passivation or encapsulation may be required to probe topological SS of Bi2Se3 by transport measurements. © 2011 American Chemical Society.

  15. The distribution and degradation of radiolabeled superparamagnetic iron oxide nanoparticles and quantum dots in mice

    Directory of Open Access Journals (Sweden)

    Denise Bargheer

    2015-01-01

    Full Text Available 51Cr-labeled, superparamagnetic, iron oxide nanoparticles (51Cr-SPIOs and 65Zn-labeled CdSe/CdS/ZnS-quantum dots (65Zn-Qdots were prepared using an easy, on demand, exchange-labeling technique and their particokinetic parameters were studied in mice after intravenous injection. The results indicate that the application of these heterologous isotopes can be used to successfully mark the nanoparticles during initial distribution and organ uptake, although the 65Zn-label appeared not to be fully stable. As the degradation of the nanoparticles takes place, the individual transport mechanisms for the different isotopes must be carefully taken into account. Although this variation in transport paths can bring new insights with regard to the respective trace element homeostasis, it can also limit the relevance of such trace material-based approaches in nanobioscience. By monitoring 51Cr-SPIOs after oral gavage, the gastrointestinal non-absorption of intact SPIOs in a hydrophilic or lipophilic surrounding was measured in mice with such high sensitivity for the first time. After intravenous injection, polymer-coated, 65Zn-Qdots were mainly taken up by the liver and spleen, which was different from that of ionic 65ZnCl2. Following the label for 4 weeks, an indication of substantial degradation of the nanoparticles and the release of the label into the Zn pool was observed. Confocal microscopy of rat liver cryosections (prepared 2 h after intravenous injection of polymer-coated Qdots revealed a colocalization with markers for Kupffer cells and liver sinusoidal endothelial cells (LSEC, but not with hepatocytes. In J774 macrophages, fluorescent Qdots were found colocalized with lysosomal markers. After 24 h, no signs of degradation could be detected. However, after 12 weeks, no fluorescent nanoparticles could be detected in the liver cryosections, which would confirm our 65Zn data showing a substantial degradation of the polymer-coated CdSe/CdS/ZnS-Qdots in

  16. Trace concentrations of vitamin E protect radiation crosslinked UHMWPE from oxidative degradation.

    Science.gov (United States)

    Kurtz, S M; Dumbleton, J; Siskey, R S; Wang, A; Manley, M

    2009-08-01

    The effect of very low concentrations of Vitamin E on the stability and mechanical behavior of UHMWPE remains unknown. We tested the hypothesis that the oxidation resistance of Vitamin E-blended UHMWPE would be influenced by trace doses of antioxidant, resin, and radiation treatment. Trace concentrations (Vitamin E) were blended separately with GUR 1020 and 1050 resins and molded into disks. From each disk, three groups of 10 mm thick blocks were machined: (1) no irradiation (control); (2) 30 kGy of gamma irradiation in nitrogen; and (3) 75 kGy of gamma irradiation in air. Specimens were subjected to three aging protocols: (a) no aging (control); (b) two weeks and (c) four weeks of accelerated aging in accordance with ASTM F 2003 (i.e., 70 degrees C and 5 atm oxygen). The minimum concentration of Vitamin E needed to stabilize UHMWPE during our accelerated tests depended upon the method of radiation processing. For the 30 and 75 kGy irradiated materials, the addition of 125 ppm or more Vitamin E was sufficient to maintain baseline mechanical and chemical properties through two weeks of accelerated aging. For these groups, the addition of 375 ppm or 500 ppm, respectively, was necessary to maintain baseline mechanical and chemical properties throughout the four-week accelerated aging period. UHMWPE resin molecular weight did not have an effect on oxidation behavior. The results of this experiment therefore supported our hypotheses that trace concentrations of Vitamin E, coupled with radiation treatment-but not resin grade-influence the mechanical and oxidative degradation behavior of UHMWPE.

  17. Kinetics of imidazolium-based ionic liquids degradation in aqueous solution by Fenton oxidation.

    Science.gov (United States)

    Domínguez, Carmen M; Munoz, Macarena; Quintanilla, Asunción; de Pedro, Zahara M; Casas, Jose A

    2017-10-15

    In the last few years, several works dealing with Fenton oxidation of ionic liquids (ILs) have proved the capability of this technology for their degradation, achieving complete ILs removal and non-toxic effluents. Nevertheless, very little is known about the kinetics of this process, crucial for its potential application. In this work, the effect of several operating conditions, including reaction temperature (50-90 °C), catalyst load (10-50 mg L -1 Fe 3+ ), initial IL concentration (100-2000 mg L -1 ), and hydrogen peroxide dose (10-200% of the stoichiometric amount for the complete IL mineralization) on 1-butyl-3-methylimidazolium chloride ([C 4 mim]Cl) oxidation has been investigated. Under the optimum operating conditions (T = 90 °C; [Fe 3+ ] 0  = 50 mg L -1 ; [H 2 O 2 ] 0  = 100% of the stoichiometric amount), the complete removal of [C 4 mim]Cl (1000 mg L -1 ) was achieved at 1.5-min reaction time. From the experimental results, a potential kinetic model capable to describe the removal of imidazolium-based ILs by Fenton oxidation has been developed. By fitting the proposed model to the experimental data, the orders of the reaction with respect to IL initial concentration, Fe 3+ amount and H 2 O 2 dose were found to be close to 1, with an apparent activation energy of 43.3 kJ mol -1 . The model resulted in a reasonable fit within the wide range of operating conditions tested in this work.

  18. Degradation of organochloride pesticides by molten salt oxidation at IPEN: spin-off nuclear activities

    International Nuclear Information System (INIS)

    Lainetti, Paulo E.O.

    2013-01-01

    Nuclear spin-off has at least two dimensions. It may provide benefits to the society such as enlarge knowledge base, strengthen infrastructure and benefit technology development. Besides this, to emphasize that some useful technologies elapsed from nuclear activities can affect favorably the public opinion about nuclear energy. In this paper is described a technology developed initially by the Rockwell Int. company in the USA more than thirty years ago to solve some problems of nuclear fuel cycle wastes. For different reasons the technology was not employed. In the last years the interest in the technology was renewed and IPEN has developed his version of the method applicable mainly to the safe degradation of hazardous wastes. This study was motivated by the world interest in the development of advanced processes of waste decomposition, due to the need of safer decomposition processes, particularly for the POPs - persistent organic pollutants and particularly for the organ chlorides. A tendency observed at several countries is the adoption of progressively more demanding legislation for the atmospheric emissions, resultants of the waste decomposition processes. The suitable final disposal of hazardous organic wastes such as PCBs (polychlorinated biphenyls), pesticides, herbicides and hospital residues constitutes a serious problem. In some point of their life cycles, these wastes should be destroyed, in reason of the risk that they represent for the human being, animals and plants. The process involves using a chemical reactor containing molten salts, sodium carbonate or some alkaline carbonates mixtures to decompose the organic waste. The decomposition is performed by submerged oxidation and the residue is injected below the surface of a turbulent salt bath along with the oxidizing agent. Decomposition of halogenated compounds, among which some pesticides, is particularly effective in molten salts. The process presents properties such as intrinsically safe

  19. 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.

  20. 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.

  1. IRIS Toxicological Review of Benzo[a]pyrene (Interagency ...

    Science.gov (United States)

    In January 2017, EPA finalized the IRIS assessment of Benzo[a]pyrene. The Toxicological Review was reviewed internally by EPA and by other federal agencies and White House Offices before public release. Consistent with the May 2009 IRIS assessment development process, all written comments on IRIS assessments submitted by other federal agencies and White House Offices are made publicly available. Accordingly, interagency comments and the interagency science discussion materials provided to other agencies, including interagency review drafts of the IRIS Toxicological Review of Benzo[a]pyrene are posted on this site. EPA is undertaking an update of the Integrated Risk Information System (IRIS) health assessment for benzo[a]pyrene (BaP). The outcome of this project is an updated Toxicological Review and IRIS Summary for BaP that will be entered into the IRIS database.

  2. Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry

    CSIR Research Space (South Africa)

    Salehiyan, Reza

    2017-05-01

    Full Text Available Time-resolved mechanical spectroscopy (TRMS) was conducted to study the thermo-oxidative degradation of linear low density polyethylene (LLDPE) samples with different thermal histories and their blends with a polyamide (PA6) in the melt state. Neat...

  3. 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.

  4. 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

  5. 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.

  6. Distribution of apparent activation energy counterparts during thermo - And thermo-oxidative degradation of Aronia melanocarpa (black chokeberry).

    Science.gov (United States)

    Janković, Bojan; Marinović-Cincović, Milena; Janković, Marija

    2017-09-01

    Kinetics of degradation for Aronia melanocarpa fresh fruits in argon and air atmospheres were investigated. The investigation was based on probability distributions of apparent activation energy of counterparts (ε a ). Isoconversional analysis results indicated that the degradation process in an inert atmosphere was governed by decomposition reactions of esterified compounds. Also, based on same kinetics approach, it was assumed that in an air atmosphere, the primary compound in degradation pathways could be anthocyanins, which undergo rapid chemical reactions. A new model of reactivity demonstrated that, under inert atmospheres, expectation values for ε a occured at levels of statistical probability. These values corresponded to decomposition processes in which polyphenolic compounds might be involved. ε a values obeyed laws of binomial distribution. It was established that, for thermo-oxidative degradation, Poisson distribution represented a very successful approximation for ε a values where there was additional mechanistic complexity and the binomial distribution was no longer valid. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. 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.

  8. Electrolytic trichloroethene degradation using mixed metal oxide coated titanium mesh electrodes.

    Science.gov (United States)

    Petersen, Matthew A; Sale, Thomas C; Reardon, Kenneth F

    2007-04-01

    Electrochemical systems provide a low cost, versatile, and controllable platform to potentially treat contaminants in water, including chlorinated solvents. Relative to bare metal or noble metal amended materials, dimensionally stable electrode materials such as mixed metal oxide coated titanium (Ti/MMO) have advantages in terms of stability and cost, important factors for sustainable remediation solutions. Here, we report the use of Ti/MMO as an effective cathode substrate for treatment of trichloroethene (TCE). TCE degradation in a batch reactor was measured as the decrease of TCE concentration over time and the corresponding evolution of chloride; notably, this occurred without the formation of commonly encountered chlorinated intermediates. The reaction was initiated when Ti/MMO cathode potentials were less than -0.8 V vs. the standard hydrogen electrode, and the rate of TCE degradation increased linearly with progressively more negative potentials. The maximum pseudo-first-order heterogeneous rate constant was approximately 0.05 cm min(-1), which is comparable to more commonly used cathode materials such as nickel. In laboratory-scale flow-though column reactors designed to simulate permeable reactive barriers (PRBs), TCE concentrations were reduced by 80-90%. The extent of TCE flux reduction increased with the applied potential difference across the electrodes and was largely insensitive to the spacing distance between the electrodes. This is the first report of the electrochemical reduction of a chlorinated organic contaminant at a Ti/MMO cathode, and these results support the use of this material in PRBs as a possible approach to manage TCE plume migration.

  9. 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.

  10. 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.

  11. Leakage Current Degradation Due to Ion Drift and Diffusion in Tantalum and Niobium Oxide Capacitors

    Directory of Open Access Journals (Sweden)

    Kuparowitz Martin

    2017-06-01

    Full Text Available High temperature and high electric field applications in tantalum and niobium capacitors are limited by the mechanism of ion migration and field crystallization in a tantalum or niobium pentoxide insulating layer. The study of leakage current (DCL variation in time as a result of increasing temperature and electric field might provide information about the physical mechanism of degradation. The experiments were performed on tantalum and niobium oxide capacitors at temperatures of about 125°C and applied voltages ranging up to rated voltages of 35 V and 16 V for tantalum and niobium oxide capacitors, respectively. Homogeneous distribution of oxygen vacancies acting as positive ions within the pentoxide layer was assumed before the experiments. DCL vs. time characteristics at a fixed temperature have several phases. At the beginning of ageing the DCL increases exponentially with time. In this period ions in the insulating layer are being moved in the electric field by drift only. Due to that the concentration of ions near the cathode increases producing a positively charged region near the cathode. The electric field near the cathode increases and the potential barrier between the cathode and insulating layer decreases which results in increasing DCL. However, redistribution of positive ions in the insulator layer leads to creation of a ion concentration gradient which results in a gradual increase of the ion diffusion current in the direction opposite to the ion drift current component. The equilibrium between the two for a given temperature and electric field results in saturation of the leakage current value. DCL vs. time characteristics are described by the exponential stretched law. We found that during the initial part of ageing an exponent n = 1 applies. That corresponds to the ion drift motion only. After long-time application of the electric field at a high temperature the DCL vs. time characteristics are described by the exponential

  12. Smouldering Combustion of Soil Organic Matter: Inverse Modelling of the Thermal and Oxidative Degradation Kinetics

    Science.gov (United States)

    Huang, Xinyan; Rein, Guillermo

    2013-04-01

    Smouldering combustion of soil organic matter (SOM) such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this work, a kinetic model, including 3-step chemical reactions and 1-step water evaporation is proposed to describe drying, pyrolysis and oxidation behaviour of peat. Peat is chosen as the most important type of SOM susceptible to smoudering, and a Chinese boreal peat sample is selected from the literature. A lumped model of mass loss based on four Arrhenius-type reactions is developed to predict its thermal and oxidative degradation under a range of heating rates. A genetic algorithm is used to solve the inverse problem, and find a group of kinetic and stoichiometric parameters for this peat that provides the best match to the thermogravimetric (TG) data from literature. A multi-objective fitness function is defined using the measurements of both mass loss and mass-loss rate in inert and normal atmospheres under a range of heating rates. Piece-wise optimization is conducted to separate the low temperature drying (450 K). Modelling results shows the proposed 3-step chemistry is the unique simplest scheme to satisfy all given TG data of this particular peat type. Afterward, this kinetic model and its kinetic parameters are incorporated into a simple one-dimensional species model to study the relative position of each reaction inside a smoulder front. Computational results show that the species model agrees with experimental observations. This is the first time that the smouldering kinetics of SOM is explained and predicted, thus helping to understanding this important natural and widespread phenomenon.

  13. Quantitative assessment on the contribution of direct photolysis and radical oxidation in photochemical degradation of 4-chlorophenol and oxytetracycline.

    Science.gov (United States)

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

    2016-07-01

    In UV-254 nm/H2O2 advanced oxidation process (AOP), the potential degradation pathways for organic pollutants include (1) hydrolysis, (2) direct H2O2 oxidation, (3) UV direct photolysis, and (4) hydroxyl radical (HO(•)) reaction. In this study, the contribution of these pathways was quantitatively assessed in the photochemical destruction of 4-chlorophenol (4-CP), demonstrating pathways (3) and (4) to be predominantly responsible for the removal of 4-CP by UV/H2O2 in 50 mM phosphate buffer solution. Increasing reaction pH could significantly enhance the contribution of direct photolysis in UV/H2O2 process. The contribution of HO(•) oxidation was improved with increasing initial H2O2 concentration probably due to the increased formation of HO(•). Presence of sodium carbonate (Na2CO3) as in UV/H2O2/Na2CO3 system promoted the degradation of 4-CP, with carbonate radical (CO3 (•-)) reaction and direct photolysis identified to be the main contributing pathways. The trends in the contribution of each factor were further evaluated and validated on the degradation of the antibiotic compound oxytetracycline (OTC). This study provides valuable information on the relative importance of different reaction pathways on the photochemical degradation of organic contaminants such as 4-CP and OTC in the presence and absence of a CO3 (•-) precursor.

  14. The anthocyanidin delphinidin mobilizes endogenous copper ions from human lymphocytes leading to oxidative degradation of cellular DNA

    International Nuclear Information System (INIS)

    Hanif, Sarmad; Shamim, Uzma; Ullah, M.F.; Azmi, Asfar S.; Bhat, Showket H.; Hadi, S.M.

    2008-01-01

    Epidemiological and experimental evidence exists to suggest that pomegranate and its juice possess chemopreventive and anticancer properties. The anthocyanidin delphinidin is a major polyphenol present in pomegranates and has been shown to be responsible for these effects. Plant polyphenols are recognized as naturally occurring antioxidants but also catalyze oxidative DNA degradation of cellular DNA either alone or in the presence of transition metal ions such as copper. In this paper we show that similar to various other classes of polyphenols, delphinidin is also capable of causing oxidative degradation of cellular DNA. Lymphocytes were exposed to various concentrations of delphinidin (10, 20, 50 μM) for 1 h and the DNA breakage was assessed using single cell alkaline gel electrophoresis (Comet assay). Inhibition of DNA breakage by several scavengers of reactive oxygen species (ROS) indicated that it is caused by the formation of ROS. Incubation of lymphocytes with neocuproine (a cell membrane permeable Cu(I) chelator) inhibited DNA degradation in intact lymphocytes in a dose dependent manner. Bathocuproine, which is unable to permeate through the cell membrane, did not cause such inhibition. We have further shown that delphinidin is able to degrade DNA in cell nuclei and that such DNA degradation is also inhibited by neocuproine suggesting that nuclear copper is mobilized in this reaction. These results indicate that the generation of ROS possibly occurs through mobilization of endogenous copper ions. The results are in support of our hypothesis that the prooxidant activity of plant polyphenols may be an important mechanism for their anticancer properties

  15. Comparative Study of Commercial Oxide Electrodes Performance in Electrochemical Degradation of Organics in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Pelegrino Rosângela L.

    2002-01-01

    Full Text Available In this paper the potentiality of two types of DSAâ commercial electrodes, for electrochemical treatment of effluents, is investigated. Oxide anodes, with nominal composition of 70TiO2/30RuO2 and 45IrO2/55Ta2O5, were used in a flow-cell reactor for the electrooxidation of phenol. Comparative results were presented as phenol concentration decay as a function of electrolysis time, as well as COD and TOC concentration reduction. The cell reactor was operated at current densities, ranging from 15 to 150 mA cm-2 and solution linear velocity was 0.24 m s-1. Results reported in this paper showed that phenol and quinones were degraded to a very low concentration, besides only a small portion of the organic carbon is reduced. Starting from 100 mg L-1, after five hours of electrolysis at 100 mA cm-2, concentrations reached 0.4 mg L-1 of phenol, 1 mg L-1 of hydroquinone, 7 mg L-1 of benzoquinone and TOC was reduced by 35%.

  16. Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

    KAUST Repository

    Croissant, Jonas G.; Fatieiev, Yevhen; Khashab, Niveen M.

    2017-01-01

    The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous

  17. 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).

  18. 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.

  19. Performance and long term degradation of 7 W micro-tubular solid oxide fuel cells for portable applications

    Science.gov (United States)

    Torrell, M.; Morata, A.; Kayser, P.; Kendall, M.; Kendall, K.; Tarancón, A.

    2015-07-01

    Micro-tubular SOFCs have shown an astonishing thermal shock resistance, many orders of magnitude larger than planar SOFCs, opening the possibility of being used in portable applications. However, only few studies have been devoted to study the degradation of large-area micro-tubular SOFCs. This work presents microstructural, electrochemical and long term degradation studies of single micro-tubular cells fabricated by high shear extrusion, operating in the intermediate range of temperatures (T∼700 °C). A maximum power of 7 W per cell has been measured in a wide range of fuel utilizations between 10% and 60% at 700 °C. A degradation rate of 360 mW/1000 h (8%) has been observed for cells operated over more than 1500 h under fuel utilizations of 40%. Higher fuel utilizations lead to strong degradations associated to nickel oxidation/reduction processes. Quick thermal cycling with heating ramp rates of 30 °C /min yielded degradation rates of 440 mW/100 cycles (9%). These reasonable values of degradation under continuous and thermal cycling operation approach the requirements for many portable applications including auxiliary power units or consumer electronics opening this typically forbidden market to the SOFC technology.

  20. 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

  1. Oxidative modifications, mitochondrial dysfunction, and impaired protein degradation in Parkinson's disease: how neurons are lost in the Bermuda triangle

    Directory of Open Access Journals (Sweden)

    Malkus Kristen A

    2009-06-01

    Full Text Available Abstract While numerous hypotheses have been proposed to explain the molecular mechanisms underlying the pathogenesis of neurodegenerative diseases, the theory of oxidative stress has received considerable support. Although many correlations have been established and encouraging evidence has been obtained, conclusive proof of causation for the oxidative stress hypothesis is lacking and potential cures have not emerged. Therefore it is likely that other factors, possibly in coordination with oxidative stress, contribute to neuron death. Using Parkinson's disease (PD as the paradigm, this review explores the hypothesis that oxidative modifications, mitochondrial functional disruption, and impairment of protein degradation constitute three interrelated molecular pathways that execute neuron death. These intertwined events are the consequence of environmental exposure, genetic factors, and endogenous risks and constitute a "Bermuda triangle" that may be considered the underlying cause of neurodegenerative pathogenesis.

  2. Benzo[a]pyrene in urban environments of eastern Moscow: pollution levels and critical loads

    Science.gov (United States)

    Kasimov, Nikolay S.; Kosheleva, Natalia E.; Nikiforova, Elena M.; Vlasov, Dmitry V.

    2017-02-01

    Polycyclic aromatic hydrocarbons (PAHs), particularly benzo[a]pyrene (BaP), are toxic compounds emitted from various anthropogenic sources. Understanding the BaP concentrations, dynamics and decomposition in soil is required to assess the critical loads of BaP in urban environments. This study is the first attempt to evaluate all major input and output components of benzo[a]pyrene (BaP) balance and to calculate the permissible load on the urban environment in different land-use zones in the Eastern district of Moscow. BaP contamination of the snow cover in the Eastern district of Moscow was related to daily BaP fallout from the atmosphere. In 2010, the mean content of the pollutant in the snow dust was 1942 ng g-1, whereas the average intensity of its fallout was 7.13 ng m-2 per day. Across the territory, BaP winter fallout intensities varied from 0.3 to 1100 ng m-2 per day. The average BaP content in the surface (0-10 cm) soil horizons was 409 ng g-1, which is 83 times higher than the local background value and 20 times higher than the maximum permissible concentration (MPC) accepted in Russia. The variations in soil and snow BaP concentrations among different land-use zones were examined. A significant contribution of BaP from the atmosphere to urban soils was identified. Based on the measurements of BaP atmospheric fallout and BaP reserves in the soils, the critical loads of BaP for the land-use zones in the Eastern district were calculated for different values of degradation intensity and different exposure times. It was established that at an annual degradation intensity of 1-10 %, ecologically safe BaP levels in the soils of all land-use zones, excluding the agricultural zone, will only be reached after many decades or centuries.

  3. Electrochemistry coupled to (LC-)MS for the simulation of oxidative biotransformation reactions of PAHs.

    Science.gov (United States)

    Wigger, Tina; Seidel, Albrecht; Karst, Uwe

    2017-06-01

    Electrochemistry coupled to liquid chromatography and mass spectrometry was used for simulating the biological and environmental fate of polycyclic aromatic hydrocarbons (PAHs) as well as for studying the PAH degradation behavior during electrochemical remediation. Pyrene and benzo[a]pyrene were selected as model compounds and oxidized within an electrochemical thin-layer cell equipped with boron-doped diamond electrode. At potentials of 1.2 and 1.6 V vs. Pd/H 2 , quinones were found to be the major oxidation products for both investigated PAHs. These quinones belong to a large group of PAH derivatives referred to as oxygenated PAHs, which have gained increasing attention in recent years due to their high abundance in the environment and their significant toxicity. Separation of oxidation products allowed the identification of two pyrene quinone and three benzo[a]pyrene quinone isomers, all of which are known to be formed via photooxidation and during mammalian metabolism. The good correlation between electrochemically generated PAH quinones and those formed in natural processes was also confirmed by UV irradiation experiments and microsomal incubations. At potentials higher than 2.0 V, further degradation of the initial oxidation products was observed which highlights the capability of electrochemistry to be used as remediation technique. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. 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.

  5. 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

  6. 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.

  7. Photo oxidative degradation of azure-B by sono-photo-Fenton and photo-Fenton reagents

    Directory of Open Access Journals (Sweden)

    Prahlad Vaishnave

    2014-12-01

    Full Text Available A model for the decomposition of azure-B by photo-Fenton reagent in the presence of ultrasound in homogeneous aqueous solution has been described. The photochemical decomposition rate of azure-B is markedly increased in the presence of ultrasound. It is a rather inexpensive reagent for wastewater treatment. The effect of different variables like the concentration of ferric ion, concentration of dye, hydrogen peroxide, pH, light intensity etc. on the reaction rate has been observed. The progress of the sono-photochemical degradation was monitored spectrophotometrically. The optimum sono-photochemical degradation conditions were experimentally determined. The results showed that the dye was completely oxidized and degraded into CO2 and H2O. A suitable tentative mechanism for sono-photochemical bleaching of azure-B by sono-photo-Fenton’s reaction has been proposed.

  8. 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.

  9. In vitro degradation of nanoparticles prepared from polymers based on DL-lactide, glycolide and poly(ethylene oxide)

    NARCIS (Netherlands)

    Zweers, M.L.T.; Engbers, G.H.M.; Grijpma, Dirk W.; Feijen, Jan

    2004-01-01

    Nanoparticles of poly(DL-lactic acid) (PDLLA), poly(DL-lactic-co-glycolic acid) (PLGA) and poly(ethylene oxide)–PLGA diblock copolymer (PEO–PLGA) were prepared by the salting-out method. The in vitro degradation of PDLLA, PLGA and PEO–PLGA nanoparticles in PBS (pH 7.4) at 37 °C was studied. The

  10. Degradation mechanism of alachlor during direct ozonation and O(3)/H(2)O(2) advanced oxidation process.

    Science.gov (United States)

    Qiang, Zhimin; Liu, Chao; Dong, Bingzhi; Zhang, Yalei

    2010-01-01

    The degradation of alachlor by direct ozonation and advanced oxidation process O(3)/H(2)O(2) was investigated in this study with focus on identification of degradation byproducts. The second-order reaction rate constant between ozone and alachlor was determined to be 2.5+/-0.1M(-1)s(-1) at pH 7.0 and 20 degrees C. Twelve and eight high-molecular-weight byproducts (with the benzene ring intact) from alachlor degradation were identified during direct ozonation and O(3)/H(2)O(2), respectively. The common degradation byproducts included N-(2,6-diethylphenyl)-methyleneamine, 8-ethyl-3,4-dihydro-quinoline, 8-ethyl-quinoline, 1-chloroacetyl-2-hydro-3-ketone-7-acetyl-indole, 2-chloro-2',6'-diacetyl-N-(methoxymethyl)acetanilide, 2-chloro-2'-acetyl-6'-ethyl-N-(methoxymethyl)-acetanilide, and two hydroxylated alachlor isomers. In direct ozonation, four more byproducts were also identified including 1-chloroacetyl-2,3-dihydro-7-ethyl-indole, 2-chloro-2',6'-ethyl-acetanilide, 2-chloro-2',6'-acetyl-acetanilide and 2-chloro-2'-ethyl-6'-acetyl-N-(methoxymethyl)-acetanilide. Degradation of alachlor by O(3) and O(3)/H(2)O(2) also led to the formation of low-molecular-weight byproducts including formic, acetic, propionic, monochloroacetic and oxalic acids as well as chloride ion (only detected in O(3)/H(2)O(2)). Nitrite and nitrate formation was negligible. Alachlor degradation occurred via oxidation of the arylethyl group, N-dealkylation, cyclization and cleavage of benzene ring. After O(3) or O(3)/H(2)O(2) treatment, the toxicity of alachlor solution examined by the Daphnia magna bioassay was slightly reduced. 2009 Elsevier Ltd. All rights reserved.

  11. Fundamental degradation mechanisms of layered oxide Li-ion battery cathode materials: Methodology, insights and novel approaches

    International Nuclear Information System (INIS)

    Hausbrand, R.; Cherkashinin, G.; Ehrenberg, H.; Gröting, M.; Albe, K.; Hess, C.; Jaegermann, W.

    2015-01-01

    Graphical abstract: - Highlights: • Description of recent in operando and in situ analysis methodology. • Surface science approach using photoemission for analysis of cathode surfaces and interfaces. • Ageing and fatigue of layered oxide Li-ion battery cathode materials from the atomistic point of view. • Defect formation and electronic structure evolution as causes for cathode degradation. • Significance of interfacial energy alignment and contact potential for side reactions. - Abstract: This overview addresses the atomistic aspects of degradation of layered LiMO 2 (M = Ni, Co, Mn) oxide Li-ion battery cathode materials, aiming to shed light on the fundamental degradation mechanisms especially inside active cathode materials and at their interfaces. It includes recent results obtained by novel in situ/in operando diffraction methods, modelling, and quasi in situ surface science analysis. Degradation of the active cathode material occurs upon overcharge, resulting from a positive potential shift of the anode. Oxygen loss and eventual phase transformation resulting in dead regions are ascribed to changes in electronic structure and defect formation. The anode potential shift results from loss of free lithium due to side reactions occurring at electrode/electrolyte interfaces. Such side reactions are caused by electron transfer, and depend on the electron energy level alignment at the interface. Side reactions at electrode/electrolyte interfaces and capacity fade may be overcome by the use of suitable solid-state electrolytes and Li-containing anodes

  12. 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.

  13. 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'.

  14. 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.

  15. 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.

  16. 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.

  17. 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

    The overarching goal of this research program has been to evaluate the potential impacts of coal-derived syngas and high-hydrogen content fuels on the degradation of turbine hot-section components through attack of protective oxides and thermal barrier coatings. The primary focus of this research program has been to explore mechanisms underpinning the observed degradation processes, and connections to the combustion environments and characteristic non-combustible constituents. Based on the mechanistic understanding of how these emerging fuel streams affect materials degradation, the ultimate goal of the program is to advance the goals of the Advanced Turbine Program by developing materials design protocols leading to turbine hot-section components with improved resistance to service lifetime degradation under advanced fuels exposures. This research program has been focused on studying how: (1) differing combustion environments – relative to traditional natural gas fired systems – affect both the growth rate of thermally grown oxide (TGO) layers and the stability of these oxides and of protective thermal barrier coatings (TBCs); and (2) how low levels of fuel impurities and characteristic non-combustibles interact with surface oxides, for instance through the development of molten deposits that lead to hot corrosion of protective TBC coatings. The overall program has been comprised of six inter-related themes, each comprising a research thrust over the program period, including: (i) evaluating the role of syngas and high hydrogen content (HHC) combustion environments in modifying component surface temperatures, heat transfer to the TBC coatings, and thermal gradients within these coatings; (ii) understanding the instability of TBC coatings in the syngas and high hydrogen environment with regards to decomposition, phase changes and sintering; (iii) characterizing ash deposition, molten phase development and infiltration, and associated corrosive

  18. Analysis of hydroxycinnamic acid degradation in Agrobacterium fabrum reveals a coenzyme A-dependent, beta-oxidative deacetylation pathway.

    Science.gov (United States)

    Campillo, Tony; Renoud, Sébastien; Kerzaon, Isabelle; Vial, Ludovic; Baude, Jessica; Gaillard, Vincent; Bellvert, Floriant; Chamignon, Cécile; Comte, Gilles; Nesme, Xavier; Lavire, Céline; Hommais, Florence

    2014-06-01

    The soil- and rhizosphere-inhabiting bacterium Agrobacterium fabrum (genomospecies G8 of the Agrobacterium tumefaciens species complex) is known to have species-specific genes involved in ferulic acid degradation. Here, we characterized, by genetic and analytical means, intermediates of degradation as feruloyl coenzyme A (feruloyl-CoA), 4-hydroxy-3-methoxyphenyl-β-hydroxypropionyl-CoA, 4-hydroxy-3-methoxyphenyl-β-ketopropionyl-CoA, vanillic acid, and protocatechuic acid. The genes atu1416, atu1417, and atu1420 have been experimentally shown to be necessary for the degradation of ferulic acid. Moreover, the genes atu1415 and atu1421 have been experimentally demonstrated to be essential for this degradation and are proposed to encode a phenylhydroxypropionyl-CoA dehydrogenase and a 4-hydroxy-3-methoxyphenyl-β-ketopropionic acid (HMPKP)-CoA β-keto-thiolase, respectively. We thus demonstrated that the A. fabrum hydroxycinnamic degradation pathway is an original coenzyme A-dependent β-oxidative deacetylation that could also transform p-coumaric and caffeic acids. Finally, we showed that this pathway enables the metabolism of toxic compounds from plants and their use for growth, likely providing the species an ecological advantage in hydroxycinnamic-rich environments, such as plant roots or decaying plant materials.

  19. A study into the impact of interface roughness development on mechanical degradation of oxides formed on zirconium alloys

    International Nuclear Information System (INIS)

    Platt, P.; Wedge, S.; Frankel, P.; Gass, M.; Howells, R.; Preuss, M.

    2015-01-01

    As a cladding material used to encapsulate nuclear fuel pellets, zirconium alloys are the primary barrier separating the fuel and a pressurised steam or lithiated water environment. Degradation mechanisms such as oxidation can be the limiting factor in the life-time of the fuel assembly. Key to controlling oxidation, and therefore allowing increased burn-up of fuel, is the development of a mechanistic understanding of the corrosion process. In an autoclave, the oxidation kinetics for zirconium alloys are typically cyclical, with periods of accelerated kinetics being observed in steps of ∼2 μm oxide growth. These periods of accelerated oxidation are immediately preceded by the development of a layer of lateral cracks near the metal-oxide interface, which may be associated with the development of interface roughness. The present work uses scanning electron microscopy to carry out a statistical analysis of changes in the metal-oxide interface roughness between three different alloys at different stages of autoclave oxidation. The first two alloys are Zircaloy-4 and ZIRLO ™ for which analysis is carried out at stages before, during and after first transition. The third alloy is an experimental low tin alloy, which under the same oxidation conditions and during the same time period does not appear to go through transition. Assessment of the metal-oxide interface roughness is primarily carried out based on the root mean square of the interface slope known as the R dq parameter. Results show clear trends with relation to transition points in the corrosion kinetics. Discussion is given to how this relates to the existing mechanistic understanding of the corrosion process, and the components required for possible future modelling approaches

  20. Application of Fenton's reagent as a pretreatment step in biological degradation of polyaromatic hydrocarbons

    International Nuclear Information System (INIS)

    Kelley, R.L.; Gauger, W.K.; Srivastava, V.J.

    1991-01-01

    Fenton's reagent (H 2 O 2 and Fe ++ ) has been used for chemical oxidation of numerous organic compounds in water treatment schemes. In this study, the Institute of Gas Technology (IGT) applied Fenton's treatment to polynuclear aromatic hydrocarbons (PAHs) and PAH-contaminated soils. Fenton's treatment was very reactive with PAHs, causing rapid modification of the parental compounds to oxidized products and complete degradation to CO 2 . This treatment was more effective on chemically reactive PAHs, such as benzo(a)pyrene and phenanthrene. Important parameters and conditions for Fenton's treatment of PAHs in solution and soil matrices have been identified. As much as 99% of the PAHs on soil matrices can be removed by treatment with Fenton's reagent

  1. Microbial degradation of high impact polystyrene (HIPS), an e-plastic with decabromodiphenyl oxide and antimony trioxide

    International Nuclear Information System (INIS)

    Sekhar, Vini C.; Nampoothiri, K. Madhavan; Mohan, Arya J.; Nair, Nimisha R.; Bhaskar, Thallada; Pandey, Ashok

    2016-01-01

    Highlights: • Biodegradation of a high impact polystyrene e − plastic. • 12.4% (w/w) e plastic film lost using an isolate, Enterobacter sp. • Noted changes in the physico-chemical characteristics of degraded e-plastic film. • Polystyrene intermediates were detected in the degradation medium. • e-plastic degrading microbes displayed extracellular depolymerase activity. - Abstract: Accumulation of electronic waste has increased catastrophically and out of that various plastic resins constitute one of the leading thrown out materials in the electronic machinery. Enrichment medium, containing high impact polystyrene (HIPS) with decabromodiphenyl oxide and antimony trioxide as sole carbon source, was used to isolate microbial cultures. The viability of these cultures in the e-plastic containing mineral medium was further confirmed by triphenyl tetrazolium chloride (TTC) reduction test. Four cultures were identified by 16S rRNA sequencing as Enterobacter sp., Citrobacter sedlakii, Alcaligenes sp. and Brevundimonas diminuta. Biodegradation experiments were carried out in flask level and gelatin supplementation (0.1% w/v) along with HIPS had increased the degradation rate to a maximum of 12.4% (w/w) within 30 days. This is the first report for this kind of material. The comparison of FTIR, NMR, and TGA analysis of original and degraded e-plastic films revealed structural changes under microbial treatment. Polystyrene degradation intermediates in the culture supernatant were also detected using HPLC analysis. The gravity of biodegradation was validated by morphological changes under scanning electron microscope. All isolates displayed depolymerase activity to substantiate enzymatic degradation of e-plastic.

  2. Microbial degradation of high impact polystyrene (HIPS), an e-plastic with decabromodiphenyl oxide and antimony trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Sekhar, Vini C. [Biotechnology Division, CSIR-National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019, Kerala (India); Nampoothiri, K. Madhavan, E-mail: madhavan85@hotmail.com [Biotechnology Division, CSIR-National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019, Kerala (India); Mohan, Arya J.; Nair, Nimisha R. [Biotechnology Division, CSIR-National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019, Kerala (India); Bhaskar, Thallada [Bio-Fuels Division (BFD), CSIR-Indian Institute of Petroleum (IIP), Dehradun, Uttarakhand 248005 (India); Pandey, Ashok [Biotechnology Division, CSIR-National Institute for Interdisciplinary Science and Technology (NIIST), Trivandrum 695 019, Kerala (India)

    2016-11-15

    Highlights: • Biodegradation of a high impact polystyrene e − plastic. • 12.4% (w/w) e plastic film lost using an isolate, Enterobacter sp. • Noted changes in the physico-chemical characteristics of degraded e-plastic film. • Polystyrene intermediates were detected in the degradation medium. • e-plastic degrading microbes displayed extracellular depolymerase activity. - Abstract: Accumulation of electronic waste has increased catastrophically and out of that various plastic resins constitute one of the leading thrown out materials in the electronic machinery. Enrichment medium, containing high impact polystyrene (HIPS) with decabromodiphenyl oxide and antimony trioxide as sole carbon source, was used to isolate microbial cultures. The viability of these cultures in the e-plastic containing mineral medium was further confirmed by triphenyl tetrazolium chloride (TTC) reduction test. Four cultures were identified by 16S rRNA sequencing as Enterobacter sp., Citrobacter sedlakii, Alcaligenes sp. and Brevundimonas diminuta. Biodegradation experiments were carried out in flask level and gelatin supplementation (0.1% w/v) along with HIPS had increased the degradation rate to a maximum of 12.4% (w/w) within 30 days. This is the first report for this kind of material. The comparison of FTIR, NMR, and TGA analysis of original and degraded e-plastic films revealed structural changes under microbial treatment. Polystyrene degradation intermediates in the culture supernatant were also detected using HPLC analysis. The gravity of biodegradation was validated by morphological changes under scanning electron microscope. All isolates displayed depolymerase activity to substantiate enzymatic degradation of e-plastic.

  3. 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.

  4. Synthesize of Graphene-Tin Oxide Nanocomposite and Its Photocatalytic Properties for the Degradation of Organic Pollutants Under Visible Light.

    Science.gov (United States)

    Shanmugam, M; Jayavel, R

    2015-09-01

    Graphene-tinoxide nanocomposite has been synthesised by coating SnO2 nanoparticles on graphene sheets by the redox reaction between graphene oxide (GO) and tin chloride. Graphene oxide was reduced to graphene and Sn2+ was oxidized to SnO2 during the redox reaction, resulting in the uniform distribution of SnO2 nanoparticles on graphene sheets. The synthesised material was characterized by XRD, SEM, AFM, FT-IR, UV-vis, TGA and Raman spectroscopic studies. SEM and AFM studies reveal the formation of wrinkled paper like structure of graphene sheets with uniform coating of SnO2 nanoparticles on either side. The strong photocatalytic degradation of Methylene orange (MO) dye was analysed using G-SnO2 nanocomposite under the visible light irradiation.

  5. 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.

  6. 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

  7. Enhanced photocatalytic performance and degradation pathway of Rhodamine B over hierarchical double-shelled zinc nickel oxide hollow sphere heterojunction

    Science.gov (United States)

    Zhang, Ying; Zhou, Jiabin; Cai, Weiquan; Zhou, Jun; Li, Zhen

    2018-02-01

    In this study, hierarchical double-shelled NiO/ZnO hollow spheres heterojunction were prepared by calcination of the metallic organic frameworks (MOFs) as a sacrificial template in air via a one-step solvothermal method. Additionally, the photocatalytic activity of the as-prepared samples for the degradation of Rhodamine B (RhB) under UV-vis light irradiation were also investigated. NiO/ZnO microsphere comprised a core and a shell with unique hierarchically porous structure. The photocatalytic results showed that NiO/ZnO hollow spheres exhibited excellent catalytic activity for RhB degradation, causing complete decomposition of RhB (200 mL of 10 g/L) under UV-vis light irradiation within 3 h. Furthermore, the degradation pathway was proposed on the basis of the intermediates during the photodegradation process using liquid chromatography analysis coupled with mass spectroscopy (LC-MS). The improvement in photocatalytic performance could be attributed to the p-n heterojunction in the NiO/ZnO hollow spheres with hierarchically porous structure and the strong double-shell binding interaction, which enhances adsorption of the dye molecules on the catalyst surface and facilitates the electron/hole transfer within the framework. The degradation mechanism of pollutant is ascribed to the hydroxyl radicals (rad OH), which is the main oxidative species for the photocatalytic degradation of RhB. This work provides a facile and effective approach for the fabrication of porous metal oxides heterojunction with high photocatalytic activity and thus can be potentially used in the environmental purification.

  8. 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.

  9. Microstructure and oxidative degradation behavior of silicon carbide fiber Hi-Nicalon type S

    International Nuclear Information System (INIS)

    Takeda, M.; Urano, A.; Sakamoto, J.; Imai, Y.

    1998-01-01

    Polycarbosilane-derived SiC fibers, Nicalon, Hi-Nicalon, and Hi-Nicalon type S were exposed for 1 to 100 h at 1273-1773 K in air. Oxide layer growth and tensile strength change of these fibers were examined after the oxidation test. As a result, three types of SiC fibers decreased their strength as oxide layer thickness increased. Fracture origins were determined at near the oxide layer-fiber interface. Adhered fibers arised from softening of silicon oxide at high temperature were also observed. In this study, Hi-Nicalon type S showed better oxidation resistance than other polycarbosilane-derived SiC fibers after 1673 K or higher temperature exposure in air for 10 h. This result was explained by the poreless silicon oxide layer structure of Hi-Nicalon type S. (orig.)

  10. Field solar degradation of pesticides and emerging water contaminants mediated by polymer films containing titanium and iron oxide with synergistic heterogeneous photocatalytic activity at neutral pH.

    Science.gov (United States)

    Mazille, F; Schoettl, T; Klamerth, N; Malato, S; Pulgarin, C

    2010-05-01

    Photocatalytic degradation of phenol, nalidixic acid, mixture of pesticides, and another of emerging contaminants in water was mediated by TiO(2) and iron oxide immobilized on functionalized polyvinyl fluoride films (PVF(f)-TiO(2)-Fe oxide) in a compound parabolic collector (CPC) solar photoreactor. During degradation, little iron leaching (compounds and less efficient for six other compounds. The significant reactivity differences between tested compounds were assigned to the differences in structure namely that the presence of complexing or chelating groups enhanced the rates. PVF(f)-TiO(2)-Fe oxide photoactivity gradually increased during 20 days of experiments. X-ray photoelectron spectroscopy (XPS) measurements revealed significant changes on the catalyst surface. These analyses confirm that during photocatalysis mediated by PVF(f)-TiO(2)-Fe oxide, some iron leaching led to enlargement of the TiO(2) surface exposed to light, increasing its synergy with iron oxides and leading to enhanced pollutant degradation.

  11. Degradation of di-2-ethylhexyl phthalate in aqueous solution by advanced oxidation process

    Directory of Open Access Journals (Sweden)

    Maryam Zarean

    2015-01-01

    Conclusion: It could be found that the UV/O3 process is a method for DEHP degradation in aqueous solution and may be recommended as a supplement with other processes for treatment of solutions containing low DEHP concentrations.

  12. 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).

  13. Sulfate radical-induced degradation of Acid Orange 7 by a new magnetic composite catalyzed peroxymonosulfate oxidation process.

    Science.gov (United States)

    Chen, Dan; Ma, Xiaolong; Zhou, Jizhi; Chen, Xi; Qian, Guangren

    2014-08-30

    We synthesized a novel magnetic composite, Fe3O4/Cu(Ni)Cr-LDH, as a heterogeneous catalyst for the degradation of organic dyes in the solution using sulfate radical-based advanced oxidation processes. The physicochemical properties of the composite synthesized via two-step microwave hydrothermal method were characterized by several techniques, such as X-ray diffraction (XRD), inductively coupled plasma (ICP), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The degradation tests were performed at 25°C with Acid Orange 7 (AO7) initial concentration of 25mg/L and AO7/peroxymonosulfate (PMS) molar ratio of 1:10, which showed that the complete degradation by Fe3O4/Cu1.5Ni0.5Cr-LDH could be achieved and the mineralization rate could reach 46%. PMS was activated by Cu (II) and Fe (II/III) of Fe3O4/Cu(Ni)Cr-LDH to generate sulfate radicals (SO4(-)). Subsequently, the organic functional groups of AO7 molecules were destroyed by sulfate radicals (SO4(-)), inducing the degradation of AO7. Moreover, the catalytic behavior of the catalysts could be reused five times. Therefore, our work suggested that the Fe3O4/Cu(Ni)Cr-LDH composite could be applied widely for the treatment of organic dyes in wastewater. Copyright © 2014. Published by Elsevier B.V.

  14. Multiscale Transient and Steady-State Study of the Influence of Microstructure Degradation and Chromium Oxide Poisoning on Solid Oxide Fuel Cell Cathode Performance

    Science.gov (United States)

    Li, Guanchen; von Spakovsky, Michael R.; Shen, Fengyu; Lu, Kathy

    2018-01-01

    Oxygen reduction in a solid oxide fuel cell cathode involves a nonequilibrium process of coupled mass and heat diffusion and electrochemical and chemical reactions. These phenomena occur at multiple temporal and spatial scales, making the modeling, especially in the transient regime, very difficult. Nonetheless, multiscale models are needed to improve the understanding of oxygen reduction and guide cathode design. Of particular importance for long-term operation are microstructure degradation and chromium oxide poisoning both of which degrade cathode performance. Existing methods are phenomenological or empirical in nature and their application limited to the continuum realm with quantum effects not captured. In contrast, steepest-entropy-ascent quantum thermodynamics can be used to model nonequilibrium processes (even those far-from equilibrium) at all scales. The nonequilibrium relaxation is characterized by entropy generation, which can unify coupled phenomena into one framework to model transient and steady behavior. The results reveal the effects on performance of the different timescales of the varied phenomena involved and their coupling. Results are included here for the effects of chromium oxide concentrations on cathode output as is a parametric study of the effects of interconnect-three-phase-boundary length, oxygen mean free path, and adsorption site effectiveness. A qualitative comparison with experimental results is made.

  15. 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.

  16. Electrochemical degradation of Novacron Yellow C-RG using boron-doped diamond and platinum anodes: Direct and Indirect oxidation

    International Nuclear Information System (INIS)

    Rocha, J.H. Bezerra; Gomes, M.M. Soares; Santos, E. Vieira dos; Moura, E.C. Martins de; Silva, D. Ribeiro da; Quiroz, M.A.; Martínez-Huitle, C.A.

    2014-01-01

    Graphical abstract: - Highlights: • Nature of electrode material decides the electrocatalytic mechanism followed. • Electrogenerated strong oxidants on BDD surface improve the color and organic load removal. • Chlorine active species act in solution cage oxidizing organic matter. - Abstract: The present study discusses the electrochemical degradation process of a textile dye, Novacron Yellow C-RG (NY), dissolved in synthetic wastewaters, via direct and indirect oxidation. Experiments were conducted using boron-doped diamond (BDD) and platinum supported on Ti (Pt/Ti) electrodes in the absence and presence of NaCl in the solution. The direct process for removing color is relatively similar for both anodes, while the electrochemical degradation is significantly accelerated by the presence of halogen salt in the solution. Interestingly, it does not depend on applied current density, but rather on NaCl concentration. Therefore, the electrochemical processes (direct/indirect) favor specific oxidation pathways depending on electrocatalytic material. Whereas, the Pt/Ti anode favors preferentially color removal by direct and indirect oxidation (100% of color removal) due to the fragmentation of the azo dye group; BDD electrode favors color and organic load removals in both processes (95% and up to 87%, respectively), due to the rupture of dye in different parts of its chemical structure. Parameters of removal efficiency and energy consumption for the electrochemical process were estimated. Finally, an explanation has been attempted for the role of halide, in relation with the oxygen evolution reaction, concomitant with the electrochemical incineration as well as electrocatalytic mechanisms, for each one of the electrodes used

  17. 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.

  18. Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water

    International Nuclear Information System (INIS)

    Ma, Wei; Zong, Panpan; Cheng, Zihong; Wang, Baodong; Sun, Qi

    2014-01-01

    Highlights: • Biomass and fly ash which were widespread for adsorption of heavy metal ions. • Preparation of catalyst by saturated adsorbents for 2-chlorophenol ozone degradation. • This work demonstrated that the O 3 /catalyst process was an effective pathway. • The use of nickel ions, fly ash and sawdust to achieve the recycling utilization of resources. -- Abstract: This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid–solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH = 7 with a 2:1 liquid–solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03–0.1 min −1 ) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH = 7.0 compared with ozonation alone

  19. Adsorption and bio-sorption of nickel ions and reuse for 2-chlorophenol catalytic ozonation oxidation degradation from water

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Wei, E-mail: chmawv@yahoo.com [School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Zong, Panpan; Cheng, Zihong [School of Chemical Engineering, Dalian University of Technology, Dalian 116024 (China); Wang, Baodong; Sun, Qi [National Institute of Clean-and-low Carbon Energy, Beijing 102209 (China)

    2014-02-15

    Highlights: • Biomass and fly ash which were widespread for adsorption of heavy metal ions. • Preparation of catalyst by saturated adsorbents for 2-chlorophenol ozone degradation. • This work demonstrated that the O{sub 3}/catalyst process was an effective pathway. • The use of nickel ions, fly ash and sawdust to achieve the recycling utilization of resources. -- Abstract: This work explored the preparation of an effective and low-cost catalyst and investigated its catalytic capacity for 2-chlorophenol ozonation oxidation degradation in wastewater by using an ozone oxidation batch reactor. The catalyst was directly prepared by the reuse of fly ash and sawdust after saturated adsorption of nickel ions from wastewater, which was proposed as an efficient and economic approach. The obtained catalyst was characterized by TGA, BET, FTIR, XRD, and SEM, the results showed that fly ash as the basic framework has high specific surface area and the addition of sawdust as the porogen agent could improve the pore structure of the catalyst. The adsorption of nickel ions by fly ash and sawdust from aqueous solution was also investigated in this study. The results obtained from the experiments indicated that adsorption of nickel ions by fly ash and biomass sawdust could be well described by Langmuir isotherm model and pseudo second order kinetic model. The catalytic performance of catalyst was studied in terms of the effect of time, liquid–solid ratio and pH on 2-chlorophenol ozonation degradation. It was found that the catalyst could effectively improve the ozonation reaction rate at pH = 7 with a 2:1 liquid–solid ratio. The kinetic study demonstrated that the reaction followed the first order model, and the rate constant increased 267% (0.03–0.1 min{sup −1}) of 2-chlorophenol ozonation degradation with 5 mmol/L concentration at pH = 7.0 compared with ozonation alone.

  20. 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.

  1. 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

  2. Degradability and Clearance of Silicon, Organosilica, Silsesquioxane, Silica Mixed Oxide, and Mesoporous Silica Nanoparticles

    KAUST Repository

    Croissant, Jonas G.

    2017-01-13

    The biorelated degradability and clearance of siliceous nanomaterials have been questioned worldwide, since they are crucial prerequisites for the successful translation in clinics. Typically, the degradability and biocompatibility of mesoporous silica nanoparticles (MSNs) have been an ongoing discussion in research circles. The reason for such a concern is that approved pharmaceutical products must not accumulate in the human body, to prevent severe and unpredictable side-effects. Here, the biorelated degradability and clearance of silicon and silica nanoparticles (NPs) are comprehensively summarized. The influence of the size, morphology, surface area, pore size, and surface functional groups, to name a few, on the degradability of silicon and silica NPs is described. The noncovalent organic doping of silica and the covalent incorporation of either hydrolytically stable or redox- and enzymatically cleavable silsesquioxanes is then described for organosilica, bridged silsesquioxane (BS), and periodic mesoporous organosilica (PMO) NPs. Inorganically doped silica particles such as calcium-, iron-, manganese-, and zirconium-doped NPs, also have radically different hydrolytic stabilities. To conclude, the degradability and clearance timelines of various siliceous nanomaterials are compared and it is highlighted that researchers can select a specific nanomaterial in this large family according to the targeted applications and the required clearance kinetics.

  3. Study on the drain bias effect on negative bias temperature instability degradation of an ultra-short p-channel metal-oxide-semiconductor field-effect transistor

    International Nuclear Information System (INIS)

    Yan-Rong, Cao; Xiao-Hua, Ma; Yue, Hao; Shi-Gang, Hu

    2010-01-01

    This paper studies the effect of drain bias on ultra-short p-channel metal-oxide-semiconductor field-effect transistor (PMOSFET) degradation during negative bias temperature (NBT) stress. When a relatively large gate voltage is applied, the degradation magnitude is much more than the drain voltage which is the same as the gate voltage supplied, and the time exponent gets larger than that of the NBT instability (NBTI). With decreasing drain voltage, the degradation magnitude and the time exponent all get smaller. At some values of the drain voltage, the degradation magnitude is even smaller than that of NBTI, and when the drain voltage gets small enough, the exhibition of degradation becomes very similar to the NBTI degradation. When a relatively large drain voltage is applied, with decreasing gate voltage, the degradation magnitude gets smaller. However, the time exponent becomes larger. With the help of electric field simulation, this paper concludes that the degradation magnitude is determined by the vertical electric field of the oxide, the amount of hot holes generated by the strong channel lateral electric field at the gate/drain overlap region, and the time exponent is mainly controlled by localized damage caused by the lateral electric field of the oxide in the gate/drain overlap region where hot carriers are produced. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  4. Assessment of the cathode contribution to the degradation of anode-supported solid oxide fuel cells

    DEFF Research Database (Denmark)

    Hagen, Anke; Liu, Yi-Lin; Barfod, Rasmus

    2008-01-01

    The degradation of anode-supported cells was studied over 1500 h as a function of cell polarization either in air or oxygen on the cathode side. Based on impedance analysis, contributions of the anode and cathode to the increase of total resistance were assigned. Accordingly, the degradation rates...... of the cathode were strongly dependent on the pO(2). Microstructural analysis of the cathode/electrolyte interface carried out after removal of the cathode showed craters on the electrolyte surface where the lanthanum strontium manganite (LSM) particles had been located. The changes of shape and size...... of these craters observed after testing correlated with the cell voltage degradation rates. The results can be interpreted in terms of element redistribution at the cathode/electrolyte interface and formation of foreign phases giving rise to a weakening of local contact points of the LSM cathode and yttria...

  5. An Overview: Recent Development of Titanium Oxide Nanotubes as Photocatalyst for Dye Degradation

    Directory of Open Access Journals (Sweden)

    Chin Wei Lai

    2014-01-01

    Full Text Available Today, organic dyes are one of the largest groups of pollutants release into environment especially from textile industry. It is highly toxic and hazardous to the living organism; thus, the removal of these dyes prior to discharge into the environment is essential. Varieties of techniques have been employed to degrade organic dyes and heterogeneous photocatalysis involving titanium dioxide (TiO2 appears to be the most promising technology. In recent years, TiO2 nanotubes have attracted much attention due to their high surface area and extraordinary characteristics. This paper presents a critical review of recent achievements in the modification of TiO2 nanotubes for dye degradation. The photocatalytic activity on dye degradation can be further enhanced by doping with cationic or anionic dopant.

  6. Degradation of superconducting Nb/NbN films by atmospheric oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Henry, Michael David; Wolfley, Steven L.; Young, Travis Ryan; Monson, Todd; Pearce, Charles Joseph; Lewis, Rupert M.; Clark, Blythe; Brunke, Lyle Brent; Missert, Nancy A.

    2017-03-01

    Niobium and niobium nitride thin films are transitioning from fundamental research toward wafer scale manufacturing with technology drivers that include superconducting circuits and electronics, optical single photon detectors, logic, and memory. Successful microfabrication requires precise control over the properties of sputtered superconducting films, including oxidation. Previous work has demonstrated the mechanism in oxidation of Nb and how film structure could have deleterious effects upon the superconducting properties. This study provides an examination of atmospheric oxidation of NbN films. By examination of the room temperature sheet resistance of NbN bulk oxidation was identified and confirmed by secondary ion mass spectrometry. As a result, Meissner magnetic measurements confirmed the bulk oxidation not observed with simple cryogenic resistivity measurements.

  7. Investigation of oxidative degradation and non‐enzymatic browning reactions in krill and fish oils

    DEFF Research Database (Denmark)

    Thomsen, Birgitte Raagaard; Haugsgjerd, Bjørn Ole; Griinari, Mikko

    2013-01-01

    conditions using the Oxipres™ at 90°C. The results from analysis of PV, AV, TBARS, conjugated dienes and trienes, and the antioxidant content suggested that krill oil was more oxidatively stable than fish oil. However, the color or other constituents of the krill oil might affect the result......The aim of this research was to investigate the oxidation progress and pathways of krill and fish oil during 21 days of incubation at 40°C. The oxidative stability of the oils was investigated through: (i) classical methods such as peroxide value (PV), anisidine value (AV), thiobarbituric reactive...... substance (TBARS), conjugated dienes and trienes, and antioxidant content, and (ii) advanced methods such as determination of volatiles content by dynamic headspace (DHS)‐GC/MS, lipid classes, and pyrrole content. In addition, the oxidative stability of the oils was evaluated under accelerated oxidation...

  8. Anode Supported Solid Oxide Fuel Cells - Deconvolution of Degradation into Cathode and Anode Contributions

    DEFF Research Database (Denmark)

    Hagen, Anke; Liu, Yi-Lin; Barfod, Rasmus

    2007-01-01

    The degradation of anode supported cells was studied over 1500 h as function of cell polarization either in air or oxygen on the cathode. Based on impedance analysis, contributions of anode and cathode to the increase of total resistance were assigned. Accordingly, the degradation rates...... of the cathode were strongly dependent on the pO(2); they were significantly smaller when testing in oxygen compared to air. Microstructural analysis of the cathode/electrolyte interface of a not-tested reference cell carried out after removal of the cathode showed sharp craters on the electrolyte surface where...

  9. Sulfate radical-induced degradation of Acid Orange 7 by a new magnetic composite catalyzed peroxymonosulfate oxidation process

    International Nuclear Information System (INIS)

    Chen, Dan; Ma, Xiaolong; Zhou, Jizhi; Chen, Xi; Qian, Guangren

    2014-01-01

    Graphical abstract: Organic dyes could be absorbed on the surface of the composite or dispersed in the solution. Sulfate radicals (SO 4 · − ) generated by the synergistic reaction between peroxymonosulfate (PMS) and the composite, attacked the organic functional groups of the dyes molecules both adsorbed on the composite surface and dispersed in the solution, which resulted in the degradation of AO7 dye. - Highlights: • A new composite was synthesized successfully via microwave hydrothermal method. • The complete degradation in the system of FLCN and PMS can be achieved. • The catalytic behavior of FLCN can be reused at least for five times. • The AO7 degradation mechanism in the system of FLCN and PMS was demonstrated. - Abstract: We synthesized a novel magnetic composite, Fe 3 O 4 /Cu(Ni)Cr-LDH, as a heterogeneous catalyst for the degradation of organic dyes in the solution using sulfate radical-based advanced oxidation processes. The physicochemical properties of the composite synthesized via two-step microwave hydrothermal method were characterized by several techniques, such as X-ray diffraction (XRD), inductively coupled plasma (ICP), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The degradation tests were performed at 25 °C with Acid Orange 7 (AO7) initial concentration of 25 mg/L and AO7/peroxymonosulfate (PMS) molar ratio of 1:10, which showed that the complete degradation by Fe 3 O 4 /Cu 1.5 Ni 0.5 Cr-LDH could be achieved and the mineralization rate could reach 46%. PMS was activated by Cu (II) and Fe (II/III) of Fe 3 O 4 /Cu(Ni)Cr-LDH to generate sulfate radicals (SO 4 · − ). Subsequently, the organic functional groups of AO7 molecules were destroyed by sulfate radicals (SO 4 · − ), inducing the degradation of AO7. Moreover, the catalytic behavior of the catalysts could be reused five times. Therefore, our work suggested that the Fe 3 O 4 /Cu(Ni)Cr-LDH composite could be applied widely for the

  10. NRC Information No. 88-98: Electrical relay degradation caused by oxidation of contact surfaces

    International Nuclear Information System (INIS)

    Rossi, C.E.

    1992-01-01

    The NRC staff was recently informed by Clinton Power Station that a reactor scram on June 24, 1988, was caused by an electrical relay failure from oxide buildup on relay contact surfaces. Other information on relay failure from contact oxidation indicates that this problem may be more prevalent than previously thought. For example, a July 17, 1988, 10 CFR Part 21 report from Palo Verde, Unit 2, reported relay failures from contact oxidation that were due to the low current application of the relays. The relay contact surfaces in both of these examples are silver-nickel alloys, and both applications were for low current (i.e., milli-ampere current). Electrical relay contacts made of silver-nickel or silver-cadmium alloys will oxidize (tarnish) when used in low current applications because of the absence of contact surface sparking from the typical relay contact ''making and breaking'' functions. The sparking in the contact surfaces promotes a self-cleaning mechanism that reduces the tarnish buildup on the silver-nickel or silver-cadmium contacts. Discussions with one relay manufacturer revealed that the normal industry practice for low current circuit applications is either to use a contact surface material that will not oxidize or to compensate for the oxidation by increased maintenance activities to ensure reliability. The applied voltage may also influence contact oxidation

  11. Degradation of quinoline by wet oxidation - kinetic aspects and reaction mechanisms

    DEFF Research Database (Denmark)

    Thomsen, A.B.

    1998-01-01

    The high temperature, high pressure wet oxidation reaction of quinoline has been studied as a function of initial concentration, pH and temperature. At neutral to acidic pH, it is effective in the oxidation of quinoline at 240 degrees C and above, whereas under alkaline conditions the reaction...... is markedly slowed down. The results indicate that the reaction is an auto-catalysed, free radical chain reaction transforming 99% of quinoline to other substances. Of the quinoline. 30-50% was oxidised to CO2 and H2O depending on the initial concentration. Wet oxidation of deuterium-labelled quinoline...

  12. Baseline levels of benzo(a)pyrene in southern California mussels

    Energy Technology Data Exchange (ETDEWEB)

    Dunn, B P [Univ. of British Columbia, Vancouver; Young, D R

    1976-12-01

    Marine mussels accumulate the carcinogen benzo(a)-pyrene from contaminated environments. Baseline studies in California indicate that levels of the carcinogen in mussels are at or near zero, except in areas of human activity. This finding runs counter to previous suggestions that benzo(a)pyrene is widely distributed in marine organisms.

  13. Oxidation of 2,4-dichlorophenoxyacetic acid by ionizing radiation: degradation, detoxification and mineralization

    Energy Technology Data Exchange (ETDEWEB)

    Zona, Robert; Solar, Sonja E-mail: sonja.solar@univie.ac.at

    2003-02-01

    The gamma-radiation-induced degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in aerated (A) and in during irradiation air saturated (AS) solutions. Whereas the decomposition rates were not influenced by AS, chloride elimination, detoxification as well as mineralization were significantly enhanced. In the range 50-500 {mu}mol dm{sup -3} 2,4-D, degradation showed proportionality to concentration, while chloride formation was successively retarded. The ratios of the pseudo first-order rate constants for degradation and chloride formation, k{sub de}/k{sub Cl}, increase in AS solutions from 1.4 (50 {mu}mol dm{sup -3}) to 2.7 (500 {mu}mol dm{sup -3}) and in A solutions from 1.4 to 3.3. In AS for total chloride release 0.7 kGy (50 {mu}mol dm{sup -3}) to 10 kGy (500 {mu}mol dm{sup -3}) were required, the reduction of organic carbon at 10 kGy was 95% (50 {mu}mol dm{sup -3}) and 50% (500 {mu}mol dm{sup -3}). Increase and decrease of toxicity during irradiation correlated well with formation and degradation of intermediate phenolic products. The doses for detoxification corresponded to those of total dehalogenation. The oxygen uptake was {approx}1.1 ppm 100 Gy{sup -1}. The presence of the inorganic components of Vienna drinking water affect the degradation parameters insignificantly.

  14. 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.

  15. 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.

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

    Directory of Open Access Journals (Sweden)

    Annabel Fernandes

    2014-12-01

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

  17. A kinetic model of municipal sludge degradation during non-catalytic wet oxidation.

    Science.gov (United States)

    Prince-Pike, Arrian; Wilson, David I; Baroutian, Saeid; Andrews, John; Gapes, Daniel J

    2015-12-15

    Wet oxidation is a successful process for the treatment of municipal sludge. In addition, the resulting effluent from wet oxidation is a useful carbon source for subsequent biological nutrient removal processes in wastewater treatment. Owing to limitations with current kinetic models, this study produced a kinetic model which predicts the concentrations of key intermediate components during wet oxidation. The model was regressed from lab-scale experiments and then subsequently validated using data from a wet oxidation pilot plant. The model was shown to be accurate in predicting the concentrations of each component, and produced good results when applied to a plant 500 times larger in size. A statistical study was undertaken to investigate the validity of the regressed model parameters. Finally the usefulness of the model was demonstrated by suggesting optimum operating conditions such that volatile fatty acids were maximised. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Eco-Friendly Magnetic Iron Oxide Pillared Montmorillonite for Advanced Catalytic Degradation of Dichlorophenol

    Science.gov (United States)

    Eco-friendly pillared montmorillonites, in which the pillars consist of iron oxide are expected to have interesting and unusual magnetic properties that are applicable for environmental decontamination. Completely “green” and effective composite was synthesized using mild reactio...

  19. Hydrothermal synthesis of fluorinated anatase TiO_2/reduced graphene oxide nanocomposites and their photocatalytic degradation of bisphenol A

    International Nuclear Information System (INIS)

    Luo, Lijun; Yang, Ye; Zhang, Ali; Wang, Min; Liu, Yongjun; Bian, Longchun; Jiang, Fengzhi; Pan, Xuejun

    2015-01-01

    Graphical abstract: - Highlights: • F–TiO_2–RGO nanocomposites were synthesized via hydrothermal method. • Presence of F ion prevents phase transformation from anatase to rutile. • The adsorbed F"− and RGO improve the photocatalytic activity of TiO_2 synergistically. • The F–TiO_2–RGO nanocomposites were applied to degrade bisphenol A. - Abstract: The surface fluorinated TiO_2/reduced graphene oxide nanocomposites (denoted as F–TiO_2–RGO) were synthesized via hydrothermal method. The as-prepared materials were characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), Raman spectroscopy, Fourier Transform Infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF). The results showed that pure anatase TiO_2 particles were anchored on the surface of reduced graphene oxide. And the HF added during the preparation process can not only prevent phase transformation from anatase to rutile, but also the F"− ion adsorbed on the surface of TiO_2–RGO surface can enhance photocatalytic activity of F–TiO_2–RGO. The photocatalytic activities of F–TiO_2–RGO nanocomposites were evaluated by decomposing bisphenol A under UV light illumination. Under optimal degradation condition, the degradation rate constant of BPA over F–TiO_2–10RGO (0.01501 min"−"1) was 3.41 times than that over P25 (0.00440 min"−"1). The result indicated that the enhanced photocatalytic activity of F–TiO_2–10RGO was ascribed to the adsorbed F ion and RGO in F–TiO_2–RGO composite, which can reduce the recombination rate of the photo-generated electrons and holes synergistically.

  20. Degradation of imidacloprid using combined advanced oxidation processes based on hydrodynamic cavitation.

    Science.gov (United States)

    Patil, Pankaj N; Bote, Sayli D; Gogate, Parag R

    2014-09-01

    The harmful effects of wastewaters containing pesticides or insecticides on human and aquatic life impart the need of effectively treating the wastewater streams containing these contaminants. In the present work, hydrodynamic cavitation reactors have been applied for the degradation of imidacloprid with process intensification studies based on different additives and combination with other similar processes. Effect of different operating parameters viz. concentration (20-60 ppm), pressure (1-8 bar), temperature (34 °C, 39 °C and 42 °C) and initial pH (2.5-8.3) has been investigated initially using orifice plate as cavitating device. It has been observed that 23.85% degradation of imidacloprid is obtained at optimized set of operating parameters. The efficacy of different process intensifying approaches based on the use of hydrogen peroxide (20-80 ppm), Fenton's reagent (H2O2:FeSO4 ratio as 1:1, 1:2, 2:1, 2:2, 4:1 and 4:2), advanced Fenton process (H2O2:Iron Powder ratio as 1:1, 2:1 and 4:1) and combination of Na2S2O8 and FeSO4 (FeSO4:Na2S2O8 ratio as 1:1, 1:2, 1:3 and 1:4) on the extent of degradation has been investigated. It was observed that near complete degradation of imidacloprid was achieved in all the cases at optimized values of process intensifying parameters. The time required for complete degradation of imidacloprid for approach based on hydrogen peroxide was 120 min where as for the Fenton and advance Fenton process, the required time was only 60 min. To check the effectiveness of hydrodynamic cavitation with different cavitating devices, few experiments were also performed with the help of slit venturi as a cavitating device at already optimized values of parameters. The present work has conclusively established that combined processes based on hydrodynamic cavitation can be effectively used for complete degradation of imidacloprid. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Experimental analysis of performance degradation of micro-tubular solid oxide fuel cells fed by different fuel mixtures

    Science.gov (United States)

    Calise, F.; Restucccia, G.; Sammes, N.

    This paper analyzes the thermodynamic and electrochemical dynamic performance of an anode supported micro-tubular solid oxide fuel cell (SOFC) fed by different types of fuel. The micro-tubular SOFC used is anode supported, consisting of a NiO and Gd 0.2Ce 0.8O 2- x (GDC) cermet anode, thin GDC electrolyte, and a La 0.6Sr 0.4Co 0.2Fe 0.8O 3- y (LSCF) and GDC cermet cathode. The fabrication of the cells under investigation is briefly summarized, with emphasis on the innovations with respect to traditional techniques. Such micro-tubular cells were tested using a Test Stand consisting of: a vertical tubular furnace, an electrical load, a galvanostast, a bubbler, gas pipelines, temperature, pressure and flow meters. The tests on the micro-SOFC were performed using H 2, CO, CH 4 and H 2O in different combinations at 550 °C, to determine the cell polarization curves under several load cycles. Long-term experimental tests were also performed in order to assess degradation of the electrochemical performance of the cell. Results of the tests were analyzed aiming at determining the sources of the cell performance degradation. Authors concluded that the cell under investigation is particularly sensitive to the carbon deposition which significantly reduces cell performance, after few cycles, when fed by light hydrocarbons. A significant performance degradation is also detected when hydrogen is used as fuel. In this case, the authors ascribe the degradation to the micro-cracks, the change in materials crystalline structure and problems with electrical connections.

  2. Photocatalytic degradation of methylene blue dye by zinc oxide nanoparticles obtained from precipitation and sol-gel methods.

    Science.gov (United States)

    Balcha, Abebe; Yadav, Om Prakash; Dey, Tania

    2016-12-01

    Zinc oxide (ZnO) nanoparticles were synthesized by precipitation and sol-gel methods. The aim of this study was to understand how different synthetic methods can affect the photocatalytic activity of ZnO nanoparticles. As-synthesized ZnO nanoparticles were characterized by X-ray diffraction (XRD) and UV-Visible spectroscopic techniques. XRD patterns of ZnO powders synthesized by precipitation and sol-gel methods revealed their hexagonal wurtzite structure with crystallite sizes of 30 and 28 nm, respectively. Their photocatalytic activities were evaluated by photocatalytic degradation of methylene blue, a common water pollutant, under UV radiation. The effects of operational parameters such as photocatalyst load and initial concentration of the dye on photocatalytic degradation of methylene blue were investigated. While the degradation of dye decreased over the studied dye concentration range of 20 to 100 mg/L, an optimum photocatalyst load of 250 mg/L was needed to achieve dye degradation as high as 81 and 92.5 % for ZnO prepared by precipitation and sol-gel methods, respectively. Assuming pseudo first-order reaction kinetics, this corresponded to rate constants of 8.4 × 10 -3 and 12.4 × 10 -3  min -1 , respectively. Hence, sol-gel method is preferred over precipitation method in order to achieve higher photocatalytic activity of ZnO nanostructures. Photocatalytic activity is further augmented by better choice of capping ligand for colloidal stabilization, starch being more effective than polyethylene glycol (PEG).

  3. Gadolinium oxide decorated multiwalled carbon nanotube/tridoped titania nanocomposites for improved dye degradation under simulated solar light irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Mamba, Gcina [Department of Applied Chemistry, University of Johannesburg, Faculty of Science, P.O. Box 17011, Doornfontein 2028 (South Africa); Nanotechnology and Water Sustainability Research Unit, College of Engineering, Science and Technology, University of South Africa Florida Science Campus, 1709 Florida (South Africa); Mbianda, Xavier Yangkou [Department of Applied Chemistry, University of Johannesburg, Faculty of Science, P.O. Box 17011, Doornfontein 2028 (South Africa); Mishra, Ajay Kumar, E-mail: mishrak@unisa.ac.za [Nanotechnology and Water Sustainability Research Unit, College of Engineering, Science and Technology, University of South Africa Florida Science Campus, 1709 Florida (South Africa)

    2016-03-15

    Graphical abstract: Illustration of the collaborative effect between MWCNT-Gd and Gd,N,S-TiO{sub 2} towards degradation of AB 74. - Highlights: • MWCNT-Gd/tridoped titania was successfully prepared via a sol-gel method. • XPS revealed the presence of Ti, C, O, S, N and Gd in MWCNT-Gd/Gd,N,S-TiO{sub 2}. • MWCNT-Gd/Gd,N,S-TiO{sub 2} displayed 100% degradation of acid blue 74 in 150 min. • Over 60% TOC removal by MWCNT-Gd/Gd,N,S-TiO{sub 2}. - Abstract: Neodymium/gadolinium/europium, nitrogen and sulphur tridoped titania (Nd/Gd/Eu, N,S-TiO{sub 2}) was hybridised with pre-synthesised gadolinium oxide decorated multiwalled carbon nanotubes (MWCNT-Gd) using a sol–gel method. Subsequent to drying and calcination, composite photocatalysts: MWCNT-Gd/Nd,N,S-TiO{sub 2}, MWCNT-Gd/Gd,N,S-TiO{sub 2} and MWCNT-Gd/Eu,N,S-TiO{sub 2}, were obtained and characterised using TEM, SEM-EDX, UV–vis, XPS, XRD and FT-IR. Acid blue 74 (AB74) was used as a model dye to investigate the photocatalytic degradation properties of the prepared materials under simulated solar light irradiation. Coupling the different tridoped titania with MWCNT-Gd enhanced their activity compared to MWCNT/TiO{sub 2}, MWCNT-Gd/TiO{sub 2} and MWCNT/Gd,N,S-TiO{sub 2}. MWCNT-Gd/Gd,N,S-TiO{sub 2} showed the highest activity towards AB74 degradation reaching 100% decolourisation after 150 min of irradiation. Total organic carbon analysis revealed that over 50% of the AB74 molecules were completely mineralised after 180 min of irradiation in the presence of MWCNT-Gd/Gd,N,S-TiO{sub 2}.

  4. 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...

  5. Modelling TCE degradation by a mixed culture of methane-oxidizing bacteria

    DEFF Research Database (Denmark)

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

    1992-01-01

    A model describing the growth of bacteria and the degradation of methane and trichloroethylene (TCE) based on the concept of competitive inhibition is proposed. The model has been applied to laboratory batch experiments representing different initial TCE concentrations (50–4300 μg/l) and initial...... methane concentrations (0.53–3.2 mg/l). The proposed model simulated successfully the data obtained for initial methane concentration (less than 1.8 mg/l), causing constant experimental growth conditions during the experiments. This indicates that the interactions between methane and TCE degradation can...... be explained as competitive inhibition. The model simulations of the results from the experiments with the highest initial methane concentration of 3.2 mg/l failed, supposedly because the growth conditions changed during the experiments. The proposed model is a useful engineering tool for design of treatment...

  6. Microstructural degradation of Ni-YSZ anodes for solid oxide fuel cells

    DEFF Research Database (Denmark)

    Thydén, Karl Tor Sune

    2008-01-01

    -reforming catalysis. In the context of electrochemically tested and technologically relevant cells, the majority of the microstructural work is performed on a cell tested at 850°C under relatively severe conditions for 17,500 hours. It is demonstrated that the major Ni rearrangements take place at the interface...... are of technological relevance, it is difficult to identify the effect from isolated parameters such as temperature, fuel gas composition and polarization. Model studies of high temperature aged Ni-YSZ cermets are generally performed in atmospheres containing relatively low concentrations of H2O. In this work......, the microstructural degradation in both electrochemically longterm tested cells and high-temperature aged model materials are studied. Since Ni particle sintering / coarsening is attributed to be the major cause of anode degradation, this subject attains the primary focus. A large part of the work is focused...

  7. Degradation of halogenated aliphatic compounds by the ammonia- oxidizing bacterium Nitrosomonas europaea.

    Science.gov (United States)

    Vannelli, T; Logan, M; Arciero, D M; Hooper, A B

    1990-01-01

    Suspensions of Nitrosomonas europaea catalyzed the ammonia-stimulated aerobic transformation of the halogenated aliphatic compounds dichloromethane, dibromomethane, trichloromethane (chloroform), bromoethane, 1,2-dibromoethane (ethylene dibromide), 1,1,2-trichloroethane, 1,1,1-trichloroethane, monochloroethylene (vinyl chloride), gem-dichloroethylene, cis- and trans-dichloroethylene, cis-dibromoethylene, trichloroethylene, and 1,2,3-trichloropropane, Tetrachloromethane (carbon tetrachloride), tetrachloroethylene (perchloroethylene), and trans-dibromoethylene were not degraded. PMID:2339874

  8. Understanding degradation of solid oxide electrolysis cells through modeling of electrochemical potential profiles

    DEFF Research Database (Denmark)

    Chatzichristodoulou, Christodoulos; Chen, Ming; Hendriksen, Peter Vang

    2016-01-01

    conductivities in the electrolyte, the gas composition, temperature, and pressure on the current density distribution over the cell and the oxygen activity distribution within the electrolyte. The developed model is further used to simulate long-term durability experiments during different stages of operation......, thereby helping to rationalize microstructural and chemical changes observed in post-mortem analysis. Finally, measures to mitigate degradation by changing conditions of operation, material or electrode properties or overall cell geometry are suggested....

  9. Aerobic TCE degradation by encapsulated toluene-oxidizing bacteria, Pseudomonas putida and Bacillus spp.

    Science.gov (United States)

    Kim, Seungjin; Bae, Wookeun; Hwang, Jungmin; Park, Jaewoo

    2010-01-01

    The degradation rates of toluene and trichloroethylene (TCE) by Pseudomonas putida and Bacillus spp. that were encapsulated in polyethylene glycol (PEG) polymers were evaluated in comparison with the results of exposure to suspended cultures. PEG monomers were polymerized together with TCE-degrading microorganisms, such that the cells were encapsulated in and protected by the matrices of the PEG polymers. TCE concentrations were varied from 0.1 to 1.5 mg/L. In the suspended cultures of P. putida, the TCE removal rate decreased as the initial TCE concentration increased, revealing TCE toxicity or a limitation of reducing power, or both. When the cells were encapsulated, an initial lag period of about 10-20 h was observed for toluene degradation. Once acclimated, the encapsulated P. putida cultures were more tolerant to TCE at an experimental range of 0.6-1.0 mg/L and gave higher transfer efficiencies (mass TCE transformed/mass toluene utilized). When the TCE concentration was low (e.g., 0.1 mg/L) the removal of TCE per unit mass of cells (specific removal) was significantly lower, probably due to a diffusion limitation into the PEG pellet. Encapsulated Bacillus spp. were able to degrade TCE cometabolically. The encapsulated Bacillus spp. gave significantly higher values than did P. putida in the specific removal and the transfer efficiency, particularly at relatively high TCE concentration of approximately 1.0±0.5 mg/L. The transfer efficiency by encapsulated Bacillus spp. in this study was 0.27 mgTCE/mgToluene, which was one to two orders of magnitude greater than the reported values.

  10. Oxidative degradation of salicylic acid by sprayed WO{sub 3} photocatalyst

    Energy Technology Data Exchange (ETDEWEB)

    Mohite, S.V.; Rajpure, K.Y., E-mail: rajpure@yahoo.com

    2015-10-15

    Highlights: • The photoactivity of sprayed WO{sub 3} thin film. • Photoelectrocatalytic degradation of salicylic acid. • Reaction kinetics and mineralization of pollutants by COD. - Abstract: The WO{sub 3} thin films were deposited using spray pyrolysis technique. The prepared WO{sub 3} thin films were characterized using photoelectrochemical (PEC), X-ray diffraction, atomic force microscopy (AFM), and UV–vis absorbance spectroscopy techniques. PEC measurements of WO{sub 3} films deposited at different deposition temperatures were carried out to study photoresponse. The maximum photocurrent (I{sub ph} = 261 μA/cm{sup 2}) was observed for the film deposited at the 225 °C. The monoclinic crystal structure of WO{sub 3} has been confirmed from X-ray diffraction studies. AFM studies were used to calculate particle size and average roughness of the films. Optical absorbance was studied to estimate the bandgap energy of WO{sub 3} thin film which was about 2.65 eV. The photoelectrocatalytic activity of WO{sub 3} film was studied by degradation of salicylic acid with reducing concentrations as function of reaction time. The WO{sub 3} photocatalyst degraded salicylic acid to about 67.14% with significant reduction in chemical oxygen demand (COD) value.

  11. 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

  12. Effect of various amounts of graphene oxide on the degradation characteristics of the ZnSe/graphene nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Hsieh, S.H. [Department of Materials Science and Engineering, National Formosa University, 64, Wunhua Road, Huwei, Yunlin 632, Taiwan (China); Chen, W.J., E-mail: chenwjau@yuntech.edu.tw [Graduate School of Materials Science, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin 64002, Taiwan (China); Yeh, T.H. [Graduate School of Materials Science, National Yunlin University of Science and Technology, 123 University Road, Section 3, Douliou, Yunlin 64002, Taiwan (China)

    2015-12-15

    Graphical abstract: When the ratio of the addition of GO to the amount of ZnSe–N{sub 2}H{sub 4} increases from 0.25 to 1, the degradation effect of GN–5 ml ZnSe on MB increases with increasing GO; the degradation efficiency of GN–ZnSe for MB increased from 35.4% to 99.6% after 6 h of visible light irradiation, which was the optimum degradation efficiency obtained in the present study. When the ratio of the addition of GO to the amount of ZnSe–N{sub 2}H{sub 4} increased from 1 to 2, the degradation efficiency of GN–5 ml ZnSe for MB decreased with the increasing addition of GO; the degradation efficiency of GN–5 ml ZnSe (2) only slightly decreased to 95.3% after 6 h of visible light irradiation. - Highlights: • The ZnSe/graphene nanocomposite was prepared using hydrothermal methods. • The ZnSe–N{sub 2}H{sub 4} reacted with different amount of GO and formed a ZnSe/graphene. • The degradation efficiency of the ZnSe/graphene depends on the amount of GO. • The photocatalytic activity was measured by the degradation of methylene blue. - Abstract: In this work, the graphene oxide (GO) sheets were synthesized by modified Hummers and Offeman's method. The GO was mixed with ZnSe that was prepared using various amounts of N{sub 2}H{sub 4} at a ratio of (0.25–2):1 to form precursors. The ZnSe/graphene nanocomposites were synthesized under hydrothermal conditions (180 °C; 12 h) from the previous precursor. Obtained ZnSe/graphene photocatalysts were characterized by X-ray diffraction analysis (XRD), Fourier transform infrared (FTIR) spectroscopy, UV–vis diffuse reflection spectroscopy, transmission electron microscope, scanning electron microscope, Raman spectra and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity under visible light is evaluated in methylene blue (MB) dye degradation reaction in aqueous phase. The results show that the formation of ZnSe/graphene nanocomposite is depend on ratio of the addition of GO to the amount of

  13. Elucidation of oxidation and degradation products of oxygen containing fuel components by combined use of a stable isotopic tracer and mass spectrometry.

    Science.gov (United States)

    Frauscher, Marcella; Besser, Charlotte; Allmaier, Günter; Dörr, Nicole

    2017-11-15

    In order to reveal the degradation products of oxygen-containing fuel components, in particular fatty acid methyl esters, a novel approach was developed to characterize the oxidation behaviour. Combination of artificial alteration under pressurized oxygen atmosphere, a stable isotopic tracer, and gas chromatography electron impact mass spectrometry (GC-EI-MS) was used to obtain detailed information on the formation of oxidation products of (9Z), (12Z)-octadecadienoic acid methyl ester (C18:2 ME). Thereby, biodiesel simulating model compound C18:2 ME was oxidized in a rotating pressurized vessel standardized for lubricant oxidation tests (RPVOT), i.e., artificially altered, under 16 O 2 as well as 18 O 2 atmosphere. Identification of the formed degradation products, mainly carboxylic acids of various chain lengths, alcohols, ketones, and esters, was performed by means of GC-EI-MS. Comparison of mass spectra of compounds under both atmospheres revealed not only the degree of oxidation and the origin of oxygen atoms, but also the sites of oxidative attack and bond cleavage. Hence, the developed and outlined strategy based on a gas-phase stable isotopic tracer and mass spectrometry provides insight into the degradation of oxygen-containing fuels and fuel components by means of the accurate differentiation of oxygen origin in a degradation product. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Advanced Chemical Reduction of Reduced Graphene Oxide and Its Photocatalytic Activity in Degrading Reactive Black 5

    Directory of Open Access Journals (Sweden)

    Christelle Pau Ping Wong

    2015-10-01

    Full Text Available Textile industries consume large volumes of water for dye processing, leading to undesirable toxic dyes in water bodies. Dyestuffs are harmful to human health and aquatic life, and such illnesses as cholera, dysentery, hepatitis A, and hinder the photosynthetic activity of aquatic plants. To overcome this environmental problem, the advanced oxidation process is a promising technique to mineralize a wide range of dyes in water systems. In this work, reduced graphene oxide (rGO was prepared via an advanced chemical reduction route, and its photocatalytic activity was tested by photodegrading Reactive Black 5 (RB5 dye in aqueous solution. rGO was synthesized by dispersing the graphite oxide into the water to form a graphene oxide (GO solution followed by the addition of hydrazine. Graphite oxide was prepared using a modified Hummers’ method by using potassium permanganate and concentrated sulphuric acid. The resulted rGO nanoparticles were characterized using ultraviolet-visible spectrophotometry (UV-Vis, X-ray powder diffraction (XRD, Raman, and Scanning Electron Microscopy (SEM to further investigate their chemical properties. A characteristic peak of rGO-48 h (275 cm−1 was observed in the UV spectrum. Further, the appearance of a broad peak (002, centred at 2θ = 24.1°, in XRD showing that graphene oxide was reduced to rGO. Based on our results, it was found that the resulted rGO-48 h nanoparticles achieved 49% photodecolorization of RB5 under UV irradiation at pH 3 in 60 min. This was attributed to the high and efficient electron transport behaviors of rGO between aromatic regions of rGO and RB5 molecules.

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

    Science.gov (United States)

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

    2012-06-30

    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. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Mechanical degradation of coating systems in high-temperature cyclic oxidation

    CSIR Research Space (South Africa)

    Pennefather, RC

    1996-01-01

    Full Text Available Cyclic oxidation tests were performed on a large variety of commercially available overlay coatings. The results confirmed that the composition of the coating as well as the processing method of the coating can affect the life of the system. Coating...

  17. Mechanical degradation of coating systems in high-temperature cyclic oxidation

    CSIR Research Space (South Africa)

    Pennefather, RC

    1995-01-01

    Full Text Available Cyclic oxidation tests were performed on a large variety of commercially available overlay coatings. The results confirmed that the composition of the coating as well as the processing method of the coating can affect the life of the system. Coating...

  18. Elevated capillary tube hematocrit reflects degradation of endothelial cell glycocalyx by oxidized LDL

    NARCIS (Netherlands)

    Constantinescu, A. A.; Vink, H.; Spaan, J. A.

    2001-01-01

    Proteoglycans and plasma proteins bound to the endothelial cell glycocalyx are essential for vascular function, but at the same time, they lower capillary tube hematocrit by reducing capillary volume available to flowing blood. Because oxidized low-density lipoproteins (oxLDL) reduce the effective

  19. Enhanced visible light photocatalytic activity of copper-doped titanium oxide-zinc oxide heterojunction for methyl orange degradation

    Science.gov (United States)

    Dorraj, Masoumeh; Alizadeh, Mahdi; Sairi, Nor Asrina; Basirun, Wan Jefrey; Goh, Boon Tong; Woi, Pei Meng; Alias, Yatimah

    2017-08-01

    A novel Cu-doped TiO2 coupled with ZnO nanoparticles (Cu-TiO2/ZnO) was prepared by sol-gel method and subsequent precipitation for methyl orange (MO) photodegradation under visible light irradiation. The compositions and shapes of the as-prepared Cu-TiO2/ZnO nanocomposites were characterized by photoluminescence spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV-vis diffuse reflectance spectra and Brunauer-Emmett-Teller adsorption isotherm techniques. The Cu-TiO2/ZnO nanocomposites showed considerably higher photocatalytic activity for MO removal from water under visible light irradiation than that of single-doped semiconductors. The effects of Cu-TiO2 and ZnO mass ratios on the photocatalytic reaction were also studied. A coupling percentage of 30% ZnO exhibited the highest photocatalytic activity. The enhanced photocatalytic activity of the Cu-TiO2/ZnO nanocomposites was mainly attributed to heterojunction formation, which allowed the efficient separation of photoinduced electron-hole pairs at the interface. Moreover, these novel nanocomposites could be recycled during MO degradation in a three-cycle experiment without evident deactivation, which is particularly important in environmental applications.

  20. Functionalized Graphene Metal-Free Carbocatalysis of Persulfate and Emerging Contaminant Oxidative Degradation

    Science.gov (United States)

    Carroll, K. C.; Chen, H.

    2016-12-01

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

  1. 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.

  2. 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.

  3. Study of herbicide ametryne degradation in HDPE packaging using the advanced oxidation process by ionizing radiation

    International Nuclear Information System (INIS)

    Andrade, Debora Cristina de

    2008-01-01

    This study is part of the project with the objective to evaluate pesticides degradation for decontamination of commercial polymeric packaging of high density polyethylene, HDPE, used in agriculture. The herbicide used to this study was the herbicide ametryne (commercial name, Gesapax 500), due to its great use, mainly on field crops and on corn. Ametryne is commercialized since 1975, and, depending on the pesticide formulation and type of application, residues may be detectable in water, soil and on the surfaces for months or years. In order to evaluate the efficiency of radiation processing on removal the pesticides contamination, HDPE packaging were irradiated using Radiation Dynamics Electron Beam Accelerator with 1,5 MeV energy and 37 kW, in batch system. The samples were irradiated with water, in various absorbed doses. Ametryne was analyzed by gas chromatography (GC Shimadzu 17A), after extraction with hexane/dichloromethane (1:1 v/v) solution. The calibration curve was obtained with a regression coefficient of 0.986, and the relative standard deviation was lower than 10%. The radiation processing yield was evaluated by the rate of ametryne degradation and by the destruction G-value (Gd). The electron beam irradiation processing, showed high efficiency in destroying ametryne in the HDPE packaging when the samples were irradiated in presence of small quantities of water. (author)

  4. Characterization of Series Resistance and Mobility Degradation Parameter and Optimizing Choice of Oxide Thickness in Thin Oxide N-Channel MOSFET

    Directory of Open Access Journals (Sweden)

    Noureddine Maouhoub

    2011-01-01

    Full Text Available We present two methods to extract the series resistance and the mobility degradation parameter in short-channel MOSFETs. The principle of the first method is based on the comparison between the exponential model and the classical model of effective mobility and for the second method is based on directly calculating the two parameters by solving a system of two equations obtained by using two different points in strong inversion at small drain bias from the characteristic (. The results obtained by these techniques have shown a better agreement with data measurements and allowed in the same time to determine the surface roughness amplitude and its influence on the maximum drain current and give the optimal oxide thickness.

  5. Influence of the oxygen electrode and inter-diffusion barrier on the degradation of solid oxide electrolysis cells

    DEFF Research Database (Denmark)

    Hjalmarsson, Per; Sun, Xiufu; Liu, Yi-Lin

    2013-01-01

    -diffusion barrier sandwiched between the YSZ electrolyte and an LSCF:CGO oxygen electrode. Impedance Spectroscopy was used during the tests to diagnose the change in electrochemical response of the different components of the SOECs. The results showed a significantly lower degradation rate for the cell with an LSCF......Two Solid Oxide Electrolysis Cells (SOECs) with different oxygen electrodes have been tested in galvanostatic tests carried out at −1.5 Acm−2 and 800 °C converting 60% of a 50:50% mixture of H2O and CO2 (co-electrolysis). One of the cells had an LSM:YSZ oxygen electrode. The other had an CGO inter...

  6. 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...

  7. 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.

  8. Practical applications of the Fenton reaction to the removal of chlorinated aromatic pollutants. Oxidative degradation of 2,4-dichlorophenol.

    Science.gov (United States)

    Detomaso, Antonia; Lopez, Antonio; Lovecchio, Giangiuseppe; Mascolo, Giuseppe; Curci, Ruggero

    2003-01-01

    Chlorophenols (CPs) constitute a group of organic pollutants that are introduced into the environment as a result of several man-made activities, such as uncontrolled use of pesticides and herbicides, and as byproducts in the paper pulp bleaching. Promising removal technologies of chlorinated aromatics consist in the application of advanced oxidation processes (AOPs) that can provide an almost total degradation of a variety of contaminants. Among these, wide application find Fenton systems based on generation of reactive species having a high oxidizing power, such as hydroxyl radical HO*. Our objective was that of determining the overall degradation efficiency of the model compound 2,4-dichlorophenol (DCP) by thermal Fenton-type oxidation systems with a view toward defining in more details relevant process parameters, the effect of reaction temperature and of co-catalyst Cu2+. Reaction conditions were similar to those generally adopted as optimal in many practical applications, i.e. pollutant/Fe2+ (as FeSO4) ratio ca. 20, Fe2+/Cu2+ (co-catalyst) 2:1, pH adjusted and controlled at pH 3, and H2O2 in excess (up to four-fold over the stoichiometric amount required for complete mineralization). The results demonstrate that it is advantageous to carry out the reaction at a temperature markedly higher (70 degrees C) than ambient. The stepwise addition of H2O2 in aliquots yields an efficient transformation, while allowing a convenient control of the reaction exothermicity. Under these conditions, the essentially complete removal of the initial DCP is accomplished using just one equiv of H2O2 during 15 min; excess H2O2 (5 equivalents) yields extensive substrate mineralization. Also relevant, at 70 degrees C dechlorination of the initial DCP (and of derived reaction intermediates) is remarkably extensive (3-5% residual TOX), already with the addition of 1 equiv of H2O2. At the end of the reaction, IC and IC-MS analyses of the solution reveal that only low-molecular weight

  9. Impact of photosensitized oxidation and singlet oxygen on degradation of stabilized polymers

    Czech Academy of Sciences Publication Activity Database

    Pospíšil, Jan; Nešpůrek, Stanislav; Pilař, Jan

    2008-01-01

    Roč. 93, č. 9 (2008), s. 1681-1688 ISSN 0141-3910 R&D Projects: GA AV ČR IAA100100622; GA AV ČR KAN400720701; GA AV ČR IAA400500804 Institutional research plan: CEZ:AV0Z40500505 Keywords : photosensitized oxidation * singlet molecular oxygen * oxygenation Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.320, year: 2008

  10. Sonocatalytic degradation of methylene blue dye using a nanosized zinc oxide powder prepared via sonochemical method

    OpenAIRE

    Stanković, Ana; Veselinović, Ljiljana; Marković, Smilja; Uskoković, Dragan

    2013-01-01

    Nanostructured semiconductor materials are of great importance for various tecnological application due to their phisical and chemical properties wich are determined by the morphology and the size of the particles. Among semiconducor oxides, ZnO is one of the most important multifunctional material with its wide direct band gap energy of 3.37 eV and its excitation binding energy around 60 meV. Nowadays, many studies focus on the application of sonochemical reactions for treatment of industria...

  11. 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.

  12. 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.

  13. 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.

  14. Fenton-like Degradation of Phenol Catalyzed by a Series of Fe-Containing Mixed Oxides Systems

    Science.gov (United States)

    Alhmoud, T. T.; Mahmoud, S. S.; Hammoudeh, A. Y.

    2018-02-01

    In our attempts to develop a solid catalyst to degrade organic pollutants in wastewater via the Fenton-like reaction, six Fe-containing mixed oxide systems were prepared by means of the sol-gel auto-combustion method to have the following stoichiometries: CuFe1.2O2.8, BaFe7.2O11.8, BaFe7.2Cu2O13.8, BaFe5.4V3O16.6, BaFe4.8Cu2V3O17.7 and Ag2Fe5.4V3O16.6. The prepared systems were thermally treated at 550°C, 650°C, 800°C and 1100°C, and then characterized by XRD to identify the present phases. The systems were tested with respect to their catalytic efficiency in the degradation of phenol (200 ppm) in water where CuFe1.2O2.8 was found to be the most reactive one (80% removal in 60 min). It showed thereby first-order kinetics and an enhanced behavior under irradiation with a 30-W LED light source. The positive role of irradiation was most obvious in the case of Ag2Fe5.4V3O16.6 in which almost complete conversion was achieved in 120 min compared to only 45% in the same period but without irradiation. However, increasing the temperature at which thermal treatment is performed was found to suppress the catalytic activity of the system. Due to their high efficiency and rather low leaching rates of constituents, CuFe1.2O2.8 or Ag2Fe5.4V3O16.6 seem to be very promising in the Fenton-like degradation of organic pollutants.

  15. A microstructural study of the degradation and calcium release from hydroxyapatite-calcium oxide ceramics made by infiltration.

    Science.gov (United States)

    Zhang, Qinghao; Schmelzer, Eva; Gerlach, Jörg C; Nettleship, Ian

    2017-04-01

    Hydroxyapatite pellets, partially densified in a low-temperature heat treatment, were infiltrated with calcium nitrate solution followed by in-situ precipitation of Ca(OH) 2 and CaCO 3 . The infiltrated bodies were then densified to high relative density and the calcium carbonate transformed to calcium oxide during sintering and resulted in biphasic hydroxyapatite-CaO ceramics. This work investigated the influence of the infiltration on surface morphology, weight change, and microstructural-level degradation caused by exposure to saline at pH=7.4 and a temperature of 20°C. The CaO rendered the materials more susceptible to degradation, and released calcium into the saline faster than single phase, calcium deficient hydroxyapatite (HA) that were used as a control. In consequence, these ceramics could be used to release calcium into the culture microenvironments of bone tissue or bone marrow cells next to a scaffold surface. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Degradation of progestagens by oxidation with potassium permanganate in wastewater effluents.

    Science.gov (United States)

    Fayad, Paul B; Zamyadi, Arash; Broseus, Romain; Prévost, Michèle; Sauvé, Sébastien

    2013-01-01

    This study investigated the oxidation of selected progestagenic steroid hormones by potassium permanganate at pH 6.0 and 8.0 in ultrapure water and wastewater effluents, using bench-scale assays. Second order rate constants for the reaction of potassium permanganate with progestagens (levonorgestrel, medroxyprogesterone, norethindrone and progesterone) was determined as a function of pH, presence of natural organic matter and temperature. This work also illustrates the advantages of using a novel analytical method, the laser diode thermal desorption (LDTD-APCI) interface coupled to tandem mass spectrometry apparatus, allowing for the quick determination of oxidation rate constants and increasing sample throughput. The second-order rate constants for progestagens with permanganate determined in bench-scale experiments ranged from 23 to 368 M(-1) sec(-1) in both wastewater and ultrapure waters with pH values of 6.0 and 8.0. Two pairs of progestagens exhibited similar reaction rate constants, i.e. progesterone and medroxyprogesterone (23 to 80 M(-1) sec(-1) in ultrapure water and 26 to 149 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0) and levonorgestrel and norethindrone (179 to 224 M(-1) sec(-1) in ultrapure water and 180 to 368 M(-1) sec(-1) in wastewaters, at pH 6.0 and 8.0). The presence of dissolved natural organic matter and the pH conditions improved the oxidation rate constants for progestagens with potassium permanganate only at alkaline pH. Reaction rates measured in Milli-Q water could therefore be used to provide conservative estimates for the oxidation rates of the four selected progestagens in wastewaters when exposed to potassium permanganate. The progestagen removal efficiencies was lower for progesterone and medroxyprogesterone (48 to 87 %) than for levonorgestrel and norethindrone (78 to 97%) in Milli-Q and wastewaters at pH 6.0-8.2 using potassium permanganate dosages of 1 to 5 mg L(-1) after contact times of 10 to 60 min. This

  17. Recovery of thermal-degraded ZnO photodetector by embedding nano silver oxide nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Zhan-Shuo [Institute of Microelectronics, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); Hung, Fei-Yi, E-mail: fyhung@mail.ncku.edu.tw [Institute of Nanotechnology and Microsystems Engineering, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); Chen, Kuan-Jen [Institute of Nanotechnology and Microsystems Engineering, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); The Instrument Center, National Cheng Kung University, Tainan 701, Taiwan (China); Chang, Shoou-Jinn [Institute of Microelectronics, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); Institute of Microelectronics and Department of Electrical Engineering, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China); Hsieh, Wei-Kang; Liao, Tsai-Yu; Chen, Tse-Pu [Institute of Microelectronics, Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan (China)

    2013-08-15

    The degraded performance of annealed ZnO-based photodetector can be recovered by embedding Ag{sub 2}O nanoparticles resulted from the transformation of as-deposited Ag layer. After thermal treatment, the electrons were attracted at the interface between ZnO and Ag{sub 2}O. The excess Ag{sup +} ions form the cluster to incorporate into the interstitial sites of ZnO lattice to create a larger amount of lattice defects for the leakage path. The photo-current of ZnO film with Ag{sub 2}O nanoparticles is less than annealed ZnO film because the photo-induced electrons would flow into Ag{sub 2}O side. ZnO photodetector with the appropriate Ag{sub 2}O nanoparticles possesses the best rejection ratio.

  18. 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

  19. p-Nitrophenol degradation by Fenton's oxidation in a bubble column reactor.

    Science.gov (United States)

    Rodrigues, Carmen S D; Borges, Ricardo A C; Lima, Vanessa N; Madeira, Luis M

    2018-01-15

    This paper reports on a study of the oxidation of p-nitrophenol (PNP) in a bubble column reactor (BCR). The use of the air stream aimed to provide perfect mixing in the liquid phase, which was successfully achieved and checked experimentally; there were no concentration gradients along the column, even at the lowest air flow rate used (Q = 1 mL/min at room temperature and atmospheric pressure). The effect of the operating variables was assessed, and a total reduction of PNP was reached, as well as mineralization of 49.2%, oxidant consumption of 90.3%, and with an efficiency of use - η H2O2 - of 0.09 mg C/mg H 2 O 2 , under the best operating conditions found - Q = 1 mL/min, [H 2 O 2 ] = 1.6 g/L, [Fe 2+ ] = 80 mg/L, pH = 3.0 and T = 22-24 °C - (after 120 min of reaction). Following this, various strategies were developed for improving the mineralization rate; it was found that the addition of H 2 O 2 every 5 min and readjusting the pH after 30 min of reaction allow the attainment of a much higher TOC removal (75.1%) and efficiency of oxidant use (η H2O2  = 0.17 mg C/mg H 2 O 2 ) with less oxidant. A reaction mechanism was proposed, based on intermediates identified that include p-nitrocatechol - PNC, p-benzoquinone - PB, hydroquinone - HQ - and carboxylic acids (oxalic, maleic and fumaric). Since the performance achieved in the BCR was good, and very similar to that obtained in a conventional batch reactor, it was possible to verify the efficacy of carrying out the Fenton process in this reactor configuration, which in our future work will focus on the treatability of industrial effluents. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Reduced graphene oxide–cuprous oxide composite via facial deposition for photocatalytic dye-degradation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, MingYan, E-mail: mingyanlyg@hotmail.com [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Intelligent Polymer Research Institute, ARC Centre of Excellence for Electromaterials Science, Australian Institute of Innovative Materials, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia); Huang, JunRao; Tong, ZhiWei [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Li, WeiHua [School of Mechanical, Materials and Mechatronic Engineering, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia); Chen, Jun, E-mail: junc@uow.edu.au [Intelligent Polymer Research Institute, ARC Centre of Excellence for Electromaterials Science, Australian Institute of Innovative Materials, University of Wollongong, Northfields Avenue, Wollongong, NSW 2522 (Australia)

    2013-08-15

    Highlights: •Cubic Cu{sub 2}O were effectively loaded on n-propylamine (PA) intercalated graphene oxide. •The addition of PA on the carbon sheets supports the stable structure of the composites. •Cu{sub 2}O/PA/rGO showed superior adsorption capacity and photocatalytic activity. -- Abstract: Cubic Cu{sub 2}O nanoparticles have been successfully synthesized on n-propylamine (PA) intercalated graphene oxide (GO) with uniform distribution followed with a subsequent hydrazine hydrate reduction process to generate Cu{sub 2}O/PA/rGO composite. For comparison, Cu{sub 2}O conjugated reduced graphene oxide (Cu{sub 2}O/rGO) composite was also synthesized using the same method. The as-prepared Cu{sub 2}O/PA/rGO and Cu{sub 2}O/rGO nanocomposites are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, infrared spectroscopy (IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) surface area analysis, and Electrochemical impedance spectra (EIS) measurements. UV/vis diffuse reflectance spectroscopy was employed to estimate band gap energies of cuprous oxide composites. The results show that the intercalation of PA into the layered GO increases the surface area of the composites and provides an efficient strategy to load Cu{sub 2}O due to the large and uniform distribution of active sites for anchoring copper ions. The surface area of the Cu{sub 2}O/PA/rGO (123 m{sup 2}/g) nanocomposite was found to be almost 2.5 times higher than that of Cu{sub 2}O/rGO (55.7 m{sup 2}/g). The as-prepared Cu{sub 2}O/PA/rGO show significant improvement on both adsorption capacity and photocatalytic activity towards organic pigment pollution compared with Cu{sub 2}O/rGO under identical performance conditions.

  1. 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

  2. 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.

  3. Degradation of ticarcillin by subcritial water oxidation method: Application of response surface methodology and artificial neural network modeling.

    Science.gov (United States)

    Yabalak, Erdal

    2018-05-18

    This study was performed to investigate the mineralization of ticarcillin in the artificially prepared aqueous solution presenting ticarcillin contaminated waters, which constitute a serious problem for human health. 81.99% of total organic carbon removal, 79.65% of chemical oxygen demand removal, and 94.35% of ticarcillin removal were achieved by using eco-friendly, time-saving, powerful and easy-applying, subcritical water oxidation method in the presence of a safe-to-use oxidizing agent, hydrogen peroxide. Central composite design, which belongs to the response surface methodology, was applied to design the degradation experiments, to optimize the methods, to evaluate the effects of the system variables, namely, temperature, hydrogen peroxide concentration, and treatment time, on the responses. In addition, theoretical equations were proposed in each removal processes. ANOVA tests were utilized to evaluate the reliability of the performed models. F values of 245.79, 88.74, and 48.22 were found for total organic carbon removal, chemical oxygen demand removal, and ticarcillin removal, respectively. Moreover, artificial neural network modeling was applied to estimate the response in each case and its prediction and optimizing performance was statistically examined and compared to the performance of central composite design.

  4. Interconnection of Key Microbial Functional Genes for Enhanced Benzo[a]pyrene Biodegradation in Sediments by Microbial Electrochemistry.

    Science.gov (United States)

    Yan, Zaisheng; He, Yuhong; Cai, Haiyuan; Van Nostrand, Joy D; He, Zhili; Zhou, Jizhong; Krumholz, Lee R; Jiang, He-Long

    2017-08-01

    Sediment microbial fuel cells (SMFCs) can stimulate the degradation of polycyclic aromatic hydrocarbons in sediments, but the mechanism of this process is poorly understood at the microbial functional gene level. Here, the use of SMFC resulted in 92% benzo[a]pyrene (BaP) removal over 970 days relative to 54% in the controls. Sediment functions, microbial community structure, and network interactions were dramatically altered by the SMFC employment. Functional gene analysis showed that c-type cytochrome genes for electron transfer, aromatic degradation genes, and extracellular ligninolytic enzymes involved in lignin degradation were significantly enriched in bulk sediments during SMFC operation. Correspondingly, chemical analysis of the system showed that these genetic changes resulted in increases in the levels of easily oxidizable organic carbon and humic acids which may have resulted in increased BaP bioavailability and increased degradation rates. Tracking microbial functional genes and corresponding organic matter responses should aid mechanistic understanding of BaP enhanced biodegradation by microbial electrochemistry and development of sustainable bioremediation strategies.

  5. Microstructural degradation of Ni-YSZ anodes for solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Thyden, K.

    2008-03-15

    Ni-YSZ cermets have been used as anode materials in SOFCs for more than 20 years. Despite this fact, the major cause of degradation within the Ni-YSZ anode, namely Ni sintering / coarsening, is still not fully understood. Even if microstructural studies of anodes in tested cells are of technological relevance, it is difficult to identify the effect from isolated parameters such as temperature, fuel gas composition and polarization. Model studies of high temperature aged Ni-YSZ cermets are generally performed in atmospheres containing relatively low concentrations of H2O. In this work, the microstructural degradation in both electrochemically longterm tested cells and high-temperature aged model materials are studied. Since Ni particle sintering / coarsening is attributed to be the major cause of anode degradation, this subject attains the primary focus. A large part of the work is focused on improving microstructural techniques and shows that the application of low acceleration voltages (<= 1 kV) in a FE-SEM makes it possible to obtain two useful types of contrast between the phases in Ni-YSZ composites. By changing between the ordinary lateral SE detector and the inlens detector, using similar microscope settings, two very different sample characteristics are probed: 1) The difference in secondary emission coefficient, delta, between the percolating and non-percolating Ni is maximized in the low-voltage range due to a high delta for the former and the suppression of delta by a positive charge for the latter. This difference yields a contrast between the two phases which is picked up by an inlens secondary electron detector. 2) The difference in backscatter coefficient, eta, between Ni and YSZ is shown to increase with decreasing voltage. The contrast is illustrated in images collected by the normal secondary detector since parts of the secondary signals are generated by backscattered electrons. High temperature aging experiments of model Ni-YSZ anode cermets show

  6. Rapid photo-degradation of 2-chlorophenol under visible light irradiation using cobalt oxide-loaded TiO2/reduced graphene oxide nanocomposite from aqueous media.

    Science.gov (United States)

    Sharma, Ajit; Lee, Byeong-Kyu

    2016-01-01

    The photocatalytic removal of 2-chlorophenol (2-CP) from water environment was investigated by TiO2-RGO-CoO. Cobalt oxide-loaded TiO2 (TiO2-CoO) supported with reduced graphene oxide (RGO) was synthesized using a sol-gel method and then annealed at 500 °C for 5 min. The material characteristics were analyzed by UV-Vis analysis, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. Incorporation of cobalt oxide and RGO into the TiO2 system (TiO2-RGO-CoO) lowered the band gap energy to 2.83 eV, which greatly enhanced the visible light absorption. The TiO2-RGO-CoO photocatalyst showed complete removal of 20 mg/L 2-CP within 8 h with the addition of 0.01% H2O2 under 100 W visible light irradiation. The photo-degradation efficiency of 2-CP (10 mg/L) was 35.2, 48.9, 58.9 and 98.2% for TiO2, TiO2-RGO, TiO2-CoO and TiO2-RGO-CoO, respectively, in the presence of visible light irradiation at solution pH of 6.0. The TiO2-RGO-CoO photocatalyst retained its high removal efficiency even after five photocatalytic cycles. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Oxidative Debromination and Degradation of Tetrabromo-bisphenol A by a Functionalized Silica-Supported Iron(III-tetrakis(p-sulfonatophenylporphyrin Catalyst

    Directory of Open Access Journals (Sweden)

    Masami Fukushima

    2013-05-01

    Full Text Available Tetrabromobisphenol A (TBBPA, a commonly used brominated flame retardant, also functions as an endocrine disruptor. Thus, the degradation of TBBPA has attracted considerable interest among the scientific community. Iron(III-porphyrin complexes are generally regarded as “green” catalysts and have been reported to catalyze the efficient degradation and dehalogenation of halogenated phenols in environmental wastewaters. However, they are quickly deactivated due to self-degradation in the presence of an oxygen donor, such as KHSO5. In the present study, an iron(III-tetrakis (p-sulfonatophenyl-porphyrin (FeTPPS was immobilized on imidazole-modified silica (FeTPPS/IPS via coordination of the Fe(III with the nitrogen atom in imidazole to suppress self-degradation and thus enhance the catalyst reusability. The oxidative degradation and debromination of TBBPA and the influence of humic acid (HA, a major component in leachates, on the oxidation of TBBPA was investigated. More than 95% of the TBBPA was degraded in the pH range from 3 to 8 in the absence of HA, while the optimal pH for the reaction was at pH 8 in the presence of HA. Although the rate of degradation was decreased in the presence of HA, over 95% of the TBBPA was degraded within 12 h in the presence of 28 mg-C L−1 of HA. At pH 8, the FeTPPS/IPS catalyst could be reused up to 10 times without any detectable loss of activity for TBBPA for degradation and debromination, even in the presence of HA.

  8. The Major Chromophore Arising from Glucose Degradation and Oxidative Stress Occurrence during Lens Proteins Glycation Induced by Glucose

    Directory of Open Access Journals (Sweden)

    Felipe Ávila

    2017-12-01

    Full Text Available Glucose autoxidation has been proposed as a key reaction associated with deleterious effects induced by hyperglycemia in the eye lens. Little is known about chromophores generated during glucose autoxidation. In this study, we analyzed the effect of oxidative and dicarbonyl stress in the generation of a major chromophore arising from glucose degradation (GDC and its association with oxidative damage in lens proteins. Glucose (5 mM was incubated with H2O2 (0.5–5 mM, Cu2+ (5–50 μM, glyoxal (0.5–5 mM or methylglyoxal (0.5–5 mM at pH 7.4, 5% O2, 37 °C, from 0 to 30 days. GDC concentration increased with incubation time, as well as when incubated in the presence of H2O2 and/or Cu2+, which were effective even at the lowest concentrations. Dicarbonylic compounds did not increase the levels of GDC during incubations. 1H, 13C and FT-IR spectra from the purified fraction containing the chromophore (detected by UV/vis spectroscopy showed oxidation products of glucose, including gluconic acid. Lens proteins solutions (10 mg/mL incubated with glucose (30 mM presented increased levels of carboxymethyl-lysine and hydrogen peroxide that were associated with GDC increase. Our results suggest a possible use of GDC as a marker of autoxidative reactions occurring during lens proteins glycation induced by glucose.

  9. Experimental study of the oxidative degradation of PBX 9501 and its components

    Energy Technology Data Exchange (ETDEWEB)

    Salazar, Michael R. [Department of Chemistry, Union University, Jackson, Tennessee (United States); Kress, Joel D. [Theoretical Division (T-12, MS B268), Los Alamos National Laboratory, Los Alamos, New Mexico (United States); Lightfoot, J.M.; Russel, Bobby G.; Rodin, Wayne A.; Woods, Lorelei [Babcock and Wilcox Technical Services Pantex, LLC (B and W Pantex), Amarillo, Texas (United States)

    2008-06-15

    The results of the constituent aging study (CAS) are given, where low-temperature (T<64 C) aging experiments were performed on over 1100 closed-container samples of various combinations of the components of the plastic-bonded explosive PBX 9501. Experiments were performed on the various combinations both in the absence and presence of free-radical stabilizers. The product gases were identified and quantified as a function of aging time. The gas data show diverse chemistry between CAS samples and initial linear increases in product gas formation. Temperature analysis of the initial production rates of gas products shows straight Arrhenius plots. The extracted activation energies and frequency factors for the formation of the individual gas products yield a single linear kinetic compensation plot suggesting a common degradation pathway for PBX 9501 and combinations of constituents that contained nitroplasticizer (a eutectic mixture of bis-2,2-dintropropyl acetal and bis-2,2-dintropropyl formal). (Abstract Copyright [2008], Wiley Periodicals, Inc.)

  10. Degradation of poly(2,6-dimethylphenylene oxide) and poly(phenylene sulfide) by gamma irradiation

    International Nuclear Information System (INIS)

    Hill, D.J.T.; Hunter, D.S.; Lewis, D.A.; O'Donnell, J.H.; Pomery, P.J.

    1990-01-01

    Electron spin resonance (ESR) spectroscopy and volatile product analysis have been used to examine the degradation of poly[oxy(2,6-dimethyl-1,4-phenylene)], PPO, and poly(thio-1,4-phenylene), PPS, by γ-radiation. Radiation chemical yields (G-values) for trapped radicals were 0.60 and 0.16 after irradiation at 77 K, and 0.33 and 0.04 after irradiation at 300 K, for PPO and PPS, respectively. The ESR spectra of PPO can be analyzed in terms of PhO·, PhCH 2 · and cyclohexadienyl radicals, whereas PPS contained predominantly photobleachable radical ions. G(H 2 ) = 0.08 and G(CH 4 ) = 0.015 for PPO irradiated at 300 K: G(H 2 ) = 0.03 for PPS. The radicals in PPO indicate main-chain scission of the Ph-O bond and loss of H from CH 3 in equal amounts. The radical ions in PPS decayed without the formation of neutral radicals indicating little bond scission and extremely high radiation resistance, which is confirmed by the low G(R) and G(H 2 ) values. (author)

  11. Phenol Photocatalytic Degradation by Advanced Oxidation Process under Ultraviolet Radiation Using Titanium Dioxide

    Directory of Open Access Journals (Sweden)

    Ali Nickheslat

    2013-01-01

    Full Text Available Background. The main objective of this study was to examine the photocatalytic degradation of phenol from laboratory samples and petrochemical industries wastewater under UV radiation by using nanoparticles of titanium dioxide coated on the inner and outer quartz glass tubes. Method. The first stage of this study was conducted to stabilize the titanium dioxide nanoparticles in anatase crystal phase, using dip-coating sol-gel method on the inner and outer surfaces of quartz glass tubes. The effect of important parameters including initial phenol concentration, TiO2 catalyst dose, duration of UV radiation, pH of solution, and contact time was investigated. Results. In the dip-coat lining stage, the produced nanoparticles with anatase crystalline structure have the average particle size of 30 nm and are uniformly distributed over the tube surface. The removal efficiency of phenol was increased with the descending of the solution pH and initial phenol concentration and rising of the contact time. Conclusion. Results showed that the light easily passes through four layers of coating (about 105 nm. The highest removal efficiency of phenol with photocatalytic UV/TiO2 process was 50% at initial phenol concentration of 30 mg/L, solution pH of 3, and 300 min contact time. The comparison of synthetic solution and petrochemical wastewater showed that at same conditions the phenol removal efficiency was equal.

  12. TiO2-Based Photocatalytic Geopolymers for Nitric Oxide Degradation

    Science.gov (United States)

    Strini, Alberto; Roviello, Giuseppina; Ricciotti, Laura; Ferone, Claudio; Messina, Francesco; Schiavi, Luca; Corsaro, Davide; Cioffi, Raffaele

    2016-01-01

    This study presents an experimental overview for the development of photocatalytic materials based on geopolymer binders as catalyst support matrices. Particularly, geopolymer matrices obtained from different solid precursors (fly ash and metakaolin), composite systems (siloxane-hybrid, foamed hybrid), and curing temperatures (room temperature and 60 °C) were investigated for the same photocatalyst content (i.e., 3% TiO2 by weight of paste). The geopolymer matrices were previously designed for different applications, ranging from insulating (foam) to structural materials. The photocatalytic activity was evaluated as NO degradation in air, and the results were compared with an ordinary Portland cement reference. The studied matrices demonstrated highly variable photocatalytic performance depending on both matrix constituents and the curing temperature, with promising activity revealed by the geopolymers based on fly ash and metakaolin. Furthermore, microstructural features and titania dispersion in the matrices were assessed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDS) analyses. Particularly, EDS analyses of sample sections indicated segregation effects of titania in the surface layer, with consequent enhancement or depletion of the catalyst concentration in the active sample region, suggesting non-negligible transport phenomena during the curing process. The described results demonstrated that geopolymer binders can be interesting catalyst support matrices for the development of photocatalytic materials and indicated a large potential for the exploitation of their peculiar features. PMID:28773634

  13. TiO2-Based Photocatalytic Geopolymers for Nitric Oxide Degradation

    Directory of Open Access Journals (Sweden)

    Alberto Strini

    2016-06-01

    Full Text Available This study presents an experimental overview for the development of photocatalytic materials based on geopolymer binders as catalyst support matrices. Particularly, geopolymer matrices obtained from different solid precursors (fly ash and metakaolin, composite systems (siloxane-hybrid, foamed hybrid, and curing temperatures (room temperature and 60 °C were investigated for the same photocatalyst content (i.e., 3% TiO2 by weight of paste. The geopolymer matrices were previously designed for different applications, ranging from insulating (foam to structural materials. The photocatalytic activity was evaluated as NO degradation in air, and the results were compared with an ordinary Portland cement reference. The studied matrices demonstrated highly variable photocatalytic performance depending on both matrix constituents and the curing temperature, with promising activity revealed by the geopolymers based on fly ash and metakaolin. Furthermore, microstructural features and titania dispersion in the matrices were assessed by scanning electron microscopy (SEM and energy dispersive X-ray (EDS analyses. Particularly, EDS analyses of sample sections indicated segregation effects of titania in the surface layer, with consequent enhancement or depletion of the catalyst concentration in the active sample region, suggesting non-negligible transport phenomena during the curing process. The described results demonstrated that geopolymer binders can be interesting catalyst support matrices for the development of photocatalytic materials and indicated a large potential for the exploitation of their peculiar features.

  14. A non-acid-assisted and non-hydroxyl-radical-related catalytic ozonation with ceria supported copper oxide in efficient oxalate degradation in water

    KAUST Repository

    Zhang, Tao

    2012-06-01

    Oxalate is usually used as a refractory model compound that cannot be effectively removed by ozone and hydroxyl radical oxidation in water. In this study, we found that ceria supported CuO significantly improved oxalate degradation in reaction with ozone. The optimum CuO loading amount was 12%. The molar ratio of oxalate removed/ozone consumption reached 0.84. The catalytic ozonation was most effective in a neutral pH range (6.7-7.9) and became ineffective when the water solution was acidic or alkaline. Moreover, bicarbonate, a ubiquitous hydroxyl radical scavenger in natural waters, significantly improved the catalytic degradation of oxalate. Therefore, the degradation relies on neither hydroxyl radical oxidation nor acid assistance, two pathways usually proposed for catalytic ozonation. These special characters of the catalyst make it suitable to be potentially used for practical degradation of refractory hydrophilic organic matter and compounds in water and wastewater. With in situ characterization, the new surface Cu(II) formed from ozone oxidation of the trace Cu(I) of the catalyst was found to be an active site in coordination with oxalate forming multi-dentate surface complex. It is proposed that the complex can be further oxidized by molecular ozone and then decomposes through intra-molecular electron transfer. The ceria support enhanced the activity of the surface Cu(I)/Cu(II) in this process. © 2012 Elsevier B.V.

  15. Poly(ethylene oxide)/poly(butylene terephthalate) segmented block copolymers: the effect of copolymer composition on physical properties and degradation behavior

    NARCIS (Netherlands)

    Deschamps, A.A.; Grijpma, Dirk W.; Feijen, Jan

    2001-01-01

    In this study, the influence of copolymer composition on the physical properties and the degradation behavior of thermoplastic elastomers based on poly(ethylene oxide) (PEO) and poly(butylene terephthalate) (PBT) segments is investigated. These materials are intended to be used in medical

  16. Reliability and degradation of oxide VCSELs due to reaction to atmospheric water vapor

    Science.gov (United States)

    Dafinca, Alexandru; Weidberg, Anthony R.; McMahon, Steven J.; Grillo, Alexander A.; Farthouat, Philippe; Ziolkowski, Michael; Herrick, Robert W.

    2013-03-01

    850nm oxide-aperture VCSELs are susceptible to premature failure if operated while exposed to atmospheric water vapor, and not protected by hermetic packaging. The ATLAS detector in CERN's Large Hadron Collider (LHC) has had approximately 6000 channels of Parallel Optic VCSELs fielded under well-documented ambient conditions. Exact time-to-failure data has been collected on this large sample, providing for the first time actual failure data at use conditions. In addition, the same VCSELs were tested under a variety of accelerated conditions to allow us to construct a more accurate acceleration model. Failure analysis information will also be presented to show what we believe causes corrosion-related failure for such VCSELs.

  17. Degradation of some ceria electrolytes under hydrogen contact nearby anode in solid oxide fuel cells (SOFCs

    Directory of Open Access Journals (Sweden)

    Malta Luiz Fernando Brum

    2004-01-01

    Full Text Available This work is concerned with thermodynamic analysis of the stability of some ceria electrolytes under contact with hydrogen gas nearby anode in fuel cells. It was considered the following types of ceria-electrolytes: pure ceria, strontium-doped ceria, calcium-doped ceria and calcium-bismuth-doped ceria. The equilibrium Log (pH2O/pH2 vs. T diagrams were constructed for x = 0.1 and 0.01, where x is the fraction of initial ceria converted to Ce2O3 (proportional to the ratio between activities of Ce3+ and Ce4+ in the ceria electrolyte, which is proportional to the fraction of electronic conduction in the electrolyte at a given temperature. The predictions of the diagrams are as follows: (a Ce1.9Ca0.1Bi0.8O5.1 and Ce0.9Sr0.1O1.9 are less stable than pure ceria for the whole temperature range (from 0 to 1000 °C; (b Ce0.9Ca0.1O1.9 is more stable than pure ceria below about 650 °C for x = 0.1 and below about 400 °C for x = 0.01; (c at each temperature in the considered range the pressure ratio pH2O(g/pH2(g has to be higher than thermodynamically predicted in order to keep CeO2 stable in the electrolyte contacting hydrogen gas. Thermodynamic predictions are entirely capable of explaining experimental data published on the subject (irreversible cell degradation in the case of SrO-doped ceria; weight loss from doped-ceria electrolyte above 700 °C; oxygen gas release during sintering of ceria.

  18. Phenol degradation in aqueous solution by photolytic oxidation with ozone and/or hydrogen peroxide

    International Nuclear Information System (INIS)

    Koepp, T.; Koether, M.; Brueckner, B.; Radeke, K.H.

    1993-01-01

    The removal of phenol in an aqueous solution as a typical pollutant by oxidation using ozone and hydrogen peroxide under ultraviolet irradiation has been studied. Both the O 3 /UV and the H 2 O 2 /UV method can be powerful to decompose the total organic carbon (TOC) to carbon dioxide and water, but the first method is more effective. In the case of H 2 O 2 /UV method a strong overdose on H 2 O 2 is necessary to remove TOC effectively, however, a favourable H 2 O 2 concentration exists. This is probably caused by undesired parallel reactions of hydrogen peroxide. The simultaneous use of ozone and hydrogen peroxide accelerates the removal of TOC in the first third of experiment in comparison to the O 3 /UV method, but the time of total decomposition of TOC is delayed. A change in measured kinetics of ozone consumption by organic molecules corresponds well with the time of total transformation of aromatic into aliphatic substances. (orig.)

  19. A novel reducing graphene/polyaniline/cuprous oxide composite hydrogel with unexpected photocatalytic activity for the degradation of Congo red

    Energy Technology Data Exchange (ETDEWEB)

    Miao, Jie; Xie, Anjian; Li, Shikuo; Huang, Fangzhi; Cao, Juan; Shen, Yuhua, E-mail: yhshen@ahu.edu.cn

    2016-01-01

    Graphical abstract: Excellent photocatalytic activity of the RGO/PANI/Cu{sub 2}O composite hydrogel for CR degradation under UV–vis light irradiation. - Highlights: • The RGO/PANI/Cu{sub 2}O composite hydrogel was first synthesized via a facile method. • Photocatalytic performance was studied under UV–vis light. • The ternary composite hydrogel shows unexpected photocatalytic activity. • A possible photocatalysis mechanism was illustrated. - Abstract: In this work, a novel reducing graphene/polyaniline/cuprous oxide (RGO/PANI/Cu{sub 2}O) composite hydrogel with a 3D porous network has been successfully prepared via a one-pot method in the presence of cubic Cu{sub 2}O nanoparticles. The as-synthesized ternary composites hydrogel shows unexpected photocatalytic activity such that Congo red (CR) degradation efficiency can reaches 97.91% in 20 min under UV–vis light irradiation, which is much higher than that of either the single component (Cu{sub 2}O nanoparticles), or two component systems (RGO/Cu{sub 2}O composite hydrogel and PANI/Cu{sub 2}O nanocomposites). Furthermore, the ternary composite hydrogel exhibits high stability and do not show any significant loss after five recycles. Such outstanding photocatalytic activity of the RGO/PANI/Cu{sub 2}O composite hydrogel was ascribed to the high absorption ability of the product for CR and the synergic effect among RGO, PANI and Cu{sub 2}O in photocatalytic process. The product of this work would provide a new sight for the construction of UV–vis light responsive photocatalyst with high performance.

  20. A novel reducing graphene/polyaniline/cuprous oxide composite hydrogel with unexpected photocatalytic activity for the degradation of Congo red

    International Nuclear Information System (INIS)

    Miao, Jie; Xie, Anjian; Li, Shikuo; Huang, Fangzhi; Cao, Juan; Shen, Yuhua

    2016-01-01

    Graphical abstract: Excellent photocatalytic activity of the RGO/PANI/Cu_2O composite hydrogel for CR degradation under UV–vis light irradiation. - Highlights: • The RGO/PANI/Cu_2O composite hydrogel was first synthesized via a facile method. • Photocatalytic performance was studied under UV–vis light. • The ternary composite hydrogel shows unexpected photocatalytic activity. • A possible photocatalysis mechanism was illustrated. - Abstract: In this work, a novel reducing graphene/polyaniline/cuprous oxide (RGO/PANI/Cu_2O) composite hydrogel with a 3D porous network has been successfully prepared via a one-pot method in the presence of cubic Cu_2O nanoparticles. The as-synthesized ternary composites hydrogel shows unexpected photocatalytic activity such that Congo red (CR) degradation efficiency can reaches 97.91% in 20 min under UV–vis light irradiation, which is much higher than that of either the single component (Cu_2O nanoparticles), or two component systems (RGO/Cu_2O composite hydrogel and PANI/Cu_2O nanocomposites). Furthermore, the ternary composite hydrogel exhibits high stability and do not show any significant loss after five recycles. Such outstanding photocatalytic activity of the RGO/PANI/Cu_2O composite hydrogel was ascribed to the high absorption ability of the product for CR and the synergic effect among RGO, PANI and Cu_2O in photocatalytic process. The product of this work would provide a new sight for the construction of UV–vis light responsive photocatalyst with high performance.

  1. Catalytic degradation of Acid Orange 7 by manganese oxide octahedral molecular sieves with peroxymonosulfate under visible light irradiation

    International Nuclear Information System (INIS)

    Duan, Lian; Sun, Binzhe; Wei, Mingyu; Luo, Shilu; Pan, Fei; Xu, Aihua; Li, Xiaoxia

    2015-01-01

    Highlights: • OMS-2/PMS/Vis system could efficiently catalyze the degradation of organic dyes. • The system showed much higher activity than that of OMS-2/PMS and OMS-2/Vis. • The OMS-2 catalyst exhibited stable performance for multiple runs. • Sulfate radicals were suggested to be the major reactive species in the system. • The radicals production might involve the redox cycle of Mn(IV)/Mn(III) and Mn(III)/Mn(II). - Abstract: In this paper, the photodegradation of Acid Orange 7 (AO7) in aqueous solutions with peroxymonosulfate (PMS) was studied with manganese oxide octahedral molecular sieves (OMS-2) as the catalyst. The activities of different systems including OMS-2 under visible light irradiation (OMS-2/Vis), OMS-2/PMS and OMS-2/PMS/Vis were evaluated. It was found that the efficiency of OMS-2/PMS was much higher than that of OMS-2/Vis and could be further enhanced by visible light irradiation. The catalyst also exhibited stable performance for multiple runs. Results from ESR and XPS analyses suggested that the highly catalytic activity of the OMS-2/PMS/Vis system possible involved the activation of PMS to sulfate radicals meditated by the redox pair of Mn(IV)/Mn(III) and Mn(III)/Mn(II), while in the OMS-2/PMS system, only the redox reaction between Mn(IV)/Mn(III) occurred. Several operational parameters, such as dye concentration, catalyst load, PMS concentration and solution pH, affected the degradation of AO7

  2. Chemical composition, anti-oxidative activity and in vitro dry matter degradability of Kinnow mandarin fruit waste

    Directory of Open Access Journals (Sweden)

    Ravleen Kour

    2014-10-01

    Full Text Available Aim: Fruit processing and consumption yield a significant amount of by-products as waste, which can be used as potential nutrient suppliers for livestock. “Kinnow” (Citrus nobilis Lour x Citrus deliciosa Tenora is one of the most important citrus fruit crops of North Indian States. Its residues are rich in carbohydrates but poor in protein and account for approximately 55-60% of the raw weight of the fruit. Present study assessed the chemical composition and anti-oxidative activity of Kinnow mandarin fruit waste (KMW and scrutinized the impact of dietary incorporation of variable levels of KMW on in vitro dry matter digestibility (IVDMD. Materials and Methods: Sun dried and ground KMW was analyzed for proximate composition, fibre fractions and calcium and phosphorus content. Antioxidant potential of KMW as total phenolic count and 1-diphenyl-2-picrylhydrazyl (DPPH scavenging activity was assayed in an alcoholic extract of KMW. The effect of inclusion of KMW at variable levels (0-40% in the isonitrogenous concentrate mixtures on in vitro degradability of composite feed (concentrate mixture:Wheat straw; 40:60 was also carried out. Results: KMW after sun-drying contained 92.05% dry matter. The crude protein content of 7.60% indicates it being marginal in protein content, whereas nitrogen free extract content of 73.69% suggests that it is primarily a carbonaceous feedstuff. This observation was also supported by low neutral detergent fiber and acid detergent fiber content of 26.35% and 19.50%, respectively. High calcium content (0.92% vis-à-vis low phosphorus content (0.08%, resulted in wide Ca:P ratio (11.5 in KMW. High anti-oxidative potential of KMW is indicated by total phenolic content values of 17.1±1.04 mg gallic acid equivalents/g and DPPH free radicle scavenging activity 96.2 μg/ml (effective concentration 50. Mean IVDMD% of all the composite rations was found to be comparable (p>0.05 irrespective of the level of KMW inclusion

  3. Visible light responsive Cu2MoS4 nanosheets incorporated reduced graphene oxide for efficient degradation of organic pollutant

    Science.gov (United States)

    Rameshbabu, R.; Vinoth, R.; Navaneethan, M.; Harish, S.; Hayakawa, Y.; Neppolian, B.

    2017-10-01

    Visible light active copper molybdenum sulfide (Cu2MoS4) nanosheets were successfully anchored on reduced graphene oxide (rGO) using facile hydrothermal method. During the hydrothermal reaction, reduction of graphene oxide into rGO and the formation of Cu2MoS4 nanosheets were successfully obtained. The charge transfer interaction between the rGO sheets and Cu2MoS4 nanosheets extended the absorption to visible region in comparison with bare Cu2MoS4 nanosheets i.e without rGO sheets. Furthermore, the notable photoluminescence quenching observed for Cu2MoS4/rGO nanocomposite revealed the effective role of rGO towards the significant inhibition of electron-hole pair recombination. The photocatalytic efficiencies of bare Cu2MoS4 and Cu2MoS4/rGO nanocomposite was evaluated for the degradation of methyl orange dye under visible irradiation (λ > 420 nm). A maximum photodegradation efficiency of 99% was achieved for Cu2MoS4/rGO nanocomposite, while only 64% photodegradation was noted for bare Cu2MoS4. The enhanced optical absorption in visible region, high surface area, and low charge carrier recombination in the presence of rGO sheets were the main reasons for the enhancement in photodegardation of MO dye. In addition, the resultant Cu2MoS4/rGO nanocomposite was found to be reusable for five successive cycles without significant loss in its photocatalytic performance.

  4. Nitric Oxide Induces Cardiac Protection by Preventing Extracellular Matrix Degradation through the Complex Caveolin-3/EMMPRIN in Cardiac Myocytes.

    Directory of Open Access Journals (Sweden)

    Irene Cuadrado

    Full Text Available Inhibition of Extracellular Matrix degradation by nitric oxide (NO induces cardiac protection against coronary ischemia/reperfusion (IR. Glycosylation of Extracellular Matrix Metalloproteinase Inducer (EMMPRIN stimulates enzymatic activation of matrix metalloproteinases (MMPs in the heart, although the mechanisms leading to EMMPRIN glycosylation are poorly understood. We sought to determine if NO may induce cardiac protection by preventing glycosylation of EMMPRIN in a mouse model of IR. Here we found that Caveolin-3 binds to low glycosylated EMMPRIN (LG-EMMPRIN in cardiac cells and in the hearts of healthy mice, whereas IR disrupted the complex in nitric oxide synthase 2 (NOS2 knockout (KO mice. By contrast, the binding was partially restored when mice were fed with an NO donor (DEA-NO in the drinking water, showing a significant reduction on infarct size (NOS2KO: 34.6±5 vs NOS2KO+DEA-NO: 20.7±9, in expression of matrix metalloproteinases, and cardiac performance was improved (left ventricular ejection fraction (LVEF. NOS2KO: 31±4 vs NOS2KO+DEA-NO: 46±6. The role of Caveolin-3/EMMPRIN in NO-mediated cardiac protection was further assayed in Caveolin-3 KO mice, showing no significant improvement on infarct size (Caveolin-3 KO: 34.8±3 vs Caveolin-3 KO+DEA-NO:33.7±5, or in the expression of MMPs, suggesting that stabilization of the complex Caveolin-3/LG-EMMPRIN may play a significant role in the cardioprotective effect of NO against IR.

  5. Nitric Oxide Induces Cardiac Protection by Preventing Extracellular Matrix Degradation through the Complex Caveolin-3/EMMPRIN in Cardiac Myocytes.

    Science.gov (United States)

    Cuadrado, Irene; Castejon, Borja; Martin, Ana M; Saura, Marta; Reventun-Torralba, Paula; Zamorano, Jose Luis; Zaragoza, Carlos

    2016-01-01

    Inhibition of Extracellular Matrix degradation by nitric oxide (NO) induces cardiac protection against coronary ischemia/reperfusion (IR). Glycosylation of Extracellular Matrix Metalloproteinase Inducer (EMMPRIN) stimulates enzymatic activation of matrix metalloproteinases (MMPs) in the heart, although the mechanisms leading to EMMPRIN glycosylation are poorly understood. We sought to determine if NO may induce cardiac protection by preventing glycosylation of EMMPRIN in a mouse model of IR. Here we found that Caveolin-3 binds to low glycosylated EMMPRIN (LG-EMMPRIN) in cardiac cells and in the hearts of healthy mice, whereas IR disrupted the complex in nitric oxide synthase 2 (NOS2) knockout (KO) mice. By contrast, the binding was partially restored when mice were fed with an NO donor (DEA-NO) in the drinking water, showing a significant reduction on infarct size (NOS2KO: 34.6±5 vs NOS2KO+DEA-NO: 20.7±9), in expression of matrix metalloproteinases, and cardiac performance was improved (left ventricular ejection fraction (LVEF). NOS2KO: 31±4 vs NOS2KO+DEA-NO: 46±6). The role of Caveolin-3/EMMPRIN in NO-mediated cardiac protection was further assayed in Caveolin-3 KO mice, showing no significant improvement on infarct size (Caveolin-3 KO: 34.8±3 vs Caveolin-3 KO+DEA-NO:33.7±5), or in the expression of MMPs, suggesting that stabilization of the complex Caveolin-3/LG-EMMPRIN may play a significant role in the cardioprotective effect of NO against IR.

  6. 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.

  7. To postpone the precipitation of manganese oxides in the degradation of tetrachloroethylene by controlling the permanganate concentration.

    Science.gov (United States)

    Yang, Weiwei; Qiu, Zhaofu; Zhao, Zhexuan; Lu, Shuguang; Sui, Qian; Gu, Xiaogang

    2017-01-01

    Controlled-release permanganate (CRP) is a relatively new technology used to treat contaminated groundwater. This study tested the encapsulation of permanganate using stearic acid to realize controlled-release properties. Batch experiments were conducted to investigate the performance of manganese oxides (MnO 2 ) in the reaction between CRP and the contaminant of interest: tetrachloroethylene (PCE). The results showed that higher ionic strengths (I = 0.1 mol/L) cause earlier precipitation of MnO 2 colloids. Using CRP to degrade PCE could decrease the amount of MnO 2 colloids produced and postpone precipitation compared to raw potassium permanganate (KMnO 4 ) under high ionic strength conditions by controlling the KMnO 4 concentration in the solution. The amount of MnO 2 colloids produced and the time of precipitation depended more on the CRP grain size than on the CRP mass ratio. Controlling the KMnO 4 concentration used in the reaction could control the formation of MnO 2 precipitates in the premise of guarantee the removal rate of PCE.

  8. Mixed phase titania nanocomposite codoped with metallic silver and vanadium oxide: New efficient photocatalyst for dye degradation

    Energy Technology Data Exchange (ETDEWEB)

    Yang Xia [School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China); School of Chemistry, Northeast Normal University, Changchun 130024 (China); Ma Fengyan; Li Kexin; Guo Yingna; Hu Jianglei; Li Wei [School of Chemistry, Northeast Normal University, Changchun 130024 (China); Huo Mingxin [School of Urban and Environmental Sciences, Northeast Normal University, Changchun 130024 (China); Guo Yihang, E-mail: guoyh@nenu.edu.cn [School of Chemistry, Northeast Normal University, Changchun 130024 (China)

    2010-03-15

    Titania nanocomposite codoped with metallic silver and vanadium oxide was prepared by a one-step sol-gel-solvothermal method in the presence of a triblock copolymer surfactant (P123). The resulting Ag/V-TiO{sub 2} three-component junction system exhibited an anatase/rutile (weight ratio of 73.8:26.2) mixed phase structure, narrower band gap (2.25 eV), and extremely small particle sizes (ca. 12 nm) with metallic Ag particles well distributed on the surface of the composite. The Ag/V-TiO{sub 2} nanocomposite was used as the visible- and UV-light-driven photocatalyst to degrade dyes rhodamine B (RB) and coomassie brilliant blue G-250 (CBB) in an aqueous solution. At 1.8% Ag and 4.9% V doping, the Ag/V-TiO{sub 2} system exhibited the highest visible- as well as UV-light photocatalytic activity; additionally, the activity of the three-component system exceeded that of Degussa P25, pure TiO{sub 2}, single-doped TiO{sub 2} system (Ag/TiO{sub 2} or V-TiO{sub 2}) as well as P123-free-Ag/V-TiO{sub 2} codoped system. The reasons for this enhanced photocatalytic activity were revealed.

  9. Catalytic degradation of Acid Orange 7 by manganese oxide octahedral molecular sieves with peroxymonosulfate under visible light irradiation.

    Science.gov (United States)

    Duan, Lian; Sun, Binzhe; Wei, Mingyu; Luo, Shilu; Pan, Fei; Xu, Aihua; Li, Xiaoxia

    2015-03-21

    In this paper, the photodegradation of Acid Orange 7 (AO7) in aqueous solutions with peroxymonosulfate (PMS) was studied with manganese oxide octahedral molecular sieves (OMS-2) as the catalyst. The activities of different systems including OMS-2 under visible light irradiation (OMS-2/Vis), OMS-2/PMS and OMS-2/PMS/Vis were evaluated. It was found that the efficiency of OMS-2/PMS was much higher than that of OMS-2/Vis and could be further enhanced by visible light irradiation. The catalyst also exhibited stable performance for multiple runs. Results from ESR and XPS analyses suggested that the highly catalytic activity of the OMS-2/PMS/Vis system possible involved the activation of PMS to sulfate radicals meditated by the redox pair of Mn(IV)/Mn(III) and Mn(III)/Mn(II), while in the OMS-2/PMS system, only the redox reaction between Mn(IV)/Mn(III) occurred. Several operational parameters, such as dye concentration, catalyst load, PMS concentration and solution pH, affected the degradation of AO7. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. COMPARATIVE KINETICS STUDY OF THE THERMAL AND THERMO-OXIDATIVE DEGRADATION OF A POLYSTYRENE-CLAY NANOCOMPOZITE BY TGA AND DSC

    Directory of Open Access Journals (Sweden)

    Ion Dranca

    2010-12-01

    Full Text Available The methods of thermogravimetry (TGA and differential scanning calorimetry (DSC have been used to study the thermal and thermo-oxidative degradation of polystyrene (PS and a PS-clay nanocomposite. An advanced isoconversional method has been applied for kinertic analysis. Introduction of the clay phase increasers the activation energy and affects the total heat of degradation, which suggests a change in the reaction mechanism. The obtained kinetic data permit a comparative assessment of the fire resistance of the studied materials

  11. 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.

  12. 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.

  13. Facile synthesis of aluminium doped zinc oxide-polyaniline hybrids for photoluminescence and enhanced visible-light assisted photo-degradation of organic contaminants

    Energy Technology Data Exchange (ETDEWEB)

    Mitra, Mousumi [Department of Physics, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103, West Bengal (India); Ghosh, Amrita; Mondal, Anup [Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103, West Bengal (India); Kargupta, Kajari [Department of Chemical Engineering, Jadavpur University, Kolkata 700032, West Bengal (India); Ganguly, Saibal [Department of Chemical Engineering, BITS Pilani, K K Birla Goa Campus, NH 17 B Bypass Road, Zuarinagar, Sancoale, Goa 403726 (India); Banerjee, Dipali, E-mail: dipalibanerjeebesu@gmail.com [Department of Physics, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711103, West Bengal (India)

    2017-04-30

    Graphical abstract: The present work focuses on the synergistic effect of a novel hybrid hetero structure (n-type aluminum doped zinc oxide and p-type polyaniline), combining both sol-gel and in-situ oxidative polymerization method and studying its photoluminescence (PL), photocatalytic, electrochemical impedance spectroscopy (EIS), linear scan voltammetry (LSV) and photocurrent properties. - Highlights: • Aluminium doped zinc oxide-polyaniline (PAZ) hybrids were prepared by polymerization of aniline using aluminium doped zinc oxide nanorod templates. • The hybrids were used as visible light photocatalysts for methyl orange (MO) and rose bengal (RB) dye degradation. • First order rate constants of the photocatalytic process were evaluated as 1.77 × 10{sup −2} min{sup −1} and 2.61 × 10{sup −2} min{sup −1} for MO and RB dyes respectively. • Photoluminescence and electrochemical properties were in accord with the photocatalytic performance of the hybrid. - Abstract: The emergence of organic-inorganic photoactive materials has led to marked progress in the field of heterogeneous visible-light photocatalysis. Visible-light active aluminium doped zinc oxide-polyaniline (PAZ) hybrid was prepared employing in-situ oxidative polymerization of polyaniline (PANI) in the presence of aluminium doped zinc oxide (AlZnO) nanorods, synthesized via sol-gel route. The compositions, structural and optical properties of the synthesized hybrids were characterized. Among various samples, the 22 wt% aluminium doped zinc oxide-polyaniline (PAZ 3) hybrid show the best photocatalytic action for the degradation of methyl orange (MO) and rose bengal (RB) dyes under visible-light illumination, even after repeated use. The performance of the photocatalytic process was determined by the first order rate constant, 1.77 × 10{sup −2} min{sup −1} and 2.61 × 10{sup −2} min{sup −1} for MO and RB dyes, respectively. Scavenger test was used to determine the role of active

  14. Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

    Energy Technology Data Exchange (ETDEWEB)

    Hermann, S.D.; Gese, N.J. [Separations Department, Idaho National Laboratory, P.O. Box 1625, Idaho Falls, ID 83415 (United States); Wurth, L.A. [Zinc Air Inc., 5314-A US Hwy 2 West, Columbia Falls, MT 59912 (United States)

    2013-07-01

    An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide. In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.

  15. Efficient Photocatalytic Degradation of Malachite Green in Seawater by the Hybrid of Zinc-Oxide Nanorods Grown on Three-Dimensional (3D Reduced Graphene Oxide(RGO/Ni Foam

    Directory of Open Access Journals (Sweden)

    Qing Wang

    2018-06-01

    Full Text Available A hybrid of ZnO nanorods grown onto three-dimensional (3D reduced graphene oxide (RGO@Ni foam (ZnO/RGO@NF is synthesized by a facile hydrothermal method. The as-prepared hybrid material is physically characterized by SEM, XRD, Raman, and X-ray photoelectron spectroscopy (XPS. When the as-prepared 3D hybrid is investigated as a photocatalyst, it demonstrates significant high photocatalytic activity for the degradation of methylene blue (MB, rhodamine (RhB, and mixed MB/RhB as organic dye pollutants. In addition, the practical application and the durability of the as-prepared catalyst to degradation of malachite green (MG in seawater are firstly assessed in a continuous flow system. The catalyst shows a high degradation efficiency and stable photocatalytic activity for 5 h continuous operation, which should be a promising catalyst for the degradation of organic dyes in seawater.

  16. Persistence of urinary excretion products of benzo(a)pyrene

    International Nuclear Information System (INIS)

    Uziel, M.; Haglund, R.; White, D.A.

    1988-01-01

    Persistence of DNA-adducts has been observed in a variety of experimental circumstances and has been suggested as one potential mechanism for explaining the long-term delay before expression of proliferative disease. In this concept, a stable DNA-adduct, which is a remnant of a prior exposure in a nondividing cell, would not express the genotoxic effect until the cells were stimulated to divide, and thus explain the long-term delay in expression of cancer. An alternative view of the observation of persistent DNA-adducts, described in this communication, is the continuing replenishment of DNA adducts by formation and turnover of these adducts from exposure to a constant supply of the ultimate carcinogenic species derived from a prior exposure. It is of interest to note that virtually all experiments where ''persistent'' adducts have been observed have been high dose exposures. During the course of experiments designed to develop improved methods for detection of DNA adducts and related derivatives derived from polynuclear aromatic hydrocarbons (PAH), we observed that there was a continuous excretion of urinary derivatives of the injected benzo(a)pyrene (BaP) beyond the initial burst of detoxification. This report describes the time dependent distribution of those derivatives in blood, urine, feces, and at the site of injection. 11 refs., 5 figs., 4 tabs

  17. Compartmental analysis of benzo[a]pyrene toxicokinetics

    International Nuclear Information System (INIS)

    Bevan, D.R.; Weyand, E.H.

    1986-01-01

    A multicompartmental model to describe quantitatively the toxicokinetics of benzo[a]pyrene (B[a]P) was developed using SAAM (Simulation, Analysis and Modeling). [ 3 H]-B[a]P dissolved in triethylene glycol was administered intratracheally to male Sprague-Dawley rats, and amounts of [ 3 H] were quantified in various tissues at selected times up to 6 hr after administration. Elimination of [ 3 H]-B[a]P and/or metabolites from lungs was biphasic, with half-times of 5.3 min. and 116 min. [ 3 H]-B[a]P and/or metabolites were subsequently distributed primarily to liver and carcass (muscle, bones, fat, skin and associated blood). Carcass contained about 20% of administered [ 3 H] at 6 hr after administration, and agreement between the model and experimental data required that the carcass be modeled as two compartments, one with rapid and one with slow exchange. Approximately 50% of the administered dose was excreted in feces in 6 hr and only 2% appeared in urine. Enterohepatic circulation was accounted for in the model. The model was then used to predict amounts of [ 3 H]-B[a]P and/or metabolites which would be excreted into bile in animals with bile duct cannulas, and good agreement between the model and data was observed

  18. Species differences in biliary excretion of benzo[a]pyrene

    International Nuclear Information System (INIS)

    Weyand, E.H.; Bevan, D.R.

    1986-01-01

    Biliary excretion of benzo[a]pyrene (B[a]P) was investigated in rats, hamsters, and guinea pigs following intratracheal administration. [ 3 H]-B[a]P, in amounts of approximately 150 ng or 350 μg, was instilled into lungs and amounts of radioactivity excreted in bile were monitored for six hrs following administration. Differences in biliary excretion of [ 3 H]-B[a]P and/or metabolites among species were observed at low doses but not at high doses. Six hours after instillation of a low dose of B[a]P, 70, 54, and 62% of the dose was excreted in bile of rats, hamsters, and guinea pigs, respectively. Upon administration of the higher dose of B[a]P, approximately 50% of the dose was excreted in bile in six hrs by all species. Thus, rats and guinea pigs exhibit differences in biliary excretion of low and high doses of B[a]P whereas hamsters do not. Profiles of phase II metabolites in rats and hamsters were similar at both low and high doses, with the majority of metabolites being glucuronides and thioether conjugates. However, differences in relative amounts of these conjugates were observed between the two doses, with a shift towards a greater proportion of glucuronides at the higher dose. Metabolites in bile from guinea pigs were primarily thioether conjugates, which accounted for 88% of metabolites at the low dose and 95% at the high dose

  19. The mechanism for enhanced oxidation degradation of dioxin-like PCBs (PCB-77) in the atmosphere by the solvation effect.

    Science.gov (United States)

    Xin, Mei-Ling; Yang, Jia-Wen; Li, Yu

    2017-07-11

    The reaction pathways of PCB-77 in the atmosphere with ·OH, O 2 , NO x , and 1 O 2 were inferred based on density functional theory calculations with the 6-31G* basis set. The structures the reactants, transition states, intermediates, and products were optimized. The energy barriers and reaction heats were obtained to determine the energetically favorable reaction pathways. To study the solvation effect, the energy barriers and reaction rates for PCB-77 with different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, acetone, dichloromethane, ethanol, methanol, acetonitrile, dimethylsulfoxide, and water) were calculated. The results showed that ·OH preferentially added to the C5 atom of PCB-77, which has no Cl atom substituent, to generate the intermediate IM5. This intermediate subsequently reacted with O 2 via pathway A to generate IM5a, with an energy barrier of 7.27 kcal/mol and total reaction rate of 8.45 × 10 -8  cm 3 /molecule s. Pathway B involved direct dehydrogenation of IM5 to produce the OH-PCBs intermediate IM5b, with an energy barrier of 28.49 kcal/mol and total reaction rate of 1.15 × 10 -5  cm 3 /molecule s. The most likely degradation pathway of PCB-77 in the atmosphere is pathway A to produce IM5a. The solvation effect results showed that cyclohexane, carbon tetrachloride, and benzene could reduce the reaction energy barrier of pathway A. Among these solvents, the solvation effect of benzene was the largest, and could reduce the total reaction energy barrier by 25%. Cyclohexane, carbon tetrachloride, benzene, dichloromethane, acetone, and ethanol could increase the total reaction rate of pathway A. The increase in the reaction rate of pathway A with benzene was 8%. The effect of solvents on oxidative degradation of PCB-77 in the atmosphere is important. Graphical abstract The reaction pathways of PCB-77 in the atmosphere with •OH, O2, NOx, and 1O2 were inferred based on density functional theory

  20. Effect of ageing on benzo[a]pyrene extractability in contrasting soils

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Luchun [CERAR-Centre for Environmental Risk Assessment and Remediation and Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE), Building X, University of South Australia, Mawson Lakes, SA 5095 (Australia); Naidu, Ravi, E-mail: Ravi.Naidu@newcastle.edu.au [CERAR-Centre for Environmental Risk Assessment and Remediation and Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE), Building X, University of South Australia, Mawson Lakes, SA 5095 (Australia); Liu, Yanju; Palanisami, Thavamani; Dong, Zhaomin; Mallavarapu, Megharaj [CERAR-Centre for Environmental Risk Assessment and Remediation and Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE), Building X, University of South Australia, Mawson Lakes, SA 5095 (Australia); Semple, Kirk T. [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom)

    2015-10-15

    Highlights: • In vitro assessment of B[a]P in contaminated soils using 4 different methods. • An exponential kinetic model fits well with the extractability data. • Fitting parameter and {sup 14}C residue correlates with key soil properties. • Fractionation of B[a]P was obtained based on extractability by extractants. - Abstract: Changes in benzo[a]pyrene (B[a]P) extractability over 160 days ageing in four contrasting soils varying in organic matter content and clay mineralogy were investigated using dichloromethane: acetone 1:1 (DCM/Ace), 60 mM hydroxypropyl-β-cyclodextrin (HPCD) solution, 1-butanol (BuOH) and Milli-Q water. The B[a]P extractability by the four methods decreased with ageing and a first-order exponential model could be used to describe the kinetics of release. Correlation of the kinetic rate constant with major soil properties showed a significant effect of clay and sand contents and pore volume fraction (<6 nm) on sequestration of the desorbable fraction (by HPCD) and the water-extractable fraction. Analysis of {sup 14}C-B[a]P in soils after ageing showed a limited loss of B[a]P via degradation. Fractionation of B[a]P pools associated with the soil matrix was analysed according to extractability of B[a]P by the different extraction methods. A summary of the different fractions is proposed for the illustration of the effect of ageing on different B[a]P-bound fractions in soils. This study provides a better understanding of the B[a]P ageing process associated with different fractions and also emphasises the extraction capacity of the different methods employed.

  1. Effect of ageing on benzo[a]pyrene extractability in contrasting soils

    International Nuclear Information System (INIS)

    Duan, Luchun; Naidu, Ravi; Liu, Yanju; Palanisami, Thavamani; Dong, Zhaomin; Mallavarapu, Megharaj; Semple, Kirk T.

    2015-01-01

    Highlights: • In vitro assessment of B[a]P in contaminated soils using 4 different methods. • An exponential kinetic model fits well with the extractability data. • Fitting parameter and 14 C residue correlates with key soil properties. • Fractionation of B[a]P was obtained based on extractability by extractants. - Abstract: Changes in benzo[a]pyrene (B[a]P) extractability over 160 days ageing in four contrasting soils varying in organic matter content and clay mineralogy were investigated using dichloromethane: acetone 1:1 (DCM/Ace), 60 mM hydroxypropyl-β-cyclodextrin (HPCD) solution, 1-butanol (BuOH) and Milli-Q water. The B[a]P extractability by the four methods decreased with ageing and a first-order exponential model could be used to describe the kinetics of release. Correlation of the kinetic rate constant with major soil properties showed a significant effect of clay and sand contents and pore volume fraction (<6 nm) on sequestration of the desorbable fraction (by HPCD) and the water-extractable fraction. Analysis of 14 C-B[a]P in soils after ageing showed a limited loss of B[a]P via degradation. Fractionation of B[a]P pools associated with the soil matrix was analysed according to extractability of B[a]P by the different extraction methods. A summary of the different fractions is proposed for the illustration of the effect of ageing on different B[a]P-bound fractions in soils. This study provides a better understanding of the B[a]P ageing process associated with different fractions and also emphasises the extraction capacity of the different methods employed

  2. Degradation of organic pollutants in the groundwater by mean of heterogeneous catalytic oxidation and a combined process of catalytic oxidation and aerobic biological degradation; Abbau von organischen Schadstoffen im Grundwasser durch heterogen-katalytische Oxidation und die Verfahrenskombination katalytische Oxidation mit aerob-biologischem Abbau

    Energy Technology Data Exchange (ETDEWEB)

    Hofmann, J.; Freier, U.; Wecks, M.; Haentzschel, D. [Inst. fuer Nichtklassische Chemie e.V. an der Univ. Leipzig, Leipzig (Germany)

    2004-07-01

    This project formed part of the SAFIRA joint project (Remediation research in regionally contaminated aquifers), which was coordinated by the project division on ''Post-industry and post-mining landscapes'' of Leizig-Halle Environmental Research Centre. The purpose of the present project was to develop various in situ methods of groundwater remediation and test them on the Bitterfeld model site. The project was focussed on developing a groundwater treatment method on the basis of the oxidative catalytic degradation of the organic pollutants. [German] Das Vorhaben war in den SAFIRA-Projektverbund (Sanierungsforschung in regional kontaminierten Aquiferen), das vom Projektbereich Industrie- und Bergbaufolgelandschaften des Umweltforschungszentrums Leipzig-Halle koordiniert wurde, eingebunden. Innerhalb dieses Vorhabens sollten unterschiedliche in-situ Methoden zur Grundwassersanierung entwickelt und am Modellstandort in Bitterfeld getestet werden. Der Schwerpunkt des Vorhabens bestand in der Entwicklung einer Grundwasserbehandlungstechnologie auf der Basis des oxidativ katalytischen Abbaus der organischen Schadstoffe. (orig.)

  3. 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.

  4. 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.

  5. Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael

    2013-02-01

    Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 ÀC. Samples included: two formulations developed at Kansas City Plant (KCP) (#6 and #10), one commercially available formulation (#21), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl #10 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl #10 was also aged under non-oxidative thermal conditions using an argon atmosphere.

  6. A comparative study of TiN and TiC: Oxidation resistance and retention of xenon at high temperature and under degraded vacuum

    International Nuclear Information System (INIS)

    Gavarini, S.; Bes, R.; Millard-Pinard, N.; Peaucelle, C.; Perrat-Mabilon, A.; Gaillard, C.; Cardinal, S.; Garnier, V.

    2011-01-01

    Dense TiN and TiC samples were prepared by hot pressing using micrometric powders. Xenon species (simulating rare gas fission products) were then implanted into the ceramics. The samples were annealed for 1 h at 1500 deg. C under several degraded vacuums with P O 2 varying from 10 -6 to 2x10 -4 mbars. The oxidation resistance of the samples and their retention properties with respect to preimplanted xenon species were analyzed using scanning electron microscopy, grazing incidence x-ray diffraction, Rutherford backscattering spectrometry, and nuclear backscattering spectrometry. Results indicate that TiC is resistant to oxidation and does not release xenon for P O 2 ≤6x10 -6 mbars. When P O 2 increases, geometric oxide crystallites appear at the surface depending on the orientation and size of TiC grains. These oxide phases are Ti 2 O 3 , Ti 3 O 5 , and TiO 2 . Apparition of oxide crystallites is associated with the beginning of xenon release. TiC surface is completely covered by the oxide phases at P O 2 =2x10 -4 mbars up to a depth of 3 μm and the xenon is then completely released. For TiN samples, the results show a progressive apparition of oxide crystallites (Ti 3 O 5 mainly) at the surface when P O 2 increases. The presence of the oxide crystallites is also directly correlated with xenon release, the more oxide crystallites are growing the more xenon is released. TiN surface is completely covered by an oxide layer at P O 2 =2x10 -4 mbars up to 1 μm. A correlation between the initial fine microstructure of TiN and the properties of the growing layer is suggested.

  7. 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.

  8. 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

  9. Mechanism of azo dye degradation in Advanced Oxidation Processes: Degradation of Sulfanilic Acid Azochromotrop and its parent compounds in aqueous solution by ionizing radiation

    International Nuclear Information System (INIS)

    Palfi, Tamas; Wojnarovits, Laszlo; Takacs, Erzsebet

    2011-01-01

    Mechanistic studies were made on hydroxyl radical and hydrated electron reaction with Sulfanilic Acid Azochromotrop (SPADNS) as model azo dye in dilute aqueous solution. SPADNS contains 4,5-dihydroxynaphthalene-2,7-disulfonic acid part and 4-sulfophenylazo group. To establish the details of the reaction mechanism the reactions of two simpler molecules without 4-sulfophenylazo part were also studied: one of them contained one (in position 4, II), the other two (in positions 4 and 5, III) -OH groups. Hydroxyl radicals react with these molecules with radical addition to the naphthalene-2,7-disulfonic acid part. The adduct hydroxycyclohexadienyl type radical decays in radical-radical reactions, or undergoes a (pH dependent) water elimination to yield naphthoxy radical. The radical decay takes place on the ms timescale. Degradation efficiencies are 0.6-0.8. Hydrated electron in the case of the two simpler molecules reacts with the rings, while in the case of dye with the azo bond. Electron scavenging is followed by protonation, this reaction in the case of II and III yields cyclohexadienyl, while with the dye hydrazo radical. The efficiency of degradation with II and III is 0.2-0.6, while for SPADNS it is close to 1.

  10. Benzo(a)pyrene diol epoxides as intermediates in nucleic acid binding in vivo and in vitro

    DEFF Research Database (Denmark)

    Weinstein, I.B.; Jeffrey, A.M.; Jennette, K.W.

    1976-01-01

    Evidence has been obtained that a specific isomer of a diol epoxide derivative of benzo(a)pyrene, (+/-)-7 beta,8alpha-dihydroxy-9alpha, 10alpha-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene, is an intermediate in the binding of benzo(a)pyrene to RNA in cultured bovine bronchial mucosa. An adduct is for...

  11. Transcriptional responses of Acropora hyacinthus embryo under the benzo(a)pyrene stress by deep sequencing.

    Science.gov (United States)

    Xiao, Rong; Zhou, Hailong; Chen, Chien-Min; Cheng, Huamin; Li, Hongwu; Xie, Jia; Zhao, Hongwei; Han, Qian; Diao, Xiaoping

    2018-04-24

    Coral embryos are a critical and sensitive period for the early growth and development of coral. Benzo(a)pyrene (BaP) is widely distributed in the ocean and has strong toxicity, but there is little information on the toxic effects to coral embryos exposed to this widespread environmental contaminant. Thus, in this study, we utilized the Illumina Hiseq™ 4000 platform to explore the gene response of Acropora hyacinthus embryos under the BaP stress. A total of 130,042 Unigenes were obtained and analyzed, and approximately 37.67% of those matched with sequences from four different species. In total, 2606 Unigenes were up-regulated, and 3872 Unigenes were down-regulated. After Gene Ontology (GO) annotation, the results show that the "cellular process" and "metabolic process" were leading in the category of biological processes, which the "binding" and "catalytic activity" were the most abundant subcategories in molecular function. Based on the Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis, the most differentially expressed genes (DEGs) were enriched, as well as down-regulated in the pathways of oxidative phosphorylation, metabolism of xenobiotics, immune-related genes, apoptosis and human disease genes. At the same time, 388,197 of Single-nucleotide Polymorphisms (SNPs) and 6164 of Simple Sequence Repeats (SSRs) were obtained, which can be served as the richer and more valuable SSRs molecular markers in the future. The results of this study can help to better understand the toxicological mechanism of coral embryo exposed to BaP, and it is also essential for the protection and restoration of coral reef ecosystem in the future. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. Screening of ectomycorrhizal fungi for degradation of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Braun-Luellemann, A.; Huettermann, A.; Majcherczyk, A. [Goettingen Univ. (Germany). Inst. fuer Forstbotanik

    2000-07-01

    Ectomycorrhizal fungi belonging to 16 species (27 strains) were tested for their ability to degrade polycyclic aromatic hydrocarbons (PAHs): Phenanthrene, chrysene, pyrene and benzo[a]pyrene. Cultivated on a complex liquid medium, most of the fungi tested were able to metabolise these compounds. Approximately 50% of the benzo[a]pyrene was removed by strains of Amanita excelsa, Leccinum versipelle, Suillus grevillei, S. luteus, and S. variegatus during a 4-week incubation period. The same amount of phenanthrene was also metabolised by A. muscaria, Paxillus involutus, and S. grevillei. The degradation of the other two PAHs was, for the most part, less effective. Only S. grevillei was able to remove 50% of the pyrene, whereas Boletus edulis and A. muscaria removed 35% of the chrysene. (orig.)

  13. Topological, functional, and dynamic properties of the protein interaction networks rewired by benzo(a)pyrene

    International Nuclear Information System (INIS)

    Ba, Qian; Li, Junyang; Huang, Chao; Li, Jingquan; Chu, Ruiai; Wu, Yongning; Wang, Hui

    2015-01-01

    Benzo(a)pyrene is a common environmental and foodborne pollutant that has been identified as a human carcinogen. Although the carcinogenicity of benzo(a)pyrene has been extensively reported, its precise molecular mechanisms and the influence on system-level protein networks are not well understood. To investigate the system-level influence of benzo(a)pyrene on protein interactions and regulatory networks, a benzo(a)pyrene-rewired protein interaction network was constructed based on 769 key proteins derived from more than 500 literature reports. The protein interaction network rewired by benzo(a)pyrene was a scale-free, highly-connected biological system. Ten modules were identified, and 25 signaling pathways were enriched, most of which belong to the human diseases category, especially cancer and infectious disease. In addition, two lung-specific and two liver-specific pathways were identified. Three pathways were specific in short and medium-term networks (< 48 h), and five pathways were enriched only in the medium-term network (6 h–48 h). Finally, the expression of linker genes in the network was validated by Western blotting. These findings establish the overall, tissue- and time-specific benzo(a)pyrene-rewired protein interaction networks and provide insights into the biological effects and molecular mechanisms of action of benzo(a)pyrene. - Highlights: • Benzo(a)pyrene induced scale-free, highly-connected protein interaction networks. • 25 signaling pathways were enriched through modular analysis. • Tissue- and time-specific pathways were identified

  14. Topological, functional, and dynamic properties of the protein interaction networks rewired by benzo(a)pyrene

    Energy Technology Data Exchange (ETDEWEB)

    Ba, Qian [Key Laboratory of Food Safety Research, Institute for Nutritional Sciences, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences, Shanghai (China); Key Laboratory of Food Safety Risk Assessment, Ministry of Health, Beijing (China); Li, Junyang; Huang, Chao [Key Laboratory of Food Safety Research, Institute for Nutritional Sciences, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences, Shanghai (China); Li, Jingquan; Chu, Ruiai [Key Laboratory of Food Safety Research, Institute for Nutritional Sciences, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences, Shanghai (China); Key Laboratory of Food Safety Risk Assessment, Ministry of Health, Beijing (China); Wu, Yongning, E-mail: wuyongning@cfsa.net.cn [Key Laboratory of Food Safety Risk Assessment, Ministry of Health, Beijing (China); Wang, Hui, E-mail: huiwang@sibs.ac.cn [Key Laboratory of Food Safety Research, Institute for Nutritional Sciences, Shanghai Institutes for Biological Sciences, Chinese Academy of Sciences, Shanghai (China); Key Laboratory of Food Safety Risk Assessment, Ministry of Health, Beijing (China); School of Life Science and Technology, ShanghaiTech University, Shanghai (China)

    2015-03-01

    Benzo(a)pyrene is a common environmental and foodborne pollutant that has been identified as a human carcinogen. Although the carcinogenicity of benzo(a)pyrene has been extensively reported, its precise molecular mechanisms and the influence on system-level protein networks are not well understood. To investigate the system-level influence of benzo(a)pyrene on protein interactions and regulatory networks, a benzo(a)pyrene-rewired protein interaction network was constructed based on 769 key proteins derived from more than 500 literature reports. The protein interaction network rewired by benzo(a)pyrene was a scale-free, highly-connected biological system. Ten modules were identified, and 25 signaling pathways were enriched, most of which belong to the human diseases category, especially cancer and infectious disease. In addition, two lung-specific and two liver-specific pathways were identified. Three pathways were specific in short and medium-term networks (< 48 h), and five pathways were enriched only in the medium-term network (6 h–48 h). Finally, the expression of linker genes in the network was validated by Western blotting. These findings establish the overall, tissue- and time-specific benzo(a)pyrene-rewired protein interaction networks and provide insights into the biological effects and molecular mechanisms of action of benzo(a)pyrene. - Highlights: • Benzo(a)pyrene induced scale-free, highly-connected protein interaction networks. • 25 signaling pathways were enriched through modular analysis. • Tissue- and time-specific pathways were identified.

  15. Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

    International Nuclear Information System (INIS)

    Moon, Young-E; Jung, Gowun; Yun, Jumi; Kim, Hyung-Il

    2013-01-01

    Graphical abstract: The photocatalytic removal of pollutants was improved by the two-step mechanism based on the adsorption of pollutants by hydrogel and the effective decomposition by combination of TiO 2 and graphene oxide. -- Highlights: • pH sensitive PVA/PAAc hydrogels were prepared by radical polymerization and condensation reaction. • PVA/PAAc/TiO 2 /graphene oxide nanocomposite hydrogels were used for treatment of basic waste water. • Photocatalytic acitivity of TiO 2 was improved by incorporation of graphene oxide. • Photocatalytic decomposition by nanocomposite hydrogel was improved by increasing pH. -- Abstract: Poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 nanocomposite hydrogels. Both TiO 2 and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO 2 and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO 2 /graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water

  16. 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.

  17. 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.

  18. Thermal Oxidation of Polyolefins by Mild Pro-Oxidant Additives Based on Iron Carboxylates and Lipophilic Amines: Degradability in the Absence of Light and Effect on the Adhesion to Paperboard

    Directory of Open Access Journals (Sweden)

    Tuan-Anh Nguyen

    2015-08-01

    Full Text Available Marine and inland pollution by non-degradable plastic bags and other plastic articles is a topic of great concern. Natural degradation processes based on oxidation of plastic pollutants could possibly contribute to limit the extent of pollution. Thermal degradation of polyolefins in the absence of light by non-polluting pro-oxidants has not been presented before. In this study, we show that two amines, stearyl amine and [(3-(11-aminoundecanoyl amino propane-1-] silsesquioxane (amino-POSS in combination with ferric stearate (FeSt3 tremendously accelerate the thermal oxidation of polyolefins compared with reference samples. Both amines and FeSt3 are to a large extent based on renewable resources. Polyethylene and polypropylene samples containing less than 100 ppm of iron and 1% of amine were extremely brittle after 10 days in a circulation oven in the absence of light. No significant degradation could be seen with samples containing iron but no amine. In a different application, the initial oxidation of polyethylene can be used in order to increase its adhesion to cardboard. Excellent adhesion between polyethylene and cardboard is important for liquid packaging based on renewable resources. Amino-POSS has been chosen for food packaging applications due to its expected lower leakage from polyethylene (PE compared with stearyl amine. Film samples of PE/amino-POSS/FeSt3 blends were partly oxidized in a circulation oven. The oxidation was documented by increased carbonyl index (CI and melt flow index (MFI. The limited extent of oxidation has been proved by unchanged tensile strength and only moderate changes in elongation at break when compared to reference polyethylene films containing no FeSt3 or amino-POSS. The PE/amino-POSS/FeSt3 blends were compression moulded to paperboard. The adhesion of non-aged blends to paperboard decreased with increasing amino-POSS content which is in good compliance with an earlier reported lubricant effect of high

  19. Assessment by HPLC of the degradation behavior of acitretin under hydrolytic, oxidative, photolytic and thermal stress conditions

    Directory of Open Access Journals (Sweden)

    Pawan K. Porwal

    2014-12-01

    Full Text Available Acitretin is a photosensitive oral retinoid with very limited data available on its degradation. The official HPLC method for acitretin determination was insufficient to resolve the degradation products generated during stability studies. Therefore, an isocratic RP-HPLC–UV method was developed for the determination of acitretin in the presence of its related impurities and degradation products. Efficient chromatographic separation was achieved on a Thermo beta-basic column C18 (100 mm×4.6 mm, 5 μm with mobile phase containing 0.3% (v/v glacial acetic acid with acetonitrile (ACN and isopropyl alcohol (IPA in an isocratic ratio of 70:30 at a flow rate of 1.0 mL/min with the eluent monitored at 360 nm. The method was validated for specificity, linearity, precision, accuracy and robustness. The calibration plot was linear over the concentration range of 50–150 μg/mL with a correlation coefficient (r2 of 0.999. The proposed method was used to investigate the degradation kinetics of acitretin under the different degradative conditions. The degradation rate constant (K, half-life (t1/2, and t90 were calculated. Degradation of acitretin followed pseudo-first-order kinetics. The drug was found to be less stable under acidic and photolytic degradation conditions: the photolytic degradation constants for acitretin in sunlight and UV light were 0.002698% and 0.0008402% min−1, respectively. The LOD for acitretin and the known impurities were at a level below 0.02%. The method shows consistent recoveries for ACTR (99.8%–101.2% and also for its known impurities (97.2–101.3%. The method was found to be accurate, precise, linear, specific, sensitive, rugged, robust, and useful for characterizing the stability of this chemical.

  20. Degradation of polyethylene induced by plasma in oxidizing atmospheres; Degradacion de polietileno inducido por plasma en atmosferas oxidantes

    Energy Technology Data Exchange (ETDEWEB)

    Colin, E.; Olayo, M.G.; Cruz, G.J. [Facultad de Quimica, UAEM, Av. Tollocan y Colon, 50000 Toluca (Mexico)

    2002-07-01

    The garbage of polyethylene is not easily degradable in normal environmental conditions . The indiscriminate use of this polymer and the enormous quantity of garbage which is generated carries a damage to the environment due to its long life as waste. The objective of this work is to study the conditions in which can be carried out the degradation of polyethylene. A form of accelerating the degradation is exposing it to plasma with reactive atmospheres. In this work a study of surface modification of polyethylene by plasmas with discharges of direct current of oxygen and nitrogen is presented. (Author)

  1. Determination of HCl and VOC Emission from Thermal Degradation of PVC in the Absence and Presence of Copper, Copper(II Oxide and Copper(II Chloride

    Directory of Open Access Journals (Sweden)

    Ahamad J. Jafari

    2009-01-01

    Full Text Available Polyvinyl chloride (PVC has played a key role in the development of the plastic industry over the past 40 years. Thermal degradation of PVC leads to formation of many toxic pollutants such as HCl, aromatic and volatile organic carbon vapors. Thermal degradation of PVC and PVC in the present of copper, cupric oxide and copper(II chloride were investigated in this study using a laboratory scale electrical furnace. HCl and Cl- ion were analyzed by a Dionex ion chromatograph and VOCs compounds were analyzed using GC or GC-MS. The results showed that HCl plus Cl- ion and benzene formed about 99% and 80% respectively in the first step of thermal degradation under air atmosphere. The presence of cupric oxide increases the percentage of short chain hydrocarbons more than 184% and decreases the amount of the major aromatic hydrocarbon and HCl plus Cl- ion to 90% and 65% respectively. The total aromatic hydrocarbon emitted less than when atmosphere was air and difference was statistically significant (Pvalue<0.000

  2. Prenatal induction of benzo(a)pyrene hydroxylases in mice

    International Nuclear Information System (INIS)

    Neubert, D.; Tapken, S.

    1988-01-01

    1. Benzo(a)pyrene hydroxylase (BPH) activity was measured in homogenates of fetal liver (day 18) or of whole-embryos of mice on day 9, 10 or 12 of gestation after maternal pretreatment with B(a)P on 3 consecutive days. A 3 H-liberation assay with 3 H-B(a)P labelled either generally or at the 6-position was used. The values obtained with the embryonic/fetal tissues were compared with those found in maternal liver. 2. Three oral doses of 17.5 mg B(a)P/kg body wt were found to just significantly induce BPH in maternal liver. An induction was observed after pretreatment with 24 mg B(a)P/kg body wt in 9, 10 or 12-day-old whole-embryos, but the V max reached was only 10-20% (1% on day 9) of that of adult non-induced liver. The K m (6-hydroxylation) for all tissues tested were in the same range (600-900 nM). The induction was demonstrable in embryos at tissue levels about one order of magnitude lower than those required for induction in maternal liver. 3. Treatment with 25 mg B(a)P/kg body wt on 3 consecutive days was required to induce BPH in fetal liver on day 18 of gestation. The required B(a)P tissue concentrations were about one half of those necessary for induction in maternal liver. 4. Among a variety of other polycyclic hydrocarbons only chrysene showed an inducing potency similar to that of B(a)P in adult and fetal liver. For all compounds tested there was no correlation found in the inducing potency between adult and fetal liver (e.g. coronene). 5. The doses required to induce BPH in the maternal or fetal liver or in whole embryos of rodents are significantly higher (mg range) than those of usual average human exposure or those taken up by smokers (ng range). (orig.)

  3. Photocatalytic Degradation of Toluene, Butyl Acetate and Limonene under UV and Visible Light with Titanium Dioxide-Graphene Oxide as Photocatalyst

    Directory of Open Access Journals (Sweden)

    Birte Mull

    2017-01-01

    Full Text Available Photocatalysis is a promising technique to reduce volatile organic compounds indoors. Titanium dioxide (TiO2 is a frequently-used UV active photocatalyst. Because of the lack of UV light indoors, TiO2 has to be modified to get its working range shifted into the visible light spectrum. In this study, the photocatalytic degradation of toluene, butyl acetate and limonene was investigated under UV LED light and blue LED light in emission test chambers with catalysts either made of pure TiO2 or TiO2 modified with graphene oxide (GO. TiO2 coated with different GO amounts (0.75%–14% were investigated to find an optimum ratio for the photocatalytic degradation of VOC in real indoor air concentrations. Most experiments were performed at a relative humidity of 0% in 20 L emission test chambers. Experiments at 40% relative humidity were done in a 1 m³ emission test chamber to determine potential byproducts. Degradation under UV LED light could be achieved for all three compounds with almost all tested catalyst samples up to more than 95%. Limonene had the highest degradation of the three selected volatile organic compounds under blue LED light with all investigated catalyst samples.

  4. Rapid and efficient visible light photocatalytic dye degradation using AFe2O4 (A = Ba, Ca and Sr) complex oxides

    International Nuclear Information System (INIS)

    Vijayaraghavan, T.; Suriyaraj, S.P.; Selvakumar, R.; Venkateswaran, R.; Ashok, Anuradha

    2016-01-01

    Highlights: • Alkaline earth ferrites AFe 2 O 4 (A = Ba, Ca and Sr) were synthesized by sol–gel method. • Visible light photocatalytic activity of these ferrites were studied using congo red dye degradation. • BaFe 2 O 4 exhibited the best photocatalytic activity under visible light (xenon lamp) irradiation; CaFe 2 O 4 was the best photocatalyst under natural sun light irradiation. - Abstract: Photocatalytic activity of spinel type complex oxides has been investigated in this study. Alkaline earth ferrites AFe 2 O 4 (A = Ba, Ca, Sr) were synthesized by sol–gel method. Structural characterizations reveal that the synthesized ferrites have orthorhombic crystal structures with different space groups and cell dimensions when they have different alkaline earth metals in their A site. All the synthesized ferrites exhibited their bandgap in the range 2.14–2.19 eV. Their photocatalytic activities were studied using congo red dye under sunlight and xenon lamp radiation. The substitution of Ba, Ca and Sr at A site of these ferrites had varying impact on dye degradation process. Under xenon lamp irradiation, BaFe 2 O 4 exhibited the highest percentage of dye degradation (92% after 75 min). However, CaFe 2 O 4 showed the fastest degradation of the dye (70% within 15 min). In the absence of irradiation, SrFe 2 O 4 showed the highest dye adsorption (44% after 75 min).

  5. In vitro degradation and biocompatibility of a strontium-containing micro-arc oxidation coating on the biodegradable ZK60 magnesium alloy

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Xiao [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Yang, Xiaoming [Panyu Hospital of Chinese Medicine, 65 Qiaodong Road, Guangzhou 511400 (China); Tan, Lili, E-mail: lltan@imr.ac.cn [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Li, Mei [Hospital of Orthopedics, Guangzhou General Hospital of Guangzhou Military Command, 111 Liuhua Road, Guangzhou 510010 (China); Wang, Xin [College of Chemistry, Liaoning University, 66 Chongshanzhong Road, Shenyang 110036 (China); Zhang, Yu, E-mail: luck_2001@126.com [Hospital of Orthopedics, Guangzhou General Hospital of Guangzhou Military Command, 111 Liuhua Road, Guangzhou 510010 (China); Yang, Ke, E-mail: kyang@imr.ac.cn [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Hu, Zhuangqi [Institute of Metal Research, Chinese Academy of Sciences, 72 Wenhua Road, Shenyang 110016 (China); Qiu, Jianhong [Trauson Medical Instrument Co., Ltd., Changzhou 213163 (China)

    2014-01-01

    Magnesium alloys are promising biodegradable implant candidates for orthopedic application. In the present study, a phosphate-based micro-arc oxidation (MAO) coating was applied on the ZK60 alloy to decrease its initial degradation rate. Strontium (Sr) was incorporated into the coating in order to improve the bioactivity of the coating. The in vitro degradation studies showed that the MAO coating containing Sr owned a better initial corrosion resistance, which was mainly attributed to the superior inner barrier layer, and a better long-term protective ability, probably owning to its larger thickness, superior inner barrier layer and the superior apatite formation ability. The degradation of MAO coating was accompanied by the formation of degradation layer and Ca-P deposition layer. The in vitro cell tests demonstrated that the incorporation of Sr into the MAO coating enhanced both the proliferation of preosteoblast cells and the alkaline phosphatase activity of the murine bone marrow stromal cells. In conclusion, the MAO coating with Sr is a promising surface treatment for the biodegradable magnesium alloys.

  6. Preparation of reduced graphene oxide/meso-TiO_2/AuNPs ternary composites and their visible-light-induced photocatalytic degradation n of methylene blue

    International Nuclear Information System (INIS)

    Yang, Yongfang; Ma, Zheng; Xu, Lidong; Wang, Hefang; Fu, Nian

    2016-01-01

    Graphical abstract: Reduced graphene oxide/meso-TiO_2/AuNPs (RGO/meso-TiO_2/AuNPs) ternary composites were prepared via the addition of graphene oxide to the dispersion of meso-TiO_2/AuNPs under a hydrothermal condition. The RGO/meso-TiO_2/AuNPs ternary composites show high photocatalytic activity toward MB. - Highlights: • RGO/meso-TiO_2/AuNPs were obtained by addition of graphene oxide to meso-TiO_2/AuNPs. • Au NPs in the mesopores of meso-TiO_2 reduce the recombination of charge carriers. • RGO covered with the surface of the meso-TiO_2 enhance the adsorption of MB. • RGO/meso-TiO_2/AuNPs composites show high photocatalytic performance toward MB. - Abstract: Reduced graphene oxide/meso-TiO_2/AuNPs (RGO/meso-TiO_2/AuNPs) ternary composites were prepared via the addition of graphene oxide to the dispersion of meso-TiO_2/AuNPs under hydrothermal conditions. The structure and the morphology of the RGO/meso-TiO_2/AuNPs materials were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The photocatalytic activity of RGO/meso-TiO_2/AuNPs was evaluated by degradation of methyl blue (MB) under visible-light illumination. The ternary composites present an extended light absorption range, efficient charge separation properties, high adsorption ability for MB and high photocatalytic degradation activity of MB compared to the meso-TiO_2 and meso-TiO_2/AuNPs.

  7. Preparation of reduced graphene oxide/meso-TiO{sub 2}/AuNPs ternary composites and their visible-light-induced photocatalytic degradation n of methylene blue

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Yongfang; Ma, Zheng; Xu, Lidong [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Wang, Hefang, E-mail: whf0618@163.com [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); Fu, Nian, E-mail: funian3678@163.com [School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130 (China); College of Physics Science and Technology of Hebei University, Baoding 071002 (China)

    2016-04-30

    Graphical abstract: Reduced graphene oxide/meso-TiO{sub 2}/AuNPs (RGO/meso-TiO{sub 2}/AuNPs) ternary composites were prepared via the addition of graphene oxide to the dispersion of meso-TiO{sub 2}/AuNPs under a hydrothermal condition. The RGO/meso-TiO{sub 2}/AuNPs ternary composites show high photocatalytic activity toward MB. - Highlights: • RGO/meso-TiO{sub 2}/AuNPs were obtained by addition of graphene oxide to meso-TiO{sub 2}/AuNPs. • Au NPs in the mesopores of meso-TiO{sub 2} reduce the recombination of charge carriers. • RGO covered with the surface of the meso-TiO{sub 2} enhance the adsorption of MB. • RGO/meso-TiO{sub 2}/AuNPs composites show high photocatalytic performance toward MB. - Abstract: Reduced graphene oxide/meso-TiO{sub 2}/AuNPs (RGO/meso-TiO{sub 2}/AuNPs) ternary composites were prepared via the addition of graphene oxide to the dispersion of meso-TiO{sub 2}/AuNPs under hydrothermal conditions. The structure and the morphology of the RGO/meso-TiO{sub 2}/AuNPs materials were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The photocatalytic activity of RGO/meso-TiO{sub 2}/AuNPs was evaluated by degradation of methyl blue (MB) under visible-light illumination. The ternary composites present an extended light absorption range, efficient charge separation properties, high adsorption ability for MB and high photocatalytic degradation activity of MB compared to the meso-TiO{sub 2} and meso-TiO{sub 2}/AuNPs.

  8. NATURAL IRON OXIDE AS A HETEROGENEOUS PHOTO-FENTON-LIKE CATALYST FOR THE DEGRADATION OF 1-NAPHTHOL UNDER ARTIFICIAL AND SOLAR LIGHT

    Directory of Open Access Journals (Sweden)

    L MAMMERI

    2014-07-01

    Full Text Available A heterogeneous photo-Fenton-like degradation process of 1-naphthol (1-NP promoted by natural iron oxide (NIO in the presence of H2O2 was studied under artificial (365 nm and solar irradiation. This is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural waters. Furthermore, iron oxides function as catalysts in chemical oxidation processes used with H2O2 for treatment of contaminated waters. The NIO used in this study was characterized by X-ray diffraction (XRD, X-ray fluorescence and Brunauer–Emmett–Teller (BET methods. The results show that the NIO is a composite material that contains predominantly crystalline hematite particales (Fe2O3. The Fe2O3 in NIO was able to initiate the Fenton-like and photo-Fenton-like reactions. The effects of initial pH, catalyst dosage, H2O2 concentration and the wavelength of the light source (UV and solar on the photodegradation of 1-NP were investigated. The optimal content of the NIO was 1 g L-1 and the optimal H2O2 concentration was 10 mM. The degradation could occur efficiently over a wide pH range of 3-8.3. Furthermore, an important effect of light was observed. The photo-oxidation of 1-NP in NIO-H2O2 system under solar light was significantly accelerated in comparison with artificial irradiation at 365 nm.

  9. Microwave-assisted in situ synthesis of reduced graphene oxide-BiVO4 composite photocatalysts and their enhanced photocatalytic performance for the degradation of ciprofloxacin.

    Science.gov (United States)

    Yan, Yan; Sun, Shaofang; Song, Yang; Yan, Xu; Guan, Weisheng; Liu, Xinlin; Shi, Weidong

    2013-04-15

    To improve the photodegradation efficiency for ciprofloxacin (CIP), a new-type microwave-assisted in situ growth method is developed for the preparation of reduced graphene oxide (RGO) -BiVO4 composite photocatalysts. The as-produced RGO-BiVO4 composite photocatalysts show extremely high enhancement of CIP degradation ratio over the pure BiVO4 photocatalyst under visible light. Specially, the 2 wt% RGO-BiVO4 composite photocatalyst exhibits the highest CIP degradation ratio (68.2%) in 60 min, which is over 3 times than that (22.7%) of the pure BiVO4 particles. The enhancement of photocatalytic activities of RGO-BiVO4 photocatalysts can be attributed to the effective separation of electron-hole pairs rather than the improvement of light absorption. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Effect of phosphate additives on the microstructure, bioactivity, and degradability of microarc oxidation coatings on Mg-Zn-Ca-Mn alloy.

    Science.gov (United States)

    Dou, Jinhe; You, Qiongya; Gu, Guochao; Chen, Chuanzhong; Zhang, Xihua

    2016-09-20

    Calcium phosphate coatings were prepared on the surface of self-designed Mg-Zn-Ca-Mn alloy using microarc oxidization technology. To characterize the microstructures, cross-section morphologies, and compositions of the coatings, the authors used scanning electron microscopy equipped with an energy-disperse spectrometer, x-ray diffraction, and Fourier transform infrared spectroscopy. Potentiodynamic polarization in the simulated body fluid (SBF) was used to evaluate the corrosion behaviors of the samples. An SBF immersion test was used to evaluate the coating bioactivity and degradability. After the immersion tests, some bonelike apatite formed on the coating surfaces indicate that bioactivity of the coatings is excellent. The coating prepared in electrolyte containing (NaPO3)6 had slower degradation rate after immersion test for 21 days.

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

    Science.gov (United States)

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

    2016-11-15

    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/IrO2-RuO2-TiO2 anodes), lead to discoloration by 92% and 89%, respectively, in 100min, 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 144h. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Separation of water-soluble metabolites of benzo[a]pyrene formed by cultured human colon

    DEFF Research Database (Denmark)

    Autrup, Herman

    1979-01-01

    A method has been developed to separate conjugated metabolites of benzo[a]pyrene into three major fractions: sulfate esters, glucuronides and glutathione conjugates. In cultured human colon, formation of sulfate esters and glutathione conjugates is the major conjugation pathway, while formation......-hydroxybenzo[a]pyrene were the major substrates for sulfotransferase in cultured human colon....

  13. Mechanism-based inactivation of benzo[a]pyrene hydroxylase by aryl acetylenes and aryl olefins

    International Nuclear Information System (INIS)

    Gan, L.S.; Lu, J.Y.L.; Alworth, W.L.

    1986-01-01

    A series of aryl acetylenes and aryl olefins have been examined as substrates and inhibitors of cytochrome P-450 dependent monooxgenases in liver microsomes from 5,6-benzoflavone or phenobarbital pretreated rats. 1-Ethynylpyrene, 3-ethynylperylene, 2-ethynylfluorene, methyl 1-pyrenyl acetylene, cis- and trans-1-(2-bromovinyl)pyrene, and 1-allylpyrene serve as mechanism-based irreversible inactivators (suicide inhibitors) of benzo[a]pyrene hydroxylase, while 1-vinylpyrene and phenyl 1-pyrenyl acetylene do not cause a detectable suicide inhibition of benzo[a]pyrene hydroxylase. The mechanism-based loss of benzo[a]pyrene hydroxylase caused by the aryl acetylenes is not accompanied by a corresponding loss of the P-450 content of the microsomes (suicide destruction). The suicide inhibition by these aryl acetylenes therefore does not involve covalent binding to the heme moiety of the monooxygenase. Nevertheless, in the presence of NADPH, 3 H-labeled 1-ethynylpyrene becomes covalently attached to the cytochrome P-450 protein; the measured stoichiometry of binding is one 1-ethynylpyrene per P-450 heme unit. The authors conclude that the inhibition of benzo[a]pyrene hydroxylase produced by 1-ethynylpyrene may be related to the mechanism of suicide inhibition of P-450 activity by chloramphenicol rather than the mechanism of suicide destruction of P-450 previously described for acetylene and propyne

  14. Solubility of Benzo[a]pyrene and Organic Matter of Soil in Subcritical Water

    Directory of Open Access Journals (Sweden)

    Svetlana Sushkova

    2015-12-01

    Full Text Available A dynamic subcritical water extraction method of benzo[a]pyrene from soils is under consideration. The optimum conditions for benzo[a]pyrene extraction from soil are described including the soil treatment by subcritical water at 250 °C and 100 atm for 30 min. The effectiveness of developed method was determined using the matrix spiking recovery technique. A comparative analysis was made to evaluate the results of benzo[a]pyrene extraction from soils using the subcritical water and organic solvents. The advantages of the subcritical water extraction involve the use of ecologically friendly solvent, a shorter time for the analysis and a higher amount of benzo[a]pyrene extracted from soil (96 %. The influence of subcritical water extraction on soil properties was measured the investigation of the processes occurring within soil under the influence the high temperature and pressure. Under appropriate conditions of the experiment there is the destruction of the soil organic matter while the composition of the soil mineral fraction remains practically unchanged.

  15. Effect of various chemicals on the metabolism of benzo(a)pyrene by cultured rat colon

    DEFF Research Database (Denmark)

    Autrup, Herman; Harris, Curtis C.; Fugaro, Steven

    1977-01-01

    The effect of various co- and anti-carcinogens of colon carcinogenesis on the metabolism of benzo(a)pyrene (BP) in cultured rat colon is reported. Rat colon enzymatically converted BP into metabolites which bind to cellular macromolecules i.e., DNA and protein. Activity of aryl hydrocarbon...

  16. On the carcinogenic polycyclic aromatic hydrocarbon benzo(a)pyrene in volcano exhausts.

    Science.gov (United States)

    Ilnitsky, A P; Belitsky, G A; Shabad, L M

    1976-05-01

    The content of benzo(a)pyrene in the juvenile ashes of the volcano Tyatya (Kunashir Island, Kuriles) and in the soil, vegetation and volcanic mud collected near volcanos in Kamchatka was studied. It was concluded that volcanic activity does not play a large role in forming the background level of this carcinogen in the human environment.

  17. Investigation of biological destruction of benzo[a]pyrene andpolycyclic aromatic hydrocarbons of biochar in soil

    Science.gov (United States)

    Okunev, R. V.; Smirnova, E. V.; Sharipova, A. R.; Gilmutdinova, I. M.; Giniyatullin, K. G.

    2018-01-01

    The biological decomposition of benzo[a]pyrene in the concentrations exceeding the MAC (maximum permissible concentration) level in soils by 2, 5 and 10 times was studied in laboratory conditions. The gray forest soil samples were contaminated with benzo[a]pyrene and incubated in optimum for bacterial growth soil moisture for 30 and 60 days. The residual amount of contaminant was monitored by HPLC after extraction with acetone-cyclohexane (2:1). Soil microbial activity was evaluated by measuring basal respiration (BR) and substrate-induced respiration (SID) rates of the soil by gas chromatography. The results of the experiment showed that in 60 days the amount of benzo[a]pyrene in contaminated soils decreased; however, this time was not enough for complete decomposition of pollutant. In this case, benzo[a]pyrene has a negative effect on the BR and SIR rates. Soil contamination affected the BR rate only at high doses (10 MPC), whereas the SIR was a more sensitive indicator of the toxic effect of the pollutant and significantly reacts already at concentrations at the level of 2 MPC. The combination of PAHs isolated from biochar has a strong negative effect on the values of BR and SIR.

  18. 3-Methylcholanthrene does not induce in vitro xenobiotic metabolism in spiny lobster hepatopancreas, or affect in vivo disposition of benzo(a)pyrene

    Energy Technology Data Exchange (ETDEWEB)

    James, M O; Little, P J

    1984-01-01

    Administration of 3-methylcholanthrene (10 mg/kg) i.m. to spiny lobsters, Panulirus argus, did not cause induction of the cytochrome P-450 content of hepatopancreas microsomes. The rate of oxidation of benzo(a)pyrene or 7-ethoxyresorufin in reductase-fortified preparations of hepatopancreas microsomes was the same for corn oil-treated or 3-methylcholanthrene-treated lobsters. Administration of 3-methylcholanthrene (10 mg/kg) i.m. to spiny lobsters one week prior to an i.v. dose of (/sup 14/C)benzo(a)pyrene (1 mg/kg) did not influence the disposition of the radiolabelled benzo(a)pyrene in lobsters. At one week after the dose of (/sup 14/C)benzo(a)pyrene, approximately 40% of the dose of (/sup 14/C)benzo(a)pyrene remained in the lobsters, regardless of treatment. The digestive tract (hepatopancreas, intestinal contents, stomach and intestine) contained most (86%) of the /sup 14/C remaining in the lobsters.

  19. Alterations to proteome and tissue recovery responses in fish liver caused by a short-term combination treatment with cadmium and benzo[a]pyrene

    International Nuclear Information System (INIS)

    Costa, P.M.; Chicano-Galvez, E.; Lopez Barea, J.; DelValls, T.A.; Costa, M.H.

    2010-01-01

    The livers of soles (Solea senegalensis) injected with subacute doses of cadmium (Cd), benzo[a]pyrene (B[a]P), or their combination, were screened for alterations to cytosolic protein expression patterns, complemented by cytological and histological analyses. Cadmium and B[a]P, but not combined, induced hepatocyte apoptosis and Kupfer cell hyperplasia. Proteomics, however, suggested that apoptosis was triggered through distinct pathways. Cadmium and B[a]P caused upregulation of different anti-oxidative enzymes (peroxiredoxin and glutathione peroxidase, respectively) although co-exposure impaired induction. Similarly, apoptosis was inhibited by co-exposure, to which may have contributed a synergistic upregulation of tissue metalloproteinase inhibitor, β-actin and a lipid transport protein. The regulation factors of nine out of eleven identified proteins of different types revealed antagonistic or synergistic effects between Cd and B[a]P at the prospected doses after 24 h of exposure. The results indicate that co-exposure to Cd and B[a]P may enhance toxicity by impairing specific responses and not through cumulative damage. - The interaction between cadmium and benzo[a]pyrene impairs specific responses to toxicity and tissue repair mechanisms.

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

    DEFF Research Database (Denmark)

    Hauch, Anne; Brodersen, Karen; Chen, Ming

    2016-01-01

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

  1. A simple Cr(VI)–S(IV)–O{sub 2} system for rapid and simultaneous reduction of Cr(VI) and oxidative degradation of organic pollutants

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Yanan; Yang, Shaojie [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, 430079 (China); Zhou, Danna, E-mail: zdncug@163.com [Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074 (China); Wu, Feng [Department of Environmental Science, Hubei Key Lab of Biomass Resource Chemistry and Environmental Biotechnology, School of Resources and Environmental Science, Wuhan University, 430079 (China)

    2016-04-15

    Highlights: • Rapid and simultaneous reduction of Cr(VI) and degradation of organic pollutants occur. • Oxysulfur radicals generated in Cr(VI)–S(IV)–O{sub 2} system oxidize the organic pollutants. • Acidic pH facilitates the reactions from both directions of reduction and oxidation. • Degradation potential of aromatic amines depends on the substituted groups. • Cr(VI)–S(IV)–O{sub 2} system is promising for “waste control by waste”. - Abstract: Hexavalent chromium (Cr(VI)), a heavy-metal contaminant, can be easily reduced to less toxic trivalent chromium (Cr(III)) by sulfite ions (S(IV)). However, S(IV) has not drawn as much attention as the ferrous ion has. We report herein a novel Cr(VI)–S(IV)–O{sub 2} system containing sulfite ions that rapidly and simultaneously reduces Cr(VI) and oxidize organic pollutants in the presence of oxygen in aqueous solutions. This Cr(VI)–S(IV)-O{sub 2} system contains the initiator Cr(VI), the reductant S(IV), and the oxidant O{sub 2}, which produce oxysulfur radicals (mainly SO{sub 4}·{sup −} and SO{sub 5}·{sup −}) and hydroxyl radicals (OH·). The Cr(VI)/S(IV) molar ratio, pH, and oxygen content play important roles in the entire reaction system. Acidic conditions (pH 3.0) facilitated degradation of organic compounds and reduction of Cr(VI) as well. In addition, experiments of rapid degradation of several kinds of organic pollutants such as azo dye (acid orange 7, AO7), aniline, phenol, bisphenol A etc were also conducted. Preliminary results show that the removal rates of the analogs of phenols or aromatic amines in this Cr(VI)–S(IV)–O{sub 2} system have a relationship with the electronic parameters (Hammett constant, σ) of the substituted groups. Thus, the Cr(VI)–S(IV)–O{sub 2} system, provides an excellent strategy of “waste control by waste” for removing multiple industrial contaminants.

  2. Oxidative degradation of 2,4-dioxohexahydro-1,3,5-triazine in aqueous medium: a radiation and photochemical study

    International Nuclear Information System (INIS)

    Joseph, J.M.; Jacob, T.A.; Manoj, V.M.; Aravindakumar, C.T.; Hari Mohan

    2000-01-01

    The kinetics and spectral nature of the intermediates resulting from the reaction of OH with 2,4-dioxohexahydro-1,3,5-triazine (DHT) have been studied by pulse radiolysis. The degradation leading to a complete disappearance of DHT induced by OH in aqueous medium was also studied using steady state radiolysis technique. The rate constant, determined by competitive kinetic methods, was 1.6 x 10 9 dm 3 mol -1 s -1 at pH 6. The complete degradation in N 2 O was observed with an absorbed dose of 7 kGy. The complete degradation in presence of ferricperchlorate using UV light was observed within 6 minute. (author)

  3. Oxidative degradation of acid doped polybenzimidazole membranes and fuel cell durability in the presence of ferrous ions

    DEFF Research Database (Denmark)

    Liao, Jianhui; Yang, Jingshuai; Li, Qingfeng

    2013-01-01

    Phosphoric acid doped polybenzimidazole membranes have been explored as proton exchange membranes for high temperature polymer electrolyte membrane fuel cells. Long-term durability of the membrane is of critical concern and has been evaluated by accelerated degradation tests under Fenton conditions...... of the polymer. Fuel cell durability tests with contaminations of ferrous ions did show considerable performance degradation, however, primarily due to the catalyst deterioration rather than the membrane degradation........ In this study effects of phosphoric acid and ferrous ions were investigated by measurements of the weight loss, intrinsic viscosity and size exclusion chromatography (SEC) of the polymer membranes. Ferrous ions resulted in, as expected, catalytic formation of peroxide radicals and hence the accelerated polymer...

  4. Origin of degradation phenomenon under drain bias stress for oxide thin film transistors using IGZO and IGO channel layers.

    Science.gov (United States)

    Bak, Jun Yong; Kang, Youngho; Yang, Shinhyuk; Ryu, Ho-Jun; Hwang, Chi-Sun; Han, Seungwu; Yoon, Sung-Min

    2015-01-20

    Top-gate structured thin film transistors (TFTs) using In-Ga-Zn-O (IGZO) and In-Ga-O (IGO) channel compositions were investigated to reveal a feasible origin for degradation phenomenon under drain bias stress (DBS). DBS-driven instability in terms of V(TH) shift, deviation of the SS value, and increase in the on-state current were detected only for the IGZO-TFT, in contrast to the IGO-TFT, which did not demonstrate V(TH) shift. These behaviors were visually confirmed via nanoscale transmission electron microscopy and energy-dispersive x-ray spectroscopy observations. To understand the degradation mechanism, we performed ab initio molecular dynamic simulations on the liquid phases of IGZO and IGO. The diffusivities of Ga and In atoms were enhanced in IGZO, confirming the degradation mechanism to be increased atomic diffusion.

  5. Oxidative degradation of the antibiotic oxytetracycline by Cu@Fe3O4 core-shell nanoparticles.

    Science.gov (United States)

    Pham, Van Luan; Kim, Do-Gun; Ko, Seok-Oh

    2018-08-01

    A core-shell nanostructure composed of zero-valent Cu (core) and Fe 3 O 4 (shell) (Cu@Fe 3 O 4 ) was prepared by a simple reduction method and was evaluated for the degradation of oxytetracycline (OTC), an antibiotic. The Cu core and the Fe 3 O 4 shell were verified by X-ray diffractometry (XRD) and transmission electron microscopy. The optimal molar ratio of [Cu]/[Fe] (1/1) in Cu@Fe 3 O 4 created an outstanding synergic effect, leading to >99% OTC degradation as well as H 2 O 2 decomposition within 10min at the reaction conditions of 1g/L Cu@Fe 3 O 4 , 20mg/L OTC, 20mM H 2 O 2 , and pH3.0 (and even at pH9.0). The OTC degradation rate by Cu@Fe 3 O 4 was higher than obtained using single nanoparticle of Cu or Fe 3 O 4 . The results of the study using radical scavengers showed that OH is the major reactive oxygen species contributing to the OTC degradation. Finally, good stability, reusability, and magnetic separation were obtained with approximately 97% OTC degradation and no notable change in XRD patterns after the Cu@Fe 3 O 4 catalyst was reused five times. These results demonstrate that Cu@Fe 3 O 4 is a novel prospective candidate for the pharmaceutical and personal care products degradation in the aqueous phase. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Effect of the pre-transient oxide on Zy-4 cladding degradation in air and air+steam atmospheres

    International Nuclear Information System (INIS)

    Duriez, C.; Guerain, M.; Lacote, P.; Mermoux, M.

    2015-01-01

    High temperature reactivity in air of Zr based alloys has been mostly investigated with initially bare cladding materials. In this study, attention is paid to the influence of a low temperature pre-oxidation scale aiming to simulate the corrosion scale existing on spent fuel. Different out of pile pre-oxidation methods, inducing significant variation in the pre-oxides microstructure, are compared. The reaction kinetics in air and in mixed air + steam atmospheres, investigated in the 700-950 C. degrees temperature range by thermogravimetry (TGA), shows that a pre-oxide scale formed at low temperature has a protective effect at high temperature by significantly delaying occurrence of the kinetic acceleration, which however still occurs. Efficiency of this protective effect appears to depend on the type of pre-oxide. To better understand the exact role of the pre-oxide, oxygen transport through the pre-oxide has been investigated using the 18 O tracer technique. 18 O distribution maps have been obtained by micro-Raman imaging, which has proved to offer interesting capabilities for that purpose. Results obtained with a 30 μm pre-oxide scale formed at 425 C. degrees in oxygen suggest that, at 850 C. degrees, only the inner part of the scale acts as a barrier against oxidation while the outermost part of the scale (5 to 15 μm in thickness) seems to be permeable to gaseous oxygen. The use of the 18 O isotope tracer technique associated with micro-Raman mapping of the scales is demonstrated to be a powerful method to investigate the transport properties of the scales and will help to gain understanding of the kinetic differences between the different pre-oxides

  7. 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

  8. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li

    2009-01-01

    Full Text Available Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms.

  9. TiO2 structures doped with noble metals and/or graphene oxide to improve the photocatalytic degradation of dichloroacetic acid.

    Science.gov (United States)

    Ribao, Paula; Rivero, Maria J; Ortiz, Inmaculada

    2017-05-01

    Noble metals have been used to improve the photocatalytic activity of TiO 2 . Noble metal nanoparticles prevent charge recombination, facilitating electron transport due to the equilibration of the Fermi levels. Furthermore, noble metal nanoparticles show an absorption band in the visible region due to a high localized surface plasmon resonance (LSPR) effect, which contributes to additional electron movements. Moreover, systems based on graphene, titanium dioxide, and noble metals have been used, considering that graphene sheets can carry charges, thereby reducing electron-hole recombination, and can be used as substrates of atomic thickness. In this work, TiO 2 -based nanocomposites were prepared by blending TiO 2 with noble metals (Pt and Ag) and/or graphene oxide (GO). The nanocomposites were mainly characterized via transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), Raman spectroscopy, and photocurrent analysis. Here, the photocatalytic performance of the composites was analyzed via oxidizing dichloroacetic acid (DCA) model solutions. The influence of the noble metal load on the composite and the ability of the graphene sheets to improve the photocatalytic activity were studied, and the composites doped with different noble metals were compared. The results indicated that the platinum structures show the best photocatalytic degradation, and, although the presence of graphene oxide in the composites is supposed to enhance their photocatalytic performance, graphene oxide does not always improve the photocatalytic process. Graphical abstract It is a schematic diagram. Where NM is Noble Metal and LSPR means Localized Surface Plasmon Resonance.

  10. Performance of electrochemical oxidation and photocatalysis in terms of kinetics and energy consumption. New insights into the p-cresol degradation.

    Science.gov (United States)

    Escudero, Carlos J; Iglesias, Olalla; Dominguez, Sara; Rivero, Maria J; Ortiz, Inmaculada

    2017-06-15

    This work reports the comparative performance of two Advanced Oxidation Processes (AOPs), electrochemical oxidation and photocatalysis, as individual technological alternatives for the treatment of effluents containing p-cresol. First, the influence of operating parameters in the oxidation and mineralization yield was carried out together with kinetic analysis. Boron Doped Diamond (BDD), RuO 2 and Pt as anodic materials, Na 2 SO 4 and NaCl as supporting electrolytes and different current densities were evaluated in electrochemical oxidation whereas the effect of TiO 2 concentration and radiation was studied in the photocatalytic degradation. Then, the parameter Electrical Energy per Order (E EO ) was calculated to compare the energy consumption in both AOPs, concluding that under the studied conditions the electrochemical treatment with BDD, Na 2 SO 4 and 125 A m -2 showed the best energy efficiency, with an E EO of 5.83 kW h m -3 order -1 for p-cresol and 58.05 kW h m -3 order -1 for DOC removal, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Degradation of cytokinins by maize cytokinin dehydrogenase is mediated by free radicals generated by enzymatic oxidation of natural benzoxazinones

    Czech Academy of Sciences Publication Activity Database

    Frébortová, Jitka; Novák, Ondřej; Frébort, Ivo; Jorda, Radek

    2010-01-01

    Roč. 61, č. 3 (2010), s. 467-481 ISSN 0960-7412 R&D Projects: GA ČR GA522/05/0448; GA ČR GA301/08/1649 Institutional research plan: CEZ:AV0Z50380511 Keywords : Degradation * cytokinins * maize Subject RIV: EF - Botanics Impact factor: 6.948, year: 2010

  12. Experimental and DFT study of the degradation of 4-chlorophenol on hierarchical micro-/nanostructured oxide films

    Czech Academy of Sciences Publication Activity Database

    Guerin, V. M.; Žouželka, Radek; Bíbová-Lipšová, Hana; Jirkovský, Jaromír; Rathouský, Jiří; Pauporté, T.

    2015-01-01

    Roč. 168, JUN 01 (2015), s. 132-140 ISSN 0926-3373 R&D Projects: GA MK(CZ) DF11P01OVV012 Keywords : 4-Chlorophenol degradation * DFT modeling * ZnO hierarchical nanostructures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.328, year: 2015

  13. Modeling the competitive effect of ammonium oxidizers and heterotrophs on the degradation of MTBE in a packed bed reactor

    DEFF Research Database (Denmark)

    Waul, Christopher Kevin; Arvin, Erik; Schmidt, Jens Ejbye

    2008-01-01

    A mathematical model was used to study effects on the degradation of methyl tert-butyl ether (MTBE) in a packed bed reactor due to the presence of contaminants such as ammonium, and the mix of benzene, toluene, ethylbenzene and xylenes (BTEX). It was shown that competition between the slower...

  14. Pre-oxidation of low-density polyethylene (LDPE) by ultraviolet light (UV) promotes enhanced degradation of LDPE in soil.

    Science.gov (United States)

    Tribedi, Prosun; Dey, Samrat

    2017-11-09

    Polyethylene represents nearly 64% of all the synthetic plastics produced and are mainly used for domestic and industrial applications. Their extensive use poses a serious environmental threat because of their non-biodegradable nature. Among all the polyethylene remediation strategies, in situ bioremediation happens to be the safest and efficient one. In the current study, efforts had been given to compare the extent of LDPE degradation under UV-treated and UV-untreated conditions by soil microcosm. Landfill soil was collected and UV-treated and UV-untreated LDPE were added separately to the soil following incubation under similar conditions. Electron microscopic images as well as the weight loss and the tensile strength results clearly revealed that UV-treated LDPE showed better degradation than the non-treated ones in soil. To elucidate the mechanism of this enhanced biodegradation, the bond spectra of differentially treated LDPE were analyzed by FTIR. The results obtained from bond spectra studies revealed that UV treatment increases both carbonyl and terminal double-bond index of the LDPE, thereby making it highly susceptible for microbial degradation. Moreover, incubation of UV-treated LDPE with soil favors better adherence of metabolically active and significantly higher number of microorganisms on it. Taken together, all these results demonstrate the higher microbial association and their better metabolic potential to the UV-treated LDPE that lead to enhanced degradation of the LDPE by the soil microorganisms.

  15. (0 0 1) Facet-exposed anatase-phase TiO{sub 2} nanotube hybrid reduced graphene oxide composite: Synthesis, characterization and application in photocatalytic degradation

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Xun [School of Chemical Engineering of Hefei University of Technology, Hefei 230009 (China); Shi, Tiejun, E-mail: stjhfut@163.com [School of Chemical Engineering of Hefei University of Technology, Hefei 230009 (China); Wu, Jing [School of Chemical Engineering of Hefei University of Technology, Hefei 230009 (China); Zhou, Haiou [School of Chemical Engineering of Hefei University of Technology, Hefei 230009 (China); School of Materials and Chemical Engineering of Anhui University of Architecture, Hefei 230901 (China)

    2013-12-15

    Reduced graphene oxide (RGO) and TiO{sub 2} nanotube (TNT) with (0 0 1) facet-exposed anatase phase are covalently bonded together to synthesize TNT hybrid RGO (RGO-TNT) through consecutive process such as hydrothermal reaction, HCl washing, lyophilization and heat treatment with graphene oxide (GO), TiO{sub 2} powder and high concentration NaOH solution as the starting materials. The TNT with the diameter between 10 and 20 nm characterized by high resolution transmission electron microscopy (HRTEM) is in anatase phase proven by X-ray diffraction (XRD) and HRTEM. Additionally, the more active (0 0 1) facet is exposed identified by HRTEM. More significantly, TNT is bridged to RGO by C-Ti bond by the measurement of X-ray photoelectron spectroscopy (XPS). The photoluminescence (PL) spectra has testified that RGO in RGO-TNT can transfer and accept photoelectrons from TNT. The photocatalytic activity of RGO-TNT for degrading methylene blue (MB) is enhanced by contrast with pure TNT, and changeable by adjusting the mass ratios of GO to TiO{sub 2} powder. Simultaneously, lyophilization is benefit for maintaining the high active surface area of RGO-TNT, which is deeply in relationship with a higher photocatalytic activity. After four running cycles of photocatalytic degradation, RGO-TNT has shown a high stability and perfect reproducibility.

  16. Ag@graphene oxide nanocomposite as an efficient visible-light plasmonic photocatalyst for the degradation of organic pollutants: A facile green synthetic approach

    International Nuclear Information System (INIS)

    Haldorai, Yuvaraj; Kim, Byung-Keuk; Jo, Youl-Lae; Shim, Jae-Jin

    2014-01-01

    We report a simple and effective supercritical route to decorate silver nanoparticles (Ag NPs) on graphene oxide (GO) using a commonly available and non-toxic glucose as a reducing agent. Transmission electron microscopy and energy-dispersive X-ray analysis confirmed that Ag NPs of size around 8–20 nm were coated on the GO surface under optimized experimental condition. Ag NPs on the GO surface were predominantly spherical in shape and well dispersed. The experimental results proved that the as-synthesized GO/Ag nanocomposite could be used as a highly efficient photocatalyst for the degradation of Rhodamine 123 dye and acetaldehyde under visible-light irradiation. The degradation results indicated that the photocatalytic performance of nanocomposite was greatly enhanced owing to the improved adsorption performance and separation efficiency of photo-generated carriers. The nanocomposite maintains a high level activity even after four times of recycle. Furthermore, the nanocomposite exhibited excellent antibacterial activity against gram-positive and gram-negative microorganisms. - Highlights: • Visible-light driven reusable photocatalyst. • Efficient degradation of Rhodamine 123 dye and acetaldehyde. • Excellent antibacterial activity. • Green synthetic approach using supercritical fluid. • New field of sustainable nanotechnology

  17. Tantalum oxide and barium sulfate as radiopacifiers in injectable calcium phosphate-poly(lactic-co-glycolic acid) cements for monitoring in vivo degradation.

    Science.gov (United States)

    Hoekstra, Jan Willem M; van den Beucken, Jeroen J J P; Leeuwenburgh, Sander C G; Bronkhorst, Ewald M; Meijer, Gert J; Jansen, John A

    2014-01-01

    Monitoring the degradation of calcium phosphate-based bone substitute materials in vivo by means of noninvasive techniques (e.g., radiography) is often a problem due to the chemical resemblance of those substitutes with the mineral phase of bone. In the view of that, the present study aimed at enhancing the radiopacity of calcium phosphate cement enriched with poly(lactic-co-glycolic acid) (CPC-PLGA) microspheres, by adding tantalum oxide (Ta2O5) or the more traditional radiopacifier barium sulfate (BaSO4). The radiopacifying capacity of these radiopacifiers was first evaluated in vitro by microcomputed tomography (μCT). Thereafter, both radiopacifiers were tested in vivo using a distal femoral condyle model in rabbits, with subsequent ex vivo μCT analysis in parallel with histomorphometry. Addition of either one of the radiopacifiers proved to enhance radiopacity of CPC-PLGA in vitro. The in vivo experiment showed that both radiopacifiers did not induce alterations in biological performance compared to plain CPC-PLGA, hence both radiopacifiers can be considered safe and biocompatible. The histomorphometrical assessment of cement degradation and bone formation showed similar values for the three experimental groups. Interestingly, μCT analysis showed that monitoring cement degradation becomes feasible upon incorporation of either type of radiopacifier, albeit that BaSO4 showed more accuracy compared to Ta2O5. Copyright © 2013 Wiley Periodicals, Inc., a Wiley Company.

  18. Microwave-assisted in situ synthesis of reduced graphene oxide-BiVO{sub 4} composite photocatalysts and their enhanced photocatalytic performance for the degradation of ciprofloxacin

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yan [School of Chemistry and Chemical Engineering, Jiangsu University, Xuefu Road 301, Zhenjiang, 212013 (China); Sun, Shaofang [School of Chemistry and Chemical Engineering, Jiangsu University, Xuefu Road 301, Zhenjiang, 212013 (China); School of Environmental Science and Engineering, Chang’an University, Yanta Road 126, Xi’an, 710054 (China); Song, Yang; Yan, Xu [School of Chemistry and Chemical Engineering, Jiangsu University, Xuefu Road 301, Zhenjiang, 212013 (China); Guan, Weisheng [School of Environmental Science and Engineering, Chang’an University, Yanta Road 126, Xi’an, 710054 (China); Liu, Xinlin [School of Material Science and Engineering, Jiangsu University, Xuefu Road 301, Zhenjiang, 212013 (China); Shi, Weidong, E-mail: swd1978@ujs.edu.cn [School of Chemistry and Chemical Engineering, Jiangsu University, Xuefu Road 301, Zhenjiang, 212013 (China)

    2013-04-15

    Highlights: ► Microwave-assisted in situ growth of RGO-BiVO{sub 4} composite was proposed. ► A relatively small particle size with organic-additives free. ► Graphene was formed during the microwave-heating by oxygen capture. ► GB-2 sample exhibits the highest CIP degradation ratio (3 times over pure BiVO{sub 4}). ► The enhancements of activities result from the effective charge separation. -- Abstract: To improve the photodegradation efficiency for ciprofloxacin (CIP), a new-type microwave-assisted in situ growth method is developed for the preparation of reduced graphene oxide (RGO) -BiVO{sub 4} composite photocatalysts. The as-produced RGO-BiVO{sub 4} composite photocatalysts show extremely high enhancement of CIP degradation ratio over the pure BiVO{sub 4} photocatalyst under visible light. Specially, the 2 wt% RGO-BiVO{sub 4} composite photocatalyst exhibits the highest CIP degradation ratio (68.2%) in 60 min, which is over 3 times than that (22.7%) of the pure BiVO{sub 4} particles. The enhancement of photocatalytic activities of RGO-BiVO{sub 4} photocatalysts can be attributed to the effective separation of electron–hole pairs rather than the improvement of light absorption.

  19. Hydrolytic Degradation and Mechanical Stability of Poly(ε-Caprolactone)/Reduced Graphene Oxide Membranes as Scaffolds for In Vitro Neural Tissue Regeneration.

    Science.gov (United States)

    Sánchez-González, Sandra; Diban, Nazely; Urtiaga, Ane

    2018-03-05

    The present work studies the functional behavior of novel poly(ε-caprolactone) (PCL) membranes functionalized with reduced graphene oxide (rGO) nanoplatelets under simulated in vitro culture conditions (phosphate buffer solution (PBS) at 37 °C) during 1 year, in order to elucidate their applicability as scaffolds for in vitro neural regeneration. The morphological, chemical, and DSC results demonstrated that high internal porosity of the membranes facilitated water permeation and procured an accelerated hydrolytic degradation throughout the bulk pathway. Therefore, similar molecular weight reduction, from 80 kDa to 33 kDa for the control PCL, and to 27 kDa for PCL/rGO membranes, at the end of the study, was observed. After 1 year of hydrolytic degradation, though monomers coming from the hydrolytic cleavage of PCL diffused towards the PBS medium, the pH was barely affected, and the rGO nanoplatelets mainly remained in the membranes which envisaged low cytotoxic effect. On the other hand, the presence of rGO nanomaterials accelerated the loss of mechanical stability of the membranes. However, it is envisioned that the gradual degradation of the PCL/rGO membranes could facilitate cells infiltration, interconnectivity, and tissue formation.

  20. Mechanistic Insight into the Degradation of Nitrosamines via Aqueous-Phase UV Photolysis or a UV-Based Advanced Oxidation Process: Quantum Mechanical Calculations

    Directory of Open Access Journals (Sweden)

    Daisuke Minakata

    2018-02-01

    Full Text Available Nitrosamines are a group of carcinogenic chemicals that are present in aquatic environments that result from byproducts of industrial processes and disinfection products. As indirect and direct potable reuse increase, the presence of trace nitrosamines presents challenges to water infrastructures that incorporate effluent from wastewater treatment. Ultraviolet (UV photolysis or UV-based advanced oxidation processes that produce highly reactive hydroxyl radicals are promising technologies to remove nitrosamines from water. However, complex reaction mechanisms involving radicals limit our understandings of the elementary reaction pathways embedded in the overall reactions identified experimentally. In this study, we perform quantum mechanical calculations to identify the hydroxyl radical-induced initial elementary reactions with N-nitrosodimethylamine (NDMA, N-nitrosomethylethylamine, and N-nitrosomethylbutylamine. We also investigate the UV-induced NDMA degradation mechanisms. Our calculations reveal that the alkyl side chains of nitrosamine affect the reaction mechanism of hydroxyl radicals with each nitrosamine investigated in this study. Nitrosamines with one- or two-carbon alkyl chains caused the delocalization of the electron density, leading to slower subsequent degradation. Additionally, three major initial elementary reactions and the subsequent radical-involved reaction pathways are identified in the UV-induced NDMA degradation process. This study provides mechanistic insight into the elementary reaction pathways, and a future study will combine these results with the kinetic information to predict the time-dependent concentration profiles of nitrosamines and their transformation products.

  1. Mechanistic Insight into the Degradation of Nitrosamines via Aqueous-Phase UV Photolysis or a UV-Based Advanced Oxidation Process: Quantum Mechanical Calculations.

    Science.gov (United States)

    Minakata, Daisuke; Coscarelli, Erica

    2018-02-28

    Nitrosamines are a group of carcinogenic chemicals that are present in aquatic environments that result from byproducts of industrial processes and disinfection products. As indirect and direct potable reuse increase, the presence of trace nitrosamines presents challenges to water infrastructures that incorporate effluent from wastewater treatment. Ultraviolet (UV) photolysis or UV-based advanced oxidation processes that produce highly reactive hydroxyl radicals are promising technologies to remove nitrosamines from water. However, complex reaction mechanisms involving radicals limit our understandings of the elementary reaction pathways embedded in the overall reactions identified experimentally. In this study, we perform quantum mechanical calculations to identify the hydroxyl radical-induced initial elementary reactions with N -nitrosodimethylamine (NDMA), N -nitrosomethylethylamine, and N -nitrosomethylbutylamine. We also investigate the UV-induced NDMA degradation mechanisms. Our calculations reveal that the alkyl side chains of nitrosamine affect the reaction mechanism of hydroxyl radicals with each nitrosamine investigated in this study. Nitrosamines with one- or two-carbon alkyl chains caused the delocalization of the electron density, leading to slower subsequent degradation. Additionally, three major initial elementary reactions and the subsequent radical-involved reaction pathways are identified in the UV-induced NDMA degradation process. This study provides mechanistic insight into the elementary reaction pathways, and a future study will combine these results with the kinetic information to predict the time-dependent concentration profiles of nitrosamines and their transformation products.

  2. Enhanced degradation of azo dye alizarin yellow R in a combined process of iron-carbon microelectrolysis and aerobic bio-contact oxidation.

    Science.gov (United States)

    Liang, Bin; Yao, Qian; Cheng, Haoyi; Gao, Shuhong; Kong, Fanying; Cui, Dan; Guo, Yuqi; Ren, Nanqi; Lee, Duu-Jong; Wang, Aijie

    2012-06-01

    With the aim of enhanced degradation of azo dye alizarin yellow R (AY) and further removal of the low-strength recalcitrant matter (LsRM) of the secondary effluent as much as possible, our research focused on the combination of aerobic bio-contact oxidation (ABO) with iron/carbon microelectrolysis (ICME) process. The combined ABO (with effective volume of 2.4 l) and ICME (with effectively volume of 0.4 l) process were studied with relatively short hydraulic retention time (HRT) of 4 or 6 h. At the HRT of 6 h with the reflux ratio of 1 and 2, the AY degradation efficiency in the final effluent was >96.5%, and the total organic carbon (TOC) removal efficiency were 69.86% and 79.44%, respectively. At the HRT of 4 h and the reflux ratio of 2, TOC removal efficiency and AY degradation efficiency were 73.94% and 94.89%, respectively. The ICME process obviously enhanced the total AY removal and the generated micromolecule acids and aldehydes then that wastewater backflow to the ABO where they were further biodegraded. The present research might provide the potential options for the advanced treatment azo dyes wastewater with short HRT and acceptable running costs.

  3. S-nitrosylation of TRIM72 at cysteine 144 is critical for protection against oxidation-induced protein degradation and cell death.

    Science.gov (United States)

    Kohr, Mark J; Evangelista, Alicia M; Ferlito, Marcella; Steenbergen, Charles; Murphy, Elizabeth

    2014-04-01

    Oxidative stress and membrane damage following myocardial ischemia/reperfusion injury are important contributors to cardiomyocyte death and the loss of myocardial function. Our previous study identified cysteine 144 (C144) of tripartite motif-containing protein 72 (TRIM72) as a potential site for S-nitrosylation (SNO). TRIM72 is a cardioprotective membrane repair protein that can be both activated and targeted for degradation by different oxidative modifications. Consistent with the potential regulation of TRIM72 by various oxidative modifications, we found that SNO levels increased at C144 of TRIM72 with ischemic preconditioning. Therefore, to investigate the role of C144 in the regulation of TRIM72 function, we mutated C144 of TRIM72 to a serine residue (TRIM72(C144S)), and expressed either TRIM72(WT) or TRIM72(C144S) in HEK-293 cells, which lack endogenous TRIM72, in order to examine the effect of this mutation on the functional stability of TRIM72 and on cell survival. We hypothesized that SNO of TRIM72 stabilizes the protein, thus allowing for membrane repair and enhanced cell survival. Upon treatment with hydrogen peroxide (H2O2), we found that TRIM72(WT) levels were decreased, but not TRIM72(C144S) and this correlated with increased H2O2-induced cell death in TRIM72(WT) cells. Additionally, we found that treatment with the cardioprotective S-nitrosylating agent S-nitrosoglutathione (GSNO), was able to preserve TRIM72(WT) protein levels and enhance TRIM72(WT)-mediated cell survival, but had no effect on TRIM72(C144S) levels. Consistent with our hypothesis, GSNO was also found to increase SNO levels and inhibit H2O2-induced irreversible oxidation for TRIM72(WT) without affecting TRIM72(C144S). In further support of our hypothesis, GSNO blocked the ischemia/reperfusion-induced decrease in TRIM72 levels and reduced infarct size in a Langendorff-perfused heart model. The results of these studies have important implications for cardioprotection and suggest that

  4. 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.

  5. Hydrothermal synthesis of fluorinated anatase TiO{sub 2}/reduced graphene oxide nanocomposites and their photocatalytic degradation of bisphenol A

    Energy Technology Data Exchange (ETDEWEB)

    Luo, Lijun [Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming, 650091 (China); Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650093 (China); Key Laboratory of Resource Clean Conversion in Ethnic Regions, Education Department of Yunnan, School of Chemistry and Biotechnology, Yunnan MinZu University, Kunming, 650500 (China); Yang, Ye [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650093 (China); Zhang, Ali [Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming, 650091 (China); Wang, Min; Liu, Yongjun; Bian, Longchun [Advanced Analysis and Measurement Center, Yunnan University, Kunming, 650091 (China); Jiang, Fengzhi, E-mail: fengzhij@ynu.edu.cn [Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, Yunnan University, Kunming, 650091 (China); Pan, Xuejun [Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650093 (China)

    2015-10-30

    Graphical abstract: - Highlights: • F–TiO{sub 2}–RGO nanocomposites were synthesized via hydrothermal method. • Presence of F ion prevents phase transformation from anatase to rutile. • The adsorbed F{sup −} and RGO improve the photocatalytic activity of TiO{sub 2} synergistically. • The F–TiO{sub 2}–RGO nanocomposites were applied to degrade bisphenol A. - Abstract: The surface fluorinated TiO{sub 2}/reduced graphene oxide nanocomposites (denoted as F–TiO{sub 2}–RGO) were synthesized via hydrothermal method. The as-prepared materials were characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), Raman spectroscopy, Fourier Transform Infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS) and X-ray fluorescence (XRF). The results showed that pure anatase TiO{sub 2} particles were anchored on the surface of reduced graphene oxide. And the HF added during the preparation process can not only prevent phase transformation from anatase to rutile, but also the F{sup −} ion adsorbed on the surface of TiO{sub 2}–RGO surface can enhance photocatalytic activity of F–TiO{sub 2}–RGO. The photocatalytic activities of F–TiO{sub 2}–RGO nanocomposites were evaluated by decomposing bisphenol A under UV light illumination. Under optimal degradation condition, the degradation rate constant of BPA over F–TiO{sub 2}–10RGO (0.01501 min{sup −1}) was 3.41 times than that over P25 (0.00440 min{sup −1}). The result indicated that the enhanced photocatalytic activity of F–TiO{sub 2}–10RGO was ascribed to the adsorbed F ion and RGO in F–TiO{sub 2}–RGO composite, which can reduce the recombination rate of the photo-generated electrons and holes synergistically.

  6. 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