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Sample records for aerobic ammonium oxidation

  1. Ammonium-oxidizing bacteria facilitate aerobic degradation of sulfanilic acid in activated sludge.

    PubMed

    Chen, Gang; Ginige, Maneesha P; Kaksonen, Anna H; Cheng, Ka Yu

    2014-01-01

    Sulfanilic acid (SA) is a toxic sulfonated aromatic amine commonly found in anaerobically treated azo dye contaminated effluents. Aerobic acclimatization of SA-degrading mixed microbial culture could lead to co-enrichment of ammonium-oxidizing bacteria (AOB) because of the concomitant release of ammonium from SA oxidation. To what extent the co-enriched AOB would affect SA oxidation at various ammonium concentrations was unclear. Here, a series of batch kinetic experiments were conducted to evaluate the effect of AOB on aerobic SA degradation in an acclimatized activated sludge culture capable of oxidizing SA and ammonium simultaneously. To account for the effect of AOB on SA degradation, allylthiourea was used to inhibit AOB activity in the culture. The results indicated that specific SA degradation rate of the mixed culture was negatively correlated with the initial ammonium concentration (0-93 mM, R²= 0.99). The presence of AOB accelerated SA degradation by reducing the inhibitory effect of ammonium (≥ 10 mM). The Haldane substrate inhibition model was used to correlate substrate concentration (SA and ammonium) and oxygen uptake rate. This study revealed, for the first time, that AOB could facilitate SA degradation at high concentration of ammonium (≥ 10 mM) in an enriched activated sludge culture.

  2. Environmental detection of octahaem cytochrome c hydroxylamine/hydrazine oxidoreductase genes of aerobic and anaerobic ammonium-oxidizing bacteria.

    PubMed

    Schmid, Markus C; Hooper, Alan B; Klotz, Martin G; Woebken, Dagmar; Lam, Phyllis; Kuypers, Marcel M M; Pommerening-Roeser, Andreas; Op den Camp, Huub J M; Jetten, Mike S M

    2008-11-01

    Bacterial aerobic ammonium oxidation and anaerobic ammonium oxidation (anammox) are important processes in the global nitrogen cycle. Key enzymes in both processes are the octahaem cytochrome c (OCC) proteins, hydroxylamine oxidoreductase (HAO) of aerobic ammonium-oxidizing bacteria (AOB), which catalyses the oxidation of hydroxylamine to nitrite, and hydrazine oxidoreductase (HZO) of anammox bacteria, which converts hydrazine to N(2). While the genomes of AOB encode up to three nearly identical copies of hao operons, genome analysis of Candidatus'Kuenenia stuttgartiensis' showed eight highly divergent octahaem protein coding regions as possible candidates for the HZO. Based on their phylogenetic relationship and biochemical characteristics, the sequences of these eight gene products grouped in three clusters. Degenerate primers were designed on the basis of available gene sequences with the aim to detect hao and hzo genes in various ecosystems. The hao primer pairs amplified gene fragments from 738 to 1172 bp and the hzo primer pairs amplified gene fragments from 289 to 876 bp in length, when tested on genomic DNA isolated from a variety of AOB and anammox bacteria. A selection of these primer pairs was also used successfully to amplify and analyse the hao and hzo genes in community DNA isolated from different ecosystems harbouring both AOB and anammox bacteria. We propose that OCC protein-encoding genes are suitable targets for molecular ecological studies on both aerobic and anaerobic ammonium-oxidizing bacteria.

  3. Responses of aerobic and anaerobic ammonia/ammonium-oxidizing microorganisms to anthropogenic pollution in coastal marine environments.

    PubMed

    Cao, Huiluo; Li, Meng; Dang, Hongyue; Gu, Ji-Dong

    2011-01-01

    Up to date, numerous studies have shown that the community structure of aerobic ammonia oxidizers including ammonia-oxidizing Betaproteobacteria (Beta-AOB) and ammonia-oxidizing archaea (AOA) and, more recently, the anaerobic ammonium-oxidizing (anammox) bacteria is responsive to environmental conditions including salinity, pH, selected metal ions, concentrations of inorganic nitrogen, total phosphorus, the ratio of organic carbon and nitrogen, and sedimentological factors such as the sediment median grain size. Identification of these responses to known anthropogenic pollution is of particular interest to better understand the growth dynamics and activities of nitrogen transforming microorganisms in marine environments. This chapter discusses currently available methods including molecular ecological analysis using clone library constructions with specific molecular genetic markers for delineating community changes of Beta-AOB, AOA, and anammox bacteria. Using data on ammonia-oxidizing microbial community structures from Jiaozhou Bay in North China and three marine environments with anthropogenic pollution gradients in South China from coastal Mai Po Nature Reserve of Hong Kong to the South China Sea as examples, statistical analyses packages (DOTUR, UniFrac, and Canoco) are presented as useful tools to illustrate the relationship between changes in nitrogen metabolizing microbial communities and established environmental variables. PMID:21514459

  4. Responses of aerobic and anaerobic ammonia/ammonium-oxidizing microorganisms to anthropogenic pollution in coastal marine environments.

    PubMed

    Cao, Huiluo; Li, Meng; Dang, Hongyue; Gu, Ji-Dong

    2011-01-01

    Up to date, numerous studies have shown that the community structure of aerobic ammonia oxidizers including ammonia-oxidizing Betaproteobacteria (Beta-AOB) and ammonia-oxidizing archaea (AOA) and, more recently, the anaerobic ammonium-oxidizing (anammox) bacteria is responsive to environmental conditions including salinity, pH, selected metal ions, concentrations of inorganic nitrogen, total phosphorus, the ratio of organic carbon and nitrogen, and sedimentological factors such as the sediment median grain size. Identification of these responses to known anthropogenic pollution is of particular interest to better understand the growth dynamics and activities of nitrogen transforming microorganisms in marine environments. This chapter discusses currently available methods including molecular ecological analysis using clone library constructions with specific molecular genetic markers for delineating community changes of Beta-AOB, AOA, and anammox bacteria. Using data on ammonia-oxidizing microbial community structures from Jiaozhou Bay in North China and three marine environments with anthropogenic pollution gradients in South China from coastal Mai Po Nature Reserve of Hong Kong to the South China Sea as examples, statistical analyses packages (DOTUR, UniFrac, and Canoco) are presented as useful tools to illustrate the relationship between changes in nitrogen metabolizing microbial communities and established environmental variables.

  5. Simultaneous nitrification and denitrification by EPSs in aerobic granular sludge enhanced nitrogen removal of ammonium-nitrogen-rich wastewater.

    PubMed

    Yan, Lilong; Zhang, Shaoliang; Hao, Guoxin; Zhang, Xiaolei; Ren, Yuan; Wen, Yan; Guo, Yihan; Zhang, Ying

    2016-02-01

    In this study, role of extracellular polymeric substances (EPSs) in enhancing nitrogen-removal from ammonium-nitrogen-rich wastewater using aerobic granular sludge (AGS) technology were analyzed. AGS enabled ammonium oxidation and denitrification to occur simultaneously. Air stripping and simultaneous nitrification-denitrification contributed to total-nitrogen removal. Clone-library analysis revealed that close relatives of Nitrosomonas eutropha and heterotrophic denitrifiers were dominant in the AGS, whereas anammox bacteria were not detected. EPSs adsorption of ammonium, nitrite, and nitrate nitrogen results in improved removal of nitrogen in batch experiments.

  6. Anaerobic ammonium oxidation for treatment of ammonium-rich wastewaters*

    PubMed Central

    Zhang, Lei; Zheng, Ping; Tang, Chong-jian; Jin, Ren-cun

    2008-01-01

    The concept of anaerobic ammonium oxidation (ANAMMOX) is presently of great interest. The functional bacteria belonging to the Planctomycete phylum and their metabolism are investigated by microbiologists. Meanwhile, the ANAMMOX is equally valuable in treatment of ammonium-rich wastewaters. Related processes including partial nitritation-ANAMMOX and completely autotrophic nitrogen removal over nitrite (CANON) have been developed, and lab-scale experiments proved that both processes were quite feasible in engineering with appropriate control. Successful full-scale practice in the Netherlands will accelerate application of the process in future. This review introduces the microbiology and more focuses on application of the ANAMMOX process. PMID:18500782

  7. The contribution of exopolysaccharides induced struvites accumulation to ammonium adsorption in aerobic granular sludge.

    PubMed

    Lin, Y M; Bassin, J P; van Loosdrecht, M C M

    2012-03-15

    Aerobic granular sludge from a lab-scale reactor with simultaneous nitrification/denitrification and enhanced biological phosphorus removal processes exhibited significant amount of ammonium adsorption (1.5 mg NH4+-N/g TSS at an ammonium concentration of 30 mg N/L). Potassium release accompanied ammonium adsorption, indicating an ion exchange process. The existence of potassium magnesium phosphate (K-struvite) as one of potassium sources in the granular sludge was studied by X-ray diffraction analysis (XRD). Artificially prepared K-struvite was indeed shown to adsorb ammonium. Alginate-like exopolysaccharides were isolated and their inducement for struvite formation was investigated as well. Potassium magnesium phosphate proved to be a major factor for ammonium adsorption on the granular sludge. Struvites (potassium/ammonium magnesium phosphate) accumulate in aerobic granular sludge due to inducing of precipitation by alginate-like exopolysaccharides.

  8. Supercritical water oxidation of ammonium picrate

    SciTech Connect

    LaJeunesse, C.A.; Mills, B.E.; Brown, B.G.

    1994-11-01

    This study demonstrates the feasibility of using supercritical water oxidation to destroy ammonium picrate. Analyses of reactor effluent composition at various temperatures, residence times, and oxidant concentrations were used to design an improved reactor configuration for achieving destruction with minimum corrosion. The engineering evaluation reactor, a room-sized laboratory scale reactor, was reconfigured to incorporate this design change. Destruction of ammonium picrate with minimized corrosion was demonstrated on this reconfigured reactor. Factors that must be considered in scaling up to pilot plant size are discussed.

  9. Controlling the catalytic aerobic oxidation of phenols.

    PubMed

    Esguerra, Kenneth Virgel N; Fall, Yacoub; Petitjean, Laurène; Lumb, Jean-Philip

    2014-05-28

    The oxidation of phenols is the subject of extensive investigation, but there are few catalytic aerobic examples that are chemo- and regioselective. Here we describe conditions for the ortho-oxygenation or oxidative coupling of phenols under copper (Cu)-catalyzed aerobic conditions that give rise to ortho-quinones, biphenols or benzoxepines. We demonstrate that each product class can be accessed selectively by the appropriate choice of Cu(I) salt, amine ligand, desiccant and reaction temperature. In addition, we evaluate the effects of substituents on the phenol and demonstrate their influence on selectivity between ortho-oxygenation and oxidative coupling pathways. These results create an important precedent of catalyst control in the catalytic aerobic oxidation of phenols and set the stage for future development of catalytic systems and mechanistic investigations. PMID:24784319

  10. Natural attenuation potential of tricholoroethene in wetland plant roots: role of native ammonium-oxidizing microorganisms.

    PubMed

    Qin, Ke; Struckhoff, Garrett C; Agrawal, Abinash; Shelley, Michael L; Dong, Hailiang

    2015-01-01

    Bench-scale microcosms with wetland plant roots were investigated to characterize the microbial contributions to contaminant degradation of trichloroethene (TCE) with ammonium. The batch system microcosms consisted of a known mass of wetland plant roots in aerobic growth media where the roots provided both an inoculum of root-associated ammonium-oxidizing microorganisms and a microbial habitat. Aqueous growth media, ammonium, and TCE were replaced weekly in batch microcosms while retaining roots and root-associated biomass. Molecular biology results indicated that ammonium-oxidizing bacteria (AOB) were enriched from wetland plant roots while analysis of contaminant and oxygen concentrations showed that those microorganisms can degrade TCE by aerobic cometabolism. Cometabolism of TCE, at 29 and 46 μg L(-1), was sustainable over the course of 9 weeks, with 20-30 mg L(-1) ammonium-N. However, at 69 μg L(-1) of TCE, ammonium oxidation and TCE cometabolism were completely deactivated in two weeks. This indicated that between 46 and 69 μg L(-1) TCE with 30 mg L(-1) ammonium-N there is a threshold [TCE] below which sustainable cometabolism can be maintained with ammonium as the primary substrate. However, cometabolism-induced microbial deactivation of ammonium oxidation and TCE degradation at 69 μg L(-1) TCE did not result in a lower abundance of the amoA gene in the microcosms, suggesting that the capacity to recover from TCE inhibition was still intact, given time and removal of stress. Our study indicates that microorganisms associated with wetland plant roots can assist in the natural attenuation of TCE in contaminated aquatic environments, such as urban or treatment wetlands, and wetlands impacted by industrial solvents.

  11. Use of aerobic granules for treating synthetic high-strength ammonium wastewaters.

    PubMed

    Yu, Xiaonan; Wan, Chunli; Lei, Zhongfang; Liu, Xiang; Zhang, Yi; Tay, Joo Hwa; Lee, Duu-Jong

    2014-08-01

    In this work, two identical sequencing batch reactors (SBRs) with mature aerobic granules were utilized to treat synthetic high-strength ammonium wastewaters with chemical oxygen demand (COD)/total nitrogen (TN) ratios of 3.9-6.9. The contributions of various mechanisms to the removal of ammonium were determined. Ammonium levels of 600-2000 mg-N l-1 had little adverse effect on the COD removal rate (91.6%-95.3%) with an influent COD of 4490-9860 mg l-1. The TN removal rate was slightly reduced from 71.3% to 59.6% as the influent ammonium concentration was increased from 600 to 2000 mg-N l-1. Experimental results indicated that aerobic granules removed 94.5% of COD and 59.6% of TN in the treatment of synthetic high-strength wastewater (9860 mg-COD l-1 and 2000 mg NH+4-Nl-1) during a 12 h cycle. Granular adsorption, air stripping and conversion by nitrification/denitrification were responsible for removing 9%, 15% and 76%, respectively, of the total removed NHf -N. Dissolved oxygen (DO) was a useful process indicator of the biological reactions in the treatment of high-level ammonium wastewaters.

  12. Ammonium nitrate: a promising rocket propellant oxidizer

    PubMed

    Oommen; Jain

    1999-06-30

    Ammonium nitrate (AN) is extensively used in the area of fertilizers and explosives. It is present as the major component in most industrial explosives. Its use as an oxidizer in the area of propellants, however, is not as extensive as in explosive compositions or gas generators. With the growing demand for environmental friendly chlorine free propellants, many attempts have been made of late to investigate oxidizers producing innocuous combustion products. AN, unlike the widely used ammonium perchlorate, produces completely ecofriendly smokeless products. Besides, it is one of the cheapest and easily available compounds. However, its use in large rocket motors is restricted due to some of its adverse characteristics like hygroscopicity, near room temperature phase transformation involving a volume change, and low burning rate (BR) and energetics. The review is an attempt to consolidate the information available on the various issues pertaining to its use as a solid propellant oxidizer. Detailed discussions on the aspects relating to phase modifications, decomposition chemistry, and BR and energetics of AN-based propellants, are presented. To make the review more comprehensive brief descriptions of the history, manufacture, safety, physical and chemical properties and various other applications of the salt are also included. Copyright 1999 Elsevier Science B.V.

  13. Oxidation of ammonium sulfite in aqueous solutions using ozone technology

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  14. Metal enzymes in "impossible" microorganisms catalyzing the anaerobic oxidation of ammonium and methane.

    PubMed

    Reimann, Joachim; Jetten, Mike S M; Keltjens, Jan T

    2015-01-01

    Ammonium and methane are inert molecules and dedicated enzymes are required to break up the N-H and C-H bonds. Until recently, only aerobic microorganisms were known to grow by the oxidation of ammonium or methane. Apart from respiration, oxygen was specifically utilized to activate the inert substrates. The presumed obligatory need for oxygen may have resisted the search for microorganisms that are capable of the anaerobic oxidation of ammonium and of methane. However extremely slowly growing, these "impossible" organisms exist and they found other means to tackle ammonium and methane. Anaerobic ammonium-oxidizing (anammox) bacteria use the oxidative power of nitric oxide (NO) by forging this molecule to ammonium, thereby making hydrazine (N2H4). Nitrite-dependent anaerobic methane oxidizers (N-DAMO) again take advantage of NO, but now apparently disproportionating the compound into dinitrogen and dioxygen gas. This intracellularly produced dioxygen enables N-DAMO bacteria to adopt an aerobic mechanism for methane oxidation.Although our understanding is only emerging how hydrazine synthase and the NO dismutase act, it seems clear that reactions fully rely on metal-based catalyses known from other enzymes. Metal-dependent conversions not only hold for these key enzymes, but for most other reactions in the central catabolic pathways, again supported by well-studied enzymes from model organisms, but adapted to own specific needs. Remarkably, those accessory catabolic enzymes are not unique for anammox bacteria and N-DAMO. Close homologs are found in protein databases where those homologs derive from (partly) known, but in most cases unknown species that together comprise an only poorly comprehended microbial world. PMID:25707470

  15. Metal enzymes in "impossible" microorganisms catalyzing the anaerobic oxidation of ammonium and methane.

    PubMed

    Reimann, Joachim; Jetten, Mike S M; Keltjens, Jan T

    2015-01-01

    Ammonium and methane are inert molecules and dedicated enzymes are required to break up the N-H and C-H bonds. Until recently, only aerobic microorganisms were known to grow by the oxidation of ammonium or methane. Apart from respiration, oxygen was specifically utilized to activate the inert substrates. The presumed obligatory need for oxygen may have resisted the search for microorganisms that are capable of the anaerobic oxidation of ammonium and of methane. However extremely slowly growing, these "impossible" organisms exist and they found other means to tackle ammonium and methane. Anaerobic ammonium-oxidizing (anammox) bacteria use the oxidative power of nitric oxide (NO) by forging this molecule to ammonium, thereby making hydrazine (N2H4). Nitrite-dependent anaerobic methane oxidizers (N-DAMO) again take advantage of NO, but now apparently disproportionating the compound into dinitrogen and dioxygen gas. This intracellularly produced dioxygen enables N-DAMO bacteria to adopt an aerobic mechanism for methane oxidation.Although our understanding is only emerging how hydrazine synthase and the NO dismutase act, it seems clear that reactions fully rely on metal-based catalyses known from other enzymes. Metal-dependent conversions not only hold for these key enzymes, but for most other reactions in the central catabolic pathways, again supported by well-studied enzymes from model organisms, but adapted to own specific needs. Remarkably, those accessory catabolic enzymes are not unique for anammox bacteria and N-DAMO. Close homologs are found in protein databases where those homologs derive from (partly) known, but in most cases unknown species that together comprise an only poorly comprehended microbial world.

  16. [Achievement of Sulfate-Reducing Anaerobic Ammonium Oxidation Reactor Started with Nitrate-Reducting Anaerobic Ammonium Oxidation].

    PubMed

    Liu, Zheng-chuan; Yuan, Lin-jiang; Zhou, Guo-biao; Li, Jing

    2015-09-01

    The transformation of nitrite-reducing anaerobic ammonium oxidation to sulfate-reducing anaerobic ammonium oxidation in an UASB was performed and the changes in microbial community were studied. The result showed that the sulfate reducing anaerobic ammonium oxidation process was successfully accomplished after 177 days' operation. The removal rate of ammonium nitrogen and sulfate were up to 58. 9% and 15. 7%, the removing load of ammonium nitrogen and sulfate were 74. 3 mg.(L.d)-1 and 77. 5 mg.(L.d)-1 while concentration of ammonium nitrogen and sulfate of influent were 130 mg.(L.d)-1 and 500 mg.(L.d)-1, respectively. The lost nitrogen and sulphur was around 2 in molar ratio. The pH value of the effluent was lower than that of the influent. Instead of Candidatus brocadia in nitrite reducing anaerobic ammonium oxidation granular sludge, Bacillus benzoevorans became the dominant species in sulfate reducing anaerobic ammonium oxidation sludge. The dominant bacterium in the two kinds of anaerobic ammonium oxidation process is different. Our results imply that the two anaerobic ammonium oxidation processes are carried out by different kind of bacterium.

  17. Ammonium removal by Agrobacterium sp. LAD9 capable of heterotrophic nitrification-aerobic denitrification.

    PubMed

    Chen, Qian; Ni, Jinren

    2012-05-01

    Characteristics of ammonium removal by a newly isolated heterotrophic nitrification-aerobic denitrification bacterium Agrobacterium sp. LAD9 were systematically investigated. Succinate and acetate were found to be the most favorable carbon sources for LAD9. Response surface methodology (RSM) analysis demonstrated that maximum removal of ammonium occurred under the conditions with an initial pH of 8.46, C/N ratio of 8.28, temperature of 27.9°C and shaking speed of 150rpm, where temperature and shaking speed produced the largest effect. Further nitrogen balance analysis revealed that 50.1% of nitrogen was removed as gas products and 40.8% was converted to the biomass. Moreover, the occurrence of aerobic denitrification was evidenced by the utilization of nitrite and nitrate as nitrogen sources, and the successful amplifications of membrane bound nitrate reductase and cytochrome cd(1) nitrite reductase genes from strain LAD9. Thus, the nitrogen removal in strain LAD9 was speculated to comply with the mechanism of heterotrophic nitrification coupled with aerobic denitrification (NH(4)(+)-NH(2)OH-NO(2)(-)-N(2)O-N(2)), in which also accompanied with the mutual transformation of nitrite and nitrate. The findings can help in applying appropriate controls over operational parameters in systems involving the use of this kind of strain.

  18. Hydrothermal oxidation of organic wastes using reclaimed ammonium nitrate

    SciTech Connect

    Proesmans, P.I.; Luan, L.; Buelow, S.J.

    1996-04-01

    Ammonium nitrate is being studied as an alternative for ammonium perchlorate as an oxidizing agent in Department of Defense 1.1 and 1.3 rocket propellants. Use of ammonium nitrate would eliminate the HCl produced by ammonium perchlorate upon thermal decomposition. To stabilize the ammonium nitrate, which suffers from phase instability, potassium dinitramide (KDN) is added. This increased use of ammonium nitrate will ultimately create a need for environmentally responsible processes to reuse ammonium nitrate extracted from demilitarized rocket motors. Ammonium Nitrate was investigated as an oxidizing agent for methanol, acetic acid and phenol. High removal of organic, ammonia and nitrate was achieved at stoichiometric concentrations. The oxidation of ammonia by nitrate was much faster than the oxidation of either methanol or acetic acid. Phenol, however, was in strong competition with ammonia for the oxidizer (nitrate). Nitrogen products included N{sub 2}, N{sub 2}O, NO{sub 2{sup {minus}}} as well as toxic NO and trace amounts of NO{sub 2}. Carbon products were CO{sub 2}, HCO{sub 3{sup {minus}}}, CO{sub 3}{sup 2{minus}}, and CO.

  19. The aerobic oxidation of alcohols with a ruthenium porphyrin catalyst in organic and fluorinated solvents.

    PubMed

    Korotchenko, Vasily N; Severin, Kay; Gagné, Michel R

    2008-06-01

    Carbonylruthenium tetrakis(pentafluorophenyl)porphyrin Ru(TPFPP)(CO) was utilized for the aerobic oxidation of alcohols. The in situ activation of the catalyst with mCPBA provided a species capable of catalyzing the oxidation of alcohols with molecular oxygen. The choice of solvent and additive was crucial to obtaining high activity and selectivity. Secondary aromatic alcohols were oxidized in the presence of the ruthenium porphyrin and tetrabutyl ammonium hydroxide in the solvent bromotrichloromethane, enabling high yields to be achieved (up to 99%). Alternatively, alcohols could be oxidized in perfluoro(methyldecalin) with the ruthenium porphyrin at higher temperatures (140 degrees C) and elevated oxygen pressures (50 psi).

  20. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    PubMed Central

    2015-01-01

    We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed. PMID:25436035

  1. A novel heterotrophic nitrifying and aerobic denitrifying bacterium, Zobellella taiwanensis DN-7, can remove high-strength ammonium.

    PubMed

    Lei, Yu; Wang, Yangqing; Liu, Hongjie; Xi, Chuanwu; Song, Liyan

    2016-05-01

    A novel heterotrophic bacterium capable of heterotrophic nitrification and aerobic denitrification was isolated from ammonium contaminated landfill leachate and physiochemical and phylogenetically identified as Zobellella taiwanensis DN-7. DN-7 converted nitrate, nitrate, and ammonium to N2 as the primary end product. Single factor experiments suggested that the optimal conditions for ammonium removal were trisodium citrate as carbon source, C/N ratio 8, pH 8.0-10.0, salinity less than 3 %, temperature 30 °C, and rotation speed more than 150 rpm. Specifically, DN-7 could remove 1000.0 and 2000.0 mg/L NH4 (+)-N completely within 96 and 216 h, with maximum removal rates of 19.6 and 17.3 mg L(-1) h(-1), respectively. These results demonstrated that DN-7 is a promising candidate for application of high-strength ammonium wastewater treatments.

  2. Liquid-phase catalytic oxidation of CO by ammonium persulfate

    SciTech Connect

    Golodov, V.A.; Abilov, M.T.; Sokol'skii, D.V.

    1984-01-01

    The catalytic oxidation of carbon monoxide in aqueous solutions is investigated. The abilities of ammonium persulfate, palladium hydroxide, and silver oxide to force the oxidation are discussed. The rates for these reactions are displayed graphically. The reaction rates as a function of the concentrations of the above-mentioned reactants are determined. An excess of persulfate is found to oxidize Pd(II) to Pd(IV), and this produces a reduction in the rate of CO oxidation. The oxidation of CO is preceeded in the reaction by the interaction of the persulfate with the metal catalyst.

  3. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    SciTech Connect

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; Chen, Edward H.; Nordlund, Dennis; Diaz, Rosa E.; Gaaton, Ophir; Englund, Dirk; Owen, Jonathan S.

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.

  4. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DOE PAGES

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; Chen, Edward H.; Nordlund, Dennis; Diaz, Rosa E.; Gaaton, Ophir; Englund, Dirk; Owen, Jonathan S.

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed.more » Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.« less

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

    PubMed

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

    2014-08-29

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

  6. Prevalence of anaerobic ammonium-oxidizing bacteria in contaminated groundwater.

    PubMed

    Moore, Tara A; Xing, Yangping; Lazenby, Brent; Lynch, Michael D J; Schiff, Sherry; Robertson, William D; Timlin, Robert; Lanza, Sadia; Ryan, M Cathryn; Aravena, Ramon; Fortin, Danielle; Clark, Ian D; Neufeld, Josh D

    2011-09-01

    Anaerobic ammonium-oxidizing (anammox) bacteria perform an important step in the global nitrogen cycle: anaerobic oxidation of ammonium and reduction of nitrite to form dinitrogen gas (N(2)). Anammox organisms appear to be widely distributed in natural and artificial environments. However, their roles in groundwater ammonium attenuation remain unclear and only limited biomarker-based data confirmed their presence prior to this study. We used complementary molecular and isotope-based methods to assess anammox diversity and activity occurring at three ammonium-contaminated groundwater sites: quantitative PCR, denaturing gradient gel electrophoresis, sequencing of 16S rRNA genes, and (15)N-tracer incubations. Here we show that anammox performing organisms were abundant bacterial community members. Although all sites were dominated by Candidatus Brocadia-like sequences, the community at one site was particularly diverse, possessing four of five known genera of anammox bacteria. Isotope data showed that anammox produced up to 18 and 36% of N(2) at these sites. By combining molecular and isotopic results we have demonstrated the diversity, abundance, and activity of these autotrophic bacteria. Our results provide strong evidence for their important biogeochemical role in attenuating groundwater ammonium contamination.

  7. Relevance of ammonium oxidation within biological soil crust communities

    USGS Publications Warehouse

    Johnson, S.L.; Budinoff, C.R.; Belnap, J.; Garcia-Pichel, F.

    2005-01-01

    Thin, vertically structured topsoil communities that become ecologically important in arid regions (biological soil crusts or BSCs) are responsible for much of the nitrogen inputs into pristine arid lands. We studied N2 fixation and ammonium oxidation (AO) at subcentimetre resolution within BSCs from the Colorado Plateau. Pools of dissolved porewater nitrate/ nitrite, ammonium and organic nitrogen in wetted BSCs were high in comparison with those typical of aridosoils. They remained stable during incubations, indicating that input and output processes were of similar magnitude. Areal N2 fixation rates (6.5-48 ??mol C2H2 m-2 h -1) were high, the vertical distribution of N2 fixation peaking close to the surface if populations of heterocystous cyanobacteria were present, but in the subsurface if they were absent. Areal AO rates (19-46 ??mol N m-2 h-1) were commensurate with N2 fixation inputs. When considering oxygen availability, AO activity invariably peaked 2-3 mm deep and was limited by oxygen (not ammonium) supply. Most probable number (MPN)-enumerated ammonia-oxidizing bacteria (6.7-7.9 ?? 103 cells g-1 on average) clearly peaked at 2-3 mm depth. Thus, AO (hence nitrification) is a spatially restricted but important process in the nitrogen cycling of BSC, turning much of the biologically fixed nitrogen into oxidized forms, the fate of which remains to be determined.

  8. A novel heterotrophic nitrifying and aerobic denitrifying bacterium, Zobellella taiwanensis DN-7, can remove high-strength ammonium.

    PubMed

    Lei, Yu; Wang, Yangqing; Liu, Hongjie; Xi, Chuanwu; Song, Liyan

    2016-05-01

    A novel heterotrophic bacterium capable of heterotrophic nitrification and aerobic denitrification was isolated from ammonium contaminated landfill leachate and physiochemical and phylogenetically identified as Zobellella taiwanensis DN-7. DN-7 converted nitrate, nitrate, and ammonium to N2 as the primary end product. Single factor experiments suggested that the optimal conditions for ammonium removal were trisodium citrate as carbon source, C/N ratio 8, pH 8.0-10.0, salinity less than 3 %, temperature 30 °C, and rotation speed more than 150 rpm. Specifically, DN-7 could remove 1000.0 and 2000.0 mg/L NH4 (+)-N completely within 96 and 216 h, with maximum removal rates of 19.6 and 17.3 mg L(-1) h(-1), respectively. These results demonstrated that DN-7 is a promising candidate for application of high-strength ammonium wastewater treatments. PMID:26762390

  9. Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

    NASA Technical Reports Server (NTRS)

    Caldwell, D.

    1985-01-01

    Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

  10. Concurrence of Anaerobic Ammonium Oxidation and Organotrophic Denitrification in Presence of p-Cresol.

    PubMed

    González-Blanco, G; Cervantes, F J; Beristain-Cardoso, R; Gómez, J

    2015-08-01

    This study was carried out to evaluate the capacity of anaerobic granular sludge for oxidizing ammonium and p-cresol with nitrate as terminal electron acceptor. Kinetics for the anaerobic oxidation of ammonium and p-cresol is described in this paper. The phenolic compound was very efficiently consumed, achieving 65 % of mineralization. Ammonium and nitrate were also consumed at 83 and 92 %, respectively, being the main product N2. Anaerobic ammonium oxidation was promoted owing to accumulation of nitrite, and it allowed the synergy of anaerobic ammonium oxidation and organotrophic denitrification for the simultaneous removal of ammonium, nitrate, and p-cresol. A carbonaceous intermediate partially identified was transiently accumulated, and it transitorily truncated the respiratory process of denitrification. These experimental results might be considered for defining strategies in order to remove nitrate, ammonium, and phenolic compounds from wastewaters. PMID:26062920

  11. Ammonium nitrate as an oxidizer in solid composite propellants

    NASA Astrophysics Data System (ADS)

    Manelis, G. B.; Lempert, D. B.

    2009-09-01

    Despite the fact that ammonium nitrate (AN) has the highest hydrogen content and fairly high oxygen balance (compared to other oxidizers), its extremely low formation enthalpy and relatively low density makes it one of the worst power oxidizers in solid composite propellants (SCP). Nevertheless, AN has certain advantages - the combustion of the compositions containing AN is virtually safe, its combustion products are ecologically clean, it is very accessible and cheap, and also very thermostable (far more stable than ammonium dinitramide (ADN)). Besides, its low density stops being a disadvantage if the propellant has to be used in deep space and therefore, must be carried there with other rocket carriers. The low cost of AN may also become a serious advantage in the AN application even in lower stages of multistage space launchers as well as in one-stage space launchers with low mass fraction of the propellant. The main specific features relevant to the creation of AN-based SCPs with the optimal energetic characteristics are discussed. The use of metals and their hydrides and proper fuel-binders as well as the recent successes in phase stabilization of AN are described.

  12. Coastal water column ammonium and nitrite oxidation are decoupled in summer

    NASA Astrophysics Data System (ADS)

    Heiss, Elise M.; Fulweiler, Robinson W.

    2016-09-01

    Water column nitrification is a key process in the nitrogen cycle as it links reduced and oxidized forms of nitrogen and also provides the substrate (nitrate) needed for reactive nitrogen removal by denitrification. We measured potential water column ammonium and nitrite oxidation rates at four sites along an estuary to continental shelf gradient over two summers. In most cases, nitrite oxidation rates outpaced ammonium oxidation rates. Overall, ammonium and nitrite oxidation rates were higher outside of the estuary, and this trend was primarily driven by higher oxidation rates in deeper waters. Additionally, both ammonium and nitrite oxidation rates were impacted by different in situ variables. Ammonium oxidation rates throughout the water column as a whole were most positively correlated to depth and salinity and negatively correlated to dissolved oxygen and light. In contrast, nitrite oxidation rates throughout the water column were negatively correlated with light and pH. Multivariate regression analysis revealed that while both surface (<20 m) and deep (>20 m) ammonium oxidation rates were most strongly predicted by depth and light, surface rates were also regulated by salinity and deep rates by temperature. Surface (<20 m) nitrite oxidation rates were best explained by [H+] (i.e. pH) alone, while salinity, [H+], temperature, and depth all played a role in predicting deep (>20 m) nitrite oxidation rates. These results support the growing body of evidence that ammonium oxidation and nitrite oxidation are not always coupled, should be measured separately, and are influenced by different environmental conditions.

  13. Environmental Factors Affecting Ammonium Oxidation Under Iron Reducing Conditions

    NASA Astrophysics Data System (ADS)

    Jaffe, P. R.; Huang, S.; Ruiz-Urigüen, M.

    2014-12-01

    Ammonium (NH4+) oxidation coupled to iron (Fe) reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) has been reported by several investigators and referred to as Feammox. Feammox is a biological reaction, where Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+ is the electron donor, which is oxidized to NO2-. Through a 180-day anaerobic incubation experiment, and using PCR-DGGE, 454-pyosequecing and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, a previously unreported species in the Acidimicrobiaceae family, might be either responsible or plays a key role in the Feammox process, We have enriched these Feammox bacteria (65.8% in terms of cell numbers) in a membrane reactor, and isolated the pure Acidimicrobiaceae bacterium A6 strain in an autotrophic medium. In samples collected and then incubated from a series of local wetland-, upland-, as well as storm-water detention pond-sediments, Feammox activity was only detected in acidic soil environments that contain Fe oxides. Using primers we developed for this purpose, Acidimicrobiaceae bacterium A6 was detected in all incubations where Feammox was observed. Anaerobic incubations of Feammox enrichment cultures adjusted to different pH, revealed that the optimal pH for Feammox is 4 ~ 5, and the reaction does not proceed when pH > 7. Feammox was still proceeding at pH as low as 2. In Feammox culture amended with different Fe(III) sources, Feammox reaction proceeded only when Fe oxides (ferrihydrite or goethite ) were supplied, whereas samples incubated with ferric chloride or ferric citrate showed no measurable NH4+ oxidation. Furthermore, we have also determined from incubation experiments conducted with a temperature gradient (10 ~ 35℃), that the Feammox process was active when the temperature is above 15℃, and the optimal temperature is 20℃. Incubations of enrichment culture with 79% Feammox bacteria appeared to remove circa 8% more NH4+ at 20ºC than at

  14. Aerobic Denitrifying Bacteria That Produce Low Levels of Nitrous Oxide

    PubMed Central

    Takaya, Naoki; Catalan-Sakairi, Maria Antonina B.; Sakaguchi, Yasushi; Kato, Isao; Zhou, Zhemin; Shoun, Hirofumi

    2003-01-01

    Most denitrifiers produce nitrous oxide (N2O) instead of dinitrogen (N2) under aerobic conditions. We isolated and characterized novel aerobic denitrifiers that produce low levels of N2O under aerobic conditions. We monitored the denitrification activities of two of the isolates, strains TR2 and K50, in batch and continuous cultures. Both strains reduced nitrate (NO3−) to N2 at rates of 0.9 and 0.03 μmol min−1 unit of optical density at 540 nm−1 at dissolved oxygen (O2) (DO) concentrations of 39 and 38 μmol liter−1, respectively. At the same DO level, the typical denitrifier Pseudomonas stutzeri and the previously described aerobic denitrifier Paracoccus denitrificans did not produce N2 but evolved more than 10-fold more N2O than strains TR2 and K50 evolved. The isolates denitrified NO3− with concomitant consumption of O2. These results indicated that strains TR2 and K50 are aerobic denitrifiers. These two isolates were taxonomically placed in the β subclass of the class Proteobacteria and were identified as P. stutzeri TR2 and Pseudomonas sp. strain K50. These strains should be useful for future investigations of the mechanisms of denitrifying bacteria that regulate N2O emission, the single-stage process for nitrogen removal, and microbial N2O emission into the ecosystem. PMID:12788710

  15. Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K. C.; Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Anthony, P.; Thalasso, F.

    2013-12-01

    Karla Martinez-Cruz* **, Armando Sepulveda-Jauregui*, Katey M. Walter Anthony*, Peter Anthony*, and Frederic Thalasso**. * Water and Environmental Research Center, Institute of Northern Engineering, University of Alaska Fairbanks, Fairbanks, Alaska. ** Biotechnology and Bioengineering Department, Cinvestav, Mexico city, D. F., Mexico. Methane (CH4) is the third most important greenhouse gas in the atmosphere, after carbon dioxide and water vapor. Boreal lakes play an important role in the current global warming by contributing as much as 6% of global atmospheric CH4 sources annually. On the other hand, aerobic methane oxidation (methanotrophy) in lake water is a fundamental process in global methane cycling that reduces the amount of CH4 emissions to the atmosphere. Several environmental factors affect aerobic methane oxidation in the water column both directly and indirectly, including concentration of CH4 and O2, temperature and carbon budgets of lakes. We analyzed the potential of aerobic methane oxidation (PMO) rates in incubations of water collected from 30 Alaskan lakes along a north-south transect during winter and summer 2011. Our findings showed an effect of CH4 and O2 concentrations, temperature and yedoma thawing permafrost on PMO activity in the lake water. The highest PMO rates were observed in summer by lakes situated on thawing yedoma permafrost, most of them located in the interior of Alaska. We also estimated that 60-80% of all CH4 produced in Alaskan lakes could be taken up by methanotrophs in the lake water column, showing the significant influence of aerobic methane oxidation of boreal lakes to the global CH4 budget.

  16. Molecular phylogeny of heterotrophic nitrifiers and aerobic denitrifiers and their potential role in ammonium removal.

    PubMed

    Srivastava, Meenakshi; Kaushik, Manish Singh; Singh, Anumeha; Singh, Deepti; Mishra, Arun Kumar

    2016-08-01

    To investigate the physiology and taxonomic composition of the key players of nitrification and denitrification processes in paddy fields, culture dependent and independent studies have been carried out. A total of 28 bacterial strains have been screened in which six were capable of reducing nitrate and nitrite as well as having significant ammonium removal potential. 16S rRNA-PCR-DGGE-based molecular typing of enriched batch culture was done with time duration to explore and identify dominant and stable soil denitrifiers. Notably, three isolates namely PDN3, PDN19, PDN14 were found to be efficiently involved in the removal of 70.32, 71.46, and 81.50% of NH4 (+) and showed closest similarity (>98%) with Bacillus cereus, Bacillus subtilis, and Pseudomonas aeruginosa strains, respectively. The bacterial strain PDN14 showed maximum growth with highest ammonium removal rate (2.78 gN/(m(3) ·h) has also been characterized based on nosZ gene which showed similarity to uncultured γ- Proteobacteria, P. aeruginosa sp. B3. Median joining (MJ) network and rRNA secondary structure have been analyzed for their detailed taxonomic diversity and derived haplotype-based co-occurrence. Results demonstrated that such strains can serve as good candidate for in situ nitrogen transformation in paddy soils and improvingly characterized by physiological and detailed phylogenetic approaches. PMID:27037833

  17. Aerobic Oxidation of an Osmium(III) N-Hydroxyguanidine Complex To Give Nitric Oxide.

    PubMed

    Xiang, Jing; Wang, Qian; Yiu, Shek-Man; Man, Wai-Lun; Kwong, Hoi-Ki; Lau, Tai-Chu

    2016-05-16

    The aerobic oxidation of the N-hydroxyguanidinum moiety of N-hydroxyarginine to NO is a key step in the biosynthesis of NO by the enzyme nitric oxide synthase (NOS). So far, there is no chemical system that can efficiently carry out similar aerobic oxidation to give NO. We report here the synthesis and X-ray crystal structure of an osmium(III) N-hydroxyguanidine complex, mer-[Os(III){NH═C(NH2)(NHOH)}(L)(CN)3](-) (OsGOH, HL = 2-(2-hydroxyphenyl)benzoxazole), which to the best of our knowledge is the first example of a transition metal N-hydroxyguanidine complex. More significantly, this complex readily undergoes aerobic oxidation at ambient conditions to generate NO. The oxidation is pH-dependent; at pH 6.8, fac-[Os(NO)(L)(CN)3](-) is formed in which the NO produced is bound to the osmium center. On the other hand, at pH 12, aerobic oxidation of OsGOH results in the formation of the ureato complex [Os(III)(NHCONH2)(L)(CN)3](2-) and free NO. Mechanisms for this aerobic oxidation at different pH values are proposed. PMID:27135258

  18. [Distribution of Aerobic Ammonia-Oxidizing Microorganisms in Sediments from Adjacent Waters of Rushan Bay].

    PubMed

    He, Hui; Zhen, Yu; Mi, Tie-zhu; Zhang, Yu; Fu, Lu-lu; Yu, Zhi-gang

    2015-11-01

    Nitrogen cycle is a key process in material circulation of marine ecosystem, which plays an important role in maintaining ecological balance. The ammonia oxidation process promoted by aerobic ammonia-oxidizing microorganism (AOM) is a rate-limiting step of nitrification. Real-time quantitative polymerase chain reaction (qPCR ), along with the determination of potential nitrification rates (PNR) was carried out in this study to understand the distribution of AOM in sediments of adjacent waters of Rushan Bay in August, 2014. The results indicated that the abundance of total ammonia-oxidizing bacteria (AOB) was always greater than that of total ammonia-oxidizing archaea (AOA) in the three sampling stations; the ratio of active AOB to total AOB was less than 1%, while no active AOA was detected in this study; the PNR significantly decreased after adding ampicillin which could inhibit the activity of AOB (P < 0.05). It was speculated that AOB might play a more important role in the ammonia oxidation in sediments of adjacent waters of Rushan Bay in August, 2014. Dissolved oxygen concentrations, temperature and ammonium concentrations played a significant role in distribution of AOM in sediments of adjacent waters of Rushan Bay.

  19. Evidence for the cooccurrence of nitrite-dependent anaerobic ammonium and methane oxidation processes in a flooded paddy field.

    PubMed

    Shen, Li-Dong; Liu, Shuai; Huang, Qian; Lian, Xu; He, Zhan-Fei; Geng, Sha; Jin, Ren-Cun; He, Yun-Feng; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping; Hu, Bao-Lan

    2014-12-01

    Anaerobic ammonium oxidation (anammox) and nitrite-dependent anaerobic methane oxidation (n-damo) are two of the most recent discoveries in the microbial nitrogen cycle. In the present study, we provide direct evidence for the cooccurrence of the anammox and n-damo processes in a flooded paddy field in southeastern China. Stable isotope experiments showed that the potential anammox rates ranged from 5.6 to 22.7 nmol N2 g(-1) (dry weight) day(-1) and the potential n-damo rates varied from 0.2 to 2.1 nmol CO2 g(-1) (dry weight) day(-1) in different layers of soil cores. Quantitative PCR showed that the abundance of anammox bacteria ranged from 1.0 × 10(5) to 2.0 × 10(6) copies g(-1) (dry weight) in different layers of soil cores and the abundance of n-damo bacteria varied from 3.8 × 10(5) to 6.1 × 10(6) copies g(-1) (dry weight). Phylogenetic analyses of the recovered 16S rRNA gene sequences showed that anammox bacteria affiliated with "Candidatus Brocadia" and "Candidatus Kuenenia" and n-damo bacteria related to "Candidatus Methylomirabilis oxyfera" were present in the soil cores. It is estimated that a total loss of 50.7 g N m(-2) per year could be linked to the anammox process, which is at intermediate levels for the nitrogen flux ranges of aerobic ammonium oxidation and denitrification reported in wetland soils. In addition, it is estimated that a total of 0.14 g CH4 m(-2) per year could be oxidized via the n-damo process, while this rate is at the lower end of the aerobic methane oxidation rates reported in wetland soils.

  20. Anaerobic Ammonium-Oxidizing Bacteria: Unique Microorganisms with Exceptional Properties

    PubMed Central

    Jetten, Mike S. M.

    2012-01-01

    Summary: Anaerobic ammonium-oxidizing (anammox) bacteria defy many microbiological concepts and share numerous properties with both eukaryotes and archaea. Among their most intriguing characteristics are their compartmentalized cell plan and archaeon-like cell wall. Here we review our current knowledge about anammox cell biology. The anammox cell is divided into three separate compartments by bilayer membranes. The anammox cell consists of (from outside to inside) the cell wall, paryphoplasm, riboplasm, and anammoxosome. Not much is known about the composition or function of both the anammox cell wall and the paryphoplasm compartment. The cell wall is proposed to be proteinaceous and to lack both peptidoglycan and an outer membrane typical of Gram-negative bacteria. The function of the paryphoplasm is unknown, but it contains the cell division ring. The riboplasm resembles the standard cytoplasmic compartment of other bacteria; it contains ribosomes and the nucleoid. The anammoxosome occupies most of the cell volume and is a so-called “prokaryotic organelle” analogous to the eukaryotic mitochondrion. This is the site where the anammox reaction takes place, coupled over the curved anammoxosome membrane, possibly giving rise to a proton motive force and subsequent ATP synthesis. With these unique properties, anammox bacteria are food for thought concerning the early evolution of the domains Bacteria, Archaea, and Eukarya. PMID:22933561

  1. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-02-13

    Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols.

  2. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-02-13

    Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450

  3. Nitrogen loss by anaerobic oxidation of ammonium in rice rhizosphere

    PubMed Central

    Nie, San'an; Li, Hu; Yang, Xiaoru; Zhang, Zhaoji; Weng, Bosen; Huang, Fuyi; Zhu, Gui-Bing; Zhu, Yong-Guan

    2015-01-01

    Anaerobic oxidation of ammonium (anammox) is recognized as an important process for nitrogen (N) cycling, yet its role in agricultural ecosystems, which are intensively fertilized, remains unclear. In this study, we investigated the presence, activity, functional gene abundance and role of anammox bacteria in rhizosphere and non-rhizosphere paddy soils using catalyzed reporter deposition–fluorescence in situ hybridization, isotope-tracing technique, quantitative PCR assay and 16S rRNA gene clone libraries. Results showed that rhizosphere anammox contributed to 31–41% N2 production with activities of 0.33–0.64 nmol N2 g−1 soil h−1, whereas the non-rhizosphere anammox bacteria contributed to only 2–3% N2 production with lower activities of 0.08–0.26 nmol N2 g−1 soil h−1. Higher anammox bacterial cells were observed (0.75–1.4 × 107 copies g−1 soil) in the rhizosphere, which were twofold higher compared with the non-rhizosphere soil (3.7–5.9 × 106 copies g−1 soil). Phylogenetic analysis of the anammox bacterial 16S rRNA genes indicated that two genera of ‘Candidatus Kuenenia' and ‘Candidatus Brocadia' and the family of Planctomycetaceae were identified. We suggest the rhizosphere provides a favorable niche for anammox bacteria, which are important to N cycling, but were previously largely overlooked. PMID:25689022

  4. Occurrence of Anaerobic Ammonium Oxidation in the Yangtze Estuary

    NASA Astrophysics Data System (ADS)

    Hou, L.

    2013-12-01

    Over the past several decades, a large quantity of reactive nitrogen has been transported into the Yangtze estuarine and coastal water, due to intense human activities in the Yangtze River Basin. At present, it annually receives a high load of anthropogenic inorganic nitrogen (about 1.1 × 1011 mol N) from increased agricultural activities, fish farming, and domestic and industrial wastewater discharge in the Yangtze River Basin, consequently leading to severe eutrophication and frequent occurrences of harmful algal blooms in the estuary and adjacent coastal areas. Hence, the microbial nitrogen transformations are of major concern in the Yangtze Estuary. Anaerobic ammonium oxidation (anammox) has been reported to play a significant role in the removal of reactive nitrogen in aquatic ecosystems. In this study, the occurrences of anammox bacteria and associated activity in the Yangtze Estuary were evidenced with molecular and isotope-tracing techniques. It is observed that the anammox bacteria at the study area mainly consisted of Candidatus Scalindua, Brocadia, Kuenenia. Salinity was found to be a key environmental factor controlling distribution and diversity of the anammox bacterial community at the estuarine ecosystem. Also, temperature and organic carbon had significant influences on anammox bacterial biodiversity. Q-PCR assays of anammox bacteria indicated that their abundance had a range of 2.63 ×106 - 9.48 ×107 copies g-1 dry sediment, with high spatiotemporal heterogeneity. The potential anammox activities measured in the present work varied between 0.94 - 6.61nmol N g-1 dry sediment h-1, which were related to temperature, nitrite and anammox bacterial abundance. On the basis of the 15N tracing experiments, the anammox process was estimated to contribute 6.6 - 12.9 % to the total nitrogen loss whereas the remainder was attributed to denitrification.

  5. Anaerobic ammonium oxidation (anammox) in Chesapeake Bay sediments.

    PubMed

    Rich, Jeremy J; Dale, Olivia R; Song, Bongkeun; Ward, Bess B

    2008-02-01

    Anaerobic ammonium oxidation (anammox) has recently been recognized as a pathway for the removal of fixed N from aquatic ecosystems. However, the quantitative significance of anammox in estuarine sediments is variable, and measurements have been limited to a few estuaries. We measured anammox and conventional denitrification activities in sediments along salinity gradients in the Chesapeake Bay and two of its sub-estuaries, the Choptank River and Patuxent River. Homogenized sediments were incubated with (14/15)N amendments of NH4+, NO3-, and NO2- to determine relative activities of anammox and denitrification. The percent of N2 production due to anammox (ra%) ranged from 0 to 22% in the Chesapeake system, with the highest ra% in the freshwater portion of the main stem of upper Chesapeake Bay, where water column NO3- concentrations are consistently high. Intermediate levels of relative anammox (10%) were detected at locations corresponding to tidal freshwater and mesohaline locations in the Choptank River, whereas anammox was not detected in the tidal freshwater location in the Patuxent River. Anammox activity was also not detected in the seaward end of Chesapeake Bay, where water column No3- concentrations are consistently low. The ra% did not correlate with NH4+ accumulation rate in anoxic sediment incubations, but ra% was related to water column NO3- concentrations and salinity. Anammox bacterial communities were also examined by amplifying DNA extracted from the upper Chesapeake Bay sediment with polymerase chain reaction (PCR) primers that are specific for 16S rRNA genes of anammox organisms. A total of 35 anammox-like sequences were detected, and phylogenetic analysis grouped the sequences in two distinct clusters belonging to the Candidatus "Scalindua" genus.

  6. Toxic effects of butyl elastomers on aerobic methane oxidation

    NASA Astrophysics Data System (ADS)

    Niemann, Helge; Steinle, Lea I.; Blees, Jan H.; Krause, Stefan; Bussmann, Ingeborg; Lehmann, Moritz F.; Treude, Tina

    2013-04-01

    Large quantities of the potent greenhouse gas methane are liberated into the water column of marine and lacustrine environments where it may be consumed by aerobic methane oxidising bacteria before reaching the atmosphere.The reliable quantification of aerobic methane oxidation (MOx) rates is consequently of paramount importance for estimating methane budgets and to understand the controls on water column methane cycling. A widely used set of methods for measuring MOx rates is based on the incubation of water samples during which the consumption of methane is monitored, for instance with radio-tracer assays. Typically, incubation vessels are sealed with butyl rubber stoppers because these elastomers are essentially impermeable for gases at the relevant time scales. We tested the effect of different stopper materials (unmodified- and halogenated butyl rubber) on MOx activity in environmental samples and in cultures of methane oxidising bacteria. MOx rates in samples sealed with unmodified butyl rubber were > 75% lower compared to parallel incubations with halogenated butyl rubber seals, suggesting inhibiting/toxic effects associated with the use of unmodified butyl elastomers. To further explore the cause of these effects, we analysed aqueous extracts of the different stoppers. Halogenated butyl rubber stoppers appeared to bleed off comparably little amounts of organics. In stark contrast, extracts of unmodified butyl rubber were contaminated with various organic compounds including potential bactericides such as benzyltoluenes, phenylalkanes and benzuothiazoles. We also found tetramethylthiourea, a scavenger of active oxygen species, which may inhibit the MOx pathway.

  7. Aerobic and anaerobic oxidation of hydrogen by acidophilic bacteria.

    PubMed

    Hedrich, Sabrina; Johnson, D Barrie

    2013-12-01

    While many prokaryotic species are known to use hydrogen as an electron donor to support their growth, this trait has only previously been reported for two acidophilic bacteria, Hydrogenobaculum acidophilum (in the presence of reduced sulfur) and Acidithiobacillus (At.) ferrooxidans. To test the hypothesis that hydrogen may be utilized more widely by acidophilic bacteria, 38 strains of acidophilic bacteria, including representatives of 20 designated and four proposed species, were screened for their abilities to grow via the dissimilatory oxidation of hydrogen. Growth was demonstrated in several species of acidophiles that also use other inorganic electron donors (ferrous iron and sulfur) but in none of the obligately heterotrophic species tested. Strains of At. ferrooxidans, At. ferridurans and At. caldus, grew chemolithotrophically on hydrogen, though those of At. thiooxidans and At. ferrivorans did not. Growth was also observed with Sulfobacillus acidophilus, Sb. benefaciens and Sb. thermosulfidooxidans, though not with other iron-oxidizing Firmicutes. Similarly, Acidimicrobium ferrooxidans grew on hydrogen, closely related acidophilic actinobacteria did not. Growth yields of At. ferrooxidans and At. ferridurans grown aerobically on hydrogen (c. 10(10)  cells mL(-1) ) were far greater than typically obtained using other electron donors. Several species also grew anaerobically by coupling hydrogen oxidation to the reduction of ferric iron.

  8. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    PubMed

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  9. Isolation of an aerobic vinyl chloride oxidizer from anaerobic groundwater.

    PubMed

    Fullerton, Heather; Rogers, Rebecca; Freedman, David L; Zinder, Stephen H

    2014-11-01

    Vinyl chloride (VC) is a known human carcinogen and common groundwater contaminant. Reductive dechlorination of VC to non-toxic ethene under anaerobic conditions has been demonstrated at numerous hazardous waste sites. However, VC disappearance without stoichiometric production of ethene has also been observed at some sites and in microcosms. In this study we identify an organism responsible for this observation in presumably anaerobic microcosms and conclude that oxygen was not detectable based on a lack of color change from added resazurin. This organism, a Mycobacterium sp. closely related to known VC oxidizing strains, was present in high numbers in 16S rRNA gene clone libraries from a groundwater microcosm. Although the oxidation/reduction indicator resazurin remained in the clear reduced state in these studies, these results suggest inadvertent oxygen contamination occurred. This study helps to elucidate the dynamic behavior of chlorinated ethenes in contaminated groundwater, through the isolation of a strictly aerobic organism that may be responsible for at least some disappearance of VC without the concomitant production of ethene in groundwater considered anaerobic.

  10. Thaumarchaeal ammonium oxidation and evidence for a nitrogen cycle in a subsurface radioactive thermal spring in the Austrian Central Alps.

    PubMed

    Gerbl, Friedrich W; Weidler, Gerhard W; Wanek, Wolfgang; Erhardt, Angelika; Stan-Lotter, Helga

    2014-01-01

    Previous studies had suggested the presence of ammonium oxidizing Thaumarchaeota as well as nitrite oxidizing Bacteria in the subsurface spring called Franz Josef Quelle (FJQ), a slightly radioactive thermal mineral spring with a temperature of 43.6-47°C near the alpine village of Bad Gastein, Austria. The microbiological consortium of the FJQ was investigated for its utilization of nitrogen compounds and the putative presence of a subsurface nitrogen cycle. Microcosm experiments made with samples from the spring water, containing planktonic microorganisms, or from biofilms, were used in this study. Three slightly different media, enriched with vitamins and trace elements, and two incubation temperatures (30 and 40°C, respectively) were employed. Under aerobic conditions, high rates of conversion of ammonium to nitrite, as well as nitrite to nitrate were measured. Under oxygen-limited conditions nitrate was converted to gaseous compounds. Stable isotope probing with (15)NH4Cl or ((15)NH4)2SO4as sole energy sources revealed incorporation of (15)N into community DNA. Genomic DNA as well as RNA were extracted from all microcosms. The following genes or fragments of genes were successfully amplified, cloned and sequenced by standard PCR from DNA extracts: Ammonia monooxygenase subunit A (amoA), nitrite oxidoreductase subunits A and B (nxrA and nxrB), nitrate reductase (narG), nitrite reductase (nirS), nitric oxide reductases (cnorB and qnorB), nitrous oxide reductase (nosZ). Reverse transcription of extracted total RNA and real-time PCR suggested the expression of each of those genes. Nitrogen fixation (as probed with nifH and nifD) was not detected. However, a geological origin of NH(+) 4 in the water of the FJQ cannot be excluded, considering the silicate, granite and gneiss containing environment. The data suggested the operation of a nitrogen cycle in the subsurface environment of the FJQ. PMID:24904540

  11. Thaumarchaeal ammonium oxidation and evidence for a nitrogen cycle in a subsurface radioactive thermal spring in the Austrian Central Alps

    PubMed Central

    Gerbl, Friedrich W.; Weidler, Gerhard W.; Wanek, Wolfgang; Erhardt, Angelika; Stan-Lotter, Helga

    2014-01-01

    Previous studies had suggested the presence of ammonium oxidizing Thaumarchaeota as well as nitrite oxidizing Bacteria in the subsurface spring called Franz Josef Quelle (FJQ), a slightly radioactive thermal mineral spring with a temperature of 43.6–47°C near the alpine village of Bad Gastein, Austria. The microbiological consortium of the FJQ was investigated for its utilization of nitrogen compounds and the putative presence of a subsurface nitrogen cycle. Microcosm experiments made with samples from the spring water, containing planktonic microorganisms, or from biofilms, were used in this study. Three slightly different media, enriched with vitamins and trace elements, and two incubation temperatures (30 and 40°C, respectively) were employed. Under aerobic conditions, high rates of conversion of ammonium to nitrite, as well as nitrite to nitrate were measured. Under oxygen-limited conditions nitrate was converted to gaseous compounds. Stable isotope probing with 15NH4Cl or (15NH4)2SO4as sole energy sources revealed incorporation of 15N into community DNA. Genomic DNA as well as RNA were extracted from all microcosms. The following genes or fragments of genes were successfully amplified, cloned and sequenced by standard PCR from DNA extracts: Ammonia monooxygenase subunit A (amoA), nitrite oxidoreductase subunits A and B (nxrA and nxrB), nitrate reductase (narG), nitrite reductase (nirS), nitric oxide reductases (cnorB and qnorB), nitrous oxide reductase (nosZ). Reverse transcription of extracted total RNA and real-time PCR suggested the expression of each of those genes. Nitrogen fixation (as probed with nifH and nifD) was not detected. However, a geological origin of NH+4 in the water of the FJQ cannot be excluded, considering the silicate, granite and gneiss containing environment. The data suggested the operation of a nitrogen cycle in the subsurface environment of the FJQ. PMID:24904540

  12. Thaumarchaeal ammonium oxidation and evidence for a nitrogen cycle in a subsurface radioactive thermal spring in the Austrian Central Alps.

    PubMed

    Gerbl, Friedrich W; Weidler, Gerhard W; Wanek, Wolfgang; Erhardt, Angelika; Stan-Lotter, Helga

    2014-01-01

    Previous studies had suggested the presence of ammonium oxidizing Thaumarchaeota as well as nitrite oxidizing Bacteria in the subsurface spring called Franz Josef Quelle (FJQ), a slightly radioactive thermal mineral spring with a temperature of 43.6-47°C near the alpine village of Bad Gastein, Austria. The microbiological consortium of the FJQ was investigated for its utilization of nitrogen compounds and the putative presence of a subsurface nitrogen cycle. Microcosm experiments made with samples from the spring water, containing planktonic microorganisms, or from biofilms, were used in this study. Three slightly different media, enriched with vitamins and trace elements, and two incubation temperatures (30 and 40°C, respectively) were employed. Under aerobic conditions, high rates of conversion of ammonium to nitrite, as well as nitrite to nitrate were measured. Under oxygen-limited conditions nitrate was converted to gaseous compounds. Stable isotope probing with (15)NH4Cl or ((15)NH4)2SO4as sole energy sources revealed incorporation of (15)N into community DNA. Genomic DNA as well as RNA were extracted from all microcosms. The following genes or fragments of genes were successfully amplified, cloned and sequenced by standard PCR from DNA extracts: Ammonia monooxygenase subunit A (amoA), nitrite oxidoreductase subunits A and B (nxrA and nxrB), nitrate reductase (narG), nitrite reductase (nirS), nitric oxide reductases (cnorB and qnorB), nitrous oxide reductase (nosZ). Reverse transcription of extracted total RNA and real-time PCR suggested the expression of each of those genes. Nitrogen fixation (as probed with nifH and nifD) was not detected. However, a geological origin of NH(+) 4 in the water of the FJQ cannot be excluded, considering the silicate, granite and gneiss containing environment. The data suggested the operation of a nitrogen cycle in the subsurface environment of the FJQ.

  13. Higher diversity of ammonia/ammonium-oxidizing prokaryotes in constructed freshwater wetland than natural coastal marine wetland.

    PubMed

    Wang, Yong-Feng; Gu, Ji-Dong

    2013-08-01

    Anaerobic ammonium-oxidizing (anammox) bacteria, aerobic ammonia-oxidizing archaea (AOA), and ammonia-oxidizing bacteria (AOB) are three groups of ammonium/ammonia-oxidizing prokaryotes (AOPs) that are involved in the nitrogen cycle. This research compared the AOP communities in a constructed freshwater wetland with a natural coastal marine wetland in the subtropical Hong Kong. Both vegetated/rhizosphere and nonvegetated sediments were investigated to identify the effects of different macrophytes on the AOP communities. The polymerase chain reaction (PCR)-amplified gene fragments of 16S rRNA and archaeal and bacterial amoA (encoding the ammonia monooxygenase alpha subunit) were applied as molecular biomarkers to analyze the AOPs' phylogeny and diversity. Quantitative PCR was used to determine the abundances of AOPs in the sediments. The results showed that the relatively more heterogeneous freshwater wetland contained a broader range of phylotypes, higher diversity, more complex community structures, and more unevenly distributed abundances of AOPs than the coastal wetland. The effects of vegetation on the community structures of AOPs were plant-specific. The exotic Typha angustifolia affected the community structures of all AOPs and enhanced their abundances in the rhizosphere region. Both Phragmites australis and Cyperus malaccensis showed some effects on the community structures of AOB, but minimal effects on those of anammox bacteria or AOA. Kandelia obovata had almost no detectable effect on all AOPs due to their smaller size. This study suggested that the freshwater and coastal marine wetlands may have different contributions to the inorganic N removal due to the variations in AOP communities and plant types. PMID:23053083

  14. Ammonium and nitrite oxidation at nanomolar oxygen concentrations in oxygen minimum zone waters.

    PubMed

    Bristow, Laura A; Dalsgaard, Tage; Tiano, Laura; Mills, Daniel B; Bertagnolli, Anthony D; Wright, Jody J; Hallam, Steven J; Ulloa, Osvaldo; Canfield, Donald E; Revsbech, Niels Peter; Thamdrup, Bo

    2016-09-20

    A major percentage of fixed nitrogen (N) loss in the oceans occurs within nitrite-rich oxygen minimum zones (OMZs) via denitrification and anammox. It remains unclear to what extent ammonium and nitrite oxidation co-occur, either supplying or competing for substrates involved in nitrogen loss in the OMZ core. Assessment of the oxygen (O2) sensitivity of these processes down to the O2 concentrations present in the OMZ core (<10 nmol⋅L(-1)) is therefore essential for understanding and modeling nitrogen loss in OMZs. We determined rates of ammonium and nitrite oxidation in the seasonal OMZ off Concepcion, Chile at manipulated O2 levels between 5 nmol⋅L(-1) and 20 μmol⋅L(-1) Rates of both processes were detectable in the low nanomolar range (5-33 nmol⋅L(-1) O2), but demonstrated a strong dependence on O2 concentrations with apparent half-saturation constants (Kms) of 333 ± 130 nmol⋅L(-1) O2 for ammonium oxidation and 778 ± 168 nmol⋅L(-1) O2 for nitrite oxidation assuming one-component Michaelis-Menten kinetics. Nitrite oxidation rates, however, were better described with a two-component Michaelis-Menten model, indicating a high-affinity component with a Km of just a few nanomolar. As the communities of ammonium and nitrite oxidizers were similar to other OMZs, these kinetics should apply across OMZ systems. The high O2 affinities imply that ammonium and nitrite oxidation can occur within the OMZ core whenever O2 is supplied, for example, by episodic intrusions. These processes therefore compete with anammox and denitrification for ammonium and nitrite, thereby exerting an important control over nitrogen loss.

  15. Ammonium and nitrite oxidation at nanomolar oxygen concentrations in oxygen minimum zone waters.

    PubMed

    Bristow, Laura A; Dalsgaard, Tage; Tiano, Laura; Mills, Daniel B; Bertagnolli, Anthony D; Wright, Jody J; Hallam, Steven J; Ulloa, Osvaldo; Canfield, Donald E; Revsbech, Niels Peter; Thamdrup, Bo

    2016-09-20

    A major percentage of fixed nitrogen (N) loss in the oceans occurs within nitrite-rich oxygen minimum zones (OMZs) via denitrification and anammox. It remains unclear to what extent ammonium and nitrite oxidation co-occur, either supplying or competing for substrates involved in nitrogen loss in the OMZ core. Assessment of the oxygen (O2) sensitivity of these processes down to the O2 concentrations present in the OMZ core (<10 nmol⋅L(-1)) is therefore essential for understanding and modeling nitrogen loss in OMZs. We determined rates of ammonium and nitrite oxidation in the seasonal OMZ off Concepcion, Chile at manipulated O2 levels between 5 nmol⋅L(-1) and 20 μmol⋅L(-1) Rates of both processes were detectable in the low nanomolar range (5-33 nmol⋅L(-1) O2), but demonstrated a strong dependence on O2 concentrations with apparent half-saturation constants (Kms) of 333 ± 130 nmol⋅L(-1) O2 for ammonium oxidation and 778 ± 168 nmol⋅L(-1) O2 for nitrite oxidation assuming one-component Michaelis-Menten kinetics. Nitrite oxidation rates, however, were better described with a two-component Michaelis-Menten model, indicating a high-affinity component with a Km of just a few nanomolar. As the communities of ammonium and nitrite oxidizers were similar to other OMZs, these kinetics should apply across OMZ systems. The high O2 affinities imply that ammonium and nitrite oxidation can occur within the OMZ core whenever O2 is supplied, for example, by episodic intrusions. These processes therefore compete with anammox and denitrification for ammonium and nitrite, thereby exerting an important control over nitrogen loss. PMID:27601665

  16. Environmental control on aerobic methane oxidation in coastal waters

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Maltby, Johanna; Engbersen, Nadine; Zopfi, Jakob; Bange, Hermann; Elvert, Marcus; Hinrichs, Kai-Uwe; Kock, Annette; Lehmann, Moritz; Treude, Tina; Niemann, Helge

    2016-04-01

    Large quantities of methane are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, where some of it is consumed by aerobic methane oxidizing bacteria (MOB). Aerobic methane oxidation (MOx) in the water column is consequently the final sink for methane before its release to the atmosphere, where it acts as a potent greenhouse gas. In the context of the ocean's contribution to atmospheric methane, coastal seas are particularly important accounting >75% of global methane emission from marine systems. Coastal oceans are highly dynamic, in particular with regard to the variability of methane and oxygen concentrations as well as temperature and salinity, all of which are potential key environmental factors controlling MOx. To determine important environmental controls on the activity of MOBs in coastal seas, we conducted a two-year time-series study with measurements of physicochemical water column parameters, MOx activity and the composition of the MOB community in a coastal inlet in the Baltic Sea (Boknis Eck Time Series Station, Eckernförde Bay - E-Bay). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, hypoxia developed in bottom waters towards the end of the stratification period. Constant methane liberation from sediments resulted in bottom water methane accumulations and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were (i) perturbations of the water column (ii) temperature and (iii) oxygen concentration. (i) Perturbations of the water column caused by storm events or seasonal mixing led to a decrease in MOx, probably caused by replacement of stagnant water with a high standing stock of MOB by 'new' waters with a lower abundance of methanotrophs. b) An increase in temperature generally led to higher MOx rates. c) Even though methane was

  17. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    PubMed

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-01

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability.

  18. Thermally Reduced Graphene Oxide Electrochemically Activated by Bis-Spiro Quaternary Alkyl Ammonium for Capacitors.

    PubMed

    He, Tieshi; Meng, Xiangling; Nie, Junping; Tong, Yujin; Cai, Kedi

    2016-06-01

    Thermally reduced graphene oxide (RGO) electrochemically activated by a quaternary alkyl ammonium-based organic electrolytes/activated carbon (AC) electrode asymmetric capacitor is proposed. The electrochemical activation process includes adsorption of anions into the pores of AC in the positive electrode and the interlayer intercalation of cations into RGO in the negative electrode under high potential (4.0 V). The EA process of RGO by quaternary alkyl ammonium was investigated by X-ray diffraction and electrochemical measurements, and the effects of cation size and structure were extensively evaluated. Intercalation by quaternary alkyl ammonium demonstrates a small degree of expansion of the whole crystal lattice (d002) and a large degree of expansion of the partial crystal lattice (d002) of RGO. RGO electrochemically activated by bis-spiro quaternary alkyl ammonium in propylene carbonate/AC asymmetric capacitor exhibits good activated efficiency, high specific capacity, and stable cyclability. PMID:27180820

  19. Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

    NASA Astrophysics Data System (ADS)

    Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

    2014-05-01

    Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

  20. Reduced graphene oxide supported Au nanoparticles as an efficient catalyst for aerobic oxidation of benzyl alcohol

    NASA Astrophysics Data System (ADS)

    Yu, Xianqin; Huo, Yujia; Yang, Jing; Chang, Sujie; Ma, Yunsheng; Huang, Weixin

    2013-09-01

    Various Au/C catalysts were prepared by Au nanoparticels supported on different carbonaceous supports including reduced graphene oxide (RGO), activated carbon (AC) and graphite (GC) using sol-immobilization method. Au/RGO shows a much higher activity than Au/AC and Au/GC in the liquid phase aerobic oxidation of benzyl alcohol. The superior catalytic performance of Au/RGO may be related to the presence of surface O-containing functional groups and moderate graphite character of RGO supports.

  1. Thaumarchaeal ammonia oxidation in an acidic forest peat soil is not influenced by ammonium amendment.

    PubMed

    Stopnisek, Nejc; Gubry-Rangin, Cécile; Höfferle, Spela; Nicol, Graeme W; Mandic-Mulec, Ines; Prosser, James I

    2010-11-01

    Both bacteria and thaumarchaea contribute to ammonia oxidation, the first step in nitrification. The abundance of putative ammonia oxidizers is estimated by quantification of the functional gene amoA, which encodes ammonia monooxygenase subunit A. In soil, thaumarchaeal amoA genes often outnumber the equivalent bacterial genes. Ecophysiological studies indicate that thaumarchaeal ammonia oxidizers may have a selective advantage at low ammonia concentrations, with potential adaptation to soils in which mineralization is the major source of ammonia. To test this hypothesis, thaumarchaeal and bacterial ammonia oxidizers were investigated during nitrification in microcosms containing an organic, acidic forest peat soil (pH 4.1) with a low ammonium concentration but high potential for ammonia release during mineralization. Net nitrification rates were high but were not influenced by addition of ammonium. Bacterial amoA genes could not be detected, presumably because of low abundance of bacterial ammonia oxidizers. Phylogenetic analysis of thaumarchaeal 16S rRNA gene sequences indicated that dominant populations belonged to group 1.1c, 1.3, and "deep peat" lineages, while known amo-containing lineages (groups 1.1a and 1.1b) comprised only a small proportion of the total community. Growth of thaumarchaeal ammonia oxidizers was indicated by increased abundance of amoA genes during nitrification but was unaffected by addition of ammonium. Similarly, denaturing gradient gel electrophoresis analysis of amoA gene transcripts demonstrated small temporal changes in thaumarchaeal ammonia oxidizer communities but no effect of ammonium amendment. Thaumarchaea therefore appeared to dominate ammonia oxidation in this soil and oxidized ammonia arising from mineralization of organic matter rather than added inorganic nitrogen.

  2. Draft Genome Sequence of an Anaerobic Ammonium-Oxidizing Bacterium, “Candidatus Brocadia sinica”

    PubMed Central

    Oshiki, Mamoru; Shinyako-Hata, Kaori; Satoh, Hisashi

    2015-01-01

    A draft genome sequence of an anaerobic ammonium-oxidizing (anammox) bacterium, “Candidatus Brocadia sinica,” was determined by pyrosequencing and by screening a fosmid library. A 4.07-Mb genome sequence comprising 3 contigs was assembled, in which 3,912 gene-coding regions, 47 tRNAs, and a single rrn operon were annotated. PMID:25883286

  3. Anaerobic Ammonium Oxidation: From Laboratory to Full-Scale Application

    PubMed Central

    Zhang, Jian

    2013-01-01

    From discovery in the early 1990s to completion of full-scale anammox reactor, it took almost two decades to uncover the secret veil of anammox bacteria. There were three milestones during the commercialization of anammox: the development of the first enrichment culture medium, the completion of the first commercial anammox reactor, and the fast start-up of full-scale anammox plant. Till now, the culture of anammox bacteria experienced a big progress through two general strategies: (a) to start up a reactor from scratch and (b) to seed the reactor with enriched anammox sludge. The first full-scale anammox reactor took 3.5 years to realize full operation using the first approach due to several reasons besides the lack of anammox sludge. On the other hand, the first Asian anammox reactor started up in two months, thanks to the availability of anammox seed. Along with the implementation of anammox plants, anammox eventually becomes the priority choice for ammonium wastewater treatment. PMID:23956985

  4. Kinetic Constants for Biological Ammonium and Nitrite Oxidation Processes Under Sulfide Inhibition.

    PubMed

    Bejarano-Ortiz, Diego Iván; Huerta-Ochoa, Sergio; Thalasso, Frédéric; Cuervo-López, Flor de María; Texier, Anne-Claire

    2015-12-01

    Inhibition of nitrification by sulfide was assessed using sludge obtained from a steady-state nitrifying reactor. Independent batch activity assays were performed with ammonium and nitrite as substrate, in order to discriminate the effect of sulfide on ammonium and nitrite oxidation. In the absence of sulfide, substrate affinity constants (K S,NH4  = 2.41 ± 0.11 mg N/L; K s, NO2  = 0.74 ± 0.03 mg N/L) and maximum specific rates (q max,NH4  = 0.086 ± 0.008 mg N/mg microbial protein h; q max,NO2  = 0.124 ± 0.001 mg N/mg microbial protein h) were determined. Inhibition of ammonium oxidation was no-competitive (inhibition constant (K i , NH4 ) of 2.54 ± 0.12 mg HS(-)-S/L) while inhibition of nitrite oxidation was mixed (competitive inhibition constant (K' i , NO2 ) of 0.22 ± 0.03 mg HS(-)-S/L and no-competitive inhibition constant (K i , NO2 ) of 1.03 ± 0.06 mg HS(-)-S/L). Sulfide has greater inhibitory effect on nitrite oxidation than ammonium oxidation, and its presence in nitrification systems should be avoided to prevent accumulation of nitrite. By simulating the effect of sulfide addition in a continuous nitrifying reactor under steady-state operation, it was shown that the maximum sulfide concentration that the sludge can tolerate without affecting the ammonium consumption efficiency and nitrate yield is 1 mg HS(-)-S/L.

  5. Nitrate-Dependent Ferrous Iron Oxidation by Anaerobic Ammonium Oxidation (Anammox) Bacteria

    PubMed Central

    Oshiki, M.; Ishii, S.; Yoshida, K.; Fujii, N.; Ishiguro, M.; Satoh, H.

    2013-01-01

    We examined nitrate-dependent Fe2+ oxidation mediated by anaerobic ammonium oxidation (anammox) bacteria. Enrichment cultures of “Candidatus Brocadia sinica” anaerobically oxidized Fe2+ and reduced NO3− to nitrogen gas at rates of 3.7 ± 0.2 and 1.3 ± 0.1 (mean ± standard deviation [SD]) nmol mg protein−1 min−1, respectively (37°C and pH 7.3). This nitrate reduction rate is an order of magnitude lower than the anammox activity of “Ca. Brocadia sinica” (10 to 75 nmol NH4+ mg protein−1 min−1). A 15N tracer experiment demonstrated that coupling of nitrate-dependent Fe2+ oxidation and the anammox reaction was responsible for producing nitrogen gas from NO3− by “Ca. Brocadia sinica.” The activities of nitrate-dependent Fe2+ oxidation were dependent on temperature and pH, and the highest activities were seen at temperatures of 30 to 45°C and pHs ranging from 5.9 to 9.8. The mean half-saturation constant for NO3− ± SD of “Ca. Brocadia sinica” was determined to be 51 ± 21 μM. Nitrate-dependent Fe2+ oxidation was further demonstrated by another anammox bacterium, “Candidatus Scalindua sp.,” whose rates of Fe2+ oxidation and NO3− reduction were 4.7 ± 0.59 and 1.45 ± 0.05 nmol mg protein−1 min−1, respectively (20°C and pH 7.3). Co-occurrence of nitrate-dependent Fe2+ oxidation and the anammox reaction decreased the molar ratios of consumed NO2− to consumed NH4+ (ΔNO2−/ΔNH4+) and produced NO3− to consumed NH4+ (ΔNO3−/ΔNH4+). These reactions are preferable to the application of anammox processes for wastewater treatment. PMID:23624480

  6. The kinetics for ammonium and nitrite oxidation under the effect of hydroxylamine.

    PubMed

    Wan, Xinyu; Xiao, Pengying; Zhang, Daijun; Lu, Peili; Yao, Zongbao; He, Qiang

    2016-01-01

    The kinetics for ammonium (NH4(+)) oxidation and nitrite (NO2(-)) oxidation under the effect of hydroxylamine (NH2OH) were studied by respirometry using the nitrifying sludge from a laboratory-scale sequencing batch reactor. Modified models were used to estimate kinetics parameters of ammonia and nitrite oxidation under the effect of hydroxylamine. An inhibition effect of hydroxylamine on the ammonia oxidation was observed under different hydroxylamine concentration levels. The self-inhibition coefficient of hydroxylamine oxidation and noncompetitive inhibition coefficient of hydroxylamine for nitrite oxidation was estimated by simulating exogenous oxygen-uptake rate profiles, respectively. The inhibitive effect of NH2OH on nitrite-oxidizing bacteria was stronger than on ammonia-oxidizing bacteria. This work could provide fundamental data for the kinetic investigation of the nitrification process. PMID:26942528

  7. Ubiquitous anaerobic ammonium oxidation in inland waters of China: an overlooked nitrous oxide mitigation process.

    PubMed

    Zhu, Guibing; Wang, Shanyun; Zhou, Leiliu; Wang, Yu; Zhao, Siyan; Xia, Chao; Wang, Weidong; Zhou, Rong; Wang, Chaoxu; Jetten, Mike S M; Hefting, Mariet M; Yin, Chengqing; Qu, Jiuhui

    2015-01-01

    Denitrification has long been regarded as the only pathway for terrestrial nitrogen (N) loss to the atmosphere. Here we demonstrate that large-scale anaerobic ammonium oxidation (anammox), an overlooked N loss process alternative to denitrification which bypasses nitrous oxide (N2O), is ubiquitous in inland waters of China and contributes significantly to N loss. Anammox rates in aquatic systems show different levels (1.0-975.9 μmol N m(-2) h(-1), n = 256) with hotspots occurring at oxic-anoxic interfaces and harboring distinct biogeochemical and biogeographical features. Extrapolation of these results to the China-national level shows that anammox could contribute about 2.0 Tg N yr(-1), which equals averagely 11.4% of the total N loss from China's inland waters. Our results indicate that a significant amount of the nitrogen lost from inland waters bypasses denitrification, which is important for constructing more accurate climate models and may significantly reduce potential N2O emission risk at a large scale. PMID:26610807

  8. Ubiquitous anaerobic ammonium oxidation in inland waters of China: an overlooked nitrous oxide mitigation process

    PubMed Central

    Zhu, Guibing; Wang, Shanyun; Zhou, Leiliu; Wang, Yu; Zhao, Siyan; Xia, Chao; Wang, Weidong; Zhou, Rong; Wang, Chaoxu; Jetten, Mike S. M.; Hefting, Mariet M.; Yin, Chengqing; Qu, Jiuhui

    2015-01-01

    Denitrification has long been regarded as the only pathway for terrestrial nitrogen (N) loss to the atmosphere. Here we demonstrate that large-scale anaerobic ammonium oxidation (anammox), an overlooked N loss process alternative to denitrification which bypasses nitrous oxide (N2O), is ubiquitous in inland waters of China and contributes significantly to N loss. Anammox rates in aquatic systems show different levels (1.0–975.9 μmol N m−2 h−1, n = 256) with hotspots occurring at oxic-anoxic interfaces and harboring distinct biogeochemical and biogeographical features. Extrapolation of these results to the China-national level shows that anammox could contribute about 2.0 Tg N yr−1, which equals averagely 11.4% of the total N loss from China’s inland waters. Our results indicate that a significant amount of the nitrogen lost from inland waters bypasses denitrification, which is important for constructing more accurate climate models and may significantly reduce potential N2O emission risk at a large scale. PMID:26610807

  9. Ubiquitous anaerobic ammonium oxidation in inland waters of China: an overlooked nitrous oxide mitigation process

    NASA Astrophysics Data System (ADS)

    Zhu, Guibing; Wang, Shanyun; Zhou, Leiliu; Wang, Yu; Zhao, Siyan; Xia, Chao; Wang, Weidong; Zhou, Rong; Wang, Chaoxu; Jetten, Mike S. M.; Hefting, Mariet M.; Yin, Chengqing; Qu, Jiuhui

    2015-11-01

    Denitrification has long been regarded as the only pathway for terrestrial nitrogen (N) loss to the atmosphere. Here we demonstrate that large-scale anaerobic ammonium oxidation (anammox), an overlooked N loss process alternative to denitrification which bypasses nitrous oxide (N2O), is ubiquitous in inland waters of China and contributes significantly to N loss. Anammox rates in aquatic systems show different levels (1.0-975.9 μmol N m-2 h-1, n = 256) with hotspots occurring at oxic-anoxic interfaces and harboring distinct biogeochemical and biogeographical features. Extrapolation of these results to the China-national level shows that anammox could contribute about 2.0 Tg N yr-1, which equals averagely 11.4% of the total N loss from China’s inland waters. Our results indicate that a significant amount of the nitrogen lost from inland waters bypasses denitrification, which is important for constructing more accurate climate models and may significantly reduce potential N2O emission risk at a large scale.

  10. Roles of urea production, ammonium excretion, and amino acid oxidation in acid-base balance.

    PubMed

    Mackenzie, W

    1986-02-01

    Atkinson and colleagues recently proposed several concepts that contrast with traditional views: first, that acid-base balance is regulated chiefly by the reactions leading to urea production in the liver; second, that ammonium excretion by the kidney plays no role in acid-base homeostasis; and third, that ammonium does not stimulate ureagenesis (except indirectly). To examine these concepts, plasma ions other than bicarbonate are categorized as 1) fixed cations (Na+, K+, Ca2+, and Mg2+, symbolized M+) and anions (Cl-), 2) buffer anions (A-), 3) other anions (X-), and 4) ammonium plus charged amino groups (N+). Since electroneutrality dictates that M+ + N+ = Cl- + HCO3- + A- + X-, it follows that delta HCO3- = delta(M+ - Cl-) - delta A- - delta X- + delta N+. Therefore acid-base disturbances (changes in HCO3-) can be categorized as to how they affect bodily content and hence plasma concentration of each of these four types of ions. The stoichiometry of ureagenesis, glutamine hydrolysis, ammonium and titratable acid excretion, oxidation of neutral, acidic, and basic amino acids, and oxidation of methionine, phosphoserine, and protein are examined to see how they alter these quantities. It is concluded that 1) although ureagenesis is pH dependent and also counteracts a tendency of amino acid oxidation to cause alkalosis, this tendency is inherently limited by the hyperammonemia (delta N+) that necessarily accompanies it, 2) ammonium excretion is equivalent to hydrogen excretion in its effects on acid-base balance if, and only if, it occurs in exchange for sodium or is accompanied by chloride excretion and only when the glutamate generated by glutamine hydrolysis is oxidized.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:3511732

  11. Environmental Controls on Aerobic Methane Oxidation in Coastal Waters

    NASA Astrophysics Data System (ADS)

    Steinle, L.; Maltby, J.; Engbersen, N.; Zopfi, J.; Bange, H. W.; Elvert, M.; Hinrichs, K. U.; Kock, A.; Lehmann, M. F.; Treude, T.; Niemann, H.

    2015-12-01

    Large quantities of the greenhouse gas CH4 are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, and later into the atmosphere. Indeed, coastal seas account for more than 75% of global oceanic CH4 emissions. Yet, aerobic CH4 oxidizing bacteria (MOB) consume an important part of CH4 in the water column, thus mitigating CH4 release to the atmosphere. Coastal oceans are highly dynamic systems, in particular with regard to the variability of temperature, salinity and oxygen concentrations, all of which are potential key environmental factors controlling MOx. To determine the most important controlling factors, we conducted a two-year time-series study with measurements of CH4, MOx, the composition of the MOB community, and physicochemical water column parameters in a coastal inlet in the Baltic Sea (Eckernförde(E-) Bay, Boknis Eck Time Series Station). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, seasonal stratification leads to hypoxia in bottom waters towards the end of the stratification period. Methane is produced year-round in the sediments, resulting in accumulation of methane in bottom waters, and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were a) perturbations of the water column caused by storm events, currents or seasonal mixing, b) temperature and c) oxygen concentration. a) Perturbations of the water column led to a sharp decrease in MOx within hours, probably caused by replacement of 'old' water with a high standing stock of MOB by 'new' waters with a lower abundance of MOB. b) An increase in temperature generally led to higher MOx rates. c) Even though CH4 was abundant at all depths, MOx was highest in bottom waters (1-5 nM/d), which usually contain the lowest O2 concentrations. Lab-based experiments with adjusted O2

  12. Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

    PubMed

    Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

    2012-11-16

    An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

  13. Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation.

    PubMed

    Seo, Hong-Ahn; Cho, Yeon-Ho; Lee, Ye-Sol; Cheon, Cheol-Hong

    2015-12-18

    A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.

  14. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy.

  15. Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water.

    PubMed

    Liu, Mingxin; Li, Chao-Jun

    2016-08-26

    The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification. PMID:27505714

  16. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy. PMID:26633757

  17. [Distribution and Diversity of Ammonium-oxidizing Archaea and Ammonium-oxidizing Bacteria in Surface Sediments of Oujiang River].

    PubMed

    Li, Hu; Huang, Fu-yi; Su, Jian-qiang; Hong, You-wei; Yu, Shen

    2015-12-01

    Ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) play important roles in the biogeochemical nitrogen cycle. Rivers are important ecosystems containing a large number of functional microbes in nitrogen cycle. In this study, denaturing gradient gel electrophoresis (DGGE ) and real-time quantitative PCR (qPCR) technology were used to analyze the distribution and diversity of AOA and AOB in sediments from Oujiang. The results showed that the AOA community structure was similar among various sites, while the AOB community structure was significantly different, in which all detected AOB sequences were classified into Nitrosospira and Nitrosomonas, and 90% affiliated to Nitrosospira. The community composition of AOA was influenced by NH₄⁺ and TS, in addition, the AOB composition was affected by NH₄⁺, EC, pH, NO₃⁻, TC and TN. Total sulfur (TS) and electrical conductivity (EC) were the major factors influencing the diversity of AOA and AOB, respectively. AOA abundance was significantly higher than that of AOB. EC, NH₄⁺-N and NO₃⁻-N were the main environmental factors affecting the abundance of AOA and AOB. This study indicated that the community composition and diversity of AOA and AOB were significantly influenced by environmental factors, and AOA might be dominant drivers in the ammonia oxidation process in Oujiang surface sediment. PMID:27012006

  18. [Distribution and Diversity of Ammonium-oxidizing Archaea and Ammonium-oxidizing Bacteria in Surface Sediments of Oujiang River].

    PubMed

    Li, Hu; Huang, Fu-yi; Su, Jian-qiang; Hong, You-wei; Yu, Shen

    2015-12-01

    Ammonia-oxidizing archaea (AOA) and ammonia-oxidizing bacteria (AOB) play important roles in the biogeochemical nitrogen cycle. Rivers are important ecosystems containing a large number of functional microbes in nitrogen cycle. In this study, denaturing gradient gel electrophoresis (DGGE ) and real-time quantitative PCR (qPCR) technology were used to analyze the distribution and diversity of AOA and AOB in sediments from Oujiang. The results showed that the AOA community structure was similar among various sites, while the AOB community structure was significantly different, in which all detected AOB sequences were classified into Nitrosospira and Nitrosomonas, and 90% affiliated to Nitrosospira. The community composition of AOA was influenced by NH₄⁺ and TS, in addition, the AOB composition was affected by NH₄⁺, EC, pH, NO₃⁻, TC and TN. Total sulfur (TS) and electrical conductivity (EC) were the major factors influencing the diversity of AOA and AOB, respectively. AOA abundance was significantly higher than that of AOB. EC, NH₄⁺-N and NO₃⁻-N were the main environmental factors affecting the abundance of AOA and AOB. This study indicated that the community composition and diversity of AOA and AOB were significantly influenced by environmental factors, and AOA might be dominant drivers in the ammonia oxidation process in Oujiang surface sediment.

  19. Combined autoradiography and immunofluorescence for estimation of single cell activity by ammonium-oxidizing bacteria

    SciTech Connect

    Ward, B.B.

    1984-03-01

    Immunofluorescence and /sup 14/CO/sub 2/ autoradiography were used for simultaneously enumerating and assaying the autotrophic activity of ammonium-oxidizing bacteria in seawater. Relative activity (/sup 14/CO/sub 2/ assimilation as measured by autoradiography) and abundance were measured in simulated in situ incubations at seven stations in the primary NO/sub 2//sup -/ maximum region of the Northeast Pacific Ocean. More than 10/sup 4/ cells-liter/sup -1/ were present; relative activity often showed a peak near the surface and an increase in the NO/sub 2//sup -/ max region below the photic zone. The method permits assessment of individual cell activity; most cells at all depths were active in CO/sub 2/ assimilation, usually at low and quite variable levels. Relative activity was positively correlated with the abundance of ammonium-oxidizing bacteria, temperature, total dark CO/sub 2/ assimilation and phenopigment concentration.

  20. Adsorption and desorption of ammonium by maple wood biochar as a function of oxidation and pH.

    PubMed

    Wang, Bing; Lehmann, Johannes; Hanley, Kelly; Hestrin, Rachel; Enders, Akio

    2015-11-01

    The objective of this work was to investigate the retention mechanisms of ammonium in aqueous solution by using progressively oxidized maple wood biochar at different pH values. Hydrogen peroxide was used to oxidize the biochar to pH values ranging from 8.1 to 3.7, with one set being adjusted to a pH of 7 afterwards. Oxidizing the biochars at their lowered pH did not increase their ability to adsorb ammonium. However, neutralizing the oxygen-containing surface functional groups on oxidized biochar to pH 7 increased ammonia adsorption two to three-fold for biochars originally at pH 3.7-6, but did not change adsorption of biochars oxidized to pH 7 and above. The adsorption characteristics of ammonium are well described by the Freundlich equation. Adsorption was not fully reversible in water, and less than 27% ammonium was desorbed in water in two consecutive steps than previously adsorbed, for biochars with a pH below 7, irrespective of oxidation. Recovery using an extraction with 2M KCl increased from 34% to 99% of ammonium undesorbed by both preceding water extractions with increasing oxidation, largely irrespective of pH adjustment. Unrecovered ammonium in all extractions and residual biochar was negligible at high oxidation, but increased to 39% of initially adsorbed amounts at high pH, likely due to low amounts adsorbed and possible ammonia volatilization losses.

  1. Anaerobic ammonium-oxidizing (anammox) bacteria and associated activity in fixed-film biofilters of a marine recirculating aquaculture system.

    PubMed

    Tal, Yossi; Watts, Joy E M; Schreier, Harold J

    2006-04-01

    Microbial communities in the biological filter and waste sludge compartments of a marine recirculating aquaculture system were examined to determine the presence and activity of anaerobic ammonium-oxidizing (anammox) bacteria. Community DNA was extracted from aerobic and anaerobic fixed-film biofilters and the anaerobic sludge waste collection tank and was analyzed by amplifying 16S rRNA genes by PCR using anammox-selective and universal GC-clamped primers. Separation of amplified PCR products by denaturing gradient gel electrophoresis and sequencing of the different phylotypes revealed a diverse biofilter microbial community. While Planctomycetales were found in all three communities, the anaerobic denitrifying biofilters contained one clone that exhibited high levels of sequence similarity to known anammox bacteria. Fluorescence in situ hybridization studies using an anammox-specific probe confirmed the presence of anammox Planctomycetales in the microbial biofilm from the denitrifying biofilters, and anammox activity was observed in these biofilters, as detected by the ability to simultaneously consume ammonia and nitrite. To our knowledge, this is the first identification of anammox-related sequences in a marine recirculating aquaculture filtration system, and our findings provide a foundation for incorporating this important pathway for complete nitrogen removal in such systems.

  2. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Cao, Yingnan; Lu, Lilin; Cheng, Zhong; Zhang, Shaowei

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  3. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    PubMed

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-01

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts. PMID:24328193

  4. Bioinspired Aerobic Oxidation of Secondary Amines and Nitrogen Heterocycles with a Bifunctional Quinone Catalyst

    PubMed Central

    Wendlandt, Alison E.; Stahl, Shannon S.

    2014-01-01

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here, we report a novel bioinspired quinone catalyst system, consisting of 1,10-phenanthroline-5,6-dione/ZnI2, that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts. PMID:24328193

  5. Asymmetric aerobic oxidative NHC-catalysed synthesis of dihydropyranones utilising a system of electron transfer mediators.

    PubMed

    Axelsson, A; Hammarvid, E; Ta, L; Sundén, H

    2016-10-01

    In the context of green chemistry, the replacement of high molecular weight stoichiometric oxidants with O2 is most desirable but difficult. Here, we report the asymmetric aerobic oxidative synthesis of dihydropyranones. The oxidation is aided by a system of electron transfer mediators and is selective toward the homoenolate. The dihydropyranones can be isolated in high to excellent yields, with high ee (up to 95%). PMID:27604573

  6. Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

    PubMed Central

    Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

    2015-01-01

    Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

  7. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2013-07-01

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- (t) Bu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction. PMID:24015373

  8. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-20

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology. PMID:22012395

  9. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-19

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

  10. High pressure structural, elastic and vibrational properties of green energetic oxidizer ammonium dinitramide

    NASA Astrophysics Data System (ADS)

    Yedukondalu, N.; Ghule, Vikas D.; Vaitheeswaran, G.

    2016-08-01

    Ammonium DiNitramide (ADN) is one of the most promising green energetic oxidizers for future rocket propellant formulations. In the present work, we report a detailed theoretical study on structural, elastic, and vibrational properties of the emerging oxidizer under hydrostatic compression using various dispersion correction methods to capture weak intermolecular (van der Waals and hydrogen bonding) interactions. The calculated ground state lattice parameters, axial compressibilities, and equation of state are in good accord with the available experimental results. Strength of intermolecular interactions has been correlated using the calculated compressibility curves and elastic moduli. Apart from this, we also observe discontinuities in the structural parameters and elastic constants as a function of pressure. Pictorial representation and quantification of intermolecular interactions are described by the 3D Hirshfeld surfaces and 2D finger print maps. In addition, the computed infra-red (IR) spectra at ambient pressure reveal that ADN is found to have more hygroscopic nature over Ammonium Perchlorate (AP) due to the presence of strong hydrogen bonding. Pressure dependent IR spectra show blue- and red-shift of bending and stretching frequencies which leads to weakening and strengthening of the hydrogen bonding below and above 5 GPa, respectively. The abrupt changes in the calculated structural, mechanical, and IR spectra suggest that ADN might undergo a first order structural transformation to a high pressure phase around 5-6 GPa. From the predicted detonation properties, ADN is found to have high and low performance characteristics (DCJ = 8.09 km/s and PCJ = 25.54 GPa) when compared with ammonium based energetic oxidizers (DCJ = 6.50 km/s and PCJ = 17.64 GPa for AP, DCJ = 7.28 km/s and PCJ = 18.71 GPa for ammonium nitrate) and well-known secondary explosives for which DCJ = ˜8-10 km/s and PCJ = ˜30-50 GPa, respectively.

  11. Isolation of an aerobic sulfur oxidizer from the SUP05/Arctic96BD-19 clade.

    PubMed

    Marshall, Katharine T; Morris, Robert M

    2013-02-01

    Bacteria from the uncultured SUP05/Arctic96BD-19 clade of gamma proteobacterial sulfur oxidizers (GSOs) have the genetic potential to oxidize reduced sulfur and fix carbon in the tissues of clams and mussels, in oxygen minimum zones and throughout the deep ocean (>200 m). Here, we report isolation of the first cultured representative from this GSO clade. Closely related cultures were obtained from surface waters in Puget Sound and from the deep chlorophyll maximum in the North Pacific gyre. Pure cultures grow aerobically on natural seawater media, oxidize sulfur, and reach higher final cell densities when glucose and thiosulfate are added to the media. This suggests that aerobic sulfur oxidation enhances organic carbon utilization in the oceans. The first isolate from the SUP05/Arctic96BD-19 clade was given the provisional taxonomic assignment 'Candidatus: Thioglobus singularis', alluding to the clade's known role in sulfur oxidation and the isolate's planktonic lifestyle. PMID:22875135

  12. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols.

    PubMed

    Hoover, Jessica M; Stahl, Shannon S

    2011-10-26

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O(2) as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)Cu(I)/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  13. Aerobic and Anaerobic Oxidation of Organic Acids in Yellowstone Hot Spring Ecosystems

    NASA Astrophysics Data System (ADS)

    Windman, T. O.; Zolotova, N.; Shock, E.

    2007-12-01

    Thermodynamic analysis of energy supply based on samples collected from continental hot spring ecosystems at Yellowstone show that aerobic reactions yield the greatest energy. In terms of energy per mole of electrons transferred, aerobic oxidation of organic acids rivals or exceeds the energy supply from aerobic oxidation of hydrogen, CO, hydrogen sulfide, pyrite, sulfur or ammonia. This analysis is derived from samples collected where hot spring fluid are in contact with the atmosphere. It is likely that oxygen will be present at lower concentrations deeper in the system, which will place hard constraints on aerobic lifestyles. If so, which metabolisms could be supported deeper in the system? How will other oxidants be used to release energy? What characterizes the transition from aerobic to anaerobic oxidation? To answer these questions, pH, temperature, and alkalinity were measured in the field while measurements of dissolved oxygen and other redox-sensitive species (nitrate, ammonia, ferrous iron, and sulfide) were made with field-portable spectrophotometers and samples were taken for analysis of organic and inorganic ions by ion chromatography. Conditions in the subsurface can be predicted by starting from measured oxygen concentrations and calculating the effect of decreasing the concentration on the overall energetics of the system. Depending on hot spring composition, the amount of energy from aerobic oxidation of organic acid anions like succinate matches that from anaerobic oxidation (by nitrate or sulfate) once the log of the activity of dissolved oxygen drops to -6 to -8. These activities are 1 to 4 orders of magnitude lower that values determined for surface water in the hot springs. At lower oxygen activities aerobic oxidation gives way to anaerobic oxidation, and organic oxidation is more likely to involve nitrate and sulfate. Preliminary estimates indicate that these changes may occur at shallow depths in hot spring sediments (perhaps within the

  14. Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

    PubMed Central

    Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

    2015-01-01

    Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

  15. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    NASA Astrophysics Data System (ADS)

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-09-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

  16. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    PubMed Central

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-01-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal. PMID:27687877

  17. Response of anaerobic ammonium oxidation to inorganic nitrogen fluctuations in temperate estuarine sediments

    NASA Astrophysics Data System (ADS)

    Teixeira, Catarina; Magalhães, Catarina; Joye, Samantha B.; Bordalo, Adriano A.

    2016-07-01

    The discovery of anaerobic ammonium oxidation (anammox) highlighted the importance of alternative metabolic pathways to inorganic nitrogen removal in natural environments, particularly in those subjected to increased nitrate inputs, such as estuaries. Laboratory enrichment experiments were used to test the effect of increasing loads of nitrate (NO3-), nitrite (NO2-), and ammonium (NH4+) on the anammox process. Three Atlantic temperate estuaries (NW Portugal) were investigated along a salinity gradient, and anammox activity was measured under different NO3-, NO2-, and NH4+ treatments, using the isotope pairing technique. Obtained results showed that NO3- stimulated denitrification but not anammox, whereas NO2- additions had a positive effect on anammox activity, confirming its role as a key environmental control. On the other hand, increasing NH4+ concentrations seemed to inhibit anammox for low salinity sites. Our findings suggested an important role of the natural availability of nitrogen compounds in regulating anammox and the magnitude of anammox versus denitrification in estuarine environments.

  18. Treatment of real industrial wastewater using the combined approach of advanced oxidation followed by aerobic oxidation.

    PubMed

    Ramteke, Lokeshkumar P; Gogate, Parag R

    2016-05-01

    Fenton oxidation and ultrasound-based pretreatment have been applied to improve the treatment of real industrial wastewater based on the use of biological oxidation. The effect of operating parameters such as Fe(2+) loading, contact time, initial pH, and hydrogen peroxide loading on the extent of chemical oxygen demand (COD) reduction and change in biochemical oxygen demand (BOD5)/COD ratio has been investigated. The optimum operating conditions established for the pretreatment were initial pH of 3.0, Fe(2+) loading of 2.0, and 2.5 g L(-1) for the US/Fenton/stirring and Fenton approach, respectively, and temperature of 25 °C with initial H2O2 loading of 1.5 g L(-1). The use of pretreatment resulted in a significant increase in the BOD5/COD ratio confirming the production of easily digestible intermediates. The effect of the type of sludge in the aerobic biodegradation was also investigated based on the use of primary activated sludge (PAS), modified activated sludge (MAS), and activated sludge (AS). Enhanced removal of the pollutants as well as higher biomass yield was observed for MAS as compared to PAS and AS. The use of US/Fenton/stirring pretreatment under the optimized conditions followed by biological oxidation using MAS resulted in maximum COD removal at 97.9 %. The required hydraulic retention time for the combined oxidation system was also significantly lower as compared to only biological oxidation operation. Kinetic studies revealed that the reduction in the COD followed a first-order kinetic model for advanced oxidation and pseudo first-order model for biodegradation. The study clearly established the utility of the combined technology for the effective treatment of real industrial wastewater.

  19. Role of anaerobic ammonium oxidation (anammox) in nitrogen removal from a freshwater aquifer

    USGS Publications Warehouse

    Smith, Richard L.; Bohlke, John Karl; B. Song,; C. Tobias,

    2015-01-01

    Anaerobic ammonium oxidation (anammox) couples the oxidation of ammonium with the reduction of nitrite, producing N2. The presence and activity of anammox bacteria in groundwater were investigated at multiple locations in an aquifer variably affected by a large, wastewater-derived contaminant plume. Anammox bacteria were detected at all locations tested using 16S rRNA gene sequencing and quantification of hydrazine oxidoreductase (hzo) gene transcripts. Anammox and denitrification activities were quantified by in situ 15NO2–tracer tests along anoxic flow paths in areas of varying ammonium, nitrate, and organic carbon abundances. Rates of denitrification and anammox were determined by quantifying changes in 28N2, 29N2, 30N2, 15NO3–, 15NO2–, and 15NH4+ with groundwater travel time. Anammox was present and active in all areas tested, including where ammonium and dissolved organic carbon concentrations were low, but decreased in proportion to denitrification when acetate was added to increase available electron supply. Anammox contributed 39–90% of potential N2 production in this aquifer, with rates on the order of 10 nmol N2–N L–1 day–1. Although rates of both anammox and denitrification during the tracer tests were low, they were sufficient to reduce inorganic nitrogen concentrations substantially during the overall groundwater residence times in the aquifer. These results demonstrate that anammox activity in groundwater can rival that of denitrification and may need to be considered when assessing nitrogen mass transport and permanent loss of fixed nitrogen in aquifers.

  20. Characterization of incubation experiments and development of an enrichment culture capable of ammonium oxidation under iron-reducing conditions

    NASA Astrophysics Data System (ADS)

    Huang, S.; Jaffé, P. R.

    2015-02-01

    Incubation experiments were conducted using soil samples from a forested riparian wetland where we have previously observed anaerobic ammonium oxidation coupled to iron reduction. Production of both nitrite and ferrous iron was measured repeatedly during incubations when the soil slurry was supplied with either ferrihydrite or goethite and ammonium chloride. Significant changes in the microbial community were observed after 180 days of incubation as well as in a continuous flow membrane reactor, using 16S rRNA gene PCR-denaturing gradient gel electrophoresis, 454 pyrosequencing, and real-time quantitative PCR analysis. We be Acidimicrobiaceae bacterium A6), belonging to the Acidimicrobiaceae family, whose closest cultivated relative is Ferrimicrobium acidiphilum (with 92% identity) and Acidimicrobium ferrooxidans (with 90% identity), might play a key role in this anaerobic biological process that uses ferric iron as an electron acceptor while oxidizing ammonium to nitrite. After ammonium was oxidized to nitrite, nitrogen loss proceeded via denitrification and/or anammox.

  1. Modeling of simultaneous anaerobic methane and ammonium oxidation in a membrane biofilm reactor.

    PubMed

    Chen, Xueming; Guo, Jianhua; Shi, Ying; Hu, Shihu; Yuan, Zhiguo; Ni, Bing-Jie

    2014-08-19

    Nitrogen removal by using the synergy of denitrifying anaerobic methane oxidation (DAMO) and anaerobic ammonium oxidation (Anammox) microorganisms in a membrane biofilm reactor (MBfR) has previously been demonstrated experimentally. In this work, a mathematical model is developed to describe the simultaneous anaerobic methane and ammonium oxidation by DAMO and Anammox microorganisms in an MBfR for the first time. In this model, DAMO archaea convert nitrate, both externally fed and/or produced by Anammox, to nitrite, with methane as the electron donor. Anammox and DAMO bacteria jointly remove the nitrite fed/produced, with ammonium and methane as the electron donor, respectively. The model is successfully calibrated and validated using the long-term (over 400 days) dynamic experimental data from the MBfR, as well as two independent batch tests at different operational stages of the MBfR. The model satisfactorily describes the methane oxidation and nitrogen conversion data from the system. Modeling results show the concentration gradients of methane and nitrogen would cause stratification of the biofilm, where Anammox bacteria mainly grow in the biofilm layer close to the bulk liquid and DAMO organisms attach close to the membrane surface. The low surface methane loadings result in a low fraction of DAMO microorganisms, but the high surface methane loadings would lead to overgrowth of DAMO bacteria, which would compete with Anammox for nitrite and decrease the fraction of Anammox bacteria. The results suggest an optimal methane supply under the given condition should be applied not only to benefit the nitrogen removal but also to avoid potential methane emissions. PMID:25055054

  2. High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Redmond, M. C.; Shiller, A. M.; Arrington, E. C.; Valentine, D. L.; Colombo, F.

    2015-12-01

    Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

  3. Effects of aerobic training on exercise-related oxidative stress in mitochondrial myopathies.

    PubMed

    Siciliano, Gabriele; Simoncini, Costanza; Lo Gerfo, Annalisa; Orsucci, Daniele; Ricci, Giulia; Mancuso, Michelangelo

    2012-12-01

    In mitochondrial myopathies with respiratory chain deficiency impairment of energy cell production may lead to in excess reactive oxygen species generation with consequent oxidative stress and cell damage. Aerobic training has been showed to increase muscle performance in patients with mitochondrial myopathies. Aim of this study has been to evaluate, in 7 patients (6 F e 1M, mean age 44.9 ± 12.1 years) affected by mitochondrial disease, concomitantly to lactate exercise curve, the occurrence of oxidative stress, as indicated by circulating levels of lipoperoxides, in rest condition and as effect of exercise, and also, to verify if an aerobic training program is able to modify, in these patients, ox-redox balance efficiency. At rest and before training blood level of lipoperoxides was 382.4 ± 37.8 AU, compared to controls (318.7 ± 63.8; P<0.05), this corresponding to a moderate oxidative stress degree according to the adopted scale. During incremental exercise blood level of lipoperoxides did not increase, but maintained significantly higher compared to controls. After an aerobic training of 10 weeks the blood level of lipoperoxides decreased by 13.7% at rest (P<0.01) and 10.4%, 8.6% and 8.5% respectively at the corresponding times during the exercise test (P=0.06). These data indicate that, in mitochondrial patients, oxidative stress occurs and that an aerobic training is useful in partially reverting this condition.

  4. A genomic view of methane oxidation by aerobic bacteria and anaerobic archaea

    PubMed Central

    Chistoserdova, Ludmila; Vorholt, Julia A; Lidstrom, Mary E

    2005-01-01

    Recent sequencing of the genome and proteomic analysis of a model aerobic methanotrophic bacterium, Methylococcus capsulatus (Bath) has revealed a highly versatile metabolic potential. In parallel, environmental genomics has provided glimpses into anaerobic methane oxidation by certain archaea, further supporting the hypothesis of reverse methanogenesis. PMID:15693955

  5. Cu-NHC-TEMPO catalyzed aerobic oxidation of primary alcohols to aldehydes.

    PubMed

    Liu, Xiaolong; Xia, Qinqin; Zhang, Yuejiao; Chen, Congyan; Chen, Wanzhi

    2013-09-01

    Imidazolium salts bearing TEMPO groups react with commercially available copper powder affording Cu-NHC complexes. The in situ generated Cu-NHC-TEMPO complexes are quite efficient catalysts for aerobic oxidation of primary alcohols into aldehydes. The catalyst is easily available, and various primary alcohols were selectively converted to aldehydes in excellent yields. PMID:23944937

  6. Phenazinium salt-catalyzed aerobic oxidative amidation of aromatic aldehydes.

    PubMed

    Leow, Dasheng

    2014-11-01

    Amides are prevalent in organic synthesis. Developing an efficient synthesis that avoids expensive oxidants and heating is highly desirable. Here the oxidative amidation of aromatic aldehydes is reported using an inexpensive metal-free visible light photocatalyst, phenazine ethosulfate, at low catalytic loading (1-2 mol %). The reaction proceeds at ambient temperature and uses air as the sole oxidant. The operationally easy procedure provides an economical, green, and mild alternative for the formation of amide bonds.

  7. NHC-catalysed highly selective aerobic oxidation of nonactivated aldehydes

    PubMed Central

    Möhlmann, Lennart; Ludwig, Stefan

    2013-01-01

    Summary This publication describes a highly selective oxidation of aldehydes to the corresponding acids or esters. The reaction proceeds under metal-free conditions by using N-heterocyclic carbenes as organocatalysts in combination with environmentally friendly oxygen as the terminal oxidation agent. PMID:23616801

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

    NASA Astrophysics Data System (ADS)

    Liu, Peng; Wang, Tingmei

    2009-12-01

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

  9. Dissolution of uranium oxides from simulated environmental swipes using ammonium bifluoride

    DOE PAGES

    Meyers, Lisa A.; Yoshida, Thomas M.; Chamberlin, Rebecca M.; Xu, Ning

    2016-04-09

    We developed an analytical chemistry method to quantitatively recover microgram quanties of solid uranium oxides from swipe media using ammonium bifluoride (ABF, NH4HF2) solution. Recovery of uranium from surrogate swipe media (filter paper) was demonstrated at initial uranium loading levels between 3 and 20 µg filter-1. Moreover, the optimal conditions for extracting U3O8 and UO2 are using 1 % ABF solution and incubating at 80 °C for one hour. The average uranium recoveries are 100 % for U3O8, and 90 % for UO2. Finally, with this method, uranium concentration as low as 3 µg filter-1 can be recovered for analysis.

  10. Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights.

    PubMed

    Wendlandt, Alison E; Suess, Alison M; Stahl, Shannon S

    2011-11-18

    The selective oxidation of C-H bonds and the use of O(2) as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is a versatile oxidant, capable of promoting a wide range of oxidative coupling reactions initiated by single-electron transfer (SET) from electron-rich organic molecules. Many of these reactions can be rendered catalytic in Cu by employing molecular oxygen as a stoichiometric oxidant to regenerate the active copper(II) catalyst. Meanwhile, numerous other recently reported Cu-catalyzed C-H oxidation reactions feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II). In some of these cases, evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism. Organometallic C-H oxidation reactions of this type represent important new opportunities for the field of Cu-catalyzed aerobic oxidations. PMID:22034061

  11. Impact of free ammonia on anammox rates (anoxic ammonium oxidation) in a moving bed biofilm reactor.

    PubMed

    Jaroszynski, L W; Cicek, N; Sparling, R; Oleszkiewicz, J A

    2012-06-01

    Using a bench scale moving bed bioreactor (MBBR), the effect of free ammonia (FA, NH(3), the un-ionized form of ammonium NH(4)(+)) concentration on anoxic ammonium oxidation (anammox) was evaluated based on the volumetric nitrogen removal rate (NRR). Although, a detailed microbial analysis was not conducted, the major NRR observed was assumed to be by anammox, based on the nitrogen conversion ratios of nitrite to ammonium and nitrate to ammonium. Since the concentration of free ammonia as a proportion of the total ammonia concentration is pH-dependent, the impact of changing the operating pH from 6.9 to 8.2, was investigated under constant nitrogen loading conditions during continuous reactor operation. Furthermore, the effect of sudden nitrogen load changes was investigated under constant pH conditions. Batch tests were conducted to determine the immediate response of the anammox consortium to shifts in pH and FA concentrations. It was found that FA was inhibiting NRR at concentrations exceeding 2 mg N L(-1). In the pH range 7-8, the decrease in anammox activity was independent of pH and related only to the concentration of FA. Nitrite concentrations of up to 120 mg N L(-1) did not negatively affect NRR for up to 3.5 h. It was concluded that a stable NRR in a moving bed biofilm reactor depended on maintaining FA concentrations below 2 mg N L(-1) when the pH was maintained between 7 and 8.

  12. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions. PMID:26694091

  13. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions.

  14. Selective aerobic oxidation mediated by TiO(2) photocatalysis.

    PubMed

    Lang, Xianjun; Ma, Wanhong; Chen, Chuncheng; Ji, Hongwei; Zhao, Jincai

    2014-02-18

    TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In

  15. Selective aerobic oxidation mediated by TiO(2) photocatalysis.

    PubMed

    Lang, Xianjun; Ma, Wanhong; Chen, Chuncheng; Ji, Hongwei; Zhao, Jincai

    2014-02-18

    TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In

  16. Physiological characteristics of the anaerobic ammonium-oxidizing bacterium 'Candidatus Brocadia sinica'.

    PubMed

    Oshiki, Mamoru; Shimokawa, Masaki; Fujii, Naoki; Satoh, Hisashi; Okabe, Satoshi

    2011-06-01

    The present study investigated the phylogenetic affiliation and physiological characteristics of bacteria responsible for anaerobic ammonium oxidization (anammox); these bacteria were enriched in an anammox reactor with a nitrogen removal rate of 26.0 kg N m(-3) day(-1). The anammox bacteria were identified as representing 'Candidatus Brocadia sinica' on the basis of phylogenetic analysis of rRNA operon sequences. Physiological characteristics examined were growth rate, kinetics of ammonium oxidation and nitrite reduction, temperature, pH and inhibition of anammox. The maximum specific growth rate (μ(max)) was 0.0041 h(-1), corresponding to a doubling time of 7 days. The half-saturation constants (K(s)) for ammonium and nitrite of 'Ca. B. sinica' were 28±4 and 86±4 µM, respectively, higher than those of 'Candidatus Brocadia anammoxidans' and 'Candidatus Kuenenia stuttgartiensis'. The temperature and pH ranges of anammox activity were 25-45 °C and pH 6.5-8.8, respectively. Anammox activity was inhibited in the presence of nitrite (50 % inhibition at 16 mM), ethanol (91 % at 1 mM) and methanol (86 % at 1 mM). Anammox activities were 80 and 70 % of baseline in the presence of 20 mM phosphorus and 3 % salinity, respectively. The yield of biomass and dissolved organic carbon production in the culture supernatant were 0.062 and 0.005 mol C (mol NH (+)(-4))(-1), respectively. This study compared physiological differences between three anammox bacterial enrichment cultures to provide a better understanding of anammox niche specificity in natural and man-made ecosystems.

  17. Biological reduction of uranium coupled with oxidation of ammonium by Acidimicrobiaceae bacterium A6 under iron reducing conditions.

    PubMed

    Gilson, Emily R; Huang, Shan; Jaffé, Peter R

    2015-11-01

    This study investigated the possibility of links between the biological immobilization of uranium (U) and ammonium oxidation under iron (Fe) reducing conditions. The recently-identified Acidimicrobiaceae bacterium A6 (ATCC, PTA-122488) derives energy from ammonium oxidation coupled with Fe reduction. This bacterium has been found in various soil and wetland environments, including U-contaminated wetland sediments. Incubations of Acidimicrobiaceae bacteria A6 with nontronite, an Fe(III)-rich clay, and approximately 10 µM U indicate that these bacteria can use U(VI) in addition to Fe(III) as an electron acceptor in the presence of ammonium. Measurements of Fe(II) production and ammonium oxidation support this interpretation. Concentrations of approximately 100 µM U were found to entirely inhibit Acidimicrobiaceae bacteria A6 activity. These results suggest that natural sites of active ammonium oxidation under Fe reducing conditions by Acidimicrobiaceae bacteria A6 could be hotspots of U immobilization by bioreduction. This is the first report of biological U reduction that is not coupled to carbon oxidation.

  18. Quaternary ammonium salts with tetrafluoroborate anion: Phytotoxicity and oxidative stress in terrestrial plants.

    PubMed

    Biczak, Robert

    2016-03-01

    This paper discusses the impact of four quaternary ammonium salts (QAS) such as tetraethylammonium tetrafluoroborate [TEA][BF4], tetrabutylammonium tetrafluoroborate [TBA][BF4], tetrahexylammonium tetrafluoroborate [THA][BF4], and tetraoctylammonium tetrafluoroborate [TOA][BF4] on the growth and development of spring barley and common radish. Analogous tests were performed with the inorganic salt ammonium tetrafluoroborate [A][BF4] for comparison purposes. Results indicated that the phytotoxicity of the QAS applied is dependent on the concentration of the substance and their number of carbon atoms. The most toxic compound was [TBA][BF4], causing the greatest drop in fresh weight of both study plants, similar to the phytotoxic effects of [A][BF4]. All the tested compounds caused oxidative stress in spring barley and common radish seedlings due to a drop in the chlorophyll content. Stress was also observed in plants, which was indicated by the increased level of ROS (reactive oxygen species) such as H2O2 and lipid peroxidation of MDA (malondialdehyde). Due to the stress, both plants displayed changes in the activity of antioxidative enzymes such as superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD). Based on the results of the study, it was concluded that changes in chlorophyll levels and peroxidase activity are the best biomarkers to determine oxidative stress in plants. PMID:26551221

  19. Anaerobic ammonium oxidation and its contribution to nitrogen removal in China’s coastal wetlands

    PubMed Central

    Hou, Lijun; Zheng, Yanling; Liu, Min; Li, Xiaofei; Lin, Xianbiao; Yin, Guoyu; Gao, Juan; Deng, Fengyu; Chen, Fei; Jiang, Xiaofen

    2015-01-01

    Over the past several decades, human activities have caused substantial enrichment of reactive nitrogen in China’s coastal wetlands. Although anaerobic ammonium oxidation (anammox), the process of oxidizing ammonium into dinitrogen gas through the reduction of nitrite, is identified as an important process for removing reactive nitrogen, little is known about the dynamics of anammox and its contribution to nitrogen removal in nitrogen-enriched environments. Here, we examine potential rates of anammox and associate them with bacterial diversity and abundance across the coastal wetlands of China using molecular and isotope tracing techniques. High anammox bacterial diversity was detected in China’s coastal wetlands and included Candidatus Scalindua, Kuenenia, Brocadia, and Jettenia. Potential anammox rates were more closely associated with the abundance of anammox bacteria than to their diversity. Among all measured environmental variables, temperature was a key environmental factor, causing a latitudinal distribution of the anammox bacterial community composition, biodiversity and activity along the coastal wetlands of China. Based on nitrogen isotope tracing experiments, anammox was estimated to account for approximately 3.8–10.7% of the total reactive nitrogen removal in the study area. Combined with denitrification, anammox can remove 20.7% of the total external terrigenous inorganic nitrogen annually transported into China’s coastal wetland ecosystems. PMID:26494435

  20. Anaerobic ammonium-oxidizing bacteria gain antibiotic resistance during long-term acclimatization.

    PubMed

    Zhang, Zheng-Zhe; Zhang, Qian-Qian; Guo, Qiong; Chen, Qian-Qian; Jiang, Xiao-Yan; Jin, Ren-Cun

    2015-09-01

    Three broad-spectrum antibiotics, amoxicillin (AMX), florfenicol (FF) and sulfamethazine (SMZ), that inhibit bacteria via different target sites, were selected to evaluate the acute toxicity and long-term effects on anaerobic ammonium oxidation (anammox) granules. The specific anammox activity (SAA) levels reduced by approximately half within the first 3 days in the presence of antibiotics but no nitrite accumulation was observed in continuous-flow experiments. However, the SAA levels and heme c content gradually recovered as the antibiotic concentrations increased. Extracellular polymeric substances (EPS) analysis suggested that anaerobic ammonium-oxidizing bacteria gradually developed a better survival strategy during long-term acclimatization, which reduced the antibiotic stress via increased EPS secretion that provided a protective 'cocoon.' In terms of nitrogen removal efficiency, anammox granules could resist 60 mg-AMX L(-1), 10 mg-FF L(-1) and 100 mg-SMZ L(-1). This study supported the feasibility of using anammox granules to treat antibiotic-containing wastewater.

  1. Anaerobic ammonium oxidation and its contribution to nitrogen removal in China's coastal wetlands.

    PubMed

    Hou, Lijun; Zheng, Yanling; Liu, Min; Li, Xiaofei; Lin, Xianbiao; Yin, Guoyu; Gao, Juan; Deng, Fengyu; Chen, Fei; Jiang, Xiaofen

    2015-10-23

    Over the past several decades, human activities have caused substantial enrichment of reactive nitrogen in China's coastal wetlands. Although anaerobic ammonium oxidation (anammox), the process of oxidizing ammonium into dinitrogen gas through the reduction of nitrite, is identified as an important process for removing reactive nitrogen, little is known about the dynamics of anammox and its contribution to nitrogen removal in nitrogen-enriched environments. Here, we examine potential rates of anammox and associate them with bacterial diversity and abundance across the coastal wetlands of China using molecular and isotope tracing techniques. High anammox bacterial diversity was detected in China's coastal wetlands and included Candidatus Scalindua, Kuenenia, Brocadia, and Jettenia. Potential anammox rates were more closely associated with the abundance of anammox bacteria than to their diversity. Among all measured environmental variables, temperature was a key environmental factor, causing a latitudinal distribution of the anammox bacterial community composition, biodiversity and activity along the coastal wetlands of China. Based on nitrogen isotope tracing experiments, anammox was estimated to account for approximately 3.8-10.7% of the total reactive nitrogen removal in the study area. Combined with denitrification, anammox can remove 20.7% of the total external terrigenous inorganic nitrogen annually transported into China's coastal wetland ecosystems.

  2. Advances in methods for detection of anaerobic ammonium oxidizing (anammox) bacteria.

    PubMed

    Li, Meng; Gu, Ji-Dong

    2011-05-01

    Anaerobic ammonium oxidation (anammox), the biochemical process oxidizing ammonium into dinitrogen gas using nitrite as an electron acceptor, has only been recognized for its significant role in the global nitrogen cycle not long ago, and its ubiquitous distribution in a wide range of environments has changed our knowledge about the contributors to the global nitrogen cycle. Currently, several groups of methods are used in detection of anammox bacteria based on their physiological and biochemical characteristics, cellular chemical composition, and both 16S rRNA gene and selective functional genes as biomarkers, including hydrazine oxidoreductase and nitrite reductase encoding genes hzo and nirS, respectively. Results from these methods coupling with advances in quantitative PCR, reverse transcription of mRNA genes and stable isotope labeling have improved our understanding on the distribution, diversity, and activity of anammox bacteria in different environments both natural and engineered ones. In this review, we summarize these methods used in detection of anammox bacteria from various environments, highlight the strengths and weakness of these methods, and also discuss the new development potentials on the existing and new techniques in the future.

  3. Combined autoradiography and immunofluorescence for estimation of single cell activity by ammonium-oxidizing bacteria

    SciTech Connect

    Ward, B.B.

    1984-03-01

    Immunofluorescence and /sup 14/CO/sub 2/ autoradiography were used for simultaneously enumerating and assaying the autotrophic activity of ammonium-oxidizing bacteria in seawater. Relative activity (/sup 14/CO/sub 2/ assimilation as measured by autoradiography) and abundance were measured in simulated in situ incubations at seven stations in the primary NO/sub 2//sup -/ maximum region of the Northeast Pacific Ocean. More than 10/sup 4/ cells liter/sup -1/ were present; relative activity often showed a peak near the surface and an increase in the NO/sub 2//sup -/ max region below the photic zone. The method permits assessment of individual cell activity; most cells at all depths were active in CO/sub 2/ assimilation, usually at low and quite variable levels. There were no differences in relative activity between samples incubated under simulated in situ conditions and in the dark. Relative activity was positively correlated with the abundance of ammonium-oxidizing bacteria, temperature, total dark CO/sub 2/ assimilation (as measured by liquid scintillation counting of replicate samples), and pheopigment concentration, and negatively correlated with oxygen concentration.

  4. Anaerobic ammonium oxidation and its contribution to nitrogen removal in China’s coastal wetlands

    NASA Astrophysics Data System (ADS)

    Hou, Lijun; Zheng, Yanling; Liu, Min; Li, Xiaofei; Lin, Xianbiao; Yin, Guoyu; Gao, Juan; Deng, Fengyu; Chen, Fei; Jiang, Xiaofen

    2015-10-01

    Over the past several decades, human activities have caused substantial enrichment of reactive nitrogen in China’s coastal wetlands. Although anaerobic ammonium oxidation (anammox), the process of oxidizing ammonium into dinitrogen gas through the reduction of nitrite, is identified as an important process for removing reactive nitrogen, little is known about the dynamics of anammox and its contribution to nitrogen removal in nitrogen-enriched environments. Here, we examine potential rates of anammox and associate them with bacterial diversity and abundance across the coastal wetlands of China using molecular and isotope tracing techniques. High anammox bacterial diversity was detected in China’s coastal wetlands and included Candidatus Scalindua, Kuenenia, Brocadia, and Jettenia. Potential anammox rates were more closely associated with the abundance of anammox bacteria than to their diversity. Among all measured environmental variables, temperature was a key environmental factor, causing a latitudinal distribution of the anammox bacterial community composition, biodiversity and activity along the coastal wetlands of China. Based on nitrogen isotope tracing experiments, anammox was estimated to account for approximately 3.8-10.7% of the total reactive nitrogen removal in the study area. Combined with denitrification, anammox can remove 20.7% of the total external terrigenous inorganic nitrogen annually transported into China’s coastal wetland ecosystems.

  5. Effects of substrates on N2O emissions in an anaerobic ammonium oxidation (anammox) reactor.

    PubMed

    Jin, Yue; Wang, Dunqiu; Zhang, Wenjie

    2016-01-01

    N2O emission in the anaerobic ammonium oxidation (anammox) process is of growing concern. In this study, effects of substrate concentrations on N2O emissions were investigated in an anammox reactor. Extremely high N2O emissions of 1.67 % were led by high NH4-N concentrations. Results showed that N2O emissions have a positive correlation with NH4-N concentrations in the anammox reactor. Reducing NH4-N concentrations by recycling pump resulted in decreasing N2O emissions. In addition, further studies were performed to identify a key biological process that is contributed to N2O emissions from the anammox reactor. Based on the results obtained, Nitrosomonas, which can oxidize ammonia to nitrite, was deemed as the main sources of N2O emissions. PMID:27376009

  6. Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters.

    PubMed

    Kong, Weiguang; Li, Bingnan; Xu, Xuezhao; Song, Qiuling

    2016-09-16

    Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O2 feature this transformation and make it a practical and sustainable protocol to afford esters. PMID:27555329

  7. Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems

    PubMed Central

    Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.

    2013-01-01

    Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2′-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols. PMID:24558634

  8. Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere.

    PubMed

    Wang, Lianyue; Shang, SenSen; Li, Guosong; Ren, Lanhui; Lv, Ying; Gao, Shuang

    2016-03-01

    We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction. PMID:26859251

  9. Activated carbon for aerobic oxidation: Benign approach toward 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles synthesis

    PubMed Central

    Bao, Kai; Li, Fuqing; Liu, Hanjing; Wang, Zhiwei; Shen, Qirong; Wang, Jian; Zhang, Weige

    2015-01-01

    A general strategy involving a novel and highly efficient aerobic benzylic oxidation promoted by cheap, reusable activated carbon in water is developed. Application of this method has been demonstrated in the benign synthesis of bioactive 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles derivatives. Furthermore, the activated carbon catalyst could be recovered and reused at least three times without significantly losing its activity. Preliminary research suggests that the oxidation mechanism may involve intermediate hydroperoxidation and that a portion of the final carbonyl product is obtained through a secondary benzylic alcohol intermediate. Finally, theoretical calculations reveal that the oxidation yield is closely associated with the electric density at the benzylic position of the substrate. PMID:26041483

  10. Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-11-01

    Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2'-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols. PMID:24558634

  11. Oxidation of ammonium sulfite by a multi-needle-to-plate gas phase pulsed corona discharge reactor

    NASA Astrophysics Data System (ADS)

    Ren, Hua; Lu, Na; Shang, Kefeng; Li, Jie; Wu, Yan

    2013-03-01

    The oxidation of ammonium sulfite in the ammonia-based flue gas desulfurization (FGD) process was investigated in a multi-needle-to-plate gas phase pulsed corona discharge reactor in this paper. The effect of several parameters, including capacitance and peak pulse voltage of discharge system, electrode gap and bubbling gas flow rate on the oxidation rate of ammonium sulfite was reviewed. The oxidation rate of ammonium sulfite could reach 47.2% at the capacitance, the peak pulse voltage, electrode gap and bubbling gas flow rate equal to 2 nF, -24.6 k V, 35 mm and 4 L min-1 within treatment time of 40 min The experimental results indicate that the gas phase pulsed discharge system with a multi-needle-to-plate electrode can oxide the ammonium sulfite. The oxidation rate increased with the applied capacitance and peak pulse voltage and decreased with the electrode gap. As the bubbling gas flow rate increased, the oxidation rate increased first and then tended to reach a stationary value. These results would be important for the process optimization of the (NH4)2SO3 to (NH4)2SO4 oxidation.

  12. Evaluation of methyl fluoride and dimethyl ether as inhibitors of aerobic methane oxidation

    USGS Publications Warehouse

    Oremland, R.S.; Culbertson, C.W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ~100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor.

  13. Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

    PubMed

    Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

    2016-05-25

    A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available. PMID:27171973

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

    SciTech Connect

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

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

  15. An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes.

    PubMed

    Bortolini, O; Chiappe, C; Fogagnolo, M; Giovannini, P P; Massi, A; Pomelli, C S; Ragno, D

    2014-02-25

    N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy. PMID:24413829

  16. Role of ammonia-oxidizing bacteria in micropollutant removal from wastewater with aerobic granular sludge.

    PubMed

    Margot, Jonas; Lochmatter, Samuel; Barry, D A; Holliger, Christof

    2016-01-01

    Nitrifying wastewater treatment plants (WWTPs) are more efficient than non-nitrifying WWTPs to remove several micropollutants such as pharmaceuticals and pesticides. This may be related to the activity of nitrifying organisms, such as ammonia-oxidizing bacteria (AOBs), which could possibly co-metabolically oxidize micropollutants with their ammonia monooxygenase (AMO). The role of AOBs in micropollutant removal was investigated with aerobic granular sludge (AGS), a promising technology for municipal WWTPs. Two identical laboratory-scale AGS sequencing batch reactors (AGS-SBRs) were operated with or without nitrification (inhibition of AMOs) to assess their potential for micropollutant removal. Of the 36 micropollutants studied at 1 μg l(-1) in synthetic wastewater, nine were over 80% removed, but 17 were eliminated by less than 20%. Five substances (bisphenol A, naproxen, irgarol, terbutryn and iohexol) were removed better in the reactor with nitrification, probably due to co-oxidation catalysed by AMOs. However, for the removal of all other micropollutants, AOBs did not seem to play a significant role. Many compounds were better removed in aerobic condition, suggesting that aerobic heterotrophic organisms were involved in the degradation. As the AGS-SBRs did not favour the growth of such organisms, their potential for micropollutant removal appeared to be lower than that of conventional nitrifying WWTPs. PMID:26877039

  17. Destruction of organic wastes by ammonium peroxydisulfate with electrolytic regeneration of the oxidant

    SciTech Connect

    Cooper, J.F.; Wang, J.F.; Krueger, R.; King, K.

    1997-07-01

    Research is reported concerning a new aqueous process for oxidative destruction of solid- and liquid organic wastes. This process uses acidified ammonium peroxydisulfate and operates at ambient pressure and at 80- to 100 {degrees}C. The oxidant may be efficiently regenerated by electrolysis of the sulfate by-product at Pt anodes, even in the presence of organic and inorganic contaminants expected to be entrained in the cycle. Integral rate constants were determined for the oxidation of 25 diverse organic compounds at low (50 ppm) concentrations through fixed-time experiments with excess oxidant and a Pt wire catalyst. For high initial concentrations, uncatalyzed mineralization rates were measured for waste surrogates including kerosene, triethylamine, ion exchange resin, oxalic acid, trinitrotoluene, and cellulose. A packed bed reactor was tested with ethylene glycol, with offgas analysis by mass spectroscopy. Rate data extrapolate to throughputs of approximately 200 kg/m{sub 3}-day. The process may benefit the destruction of highly toxic or specialized industrial wastes as well as the organic fraction of mixed wastes.

  18. Stimulation by ammonium-based fertilizers of methane oxidation in soil around rice roots.

    PubMed

    Bodelier, P L; Roslev, P; Henckel, T; Frenzel, P

    2000-01-27

    Methane is involved in a number of chemical and physical processes in the Earth's atmosphere, including global warming. Atmospheric methane originates mainly from biogenic sources, such as rice paddies and natural wetlands; the former account for at least 30% of the global annual emission of methane to the atmosphere. As an increase of rice production by 60% is the most appropriate way to sustain the estimated increase of the human population during the next three decades, intensified global fertilizer application will be necessary: but it is known that an increase of the commonly used ammonium-based fertilizers can enhance methane emission from rice agriculture. Approximately 10-30% of the methane produced by methanogens in rice paddies is consumed by methane-oxidizing bacteria associated with the roots of rice; these bacteria are generally thought to be inhibited by ammonium-based fertilizers, as was demonstrated for soils and sediments. In contrast, we show here that the activity and growth of such bacteria in the root zone of rice plants are stimulated after fertilization. Using a combination of radioactive fingerprinting and molecular biology techniques, we identify the bacteria responsible for this effect. We expect that our results will make necessary a re-evaluation of the link between fertilizer use and methane emissions, with effects on global warming studies.

  19. Evidence for anaerobic ammonium oxidation process in freshwater sediments of aquaculture ponds.

    PubMed

    Shen, Li-dong; Wu, Hong-sheng; Gao, Zhi-qiu; Ruan, Yun-jie; Xu, Xiang-hua; Li, Ji; Ma, Shi-jie; Zheng, Pei-hui

    2016-01-01

    The anaerobic ammonium oxidation (anammox) process, which can simultaneously remove ammonium and nitrite, both toxic to aquatic animals, can be very important to the aquaculture industry. Here, the presence and activity of anammox bacteria in the sediments of four different freshwater aquaculture ponds were investigated by using Illumina-based 16S rRNA gene sequencing, quantitative PCR assays and (15)N stable isotope measurements. Different genera of anammox bacteria were detected in the examined pond sediments, including Candidatus Brocadia, Candidatus Kuenenia and Candidatus Anammoxoglobus, with Candidatus Brocadia being the dominant anammox genus. Quantitative PCR of hydrazine synthase genes showed that the abundance of anammox bacteria ranged from 5.6 × 10(4) to 2.1 × 10(5) copies g(-1) sediment in the examined ponds. The potential anammox rates ranged between 3.7 and 19.4 nmol N2 g(-1) sediment day(-1), and the potential denitrification rates varied from 107.1 to 300.3 nmol N2 g(-1) sediment day(-1). The anammox process contributed 1.2-15.3% to sediment dinitrogen gas production, while the remainder would be due to denitrification. It is estimated that a total loss of 2.1-10.9 g N m(-2) per year could be attributed to the anammox process in the examined ponds, suggesting that this process could contribute to nitrogen removal in freshwater aquaculture ponds.

  20. Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Anthony, K. Walter; Thalasso, F.

    2015-03-01

    Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends on lake CH4 and oxygen (O2) concentrations, temperature, and organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was in deficit compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. These results confirm that landscape processes play an important role in lake CH4 cycling.

  1. Supplementation with vitamin A enhances oxidative stress in the lungs of rats submitted to aerobic exercise.

    PubMed

    Gasparotto, Juciano; Petiz, Lyvia Lintzmaier; Girardi, Carolina Saibro; Bortolin, Rafael Calixto; de Vargas, Amanda Rodrigues; Henkin, Bernardo Saldanha; Chaves, Paloma Rodrigues; Roncato, Sabrina; Matté, Cristiane; Zanotto-Filho, Alfeu; Moreira, José Cláudio Fonseca; Gelain, Daniel Pens

    2015-12-01

    Exercise training induces reactive oxygen species production and low levels of oxidative damage, which are required for induction of antioxidant defenses and tissue adaptation. This process is physiological and essential to improve physical conditioning and performance. During exercise, endogenous antioxidants are recruited to prevent excessive oxidative stress, demanding appropriate intake of antioxidants from diet or supplements; in this context, the search for vitamin supplements that enhance the antioxidant defenses and improve exercise performance has been continuously increasing. On the other hand, excess of antioxidants may hinder the pro-oxidant signals necessary for this process of adaptation. The aim of this study was to investigate the effects of vitamin A supplementation (2000 IU/kg, oral) upon oxidative stress and parameters of pro-inflammatory signaling in lungs of rats submitted to aerobic exercise (swimming protocol). When combined with exercise, vitamin A inhibited biochemical parameters of adaptation/conditioning by attenuating exercise-induced antioxidant enzymes (superoxide dismutase and glutathione peroxidase) and decreasing the content of the receptor for advanced glycation end-products. Increased oxidative damage to proteins (carbonylation) and lipids (lipoperoxidation) was also observed in these animals. In sedentary animals, vitamin A decreased superoxide dismutase and increased lipoperoxidation. Vitamin A also enhanced the levels of tumor necrosis factor alpha and decreased interleukin-10, effects partially reversed by aerobic training. Taken together, the results presented herein point to negative effects associated with vitamin A supplementation at the specific dose here used upon oxidative stress and pro-inflammatory cytokines in lung tissues of rats submitted to aerobic exercise.

  2. Dissolution of Fe(III)(hydr)oxides by an Aerobic Bacterium

    SciTech Connect

    Maurice, P.

    2004-12-13

    This project investigated the effects of an aerobic Pseudomonas mendocina bacterium on the dissolution of Fe(III)(hydr)oxides. The research is important because metals and radionuclides that adsorb to Fe(III)(hydr)oxides could potentially be remobilized by dissolving bacteria. We showed that P. mendocina is capable of dissolving Fe-bearing minerals by a variety of mechanisms, including production of siderophores, pH changes, and formation of reductants. The production of siderophores by P. mendocina was quantified under a variety of growth conditions. Finally, we demonstrated that microbial siderophores may adsorb to and enhance dissolution of clay minerals.

  3. Long-term aerobic exercise increases redox-active iron through nitric oxide in rat hippocampus.

    PubMed

    Chen, Qian; Xiao, De-Sheng

    2014-01-30

    Adult hippocampus is highly vulnerable to iron-induced oxidative stress. Aerobic exercise has been proposed to reduce oxidative stress but the findings in the hippocampus are conflicting. This study aimed to observe the changes of redox-active iron and concomitant regulation of cellular iron homeostasis in the hippocampus by aerobic exercise, and possible regulatory effect of nitric oxide (NO). A randomized controlled study was designed in the rats with swimming exercise treatment (for 3 months) and/or an unselective inhibitor of NO synthase (NOS) (L-NAME) treatment. The results from the bleomycin-detectable iron assay showed additional redox-active iron in the hippocampus by exercise treatment. The results from nonheme iron content assay, combined with the redox-active iron content, showed increased storage iron content by exercise treatment. NOx (nitrate plus nitrite) assay showed increased NOx content by exercise treatment. The results from the Western blot assay showed decreased ferroportin expression, no changes of TfR1 and DMT1 expressions, increased IRP1 and IRP2 expression, increased expressions of eNOS and nNOS rather than iNOS. In these effects of exercise treatment, the increased redox-active iron content, storage iron content, IRP1 and IRP2 expressions were completely reversed by L-NAME treatment, and decreased ferroportin expression was in part reversed by L-NAME. L-NAME treatment completely inhibited increased NOx and both eNOS and nNOS expression in the hippocampus. Our findings suggest that aerobic exercise could increase the redox-active iron in the hippocampus, indicating an increase in the capacity to generate hydroxyl radicals through the Fenton reactions, and aerobic exercise-induced iron accumulation in the hippocampus might mainly result from the role of the endogenous NO.

  4. Development of Electroactive and Anaerobic Ammonium-Oxidizing (Anammox) Biofilms from Digestate in Microbial Fuel Cells.

    PubMed

    Di Domenico, Enea Gino; Petroni, Gianluca; Mancini, Daniele; Geri, Alberto; Di Palma, Luca; Ascenzioni, Fiorentina

    2015-01-01

    Microbial Fuel cells (MFCs) have been proposed for nutrient removal and energy recovery from different wastes. In this study the anaerobic digestate was used to feed H-type MFC reactors, one with a graphite anode preconditioned with Geobacter sulfurreducens and the other with an unconditioned graphite anode. The data demonstrate that the digestate acts as a carbon source, and even in the absence of anode preconditioning, electroactive bacteria colonise the anodic chamber, producing a maximum power density of 172.2 mW/m(2). The carbon content was also reduced by up to 60%, while anaerobic ammonium oxidation (anammox) bacteria, which were found in the anodic compartment of the reactors, contributed to nitrogen removal from the digestate. Overall, these results demonstrate that MFCs can be used to recover anammox bacteria from natural sources, and it may represent a promising bioremediation unit in anaerobic digestor plants for the simultaneous nitrogen removal and electricity generation using digestate as substrate.

  5. Development of Electroactive and Anaerobic Ammonium-Oxidizing (Anammox) Biofilms from Digestate in Microbial Fuel Cells.

    PubMed

    Di Domenico, Enea Gino; Petroni, Gianluca; Mancini, Daniele; Geri, Alberto; Di Palma, Luca; Ascenzioni, Fiorentina

    2015-01-01

    Microbial Fuel cells (MFCs) have been proposed for nutrient removal and energy recovery from different wastes. In this study the anaerobic digestate was used to feed H-type MFC reactors, one with a graphite anode preconditioned with Geobacter sulfurreducens and the other with an unconditioned graphite anode. The data demonstrate that the digestate acts as a carbon source, and even in the absence of anode preconditioning, electroactive bacteria colonise the anodic chamber, producing a maximum power density of 172.2 mW/m(2). The carbon content was also reduced by up to 60%, while anaerobic ammonium oxidation (anammox) bacteria, which were found in the anodic compartment of the reactors, contributed to nitrogen removal from the digestate. Overall, these results demonstrate that MFCs can be used to recover anammox bacteria from natural sources, and it may represent a promising bioremediation unit in anaerobic digestor plants for the simultaneous nitrogen removal and electricity generation using digestate as substrate. PMID:26273609

  6. Tetranitroacetimidic acid: a high oxygen oxidizer and potential replacement for ammonium perchlorate.

    PubMed

    Vo, Thao T; Parrish, Damon A; Shreeve, Jean'ne M

    2014-08-27

    Considerable work has been focused on developing replacements for ammonium perchlorate (AP), a primary choice for solid rocket and missile propellants, due to environmental concerns resulting from the release of perchlorate into groundwater systems [corrected]. Additionally, the generation of hydrochloric acid contributes to high concentrations of acid rain and to ozone layer depletion. En route to synthesizing salts that contain cationic FOX-7, a novel, high oxygen-containing oxidizer, tetranitroacetimidic acid (TNAA), has been synthesized and fully characterized. The properties of TNAA were found to be exceptional, with a calculated specific impulse exceeding that of AP, leading to its high potential as a replacement for AP. TNAA can be synthesized easily in a one-step process by the nitration of FOX-7 in high yield (>93%). The synthesis, properties, and chemical reactivity of TNAA have been examined.

  7. Anaerobic ammonium oxidation (anammox) under realistic seasonal temperature variations: Characteristics of biogranules and process performance.

    PubMed

    Guo, Qiong; Xing, Bao-Shan; Li, Peng; Xu, Jia-Li; Yang, Chen-Chen; Jin, Ren-Cun

    2015-09-01

    In this study, the effects of realistic seasonal temperatures on the nitrogen removal performance of anaerobic ammonium oxidation (anammox) and the properties of the anammox granules were comparatively investigated for 330 days. The results demonstrated that the nitrogen removal efficiency (NRE), nitrogen loading rate (NLR) and nitrogen removal rate (NRR) were decreased dramatically, as the temperature decreased from 31.2 to 2.5 °C. However, the nitrogen removal performance recovered andante as the temperature increased gradually. After low temperature exposure, the settleability tended to worsen, and granules appeared to be more irregular with a smaller average granule diameter, and the extracellular polymeric substances (EPS) content increased slightly, while the specific anammox activity (SAA) decreased obviously. This realistic seasonal temperatures based research was an illation of the actual operation, and could be potentially implemented to maintain stability for the application of anammox technology.

  8. Development of Electroactive and Anaerobic Ammonium-Oxidizing (Anammox) Biofilms from Digestate in Microbial Fuel Cells

    PubMed Central

    Di Domenico, Enea Gino; Petroni, Gianluca; Mancini, Daniele; Geri, Alberto; Palma, Luca Di; Ascenzioni, Fiorentina

    2015-01-01

    Microbial Fuel cells (MFCs) have been proposed for nutrient removal and energy recovery from different wastes. In this study the anaerobic digestate was used to feed H-type MFC reactors, one with a graphite anode preconditioned with Geobacter sulfurreducens and the other with an unconditioned graphite anode. The data demonstrate that the digestate acts as a carbon source, and even in the absence of anode preconditioning, electroactive bacteria colonise the anodic chamber, producing a maximum power density of 172.2 mW/m2. The carbon content was also reduced by up to 60%, while anaerobic ammonium oxidation (anammox) bacteria, which were found in the anodic compartment of the reactors, contributed to nitrogen removal from the digestate. Overall, these results demonstrate that MFCs can be used to recover anammox bacteria from natural sources, and it may represent a promising bioremediation unit in anaerobic digestor plants for the simultaneous nitrogen removal and electricity generation using digestate as substrate. PMID:26273609

  9. Perfluorinated quaternary ammonium salts of polyoxometalate anions: Fluorous biphasic oxidation catalysis with and without fluorous solvents

    SciTech Connect

    Maayan, Galia; Fish, Richard H.; Neumann, Ronny

    2003-05-28

    Perfluorinated quaternary ammonium cations, [CF{sub 3}(CF{sub 2}){sub 7}(CH{sub 2}){sub 3}]{sub 3}CH{sub 3}N{sup +} (RFN{sup +}), were synthesized and used as counter cations for the [WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW{sub 9}O{sub 34}){sub 2}]{sup 12-} (M = Mn(II), Zn(II)), polyoxometalate. The (RFN{sup +}){sub 12}[WZnM{sub 2}(H{sub 2}O){sub 2}(ZnW9O{sub 34}){sub 2}] compounds were fluorous biphasic catalysts for alcohol and alkenol oxidation, and alkene epoxidation with aqueous hydrogen peroxide. Reaction protocols with or without a fluorous solvent were tested. The catalytic activity and selectivity was affected both by the hydrophobicity of the solvent and the substrate.

  10. Suppression of anaerobic ammonium oxidizers under high organic content in high-rate Anammox UASB reactor.

    PubMed

    Tang, Chong-jian; Zheng, Ping; Wang, Cai-hua; Mahmood, Qaisar

    2010-03-01

    The effect of organic matter on the nitrogen removal performance of anaerobic ammonium oxidation (Anammox) process was investigated in an upflow anaerobic sludge blanket (UASB) reactor fed with nitrogen loading rate of 13.92 kg Nm(-3)day(-1) at an HRT of 0.83 h. Mass balance showed that the heterotrophic denitrification prevailed in the UASB reactor, and became the dominant reactions when high influent COD/NO(2)(-)-N ratios of 2.92 were applied. The Anammox bacterial growth was significantly suppressed by denitrifying communities under high organic matter content due to the weaker competition for nitrite (electron acceptor) and living space. Long-term operation of the Anammox UASB reactor under relatively high organic content resulted in weak recovery performance.

  11. The optical constants of several atmospheric aerosol species - Ammonium sulfate, aluminum oxide, and sodium chloride

    NASA Technical Reports Server (NTRS)

    Toon, O. B.; Pollack, J. B.; Khare, B. N.

    1976-01-01

    An investigation is conducted of problems which are related to a use of measured optical constants in the simulation of the optical constants of real atmospheric aerosols. The techniques of measuring optical constants are discussed, taking into account transmission measurements through homogeneous and inhomogeneous materials, the immersion of a material in a liquid of a known refractive index, the consideration of the minimum deviation angle of prism measurement, the interference of multiply reflected light, reflectivity measurements, and aspects of mathematical analysis. Graphs show the real and the imaginary part of the refractive index as a function of wavelength for aluminum oxide, NaCl, and ammonium sulfate. Tables are provided for the dispersion parameters and the optical constants.

  12. Integral approaches to wastewater treatment plant upgrading for odor prevention: Activated Sludge and Oxidized Ammonium Recycling.

    PubMed

    Estrada, José M; Kraakman, N J R; Lebrero, R; Muñoz, R

    2015-11-01

    Traditional physical/chemical end-of-the-pipe technologies for odor abatement are relatively expensive and present high environmental impacts. On the other hand, biotechnologies have recently emerged as cost-effective and environmentally friendly alternatives but are still limited by their investment costs and land requirements. A more desirable approach to odor control is the prevention of odorant formation before being released to the atmosphere, but limited information is available beyond good design and operational practices of the wastewater treatment process. The present paper reviews two widely applicable and economic alternatives for odor control, Activated Sludge Recycling (ASR) and Oxidized Ammonium Recycling (OAR), by discussing their fundamentals, key operating parameters and experience from the available pilot and field studies. Both technologies present high application potential using readily available plant by-products with a minimum plant upgrading, and low investment and operating costs, contributing to the sustainability and economic efficiency of odor control at wastewater treatment facilities. PMID:26316402

  13. Nitrated graphene oxide and its catalytic activity in thermal decomposition of ammonium perchlorate

    SciTech Connect

    Zhang, Wenwen; Luo, Qingping; Duan, Xiaohui; Zhou, Yong; Pei, Chonghua

    2014-02-01

    Highlights: • The NGO was synthesized by nitrifying homemade GO. • The N content of resulted NGO is up to 1.45 wt.%. • The NGO can facilitate the decomposition of AP and release much heat. - Abstract: Nitrated graphene oxide (NGO) was synthesized by nitrifying homemade GO with nitro-sulfuric acid. Fourier transform infrared spectroscopy (FTIR), laser Raman spectroscopy, CP/MAS {sup 13}C NMR spectra and X-ray photoelectron spectroscopy (XPS) were used to characterize the structure of NGO. The thickness and the compositions of GO and NGO were analyzed by atomic force microscopy (AFM) and elemental analysis (EA), respectively. The catalytic effect of the NGO for the thermal decomposition of ammonium perchlorate (AP) was investigated by differential scanning calorimetry (DSC). Adding 10% of NGO to AP decreases the decomposition temperature by 106 °C and increases the apparent decomposition heat from 875 to 3236 J/g.

  14. Lysozyme and Penicillin Inhibit the Growth of Anaerobic Ammonium-Oxidizing Planctomycetes

    PubMed Central

    Hu, Ziye; van Alen, Theo; Jetten, Mike S. M.

    2013-01-01

    Anaerobic ammonium-oxidizing (anammox) planctomycetes oxidize ammonium in the absence of molecular oxygen with nitrite as the electron acceptor. Although planctomycetes are generally assumed to lack peptidoglycan in their cell walls, recent genome data imply that the anammox bacteria have the genes necessary to synthesize peptidoglycan-like cell wall structures. In this study, we investigated the effects of two antibacterial agents that target the integrity and synthesis of peptidoglycan (lysozyme and penicillin G) on the anammox bacterium Kuenenia stuttgartiensis. The effects of these compounds were determined in both short-term batch incubations and long-term (continuous-cultivation) growth experiments in membrane bioreactors. Lysozyme at 1 g/liter (20 mM EDTA) lysed anammox cells in less than 60 min, whereas penicillin G did not have any observable short-term effects on anammox activity. Penicillin G (0.5, 1, and 5 g/liter) reversibly inhibited the growth of anammox bacteria in continuous-culture experiments. Furthermore, transcriptome analyses of the penicillin G-treated reactor and the control reactor revealed that penicillin G treatment resulted in a 10-fold decrease in the ribosome levels of the cells. One of the cell division proteins (Kustd1438) was downregulated 25-fold. Our results suggested that anammox bacteria contain peptidoglycan-like components in their cell wall that can be targeted by lysozyme and penicillin G-sensitive proteins were involved in their synthesis. Finally, we showed that a continuous membrane reactor system with free-living planktonic cells was a very powerful tool to study the physiology of slow-growing microorganisms under physiological conditions. PMID:24096424

  15. Lysozyme and penicillin inhibit the growth of anaerobic ammonium-oxidizing planctomycetes.

    PubMed

    Hu, Ziye; van Alen, Theo; Jetten, Mike S M; Kartal, Boran

    2013-12-01

    Anaerobic ammonium-oxidizing (anammox) planctomycetes oxidize ammonium in the absence of molecular oxygen with nitrite as the electron acceptor. Although planctomycetes are generally assumed to lack peptidoglycan in their cell walls, recent genome data imply that the anammox bacteria have the genes necessary to synthesize peptidoglycan-like cell wall structures. In this study, we investigated the effects of two antibacterial agents that target the integrity and synthesis of peptidoglycan (lysozyme and penicillin G) on the anammox bacterium Kuenenia stuttgartiensis. The effects of these compounds were determined in both short-term batch incubations and long-term (continuous-cultivation) growth experiments in membrane bioreactors. Lysozyme at 1 g/liter (20 mM EDTA) lysed anammox cells in less than 60 min, whereas penicillin G did not have any observable short-term effects on anammox activity. Penicillin G (0.5, 1, and 5 g/liter) reversibly inhibited the growth of anammox bacteria in continuous-culture experiments. Furthermore, transcriptome analyses of the penicillin G-treated reactor and the control reactor revealed that penicillin G treatment resulted in a 10-fold decrease in the ribosome levels of the cells. One of the cell division proteins (Kustd1438) was downregulated 25-fold. Our results suggested that anammox bacteria contain peptidoglycan-like components in their cell wall that can be targeted by lysozyme and penicillin G-sensitive proteins were involved in their synthesis. Finally, we showed that a continuous membrane reactor system with free-living planktonic cells was a very powerful tool to study the physiology of slow-growing microorganisms under physiological conditions. PMID:24096424

  16. Oxidative stress in spring barley and common radish exposed to quaternary ammonium salts with hexafluorophosphate anion.

    PubMed

    Biczak, Robert; Telesiński, Arkadiusz; Pawłowska, Barbara

    2016-10-01

    Quaternary ammonium salts (QAS), including ionic liquids (ILs), constitute a huge group of substances, which due to their desirable physical and chemical properties still attracts great interest in many industrial sectors. An increased concentration of this compound in the environment may lead to the contamination of the natural environment and may pose a potential threat to all organisms, including terrestrial higher plants. The present study demonstrates the interaction of three QAS with PF6(-) anions - tetramethylammonium [TMA][PF6], tetrabutylammonium [TBA][PF6], and tetrahexylammonium [THA][PF6] hexafluorophosphates - and its impact on the physiological and biochemical changes in spring barley seedlings and common radish plants. A similar study was also carried out by introducing the inorganic salt - ammonium hexafluorophosphate [A][PF6] to the soil; the results showed the soil became highly toxic to both plants. All the salts used led to significant changes in the metabolism of both spring barley and common radish which can be evidenced, for example, by a decrease in the content of chlorophyll a (Chla), chlorophyll b (Chlb), and total chlorophyll (Chla + b), as well as carotenoids (Car). The decrease in assimilation pigments was linearly correlated with an increasing concentration of QAS in the soil. QAS and [A][PF6] led to the formation of oxidative stress in both experimental plants, as evidenced by an increase in malondialdehyde (MDA) content in their cells and the changes in H2O2 level. In response to stress, the plants synthesized enzymatic free radicals (ROS) scavengers that lead to changes in the activity of superoxide dismutase (SOD) and catalase (CAT), as well as significantly increased peroxidase (POD) activity. A decrease in the content of assimilation pigments and an increased POD activity are the most reliable indices of oxidative stress, and concurrently the signs of premature plants aging. Common radish proved to be more resistant to the

  17. Aerobic and anaerobic methane oxidation in terrestrial mud volcanoes in the Northern Apennines

    NASA Astrophysics Data System (ADS)

    Wrede, C.; Brady, S.; Rockstroh, S.; Dreier, A.; Kokoschka, S.; Heinzelmann, S. M.; Heller, C.; Reitner, J.; Taviani, M.; Daniel, R.; Hoppert, M.

    2012-07-01

    Methane oxidizing prokaryotes are ubiquitous in oxic and anoxic habitats wherever C1-compounds are present. Thus, methane saturated mud volcano fluids should be a preferred habitat of methane consuming prokaryotes, using the readily available electron donors. In order to understand the relevance of methane as a carbon and energy source in mud volcano communities, we investigate the diversity of prokaryotic organisms involved in oxidation of methane in fluid samples from the Salse di Nirano mud volcano field situated in the Northern Apennines. Cell counts were at approximately 0.7 × 106 microbial cells/ml. A fraction of the microbial biomass was identified as ANME (anaerobic methanotroph) archaea by fluorescence in situ hybridization (FISH) analysis. They are associated in densely colonized flakes, of some tens of μm in diameter, embedded in a hyaline matrix. Diversity analysis based on the 16S rDNA genes, retrieved from amplified and cloned environmental DNA, revealed a high proportion of archaea, involved in anaerobic oxidation of methane (AOM). Aerobic methane-oxidizing proteobacteria could be highly enriched from mud volcano fluids, indicating the presence of aerobic methanotrophic bacteria, which may contribute to methane oxidation, whenever oxygen is readily available. The results imply that biofilms, dominated by ANME archaea, colonize parts of the mud volcano venting system.

  18. Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

    SciTech Connect

    Deng, Yi; Zhang, Guanghui; Qi, Xiaotian; Liu, Chao; Miller, Jeffrey T.; Kropf, A. Jeremy; Bunel, Emilio E.; Lan, Yu; Lei, Aiwen

    2015-01-01

    In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

  19. Denitrification and nitric oxide reduction in an aerobic toluene-treating biofilter

    SciTech Connect

    Plessis, C.A. du; Kinney, K.A.; Schroeder, E.D.; Chang, D.P.Y.; Scow, K.M.

    1998-05-20

    The presence of significant denitrification activity in an aerobic toluene-treating biofilter was demonstrated under batch and flow-through conditions. N{sub 2}O concentrations of 9.2 ppm{sub v} were produced by denitrifying bacteria in the presence of 15% acetylene, in a flow-through system with a bulk gas phase O{sub 2} concentration of >17%. The carbon source for denitrification was not toluene but a byproduct or metabolite of toluene catabolism. Denitrification conditions were successfully used for the reduction of 60 ppm{sub v} nitric oxide to 15 ppm{sub v} at a flow rate of 3 L/min (EBRT of 3 min) in a fully aerated, 17%/v/v O{sub 2} (superficially aerobic) biofilter. Higher NO removal efficiency (97%) was obtained by increasing the toluene supply to the biofilter.

  20. [Effects of urease and nitrification inhibitors on alleviating the oxidation and leaching of soil urea's hydrolyzed product ammonium].

    PubMed

    Chen, Zhenhua; Chen, Lijun; Wu, Zhijie

    2005-02-01

    With simulation test of in-situ soil column, this paper studied the effects of urease inhibitor hydroquinone (HQ), nitrification inhibitors coated calcium carbide (ECC) and dicyandiamide (DCD),and their different combinations on the persistence, oxidation, and leaching of soil urea's hydrolyzed product ammonium. The results showed that compared with other treatments, the combination of HQ and DCD could effectively inhibit the oxidation of the ammonium, and make it as exchangeable form reserve in soil in a larger amount and a longer period. The inhibition of this oxidation not only decreased the accumulation of oxidized product NO3- in soil, but also decreased the potential of NO3- leaching, making the NO3- only leach to 5-10 cm in depth, and the leached amount significantly decreased. PMID:15852915

  1. [Effects of urease and nitrification inhibitors on alleviating the oxidation and leaching of soil urea's hydrolyzed product ammonium].

    PubMed

    Chen, Zhenhua; Chen, Lijun; Wu, Zhijie

    2005-02-01

    With simulation test of in-situ soil column, this paper studied the effects of urease inhibitor hydroquinone (HQ), nitrification inhibitors coated calcium carbide (ECC) and dicyandiamide (DCD),and their different combinations on the persistence, oxidation, and leaching of soil urea's hydrolyzed product ammonium. The results showed that compared with other treatments, the combination of HQ and DCD could effectively inhibit the oxidation of the ammonium, and make it as exchangeable form reserve in soil in a larger amount and a longer period. The inhibition of this oxidation not only decreased the accumulation of oxidized product NO3- in soil, but also decreased the potential of NO3- leaching, making the NO3- only leach to 5-10 cm in depth, and the leached amount significantly decreased.

  2. An efficient, regioselective amination of 3,5-disubstituted pyridine N-oxides using saccharin as an ammonium surrogate.

    PubMed

    Farrell, Robert P; Silva Elipe, Maria Victoria; Bartberger, Michael D; Tedrow, Jason S; Vounatsos, Filisaty

    2013-01-01

    A process for the regioselective amination of unsymmetrical 3,5-substituted pyridine N-oxides has been developed utilizing cheap, readily available saccharin as an ammonium surrogate. High conversions of the corresponding saccharin adducts have been achieved under mild reaction conditions. In situ deprotection under acidic conditions allows for a one-pot process to substituted aminopyridines. High regioselectivities were obtained from a variety of 3,5-disubstituted pyridine N-oxides.

  3. Inhibition of anaerobic ammonium oxidizing (anammox) enrichment cultures by substrates, metabolites and common wastewater constituents.

    PubMed

    Carvajal-Arroyo, José M; Sun, Wenjie; Sierra-Alvarez, Reyes; Field, Jim A

    2013-03-01

    Anaerobic ammonium oxidation (anammox) is an emerging technology for nitrogen removal that provides a more environmentally sustainable and cost effective alternative compared to conventional biological treatment methods. The objective of this study was to investigate the inhibitory impact of anammox substrates, metabolites and common wastewater constituents on the microbial activity of two different anammox enrichment cultures (suspended and granular), both dominated by bacteria from the genus Brocadia. Inhibition was evaluated in batch assays by comparing the N(2) production rates in the absence or presence of each compound supplied in a range of concentrations. The optimal pH was 7.5 and 7.3 for the suspended and granular enrichment cultures, respectively. Among the substrates or products, ammonium and nitrate caused low to moderate inhibition, whereas nitrite caused almost complete inhibition at concentrations higher than 15 mM. The intermediate, hydrazine, either stimulated or caused low inhibition of anammox activity up to 3mM. Of the common constituents in wastewater, hydrogen sulfide was the most severe inhibitor, with 50% inhibitory concentrations (IC(50)) as low as 0.03 mM undissociated H(2)S. Dissolved O(2) showed moderate inhibition (IC(50)=2.3-3.8 mg L(-1)). In contrast, phosphate and salinity (NaCl) posed very low inhibition. The suspended- and granular anammox enrichment cultures had similar patterns of response to the various inhibitory stresses with the exception of phosphate. The findings of this study provide comprehensive insights on the tolerance of the anammox process to a wide variety of potential inhibiting compounds.

  4. Molecular Detection of Anaerobic Ammonium-Oxidizing (Anammox) Bacteria in High-Temperature Petroleum Reservoirs

    PubMed Central

    Li, Hui; Chen, Shuo; Mu, Bo-Zhong

    2010-01-01

    Anaerobic ammonium-oxidizing (anammox) process plays an important role in the nitrogen cycle of the worldwide anoxic and mesophilic habitats. Recently, the existence and activity of anammox bacteria have been detected in some thermophilic environments, but their existence in the geothermal subterranean oil reservoirs is still not reported. This study investigated the abundance, distribution and functional diversity of anammox bacteria in nine out of 17 high-temperature oil reservoirs by molecular ecology analysis. High concentration (5.31–39.2 mg l−1) of ammonium was detected in the production water from these oilfields with temperatures between 55°C and 75°C. Both 16S rRNA and hzo molecular biomarkers indicated the occurrence of anammox bacteria in nine out of 17 samples. Most of 16S rRNA gene phylotypes are closely related to the known anammox bacterial genera Candidatus Brocadia, Candidatus Kuenenia, Candidatus Scalindua, and Candidatus Jettenia, while hzo gene phylotypes are closely related to the genera Candidatus Anammoxoglobus, Candidatus Kuenenia, Candidatus Scalindua, and Candidatus Jettenia. The total bacterial and anammox bacterial densities were 6.4 ± 0.5 × 103 to 2.0 ± 0.18 × 106 cells ml−1 and 6.6 ± 0.51 × 102 to 4.9 ± 0.36 × 104 cell ml−1, respectively. The cluster I of 16S rRNA gene sequences showed distant identity (<92%) to the known Candidatus Scalindua species, inferring this cluster of anammox bacteria to be a new species, and a tentative name Candidatus “Scalindua sinooilfield” was proposed. The results extended the existence of anammox bacteria to the high-temperature oil reservoirs. PMID:20740282

  5. Electron Shuttles Enhance Anaerobic Ammonium Oxidation Coupled to Iron(III) Reduction.

    PubMed

    Zhou, Guo-Wei; Yang, Xiao-Ru; Li, Hu; Marshall, Christopher W; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

    2016-09-01

    Anaerobic ammonium oxidation coupled to iron(III) reduction, termed Feammox, is a newly discovered nitrogen cycling process. However, little is known about the roles of electron shuttles in the Feammox reactions. In this study, two forms of Fe(III) (oxyhydr)oxide ferrihydrite (ex situ ferrihydrite and in situ ferrihydrite) were used in dissimilatory Fe(III) reduction (DIR) enrichments from paddy soil. Evidence for Feammox in DIR enrichments was demonstrated using the (15)N-isotope tracing technique. The extent and rate of both the (30)N2-(29)N2 and Fe(II) formation were enhanced when amended with electron shuttles (either 9,10-anthraquinone-2,6-disulfonate (AQDS) or biochar) and further simulated when these two shuttling compounds were combined. Although the Feammox-associated Fe(III) reduction accounted for only a minor proportion of total Fe(II) formation compared to DIR, it was estimated that the potentially Feammox-mediated N loss (0.13-0.48 mg N L(-1) day(-1)) was increased by 17-340% in the enrichments by the addition of electron shuttles. The addition of electron shuttles led to an increase in the abundance of unclassified Pelobacteraceae, Desulfovibrio, and denitrifiers but a decrease in Geobacter. Overall, we demonstrated a stimulatory effect of electron shuttles on Feammox that led to higher N loss, suggesting that electron shuttles might play a crucial role in Feammox-mediated N loss from soils. PMID:27494694

  6. Potential roles of anaerobic ammonium and methane oxidation in the nitrogen cycle of wetland ecosystems.

    PubMed

    Zhu, Guibing; Jetten, Mike S M; Kuschk, Peter; Ettwig, Katharina F; Yin, Chengqing

    2010-04-01

    Anaerobic ammonium oxidation (anammox) and anaerobic methane oxidation (ANME coupled to denitrification) with nitrite as electron acceptor are two of the most recent discoveries in the microbial nitrogen cycle. Currently the anammox process has been relatively well investigated in a number of natural and man-made ecosystems, while ANME coupled to denitrification has only been observed in a limited number of freshwater ecosystems. The ubiquitous presence of anammox bacteria in marine ecosystems has changed our knowledge of the global nitrogen cycle. Up to 50% of N(2) production in marine sediments and oxygen-depleted zones may be attributed to anammox bacteria. However, there are only few indications of anammox in natural and constructed freshwater wetlands. In this paper, the potential role of anammox and denitrifying methanotrophic bacteria in natural and artificial wetlands is discussed in relation to global warming. The focus of the review is to explore and analyze if suitable environmental conditions exist for anammox and denitrifying methanotrophic bacteria in nitrogen-rich freshwater wetlands.

  7. Electron Shuttles Enhance Anaerobic Ammonium Oxidation Coupled to Iron(III) Reduction.

    PubMed

    Zhou, Guo-Wei; Yang, Xiao-Ru; Li, Hu; Marshall, Christopher W; Zheng, Bang-Xiao; Yan, Yu; Su, Jian-Qiang; Zhu, Yong-Guan

    2016-09-01

    Anaerobic ammonium oxidation coupled to iron(III) reduction, termed Feammox, is a newly discovered nitrogen cycling process. However, little is known about the roles of electron shuttles in the Feammox reactions. In this study, two forms of Fe(III) (oxyhydr)oxide ferrihydrite (ex situ ferrihydrite and in situ ferrihydrite) were used in dissimilatory Fe(III) reduction (DIR) enrichments from paddy soil. Evidence for Feammox in DIR enrichments was demonstrated using the (15)N-isotope tracing technique. The extent and rate of both the (30)N2-(29)N2 and Fe(II) formation were enhanced when amended with electron shuttles (either 9,10-anthraquinone-2,6-disulfonate (AQDS) or biochar) and further simulated when these two shuttling compounds were combined. Although the Feammox-associated Fe(III) reduction accounted for only a minor proportion of total Fe(II) formation compared to DIR, it was estimated that the potentially Feammox-mediated N loss (0.13-0.48 mg N L(-1) day(-1)) was increased by 17-340% in the enrichments by the addition of electron shuttles. The addition of electron shuttles led to an increase in the abundance of unclassified Pelobacteraceae, Desulfovibrio, and denitrifiers but a decrease in Geobacter. Overall, we demonstrated a stimulatory effect of electron shuttles on Feammox that led to higher N loss, suggesting that electron shuttles might play a crucial role in Feammox-mediated N loss from soils.

  8. Anaerobic ammonium oxidation by nitrite (anammox): Implications for N 2 production in coastal marine sediments

    NASA Astrophysics Data System (ADS)

    Engström, Pia; Dalsgaard, Tage; Hulth, Stefan; Aller, Robert C.

    2005-04-01

    The respiratory reduction of nitrate (denitrification) is acknowledged as the most important process that converts biologically available nitrogen to gaseous dinitrogen (N 2) in marine ecosystems. Recent findings, however, indicate that anaerobic ammonium oxidation by nitrite (anammox) may be an important pathway for N 2 formation and N removal in coastal marine sediments and in anoxic water columns of the oceans. In the present study, we explored this novel mechanism during N mineralization by 15N amendments (single and coupled additions of 15NH 4+, 14NO 3- and 15NO 3-) to surface sediments with a wide range of characteristics and overall reactivity. Patterns of 29/30N 2 production in the pore water during closed sediment incubations demonstrated anammox at all 7 of the investigated sites. Stoichiometric calculations revealed that 4% to 79% of total N 2 production was due to this novel route. The relative importance of anammox for N 2 release was inversely correlated with remineralized solute production, benthic O 2 consumption, and surface sediment Chl a. The observed correlations indicate competition between reductants for pore water nitrite during early diagenesis and that additional factors (e.g. availability of Mn-oxides), superimposed on overall patterns of diagenetic activity, are important for determining absolute and relative rates of anammox in coastal marine sediments.

  9. Hydroxylamine-dependent anaerobic ammonium oxidation (anammox) by "Candidatus Brocadia sinica".

    PubMed

    Oshiki, Mamoru; Ali, Muhammad; Shinyako-Hata, Kaori; Satoh, Hisashi; Okabe, Satoshi

    2016-09-01

    Although metabolic pathways and associated enzymes of anaerobic ammonium oxidation (anammox) of 'Ca. Kuenenia stuttgartiensis' have been studied, those of other anammox bacteria are still poorly understood. NO2- reduction to NO is considered to be the first step in the anammox metabolism of 'Ca. K. stuttgartiensis', however, 'Ca. Brocadia' lacks the genes that encode canonical NO-forming nitrite reductases (NirS or NirK) in its genome, which is different from 'Ca. K. stuttgartiensis'. Here, we studied the anammox metabolism of 'Ca. Brocadia sinica'. (15) N-tracer experiments demonstrated that 'Ca. B. sinica' cells could reduce NO2- to NH2 OH, instead of NO, with as yet unidentified nitrite reductase(s). Furthermore, N2 H4 synthesis, downstream reaction of NO2- reduction, was investigated using a purified 'Ca. B. sinica' hydrazine synthase (Hzs) and intact cells. Both the 'Ca. B. sinica' Hzs and cells utilized NH2 OH and NH4+, but not NO and NH4+, for N2 H4 synthesis and further oxidized N2 H4 to N2 gas. Taken together, the metabolic pathway of 'Ca. B. sinica' is NH2 OH-dependent and different from the one of 'Ca. K. stuttgartiensis', indicating metabolic diversity of anammox bacteria.

  10. Diversity and distribution of planktonic anaerobic ammonium-oxidizing bacteria in the Dongjiang River, China.

    PubMed

    Sun, Wei; Xia, Chunyu; Xu, Meiying; Guo, Jun; Wang, Aijie; Sun, Guoping

    2014-12-01

    Anaerobic ammonium-oxidizing (anammox) process has recently been recognized as an important pathway for removing fixed nitrogen (N) from aquatic ecosystems. Anammox organisms are widely distributed in freshwater environments. However, little is known about their presence in the water column of riverine ecosystems. Here, the existence of a diverse anammox community was revealed in the water column of the Dongjiang River by analyzing 16S rRNA and hydrazine oxidation (hzo) genes of anammox bacteria. Phylogenetic analyses of hzo genes showed that Candidatus Jettenia related clades of anammox bacteria were dominant in the river, suggesting the ecological microniche distinction from freshwater/estuary and marine anammox bacteria with Ca. Brocadia and Kuenenia genera mainly detected in freshwater/estuary ecosystems, and Ca. Scalindua genus mainly detected in marine ecosystems. The abundance and diversity of anammox bacteria along the river were both significantly correlated with concentrations of NH4(+)-N based on Pearson and partial correlation analyses. Redundancy analyses showed the contents of NH4(+)-N, NO3(-)-N and the ratio of NH4(+)-N to NO2(-)-N significantly influenced the spatial distributions of anammox bacteria in the water column of the Dongjiang River. These results expanded our understanding of the distribution and potential roles of anammox bacteria in the water column of the river ecosystem.

  11. Hydroxylamine-dependent anaerobic ammonium oxidation (anammox) by "Candidatus Brocadia sinica".

    PubMed

    Oshiki, Mamoru; Ali, Muhammad; Shinyako-Hata, Kaori; Satoh, Hisashi; Okabe, Satoshi

    2016-09-01

    Although metabolic pathways and associated enzymes of anaerobic ammonium oxidation (anammox) of 'Ca. Kuenenia stuttgartiensis' have been studied, those of other anammox bacteria are still poorly understood. NO2- reduction to NO is considered to be the first step in the anammox metabolism of 'Ca. K. stuttgartiensis', however, 'Ca. Brocadia' lacks the genes that encode canonical NO-forming nitrite reductases (NirS or NirK) in its genome, which is different from 'Ca. K. stuttgartiensis'. Here, we studied the anammox metabolism of 'Ca. Brocadia sinica'. (15) N-tracer experiments demonstrated that 'Ca. B. sinica' cells could reduce NO2- to NH2 OH, instead of NO, with as yet unidentified nitrite reductase(s). Furthermore, N2 H4 synthesis, downstream reaction of NO2- reduction, was investigated using a purified 'Ca. B. sinica' hydrazine synthase (Hzs) and intact cells. Both the 'Ca. B. sinica' Hzs and cells utilized NH2 OH and NH4+, but not NO and NH4+, for N2 H4 synthesis and further oxidized N2 H4 to N2 gas. Taken together, the metabolic pathway of 'Ca. B. sinica' is NH2 OH-dependent and different from the one of 'Ca. K. stuttgartiensis', indicating metabolic diversity of anammox bacteria. PMID:27112128

  12. Climatic thresholds for pedogenic iron oxides under aerobic conditions: Processes and their significance in paleoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Long, Xiaoyong; Ji, Junfeng; Barrón, Vidal; Torrent, José

    2016-10-01

    Iron oxides are widely distributed across the surface of the Earth as a result of the aerobic weathering of primary Fe-bearing minerals. Pedogenic iron oxides which consist mainly of hematite (Hm), goethite (Gt), maghemite (Mgh), are often concentrated synchronously in aerobic soils under low to moderate rainfall regimes. Magnetic susceptibility (χ) and redness, which respectively reflect the content of Mgh and Hm in soils, are considered reasonable pedogenic and climatic indicators in soil taxonomy and paleorainfall reconstruction. However, under high rainfall regimes, the grain growth of Mgh and transformation to Hm, combined with the prior formation of Gt under conditions of high relative humidity (RH), can result in magnetic reduction and dramatic yellowing of soils and sediments, which explains the existence of rainfall thresholds for Mgh and Hm at a large scale even before the pedogenic environment turns anaerobic. In order to capture the rainfall thresholds for Mgh and Hm occurring under aerobic conditions, we explored a tropical transect across a granitic region where the soil color turned from red to yellow under a wide rainfall range of 900-2200 mm/yr and a corresponding mean annual RH range of 77%-85%. We observed a lower rainfall threshold of ∼1500 mm/yr and a corresponding RH ∼80% for Mgh and Hm along this transect, as well as a higher rainfall threshold of ∼1700 mm/yr and a corresponding RH of ∼81% for Gt and total pedogenic iron oxides (citrate/bicarbonate/dithionite-extractable Fe, Fed). Cross-referencing with comparable studies in temperate and subtropical regions, we noted that the rainfall or RH thresholds for Fed and Hm or Mgh likewise increase with temperature. Moreover, the different thresholds for total and individual iron oxide phase indicates that a negative correlation between chemical weathering intensity and redness or χ in sediment sequences can occur under the prevalent climate regime just between their thresholds. Finally

  13. Quaternary Ammonium Oxidative Demethylation: X-ray Crystallographic, Resonance Raman and UV-visible Spectroscopic Analysis of a Rieske-type Demethylase

    SciTech Connect

    Daughtry K. D.; Orville A.; Xiao, Y.; Stoner-Ma, D.; Cho, E.; Liu, P.; Allen, K. N.

    2012-02-01

    Herein, the structure resulting from in situ turnover in a chemically challenging quaternary ammonium oxidative demethylation reaction was captured via crystallographic analysis and analyzed via single-crystal spectroscopy. Crystal structures were determined for the Rieske-type monooxygenase, stachydrine demethylase, in the unliganded state (at 1.6 {angstrom} resolution) and in the product complex (at 2.2 {angstrom} resolution). The ligand complex was obtained from enzyme aerobically cocrystallized with the substrate stachydrine (N,N-dimethylproline). The ligand electron density in the complex was interpreted as proline, generated within the active site at 100 K by the absorption of X-ray photon energy and two consecutive demethylation cycles. The oxidation state of the Rieske iron-sulfur cluster was characterized by UV-visible spectroscopy throughout X-ray data collection in conjunction with resonance Raman spectra collected before and after diffraction data. Shifts in the absorption band wavelength and intensity as a function of absorbed X-ray dose demonstrated that the Rieske center was reduced by solvated electrons generated by X-ray photons; the kinetics of the reduction process differed dramatically for the liganded complex compared to unliganded demethylase, which may correspond to the observed turnover in the crystal.

  14. Evidence of Nitrogen Loss from Anaerobic Ammonium Oxidation Coupled with Ferric Iron Reduction in an Intertidal Wetland.

    PubMed

    Li, Xiaofei; Hou, Lijun; Liu, Min; Zheng, Yanling; Yin, Guoyu; Lin, Xianbiao; Cheng, Lv; Li, Ye; Hu, Xiaoting

    2015-10-01

    Anaerobic ammonium oxidation coupled with nitrite reduction is an important microbial pathway of nitrogen removal in intertidal wetlands. However, little is known about the role of anaerobic ammonium oxidation coupled with ferric iron reduction (termed Feammox) in intertidal nitrogen cycling. In this study, sediment slurry incubation experiments were combined with an isotope-tracing technique to examine the dynamics of Feammox and its association with tidal fluctuations in the intertidal wetland of the Yangtze Estuary. Feammox was detected in the intertidal wetland sediments, with potential rates of 0.24-0.36 mg N kg(-1) d(-1). The Feammox rates in the sediments were generally higher during spring tides than during neap tides. The tidal fluctuations affected the growth of iron-reducing bacteria and reduction of ferric iron, which mediated Feammox activity and the associated nitrogen loss from intertidal wetlands to the atmosphere. An estimated loss of 11.5-18 t N km(-2) year(-1) was linked to Feammox, accounting for approximately 3.1-4.9% of the total external inorganic nitrogen transported into the Yangtze Estuary wetland each year. Overall, the co-occurrence of ferric iron reduction and ammonium oxidation suggests that Feammox can act as an ammonium removal mechanism in intertidal wetlands.

  15. Characterization of incubation experiments and development of an enrichment culture capable of ammonium oxidation under iron reducing conditions

    NASA Astrophysics Data System (ADS)

    Huang, S.; Jaffé, P. R.

    2014-08-01

    Incubation experiments were conducted using soil samples from a forested riparian wetland where we have previously observed anaerobic ammonium oxidation coupled to iron reduction. Production of both nitrite and ferrous iron were measured repeatedly during incubations when the soil slurry was supplied with either ferrihydrite or goethite and ammonium chloride. Significant changes in the microbial community were observed after 180 days of incubation as well as in a continuous flow membrane reactor, using 16S rRNA gene PCR-denaturing gradient gel electrophoresis, 454-pyrosequencing, and real-time quantitative PCR analysis. We believe that one of the dominant microbial species in our system (an uncultured Acidimicrobiaceae bacterium A6), belonging to the Acidimicrobiaceae family, whose closest cultivated relative is Ferrimicrobium acidiphilum (with 92% identity) and Acidimicrobium ferrooxidans (with 90% identity), might play a key role in this anaerobic biological process that uses ferric iron as an electron acceptor while oxidizing ammonium to nitrite. After ammonium was oxidized to nitrite, nitrogen loss proceeded via denitrification and/or anammox.

  16. Evidence of Nitrogen Loss from Anaerobic Ammonium Oxidation Coupled with Ferric Iron Reduction in an Intertidal Wetland.

    PubMed

    Li, Xiaofei; Hou, Lijun; Liu, Min; Zheng, Yanling; Yin, Guoyu; Lin, Xianbiao; Cheng, Lv; Li, Ye; Hu, Xiaoting

    2015-10-01

    Anaerobic ammonium oxidation coupled with nitrite reduction is an important microbial pathway of nitrogen removal in intertidal wetlands. However, little is known about the role of anaerobic ammonium oxidation coupled with ferric iron reduction (termed Feammox) in intertidal nitrogen cycling. In this study, sediment slurry incubation experiments were combined with an isotope-tracing technique to examine the dynamics of Feammox and its association with tidal fluctuations in the intertidal wetland of the Yangtze Estuary. Feammox was detected in the intertidal wetland sediments, with potential rates of 0.24-0.36 mg N kg(-1) d(-1). The Feammox rates in the sediments were generally higher during spring tides than during neap tides. The tidal fluctuations affected the growth of iron-reducing bacteria and reduction of ferric iron, which mediated Feammox activity and the associated nitrogen loss from intertidal wetlands to the atmosphere. An estimated loss of 11.5-18 t N km(-2) year(-1) was linked to Feammox, accounting for approximately 3.1-4.9% of the total external inorganic nitrogen transported into the Yangtze Estuary wetland each year. Overall, the co-occurrence of ferric iron reduction and ammonium oxidation suggests that Feammox can act as an ammonium removal mechanism in intertidal wetlands. PMID:26360245

  17. Nitrous oxide: emission from soils during nitrification of fertilizer nitrogen.

    PubMed

    Bremner, J M; Blackmer, A M

    1978-01-20

    Nitrous oxide is released from soils to the atmosphere during nitrification of ammonium and ammonium-producing fertilizers under aerobic conditions as well as by denitrification of nitrate under anaerobic conditions. Emissions of nitrous oxide during nitrification of fertilizer nitrogen may be significant in regard to the potential threat of fertilizer-derived nitrous oxide to the stratospheric ozone layer. Such emissions can be greatly reduced through the use of nitrapyrin, which inhibits nitrification of ammonium by soil microorganisms.

  18. The effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation

    NASA Astrophysics Data System (ADS)

    Daines, Stuart J.; Lenton, Timothy M.

    2016-01-01

    The balance of evidence suggests that oxygenic photosynthesis had evolved by 3.0-2.7 Ga, several hundred million years prior to the Great Oxidation ≈2.4 Ga. Previous work has shown that if oxygenic photosynthesis spread globally prior to the Great Oxidation, this could have supported widespread aerobic ecosystems in the surface ocean, without oxidising the atmosphere. Here we use a suite of models to explore the implications for carbon cycling and the Great Oxidation. We find that recycling of oxygen and carbon within early aerobic marine ecosystems would have restricted the balanced fluxes of methane and oxygen escaping from the ocean, lowering the atmospheric concentration of methane in the Great Oxidation transition and its aftermath. This in turn would have minimised any bi-stability of atmospheric oxygen, by weakening a stabilising feedback on oxygen from hydrogen escape to space. The result would have been a more reversible and probably episodic rise of oxygen at the Great Oxidation transition, consistent with existing geochemical evidence. The resulting drop in methane levels to ≈10 ppm is consistent with climate cooling at the time but adds to the puzzle of what kept the rest of the Proterozoic warm. A key test of the scenario of abundant methanotrophy in oxygen oases before the Great Oxidation is its predicted effects on the organic carbon isotope (δ13Corg) record. Our open ocean general circulation model predicts δC13org ≈ - 30 to -45‰ consistent with most data from 2.65 to 2.45 Ga. However, values of δC13org ≈ - 50 ‰ require an extreme scenario such as concentrated methanotroph production where shelf-slope upwelling of methane-rich water met oxic shelf water.

  19. Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Anthony, K. Walter; Thalasso, F.

    2015-08-01

    Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends mainly on lake CH4 and oxygen (O2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was scarce compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH4 cycling.

  20. Molecular Engineering of Trifunctional Supported Catalysts for the Aerobic Oxidation of Alcohols.

    PubMed

    Fernandes, Antony E; Riant, Olivier; Jensen, Klavs F; Jonas, Alain M

    2016-09-01

    We describe a simple and general method for the preparation and molecular engineering of supported trifunctional catalysts and their application in the representative Cu/TEMPO/NMI-catalyzed aerobic oxidation of benzyl alcohol. The methodology allows in one single step to immobilize, with precise control of surface composition, both pyta, Cu(I) , TEMPO, and NMI sites on azide-functionalized silica particles. To optimize the performance of the heterogeneous trifunctional catalysts, synergistic interactions are finely engineered through modulating the degree of freedom of the imidazole site as well as tuning the relative surface composition, leading to catalysts with an activity significantly superior to the corresponding homogeneous catalytic system.

  1. Molecular Engineering of Trifunctional Supported Catalysts for the Aerobic Oxidation of Alcohols.

    PubMed

    Fernandes, Antony E; Riant, Olivier; Jensen, Klavs F; Jonas, Alain M

    2016-09-01

    We describe a simple and general method for the preparation and molecular engineering of supported trifunctional catalysts and their application in the representative Cu/TEMPO/NMI-catalyzed aerobic oxidation of benzyl alcohol. The methodology allows in one single step to immobilize, with precise control of surface composition, both pyta, Cu(I) , TEMPO, and NMI sites on azide-functionalized silica particles. To optimize the performance of the heterogeneous trifunctional catalysts, synergistic interactions are finely engineered through modulating the degree of freedom of the imidazole site as well as tuning the relative surface composition, leading to catalysts with an activity significantly superior to the corresponding homogeneous catalytic system. PMID:27430481

  2. Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: a highly selective approach to diaryl ketones.

    PubMed

    Ren, Long; Jiao, Ning

    2014-09-01

    A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2 , which makes this method practical for further applications. PMID:24990473

  3. Modeling of simultaneous denitrification--anaerobic digestion--organic matter aerobic oxidation and nitrification in an anoxic-anaerobic-aerobic compact filter reactor.

    PubMed

    Moya, Jaime; Huiliñir, César; Peredo, Karol; Aspé, Estrella; Roeckel, Marlene

    2012-08-31

    A mathematical model was developed for a compact anoxic-anaerobic-aerobic filter reactor with liquid recirculation for the treatment of fishing effluents. The model includes denitrification, anaerobic digestion, aerobic carbon oxidation and nitrification steps, as well as an evaluation of the liquid gas mass transfer and pH. The model was calibrated using one experimental condition at a recycling ratio (R)=10, and was validated with R equal to 2 and 0, with an organic concentration of 554±24 mg TOCL(-1), salinity of 24 g L(-1) and hydraulic retention time (HRT) of 2 d. Carbon total removal is higher than 98%, while maximum nitrogen removal is 62% using total nitrification in the aerobic zone, due to a higher quantity of NO(x) produced which were recirculated to the anoxic zone. In the aerobic zone, simultaneous nitrification and denitrification processes occur, because the diffusion limitations cause a low oxygen penetration in the biofilm. In the anoxic-anaerobic zone, denitrification or methanogenesis inhibition by DO (caused by the recycled oxygen) is not observed.

  4. Microbial Anaerobic Ammonium Oxidation Under Iron Reducing Conditions, Alternative Electron Acceptors

    NASA Astrophysics Data System (ADS)

    Ruiz-Urigüen, M.; Jaffe, P. R.

    2015-12-01

    Autotrophic Acidimicrobiaceae-bacterium named A6 (A6), part of the Actinobacteria phylum have been linked to anaerobic ammonium (NH4+) oxidation under iron reducing conditions. These organisms obtain their energy by oxidizing NH4+ and transferring the electrons to a terminal electron acceptor (TEA). Under environmental conditions, the TEAs are iron oxides [Fe(III)], which are reduced to Fe(II), this process is known as Feammox. Our studies indicate that alternative forms of TEAs can be used by A6, e.g. iron rich clays (i.e. nontronite) and electrodes in bioelectrochemical systems such as Microbial Electrolysis Cells (MECs), which can sustain NH4+removal and A6 biomass production. Our results show that nontronite can support Feammox and promote bacterial cell production. A6 biomass increased from 4.7 x 104 to 3.9 x 105 cells/ml in 10 days. Incubations of A6 in nontronite resulted in up to 10 times more NH4+ removal and 3 times more biomass production than when ferrihydrite is used as the Fe(III) source. Additionally, Fe in nontronite can be reoxidized by aeration and A6 can reutilize it; however, Fe is still finite in the clay. In contrast, in MECs, A6 harvest electrons from NH4+ and use an anode as an unlimited TEA, as a result current is produced. We operated multiple MECs in parallel using a single external power source, as described by Call & Logan (2011). MECs were run with an applied voltage of 0.7V and different growing mediums always containing initial 5mM NH4+. Results show that current production is favored when anthraquinone-2,6-disulfonate (AQDS), an electron shuttled, is present in the medium as it facilitates the transfer of electrons from the bacterial cell to the anode. Additionally, A6 biomass increased from 1 x 104 to 9.77 x 105cells/ml in 14 days of operation. Due to Acidimicrobiaceae-bacterium A6's ability to use various TEAs, MECs represent an alternative, iron-free form, for optimized biomass production of A6 and its application in NH4

  5. Complete genome sequence of Nitrosomonas sp. Is79, an ammonia oxidizing bacterium adapted to low ammonium concentrations

    SciTech Connect

    Bollmann, Annette; Sedlacek, Christopher J; Laanbroek, Hendrikus J; Suwa, Yuichi; Stein, Lisa Y; Klotz, Martin G; Arp, D J; Sayavedra-Soto, LA; Lu, Megan; Bruce, David; Detter, J. Chris; Tapia, Roxanne; Han, James; Woyke, Tanja; Lucas, Susan; Pitluck, Sam; Pennacchio, Len; Nolan, Matt; Land, Miriam L; Huntemann, Marcel; Deshpande, Shweta; Han, Cliff; Chen, Amy; Kyrpides, Nikos C; Mavromatis, K; Markowitz, Victor; Szeto, Ernest; Ivanova, N; Mikhailova, Natalia; Pagani, Ioanna; Pati, Amrita; Peters, Lin; Ovchinnikova, Galina; Goodwin, Lynne A.

    2013-01-01

    Nitrosomonas sp. Is79 is a chemolithoautotrophic ammonia-oxidizing bacterium that belongs to the family Nitrosomonadaceae within the phylum Proteobacteria. Ammonia oxidation is the first step of nitrification, an important process in the global nitrogen cycle ultimately resulting in the production of nitrate. Nitrosomonas sp. Is79 is an ammonia oxidizer of high interest because it is adapted to low ammonium and can be found in freshwater environments around the world. The 3,783,444-bp chromosome with a total of 3,553 protein coding genes and 44 RNA genes was sequenced by the DOE-Joint Genome Institute Program CSP 2006.

  6. Enhancement of anaerobic ammonium oxidation in lake sediment by applying drinking water treatment residuals.

    PubMed

    Wang, Ziyuan; Wang, Changhui; Wang, Zhixin; Pei, Yuansheng

    2013-08-01

    In this study, the effect of drinking water treatment residuals (WTRs), non-hazardous byproducts from drinking water treatment plants, on anaerobic ammonium oxidation (anammox) in lake sediments were investigated, qualitatively and quantitatively based on enrichment tests. The results suggested that after the enrichment, anammox were strengthened significantly in enriched sediments with no WTRs (ESNW) and with WTRs (ESW). Comparatively, anammox bacteria in ESW were more aggregated than ESNW. The activity (9.2 nmol g(-1)h(-1)) and abundance (9.8×10(7)copies g(-1)) of anammox bacteria in ESW were also higher than ESNW (6.1 nmol g(-1)h(-1)and 8.9×10(7) copies g(-1)). Further analysis suggested that after enrichment, anammox bacteria in sediments were phylogenetically more distant from Candidatus Kuenenia; anammox bacteria in ESW were closely related to Candidatus Brocadia. Overall, WTRs promoted aggregation, strengthened activity and increased abundance of anammox bacteria in lake sediments. Therefore, WTRs can enhance anammox in lake sediments.

  7. Importance and controls of anaerobic ammonium oxidation influenced by riverbed geology

    NASA Astrophysics Data System (ADS)

    Lansdown, K.; McKew, B. A.; Whitby, C.; Heppell, C. M.; Dumbrell, A. J.; Binley, A.; Olde, L.; Trimmer, M.

    2016-05-01

    Rivers are an important global sink for excess bioavailable nitrogen: they convert approximately 40% of terrestrial N runoff per year (~47 Tg) to biologically unavailable N2 gas and return it to the atmosphere. At present, riverine N2 production is conceptualized and modelled as denitrification. Anaerobic ammonium oxidation, known as anammox, is an alternative pathway of N2 production important in marine environments, but its contribution to riverine N2 production is not well understood. Here we use in situ and laboratory measurements of anammox activity using 15N tracers and molecular analyses of microbial communities to evaluate anammox in clay-, sand- and chalk-dominated river beds in the Hampshire Avon catchment, UK during summer 2013. Abundance of the hzo gene, which encodes an enzyme central to anammox metabolism, varied across the contrasting geologies. Anammox rates were similar across geologies but contributed different proportions of N2 production because of variation in denitrification rates. In spite of requiring anoxic conditions, anammox, most likely coupled to partial nitrification, contributed up to 58% of in situ N2 production in oxic, permeable riverbeds. In contrast, denitrification dominated in low-permeability clay-bed rivers, where anammox contributes roughly 7% to the production of N2 gas. We conclude that anammox can represent an important nitrogen loss pathway in permeable river sediments.

  8. Evaluation of granular anaerobic ammonium oxidation process for the disposal of pre-treated swine manure.

    PubMed

    Ni, Shou-Qing; Yang, Ning

    2014-01-01

    With rising environmental concerns on potable water safety and eutrophication, increased media attention and tighter environmental regulations, managing animal waste in an environmentally responsible and economically feasible way can be a challenge. In this study, the possibility of using granular anammox process for ammonia removal from swine waste treatment water was investigated. A rapid decrease of NO2 (-)-N and NH4 (+)-N was observed during incubation with wastewater from an activated sludge deodorization reactor and anaerobic digestion-partial oxidation treatment process treating swine manure and its corresponding control artificial wastewaters. Ammonium removal dropped from 98.0 ± 0.6% to 66.9 ± 2.7% and nearly absent when the organic load in the feeding increased from 232 mg COD/L to 1160 mg COD/L and 2320 mg COD/L. The presence of organic carbon had limited effect on nitrite and total nitrogen removal. At a COD to N ratio of 0.9, COD inhibitory organic load threshold concentration was 727 mg COD/L. Mass balance indicated that denitrifiers played an important role in nitrite, nitrate and organic carbon removal. These results demonstrated that anammox system had the potential to effectively treat swine manure that can achieve high nitrogen standards at reduced costs. PMID:24765570

  9. Stoichiometry and kinetics of the anaerobic ammonium oxidation (Anammox) with trace hydrazine addition.

    PubMed

    Yao, Zongbao; Lu, Peili; Zhang, Daijun; Wan, Xinyu; Li, Yulian; Peng, Shuchan

    2015-12-01

    Purpose of this study is to investigate the stoichiometry and kinetics of anaerobic ammonium oxidation (Anammox) with trace hydrazine addition. The stoichiometry was established based on the electron balance of Anammox process with trace N2H4 addition. The stoichiometric coefficients were determined by the proton consumption and the changes in substrates and products. It was found that trace N2H4 addition can increase the yield of Anammox bacteria (AnAOB) and reduce NO3(-) yield, which enhances the Anammox. Subsequently, kinetic model of Anammox with trace N2H4 addition was developed, and the parameters of the anaerobic degradation model of N2H4 were obtained for the first time. The maximum specific substrate utilization rate, half-saturation constant and inhibition constant of N2H4 were 25.09mgN/g VSS/d, 10.42mgN/L and 1393.88mgN/L, respectively. These kinetic parameters might provide important information for the engineering applications of Anammox with trace N2H4 addition.

  10. Nitrous Oxide and Methane Fluxes Following Ammonium Sulfate and Vinasse Application on Sugar Cane Soil.

    PubMed

    Paredes, Debora da S; Alves, Bruno J R; dos Santos, Marco A; Bolonhezi, Denizart; Sant'Anna, Selenobaldo A C; Urquiaga, Segundo; Lima, Magda A; Boddey, Robert M

    2015-09-15

    This study aimed to quantify nitrous oxide (N2O) and methane (CH4) emission/sink response from sugar cane soil treated with fertilizer nitrogen (N) and vinasse applied separately or in sequence, the latter being investigated with regard to the time interval between applications for a possible effect on emissions. The study was carried out in a traditional area of unburned sugar cane in São Paulo state, Brazil. Two levels of N fertilization (0 and 100 kg N ha(-1)) with no added vinasse and combined with vinasse additions at different times (100 m(-3) ha(-1) at 3 and 15 days after N fertilization) were evaluated. Methane and N2O fluxes were monitored for 211 days. On average, the soil was a sink for CH4, which was not affected by the treatments. Emissions of N2O were induced by N fertilizer and vinasse applications. For ammonium sulfate, 0.6% of the added N was emitted as N2O, while for vinasse, this ranged from 1.0 to 2.2%. Changes in N2O fluxes were detected the day after application of vinasse on the N fertilized areas, but although the emission factor (EF) was 34% greater, the EF was not significantly different from fertilizer N alone. Nevertheless, we recommend to not apply vinasse after N fertilization to avoid boosting N2O emissions. PMID:26295867

  11. Dual Action Antimicrobials: Nitric Oxide Release from Quaternary Ammonium-Functionalized Silica Nanoparticles

    PubMed Central

    Carpenter, Alexis W.; Worley, Brittany V.; Slomberg, Danielle L.; Schoenfisch, Mark H.

    2012-01-01

    The synthesis of quaternary ammonium (QA)-functionalized silica nanoparticles with and without nitric oxide (NO) release capabilities is described. Glycidyltrialkylammonium chlorides of varied alkyl chain lengths (i.e., methyl, butyl, octyl, and dodecyl) were tethered to the surface of amine-containing silica nanoparticles via a ring-opening reaction. Secondary amines throughout the particle were then functionalized with N-diazeniumdiolates NO donors to yield dual functional nanomaterials with surface QAs and total NO payloads of ca. 0.3 μmol/mg. The bactericidal activities of singly (i.e., only NO-releasing or only QA-functionalized) and dual (i.e., NO-releasing and QA-functionalized) functional nanoparticles were tested against Grampositive Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa. Particles with only NO release capabilities alone were found to be more effective against P. aeruginosa, while particles with only QA-functionalities exhibited greater toxicity toward S. aureus. The minimum bactericidal concentrations (MBC) of QA-functionalized particles decreased with increasing alkyl chain length against both microbes tested. Combining NO release and QA-functionalities on the same particle resulted in an increase in bactericidal efficacy against S. aureus; however, no change in activity against P. aeruginosa was observed compared to NO-releasing particles alone. PMID:22998760

  12. The contribution of anaerobic ammonium oxidation to nitrogen loss in two temperate eutrophic estuaries

    NASA Astrophysics Data System (ADS)

    Teixeira, Catarina; Magalhães, Catarina; Joye, Samantha B.; Bordalo, Adriano A.

    2014-04-01

    Studies of anaerobic ammonium oxidation (anammox) continue to show the significance of this metabolic pathway for the removal of nitrogen (N) in several natural environments, including estuaries. However, the seasonal dynamics of the anammox process and related environmental controls within estuarine systems remains poorly explored. We evaluated the seasonal anammox activity along a salinity gradient in two temperate Atlantic estuaries, the Ave and the Douro (NW Portugal). Anammox potential rates were measured in anaerobic sediment slurries using 15N-labeled NO3- and NH4+ amendments. Production of 29N2 and 30N2 in the slurries was quantified using membrane inlet mass spectrometry (MIMS). Environmental characteristics of the sediment and water column were also monitored. Anammox potentials in the Ave and Douro estuarine sediments varied between 0.8-8.4, and 0-2.9 nmol cm-3 wet sediment h-1, respectively, with high seasonal and spatial fluctuations. Inorganic nitrogen availability emerged as the primary environmental control of anammox activity, while water temperature appeared to modulate seasonal variations. The contribution of anammox to overall N2 production averaged over 20%, suggesting that the role of anammox in removing fixed N from these two systems cannot be neglected.

  13. Evaluation of granular anaerobic ammonium oxidation process for the disposal of pre-treated swine manure

    PubMed Central

    Yang, Ning

    2014-01-01

    With rising environmental concerns on potable water safety and eutrophication, increased media attention and tighter environmental regulations, managing animal waste in an environmentally responsible and economically feasible way can be a challenge. In this study, the possibility of using granular anammox process for ammonia removal from swine waste treatment water was investigated. A rapid decrease of NO2−–N and NH4+–N was observed during incubation with wastewater from an activated sludge deodorization reactor and anaerobic digestion-partial oxidation treatment process treating swine manure and its corresponding control artificial wastewaters. Ammonium removal dropped from 98.0 ± 0.6% to 66.9 ± 2.7% and nearly absent when the organic load in the feeding increased from 232 mg COD/L to 1160 mg COD/L and 2320 mg COD/L. The presence of organic carbon had limited effect on nitrite and total nitrogen removal. At a COD to N ratio of 0.9, COD inhibitory organic load threshold concentration was 727 mg COD/L. Mass balance indicated that denitrifiers played an important role in nitrite, nitrate and organic carbon removal. These results demonstrated that anammox system had the potential to effectively treat swine manure that can achieve high nitrogen standards at reduced costs. PMID:24765570

  14. Cultivation of Planktonic Anaerobic Ammonium Oxidation (Anammox) Bacteria Using Membrane Bioreactor

    PubMed Central

    Oshiki, Mamoru; Awata, Takanori; Kindaichi, Tomonori; Satoh, Hisashi; Okabe, Satoshi

    2013-01-01

    Enrichment cultures of anaerobic ammonium oxidation (anammox) bacteria as planktonic cell suspensions are essential for studying their ecophysiology and biochemistry, while their cultivation is still laborious. The present study aimed to cultivate two phylogenetically distinct anammox bacteria, “Candidatus Brocadia sinica” and “Ca. Scalindua sp.” in the form of planktonic cells using membrane bioreactors (MBRs). The MBRs were continuously operated for more than 250 d with nitrogen loading rates of 0.48–1.02 and 0.004–0.09 kgN m−3 d−1 for “Ca. Brocadia sinica” and “Ca. Scalindua sp.”, respectively. Planktonic anammox bacterial cells were successfully enriched (>90%) in the MBRs, which was confirmed by fluorescence in-situ hybridization and 16S rRNA gene sequencing analysis. The decay rate and half-saturation constant for NO2− of “Ca. Brocadia sinica” were determined to be 0.0029–0.0081 d−1 and 0.47 mgN L−1, respectively, using enriched planktonic cells. The present study demonstrated that MBR enables the culture of planktonic anammox bacterial cells, which are suitable for studying their ecophysiology and biochemistry. PMID:24200833

  15. [Study on the start-up of anaerobic ammonium oxidation process in biological activated carbon reactor].

    PubMed

    Lai, Wei-Yi; Zhou, Wei-Li; He, Sheng-Bing

    2013-08-01

    In order to shorten the start-up time of anaerobic ammonium oxidation (ANAMMOX) reactor, biological activated cabon reactor was applied. Three lab scale UASB reactors were seeded with anaerobic sludge, fed with synthetic wastewater containing ammonia and nitrite, and supplemented with granular activated carbon on day 0, 33 and 56, respectively. The nitrogen removal performance of the first reactor, into which GAC was added on day 0, showed no significant improvement in 90 days. After being suspended for about one month, the secondary start-up of this reactor succeeded in another 33 days (totally 123 days). 49 d and 85 d were taken for the other two reactors started up by the addition of GAC on day 33 and 56, respectively. After the reactors were started up, the average removal rates of total nitrogen were 89.8%, 86.7% and 86.7%, respectively. The start-up process could be divided into four stages, namely, the bacterial autolysis phase, the lag phase, the improve phase and the stationary phase, and the best time for adding GAC carrier was right after the start of the lag phase.

  16. Studies on a Novel Actinobacteria Species Capable of Oxidizing Ammonium under Iron Reduction Conditions

    NASA Astrophysics Data System (ADS)

    Huanh, Shan; Ruiz-Urigüen, Melany; Jaffe, Peter R.

    2014-05-01

    Ammonium (NH4+) oxidation coupled to iron reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) was noted in a forested riparian wetland in New Jersey (1,2), and in tropical rainforest soils (3), and was coined Feammox (4). Through a 180-days anaerobic incubation of soil samples collected at the New Jersey site, and using 16S rDNA PCR-DGGE, 454-pyosequecing, and qPCR analysis, we have shown that an Acidimicrobiaceae bacterium A6, belonging to the phylum Actinobacteria, is responsible for this Feammox process, described previously (1,2). We have enriched these Feammox bacteria in a high efficiency Feammox membrane reactor (with 85% NH4+removal per 48h), and isolated the pure Acidimicrobiaceae bacterium A6 strain 5, in an autotrophic medium. To determine if the Feammox bacteria found in this study are common, at least at the regional scale, we analyzed a series of local wetland-, upland-, as well as storm-water detention pond-sediments. Through anaerobic incubations and molecular biology analysis, the Feammox reaction and Acidimicrobiaceae bacterium A6 were found in three of twenty soil samples collected, indicating that the Feammox pathway might be widespread in selected soil environments. Results show that soil pH and Fe(III) content are key environmental factors controlling the distributions of Feammox bacteria, which require acidic conditions and the presence of iron oxides. Results from incubation experiments conducted at different temperatures have shown that, in contrast to another anaerobic ammonium oxidation pathways (e.g., anammox), the optimal temperature of the Feammox process is ~ 20° and that the organisms are still active when the temperature is around 10°. An incubation experiment amended with acetylene gas (C2H2) as a selected inhibitor showed that in the Feammox reaction, Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+is the electron donor, which is oxidized to NO2-. After this process, NO2- is converted to

  17. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers.

  18. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers. PMID:25910677

  19. On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

    NASA Astrophysics Data System (ADS)

    Pusede, S. E.; Duffey, K. C.; Shusterman, A. A.; Saleh, A.; Laughner, J. L.; Wooldridge, P. J.; Zhang, Q.; Parworth, C. L.; Kim, H.; Capps, S. L.; Valin, L. C.; Cappa, C. D.; Fried, A.; Walega, J.; Nowak, J. B.; Weinheimer, A. J.; Hoff, R. M.; Berkoff, T. A.; Beyersdorf, A. J.; Olson, J.; Crawford, J. H.; Cohen, R. C.

    2016-03-01

    Nitrogen oxides (NOx) have fallen steadily across the US over the last 15 years. At the same time, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations but also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

  20. Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

    SciTech Connect

    Smith, Steven C.; Peper, Shane M.; Douglas, Matthew; Ziegelgruber, Kate L.; Finn, Erin C.

    2009-09-12

    Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 in 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.

  1. Exogenous nitrate attenuates nitrite toxicity to anaerobic ammonium oxidizing (anammox) bacteria.

    PubMed

    Li, Guangbin; Vilcherrez, David; Carvajal-Arroyo, Jose Maria; Sierra-Alvarez, Reyes; Field, Jim A

    2016-02-01

    Anaerobic ammonium oxidizing bacteria (anammox) can be severely inhibited by one of its main substrates, nitrite (NO2(-)). At present, there is limited information on the processes by which anammox bacteria are able to tolerate toxic NO2(-). Intracellular consumption or electrochemically driven (transmembrane proton motive force) NO2(-) export are considered the main mechanisms of NO2(-) detoxification. In this work, we evaluated the potential of exogenous nitrate (NO3(-)) on relieving NO2(-) toxicity, putatively facilitated by NarK, a NO3(-)/NO2(-) transporter encoded in the anammox genome. The relative contribution of NO3(-) to NO2(-) detoxification was found to be pH dependent. Exposure of anammox cells to NO2(-) in absence of their electron donating substrate, ammonium (NH4(+)), causes NO2(-) stress. At pH 6.7 and 7.0, the activity of NO2(-) stressed cells was respectively 0 and 27% of the non-stressed control activity (NO2(-) and NH4(+) fed simultaneously). Exogenous NO3(-) addition caused the recovery to 42% and 80% of the control activity at pH 6.7 and 7.0, respectively. The recovery of the activity of NO2(-) stressed cells improved with increasing NO3(-) concentration, the maximum recovery being achieved at 0.85 mM. The NO3(-) pre-incubation time is less significant at pH 7.0 than at pH 6.7 due to a more severe NO2(-) toxicity at lower pH. Additionally, NO3(-) caused almost complete attenuation of NO2(-) toxicity in cells exposed to the proton gradient disruptor carbonyl cyanide m-chlorophenyl hydrazone at pH 7.5, providing evidence that the NO3(-) attenuation is independent of the proton motive force. The absence of a measurable NO3(-) consumption (or NO3(-) dependent N2 production) during the batch tests leaves NO3(-) dependent active transport of NO2(-) as the only plausible explanation for the relief of NO2(-) inhibition. We suggest that anammox cells can use a secondary transport system facilitated by exogenous NO3(-) to alleviate NO2(-) toxicity. PMID

  2. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones.

    PubMed

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M; Revsbech, Niels Peter; Löscher, Carolin; Schunck, Harald; Desai, Dhwani K; Hauss, Helena; Kiko, Rainer; Holtappels, Moritz; LaRoche, Julie; Schmitz, Ruth A; Graco, Michelle I; Kuypers, Marcel M M

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically and laterally advected, oxygenated waters in this zone by aerobic microorganisms. In accordance, metagenomic and metatranscriptomic analyses identified genes encoding for aerobic terminal oxidases and demonstrated their expression by diverse microbial communities, even in virtually anoxic waters. Our results suggest that microaerobic respiration is a major mode of organic matter remineralization and source of ammonium (~45-100%) in the upper oxygen minimum zones, and reconcile hitherto observed mismatches between ammonium producing and consuming processes therein. PMID:26192623

  3. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones.

    PubMed

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M; Revsbech, Niels Peter; Löscher, Carolin; Schunck, Harald; Desai, Dhwani K; Hauss, Helena; Kiko, Rainer; Holtappels, Moritz; LaRoche, Julie; Schmitz, Ruth A; Graco, Michelle I; Kuypers, Marcel M M

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically and laterally advected, oxygenated waters in this zone by aerobic microorganisms. In accordance, metagenomic and metatranscriptomic analyses identified genes encoding for aerobic terminal oxidases and demonstrated their expression by diverse microbial communities, even in virtually anoxic waters. Our results suggest that microaerobic respiration is a major mode of organic matter remineralization and source of ammonium (~45-100%) in the upper oxygen minimum zones, and reconcile hitherto observed mismatches between ammonium producing and consuming processes therein.

  4. Aerobic Microbial Respiration In Oceanic Oxygen Minimum Zones

    PubMed Central

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M.; Revsbech, Niels Peter; Löscher, Carolin; Schunck, Harald; Desai, Dhwani K.; Hauss, Helena; Kiko, Rainer; Holtappels, Moritz; LaRoche, Julie; Schmitz, Ruth A.; Graco, Michelle I.; Kuypers, Marcel M. M.

    2015-01-01

    Oxygen minimum zones are major sites of fixed nitrogen loss in the ocean. Recent studies have highlighted the importance of anaerobic ammonium oxidation, anammox, in pelagic nitrogen removal. Sources of ammonium for the anammox reaction, however, remain controversial, as heterotrophic denitrification and alternative anaerobic pathways of organic matter remineralization cannot account for the ammonium requirements of reported anammox rates. Here, we explore the significance of microaerobic respiration as a source of ammonium during organic matter degradation in the oxygen-deficient waters off Namibia and Peru. Experiments with additions of double-labelled oxygen revealed high aerobic activity in the upper OMZs, likely controlled by surface organic matter export. Consistently observed oxygen consumption in samples retrieved throughout the lower OMZs hints at efficient exploitation of vertically and laterally advected, oxygenated waters in this zone by aerobic microorganisms. In accordance, metagenomic and metatranscriptomic analyses identified genes encoding for aerobic terminal oxidases and demonstrated their expression by diverse microbial communities, even in virtually anoxic waters. Our results suggest that microaerobic respiration is a major mode of organic matter remineralization and source of ammonium (~45-100%) in the upper oxygen minimum zones, and reconcile hitherto observed mismatches between ammonium producing and consuming processes therein. PMID:26192623

  5. Impact of oxidative stress defense on bacterial survival and morphological change in Campylobacter jejuni under aerobic conditions.

    PubMed

    Oh, Euna; McMullen, Lynn; Jeon, Byeonghwa

    2015-01-01

    Campylobacter jejuni, a microaerophilic foodborne pathogen, inescapably faces high oxygen tension during its transmission to humans. Thus, the ability of C. jejuni to survive under oxygen-rich conditions may significantly impact C. jejuni viability in food and food safety as well. In this study, we investigated the impact of oxidative stress resistance on the survival of C. jejuni under aerobic conditions by examining three mutants defective in key antioxidant genes, including ahpC, katA, and sodB. All the three mutants exhibited growth reduction under aerobic conditions compared to the wild-type (WT), and the ahpC mutant showed the most significant growth defect. The CFU reduction in the mutants was recovered to the WT level by complementation. Higher levels of reactive oxygen species were accumulated in C. jejuni under aerobic conditions than microaerobic conditions, and supplementation of culture media with an antioxidant recovered the growth of C. jejuni. The levels of lipid peroxidation and protein oxidation were significantly increased in the mutants compared to WT. Additionally, the mutants exhibited different morphological changes under aerobic conditions. The ahpC and katA mutants developed coccoid morphology by aeration, whereas the sodB mutant established elongated cellular morphology. Compared to microaerobic conditions, interestingly, aerobic culture conditions substantially induced the formation of coccoidal cells, and antioxidant treatment reduced the emergence of coccoid forms under aerobic conditions. The ATP concentrations and PMA-qPCR analysis supported that oxidative stress is a factor that induces the development of a viable-but-non-culturable state in C. jejuni. The findings in this study clearly demonstrated that oxidative stress resistance plays an important role in the survival and morphological changes of C. jejuni under aerobic conditions. PMID:25914692

  6. Nitrososphaera viennensis gen. nov., sp. nov., an aerobic and mesophilic, ammonia-oxidizing archaeon from soil and a member of the archaeal phylum Thaumarchaeota

    PubMed Central

    Stieglmeier, Michaela; Klingl, Andreas; Alves, Ricardo J. E.; Rittmann, Simon K.-M. R.; Melcher, Michael; Leisch, Nikolaus

    2014-01-01

    A mesophilic, neutrophilic and aerobic, ammonia-oxidizing archaeon, strain EN76T, was isolated from garden soil in Vienna (Austria). Cells were irregular cocci with a diameter of 0.6–0.9 µm and possessed archaella and archaeal pili as cell appendages. Electron microscopy also indicated clearly discernible areas of high and low electron density, as well as tubule-like structures. Strain EN76T had an S-layer with p3 symmetry, so far only reported for members of the Sulfolobales. Crenarchaeol was the major core lipid. The organism gained energy by oxidizing ammonia to nitrite aerobically, thereby fixing CO2, but growth depended on the addition of small amounts of organic acids. The optimal growth temperature was 42 °C and the optimal pH was 7.5, with ammonium and pyruvate concentrations of 2.6 and 1 mM, respectively. The genome of strain EN76T had a DNA G+C content of 52.7 mol%. Phylogenetic analyses of 16S rRNA genes showed that strain EN76T is affiliated with the recently proposed phylum Thaumarchaeota, sharing 85 % 16S rRNA gene sequence identity with the closest cultivated relative ‘Candidatus Nitrosopumilus maritimus’ SCM1, a marine ammonia-oxidizing archaeon, and a maximum of 81 % 16S rRNA gene sequence identity with members of the phyla Crenarchaeota and Euryarchaeota and any of the other recently proposed phyla (e.g. ‘Korarchaeota’ and ‘Aigarchaeota’). We propose the name Nitrososphaera viennensis gen. nov., sp. nov. to accommodate strain EN76T. The type strain of Nitrososphaera viennensis is strain EN76T ( = DSM 26422T = JMC 19564T). Additionally, we propose the family Nitrososphaeraceae fam. nov., the order Nitrososphaerales ord. nov. and the class Nitrososphaeria classis nov. PMID:24907263

  7. Antibacterial Action of Nitric Oxide-Releasing Chitosan Oligosaccharides against Pseudomonas aeruginosa under Aerobic and Anaerobic Conditions

    PubMed Central

    Reighard, Katelyn P.

    2015-01-01

    Chitosan oligosaccharides were modified with N-diazeniumdiolates to yield biocompatible nitric oxide (NO) donor scaffolds. The minimum bactericidal concentrations and MICs of the NO donors against Pseudomonas aeruginosa were compared under aerobic and anaerobic conditions. Differential antibacterial activities were primarily the result of NO scavenging by oxygen under aerobic environments and not changes in bacterial physiology. Bacterial killing was also tested against nonmucoid and mucoid biofilms and compared to that of tobramycin. Smaller NO payloads were required to eradicate P. aeruginosa biofilms under anaerobic versus aerobic conditions. Under oxygen-free environments, the NO treatment was 10-fold more effective at killing biofilms than tobramycin. These results demonstrate the potential utility of NO-releasing chitosan oligosaccharides under both aerobic and anaerobic environments. PMID:26239983

  8. Osmium(ii) complexes for light-driven aerobic oxidation of amines to imines.

    PubMed

    Li, Yong-Hui; Liu, Xiao-Le; Yu, Zhen-Tao; Li, Zhao-Sheng; Yan, Shi-Cheng; Chen, Guang-Hui; Zou, Zhi-Gang

    2016-08-01

    Herein, we describe the synthesis and characterization of three Os(ii) complexes (i.e., [Os(fptz)2(PPhMe2)2] (1, fptzH = 3-trifluoromethyl-5-pyridyl-1,2,4-triazole), [Os(fptz)2(CO)(L1)] (2, L1 = PPh3; 3, L1 = pyridine)) that have been successfully utilized as good photocatalysts to promote aerobic oxidative coupling of amines to imines with molecular oxygen in air as a green oxidant. Complex 1 is the most effective catalyst for the oxidative coupling of benzylamine with molecular O2 (air) as the oxidant because of the complex's strong absorption of visible light and long-lived triplet state. The application of a low catalyst loading (0.06 mol%) of complex 1 to the oxidative coupling of a wide range of amines affords the corresponding imines efficiently and selectively in most cases. The reaction mechanism was investigated via relevant control and quenching experiments. The results indicated that the reaction occurs via an active (1)O2-involved pathway. The (1)O2-generating ability of complex 1 as a photosensitizer was evaluated using 9,10-dimethylanthracene (DMA) as a chemical trap for (1)O2. PMID:27431765

  9. KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation.

    PubMed

    Miles, Kelsey C; Abrams, M Leigh; Landis, Clark R; Stahl, Shannon S

    2016-08-01

    A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.

  10. Ammonium Oxidation Under Iron Reducing Conditions: Environmental Factors Characterization and Process Optimization

    NASA Astrophysics Data System (ADS)

    Huang, Shan; Ruiz, Melany; Jaffe, Peter

    2015-04-01

    Ammonium (NH4+) oxidation coupled to iron (Fe) reduction in the absence of oxygen and nitrate/nitrite (NO3-/NO2-) has been reported by several investigators and is referred to as Feammox. Feammox is a biological reaction, where Fe(III) is the electron acceptor, which is reduced to Fe(II), and NH4+ is the electron donor, which is oxidized to NO2-. An Acidimicrobiaceae bacterium named A6, a previously unreported species in the Acidimicrobiaceae family, has been identified as being responsible for the Feammox process(1, 2) Feammox process was noted in riparian wetland soils in New Jersey(1,3), in tropical rainforest soils in Puerto Rico (4) and in paddy soils in China (5). In addition to these published locations, Feammox process was also found in samples collected from a series of local wetland-, upland-, as well as storm-water detention pond-sediments in New Jersey, river sediments from South Carolina, and forested soils near an acid mine drainage (Dabaoshan, Guangdong province) in China. Using primers acm342f - 439r (2), Acidimicrobiaceae bacterium A6 was detected in samples where Feammox was observed, after strictly anaerobic incubations. According to a canonical correspondence analysis with environmental characteristics and soil microbial communities, the species-environment relationship indicated that pH and Fe oxides content were the primary factors controlling Feammox process. Anaerobic incubations of Feammox enrichment cultures adjusted to different pH, revealed that the optimal pH for Feammox is 4 ~ 5, and the reaction does not proceed when pH > 7. No correlation was found between the distributions of Feammox bacteria and other NH4+ oxidation bacteria. Pure Acidimicrobiaceae bacterium A6 strain was isolated in an autotrophic medium, from an active Feammox membrane reactor (A6 was enriched to 65.8% of the total bacteria). A 13C labeled CO2 amendment was conducted, and the 13C in cells of A6 increased from 1.80% to 10.3% after 14 days incubation. In a separate

  11. Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

    PubMed Central

    Malysheva, Svetlana F; Artem’ev, Alexander V; Gusarova, Nina K; Belogorlova, Nataliya A; Albanov, Alexander I; Liu, C W

    2015-01-01

    Summary Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7–30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides in 70–93% yields. PMID:26664618

  12. Simple, rapid and effective preservation and reactivation of anaerobic ammonium oxidizing bacterium "Candidatus Brocadia sinica".

    PubMed

    Ali, Muhammad; Oshiki, Mamoru; Okabe, Satoshi

    2014-06-15

    It is still the biggest challenge to secure enough seeding biomass for rapid start-up of full-scale (anaerobic ammonium oxidation) anammox processes due to slow growth. Preservation of active anammox biomass could be one of the solutions. In this study, biomass of anammox bacterium, "Candidatus Brocadia sinica", immersed in various nutrient media were preserved at -80 °C, 4 °C and room temperature. After 45, 90 and 150 days of preservation, specific anammox activity (SAA) of the preserved anammox biomass was determined by measuring (29)N2 production rate and transcription levels of hzsA gene encoding hydrazine synthase alpha subunit. Storage in nutrient medium containing 3 mM of molybdate at room temperature with periodical (every 45 days) supply of NH4(+) and NO2(-) was proved to be the most effective storage technique for "Ca. Brocadia sinica" biomass. Using this preservation condition, 96, 92 and 65% of the initial SAA was sustained after 45, 90 and 150 days of storage, respectively. Transcription levels of hzsA gene in biomass correlated with the SAA (R(2) = 0.83), indicating it can be used as a genetic marker to evaluate the anammox activity of preserved biomass. Furthermore, the 90-day-stored biomass was successfully reactivated by immobilizing in polyvinyl alcohol (6%, w/v) and sodium alginate (2%, w/v) gel and then inoculated to up-flow column reactors. Total nitrogen removal rates rapidly increased to 7 kg-N m(-3) d(-1) within 35 days of operation. Based on these results, the room temperature preservation with molybdate addition is simple, cost-effective and feasible at a practical scale, which will accelerate the practical use of anammox process for wastewater treatment.

  13. Simple, rapid and effective preservation and reactivation of anaerobic ammonium oxidizing bacterium "Candidatus Brocadia sinica".

    PubMed

    Ali, Muhammad; Oshiki, Mamoru; Okabe, Satoshi

    2014-06-15

    It is still the biggest challenge to secure enough seeding biomass for rapid start-up of full-scale (anaerobic ammonium oxidation) anammox processes due to slow growth. Preservation of active anammox biomass could be one of the solutions. In this study, biomass of anammox bacterium, "Candidatus Brocadia sinica", immersed in various nutrient media were preserved at -80 °C, 4 °C and room temperature. After 45, 90 and 150 days of preservation, specific anammox activity (SAA) of the preserved anammox biomass was determined by measuring (29)N2 production rate and transcription levels of hzsA gene encoding hydrazine synthase alpha subunit. Storage in nutrient medium containing 3 mM of molybdate at room temperature with periodical (every 45 days) supply of NH4(+) and NO2(-) was proved to be the most effective storage technique for "Ca. Brocadia sinica" biomass. Using this preservation condition, 96, 92 and 65% of the initial SAA was sustained after 45, 90 and 150 days of storage, respectively. Transcription levels of hzsA gene in biomass correlated with the SAA (R(2) = 0.83), indicating it can be used as a genetic marker to evaluate the anammox activity of preserved biomass. Furthermore, the 90-day-stored biomass was successfully reactivated by immobilizing in polyvinyl alcohol (6%, w/v) and sodium alginate (2%, w/v) gel and then inoculated to up-flow column reactors. Total nitrogen removal rates rapidly increased to 7 kg-N m(-3) d(-1) within 35 days of operation. Based on these results, the room temperature preservation with molybdate addition is simple, cost-effective and feasible at a practical scale, which will accelerate the practical use of anammox process for wastewater treatment. PMID:24726991

  14. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation.

    PubMed

    Könneke, Martin; Schubert, Daniel M; Brown, Philip C; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J; Stahl, David A; Berg, Ivan A

    2014-06-01

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments.

  15. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation.

    PubMed

    Könneke, Martin; Schubert, Daniel M; Brown, Philip C; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J; Stahl, David A; Berg, Ivan A

    2014-06-01

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments. PMID:24843170

  16. Aerobic exercise improves oxidant-antioxidant balance in patients with rheumatoid arthritis.

    PubMed

    Tuna, Zeynep; Duger, Tulin; Atalay-Guzel, Nevin; Aral, Arzu; Basturk, Bilkay; Haznedaroglu, Seminur; Goker, Berna

    2015-04-01

    [Purpose] Although oxidative stress is known to be present in rheumatoid arthritis (RA), the effects of exercise on oxidative parameters are unknown. The aim of this study was to investigate the effects of acute aerobic exercise on serum oxidant and antioxidant levels in patients with RA. [Subjects and Methods] Sixteen patients with RA and 10 age-matched healthy volunteers participated in this study. All participants wore polar telemeters and walked on a treadmill for 30 minutes at a speed eliciting 60-75% of maximal heart rates. Blood samples were obtained before, immediately and 24 hours after exercise and malondialdehyde (MDA) and total sulfhydrile group (RSH) levels were measured. [Results] Both groups had similar heart rates during the test but the treadmill speed of the RA patients was significantly lower than that of the healthy volunteers. Serum MDA levels were lower than in both groups immediately after exercise, with greater decrements in the RA patients than controls. MDA levels returned to baseline 24 hours after the exercise only in the controls; they remained low in the RA patients. There was a slight increase in serum RSH levels after exercise compared to baseline in both groups. [Conclusion] Moderate intensity treadmill exercise did not have any adverse effect on the oxidant-antioxidant balance. The results suggest that such an exercise may be safely added to the rehabilitation program of RA for additional antioxidant effects. Morever, this antioxidant environment is maintained longer in RA patients.

  17. Metabolic reprogramming during neuronal differentiation from aerobic glycolysis to neuronal oxidative phosphorylation

    PubMed Central

    Zheng, Xinde; Boyer, Leah; Jin, Mingji; Mertens, Jerome; Kim, Yongsung; Ma, Li; Ma, Li; Hamm, Michael; Gage, Fred H; Hunter, Tony

    2016-01-01

    How metabolism is reprogrammed during neuronal differentiation is unknown. We found that the loss of hexokinase (HK2) and lactate dehydrogenase (LDHA) expression, together with a switch in pyruvate kinase gene splicing from PKM2 to PKM1, marks the transition from aerobic glycolysis in neural progenitor cells (NPC) to neuronal oxidative phosphorylation. The protein levels of c-MYC and N-MYC, transcriptional activators of the HK2 and LDHA genes, decrease dramatically. Constitutive expression of HK2 and LDHA during differentiation leads to neuronal cell death, indicating that the shut-off aerobic glycolysis is essential for neuronal survival. The metabolic regulators PGC-1α and ERRγ increase significantly upon neuronal differentiation to sustain the transcription of metabolic and mitochondrial genes, whose levels are unchanged compared to NPCs, revealing distinct transcriptional regulation of metabolic genes in the proliferation and post-mitotic differentiation states. Mitochondrial mass increases proportionally with neuronal mass growth, indicating an unknown mechanism linking mitochondrial biogenesis to cell size. DOI: http://dx.doi.org/10.7554/eLife.13374.001 PMID:27282387

  18. Severe acute oxidant exposure: morphological damage and aerobic metabolism in the lung

    SciTech Connect

    Montgomery, M.R.; Teuscher, F.; LaSota, I.; Niewoehner, D.E.

    1986-09-01

    Groups of male rats were exposed to acute doses of oxygen, ozone, or paraquat which produced equivalent mortality (25-30%) over a 28 day post-exposure period. Quantitative evaluation of morphological changes indicated the primary response to be edema and inflammation with only slight fibrosis being apparent by the end of the observation period. Aerobic pulmonary metabolism was inhibited in lungs from animals exposed to oxygen and ozone as evidenced by decreased oxygen consumption; however, this was transient and O/sub 2/ consumption returned to normal within 24 hours after removal from the exposure chamber. Conversely, treatment with paraquat caused an immediate, transient stimulation of O/sub 2/ consumption. Glucose metabolism was unaltered by the gas exposures and, as previously reported, was initially stimulated by paraquat treatment. In vitro, only paraquat altered both O/sub 2/ consumption and glucose metabolism when added to lung slice preparations; ozone had no effect. Oxygen did not alter O/sub 2/ consumption but caused a slight biphasic response in glucose metabolism. Aerobic metabolism is relatively unchanged by these doses of oxygen and ozone which result in the death of 25-30% of all treated animals. Even though paraquat produces similar morphologic changes, it may represent a more severe metabolic insult than ''equivalent'' doses of oxygen or ozone. Also, if interstitial pulmonary fibrosis is a desired result of experimental exposure, rats may not be a suitable model for oxidant induced lung injury.

  19. Impact of aerobic and anaerobic exercise training on oxidative stress and antioxidant defense in athletes.

    PubMed

    Park, Song-Young; Kwak, Yi-Sub

    2016-04-01

    Exercise mediates an excessive free radical production leading to oxidative stress (OS). The body has natural antioxidant systems that help decrease OS, and these systems may be enhanced with exercise training. However, only a few studies have investigated the differences in resting OS and antioxidant capacity (AOC) between aerobically trained athletes (ET), anaerobically trained athletes (RT), and untrained individuals (UT). Therefore, this study sought to investigate the resting and postexercise OS and AOC in ET, RT, and UT. Sixty healthy young males (26.6±0.8 yr) participated in this study. Subjects were divided into three groups, ET, RT, and UT by distinct training background. Resting plasma malondialdehyde (MDA) and protein carbonyls (PC) were not significantly different in ET, RT, and UT. However, MDA and PC were significantly increased following a graded exercise test (GXT) in UT but not in ET and RT. Resting total antioxidant capacity (TAC) levels and TAC were not different in ET, RT, and UT. Interestingly, TAC levels significantly decreased after the GXT in all groups. Additionally, UT showed lower post-exercise TAC levels compared to ET and RT. These results showed that ET, RT, and UT have similar OS and AOC at rest. However, both ET and RT have greater AOC against exercise mediated OS compared to UT. These findings may explain, at least in part, why both aerobic and anaerobic types of exercise training improve redox balance. However, it appears there is no specific exercise type effect in terms of redox balance.

  20. Impact of aerobic and anaerobic exercise training on oxidative stress and antioxidant defense in athletes.

    PubMed

    Park, Song-Young; Kwak, Yi-Sub

    2016-04-01

    Exercise mediates an excessive free radical production leading to oxidative stress (OS). The body has natural antioxidant systems that help decrease OS, and these systems may be enhanced with exercise training. However, only a few studies have investigated the differences in resting OS and antioxidant capacity (AOC) between aerobically trained athletes (ET), anaerobically trained athletes (RT), and untrained individuals (UT). Therefore, this study sought to investigate the resting and postexercise OS and AOC in ET, RT, and UT. Sixty healthy young males (26.6±0.8 yr) participated in this study. Subjects were divided into three groups, ET, RT, and UT by distinct training background. Resting plasma malondialdehyde (MDA) and protein carbonyls (PC) were not significantly different in ET, RT, and UT. However, MDA and PC were significantly increased following a graded exercise test (GXT) in UT but not in ET and RT. Resting total antioxidant capacity (TAC) levels and TAC were not different in ET, RT, and UT. Interestingly, TAC levels significantly decreased after the GXT in all groups. Additionally, UT showed lower post-exercise TAC levels compared to ET and RT. These results showed that ET, RT, and UT have similar OS and AOC at rest. However, both ET and RT have greater AOC against exercise mediated OS compared to UT. These findings may explain, at least in part, why both aerobic and anaerobic types of exercise training improve redox balance. However, it appears there is no specific exercise type effect in terms of redox balance. PMID:27162773

  1. Effects of Sodium Citrate on the Ammonium Sulfate Recycled Leaching of Low-Grade Zinc Oxide Ores

    NASA Astrophysics Data System (ADS)

    Yang, Kun; Li, Shi-wei; Zhang, Li-bo; Peng, Jin-hui; Ma, Ai-yuan; Wang, Bao-bao

    2016-03-01

    The effects of sodium citrate on ammonium sulfate recycled leaching of low-grade zinc oxide ores were studied. By applying various kinds of detection and analysis techniques such as chemical composition analysis, chemical phase method, scanning electron microscopy and energy dispersive spectrum (SEM/EDS), X-ray diffraction (XRD) and Fourier-transforming infrared spectrum (FT-IR), zinc raw ore, its leaching slag and the functional mechanism of sodium citrate were investigated. Based on a comprehensive analysis, it can be concluded that in contrast to hemimorphite (Zn4Si2O7(OH)2 · H2O), amorphous smithsonite (ZnCO3) and zinc silicate (Zn2SiO4) prove to be refractory phases under ammonium sulfate leaching, while sodium citrate has a better chelating action with the refractory phases, resulting in a higher zinc leaching rate. Under conditions of [NH3]/[NH3]T molar ratio being 0.5, [NH3]T being 7.5 mol/L, [Na3C6H5O7] being 0.2 mol/L, S/L ratio being 1:5, temperature being 303 K, holding time being 1 h in each of the two stages, and stirring rate being 300 rpm, the leaching rate of zinc reached 93.4%. In this article, sulfate ammonium recycled technology also reveals its unique advantage in processing low-grade zinc oxide ores accompanied by high silicon and high alkaline gangue.

  2. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph

    PubMed Central

    Harrold, Zoë R.; Skidmore, Mark L.; Hamilton, Trinity L.; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E.

    2015-01-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O32−), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O32− that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO42−) several orders of magnitude higher than those of S2O32−. Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O32−, CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O32− as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O32−-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O32− by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  3. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2016-03-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  4. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  5. Soluble porous coordination polymers by mechanochemistry: from metal-containing films/membranes to active catalysts for aerobic oxidation.

    PubMed

    Zhang, Pengfei; Li, Haiying; Veith, Gabriel M; Dai, Sheng

    2015-01-14

    Soluble porous coordination polymers from mechanochemical synthesis are presented through a coordination polymerization between highly contorted, rigid tetraphenol and a broad variety of transition metal ions. These polymers can be easily cast as metal-containing films or freestanding membranes. Importantly, as-made coordination polymers are highly active and stable in the aerobic oxidation of allylic C-H bonds. PMID:25389070

  6. Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

    PubMed

    Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

    2016-02-01

    A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

  7. A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

    PubMed

    Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

    2016-01-01

    Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance. PMID:26502800

  8. Oxidative stress in response to aerobic and anaerobic power testing: influence of exercise training and carnitine supplementation.

    PubMed

    Bloomer, Richard J; Smith, Webb A

    2009-01-01

    The purpose of this study is to compare the oxidative stress response to aerobic and anaerobic power testing, and to determine the impact of exercise training with or without glycine propionyl-L-carnitine (GPLC) in attenuating the oxidative stress response. Thirty-two subjects were assigned (double blind) to placebo, GPLC-1 (1g PLC/d), GPLC-3 (3g PLC/d) for 8 weeks, plus aerobic exercise. Aerobic (graded exercise test: GXT) and anaerobic (Wingate cycle) power tests were performed before and following the intervention. Blood was taken before and immediately following exercise tests and analyzed for malondialdehyde (MDA), hydrogen peroxide (H2O2), and xanthine oxidase activity (XO). No interaction effects were noted. MDA was minimally effected by exercise but lower at rest for both GPLC groups following the intervention (p = 0.044). A time main effect was noted for H2O2 (p = 0.05) and XO (p = 0.003), with values increasing from pre- to postexercise. Both aerobic and anaerobic power testing increase oxidative stress to a similar extent. Exercise training plus GPLC can decrease resting MDA, but it has little impact on exercise-induced oxidative stress biomarkers.

  9. The effect of aerobic exercise on hepatotoxicity induced by intratracheal instillation of iron oxide nanoparticles in Wistar rats.

    PubMed

    Vasili, Azadeh; Sharifi, Gholamreza; Faramarzi, Mohammad; Noori, Ali; Yazdanshenas, Shora

    2016-01-01

    Iron oxide nanoparticles (IONPs) can cause significant health problems due to their unique physicochemical properties and environmental characteristics. They are found as ultrafine particles in ambient air. After inhalation, these particles move from the lung to phagocytosis tissues, especially the liver. The aim of present study was to investigate the effect of concurrent aerobic exercise and IONPs on liver enzymes and histological hepatic appearance. 48 rats were divided into six groups: experimental 1 (aerobic exercise), experimental 2 (nanoparticle, anesthesia), experimental 3 (aerobic exercise, nanoparticles, anesthesia), placebo 4 (distilled water, anesthesia), placebo 5 (aerobic exercise, anesthesia), and control group. In groups 2 and 3, 40 mg/kg/b.w. of IONPs was injected via intratracheal installation every other day for 14 days. Groups 1, 3, and 5 [corrected] run on treadmill for 30 minutes with the intensity of 35-40% VO2max (maximal oxygen consumption) every day. ALT was increased in group 1 but decreased in groups 2 and 3. AST was not significant in any of the groups, while ALP was reduced significantly in groups 2 and 3 (p < 0.05). Histological examination of the liver showed that, in groups 2 and 3, hepatic cells were damaged and also the congestion, inflammation, mononuclear cell infiltration, and ballooning degeneration were occurred. Tissue injuries in group 3 were less than those of group 2. These findings indicated that hepatotoxicity was caused by iron oxide nanoparticles; however, low-intensity aerobic exercise could decrease the damage somewhat. PMID:26492071

  10. Oxidation of aquatic pollutants by ferrous-oxalate complexes under dark aerobic conditions.

    PubMed

    Lee, Jaesang; Kim, Jungwon; Choi, Wonyong

    2014-06-15

    This study evaluates the ability of Fe(II)-oxalate complexes for the generation of OH through oxygen reduction and the oxidative degradation of aquatic pollutants under dark aerobic conditions (i.e., with oxygen but without light). The degradation of 4-chlorophenol (4-CP) was rapid in the mixture of Fe(2+) and oxalate prepared using ultrapure water, but was absent without either Fe(2+) or oxalate. The formation of Fe(II)-oxalate complexes enables two-electron reduction of oxygen to generate H2O2 and subsequent production of OH. The significant inhibition of 4-CP degradation in the presence of H2O2 and OH scavenger confirms such mechanisms. The degradation experiments with varying [Fe(2+)], [oxalate], and initial pH demonstrated that the degradation rate depends on [Fe(II)(Ox)2(2-)], but the degree of degradation is primarily determined by [Fe(II)(Ox)2(2-)]+[Fe(II)(Ox)(0)]. Efficient degradation of diverse aquatic pollutants, especially phenolic pollutants, was observed in the Fe(II)-oxalate complexes system, wherein the oxidation efficacy was primarily correlated with the reaction rate constant between pollutant and OH. The effect of various organic ligands (oxalate, citrate, EDTA, malonate, and acetate) on the degradation kinetics of 4-CP was investigated. The highest efficiency of oxalate for the oxidative degradation is attributed to its high capability to enhance the reducing power and low reactivity with OH.

  11. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  12. Oxidative stability of pork emulsion containing tomato products and pink guava pulp during refrigerated aerobic storage.

    PubMed

    Joseph, Serlene; Chatli, Manish K; Biswas, Ashim K; Sahoo, Jhari

    2014-11-01

    Lipid oxidation-induced quality problems can be minimized with the use of natural antioxidants. Antioxidant potential of tomato puree (10 %; T-1), tomato pulp (12.5 %; T-2), lyophilized tomato peel (6 %; T-3), and pink guava pulp (10 %; T-4) was evaluated in raw pork emulsion during refrigerated storage for 9 days under aerobic packaging. The lycopene and β-carotene content varied in pork emulsion as T-3 > T-1 > T-2 > T-4 and decreased (P < 0.05) during storage. The surface redness (a* value) increased (P < 0.05) with the incorporation of tomato products and pink guava pulp. Furthermore, metmyoglobin formation and lipid oxidation were lower (P < 0.05) in tomato- and guava-treated emulsions than in control. Overall, incorporation of tomato products and pink guava pulp improved the visual colour and odour scores of raw pork emulsion. These results indicated that tomato products and guava pulp can be utilized as sources of natural antioxidants in raw pork products to minimize lipid oxidation, off-odour development, and surface discolouration. PMID:26396313

  13. Nitrosomonas stercoris sp. nov., a Chemoautotrophic Ammonia-Oxidizing Bacterium Tolerant of High Ammonium Isolated from Composted Cattle Manure

    PubMed Central

    Nakagawa, Tatsunori; Takahashi, Reiji

    2015-01-01

    Among ammonia-oxidizing bacteria, Nitrosomonas eutropha-like microbes are distributed in strongly eutrophic environments such as wastewater treatment plants and animal manure. In the present study, we isolated an ammonia-oxidizing bacterium tolerant of high ammonium levels, designated strain KYUHI-ST, from composted cattle manure. Unlike the other known Nitrosomonas species, this isolate grew at 1,000 mM ammonium. Phylogenetic analyses based on 16S rRNA and amoA genes indicated that the isolate belonged to the genus Nitrosomonas and formed a unique cluster with the uncultured ammonia oxidizers found in wastewater systems and animal manure composts, suggesting that these ammonia oxidizers contributed to removing higher concentrations of ammonia in strongly eutrophic environments. Based on the physiological and phylogenetic data presented here, we propose and call for the validation of the provisional taxonomic assignment Nitrosomonas stercoris, with strain KYUHI-S as the type strain (type strain KYUHI-ST = NBRC 110753T = ATCC BAA-2718T). PMID:26156554

  14. Effect of ammonium-salt solutions on the surface properties of carbon fibers in electrochemical anodic oxidation

    NASA Astrophysics Data System (ADS)

    Qian, Xin; Wang, Xuefei; Ouyang, Qin; Chen, Yousi; Yan, Qing

    2012-10-01

    The surfaces of polyacrylonitrile-based carbon fibers were treated by an electrochemical anodic method. Three different kinds of ammonium-salt solutions namely NH4HCO3, (NH4)2CO3 and (NH4)3PO4 were respectively chosen as the electrolytes. The effect of these electrolytes on the surface structure was studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed that longitudinal grooves on the fiber surface became more well-defined and much deeper after surface treatment, and the root mean square roughness (RMS) of carbon fiber surface increased from 4.6 nm for untreated fibers to 13.5 nm for treated fibers in (NH4)3PO4 electrolytes. The concentration of oxygen and nitrogen atomic on the fiber surface increased after surface treatment. The tensile strength of oxidized fibers had an obvious decrease, whereas the interlaminar shear strength (ILSS) value of corresponding carbon fiber reinforced polymers (CFRPs) increased in a large extent. The intensity of oxidative reaction varied with the change of ammonium-salt solutions and electrochemical oxidation in (NH4)3PO4 electrolyte was of the most violence. The corresponding mechanism was also discussed and the result showed that the higher the concentration of OH- ions in the electrolytes, the violent the oxidative reaction happened.

  15. Isolation and characterization of heterotrophic bacteria able to grow aerobically with quaternary ammonium alcohols as sole source of carbon and nitrogen.

    PubMed

    Kaech, Andres; Vallotton, Nathalie; Egli, Thomas

    2005-04-01

    The quaternary ammonium alcohols (QAAs) 2,3-dihydroxypropyl-trimethyl-ammonium (TM), dimethyl-diethanol-ammonium (DM) and methyl-triethanol-ammonium (MM) are hydrolysis products of their parent esterquat surfactants, which are widely used as softeners in fabric care. We isolated several bacteria growing with QAAs as the sole source of carbon and nitrogen. The strains were compared with a previously isolated TM-degrading bacterium, which was identified as a representative of the species Pseudomonas putida (Syst. Appl. Microbiol. 24 (2001) 252). Two bacteria were isolated with DM, referred to as strains DM 1 and DM 2, respectively. Based on 16S-rDNA analysis, they provided 97% (DM 1) and 98% (DM 2) identities to the closest related strain Zoogloea ramigera Itzigsohn 1868AL. Both strains were long, slim, motile rods but only DM 1 showed the floc forming activity, which is typical for representatives of the genus Zoogloea. Using MM we isolated a Gram-negative, non-motile rod referred to as strain MM 1. The 16S-rDNA sequence of the isolated bacterium revealed 94% identities (best match) to Rhodobacter sphaeroides only. The strains MM 1 and DM 1 exclusively grew with the QAA which was used for their isolation. DM 2 was also utilizing TM as sole source of carbon and nitrogen. However, all of the isolated bacteria were growing with the natural and structurally related compound choline. PMID:15900970

  16. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    PubMed Central

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  17. Nitrous oxide emission and nutrient removal in aerobic granular sludge sequencing batch reactors.

    PubMed

    Quan, Xiangchun; Zhang, Mingchuan; Lawlor, Peadar G; Yang, Zhifeng; Zhan, Xinmin

    2012-10-15

    Application of aerobic granular sludge into wastewater treatment is promising due to its excellent settling ability and high microbial concentrations. However, its spatial structure could induce incomplete denitrification, leading to generation of nitrous oxide (N(2)O) - a potent greenhouse gas. Under the temperature of 14 ± 4 °C, three identical laboratory-scale aerobic granular sludge sequencing batch reactors (SBRs) were established to treat synthetic wastewater simulating a mixture of liquid pig manure digestate and municipal wastewater at three aeration rates (0.2, 0.6 and 1.0 L air/min) and three COD:N ratios (1:0.22, 1:0.15 and 1:0.11). The studies show the proportions of N(2)O emission to the influent nitrogen loading rate at the aeration rates of 0.2, 0.6 and 1.0 L air/min were 8.2%, 6.1% and 3.8% at a COD:N ratio of 1:0.22; 7.0%, 5.1% and 3.5% at a COD:N ratio of 1:0.15; and 4.4%, 2.9% and 2.2% at a COD:N ratio of 1:0.11, respectively. With NO(2)(-) as the only nitrogen source in the liquid phase, the specific N(2)O generation rates via denitrification were 1.7, 1.6 and 1.3 μg N(2)O/(g SS· min) at the aeration rates of 0.2, 0.6 and 1.0 L air/min, respectively, which were 40.9%, 44.8%, 39.9% higher than those with NO(3)(-) as the only nitrogen source, respectively. N(2)O generation by aerobic granular sludge due to NH(4)(+)-N nitrification was not sensitive to the aeration rate, and the average specific N(2)O generation rate was 0.8 ± 0.02 μg N(2)O/(g SS· min).

  18. Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

    PubMed Central

    2015-01-01

    Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

  19. Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: alleviating steric and electronic constraints of Cu/TEMPO catalyst systems.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2013-10-23

    Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of ((MeO)bpy)Cu(I)(OTf) and ABNO ((MeO)bpy = 4,4'-dimethoxy-2,2'-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant. PMID:24128057

  20. Doped graphene as a metal-free carbocatalyst for the selective aerobic oxidation of benzylic hydrocarbons, cyclooctane and styrene.

    PubMed

    Dhakshinamoorthy, Amarajothi; Primo, Ana; Concepcion, Patricia; Alvaro, Mercedes; Garcia, Hermenegildo

    2013-06-01

    Nitrogen (N)-, boron (B)-, and boron,nitrogen (B,N)-doped graphene (G) act as carbocatalysts, promoting the aerobic oxidation of the benzylic positions of aromatic hydrocarbons and cyclooctane to the corresponding alcohol/ketone mixture with more than 90 % selectivity. The most active material was the co-doped (B,N)G, which, in the absence of solvent and with a substrate/(B,N)G ratio of 200, achieved 50 % tetralin conversion in 24 h with a alcohol/ketone selectivity of 80 %. An FT-Raman spectroscopic study of a sample of (B,N)G heated at 100 °C in the presence of oxygen revealed new bands that disappeared upon evacuation and that have been attributed to hydroperoxide-like species formed on the G sheet based on the isotopic shift of the peak from 819 to 779 cm(-1) when (18)O2 was used as the oxidizing reagent. Furthermore, (B)G and (N)G exhibited high catalytic activity in the aerobic oxidation of styrene to benzaldehyde (BA) in 4 h. However, the product distribution changed over time and after 10 h a significant percentage of styrene oxide (SO) was observed under the same conditions. The use of doped G as catalyst appears to offer broad scope for the aerobic oxidation of benzylic compounds and styrene, for which low catalyst loading, mild reaction temperatures, and no additional solvents are required.

  1. Release of ANP and fat oxidation in overweight persons during aerobic exercise in water.

    PubMed

    Fenzl, M; Schnizer, W; Aebli, N; Schlegel, C; Villiger, B; Disch, A; Gredig, J; Zaugg, T; Krebs, J

    2013-09-01

    Exercise in water compared to land-based exercise (LE) results in a higher release of natriuretic peptides, which are involved in the regulation of exercise-induced adipose tissue lipolysis. The present study was performed to compare the release of atrial natriuretic peptide (ANP) and free fatty acids (FFA) during prolonged aerobic water-based exercise (WE) with the release after an identical LE. 14 untrained overweight subjects performed 2 steady state workload tests on the same ergometer in water and on land. Before and after exercise, venous blood samples were collected for measuring ANP, FFA, epinephrine, norepinephrine, insulin and glucose. The respiratory exchange ratio (RER) was determined for fat oxidation.The exercises resulted in a significant increase in ANP in LE (61%) and in WE (177%), and FFA increased about 3-fold in LE and WE with no significant difference between the groups. Epinephrine increased, while insulin decreased similarly in both groups. The RER values decreased during the exercises, but there was no significant difference between LE and WE. In conclusion, the higher ANP concentrations in WE had no additional effect on lipid mobilization, FFA release and fat oxidation. Moderate-intensity exercises in water offer no benefit regarding adipose tissue lipolysis in comparison to LE.

  2. Mathematical modeling of competition for ammonium among Bacteria, Archaea and cyanobacteria within cyanobacterial mats: Can ammonia-oxidizers force nitrogen fixation?

    NASA Astrophysics Data System (ADS)

    Boyett, Matthew R.; Tavakkoli, Alireza; Sobolev, Dmitri

    2013-09-01

    Molecular analysis of cyanobacterial mat communities indicated that cyanobacteria, ammonia-oxidizing Archaea (AOA), and ammonia-oxidizing bacteria (AOB) coexist in those systems, competing for ammonium; this situation would imply competitive exclusion. We attempted to model how ammonia utilization niche partitioning occurs, and how ammonium levels can influence the interaction between those groups in a one-dimensional diffusionlimited system using Michaelis-Menten kinetics to describe ammonium consumption by each of those three groups. In our model, AOAs were able to dominate ammonium uptake by the community under most circumstances, except for unrealistically high (millimolar) levels of ammonium, where AOBs gained advantage. Cyanobacteria were unable to effectively compete for ammonium with either AOBs or AOAs throughout the mat at all ammonium concentrations and cell counts, suggesting that the presence of AOAs or AOBs forces cyanobacteria into nitrogen fixation mode. Such interaction can make cyanobacterial mats a net nitrogen source, as well as provide a carbon-independent energy transfer pathway from primary producers to the rest of the ecosystem.

  3. Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the

  4. Microsensor measurements of sulfate reduction and sulfide oxidation in compact microbial communities of aerobic biofilms

    SciTech Connect

    Kuehl, M.; Joergensen, B.B. )

    1992-04-01

    The microzonation of O{sub 2} respiration, H{sub 2}S oxidation, and SO{sub 4}{sup 2{minus}} reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 {mu}m) with microsensors for O{sub 2}, S{sup 2{minus}}, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H{sub 2}S produced from sulfate reduction was reoxidized by O{sub 2} in a narrow reaction zone, and no H{sub 2}S escaped to the overlying water. Turnover times of H{sub 2}S and O{sub 2} in the reaction zone were only a few seconds owing to rapid bacterial H{sub 2}S oxidation. Anaerobic H{sub 2}S oxidation with NO{sub 3}{sup {minus}} could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO{sub 4}{sup 2{minus}} or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively.

  5. Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

    NASA Astrophysics Data System (ADS)

    Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

    2009-12-01

    The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration

  6. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    NASA Astrophysics Data System (ADS)

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-01

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  7. Oxidation of ferrocene by thiocyanic acid in the presence of ammonium oxalate

    SciTech Connect

    Ruslin, Farah bt; Yamin, Bohari M.

    2014-09-03

    A flake-like crystalline salt was obtained from the reaction of ferrocene, oxalic acid and ammonium thiocyanate in ethanol The elemental analysis and spectroscopic data were in agreement with the preliminary X-ray molecular structure. The compound consists of four ferrocenium moieties and a counter anion consisting of two (tetraisothiocyanato)iron(III) linked by an oxalato bridging group in such a way that both iron central atoms adopt octahedral geometries.

  8. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  9. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  10. The impact of influent total ammonium nitrogen concentration on nitrite-oxidizing bacteria inhibition in moving bed biofilm reactor.

    PubMed

    Kouba, Vojtech; Catrysse, Michael; Stryjova, Hana; Jonatova, Ivana; Volcke, Eveline I P; Svehla, Pavel; Bartacek, Jan

    2014-01-01

    The application of nitrification-denitrification over nitrite (nitritation-denitritation) with municipal (i.e. diluted and cold (or low-temperature)) wastewater can substantially improve the energy balance of municipal wastewater treatment plants. For the accumulation of nitrite, it is crucial to inhibit nitrite-oxidizing bacteria (NOB) with simultaneous proliferation of ammonium-oxidizing bacteria (AOB). The present study describes the effect of the influent total ammonium nitrogen (TAN) concentration on AOB and NOB activity in two moving bed biofilm reactors operated as sequencing batch reactors (SBR) at 15 °C (SBR I) and 21 °C (SBR II). The reactors were fed with diluted reject water containing 600, 300, 150 and 75 mg TAN L(-1). The only factor limiting NOB activity in these reactors was the high concentrations of free ammonia and/or free nitrous acid (FNA) during the SBR cycles. Nitrite accumulation was observed with influents containing 600, 300 and 150 mg TAN L(-1) in SBR I and 600 and 300 in SBR II. Once nitrate production established in the reactors, the increase of influent TAN concentration up to the original 600 mg TAN L(-1) did not limit NOB activity. This was due to the massive development of NOB clusters throughout the biofilm that were able to cope with faster formation of FNA. The results of the fluorescence in situ hybridization analysis preliminarily showed the stratification of bacteria in the biofilm.

  11. Copper-catalyzed aerobic conversion of the C=O bond of ketones to a C≡N bond using ammonium salts as the nitrogen source.

    PubMed

    Xu, Bin; Jiang, Qing; Zhao, An; Jia, Jing; Liu, Qiang; Luo, Weiping; Guo, Cancheng

    2015-06-30

    The conversion of the C[double bond, length as m-dash]O bond of ketones to a C[triple bond, length as m-dash]N bond is described. This conversion is catalyzed by copper salts with ammonium salts as the nitrogen source in the presence of molecular oxygen. A wide variety of ketones can be converted into the corresponding compounds containing a C[triple bond, length as m-dash]N bond. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.

  12. Aerobic oxidation of alkylaromatics using a lipophilic N-hydroxyphthalimide: overcoming the industrial limit of catalyst solubility.

    PubMed

    Petroselli, Manuel; Franchi, Paola; Lucarini, Marco; Punta, Carlo; Melone, Lucio

    2014-09-01

    4,4'-(4,4'-Isopropylidenediphenoxy)bis(N-hydroxyphthalimide), which is a new lipophilic analogue of N-hydroxyphthalimide, can act as an effective catalyst in the aerobic oxidation of alkylaromatics under reduced amounts of polar cosolvent. The catalyst was selected on the basis of an in-depth study of the influence that substituents on the aromatic ring of N-hydroxyphthalimide exert on determining the NO-H bond dissociation energy (BDE). BDE values for a range of model molecules are calculated by DFT and measured by EPR spectroscopy. The new catalyst can be successfully employed in the aerobic oxidation of cumene, ethylbenzene, and cyclohexylbenzene, affording, in all cases, good conversions and high selectivity for the corresponding hydroperoxide. The effect of solvent, catalyst, and temperature has also been investigated.

  13. [Enhanced Resistance of Pea Plants to Oxidative: Stress Caused by Paraquat during Colonization by Aerobic Methylobacteria].

    PubMed

    Agafonova, N V; Doronina, N Y; Trotsenko, Yu A

    2016-01-01

    The influence of colonization of the pea (Pisum sativum L.) by aerobic methylobacteria of five different species (Methylophilus flavus Ship, Methylobacterium extorquens G10, Methylobacillus arboreus Iva, Methylopila musalis MUSA, Methylopila turkiensis Sidel) on plant resistance to paraquat-induced stresses has been studied. The normal conditions of pea colonization by methylobacteria were characterized by a decrease in the activity of antioxidant enzymes (superoxide dismutase, catalase, and peroxidases) and in the concentrations of endogenous H2O2, proline, and malonic dialdehyde, which is a product of lipid peroxidation and indicator of damage to plant cell membranes, and an increase in the activity of the photosynthetic apparatus (the content of chlorophylls a, b and carotenoids). In the presence of paraquat, the colonized plants had higher activities of antioxidant enzymes, stable photosynthetic indices, and a less intensive accumulation of the products of lipid peroxidation as compared to noncolonized plants. Thus, colonization by methylobacteria considerably increased the adaptive protection of pea plants to the paraquat-induced oxidative stress.

  14. Praseodymium incorporated AIPO-5 molecular sieves for aerobic oxidation of ethylbenzene.

    PubMed

    Sundaravel, B; Babu, C M; Palanisamy, B; Palanichamy, M; Shanthi, K; Murugesan, V

    2013-04-01

    PrAlPO-5 with (Al + P)/Pr ratios of 25, 50, 75 and 100 molecular sieves were successfully synthesized by hydrothermal method. These molecular sieves were characterised using XPS, TPD-NH3, ex-situ pyridine adsorbed IR, TPR, TGA, 27Al and 31P MAS-NMR and ESR studies. The incorporation of praseodymium in the framework of AlPO-5 was confirmed by XRD, DRS UV-vis and 27Al and 31P MAS-NMR analysis. ESR spectrum showed the presence of adsorbed oxygen. The nature and strength of acid sites were identified by ex-situ pyridine adsorbed IR and TPD-NH3. The BET surface area was found to be in the range of 238-272 m2 g(-1). The catalytic activity of the molecular sieves was tested for the liquid phase aerobic oxidation of ethylbenzene. Acetophenone was found to be the major product with more than 90% ethylbenzene conversion. ICP-OES analysis revealed the presence of praseodymium intact in the framework of AlPO-5 up to five cycles.

  15. [Enhanced Resistance of Pea Plants to Oxidative: Stress Caused by Paraquat during Colonization by Aerobic Methylobacteria].

    PubMed

    Agafonova, N V; Doronina, N Y; Trotsenko, Yu A

    2016-01-01

    The influence of colonization of the pea (Pisum sativum L.) by aerobic methylobacteria of five different species (Methylophilus flavus Ship, Methylobacterium extorquens G10, Methylobacillus arboreus Iva, Methylopila musalis MUSA, Methylopila turkiensis Sidel) on plant resistance to paraquat-induced stresses has been studied. The normal conditions of pea colonization by methylobacteria were characterized by a decrease in the activity of antioxidant enzymes (superoxide dismutase, catalase, and peroxidases) and in the concentrations of endogenous H2O2, proline, and malonic dialdehyde, which is a product of lipid peroxidation and indicator of damage to plant cell membranes, and an increase in the activity of the photosynthetic apparatus (the content of chlorophylls a, b and carotenoids). In the presence of paraquat, the colonized plants had higher activities of antioxidant enzymes, stable photosynthetic indices, and a less intensive accumulation of the products of lipid peroxidation as compared to noncolonized plants. Thus, colonization by methylobacteria considerably increased the adaptive protection of pea plants to the paraquat-induced oxidative stress. PMID:27266250

  16. Aerobic oxidation of diverse primary alcohols to methyl esters with a readily accessible heterogeneous Pd/Bi/Te catalyst.

    PubMed

    Powell, Adam B; Stahl, Shannon S

    2013-10-01

    Efficient aerobic oxidative methyl esterification of primary alcohols has been achieved with a heterogeneous catalyst consisting of 1 mol % Pd/charcoal (5 wt %) in combination with bismuth(III) nitrate and tellurium metal. The Bi and Te additives significantly increase the reaction rate, selectivity, and overall product yields. This readily accessible catalyst system exhibits a broad substrate scope and is effective with both activated (benzylic) and unactivated (aliphatic) alcohols bearing diverse functional groups. PMID:24050194

  17. Methacryloxylethyl Cetyl Ammonium Chloride Induces DNA Damage and Apoptosis in Human Dental Pulp Cells via Generation of Oxidative Stress.

    PubMed

    Jiao, Yang; Ma, Sai; Wang, Yirong; Li, Jing; Shan, Lequn; Sun, Jinlong; Chen, Jihua

    2016-01-01

    The polymerizable antibacterial monomer methacryloxylethyl cetyl ammonium chloride (DMAE-CB) has provided an effective strategy to combat dental caries. However, the application of such material raises the question about the biological safety and the question remains open. The mechanism of this toxic action, however, is not yet clearly understood. The present study aims at providing novel insight into the possible causal link between cellular oxidative stress and DNA damage, as well as apoptosis in human dental pulp cells exposed to DMAE-CB. The enhanced formation of reactive oxygen species and depletion of glutathione, as well as differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase in DMAE-CB-treated cells indicated oxidative stress. By using substances that can alter GSH synthesis, we found that GSH was the key component in the regulation of cell response towards oxidative stress induced by DMAE-CB. The increase in oxidative stress-sensitive 8-Oxo-2'-deoxyguanosine (8-OHdG) content, formation of γ-H2AX and cell cycle G1 phase arrest indicated that DNA damage occurred as a result of the interaction between DNA base and ROS beyond the capacities of antioxidant mechanisms in cells exposed to DMAE-CB. Such oxidative DNA damage thus triggers the activation of ataxia telangiectasia-mutated (ATM) signaling, the intrinsic apoptotic pathway, and destruction of mitochondrial morphology and function. PMID:27143955

  18. Methacryloxylethyl Cetyl Ammonium Chloride Induces DNA Damage and Apoptosis in Human Dental Pulp Cells via Generation of Oxidative Stress

    PubMed Central

    Jiao, Yang; Ma, Sai; Wang, Yirong; Li, Jing; Shan, Lequn; Sun, Jinlong; Chen, Jihua

    2016-01-01

    The polymerizable antibacterial monomer methacryloxylethyl cetyl ammonium chloride (DMAE-CB) has provided an effective strategy to combat dental caries. However, the application of such material raises the question about the biological safety and the question remains open. The mechanism of this toxic action, however, is not yet clearly understood. The present study aims at providing novel insight into the possible causal link between cellular oxidative stress and DNA damage, as well as apoptosis in human dental pulp cells exposed to DMAE-CB. The enhanced formation of reactive oxygen species and depletion of glutathione, as well as differential changes in activities of superoxide dismutase, glutathione peroxidase, and catalase in DMAE-CB-treated cells indicated oxidative stress. By using substances that can alter GSH synthesis, we found that GSH was the key component in the regulation of cell response towards oxidative stress induced by DMAE-CB. The increase in oxidative stress-sensitive 8-Oxo-2'-deoxyguanosine (8-OHdG) content, formation of γ-H2AX and cell cycle G1 phase arrest indicated that DNA damage occurred as a result of the interaction between DNA base and ROS beyond the capacities of antioxidant mechanisms in cells exposed to DMAE-CB. Such oxidative DNA damage thus triggers the activation of ataxia telangiectasia-mutated (ATM) signaling, the intrinsic apoptotic pathway, and destruction of mitochondrial morphology and function. PMID:27143955

  19. Investigating the chemical and isotopic kinetics of aerobic methane oxidation in the Northern US Atlantic Margin, Hudson Canyon

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Shiller, A. M.; Redmond, M. C.; Arrington, E. C.; Valentine, D. L.

    2015-12-01

    Recent discoveries of methane seepage along the US Atlantic margin have led to speculation on the fate of the released methane. Here we examine the kinetics of aerobic methane oxidation to gain a fundamental understanding of this methane sink. In order to look at this process in its entirety, a unique mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) to monitor in real time the chemical and isotopic changes involved with aerobic methane oxidation. This system measures changes in methane, carbon dioxide, and oxygen concentrations as well as the stable carbon isotopes of methane and carbon dioxide with time. In addition samples are strategically removed to characterize trace metals, nutrients, cell counts, and microbial community genetics. This presentation will detail the results obtained from samples collected inside the Hudson Canyon at the edge of the methane clathrate stability zone and outside the Hudson Canyon, not influenced by the methane seepage. These results show that in both environments along the Atlantic margin, methane was consumed aggressively but the timing of consumption varied based on location. In addition, these results are leading to insights into the chemical requirements needed for aerobic methane oxidation and the resulting isotopic fractionation.

  20. Aerobic methane oxidation in a coastal environment with seasonal hypoxia - a time series study

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Bethke, Christina; Schweers, Johanna; Bange, Hermann; Kock, Annette; Lehmann, Moritz F.; Treude, Tina; Niemann, Helge

    2014-05-01

    In the coastal ocean, methane is generally produced in anoxic sediments from where it can migrate through the water column to the atmosphere. A significant amount of methane is consumed along this passage by a series of microbial filter systems. Over the last 15 years, researchers focused on the first filter in marine sediments, the anaerobic oxidation of methane (AOM). Comparably little is known about the second filter, the aerobic methane oxidation (MOx), which is mediated by bacteria and takes place in the oxic water column. MOx is particularly important in shallow coastal environments that account for more than 75 % of the global oceanic methane emissions. Key environmental factors possibly controlling MOx in these systems are subjected to strong temporal variations since coastal regions are highly dynamic systems. We will present results from a time-series study on methane cycling in the water column of a coastal inlet in the southwestern Baltic Sea (Eckernförde Bay, Boknis Eck Time Series Station, 54°31.823 N, 10°02.764 E, 28m water depth; www.bokniseck.de). Results from monthly samplings for the last 8 years revealed year-round methane seepage from the seafloor and methane supersaturation (with respect to the atmospheric equilibrium) of surface waters. Seasonal stratification during the summer months leads to intermittent oxygen depletion (hypoxic to anoxic) in bottom waters in late summer to early fall. The frequency of these low-oxygen events increased over the last 20 years. In addition to oxygen fluctuations, bottom water salinity can vary strongly (17-24 psu) due to regular inflows of salty North Sea water through the Kattegat. Over the course of one and a half years, we investigated MOx rates, the methanotrophic community, methane concentrations and physicochemical parameters of the water column on a quarterly basis. Albeit methane concentrations were high throughout the water column (20-120 nM), methane turnover showed a clear spatial pattern. That

  1. Diversity and abundance of aerobic and anaerobic methane oxidizers at the Haakon Mosby Mud Volcano, Barents Sea.

    PubMed

    Lösekann, Tina; Knittel, Katrin; Nadalig, Thierry; Fuchs, Bernhard; Niemann, Helge; Boetius, Antje; Amann, Rudolf

    2007-05-01

    Submarine mud volcanoes are formed by expulsions of mud, fluids, and gases from deeply buried subsurface sources. They are highly reduced benthic habitats and often associated with intensive methane seepage. In this study, the microbial diversity and community structure in methane-rich sediments of the Haakon Mosby Mud Volcano (HMMV) were investigated by comparative sequence analysis of 16S rRNA genes and fluorescence in situ hybridization. In the active volcano center, which has a diameter of about 500 m, the main methane-consuming process was bacterial aerobic oxidation. In this zone, aerobic methanotrophs belonging to three bacterial clades closely affiliated with Methylobacter and Methylophaga species accounted for 56%+/-8% of total cells. In sediments below Beggiatoa mats encircling the center of the HMMV, methanotrophic archaea of the ANME-3 clade dominated the zone of anaerobic methane oxidation. ANME-3 archaea form cell aggregates mostly associated with sulfate-reducing bacteria of the Desulfobulbus (DBB) branch. These ANME-3/DBB aggregates were highly abundant and accounted for up to 94%+/-2% of total microbial biomass at 2 to 3 cm below the surface. ANME-3/DBB aggregates could be further enriched by flow cytometry to identify their phylogenetic relationships. At the outer rim of the mud volcano, the seafloor was colonized by tubeworms (Siboglinidae, formerly known as Pogonophora). Here, both aerobic and anaerobic methane oxidizers were found, however, in lower abundances. The level of microbial diversity at this site was higher than that at the central and Beggiatoa species-covered part of the HMMV. Analysis of methyl-coenzyme M-reductase alpha subunit (mcrA) genes showed a strong dominance of a novel lineage, mcrA group f, which could be assigned to ANME-3 archaea. Our results further support the hypothesis of Niemann et al. (54), that high methane availability and different fluid flow regimens at the HMMV provide distinct niches for aerobic and

  2. Diversity and Abundance of Aerobic and Anaerobic Methane Oxidizers at the Haakon Mosby Mud Volcano, Barents Sea▿

    PubMed Central

    Lösekann, Tina; Knittel, Katrin; Nadalig, Thierry; Fuchs, Bernhard; Niemann, Helge; Boetius, Antje; Amann, Rudolf

    2007-01-01

    Submarine mud volcanoes are formed by expulsions of mud, fluids, and gases from deeply buried subsurface sources. They are highly reduced benthic habitats and often associated with intensive methane seepage. In this study, the microbial diversity and community structure in methane-rich sediments of the Haakon Mosby Mud Volcano (HMMV) were investigated by comparative sequence analysis of 16S rRNA genes and fluorescence in situ hybridization. In the active volcano center, which has a diameter of about 500 m, the main methane-consuming process was bacterial aerobic oxidation. In this zone, aerobic methanotrophs belonging to three bacterial clades closely affiliated with Methylobacter and Methylophaga species accounted for 56% ± 8% of total cells. In sediments below Beggiatoa mats encircling the center of the HMMV, methanotrophic archaea of the ANME-3 clade dominated the zone of anaerobic methane oxidation. ANME-3 archaea form cell aggregates mostly associated with sulfate-reducing bacteria of the Desulfobulbus (DBB) branch. These ANME-3/DBB aggregates were highly abundant and accounted for up to 94% ± 2% of total microbial biomass at 2 to 3 cm below the surface. ANME-3/DBB aggregates could be further enriched by flow cytometry to identify their phylogenetic relationships. At the outer rim of the mud volcano, the seafloor was colonized by tubeworms (Siboglinidae, formerly known as Pogonophora). Here, both aerobic and anaerobic methane oxidizers were found, however, in lower abundances. The level of microbial diversity at this site was higher than that at the central and Beggiatoa species-covered part of the HMMV. Analysis of methyl-coenzyme M-reductase alpha subunit (mcrA) genes showed a strong dominance of a novel lineage, mcrA group f, which could be assigned to ANME-3 archaea. Our results further support the hypothesis of Niemann et al. (54), that high methane availability and different fluid flow regimens at the HMMV provide distinct niches for aerobic and

  3. Characterization of a Mutant Deficient for Ammonium and Nitric Oxide Signalling in the Model System Chlamydomonas reinhardtii.

    PubMed

    Sanz-Luque, Emanuel; Ocaña-Calahorro, Francisco; Galván, Aurora; Fernández, Emilio; de Montaigu, Amaury

    2016-01-01

    The ubiquitous signalling molecule Nitric Oxide (NO) is characterized not only by the variety of organisms in which it has been described, but also by the wealth of biological processes that it regulates. In contrast to the expanding repertoire of functions assigned to NO, however, the mechanisms of NO action usually remain unresolved, and genes that work within NO signalling cascades are seldom identified. A recent addition to the list of known NO functions is the regulation of the nitrogen assimilation pathway in the unicellular alga Chlamydomonas reinhardtii, a well-established model organism for genetic and molecular studies that offers new possibilities in the search for mediators of NO signalling. By further exploiting a collection of Chlamydomonas insertional mutant strains originally isolated for their insensitivity to the ammonium (NH4+) nitrogen source, we found a mutant which, in addition to its ammonium insensitive (AI) phenotype, was not capable of correctly sensing the NO signal. Similarly to what had previously been described in the AI strain cyg56, the expression of nitrogen assimilation genes in the mutant did not properly respond to treatments with various NO donors. Complementation experiments showed that NON1 (NO Nitrate 1), a gene that encodes a protein containing no known functional domain, was the gene underlying the mutant phenotype. Beyond the identification of NON1, our findings broadly demonstrate the potential for Chlamydomonas reinhardtii to be used as a model system in the search for novel components of gene networks that mediate physiological responses to NO.

  4. Characterization of a Mutant Deficient for Ammonium and Nitric Oxide Signalling in the Model System Chlamydomonas reinhardtii

    PubMed Central

    Sanz-Luque, Emanuel; Ocaña-Calahorro, Francisco; Galván, Aurora; Fernández, Emilio; de Montaigu, Amaury

    2016-01-01

    The ubiquitous signalling molecule Nitric Oxide (NO) is characterized not only by the variety of organisms in which it has been described, but also by the wealth of biological processes that it regulates. In contrast to the expanding repertoire of functions assigned to NO, however, the mechanisms of NO action usually remain unresolved, and genes that work within NO signalling cascades are seldom identified. A recent addition to the list of known NO functions is the regulation of the nitrogen assimilation pathway in the unicellular alga Chlamydomonas reinhardtii, a well-established model organism for genetic and molecular studies that offers new possibilities in the search for mediators of NO signalling. By further exploiting a collection of Chlamydomonas insertional mutant strains originally isolated for their insensitivity to the ammonium (NH4+) nitrogen source, we found a mutant which, in addition to its ammonium insensitive (AI) phenotype, was not capable of correctly sensing the NO signal. Similarly to what had previously been described in the AI strain cyg56, the expression of nitrogen assimilation genes in the mutant did not properly respond to treatments with various NO donors. Complementation experiments showed that NON1 (NO Nitrate 1), a gene that encodes a protein containing no known functional domain, was the gene underlying the mutant phenotype. Beyond the identification of NON1, our findings broadly demonstrate the potential for Chlamydomonas reinhardtii to be used as a model system in the search for novel components of gene networks that mediate physiological responses to NO. PMID:27149516

  5. High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    SciTech Connect

    Gerken, James B.; Stahl, Shannon S.

    2015-07-15

    Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  6. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  7. Aerobic cometabolic degradation of trichloroethene by methane and ammonia oxidizing microorganisms naturally associated with Carex comosa roots.

    PubMed

    Powell, C L; Nogaro, G; Agrawal, A

    2011-06-01

    The degradation potential of trichloroethene by the aerobic methane- and ammonia-oxidizing microorganisms naturally associated with wetland plant (Carex comosa) roots was examined in this study. In bench-scale microcosm experiments with washed (soil free) Carex comosa roots, the activity of root-associated methane- and ammonia-oxidizing microorganisms, which were naturally present on the root surface and/or embedded within the roots, was investigated. Significant methane and ammonia oxidation were observed reproducibly in batch reactors with washed roots incubated in growth media, where methane oxidation developed faster (2 weeks) compared to ammonia oxidation (4 weeks) in live microcosms. After enrichment, the methane oxidizers demonstrated their ability to degrade 150 μg l(-1) TCE effectively at 1.9 mg l(-1) of aqueous CH(4). In contrast, ammonia oxidizers showed a rapid and complete inhibition of ammonia oxidation with 150 μg l(-1) TCE at 20 mg l(-1) of NH(4)(+)-N, which may be attributed to greater sensitivity of ammonia oxidizers to TCE or its degradation product. No such inhibitory effect of TCE degradation was detected on methane oxidation at the above experimental conditions. The results presented here suggest that microorganisms associated with wetland plant roots can assist in the natural attenuation of TCE in contaminated aquatic environments.

  8. Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions

    PubMed Central

    Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

    2014-01-01

    Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD. PMID:24245852

  9. Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions.

    PubMed

    Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

    2014-01-01

    Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD.

  10. The importance of biological oxidation of iron in the aerobic cells of the Wheal Jane pilot passive treatment system.

    PubMed

    Hall, G; Swash, P; Kotilainen, S

    2005-02-01

    The passive treatment system designed to treat the mine water discharge of the abandoned Wheal Jane tin mine in Cornwall consisted of a sequence of artificial wetland cells, an anaerobic cell and a final series of rock filters. Three systems were operated which differed only in the pre-treatment of the mine water before discharge to the aerobic wetland cells. The aerobic cells were designed to promote aerobic oxidation and precipitation of iron which could exceed a concentration of 100 mg/l in the raw mine water discharge. The largest investment of land area was to the artificial wetland cells and it was important to understand the processes of oxidation and precipitation of iron so that the performance of this aspect the pilot passive treatment plant (PPTP) could be managed as efficiently as possible. The generally low pH of the influent mine water and inevitable trend of decreasing pH due to hydrolysis of Fe(III) meant that distinguishing between biotic and abiotic mechanisms was fundamental for further design planning of passive treatment systems. This paper describes these observations. PMID:15680627

  11. Evaluation of performance in a combined UASB and aerobic contact oxidation process treating acrylic wastewater.

    PubMed

    Li, Anfeng; Dong, Na; He, Manni; Pan, Tao

    2015-01-01

    The lab-scale and full-scale performance of a combined mesophilic up-flow anaerobic sludge blanket (UASB) and aerobic contact oxidation (ACO) process for treating acrylic wastewater was studied. During lab-scale experiment, the overwhelmed volumetric load for UASB was above 6 kg chemical oxygen demand (COD) ·(m(-3)·d(-1)) since COD removal efficiency dropped dramatically from 73% at 6 kg COD·(m(-3)·d(-1)) to 61% at 7 kg COD·(m(-3)·d(-1)) and 53% at 8 kg COD·(m(-3)·d(-1)). Further results showed that an up-flow fluid velocity of 0.5 m h(-1) for UASB obtained a highest COD removal efficiency of 75%, and the optimum COD volumetric load for the corresponding ACO was 1.00 kg COD·(m(-3)·d(-1)). Based on the configuration of the lab-scale experiment, a full-scale application with an acrylic wastewater treatment capacity of 8 m3 h(-1) was constructed and operated at a volumetric load of 5.5 kg COD·(m(-3)·d(-1)), an up-flow fluid velocity of 0.5 m h(-1) for UASB and a volumetric load of 0.9 kg COD·(m(-3)·d(-1)) for ACO; and the final effluent COD was around 740 mg L(-1). The results suggest that a combined UASB-ACO process is promising for treating acrylic wastewater. PMID:25204720

  12. Silver(I) as a widely applicable, homogeneous catalyst for aerobic oxidation of aldehydes toward carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic

    PubMed Central

    Liu, Mingxin; Wang, Haining; Zeng, Huiying; Li, Chao-Jun

    2015-01-01

    The first example of a homogeneous silver(I)-catalyzed aerobic oxidation of aldehydes in water is reported. More than 50 examples of different aliphatic and aromatic aldehydes, including natural products, were tested, and all of them successfully underwent aerobic oxidation to give the corresponding carboxylic acids in extremely high yields. The reaction conditions are very mild and greener, requiring only a very low silver(I) catalyst loading, using atmospheric oxygen as the oxidant and water as the solvent, and allowing gram-scale oxidation with only 2 mg of our catalyst. Chromatography is completely unnecessary for purification in most cases. PMID:26601150

  13. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    NASA Astrophysics Data System (ADS)

    Venterea, Rodney T.; Clough, Timothy J.; Coulter, Jeffrey A.; Breuillin-Sessoms, Florence

    2015-07-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils (‘L’ and ‘W’) having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3-) levels than soil L, but was more resistant to nitrite (NO2-) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2- oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2- was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2-. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2- oxidization leading to greater NO2- levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2-, N2O and nitrifier genes, and the first to show how ASC can regulate NO2- levels and N2O production.

  14. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    NASA Astrophysics Data System (ADS)

    Venterea, R. T.; Sadowsky, M.; Breuillin-Sessoms, F.; Wang, P.; Clough, T. J.; Coulter, J. A.

    2015-12-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted 'hot spots' and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils ('L' and 'W') having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3-) levels than soil L, but was more resistant to nitrite (NO2-) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2- oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2- was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2-. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2- oxidization leading to greater NO2- levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2-, N2O and nitrifier genes, and the first to show how ASC can regulate NO2- levels and N2O production.

  15. Abundance and diversity of ammonia-oxidizing bacteria in relation to ammonium in a chinese shallow eutrophic urban lake

    PubMed Central

    Qiu, Shanlian; Chen, Guoyuan; Zhou, Yiyong

    2010-01-01

    The measures of most-probable-number and restriction fragment length polymorphism analysis were used to analyze the abundance and diversity of ammonia-oxidizing bacteria in sediment of a Chinese shallow eutrophic urban lake (Lake Yuehu). Among the 5 sampling sites, ammonia concentration in interstitial water was positively proportional not only to the content of organic matter, but also to ammonia-oxidizing bacteria numbers (at a magnitude of 105 cells g-1 dry weight) in sediment significantly. Furthermore, the diversity of ammonia-oxidizing bacteria were determined by means of PCR primers targeting the amoA gene with five gene libraries created and restriction pattern analysis. The 13 restriction patterns were recorded with 4 ones being common among all sampling sites. The 8 restriction patterns including 4 unique ones were found at the site with the highest NH4+ concentrations in interstitial water, while, there were only common patterns without unique ones at the site with the lowest NH4+ concentrations in interstitial water. Phylogenetic analysis showed that the amoA fragments retrieved belong to Nitrosomonas oligotropha & ureae lineage, N. europaea lineage, N. communis lineage and Nitrosospira lineage, most of which were affiliated with the genus Nitrosomonas. The N. oligotropha & ureae-like bacteria were the dominant species. Thus, the abundance and diversity of sediment AOB is closely linked to ammonium status in eutrophic lakes. PMID:24031484

  16. Whole-Genome Transcriptional Analysis of Chemolithoautotrophic Thiosulfate Oxidation by Thiobacillus denitrificans Under Aerobic vs. Denitrifying Conditions

    SciTech Connect

    Beller, H R; Letain, T E; Chakicherla, A; Kane, S R; Legler, T C; Coleman, M A

    2006-04-22

    Thiobacillus denitrificans is one of the few known obligate chemolithoautotrophic bacteria capable of energetically coupling thiosulfate oxidation to denitrification as well as aerobic respiration. As very little is known about the differential expression of genes associated with ke chemolithoautotrophic functions (such as sulfur-compound oxidation and CO2 fixation) under aerobic versus denitrifying conditions, we conducted whole-genome, cDNA microarray studies to explore this topic systematically. The microarrays identified 277 genes (approximately ten percent of the genome) as differentially expressed using Robust Multi-array Average statistical analysis and a 2-fold cutoff. Genes upregulated (ca. 6- to 150-fold) under aerobic conditions included a cluster of genes associated with iron acquisition (e.g., siderophore-related genes), a cluster of cytochrome cbb3 oxidase genes, cbbL and cbbS (encoding the large and small subunits of form I ribulose 1,5-bisphosphate carboxylase/oxygenase, or RubisCO), and multiple molecular chaperone genes. Genes upregulated (ca. 4- to 95-fold) under denitrifying conditions included nar, nir, and nor genes (associated respectively with nitrate reductase, nitrite reductase, and nitric oxide reductase, which catalyze successive steps of denitrification), cbbM (encoding form II RubisCO), and genes involved with sulfur-compound oxidation (including two physically separated but highly similar copies of sulfide:quinone oxidoreductase and of dsrC, associated with dissimilatory sulfite reductase). Among genes associated with denitrification, relative expression levels (i.e., degree of upregulation with nitrate) tended to decrease in the order nar > nir > nor > nos. Reverse transcription, quantitative PCR analysis was used to validate these trends.

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

    NASA Astrophysics Data System (ADS)

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

    2012-10-01

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

  18. A comparative study of silver-graphene oxide nanocomposites as a recyclable catalyst for the aerobic oxidation of benzyl alcohol: Support effect

    NASA Astrophysics Data System (ADS)

    Zahed, Bahareh; Hosseini-Monfared, Hassan

    2015-02-01

    Three different nanocomposites of silver and graphene oxide, namely silver nanoparticles (AgNPs) immobilized on reduced graphene oxide (AgNPs/rGO), partially reduced graphene oxide (AgNPs/GO) and thiolated partially reduced graphene oxide (AgNPs/GOSH), were synthesized in order to compare their properties. Characterizations were carried out by infrared and UV-Vis and Raman spectroscopy, ICP, X-ray diffraction, SEM and TEM, confirming both the targeted chemical modification and the composite formation. The nanocomposites were successfully employed in the aerobic oxidation of benzyl alcohol at atmospheric pressure. AgNPs/GOSH is stable and recyclable catalyst which showed the highest activity in the aerobic oxidation of benzyl alcohol in the presence of N-hydroxyphthalimide (NHPI) to give benzaldehyde with 58% selectivity in 24 h at 61% conversion. The favorite properties of AgNPs/GOSH are reasonably attributed to the stable and well distributed AgNPs over GOSH due to strong adhesion between AgNPs and GOSH.

  19. Ammonium nitrate explosive systems

    DOEpatents

    Stinecipher, Mary M.; Coburn, Michael D.

    1981-01-01

    Novel explosives which comprise mixtures of ammonium nitrate and an ammonium salt of a nitroazole in desired ratios are disclosed. A preferred nitroazole is 3,5-dinitro-1,2,4-triazole. The explosive and physical properties of these explosives may readily be varied by the addition of other explosives and oxidizers. Certain of these mixtures have been found to act as ideal explosives.

  20. Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 2. Application for the analysis of Loy Yang coal oxidation products

    SciTech Connect

    Kawamura, K.; Okuwaki, A.; Verheyen, T.V.; Perry, G.J.

    2006-07-01

    In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt was optimized using the solvent gradient method. This method was applied for the analysis of Loy Yang coal oxidation products. It was confirmed that the analytical data using this method were consistent with those determined using gas chromatography.

  1. Spatial distribution of iron oxidation in the aerobic cells of the Wheal Jane Pilot Passive Treatment Plant.

    PubMed

    Hall, G H; Puhlmann, T

    2005-02-01

    The wetland cells of the Wheal Jane Pilot Passive Treatment Plant (PPTP) were designed to promote aerobic oxidation and precipitation of iron which could exceed a concentration of 100 mg l-1 in the raw mine water. The largest investment of land area was to the wetland (also called aerobic) cells and it was important to understand the processes of oxidation and precipitation of iron so that the performance of this part of the pilot passive treatment plant (PPTP) could be managed efficiently. The results of a high-resolution sampling programme on the distribution of Fe(II) within the first wetland cell of each treatment system are described. Comparison of inflow and outflow concentrations of iron adequately described the performance of the lime-dosed (LD) system. However, precipitation of iron in the anoxic limestone drain (ALD) and lime-free systems (LFS) was more efficient. On average, about 90% of the iron present in the inflow was removed using only 50% and 33% of the first aerobic cells of the ALD and LFS systems, respectively. As the concentration of iron approached 20 mg l-1, the rate of oxidation slowed considerably. This was probably due to be due to low pH levels caused by hydrolysis of Fe(III). With the introduction of passive pH control mechanisms, there was capacity to increase the volume of mine water treated by the ALD and LDS systems by 10 and 15 times, respectively, but it is uncertain as to whether or not other aspects of the passive treatment system would have sufficient capacity to deal with the increased volumes of mine water. PMID:15680628

  2. Mechanistic Studies of Wacker-Type Intramolecular Aerobic Oxidative Amination of Alkenes Catalyzed by Pd(OAc)2/Pyridine

    PubMed Central

    Ye, Xuan; Liu, Guosheng; Popp, Brian V.; Stahl, Shannon S.

    2011-01-01

    Wacker-type oxidative cyclization reactions have been the subject of extensive research for several decades, but few systematic mechanistic studies of these reactions have been reported. The present study features experimental and DFT computational studies of Pd(OAc)2/pyridine-catalyzed intramolecular aerobic oxidative amination of alkenes. The data support a stepwise catalytic mechanism that consists of (1) steady-state formation of a PdII-amidate-alkene chelate with release of one equivalent of pyridine and AcOH from the catalyst center, (2) alkene insertion into a Pd–N bond, (3) reversible β-hydride elimination, (4) irreversible reductive elimination of AcOH, and (5) aerobic oxidation of palladium(0) to regenerate the active trans-Pd(OAc)2(py)2 catalyst. Evidence is obtained for two energetically viable pathways for the key C–N bond-forming step, featuring a pyridine-ligated and a pyridine-dissociated PdII species. Analysis of natural charges and bond lengths of the alkene-insertion transition state suggest that this reaction is best described as an intramolecular nucleophilic attack of the amidate ligand on the coordinated alkene. PMID:21250706

  3. Complete Genome Sequence of the Aerobic CO-Oxidizing Thermophile Thermomicrobium roseum

    PubMed Central

    Wu, Dongying; Raymond, Jason; Wu, Martin; Chatterji, Sourav; Ren, Qinghu; Graham, Joel E.; Bryant, Donald A.; Robb, Frank; Colman, Albert; Tallon, Luke J.; Badger, Jonathan H.; Madupu, Ramana; Ward, Naomi L.; Eisen, Jonathan A.

    2009-01-01

    In order to enrich the phylogenetic diversity represented in the available sequenced bacterial genomes and as part of an “Assembling the Tree of Life” project, we determined the genome sequence of Thermomicrobium roseum DSM 5159. T. roseum DSM 5159 is a red-pigmented, rod-shaped, Gram-negative extreme thermophile isolated from a hot spring that possesses both an atypical cell wall composition and an unusual cell membrane that is composed entirely of long-chain 1,2-diols. Its genome is composed of two circular DNA elements, one of 2,006,217 bp (referred to as the chromosome) and one of 919,596 bp (referred to as the megaplasmid). Strikingly, though few standard housekeeping genes are found on the megaplasmid, it does encode a complete system for chemotaxis including both chemosensory components and an entire flagellar apparatus. This is the first known example of a complete flagellar system being encoded on a plasmid and suggests a straightforward means for lateral transfer of flagellum-based motility. Phylogenomic analyses support the recent rRNA-based analyses that led to T. roseum being removed from the phylum Thermomicrobia and assigned to the phylum Chloroflexi. Because T. roseum is a deep-branching member of this phylum, analysis of its genome provides insights into the evolution of the Chloroflexi. In addition, even though this species is not photosynthetic, analysis of the genome provides some insight into the origins of photosynthesis in the Chloroflexi. Metabolic pathway reconstructions and experimental studies revealed new aspects of the biology of this species. For example, we present evidence that T. roseum oxidizes CO aerobically, making it the first thermophile known to do so. In addition, we propose that glycosylation of its carotenoids plays a crucial role in the adaptation of the cell membrane to this bacterium's thermophilic lifestyle. Analyses of published metagenomic sequences from two hot springs similar to the one from which this strain

  4. Reducing nitrous oxide emissions by changing N fertiliser use from calcium ammonium nitrate (CAN) to urea based formulations.

    PubMed

    Harty, M A; Forrestal, P J; Watson, C J; McGeough, K L; Carolan, R; Elliot, C; Krol, D; Laughlin, R J; Richards, K G; Lanigan, G J

    2016-09-01

    The accelerating use of synthetic nitrogen (N) fertilisers, to meet the world's growing food demand, is the primary driver for increased atmospheric concentrations of nitrous oxide (N2O). The IPCC default emission factor (EF) for N2O from soils is 1% of the N applied, irrespective of its form. However, N2O emissions tend to be higher from nitrate-containing fertilisers e.g. calcium ammonium nitrate (CAN) compared to urea, particularly in regions, which have mild, wet climates and high organic matter soils. Urea can be an inefficient N source due to NH3 volatilisation, but nitrogen stabilisers (urease and nitrification inhibitors) can improve its efficacy. This study evaluated the impact of switching fertiliser formulation from calcium ammonium nitrate (CAN) to urea-based products, as a potential mitigation strategy to reduce N2O emissions at six temperate grassland sites on the island of Ireland. The surface applied formulations included CAN, urea and urea with the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) and/or the nitrification inhibitor dicyandiamide (DCD). Results showed that N2O emissions were significantly affected by fertiliser formulation, soil type and climatic conditions. The direct N2O emission factor (EF) from CAN averaged 1.49% overall sites, but was highly variable, ranging from 0.58% to 3.81. Amending urea with NBPT, to reduce ammonia volatilisation, resulted in an average EF of 0.40% (ranging from 0.21 to 0.69%)-compared to an average EF of 0.25% for urea (ranging from 0.1 to 0.49%), with both fertilisers significantly lower and less variable than CAN. Cumulative N2O emissions from urea amended with both NBPT and DCD were not significantly different from background levels. Switching from CAN to stabilised urea formulations was found to be an effective strategy to reduce N2O emissions, particularly in wet, temperate grassland.

  5. Reducing nitrous oxide emissions by changing N fertiliser use from calcium ammonium nitrate (CAN) to urea based formulations.

    PubMed

    Harty, M A; Forrestal, P J; Watson, C J; McGeough, K L; Carolan, R; Elliot, C; Krol, D; Laughlin, R J; Richards, K G; Lanigan, G J

    2016-09-01

    The accelerating use of synthetic nitrogen (N) fertilisers, to meet the world's growing food demand, is the primary driver for increased atmospheric concentrations of nitrous oxide (N2O). The IPCC default emission factor (EF) for N2O from soils is 1% of the N applied, irrespective of its form. However, N2O emissions tend to be higher from nitrate-containing fertilisers e.g. calcium ammonium nitrate (CAN) compared to urea, particularly in regions, which have mild, wet climates and high organic matter soils. Urea can be an inefficient N source due to NH3 volatilisation, but nitrogen stabilisers (urease and nitrification inhibitors) can improve its efficacy. This study evaluated the impact of switching fertiliser formulation from calcium ammonium nitrate (CAN) to urea-based products, as a potential mitigation strategy to reduce N2O emissions at six temperate grassland sites on the island of Ireland. The surface applied formulations included CAN, urea and urea with the urease inhibitor N-(n-butyl) thiophosphoric triamide (NBPT) and/or the nitrification inhibitor dicyandiamide (DCD). Results showed that N2O emissions were significantly affected by fertiliser formulation, soil type and climatic conditions. The direct N2O emission factor (EF) from CAN averaged 1.49% overall sites, but was highly variable, ranging from 0.58% to 3.81. Amending urea with NBPT, to reduce ammonia volatilisation, resulted in an average EF of 0.40% (ranging from 0.21 to 0.69%)-compared to an average EF of 0.25% for urea (ranging from 0.1 to 0.49%), with both fertilisers significantly lower and less variable than CAN. Cumulative N2O emissions from urea amended with both NBPT and DCD were not significantly different from background levels. Switching from CAN to stabilised urea formulations was found to be an effective strategy to reduce N2O emissions, particularly in wet, temperate grassland. PMID:27155080

  6. Stable TEMPO and ABNO Catalyst Solutions for User-Friendly (bpy)Cu/Nitroxyl-Catalyzed Aerobic Alcohol Oxidation.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2015-11-01

    Two solutions, one consisting of bpy/TEMPO/NMI and the other bpy/ABNO/NMI (bpy =2,2'-bipyridyl; TEMPO = 2,2,6,6-tetramethylpiperidine N-oxyl, ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl; NMI = N-methylimidazole), in acetonitrile are shown to have good long-term stability (≥1 year) under air at 5 °C. The solutions may be combined in appropriate quantities with commercially available [Cu(MeCN)4]OTf to provide a convenient catalyst system for the aerobic oxidation of primary and secondary alcohols.

  7. Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry

    PubMed Central

    2015-01-01

    Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. The data obtained from these studies help define safe operating conditions for the use of oxygen with organic solvents. PMID:26622165

  8. Stable TEMPO and ABNO Catalyst Solutions for User-Friendly (bpy)Cu/Nitroxyl-Catalyzed Aerobic Alcohol Oxidation.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2015-11-01

    Two solutions, one consisting of bpy/TEMPO/NMI and the other bpy/ABNO/NMI (bpy =2,2'-bipyridyl; TEMPO = 2,2,6,6-tetramethylpiperidine N-oxyl, ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl; NMI = N-methylimidazole), in acetonitrile are shown to have good long-term stability (≥1 year) under air at 5 °C. The solutions may be combined in appropriate quantities with commercially available [Cu(MeCN)4]OTf to provide a convenient catalyst system for the aerobic oxidation of primary and secondary alcohols. PMID:26457658

  9. Effect of Copper Oxide, Titanium Dioxide, and Lithium Fluoride on the Thermal Behavior and Decomposition Kinetics of Ammonium Nitrate

    NASA Astrophysics Data System (ADS)

    Vargeese, Anuj A.; Mija, S. J.; Muralidharan, Krishnamurthi

    2014-07-01

    Ammonium nitrate (AN) is crystallized along with copper oxide, titanium dioxide, and lithium fluoride. Thermal kinetic constants for the decomposition reaction of the samples were calculated by model-free (Friedman's differential and Vyzovkins nonlinear integral) and model-fitting (Coats-Redfern) methods. To determine the decomposition mechanisms, 12 solid-state mechanisms were tested using the Coats-Redfern method. The results of the Coats-Redfern method show that the decomposition mechanism for all samples is the contracting cylinder mechanism. The phase behavior of the obtained samples was evaluated by differential scanning calorimetry (DSC), and structural properties were determined by X-ray powder diffraction (XRPD). The results indicate that copper oxide modifies the phase transition behavior and can catalyze AN decomposition, whereas LiF inhibits AN decomposition, and TiO2 shows no influence on the rate of decomposition. Possible explanations for these results are discussed. Supplementary materials are available for this article. Go to the publisher's online edition of the Journal of Energetic Materials to view the free supplemental file.

  10. UV-Vis spectrophotometric studies of self-oxidation/dissociation of quaternary ammonium permanganates (QAP) - impact of solvent polarity.

    PubMed

    Bank, Suraj Prakash; Guru, Partha Sarathi; Dash, Sukalyan

    2015-05-01

    Self-oxidation/dissociation of some quaternary ammonium permanganates (QAPs), such as cetyltrimethylammonium permanganate (CTAP) and tetrabutylammonium permanganate (TBAP), have been studied spectrophotometrically in six different organic solvent media of different polarities wherein the compounds show good solubility and stability. The optical densities of the substrates at zero time (ODo) and first-order rate constants of dissociation (k1) have been determined from their successive scanning for 40min. At comparable experimental conditions, absorption capabilities of the substrates are compared from the ODo values in various organic media; the stability of the solutions is compared from the successive scan spectra in those media. The ODo values and the k1 values have been plotted against some solvent parameters to understand their effects on the absorbance and reactivity of the QAPs. These data are also subjected to multiple regression analysis to explain the influence of various solvent parameters on the ion-pairing properties of the substrates, thus elucidating their effects on the process of self-oxidation/dissociation of the substrates.

  11. Thermodynamics and kinetics of extracting zinc from zinc oxide ore by the ammonium sulfate roasting method

    NASA Astrophysics Data System (ADS)

    Sun, Yi; Shen, Xiao-yi; Zhai, Yu-chun

    2015-05-01

    Thermodynamic analyses and kinetic studies were performed on zinc oxide ore treatment by (NH4)2SO4 roasting technology. The results show that it is theoretically feasible to realize a roasting reaction between the zinc oxide ore and (NH4)2SO4 in a temperature range of 573-723 K. The effects of reaction temperature and particle size on the extraction rate of zinc were also examined. It is found that a surface chemical reaction is the rate-controlling step in roasting kinetics. The calculated activation energy of this process is about 45.57 kJ/mol, and the kinetic model can be expressed as follows: 1 - (1 - α)1/3 = 30.85 exp(-45.57/ RT)· t. An extraction ratio of zinc as high as 92% could be achieved under the optimum conditions.

  12. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    PubMed Central

    Venterea, Rodney T.; Clough, Timothy J.; Coulter, Jeffrey A.; Breuillin-Sessoms, Florence

    2015-01-01

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and genes associated with nitrification in two soils (‘L’ and ‘W’) having similar texture, pH, C, and C/N ratio. Solution-phase ammonia (slNH3) was also calculated accounting for non-linear ammonium (NH4+) sorption capacities (ASC). Soil W displayed greater nitrification rates and nitrate (NO3−) levels than soil L, but was more resistant to nitrite (NO2−) accumulation and produced two to ten times less N2O than soil L. Genes associated with NO2− oxidation (nxrA) increased substantially in soil W but remained static in soil L. Soil NO2− was strongly correlated with N2O production, and cumulative (c-) slNH3 explained 87% of the variance in c-NO2−. Differences between soils were explained by greater slNH3 in soil L which inhibited NO2− oxidization leading to greater NO2− levels and N2O production. This is the first study to correlate the dynamics of soil slNH3, NO2−, N2O and nitrifier genes, and the first to show how ASC can regulate NO2− levels and N2O production. PMID:26179972

  13. P-Doped Porous Carbon as Metal Free Catalysts for Selective Aerobic Oxidation with an Unexpected Mechanism.

    PubMed

    Patel, Mehulkumar A; Luo, Feixiang; Khoshi, M Reza; Rabie, Emann; Zhang, Qing; Flach, Carol R; Mendelsohn, Richard; Garfunkel, Eric; Szostak, Michal; He, Huixin

    2016-02-23

    An extremely simple and rapid (seconds) approach is reported to directly synthesize gram quantities of P-doped graphitic porous carbon materials with controlled P bond configuration. For the first time, it is demonstrated that the P-doped carbon materials can be used as a selective metal free catalyst for aerobic oxidation reactions. The work function of P-doped carbon materials, its connectivity to the P bond configuration, and the correlation with its catalytic efficiency are studied and established. In direct contrast to N-doped graphene, the P-doped carbon materials with higher work function show high activity in catalytic aerobic oxidation. The selectivity trend for the electron donating and withdrawing properties of the functional groups attached to the aromatic ring of benzyl alcohols is also different from other metal free carbon based catalysts. A unique catalytic mechanism is demonstrated, which differs from both GO and N-doped graphene obtained by high temperature nitrification. The unique and unexpected catalytic pathway endows the P-doped materials with not only good catalytic efficiency but also recyclability. This, combined with a rapid, energy saving approach that permits fabrication on a large scale, suggests that the P-doped porous materials are promising materials for "green catalysis" due to their higher theoretical surface area, sustainability, environmental friendliness, and low cost.

  14. The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction.

    PubMed

    Miao, Zongcheng; Luan, Yi; Qi, Chao; Ramella, Daniele

    2016-09-21

    A novel one-pot aerobic oxidation/Knoevenagel condensation reaction system was developed employing a Cu(ii)/amine bifunctional, basic metal-organic framework (MOF) as the catalyst. The sequential aerobic alcohol oxidation/Knoevenagel condensation reaction was efficiently promoted by the Cu3TATAT MOF catalyst in the absence of basic additives. The benzylidenemalononitrile product was produced in high yield and selectivity from an inexpensive benzyl alcohol starting material under an oxygen atmosphere. The role of the basic functionality was studied to demonstrate its role in the aerobic oxidation and Knoevenagel condensation reactions. The reaction progress was monitored in order to identify the reaction intermediate and follow the accumulation of the desired product. Lastly, results showed that the yield was not significantly compromised by the reuse of a batch of catalyst, even after more than five cycles.

  15. The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction.

    PubMed

    Miao, Zongcheng; Luan, Yi; Qi, Chao; Ramella, Daniele

    2016-09-21

    A novel one-pot aerobic oxidation/Knoevenagel condensation reaction system was developed employing a Cu(ii)/amine bifunctional, basic metal-organic framework (MOF) as the catalyst. The sequential aerobic alcohol oxidation/Knoevenagel condensation reaction was efficiently promoted by the Cu3TATAT MOF catalyst in the absence of basic additives. The benzylidenemalononitrile product was produced in high yield and selectivity from an inexpensive benzyl alcohol starting material under an oxygen atmosphere. The role of the basic functionality was studied to demonstrate its role in the aerobic oxidation and Knoevenagel condensation reactions. The reaction progress was monitored in order to identify the reaction intermediate and follow the accumulation of the desired product. Lastly, results showed that the yield was not significantly compromised by the reuse of a batch of catalyst, even after more than five cycles. PMID:27523776

  16. Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

    PubMed

    Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

    2016-03-01

    Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations.

  17. Comparison of nitrogen removal rates and nitrous oxide production from enriched anaerobic ammonium oxidizing bacteria in suspended and attached growth reactors.

    PubMed

    Panwivia, Supaporn; Sirvithayapakorn, Sanya; Wantawin, Chalermraj; Noophan, Pongsak Lek; Munakata-Marr, Junko

    2014-01-01

    Attached growth-systems for the anaerobic ammonium oxidation (anammox) process have been postulated for implementation in the field. However, information about the anammox process in attached growth-systems is limited. This study compared nitrogen removal rates and nitrous oxide (N2O) production of enriched anammox cultures in both suspended and attached growth sequencing batch reactors (SBRs). Suspended growth reactors (SBR-S) and attached growth reactors using polystyrene sponge as a medium (SBR-A) were used in these experiments. After inoculation with an enriched anammox culture, significant nitrogen removals of ammonium (NH4 (+)) and nitrite (NO2 (-)) were observed under NH4 (+):NO2 (-) ratios ranging from 1:1 to 1:2 in both types of SBRs. The specific rates of total nitrogen removal in SBR-S and SBR-A were 0.52 mg N/mg VSS-d and 0.44 mg N/mg VSS-d, respectively, at an NH4 (+):NO2 (-) ratio of 1:2. N2O production by the enriched anammox culture in both SBR-S and SBR-A was significantly higher at NH4 (+):NO2 (-) ratio of 1:2 than at NH4 (+):NO2 (-) ratios of 1:1 and 1:1.32. In addition, N2O production was higher at a pH of 6.8 than at pH 7.3, 7.8, and 8.3 in both SBR-S and SBR-A. The results of this investigation demonstrate that the anammox process may avoid N2O emission by maintaining an NH4 (+):NO2 (-) ratio of less than 1:2 and pH higher than 6.8.

  18. Sequential chemical oxidation and aerobic biodegradation of equivalent carbon number-based hydrocarbon fractions in jet fuel.

    PubMed

    Xie, Guibo; Barcelona, Michael J

    2003-10-15

    Remediation of petroleum mixtures is complicated by the differing environmental degradabilities of hundreds of individual hydrocarbons in the mixtures. By grouping the individual hydrocarbons into a few fractions based on equivalent carbon number (EC), the present study examined the chemical and biological degradation of the fractions. With or without prechemical oxidation (25 days) by three oxidants (KMnO4, H202, MgO2), sterile and live microcosms were constituted with aquifer samples for aerobic biodegradation (134 days) of JP-4 jet fuel. Eighty-seven hydrocarbons were recovered and grouped into nine EC fractions. The apparent removal and actual transformation rate constants were estimated for both chemical and biological degradations. The data show that prechemical oxidations facilitated removal of total petroleum hydrocarbons (TPH) (up to 80%) within shorter times (<50 days) than biological alone. KMnO4 and H202 were better oxidants in terms of mass reduction in shorter times yet to some extent inhibited the subsequent microbial activity. MgO2 was a moderate oxidant with less inhibition of microbial activity. Selective degradation of the EC fractions was observed for both chemical and biological processes. The biological processes were much less effective than the prechemical oxidations in transforming aromatic fractions, the more toxic fractions. The favorable substrates (i.e., aliphatic EC approximately 10) for microbial growth were also those most subject to chemical oxidation. The results suggest that for remediation of petroleum contaminants, sequential chemical and biological technologies may surpass biological alone and more moderate oxidants such as MgO2 may be better candidates. More work is needed on the optimal dose and residence time for applied oxidants and on the application to engineering design and formulation of cleanup standards.

  19. Fractionation of the methane isotopologues 13CH4, 12CH3D, and 13CH3D during aerobic oxidation of methane by Methylococcus capsulatus (Bath)

    NASA Astrophysics Data System (ADS)

    Wang, David T.; Welander, Paula V.; Ono, Shuhei

    2016-11-01

    Aerobic oxidation of methane plays a major role in reducing the amount of methane emitted to the atmosphere from freshwater and marine settings. We cultured an aerobic methanotroph, Methylococcus capsulatus (Bath) at 30 and 37 °C, and determined the relative abundance of 12CH4, 13CH4, 12CH3D, and 13CH3D (a doubly-substituted, or "clumped" isotopologue of methane) to characterize the clumped isotopologue effect associated with aerobic methane oxidation. In batch culture, the residual methane became enriched in 13C and D relative to starting methane, with D/H fractionation a factor of 9.14 (Dε/13ε) larger than that of 13C/12C. As oxidation progressed, the Δ13CH3D value (a measure of the excess in abundance of 13CH3D relative to a random distribution of isotopes among isotopologues) of residual methane decreased. The isotopologue fractionation factor for 13CH3D/12CH4 was found to closely approximate the product of the measured fractionation factors for 13CH4/12CH4 and 12CH3D/12CH4 (i.e., 13C/12C and D/H). The results give insight into enzymatic reversibility in the aerobic methane oxidation pathway. Based on the experimental data, a mathematical model was developed to predict isotopologue signatures expected for methane in the environment that has been partially-oxidized by aerobic methanotrophy. Measurement of methane clumped isotopologue abundances can be used to distinguish between aerobic methane oxidation and alternative methane-cycling processes.

  20. Bio-augmentation for mitigating the impact of transient oxytetracycline shock on anaerobic ammonium oxidation (ANAMMOX) performance.

    PubMed

    Jin, Ren-Cun; Zhang, Qian-Qian; Zhang, Zheng-Zhe; Liu, Jia-Hong; Yang, Bi-E; Guo, Li-Xin; Wang, Hui-Zhong

    2014-07-01

    The feasibility of applying bio-augmentation tactics to remit the influence of transient oxytetracycline (OTC) shock on the anaerobic ammonium oxidation (ANAMMOX) process was evaluated. The bio-augmentation was applied together with shock test, with OTC shock concentration of 518 mg L(-1) and 1-h duration. 0.655-2.62 g volatile suspended solid (VSS) sludges were varied to optimize bio-augmentation dosage (BAD), and appropriate bio-augmentation time (BAT) was determined. The validity of the bio-augmentation was indicated by recovery performance and sludge characteristics. The restoring time of 38 h for bio-augmented reactor was shorter than that of non-bio-augmented reactor (45 h), and heme c content was increased respectively from 0.195 ± 0.001, 0.267 ± 0.047, 0.301 ± 0.049, to 0.340 ± 0.053 μmol g(-1) VSS with the BAD of 0.655, 1.31, 1.97, 2.62 g-VSS. The results suggest that bio-augmentation enhances the recovery of ANAMMOX performance following OTC shock and BAT and BAD are key operational factors.

  1. Appropriate Fe (II) Addition Significantly Enhances Anaerobic Ammonium Oxidation (Anammox) Activity through Improving the Bacterial Growth Rate

    PubMed Central

    Liu, Yiwen; Ni, Bing-Jie

    2015-01-01

    The application of anaerobic ammonium oxidation (Anammox) process is often limited by the slow growth rate of Anammox bacteria. As the essential substrate element that required for culturing Anammox sludge, Fe (II) is expected to affect Anammox bacterial growth. This work systematically studied the effects of Fe (II) addition on Anammox activity based on the kinetic analysis of specific growth rate using data from batch tests with an enriched Anammox sludge at different dosing levels. Results clearly demonstrated that appropriate Fe (II) dosing (i.e., 0.09 mM) significantly enhanced the specific Anammox growth rate up to 0.172 d−1 compared to 0.118 d−1 at regular Fe (II) level (0.03 mM). The relationship between Fe (II) concentration and specific Anammox growth rate was found to be well described by typical substrate inhibition kinetics, which was integrated into currently well-established Anammox model to describe the enhanced Anammox growth with Fe (II) addition. The validity of the integrated Anammox model was verified using long-term experimental data from three independent Anammox reactors with different Fe (II) dosing levels. This Fe (II)-based approach could be potentially implemented to enhance the process rate for possible mainstream application of Anammox technology, in order for an energy autarchic wastewater treatment. PMID:25644239

  2. Appropriate Fe (II) Addition Significantly Enhances Anaerobic Ammonium Oxidation (Anammox) Activity through Improving the Bacterial Growth Rate

    NASA Astrophysics Data System (ADS)

    Liu, Yiwen; Ni, Bing-Jie

    2015-02-01

    The application of anaerobic ammonium oxidation (Anammox) process is often limited by the slow growth rate of Anammox bacteria. As the essential substrate element that required for culturing Anammox sludge, Fe (II) is expected to affect Anammox bacterial growth. This work systematically studied the effects of Fe (II) addition on Anammox activity based on the kinetic analysis of specific growth rate using data from batch tests with an enriched Anammox sludge at different dosing levels. Results clearly demonstrated that appropriate Fe (II) dosing (i.e., 0.09 mM) significantly enhanced the specific Anammox growth rate up to 0.172 d-1 compared to 0.118 d-1 at regular Fe (II) level (0.03 mM). The relationship between Fe (II) concentration and specific Anammox growth rate was found to be well described by typical substrate inhibition kinetics, which was integrated into currently well-established Anammox model to describe the enhanced Anammox growth with Fe (II) addition. The validity of the integrated Anammox model was verified using long-term experimental data from three independent Anammox reactors with different Fe (II) dosing levels. This Fe (II)-based approach could be potentially implemented to enhance the process rate for possible mainstream application of Anammox technology, in order for an energy autarchic wastewater treatment.

  3. Appropriate Fe (II) addition significantly enhances anaerobic ammonium oxidation (Anammox) activity through improving the bacterial growth rate.

    PubMed

    Liu, Yiwen; Ni, Bing-Jie

    2015-01-01

    The application of anaerobic ammonium oxidation (Anammox) process is often limited by the slow growth rate of Anammox bacteria. As the essential substrate element that required for culturing Anammox sludge, Fe (II) is expected to affect Anammox bacterial growth. This work systematically studied the effects of Fe (II) addition on Anammox activity based on the kinetic analysis of specific growth rate using data from batch tests with an enriched Anammox sludge at different dosing levels. Results clearly demonstrated that appropriate Fe (II) dosing (i.e., 0.09 mM) significantly enhanced the specific Anammox growth rate up to 0.172 d(-1) compared to 0.118 d(-1) at regular Fe (II) level (0.03 mM). The relationship between Fe (II) concentration and specific Anammox growth rate was found to be well described by typical substrate inhibition kinetics, which was integrated into currently well-established Anammox model to describe the enhanced Anammox growth with Fe (II) addition. The validity of the integrated Anammox model was verified using long-term experimental data from three independent Anammox reactors with different Fe (II) dosing levels. This Fe (II)-based approach could be potentially implemented to enhance the process rate for possible mainstream application of Anammox technology, in order for an energy autarchic wastewater treatment. PMID:25644239

  4. Palladium-Catalyzed Aerobic Oxidative Dehydrogenation of Cyclohexenes to Substituted Arene Derivatives

    PubMed Central

    Iosub, Andrei V.; Stahl, Shannon S.

    2015-01-01

    A palladium(II) catalyst system has been identified for aerobic dehydrogenation of substituted cyclohexenes to the corresponding arene derivatives. Use of sodium anthraquinone-2-sulfonate (AMS) as a co-catalyst enhances the product yields. A wide range of functional groups are tolerated in the reactions, and the scope and limitations of the method are described. The catalytic dehydrogenation of cyclohexenes is showcased in an efficient route to a phthalimide-based TRPA1 activity modulator. PMID:25734414

  5. Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

    NASA Astrophysics Data System (ADS)

    Amos, Richard T.; Bekins, Barbara A.; Delin, Geoffrey N.; Cozzarelli, Isabelle M.; Blowes, David W.; Kirshtein, Julie D.

    2011-07-01

    High resolution direct-push profiling over short vertical distances was used to investigate CH 4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH 4 and CO 2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ 13C CH4 from an average of - 57.6‰ (± 1.7‰) in the methanogenic zone to - 39.6‰ (± 8.7‰) at 105 m downgradient, strongly suggest CH 4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O 2 across the water table is leading to aerobic degradation of CH 4 at this interface. Dissolved N 2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O 2 through aerobic degradation of CH 4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O 2 transport mechanisms.

  6. Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

    USGS Publications Warehouse

    Amos, R.T.; Bekins, B.A.; Delin, G.N.; Cozzarelli, I.M.; Blowes, D.W.; Kirshtein, J.D.

    2011-01-01

    High resolution direct-push profiling over short vertical distances was used to investigate CH4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH4 and CO2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in ??13CCH4 from an average of - 57.6??? (?? 1.7???) in the methanogenic zone to - 39.6??? (?? 8.7???) at 105 m downgradient, strongly suggest CH4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O2 across the water table is leading to aerobic degradation of CH4 at this interface. Dissolved N2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O2 through aerobic degradation of CH4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O2 transport mechanisms. ?? 2011 Elsevier B.V. All rights reserved.

  7. Optimized inhibition assays reveal different inhibitory responses of hydroxylamine oxidoreductases from beta- and gamma-proteobacterial ammonium-oxidizing bacteria.

    PubMed

    Nishigaya, Yuki; Fujimoto, Zui; Yamazaki, Toshimasa

    2016-07-29

    Ammonia-oxidizing bacteria (AOB), ubiquitous chemoautotrophic bacteria, convert ammonia (NH3) to nitrite (NO2(-)) via hydroxylamine as energy source. Excessive growth of AOB, enhanced by applying large amounts of ammonium-fertilizer to the farmland, leads to nitrogen leaching and nitrous oxide gas emission. To suppress these unfavorable phenomena, nitrification inhibitors, AOB specific bactericides, are widely used in fertilized farmland. However, new nitrification inhibitors are desired because of toxicity and weak-effects of currently used inhibitors. Toward development of novel nitrification inhibitors that target hydroxylamine oxidoreductase (HAO), a key enzyme of nitrification in AOB, we established inhibitor evaluation systems that include simplified HAO purification procedure and high-throughput HAO activity assays for the purified enzymes and for the live AOB cells. The new assay systems allowed us to observe distinct inhibitory responses of HAOs from beta-proteobacterial AOB (βAOB) Nitrosomonas europaea (NeHAO) and gamma-proteobacterial AOB (γAOB) Nitrosococcus oceani (NoHAO) against phenylhydrazine, a well-known suicide inhibitor for NeHAO. Consistently, the live cells of N. europaea, Nitrosomonas sp. JPCCT2 and Nitrosospira multiformis of βAOB displayed higher responses to phenylhydrazine than those of γAOB N. oceani. Our homology modeling studies suggest that different inhibitory responses of βAOB and γAOB are originated from different local environments around the substrate-binding sites of HAOs in these two classes of bacteria due to substitutions of two residues. The results reported herein strongly recommend inhibitor screenings against both NeHAO of βAOB and NoHAO of γAOB to develop HAO-targeting nitrification inhibitors with wide anti-AOB spectra.

  8. Co-occurrence of nitrite-dependent anaerobic ammonium and methane oxidation processes in subtropical acidic forest soils.

    PubMed

    Meng, Han; Wang, Yong-Feng; Chan, Ho-Wang; Wu, Ruo-Nan; Gu, Ji-Dong

    2016-09-01

    Anaerobic ammonium oxidation (anammox) and nitrite-dependent anaerobic methane oxidation (n-damo) are two new processes of recent discoveries linking the microbial nitrogen and carbon cycles. In this study, 16S ribosomal RNA (rRNA) gene of anammox bacteria and pmoA gene of n-damo bacteria were used to investigate their distribution and diversity in natural acidic and re-vegetated forest soils. The 16S rRNA gene sequences retrieved featured at least three species in two genera known anammox bacteria, namely Candidatus Brocadia anammoxidans, Candidatus Brocadia fulgida, and Candidatus Kuenenia stuttgartiensis while the pmoA gene amplified was affiliated with two species of known n-damo bacteria Candidatus Methylomirabilis oxyfera and a newly established Candidatus Methylomirabilis sp. According to the results, the diversity of anammox bacteria in natural forests was lower than in re-vegetated forests, but no significant difference was observed in n-damo community between them. Quantitative real-time PCR showed that both anammox and n-damo bacteria were more abundant in the lower layer (10-20 cm) than the surface layer (0-5 cm). The abundance of anammox bacteria varied from 2.21 × 10(5) to 3.90 × 10(6) gene copies per gram dry soil, and n-damo bacteria quantities were between 1.69 × 10(5) and 5.07 × 10(6) gene copies per gram dry soil in the two different layers. Both anammox and n-damo bacteria are reported for the first time to co-occur in acidic forest soil in this study, providing a more comprehensive information on more defined microbial processes contributing to C and N cycles in the ecosystems. PMID:27178181

  9. Ultrafine MnO2 nanoparticles decorated on graphene oxide as a highly efficient and recyclable catalyst for aerobic oxidation of benzyl alcohol.

    PubMed

    Hu, Zonggao; Zhao, Yafei; Liu, Jindun; Wang, Jingtao; Zhang, Bing; Xiang, Xu

    2016-12-01

    The highly active and selective aerobic oxidation of aromatic alcohols over earth-abundant, inexpensive and recyclable catalysts is highly desirable. We fabricated herein MnO2/graphene oxide (GO) composites by a facile in-situ growth approach at room temperature and used them in selective aerobic oxidation of benzyl alcohol to benzaldehyde. TEM, XRD, FTIR, XPS and N2 adsorption/desorption analysis were employed to systematically investigate the morphology, particle size, structure and surface properties of the catalysts. The 96.8% benzyl alcohol conversion and 100% benzaldehyde selectivity over the MnO2/GO (10/100) catalyst with well dispersive ultrafine MnO2 nanoparticles (ca. 3nm) can be obtained within 3h under 383K. Simultaneously, no appreciable loss of activity and selectivity occurred after recycling use up to six times. Due to their significant low cost, excellent catalytic performance, the MnO2/GO composites have huge application prospect in organic synthesis. PMID:27544446

  10. Large-scale synthesis of ultrathin tungsten oxide nanowire networks: an efficient catalyst for aerobic oxidation of toluene to benzaldehyde under visible light.

    PubMed

    Bai, Hua; Yi, Wencai; Liu, Jingyao; Lv, Qing; Zhang, Qing; Ma, Qiang; Yang, Haifeng; Xi, Guangcheng

    2016-07-14

    As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%.

  11. Nitrate removal by organotrophic anaerobic ammonium oxidizing bacteria with C2/C3 fatty acid in upflow anaerobic sludge blanket reactors.

    PubMed

    Liang, Yuhai; Li, Dong; Zhang, Xiaojing; Zeng, Huiping; Yang, Yin; Zhang, Jie

    2015-10-01

    In anaerobic ammonium oxidation (Anammox) process, a harsh ratio of nitrite to ammonia in influent was demanded, and the max nitrogen removal efficiency could only achieve to 89%, both of which limited the development of Anammox. The aim of this work was to study the nitrate removal by organotrophic anaerobic ammonium oxidizing bacteria (AAOB) with C2/C3 fatty acid in upflow anaerobic sludge blanket (UASB) reactors. In this study, organotrophic AAOB was successfully enriched by adding acetate and propionate with the total organic carbon to nitrogen (TOC/N) ratio of 0.1. In the condition of low substrate, the TN removal efficiency reached 90%, with the effluent TN of around 11.8 mg L(-1). After the addition of acetate and propionate, the predominant species in Anammox granular sludge transformed to Candidatus Jettenia that belonging to organotrophic AAOB from the Candidatus Kuenenia relating to general AAOB. PMID:26151852

  12. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles

    PubMed Central

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-01-01

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications. PMID:26300041

  13. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles

    NASA Astrophysics Data System (ADS)

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-08-01

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications.

  14. Organization of the Escherichia coli aerobic enzyme complexes of oxidative phosphorylation in dynamic domains within the cytoplasmic membrane

    PubMed Central

    Erhardt, Heiko; Dempwolff, Felix; Pfreundschuh, Moritz; Riehle, Marc; Schäfer, Caspar; Pohl, Thomas; Graumann, Peter; Friedrich, Thorsten

    2014-01-01

    The Escherichia coli cytoplasmic membrane contains the enzyme complexes of oxidative phosphorylation (OXPHOS). Not much is known about their supramolecular organization and their dynamics within the membrane in this model organism. In mitochondria and other bacteria, it was demonstrated by nondenaturing electrophoretic methods and electron microscopy that the OXPHOS complexes are organized in so-called supercomplexes, stable assemblies with a defined number of the individual enzyme complexes. To investigate the organization of the E. coli enzyme complexes of aerobic OXPHOS in vivo, we established fluorescent protein fusions of the NADH:ubiquinone oxidoreductase, the succinate:ubiquinone oxidoreductase, the cytochrome bd-I, and the cytochrome bo3 terminal oxidases, and the FoF1 ATP-synthase. The fusions were integrated in the chromosome to prevent artifacts caused by protein overproduction. Biochemical analysis revealed that all modified complexes were fully assembled, active, and stable. The distribution of the OXPHOS complexes in living cells was determined using total internal reflection fluorescence microscopy. The dynamics within the membrane were detected by fluorescence recovery after photobleaching. All aerobic OXPHOS complexes showed an uneven distribution in large mobile patches within the E. coli cytoplasmic membrane. It is discussed whether the individual OXPHOS complexes are organized as clustered individual complexes, here called “segrazones.” PMID:24729508

  15. Organization of the Escherichia coli aerobic enzyme complexes of oxidative phosphorylation in dynamic domains within the cytoplasmic membrane.

    PubMed

    Erhardt, Heiko; Dempwolff, Felix; Pfreundschuh, Moritz; Riehle, Marc; Schäfer, Caspar; Pohl, Thomas; Graumann, Peter; Friedrich, Thorsten

    2014-06-01

    The Escherichia coli cytoplasmic membrane contains the enzyme complexes of oxidative phosphorylation (OXPHOS). Not much is known about their supramolecular organization and their dynamics within the membrane in this model organism. In mitochondria and other bacteria, it was demonstrated by nondenaturing electrophoretic methods and electron microscopy that the OXPHOS complexes are organized in so-called supercomplexes, stable assemblies with a defined number of the individual enzyme complexes. To investigate the organization of the E. coli enzyme complexes of aerobic OXPHOS in vivo, we established fluorescent protein fusions of the NADH:ubiquinone oxidoreductase, the succinate:ubiquinone oxidoreductase, the cytochrome bd-I, and the cytochrome bo3 terminal oxidases, and the FoF1 ATP-synthase. The fusions were integrated in the chromosome to prevent artifacts caused by protein overproduction. Biochemical analysis revealed that all modified complexes were fully assembled, active, and stable. The distribution of the OXPHOS complexes in living cells was determined using total internal reflection fluorescence microscopy. The dynamics within the membrane were detected by fluorescence recovery after photobleaching. All aerobic OXPHOS complexes showed an uneven distribution in large mobile patches within the E. coli cytoplasmic membrane. It is discussed whether the individual OXPHOS complexes are organized as clustered individual complexes, here called "segrazones."

  16. A convenient and selective palladium-catalyzed aerobic oxidation of alcohols.

    PubMed

    Gowrisankar, Saravanan; Neumann, Helfried; Gördes, Dirk; Thurow, Kerstin; Jiao, Haijun; Beller, Matthias

    2013-11-18

    An efficient procedure for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively, with molecular oxygen under ambient conditions has been achieved. By applying catalytic amounts of Pd(OAc)2 in the presence of tertiary phosphine oxides (O=PR3) as ligands, a variety of substrates are selectively oxidized without formation of ester byproducts. Spectroscopic investigations and DFT calculations suggest stabilization of the active palladium(II) catalyst by phosphine oxide ligands.

  17. Shifts in the community structure and activity of anaerobic ammonium oxidation bacteria along an estuarine salinity gradient

    NASA Astrophysics Data System (ADS)

    Zheng, Yanling; Jiang, Xiaofen; Hou, Lijun; Liu, Min; Lin, Xianbiao; Gao, Juan; Li, Xiaofei; Yin, Guoyu; Yu, Chendi; Wang, Rong

    2016-06-01

    Anaerobic ammonium oxidation (anammox) is a major microbial pathway for nitrogen (N) removal in estuarine and coastal environments. However, understanding of anammox bacterial dynamics and associations with anammox activity remains scarce along estuarine salinity gradient. In this study, the diversity, abundance, and activity of anammox bacteria, and their potential contributions to total N2 production in the sediments along the salinity gradient (0.1-33.8) of the Yangtze estuarine and coastal zone, were studied using 16S rRNA gene clone library, quantitative polymerase chain reaction assay, and isotope-tracing technique. Phylogenetic analysis showed a significant change in anammox bacterial community structure along the salinity gradient (P < 0.01), with the dominant genus shifting from Brocadia in the freshwater region to Scalindua in the open ocean. Anammox bacterial abundance ranged from 3.67 × 105 to 8.22 × 107 copies 16S rRNA gene g-1 and related significantly with salinity (P < 0.05). The anammox activity varied between 0.08 and 6.46 nmol N g-1 h-1 and related closely with anammox bacterial abundance (P < 0.01). Contributions of anammox activity to total N loss were highly variable along the salinity gradient, ranging from 5 to 77% and were significantly negatively correlated with salinity (P < 0.01). Sediment organic matter was also recognized as an important factor in controlling the relative role of anammox to total N2 production in the Yangtze estuarine and coastal zone. Overall, our data demonstrated a biogeographical distribution of anammox bacterial diversity, abundance, and activity along the estuarine salinity gradient and suggested that salinity is a major environmental control on anammox process in the estuarine and coastal ecosystems.

  18. Community composition and activity of anaerobic ammonium oxidation bacteria in the rhizosphere of salt-marsh grass Spartina alterniflora.

    PubMed

    Zheng, Yanling; Hou, Lijun; Liu, Min; Yin, Guoyu; Gao, Juan; Jiang, Xiaofen; Lin, Xianbiao; Li, Xiaofei; Yu, Chendi; Wang, Rong

    2016-09-01

    Anaerobic ammonium oxidation (anammox) as an important nitrogen removal pathway has been investigated in intertidal marshes. However, the rhizosphere-driven anammox process in these ecosystems is largely overlooked so far. In this study, the community dynamics and activities of anammox bacteria in the rhizosphere and non-rhizosphere sediments of salt-marsh grass Spartina alterniflora (a widely distributed plant in estuaries and intertidal ecosystems) were investigated using clone library analysis, quantitative PCR assay, and isotope-tracing technique. Phylogenetic analysis showed that anammox bacterial diversity was higher in the non-rhizosphere sediments (Scalindua and Kuenenia) compared with the rhizosphere zone (only Scalindua genus). Higher abundance of anammox bacteria was detected in the rhizosphere (6.46 × 10(6)-1.56 × 10(7) copies g(-1)), which was about 1.5-fold higher in comparison with that in the non-rhizosphere zone (4.22 × 10(6)-1.12 × 10(7) copies g(-1)). Nitrogen isotope-tracing experiments indicated that the anammox process in the rhizosphere contributed to 12-14 % N2 generation with rates of 0.43-1.58 nmol N g(-1) h(-1), while anammox activity in the non-rhizosphere zone contributed to only 4-7 % N2 production with significantly lower activities (0.28-0.83 nmol N g(-1) h(-1)). Overall, we propose that the rhizosphere microenvironment in intertidal marshes might provide a favorable niche for anammox bacteria and thus plays an important role in nitrogen cycling. PMID:27225476

  19. Large-scale synthesis of ultrathin tungsten oxide nanowire networks: an efficient catalyst for aerobic oxidation of toluene to benzaldehyde under visible light

    NASA Astrophysics Data System (ADS)

    Bai, Hua; Yi, Wencai; Liu, Jingyao; Lv, Qing; Zhang, Qing; Ma, Qiang; Yang, Haifeng; Xi, Guangcheng

    2016-07-01

    As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%.As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%. Electronic supplementary information (ESI) available: Experimental procedure, XRD patterns, TEM and HRTEM images, energy-dispersive X-ray spectra, UV-vis spectra, X-ray photoelectron spectroscopy (XPS), and EDS. See DOI: 10.1039/c6nr02949c

  20. Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper(II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature.

    PubMed

    Mahyari, Mojtaba; Laeini, Mohammad Sadegh; Shaabani, Ahmad

    2014-07-25

    Copper(ii) tetrasulfophthalocyanine supported on three-dimensional nitrogen-doped graphene-based frameworks was synthesized and introduced as a bifunctional catalyst for selective aerobic oxidation of alkyl arenes and alcohols to the corresponding carbonyl compounds. The ease of catalyst separation, high turnover, low catalyst loading and recyclability could potentially render it applicable in industrial setting. PMID:24912023

  1. Nitrous oxide production pathways in a partial nitritation-anammox reactor: Isotopic evidence for nitrous oxide production associated anaerobic ammonium oxidation?

    NASA Astrophysics Data System (ADS)

    Wunderlin, P.; Harris, E. J.; Joss, A.; Emmenegger, L.; Kipf, M.; Mohn, J.; Siegrist, H.

    2014-12-01

    Nitrous oxide (N2O) is a strong greenhouse gas and a major sink for stratospheric ozone. In biological wastewater treatment N2O can be produced via several pathways. This study investigates the dynamics of N2O emissions from a nitritation-anammox reactor, and links its interpretation to the nitrogen and oxygen isotopic signature of the emitted N2O. A 400-litre single-stage nitritation-anammox reactor was operated and continuously fed with digester liquid. The isotopic composition of N2O emissions was monitored online with quantum cascade laser absorption spectroscopy (QCLAS; Aerodyne Research, Inc.; Waechter et al., 2008). Dissolved ammonium and nitrate were monitored online (ISEmax, Endress + Hauser), while nitrite was measured with test strips (Nitrite-test 0-24mgN/l, Merck). Table 1. Summary of experiments conducted to understand N2O emissions Experimental conditions O2[mgO2/L] NO2-[mgN/L] NH4+[mgN/L] N2O/NH4+[%] Normal operation <0.1 <0.5 10 0.6 Normal operation, high NH4+ <0.1 <0.5 100 6.1 High aeration 0.5 to 1.5 up to 50 10 and 50 4.9 NO2- addition (oxic) <0.1 <0.5 to 4 10 5.8 NO2- addition (anoxic) 0 <0.5 to 4 10 3.2 NH2OH addition <0.1 <0.5 10 2.5 Results showed that under normal operating conditions, the N2O isotopic site preference (SP = d15Nα - d15Nβ) was much higher than expected - up to 41‰ - strongly suggesting an unknown N2O production pathway, which is hypothesized to be mediated by anammox activity (Figure 1). A less likely explanation is that the SP of N2O was increased by partial N2O reduction by heterotrophic denitrification. Various experiments were conducted to further investigate N2O formation pathways in the reactor. Our data reveal that N2O emissions increased when reactor operation was not ideal, for example when dissolved oxygen was too high (Table 1). SP measurements confirmed that these N2O peaks were due to enhanced nitrifier denitrification, generally related to nitrite build-up in the reactor (Figure 1; Table 1). Overall

  2. New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

    PubMed

    Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

    2016-08-01

    Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. PMID:27088192

  3. Investigation of oxidative phosphorylation in continuous cultures. A non-equilibrium thermodynamic approach to energy transduction for Escherichia coli in aerobic condition

    NASA Astrophysics Data System (ADS)

    Ghafuri, Mohazabeh; Nosrati, Mohsen; Hosseinkhani, Saman

    2015-03-01

    Adenosine triphosphate (ATP) production in living cells is very important. Different researches have shown that in terms of mathematical modeling, the domain of these investigations is essentially restricted. Recently the thermodynamic models have been suggested for calculation of the efficiency of oxidative phosphorylation process and rate of energy loss in animal cells using chemiosmotic theory and non-equilibrium thermodynamics equations. In our previous work, we developed a mathematical model for mitochondria of animal cells. In this research, according to similarities between oxidative phosphorylation process in microorganisms and animal cells, Golfar's model was developed to predict the non-equilibrium thermodynamic behavior of the oxidative phosphorylation process for bacteria in aerobic condition. With this model the rate of energy loss, P/O ratio, and efficiency of oxidative phosphorylation were calculated for Escherichia coli in aerobic condition. The results then were compared with experimental data given by other authors. The thermodynamic model had an acceptable agreement with the experimental data.

  4. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    PubMed

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

  5. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, William A.

    1998-01-01

    A biofilter for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described.

  6. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, W.A.

    1998-08-18

    A biofilter is described for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method is described of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described. 6 figs.

  7. Ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium in two US Great Basin hot springs with abundant ammonia-oxidizing archaea.

    PubMed

    Dodsworth, Jeremy A; Hungate, Bruce A; Hedlund, Brian P

    2011-08-01

    Many thermophiles catalyse free energy-yielding redox reactions involving nitrogenous compounds; however, little is known about these processes in natural thermal environments. Rates of ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were measured in source water and sediments of two ≈ 80°C springs in the US Great Basin. Ammonia oxidation and denitrification occurred mainly in sediments. Ammonia oxidation rates measured using (15)N-NO(3)(-) pool dilution ranged from 5.5 ± 0.8 to 8.6 ± 0.9 nmol N g(-1) h(-1) and were unaffected or only mildly stimulated by amendment with NH(4) Cl. Denitrification rates measured using acetylene block ranged from 15.8 ± 0.7 to 51 ± 12 nmol N g(-1) h(-1) and were stimulated by amendment with NO(3)(-) and complex organic compounds. The DNRA rate in one spring sediment measured using an (15)N-NO(3)(-) tracer was 315 ± 48 nmol N g(-1) h(-1). Both springs harboured distinct planktonic and sediment microbial communities. Close relatives of the autotrophic, ammonia-oxidizing archaeon 'Candidatus Nitrosocaldus yellowstonii' represented the most abundant OTU in both spring sediments by 16S rRNA gene pyrotag analysis. Quantitative PCR (qPCR) indicated that 'Ca. N. yellowstonii'amoA and 16S rRNA genes were present at 3.5-3.9 × 10(8) and 6.4-9.0 × 10(8) copies g(-1) sediment. Potential denitrifiers included members of the Aquificales and Thermales. Thermus spp. comprised <1% of 16S rRNA gene pyrotags in both sediments and qPCR for T. thermophilus narG revealed sediment populations of 1.3-1.7 × 10(6) copies g(-1) sediment. These data indicate a highly active nitrogen cycle (N-cycle) in these springs and suggest that ammonia oxidation may be a major source of energy fuelling primary production.

  8. Ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium in two US Great Basin hot springs with abundant ammonia-oxidizing archaea.

    PubMed

    Dodsworth, Jeremy A; Hungate, Bruce A; Hedlund, Brian P

    2011-08-01

    Many thermophiles catalyse free energy-yielding redox reactions involving nitrogenous compounds; however, little is known about these processes in natural thermal environments. Rates of ammonia oxidation, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were measured in source water and sediments of two ≈ 80°C springs in the US Great Basin. Ammonia oxidation and denitrification occurred mainly in sediments. Ammonia oxidation rates measured using (15)N-NO(3)(-) pool dilution ranged from 5.5 ± 0.8 to 8.6 ± 0.9 nmol N g(-1) h(-1) and were unaffected or only mildly stimulated by amendment with NH(4) Cl. Denitrification rates measured using acetylene block ranged from 15.8 ± 0.7 to 51 ± 12 nmol N g(-1) h(-1) and were stimulated by amendment with NO(3)(-) and complex organic compounds. The DNRA rate in one spring sediment measured using an (15)N-NO(3)(-) tracer was 315 ± 48 nmol N g(-1) h(-1). Both springs harboured distinct planktonic and sediment microbial communities. Close relatives of the autotrophic, ammonia-oxidizing archaeon 'Candidatus Nitrosocaldus yellowstonii' represented the most abundant OTU in both spring sediments by 16S rRNA gene pyrotag analysis. Quantitative PCR (qPCR) indicated that 'Ca. N. yellowstonii'amoA and 16S rRNA genes were present at 3.5-3.9 × 10(8) and 6.4-9.0 × 10(8) copies g(-1) sediment. Potential denitrifiers included members of the Aquificales and Thermales. Thermus spp. comprised <1% of 16S rRNA gene pyrotags in both sediments and qPCR for T. thermophilus narG revealed sediment populations of 1.3-1.7 × 10(6) copies g(-1) sediment. These data indicate a highly active nitrogen cycle (N-cycle) in these springs and suggest that ammonia oxidation may be a major source of energy fuelling primary production. PMID:21631688

  9. High performance ammonium nitrate propellant

    NASA Technical Reports Server (NTRS)

    Anderson, F. A. (Inventor)

    1979-01-01

    A high performance propellant having greatly reduced hydrogen chloride emission is presented. It is comprised of: (1) a minor amount of hydrocarbon binder (10-15%), (2) at least 85% solids including ammonium nitrate as the primary oxidizer (about 40% to 70%), (3) a significant amount (5-25%) powdered metal fuel, such as aluminum, (4) a small amount (5-25%) of ammonium perchlorate as a supplementary oxidizer, and (5) optionally a small amount (0-20%) of a nitramine.

  10. Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air.

    PubMed

    Bai, Xing-Feng; Ye, Fei; Zheng, Long-Sheng; Lai, Guo-Qiao; Xia, Chun-Gu; Xu, Li-Wen

    2012-09-01

    In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields.

  11. Hydrosilane and bismuth-accelerated palladium catalyzed aerobic oxidative esterification of benzylic alcohols with air.

    PubMed

    Bai, Xing-Feng; Ye, Fei; Zheng, Long-Sheng; Lai, Guo-Qiao; Xia, Chun-Gu; Xu, Li-Wen

    2012-09-01

    In a palladium-catalyzed oxidative esterification, hydrosilane can serve as an activator of palladium catalyst with bismuth, thus leading to a novel ligand- and silver-free palladium catalyst system for facile oxidative esterification of a variety of benzylic alcohols in good yields. PMID:22814568

  12. The history of aerobic ammonia oxidizers: from the first discoveries to today.

    PubMed

    Monteiro, Maria; Séneca, Joana; Magalhães, Catarina

    2014-07-01

    Nitrification, the oxidation of ammonia to nitrite and nitrate, has long been considered a central biological process in the global nitrogen cycle, with its first description dated 133 years ago. Until 2005, bacteria were considered the only organisms capable of nitrification. However, the recent discovery of a chemoautotrophic ammonia-oxidizing archaeon, Nitrosopumilus maritimus, changed our concept of the range of organisms involved in nitrification, highlighting the importance of ammonia-oxidizing archaea (AOA) as potential players in global biogeochemical nitrogen transformations. The uniqueness of these archaea justified the creation of a novel archaeal phylum, Thaumarchaeota. These recent discoveries increased the global scientific interest within the microbial ecology society and have triggered an analysis of the importance of bacterial vs archaeal ammonia oxidation in a wide range of natural ecosystems. In this mini review we provide a chronological perspective of the current knowledge on the ammonia oxidation pathway of nitrification, based on the main physiological, ecological and genomic discoveries.

  13. Aerobic oxidation of lignin models using a base metal vanadium catalyst.

    PubMed

    Hanson, Susan K; Baker, R Tom; Gordon, John C; Scott, Brian L; Thorn, David L

    2010-06-21

    Dipicolinate vanadium(V) complexes oxidize lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), 1-phenyl-2-phenoxyethanol (C), and 1,2-diphenyl-2-methoxyethanol (D). With substrates having C-H bonds adjacent to the alcohol moiety (B-D), the C-H bond is broken in pyridine-d(5) solvent, yielding 2-phenoxyacetaldehyde from B, 2-phenoxyacetophenone from C, and benzoin methyl ether from D. In DMSO-d(6) solvent the reaction is slower, and both C-H and C-C bond cleavage products are observed for D. The vanadium(IV) products of these reactions have been identified and characterized. Catalytic oxidation of C and D has been demonstrated using air and (dipic)V(O)O(i)Pr. For both substrates, the C-C bond between the alcohol and ether groups is broken in the catalytic oxidation. 1-Phenyl-2-phenoxyethanol is oxidized to a mixture of phenol, formic acid, benzoic acid, and 2-methoxyacetophenone. The products of oxidation of 1,2-diphenyl-2-methoxyethanol depend on the solvent; in DMSO benzaldehyde and methanol are the major products, while benzoic acid and methyl benzoate are the major products obtained in pyridine solvent. Phenyl substituents on the model complex facilitate the oxidation, with relative rates of oxidation D > C > B.

  14. Metal-free aerobic alcohol oxidation: intensification under three-phase flow conditions.

    PubMed

    Aellig, Christof; Scholz, David; Hermans, Ive

    2012-09-01

    The selective oxidation of alcohols is a pivotal transformation within industrial and synthetic chemistry. In this contribution we use O₂ as terminal oxidant and (H)NO(x) species as oxygen shuttle in order to mediate the oxidation of primary and secondary alcohols under the influence of a solid acid catalyst. Process optimization and intensification through the use of a continuous three-phase flow reactor is demonstrated. Space-time yields were found to increase by two orders of magnitude with respect to batch experiments, along with additional gains in selectivity and a decrease of N₂O formation.

  15. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    DOEpatents

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  16. Systemic Oxidative Stress Is Associated With Lower Aerobic Capacity and Impaired Skeletal Muscle Energy Metabolism in Patients With Metabolic Syndrome

    PubMed Central

    Yokota, Takashi; Kinugawa, Shintaro; Yamato, Mayumi; Hirabayashi, Kagami; Suga, Tadashi; Takada, Shingo; Harada, Kuniaki; Morita, Noriteru; Oyama-Manabe, Noriko; Kikuchi, Yasuka; Okita, Koichi; Tsutsui, Hiroyuki

    2013-01-01

    OBJECTIVE Systemic oxidative stress is associated with insulin resistance and obesity. We tested the hypothesis that systemic oxidative stress is linked to lower aerobic capacity and skeletal muscle dysfunction in metabolic syndrome (MetS). RESEARCH DESIGN AND METHODS The incremental exercise testing with cycle ergometer was performed in 14 male patients with MetS and 13 age-, sex-, and activity-matched healthy subjects. Systemic lipid peroxidation was assessed by serum thiobarbituric acid reactive substances (TBARS), and systemic antioxidant defense capacity was assessed by serum total thiols and enzymatic activity of superoxide dismutase (SOD). To assess skeletal muscle energy metabolism, we measured high-energy phosphates in the calf muscle during plantar flexion exercise and intramyocellular lipid (IMCL) in the resting leg muscle, using 31P- and 1proton-magnetic resonance spectroscopy, respectively. RESULTS Serum TBARS were elevated (12.4 ± 7.1 vs. 3.7 ± 1.1 μmol/L; P < 0.01), and serum total thiols and SOD activity were decreased (290.8 ± 51.2 vs. 398.7 ± 105.2 μmol/L, P < 0.01; and 22.2 ± 8.4 vs. 31.5 ± 8.5 units/L, P < 0.05, respectively) in patients with MetS compared with healthy subjects. Peak VO2 and anaerobic threshold normalized to body weight were significantly lower in MetS patients by 25 and 31%, respectively, and inversely correlated with serum TBARS (r = −0.49 and r = −0.50, respectively). Moreover, muscle phosphocreatine loss during exercise was 1.4-fold greater in patients with MetS (P < 0.05), and IMCL content was 2.9-fold higher in patients with MetS (P < 0.01), indicating impaired skeletal muscle energy metabolism, and these indices positively correlated with serum TBARS (r = 0.45 and r = 0.63, respectively). CONCLUSIONS Systemic oxidative stress was associated with lower aerobic capacity and impaired skeletal muscle energy metabolism in patients with MetS. PMID:23393211

  17. Ammonium methacrylate

    Integrated Risk Information System (IRIS)

    Ammonium methacrylate ; CASRN 16325 - 47 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcin

  18. Ammonium sulfamate

    Integrated Risk Information System (IRIS)

    Ammonium sulfamate ; CASRN 7773 - 06 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogen

  19. Ammonium acetate

    Integrated Risk Information System (IRIS)

    Ammonium acetate ; CASRN 631 - 61 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  20. Extraction of beryllium from refractory beryllium oxide with dilute ammonium bifluoride and determination by fluorescence: a multiparameter performance evaluation.

    PubMed

    Goldcamp, Michael J; Goldcamp, Diane M; Ashley, Kevin; Fernback, Joseph E; Agrawal, Anoop; Millson, Mark; Marlow, David; Harrison, Kenneth

    2009-12-01

    Beryllium exposure can cause a number of deleterious health effects, including beryllium sensitization and the potentially fatal chronic beryllium disease. Efficient methods for monitoring beryllium contamination in workplaces are valuable to help prevent dangerous exposures to this element. In this work, performance data on the extraction of beryllium from various size fractions of high-fired beryllium oxide (BeO) particles (from < 32 microm up to 212 microm) using dilute aqueous ammonium bifluoride (ABF) solution were obtained under various conditions. Beryllium concentrations were determined by fluorescence using a hydroxybenzoquinoline fluorophore. The effects of ABF concentration and volume, extraction temperature, sample tube types, and presence of filter or wipe media were examined. Three percent ABF extracts beryllium nearly twice as quickly as 1% ABF; extraction solution volume has minimal influence. Elevated temperatures increase the rate of extraction dramatically compared with room temperature extraction. Sample tubes with constricted tips yield poor extraction rates owing to the inability of the extraction medium to access the undissolved particles. The relative rates of extraction of Be from BeO of varying particle sizes were examined. Beryllium from BeO particles in fractions ranging from less than 32 microm up to 212 microm were subjected to various extraction schemes. The smallest BeO particles are extracted more quickly than the largest particles, although at 90 degrees C even the largest BeO particles reach nearly quantitative extraction within 4 hr in 3% ABF. Extraction from mixed cellulosic-ester filters, cellulosic surface-sampling filters, wetted cellulosic dust wipes, and cotton gloves yielded 90% or greater recoveries. Scanning electron microscopy of BeO particles, including partially dissolved particles, shows that dissolution in dilute ABF occurs not just on the exterior surface but also via accessing particles' interiors due to porosity

  1. Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids.

    PubMed

    Jiang, Xingguo; Zhang, Jiasheng; Ma, Shengming

    2016-07-13

    Oxidation from alcohols to carboxylic acids, a class of essential chemicals in daily life, academic laboratories, and industry, is a fundamental reaction, usually using at least a stoichiometric amount of an expensive and toxic oxidant. Here, an efficient and practical sustainable oxidation technology of alcohols to carboxylic acids using pure O2 or even O2 in air as the oxidant has been developed: utilizing a catalytic amount each of Fe(NO3)3·9H2O/TEMPO/MCl, a series of carboxylic acids were obtained from alcohols (also aldehydes) in high yields at room temperature. A 55 g-scale reaction was demonstrated using air. As a synthetic application, the first total synthesis of a naturally occurring allene, i.e., phlomic acid, was accomplished.

  2. Sustainable synthesis of diverse privileged heterocycles by palladium-catalyzed aerobic oxidative isocyanide insertion.

    PubMed

    Vlaar, Tjøstil; Cioc, Razvan C; Mampuys, Pieter; Maes, Bert U W; Orru, Romano V A; Ruijter, Eelco

    2012-12-21

    O(2) in, H(2)O out: Various diamines and related bisnucleophiles readily undergo oxidative isocyanide insertion with Pd(OAc)(2) (1 mol %) as the catalyst and O(2) as the terminal oxidant to give a diverse array of medicinally relevant N heterocycles. The utility of this highly sustainable method is demonstrated by a formal synthesis of the antihistamines astemizole and norastemizole. PMID:23161862

  3. Potential application of aerobic denitrifying bacterium Pseudomonas aeruginosa PCN-2 in nitrogen oxides (NOx) removal from flue gas.

    PubMed

    Zheng, Maosheng; Li, Can; Liu, Shufeng; Gui, Mengyao; Ni, Jinren

    2016-11-15

    Conventional biological removal of nitrogen oxides (NOx) from flue gas has been severely restricted by the presence of oxygen. This paper presents an efficient alternative for NOx removal at varying oxygen levels using the newly isolated bacterial strain Pseudomonas aeruginosa PCN-2 which was capable of aerobic and anoxic denitrification. Interestingly, nitric oxide (NO), as the obligatory intermediate, was negligibly accumulated during nitrate and nitrite reduction. Moreover, normal nitrate reduction with decreasing NO accumulation was realized under O2 concentration ranging from 0 to 100%. Reverse transcription and real-time quantitative polymerase chain reaction (RT-qPCR) analysis revealed that high efficient NO removal was attributed to the coordinate regulation of gene expressions including napA (for periplasmic nitrate reductase), nirS (for cytochrome cd1 nitrite reductase) and cnorB (for NO reductase). Further batch experiments demonstrated the immobilized strain PCN-2 possessed high capability of removing NO and nitrogen dioxide (NO2) at O2 concentration of 0-10%. A biotrickling filter established with present strain achieved high NOx removal efficiencies of 91.94-96.74% at inlet NO concentration of 100-500ppm and O2 concentration of 0-10%, which implied promising potential applications in purifying NOx contaminated flue gas.

  4. Potential application of aerobic denitrifying bacterium Pseudomonas aeruginosa PCN-2 in nitrogen oxides (NOx) removal from flue gas.

    PubMed

    Zheng, Maosheng; Li, Can; Liu, Shufeng; Gui, Mengyao; Ni, Jinren

    2016-11-15

    Conventional biological removal of nitrogen oxides (NOx) from flue gas has been severely restricted by the presence of oxygen. This paper presents an efficient alternative for NOx removal at varying oxygen levels using the newly isolated bacterial strain Pseudomonas aeruginosa PCN-2 which was capable of aerobic and anoxic denitrification. Interestingly, nitric oxide (NO), as the obligatory intermediate, was negligibly accumulated during nitrate and nitrite reduction. Moreover, normal nitrate reduction with decreasing NO accumulation was realized under O2 concentration ranging from 0 to 100%. Reverse transcription and real-time quantitative polymerase chain reaction (RT-qPCR) analysis revealed that high efficient NO removal was attributed to the coordinate regulation of gene expressions including napA (for periplasmic nitrate reductase), nirS (for cytochrome cd1 nitrite reductase) and cnorB (for NO reductase). Further batch experiments demonstrated the immobilized strain PCN-2 possessed high capability of removing NO and nitrogen dioxide (NO2) at O2 concentration of 0-10%. A biotrickling filter established with present strain achieved high NOx removal efficiencies of 91.94-96.74% at inlet NO concentration of 100-500ppm and O2 concentration of 0-10%, which implied promising potential applications in purifying NOx contaminated flue gas. PMID:27469045

  5. Effect of Aloe barbadensis Miller juice on oxidative stress biomarkers in aerobic cells using Artemia franciscana as a model.

    PubMed

    Sirdaarta, J; Cock, I E

    2010-03-01

    This study reports on the induction of oxidative stress in aerobic cell systems by Aloe barbadensis Miller (Aloe vera) juice using the salt water crustacean Artemia franciscana as a model. A consistent pattern was observed in which Artemia franciscana nauplii responded to Aloe vera juice exposure with a decrease in the overall activity of redox related enzymes. Exposure of Artemia franciscana to sub-lethal levels of Aloe vera juice resulted in a decreased activity of thioredoxin reductase, glutathione reductase and glutathione peroxidase by 34% (66% enzymatic activity), 79% (21% enzymatic activity) and 90% (10% enzymatic activity), respectively. Similarly apparent was the trend whereby the co-exposure of the nauplii to vitamin E counteracted this effect. For each of the biomarker enzymes tested, vitamin E co-exposure resulted in enzyme activities closer to the control value (78%, 56% and 32% of control enzymatic activities for thioredoxin reductase, glutathione reductase and glutathione peroxidase activity, respectively). These results indicate that exposure to sub-lethal doses of Aloe vera juice induces alterations in the cellular redox status of Artemia franciscana and that the addition of vitamin E helps the Artemia franciscana nauplii to overcome/block the juice induced oxidative stress.

  6. Extraction of benzene and naphthalene carboxylic acids using quaternary ammonium salts as a model study for the separation of coal oxidation products

    SciTech Connect

    Kawamura, K.; Nagano, H.; Okuwaki, A.

    2005-07-01

    The ion-pair solvent extraction of benzene- and naphthalene-carboxylic acids has been investigated as a model study for the separation of coal oxidation products, which are formed by treatment with alkaline solutions at high temperatures. It was possible that benzene- and naphthalene-dicarboxylic acids are extracted into several types of organic solvents with quaternary ammonium ions. The extraction equilibrium constants (K{sub ex}) for benzoic acid, 1,2-benzenedicarboxylic acid, 1,3-benzenedicarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, 2,3-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid into chloroform were determined at 20{sup o}C. The difference of K{sub ex} among the aromatic acids was sufficiently large for designing a separation method for these aromatic acids. It was unexpected that the extraction of dicarboxylic acids was slower than that of monocarboxylic acids, although the ion-pair formation of aromatic carboxylate ion with quaternary ammonium ion is normally considered as a diffusion control reaction in aqueous phase. Thus, this fact suggests that the phase transfer of the ion-pair from aqueous to organic phase is the rate-determining step. Liner-free-energy relationship was observed for the monocarboxylic acids using different quaternary ammonium salts while that was ambiguous for the dicarboxylic acids. This is due to the steric influence of the counter ions for the magnitude of K{sub ex}.

  7. Aerobic fitness determines whole-body fat oxidation rate during exercise in the heat.

    PubMed

    Del Coso, Juan; Hamouti, Nassim; Ortega, Juan Fernando; Mora-Rodriguez, Ricardo

    2010-12-01

    The purpose of this study was to determine whole-body fat oxidation in endurance-trained (TR) and untrained (UNTR) subjects exercising at different intensities in the heat. On 3 occasions, 10 TR cyclists and 10 UNTR healthy subjects (peak oxygen uptake = 60 ± 6 vs. 44 ± 3 mL·kg-1·min-1; p < 0.05) exercised at 40%, 60%, and 80% peak oxygen uptake in a hot, dry environment (36 °C; 25% relative humidity). To complete the same amount of work in all 3 trials, exercise duration varied (107 ± 4, 63 ± 1, and 45 ± 0 min for 40%, 60%, and 80% peak oxygen uptake, respectively). Substrate oxidation was calculated using indirect calorimetry. Blood samples were collected at the end of exercise to determine plasma epinephrine ([EPI]plasma) and norepinephrine ([NEPI]plasma) concentrations. The maximal rate of fat oxidation was achieved at 60% peak oxygen uptake for the TR group (0.41 ± 0.01 g·min-1) and at 40% peak oxygen uptake for the UNTR group (0.28 ± 0.01 g·min-1). TR subjects oxidized absolutely (g·min-1) and relatively (% of total energy expenditure) more fat than UNTR subjects at 60% and 80% peak oxygen uptake (p < 0.05). At these exercise intensities, TR subjects also had higher [NEPI]plasma concentrations than UNTR subjects (p < 0.05). In the heat, whole-body peak fat oxidation occurs at higher relative exercise intensities in TR than in UNTR subjects (60% vs. 40% peak oxygen uptake). Moreover, TR subjects oxidize more fat than UNTR subjects when exercising at moderate to high intensities (>60% peak oxygen uptake).

  8. Uniform distributions of glucose oxidation and oxygen extraction in gray matter of normal human brain: No evidence of regional differences of aerobic glycolysis.

    PubMed

    Hyder, Fahmeed; Herman, Peter; Bailey, Christopher J; Møller, Arne; Globinsky, Ronen; Fulbright, Robert K; Rothman, Douglas L; Gjedde, Albert

    2016-05-01

    Regionally variable rates of aerobic glycolysis in brain networks identified by resting-state functional magnetic resonance imaging (R-fMRI) imply regionally variable adenosine triphosphate (ATP) regeneration. When regional glucose utilization is not matched to oxygen delivery, affected regions have correspondingly variable rates of ATP and lactate production. We tested the extent to which aerobic glycolysis and oxidative phosphorylation power R-fMRI networks by measuring quantitative differences between the oxygen to glucose index (OGI) and the oxygen extraction fraction (OEF) as measured by positron emission tomography (PET) in normal human brain (resting awake, eyes closed). Regionally uniform and correlated OEF and OGI estimates prevailed, with network values that matched the gray matter means, regardless of size, location, and origin. The spatial agreement between oxygen delivery (OEF≈0.4) and glucose oxidation (OGI ≈ 5.3) suggests that no specific regions have preferentially high aerobic glycolysis and low oxidative phosphorylation rates, with globally optimal maximum ATP turnover rates (VATP ≈ 9.4 µmol/g/min), in good agreement with (31)P and (13)C magnetic resonance spectroscopy measurements. These results imply that the intrinsic network activity in healthy human brain powers the entire gray matter with ubiquitously high rates of glucose oxidation. Reports of departures from normal brain-wide homogeny of oxygen extraction fraction and oxygen to glucose index may be due to normalization artefacts from relative PET measurements. PMID:26755443

  9. Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise.

    PubMed

    Seifi-Skishahr, Farnaz; Damirchi, Arsalan; Farjaminezhad, Manoochehr; Babaei, Parvin

    2016-01-01

    Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

  10. Nitrite-Driven Nitrous Oxide Production Under Aerobic Soil Conditions: Kinetics and Biochemical Controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

  11. Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise

    PubMed Central

    Damirchi, Arsalan; Farjaminezhad, Manoochehr

    2016-01-01

    Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

  12. Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

    PubMed

    Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

    2016-05-23

    A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. PMID:27101568

  13. Confined iron nanowires enhance the catalytic activity of carbon nanotubes in the aerobic oxidation of cyclohexane.

    PubMed

    Yang, Xixian; Yu, Hao; Peng, Feng; Wang, Hongjuan

    2012-07-01

    Inside job: New applications of carbon materials pave the way towards greener chemical syntheses. The encapsulation of metallic Fe within CNTs improves electron transfer between the metal and the CNTs. The resulting material offers a high catalytic activity and easy magnetic separation of catalyst in the heterogeneous selective oxidation of cyclohexane. PMID:22488987

  14. Aerobic oxidation of hydroxymethylfurfural and furfural by using heterogeneous Cox Oy -N@C catalysts.

    PubMed

    Deng, Jin; Song, Hai-Jie; Cui, Min-Shu; Du, Yi-Ping; Fu, Yao

    2014-12-01

    2,5-Furandicarboxylic acid (FDCA) is considered to be a promising replacement for terephthalic acid since they share similar structures and properties. In contrast to FDCA, 2,5-furandicarboxylic acid methyl (FDCAM) has properties that allow it to be easily purified. In this work, we reported an oxidative esterification of 5-hydroxymethylfurfural (HMF) and furfural to prepare corresponding esters over Cox Oy -N@C catalysts using O2 as benign oxidant. High yield and selectivity of FDCAM and methyl 2-furoate were obtained under optimized conditions. Factors which influenced the product distribution were examined thoroughly. The Cox Oy -N@C catalysts were recycled five times and no significant loss of activity was detected. Characterization of the catalysts could explain such phenomena. Using XPS and TGA, we made a thorough investigation of the effects of ligand and pyrolysis temperature on catalyst activity.

  15. A mild copper-catalyzed aerobic oxidative thiocyanation of arylboronic acids with TMSNCS.

    PubMed

    Sun, Nan; Che, Liusheng; Mo, Weimin; Hu, Baoxiang; Shen, Zhenlu; Hu, Xinquan

    2015-01-21

    A facile and efficient transformation of arylboronic acids to their corresponding aryl thiocyanates has been successfully developed. Based on the CuCl-catalyzed oxidative cross-coupling reaction between arylboronic acids and trimethylsilylisothiocyanate (TMSNCS) under oxygen atmosphere, the transformation can be readily conducted at ambient temperature. The newly-developed protocol provided a competitive synthetic approach to aryl thiocyanates that can tolerate a broad range of reactive functional groups and/or strong electron-withdrawing groups. PMID:25514847

  16. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    PubMed

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge

    2015-01-19

    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity. PMID:25430789

  17. Special role of corn flour as an ideal carbon source for aerobic denitrification with minimized nitrous oxide emission.

    PubMed

    Zhu, Shuangyue; Zheng, Maosheng; Li, Can; Gui, Mengyao; Chen, Qian; Ni, Jinren

    2015-06-01

    Much effort has been made for reducing nitrous oxide (N2O) emission in wastewater treatment processes. This paper presents an interesting way to minimize N2O in aerobic denitrification by strain Pseudomonas stutzeri PCN-1 with help of corn flour as cheaper additional carbon source. Experimental results showed that maximal N2O accumulation by strain PCN-1 was only 0.02% of removed nitrogen if corn flour was used as sole carbon source, which was significantly reduced by 52.07-99.81% comparing with others such as succinate, glucose, acetate and citrate. Sustained release of reducing sugar from starch and continuous expression of nosZ coding for N2O reductase contributed to the special role of corn flour as the ideal carbon source for strain PCN-1. Further experiments in sequencing batch reactors (SBRs) demonstrated similarly efficient nitrogen removal with much less N2O emission due to synergy of the novel strain and activated sludge, which was then confirmed by quantitative PCR analysis. PMID:25802047

  18. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  19. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters.

    PubMed

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the "structure-activity" relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au(3+) ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  20. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    PubMed Central

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  1. Integrated thermophilic submerged aerobic membrane bioreactor and electrochemical oxidation for pulp and paper effluent treatment--towards system closure.

    PubMed

    Qu, X; Gao, W J; Han, M N; Chen, A; Liao, B Q

    2012-07-01

    A novel integrated thermophilic submerged aerobic membrane bioreactor (TSAMBR) and electrochemical oxidation (EO) technology was developed for thermomechanical pulping pressate treatment with the aim of system closure. The TSAMBR was able to achieve a chemical oxygen demand (COD) removal efficiency of 88.6 ± 1.9-92.3 ± 0.7% under the organic loading rate of 2.76 ± 0.13-3.98 ± 0.23 kg COD/(m(3) d). An optimal hydraulic retention time (HRT) of 1.1 ± 0.1d was identified for COD removal. Cake formation was identified as the dominant mechanism of membrane fouling. The EO of the TSAMBR permeate was performed using a Ti/SnO(2)-Sb(2)O(5)-IrO(2) electrode. After 6-h EO, a complete decolourization was achieved and the COD removal efficiency was increased to 96.2 ± 1.2-98.2 ± 0.3%. The high-quality effluent produced by the TSAMBR-EO system can be reused as process water for system closure in pulp and paper mill.

  2. Selective aerobic oxidation of 1,3-propanediol to 3-hydroxypropanoic acid using hydrotalcite supported bimetallic gold nanoparticle catalyst in water

    NASA Astrophysics Data System (ADS)

    Mohammad, Mujahid; Nishimura, Shun; Ebitani, Kohki

    2015-02-01

    Selective oxidation of 1,3-propanediol (1,3-PD) to 3-hydroxypropanoic acid (3-HPA), an important industrial building block, was successfully achieved using hydrotalcite-supported bimetallic Au nanoparticle catalysts in water at 343 K under aerobic and base-free conditions. The highest yield of 42% with 73% selectivity towards 3-HPA was afforded by 1wt% Au0.8Pd0.2-PVP/HT catalyst.

  3. (E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

    PubMed

    Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

    2015-02-21

    A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO. PMID:25610923

  4. N-Doped Sub-3 nm Co Nanoparticles as Highly Efficient and Durable Aerobic Oxidative Coupling Catalysts.

    PubMed

    Han, Junxing; Gu, Feifei; Li, Yuchao

    2016-09-20

    A nano-coating associated with sulfuric acid leaching protocol was developed to prepare N-doped sub-3 nm Co-based nanoparticle catalyst (Co-N/C) using melamine-formaldehyde resin as the N-containing precursor, active carbon as the support, and Co(NO3 )2 as the Co-containing precursor. By thermal treatment under nitrogen atmosphere at 800 °C and leached with sulfuric acid solution, a stable and highly dispersive Co-N coordination structure was uniformly dispersed on the formed Co-N/C catalyst with a Co loading of 0.47 wt % and Co nanoparticle size of 2.55 nm. The Co-N/C catalyst was characterized with XRD, XPS, Raman, SEM, TEM, ICP, and elemental analysis. The Co-N/C catalyst showed extremely high catalytic efficiency with a TON of 257 for the aerobic oxidative coupling of aldehydes with methanol to directly synthesize methyl esters with molecular oxygen as the final oxidant. The Co-N/C catalyst also showed broad substrate range and stable recyclability. After recycling for 7 times, no obvious deactivation was detected. It was confirmed that the sub-3 nm Co-N coordination structure formed between metallic Co nanoparticles and pyridinic nitrogen doping into graphitic layers functions as the active site to activate molecular oxygen for the β-H elimination from generated hemiacetal intermediates to produce methyl esters. The nano-coating associated with acid leaching protocol provides a novel strategy to prepare highly efficient non-precious metal-based catalysts. PMID:27461935

  5. Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: efficient access to α-alkyl vinylarenes.

    PubMed

    Zheng, Changwu; Stahl, Shannon S

    2015-08-18

    Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.

  6. Catalytic Amine Oxidation under Ambient Aerobic Conditions: Mimicry of Monoamine Oxidase B.

    PubMed

    Murray, Alexander T; Dowley, Myles J H; Pradaux-Caggiano, Fabienne; Baldansuren, Amgalanbaatar; Fielding, Alistair J; Tuna, Floriana; Hendon, Christopher H; Walsh, Aron; Lloyd-Jones, Guy C; John, Matthew P; Carbery, David R

    2015-07-27

    The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity.

  7. [Effects of Total Nitrogen and BOD5/TN on Anaerobic Ammonium Oxidation-Denitrification Synergistic Interaction of Mature Landfill Leachate in Aged Refuse Bioreactor].

    PubMed

    Yang, Ying-ying; Chen, Yi; Lj, Ming-jie; Xie, Bing

    2015-04-01

    Mature landfill leachate, featured with high ammonium (NH4+) content and low biodegrade ability (low BOD5/COD ratio), is hard to be treated. This study mainly focused on the effects of influent TN (total nitrogen) loading and BOD5/TN ratios on the nitrogen removal efficiency of landfill leachate by landfill bioreactors. The results showed that when the influent total nitrogen loading was in the range of 15 g x (m3 x d)(-1) to 25 g x (m3 x d)(-1), the TN removal loading could remain stable between 10 g x (m3 x d)(-1) and 12 g x (m3 x d)(-1), while the TN removal efficiency decreased from 67.7% to 60.2% with the increasing loading. Therefore, TN loading shocks would lower the bioreactor's TN removal rate, but would not affect its TN removal loading. When the influent BOD5/TN ratio was increased from 0.3 to 0.4 and the TN loading was controlled at 9 g x (m3 x d)(-1), the TN removal rates were increased from 79.9% to 89.9% and 86.2% in anaerobic and aerobic, respectively. This implied that properly enhancing BOD5/TN ratio could significantly increase the TN removal efficiency of the bioreactor, and the effect was more significant under anaerobic condition. Analysis of nitrogen removal pathways showed that denitrification and anammox could take place synergistically in landfill bioreactor.

  8. Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

    PubMed

    Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

    2014-12-01

    Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere. PMID:25225767

  9. Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

    PubMed

    Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

    2014-12-01

    Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere.

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

    SciTech Connect

    Paul Fallgren

    2009-03-06

    Western Research Institute in conjunction with Sierra West Consultants, Inc., Tetra Tech, Inc., and the U.S. Department of Energy conducted laboratory and field studies to test different approaches to enhance degradation of hydrocarbons and associated contaminants. WRI in conjunction with Sierra West Consultants, Inc., conducted a laboratory and field study for using ozone to treat a site contaminated with MTBE and other hydrocarbons. Results from this study demonstrate that a TOD test can be used to resolve the O{sub 3} dosage problem by establishing a site-specific benchmark dosage for field ozone applications. The follow-up testing of the laboratory samples provided indications that intrinsic biodegradation could be stimulated by adding oxygen. Laboratory studies also suggests that O3 dosage in the full-scale field implementation could be dialed lower than stoichiometrically designed to eliminate the formation of Cr(VI). WRI conducted a study involving a series of different ISCO oxidant applications to diesel-contaminated soil and determined the effects on enhancing biodegradation to degrade the residual hydrocarbons. Soils treated with permanganate followed by nutrients and with persulfate followed by nutrients resulted in the largest decrease in TPH. The possible intermediates and conditions formed from NOM and TPH oxidation by permanganate and activated persulfate favors microbial TPH degrading activity. A 'passive-oxidation' method using microbial fuel cell (MFC) technology was conducted by WRI in conjunction with Tetra Tech, Inc., to degrade MTBE in groundwater. These experiments have demonstrated that a working MFC (i.e., one generating power) could be established in the laboratory using contaminated site water or buffered media inoculated with site water and spiked with MTBE, benzene, or toluene. Electrochemical methods were studied by WRI with goal of utilizing low voltage and amperage electrical sources for 'geo-oxidation' of organic contaminants. The

  11. Effects of oxidation reduction potential in the bypass micro-aerobic sludge zone on sludge reduction for a modified oxic-settling-anaerobic process.

    PubMed

    Li, Kexun; Wang, Yi; Zhang, Zhongpin; Liu, Dongfang

    2014-01-01

    Batch experiments were conducted to determine the effect of oxidation reduction potential (ORP) on sludge reduction in a bypass micro-aerobic sludge reduction system. The system was composed of a modified oxic-settling-anaerobic process with a sludge holding tank in the sludge recycle loop. The ORPs in the micro-aerobic tanks were set at approximately +350, -90, -150, -200 and -250 mV, by varying the length of aeration time for the tanks. The results show that lower ORP result in greater sludge volume reduction, and the sludge production was reduced by 60% at the lowest ORP. In addition, low ORP caused extracellular polymer substances dissociation and slightly reduced sludge activity. Comparing the sludge backflow characteristics of the micro-aerobic tank's ORP controlled at -250 mV with that of +350 mV, the average soluble chemical oxygen (SCOD), TN and TP increased by 7, 0.4 and 2 times, median particle diameter decreased by 8.5 μm and the specific oxygen uptake rate (SOUR) decreased by 0.0043 milligram O2 per gram suspended solids per minute. For the effluent, SCOD and TN and TP fluctuated around 30, 8.7 and 0.66 mg/L, respectively. Therefore, the effective assignment of ORP in the micro-aerobic tank can remarkably reduce sludge volume and does not affect final effluent quality.

  12. Copper(II)-catalyzed room temperature aerobic oxidation of hydroxamic acids and hydrazides to acyl-nitroso and azo intermediates, and their Diels-Alder trapping.

    PubMed

    Chaiyaveij, Duangduan; Cleary, Leah; Batsanov, Andrei S; Marder, Todd B; Shea, Kenneth J; Whiting, Andrew

    2011-07-01

    CuCl(2), in the presence of a 2-ethyl-2-oxazoline ligand, is an effective catalyst for the room temperature, aerobic oxidation of hydroxamic acids and hydrazides, to acyl-nitroso and azo dienophiles respectively, which are efficiently trapped in situ via both inter- and intramolecular hetero-Diels-Alder reactions with dienes. Both inter- and intramolecular variants of the Diels-Alder reaction are suitable under the reaction conditions using a variety of solvents. Under the same conditions, an acyl hydrazide was also oxidized to give an acyl-azo dienophile which was trapped intramolecularly by a diene. PMID:21644530

  13. [Heterotrophic Nitrification and Aerobic Denitrification of the Hypothermia Aerobic Denitrification Bacterium: Arthrobacter arilaitensis].

    PubMed

    He, Teng-xia; Ni, Jiu-pai; Li, Zhen-lun; Sun, Quan; Ye Qing; Xu, Yi

    2016-03-15

    High concentrations of ammonium, nitrate and nitrite nitrogen were employed to clarify the abilities of heterotrophic nitrification and aerobic denitrification of Arthrobacter arilaitensis strain Y-10. Meanwhile, by means of inoculating the strain suspension into the mixed ammonium and nitrate, ammonium and nitrite nitrogen simulated wastewater, we studied the simultaneous nitrification and denitrification ability of Arthrobacter arilaitensis strain Y-10. In addition, cell optical density was assayed in each nitrogen removal process to analyze the relationship of cell growth and nitrogen removal efficiency. The results showed that the hypothermia denitrification strain Arthrobacter arilaitensis Y-10 exhibited high nitrogen removal efficiency during heterotrophic nitrification and aerobic denitrification. The ammonium, nitrate and nitrite removal rates were 65.0%, 100% and 61.2% respectively when strain Y-10 was cultivated for 4 d at 15°C with initial ammonium, nitrate and nitrite nitrogen concentrations of 208.43 mg · L⁻¹, 201.16 mg · L⁻¹ and 194.33 mg · L⁻¹ and initial pH of 7.2. Nitrite nitrogen could only be accumulated in the medium containing nitrate nitrogen during heterotrophic nitrification and aerobic denitrification process. Additionally, the ammonium nitrogen was mainly removed in the inorganic nitrogen mixed synthetic wastewater. In short, Arthrobacter arilaitensis Y-10 could conduct nitrification and denitrification effectively under aerobic condition and the ammonium nitrogen removal rate was more than 80.0% in the inorganic nitrogen mixed synthetic wastewater. PMID:27337904

  14. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis.

    PubMed

    Gerken, James B; Stahl, Shannon S

    2015-08-26

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NO x ) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NO x species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NO x species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NO x species, together with kinetically efficient reduction of oxidized NO x species by TEMPO and other organic nitroxyls.

  15. Potential contribution of planktonic components to ammonium cycling in the coastal area off central-southern Chile during non-upwelling conditions

    NASA Astrophysics Data System (ADS)

    Molina, Veronica; Morales, Carmen E.; Farías, Laura; Cornejo, Marcela; Graco, Michelle; Eissler, Yoanna; Cuevas, Luis A.

    2012-01-01

    The potential contributions of different microbial components (<20 μm) and metabolisms to ammonium cycling were assessed during non-upwelling conditions in a coastal area off Concepción (∼36.5°S). Assays with specific inhibitors to estimate rates of ammonium consumption and production, and carbon assimilation associated with photolithotrophic and chemolithoautotrophic (nitrification) metabolisms in the water column were performed. Despite low water column concentrations of ammonium in wintertime, intense ammonium transformations were registered. Prokaryotes (or bacterioplankton) contributed most to ammonium generation rates over the entire water column; these rates increased with depth (0.4-3.1 μM d -1). In surface waters (10 m depth), aerobic ammonium oxidation (potentially by Bacteria and Archaea) was the dominant consumption process (average 0.7 μM d -1) whereas in the subsurface layer (20 and 50 m depth), unexpectedly, eukaryotes accounted for most of its consumption (average 2.1 μM d -1). Nitrification oxidized an important proportion of the ammonium in both layers (from 25% to 100%) and provided regenerated nitrate. The integrated water column rates of chemosynthesis (0.005 g C m -2 d -1) represented a large proportion (51%) of the total dark carbon fixation during the non-upwelling season when integrated rates of photosynthesis are relatively low (0.42 g C m -2 d -1) and microbial food webs dominate the transfer of carbon within this coastal system.

  16. Continuous Aerobic Training in Individualized Intensity Avoids Spontaneous Physical Activity Decline and Improves MCT1 Expression in Oxidative Muscle of Swimming Rats

    PubMed Central

    Scariot, Pedro P. M.; Manchado-Gobatto, Fúlvia de Barros; Torsoni, Adriana S.; dos Reis, Ivan G. M.; Beck, Wladimir R.; Gobatto, Claudio A.

    2016-01-01

    Although aerobic training has been shown to affect the lactate transport of skeletal muscle, there is no information concerning the effect of continuous aerobic training on spontaneous physical activity (SPA). Because every movement in daily life (i.e., SPA) is generated by skeletal muscle, we think that it is possible that an improvement of SPA could affect the physiological properties of muscle with regard to lactate transport. The aim of this study was to evaluate the effect of 12 weeks of continuous aerobic training in individualized intensity on SPA of rats and their gene expressions of monocarboxylate transporters (MCT) 1 and 4 in soleus (oxidative) and white gastrocnemius (glycolytic) muscles. We also analyzed the effect of continuous aerobic training on aerobic and anaerobic parameters using the lactate minimum test (LMT). Sixty-day-old rats were randomly divided into three groups: a baseline group in which rats were evaluated prior to initiation of the study; a control group (Co) in which rats were kept without any treatment during 12 weeks; and a chronic exercise group (Tr) in which rats swam for 40 min/day, 5 days/week at 80% of anaerobic threshold during 12 weeks. After the experimental period, SPA of rats was measured using a gravimetric method. Rats had their expression of MCTs determined by RT-PCR analysis. In essence, aerobic training is effective in maintaining SPA, but did not prevent the decline of aerobic capacity and anaerobic performance, leading us to propose that the decline of SPA is not fully attributed to a deterioration of physical properties. Changes in SPA were concomitant with changes in MCT1 expression in the soleus muscle of trained rats, suggestive of an additional adaptive response toward increased lactate clearance. This result is in line with our observation showing a better equilibrium on lactate production-remotion during the continuous exercise (LMT). We propose an approach to combat the decline of SPA of rats in their home

  17. Continuous Aerobic Training in Individualized Intensity Avoids Spontaneous Physical Activity Decline and Improves MCT1 Expression in Oxidative Muscle of Swimming Rats.

    PubMed

    Scariot, Pedro P M; Manchado-Gobatto, Fúlvia de Barros; Torsoni, Adriana S; Dos Reis, Ivan G M; Beck, Wladimir R; Gobatto, Claudio A

    2016-01-01

    Although aerobic training has been shown to affect the lactate transport of skeletal muscle, there is no information concerning the effect of continuous aerobic training on spontaneous physical activity (SPA). Because every movement in daily life (i.e., SPA) is generated by skeletal muscle, we think that it is possible that an improvement of SPA could affect the physiological properties of muscle with regard to lactate transport. The aim of this study was to evaluate the effect of 12 weeks of continuous aerobic training in individualized intensity on SPA of rats and their gene expressions of monocarboxylate transporters (MCT) 1 and 4 in soleus (oxidative) and white gastrocnemius (glycolytic) muscles. We also analyzed the effect of continuous aerobic training on aerobic and anaerobic parameters using the lactate minimum test (LMT). Sixty-day-old rats were randomly divided into three groups: a baseline group in which rats were evaluated prior to initiation of the study; a control group (Co) in which rats were kept without any treatment during 12 weeks; and a chronic exercise group (Tr) in which rats swam for 40 min/day, 5 days/week at 80% of anaerobic threshold during 12 weeks. After the experimental period, SPA of rats was measured using a gravimetric method. Rats had their expression of MCTs determined by RT-PCR analysis. In essence, aerobic training is effective in maintaining SPA, but did not prevent the decline of aerobic capacity and anaerobic performance, leading us to propose that the decline of SPA is not fully attributed to a deterioration of physical properties. Changes in SPA were concomitant with changes in MCT1 expression in the soleus muscle of trained rats, suggestive of an additional adaptive response toward increased lactate clearance. This result is in line with our observation showing a better equilibrium on lactate production-remotion during the continuous exercise (LMT). We propose an approach to combat the decline of SPA of rats in their home

  18. Spontaneous intercalation of long-chain alkyl ammonium into edge-selectively oxidized graphite to efficiently produce high-quality graphene

    PubMed Central

    Wei, Liangming; Wu, Fei; Shi, Diwen; Hu, Changchen; Li, Xiaolin; Yuan, Weien; Wang, Jian; Zhao, Jiang; Geng, Huijuan; Wei, Hao; Wang, Ying; Hu, Nantao; Zhang, Yafei

    2013-01-01

    Mass production of high-quality graphene nanosheets (GNs) is essential for practical applications. We report that oxidation of graphite by low concentration KMnO4 at relatively high temperature (60°C) leads to edge-selectively oxidized graphite (EOG) which preserves the high crystalline graphitic structure on its basal planes while the edges are functionalized by oxygen-containing groups. Long-chain tetradecyl-ammonium salt (C14N+) could be spontaneously intercalated into EOG to form intercalated EOG-C14N+ compounds. Gentle and short-time sonication of EOG-C14N+ in toluene can full exfoliate EOG into edge-oxidized graphene nanosheets (EOGNs) with concentration of 0.67 mg/ml, monolayer population up to 90% and lateral size from 1 μm to >100 μm. The EOG and EOGN films show excellent electrical conductance, which is far superior to their graphene oxide (GO) counterparts. Our method provides an efficient way to produce high-quality GNs, and the resultant EOG also can be directly used for production of multifunctional materials and devices. PMID:24022463

  19. Water- and organo-dispersible gold nanoparticles supported by using ammonium salts of hyperbranched polystyrene: preparation and catalysis.

    PubMed

    Gao, Lei; Nishikata, Takashi; Kojima, Keisuke; Chikama, Katsumi; Nagashima, Hideo

    2013-12-01

    Gold nanoparticles (1 nm in size) stabilized by ammonium salts of hyperbranched polystyrene are prepared. Selection of the R groups provides access to both water- and organo-dispersible gold nanoparticles. The resulting gold nanoparticles are subjected to studies on catalysis in solution, which include reduction of 4-nitrophenol with sodium borohydride, aerobic oxidation of alcohols, and homocoupling of phenylboronic acid. In the reduction of 4-nitrophenol, the catalytic activity is clearly dependent on the size of the gold nanoparticles. For the aerobic oxidation of alcohols, two types of biphasic oxidation are achieved: one is the catalyst dispersing in the aqueous phase, whereas the other is in the organic phase. The catalysts are reusable more than four times without loss of the catalytic activity. Selective synthesis of biphenyl is achieved by the homocoupling of phenylboronic acid catalyzed by organo-dispersible gold nanoparticles.

  20. The effect of low-level laser therapy on oxidative stress and functional fitness in aged rats subjected to swimming: an aerobic exercise.

    PubMed

    Guaraldo, Simone A; Serra, Andrey Jorge; Amadio, Eliane Martins; Antônio, Ednei Luis; Silva, Flávio; Portes, Leslie Andrews; Tucci, Paulo José Ferreira; Leal-Junior, Ernesto Cesar Pinto; de Carvalho, Paulo de Tarso Camillo

    2016-07-01

    The aim of the present study was to determine whether low-level laser therapy (LLLT) in conjunction with aerobic training interferes with oxidative stress, thereby influencing the performance of old rats participating in swimming. Thirty Wistar rats (Norvegicus albinus) (24 aged and six young) were tested. The older animals were randomly divided into aged-control, aged-exercise, aged-LLLT, aged-LLLT/exercise, and young-control. Aerobic capacity (VO2max(0.75)) was analyzed before and after the training period. The exercise groups were trained for 6 weeks, and the LLLT was applied at 808 nm and 4 J energy. The rats were euthanized, and muscle tissue was collected to analyze the index of lipid peroxidation thiobarbituric acid reactive substances (TBARS), glutathione (GSH), superoxide dismutase (SOD), and catalase (CAT) activities. VO2 (0.75)max values in the aged-LLLT/exercise group were significantly higher from those in the baseline older group (p <0.01) and the LLLT and exercise group (p <0.05). The results indicate that the activities of CAT, SOD, and GPx were higher and statistically significant (p <0.05) in the LLLT/exercise group than those in the LLLT and exercise groups. Young animals presented lesser and statistically significant activities of antioxidant enzymes compared to the aged group. The LLLT/exercise group and the LLLT and exercise group could also mitigate the concentration of TBARS (p > 0.05). Laser therapy in conjunction with aerobic training may reduce oxidative stress, as well as increase VO2 (0.75)max, indicating that an aerobic exercise such as swimming increases speed and improves performance in aged animals treated with LLLT. PMID:26861983

  1. A factorial randomized controlled trial to evaluate the effect of micronutrients supplementation and regular aerobic exercise on maternal endothelium-dependent vasodilatation and oxidative stress of the newborn

    PubMed Central

    2011-01-01

    Background Many studies have suggested a relationship between metabolic abnormalities and impaired fetal growth with the development of non-transmissible chronic diseases in the adulthood. Moreover, it has been proposed that maternal factors such as endothelial function and oxidative stress are key mechanisms of both fetal metabolic alterations and subsequent development of non-transmissible chronic diseases. The objective of this project is to evaluate the effect of micronutrient supplementation and regular aerobic exercise on endothelium-dependent vasodilation maternal and stress oxidative of the newborn. Methods and design 320 pregnant women attending to usual prenatal care in Cali, Colombia will be included in a factorial randomized controlled trial. Women will be assigned to the following intervention groups: 1. Control group: usual prenatal care (PC) and placebo (maltodextrine). 2. Exercise group: PC, placebo and aerobic physical exercise. 3. Micronutrients group: PC and a micronutrients capsule consisting of zinc (30 mg), selenium (70 μg), vitamin A (400 μg), alphatocopherol (30 mg), vitamin C (200 mg), and niacin (100 mg). 4. Combined interventions Group: PC, supplementation of micronutrients, and aerobic physical exercise. Anthropometric measures will be taken at the start and at the end of the interventions. Discussion Since in previous studies has been showed that the maternal endothelial function and oxidative stress are related to oxidative stress of the newborn, this study proposes that complementation with micronutrients during pregnancy and/or regular physical exercise can be an early and innovative alternative to strengthen the prevention of chronic diseases in the population. Trial registration NCT00872365. PMID:21356082

  2. Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor

    NASA Astrophysics Data System (ADS)

    Chen, Xueming; Liu, Yiwen; Peng, Lai; Yuan, Zhiguo; Ni, Bing-Jie

    2016-04-01

    In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously.

  3. Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor

    PubMed Central

    Chen, Xueming; Liu, Yiwen; Peng, Lai; Yuan, Zhiguo; Ni, Bing-Jie

    2016-01-01

    In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously. PMID:27112502

  4. Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor.

    PubMed

    Chen, Xueming; Liu, Yiwen; Peng, Lai; Yuan, Zhiguo; Ni, Bing-Jie

    2016-01-01

    In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously. PMID:27112502

  5. Study of anaerobic ammonium oxidation bacterial community in the aged refuse bioreactor with 16S rRNA gene library technique.

    PubMed

    Wang, Chao; Xie, Bing; Han, Lu; Xu, Xiaofan

    2013-10-01

    In order to investigate the anaerobic ammonium-oxidation (Anammox) nitrogen removal pathway of the aged refuse bioreactor treating landfill leachate, a lab-scale bioreactor was established and run for 35 weeks, the performance of the bioreactor and its bacterial community structure of Planctomycetes were analyzed. The results showed that the average TN removal rate of landfill leachate could be reached to 89%. 16S rRNA gene library of Planctomycetes revealed that Anammox sequences accounted for 28.3% of the total Planctomycetes sequences in the bioreactor, and previously recognized Anammox bacterium Candidatus Kuenenia stuttgartiensis was the only detected Anammox species in the reactor. It was also found that Anammox bacteria distributed at different sites of the bioreactor while mostly concentrated in the middle and low-middle part. Results above confirmed that Anammox process could happen in aged refuse bioreactor treating landfill leachate and provided an alternative nitrogen removal pathway in practical landfills.

  6. Effect of a cold shock on the activity and composition of the communities of ammonium-oxidizing microorganisms in a chestnut soil

    NASA Astrophysics Data System (ADS)

    Cherobaeva, A. S.; Stepanov, A. L.; Kravchenko, I. K.

    2012-05-01

    The simulation of a cold shock was performed in an incubation experiment with soil microcosms by a sharp decrease of the temperature to negative values and the subsequent analysis of the nitrification rate of the ammonium-oxidizing microorganisms. Three procedures of the cold shock effect were selected: long, short-time, and cyclic. A significant decrease of the nitrifying activity was recorded after the long effect, whereas the 8-, 16-, and 24-hour cold shocks did not affect the intensity of nitrification. A cyclic temperature decrease alternating with periods of incubation under high temperatures also did not affect the nitrifying activity of the microorganisms. We suppose that the domination of mesophilic microorganisms with a resistant enzyme system or of psychrophilic and psychrotolerant microorganisms contributes to the preservation of a high nitrification level in soils with frequent alternations of high and low temperatures.

  7. CO2/ethylene oxide copolymerization and ligand variation for a highly active salen-cobalt(III) complex tethering 4 quaternary ammonium salts.

    PubMed

    Jeon, Jong Yeob; Lee, Jung Jae; Varghese, Jobi Kodiyan; Na, Sung Jae; Sujith, S; Go, Min Jeong; Lee, Junseong; Ok, Myung-Ahn; Lee, Bun Yeoul

    2013-07-01

    A cobalt(III) complex (1) of a salcy-type ligand tethering 4 quaternary ammonium salts, which is thought to act as a highly active catalyst for CO2/propylene oxide (PO) copolymerization, also shows high activity (TOF, 25,900 h(-1); TON, 518,000; 2.72 kg polymer per g cat) and selectivity (>98%) for CO2/ethylene oxide (EO) copolymerization that results in high-molecular-weight polymers (M(n), 200,000-300,000) that have strictly alternating repeating units. The related cobalt(III) complexes 11-14 were prepared through variations of the ligand framework of 1 by replacing the trans-1,2-diaminocyclohexane unit with 2,2-dimethyl-1,3-propanediamine, trans-1,2-diaminocyclopentane, or 1,1'-binaphthyl-2,2'-diamine or by replacing the aldimine bond with ketimine. These ligand frameworks are thought to favour the formation of the cis-β configuration in complexation, and the formation of the cis-β configuration in 11-14 was confirmed through NMR studies or X-ray crystallographic studies of model complexes not bearing the quaternary ammonium salts. Complexes 11, 13, and 14, which adopt the cis-β configuration even in DMSO did not show any activity for CO2/PO copolymerization. Complex 12, which was constructed with trans-1,2-diaminocyclopentane and fluctuated in DMSO between the coordination and de-coordination of the acetate ligand as observed for 1, showed fairly high activity (TOF, 12,400 h(-1)). This fluctuating behaviour may play a role in polymerization. However, complex 12 did not compete with 1 in terms of activity, selectivity, and the catalyst cost.

  8. Aerobic Microbial Respiration in Oceanic Oxygen Minimum Zones

    NASA Astrophysics Data System (ADS)

    Kalvelage, Tim; Lavik, Gaute; Jensen, Marlene M.; Revsbech, Niels Peter; Schunck, Harald; Loescher, Carolin; Desai, Dhwani K.; LaRoche, Julie; Schmitz-Streit, Ruth; Kuypers, Marcel M. M.

    2014-05-01

    In the oxygen minimum zones (OMZs) of the tropical oceans, sluggish ventilation combined with strong microbial respiration of sinking organic matter results in the depletion of oxygen (O2). When O2 concentrations drop below ~5 µmol/L, organic matter is generally assumed to be respired with nitrate, ultimately leading to the loss of fixed inorganic nitrogen via anammox and denitrification. However, direct measurements of microbial O2 consumption at low O2 levels are - apart from a single experiment conducted in the OMZ off Peru - so far lacking. At the same time, consistently observed active aerobic ammonium and nitrite oxidation at non-detectable O2 concentrations (<1 µmol/L) in all major OMZs, suggests aerobic microorganisms, likely including heterotrophs, to be well adapted to near-anoxic conditions. Consequently, microaerobic (≤5 µmol/L) remineralization of organic matter, and thus release of ammonium, in low- O2 environments might be significantly underestimated at present. Here we present extensive measurements of microbial O2 consumption in OMZ waters, combined with highly sensitive O2 (STOX) measurements and meta-omic functional gene analyses. Short-term incubation experiments with labelled O2 (18-18O2) carried out in the Namibian and Peruvian OMZ, revealed persistent aerobic microbial activity at depths with non-detectable concentrations of O2 (≤50 nmol/L). In accordance, examination of metagenomes and metatranscriptomes from Chilean and Peruvian OMZ waters identified genes encoding for terminal respiratory oxidases with high O2 affinities as well as their expression by diverse microbial communities. Oxygen consumption was particularly enhanced near the upper OMZ boundaries and could mostly (~80%) be assigned to heterotrophic microbial activity. Compared to previously identified anaerobic microbial processes, microaerobic organic matter respiration was the dominant remineralization pathway and source of ammonium (~90%) in the upper Namibian and

  9. Methane oxidation activity and diversity of aerobic methanotrophs in pH-neutral and semi-neutral thermal springs of the Kunashir Island, Russian Far East.

    PubMed

    Kizilova, A K; Sukhacheva, M V; Pimenov, N V; Yurkov, A M; Kravchenko, I K

    2014-03-01

    Aerobic methane oxidation has been mostly studied in environments with moderate to low temperatures. However, the process also occurs in terrestrial thermal springs, where little research on the subject has been done to date. The potential activity of methane oxidation and diversity of aerobic methanotrophic bacteria were studied in sediments of thermal springs with various chemical and physical properties, sampled across the Kunashir Island, the Kuriles archipelago. Activity was measured by means of the radioisotope tracer technique utilizing (14)C-labeled methane. Biodiversity assessments were based on the particulate methane monooxygenase (pmoA) gene, which is found in all known thermophilic and thermotolerant methanotrophs. We demonstrated the possibility of methane oxidation in springs with temperature exceeding 74 °C, and the most intensive methane uptake was shown in springs with temperatures about 46 °C. PmoA was detected in 19 out of 30 springs investigated and the number of pmoA gene copies varied between 10(4) and 10(6) copies per ml of sediment. Phylogenetic analysis of PmoA sequences revealed the presence of methanotrophs from both the Alpha- and Gammaproteobacteria. Our results suggest that methanotrophs inhabiting thermal springs with temperature exceeding 50 °C may represent novel thermophilic and thermotolerant species of the genera Methylocystis and Methylothermus, as well as previously undescribed Gammaproteobacteria. PMID:24343375

  10. Theoretical study on the catalytic reactivity of N-hydroxyphthalimide tuned by different heterocyclic substitutions on its phenyl ring for aerobic oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Kexian; Xie, Haiying; Jiang, Kezhi; Mao, Jianyong

    2016-07-01

    The structure-reactivity relationship of new hydroxyimide organocatalysts based on the heterocyclic replacements of the phenyl ring of N-hydroxyphthalimide (NHPI) has been theoretically investigated to gain a mature understanding of this particular catalysis for aerobic oxidation. We find that the reactivity of catalysts with the common five-member aromatic rings is lower than that of NHPI. The catalyst with the recyclable structure of imidazolium ionic liquid may serve as a novel model catalyst for further improvements due to its reactivity comparable to that of NHPI. The catalytic reactivity of multi-nitroxyl catalysts is theoretically more fascinating than that of the highly efficient N,N-dihydroxypyromellitimide.

  11. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    PubMed

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process. PMID:25251943

  12. Benzylic Ammonium Ylide Mediated Epoxidations

    PubMed Central

    Roiser, Lukas; Robiette, Raphaël; Waser, Mario

    2016-01-01

    A high yielding synthesis of stilbene oxides using ammonium ylides has been developed. It turned out that the amine leaving group plays a crucial role as trimethylamine gives higher yields than DABCO or quinuclidine. The amine group also influences the diastereoselectivity, and detailed DFT calculations to understand the key parameters of these reactions have been carried out. PMID:27766017

  13. Ammonium sorption and ammonia inhibition of nitrite-oxidizing bacteria explain contrasting soil N2O production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Better understanding of process controls over nitrous oxide (N2O) production in urine-impacted ‘hot spots’ and fertilizer bands is needed to improve mitigation strategies and emission models. Following amendment with bovine (Bos taurus) urine (Bu) or urea (Ur), we measured inorganic N, pH, N2O, and...

  14. Treatment of high salt oxidized modified starch waste water using micro-electrolysis, two-phase anaerobic aerobic and electrolysis for reuse

    NASA Astrophysics Data System (ADS)

    Yi, Xuenong; Wang, Yulin

    2016-08-01

    A combined process of micro-electrolysis, two-phase anaerobic, aerobic and electrolysis was investigated for the treatment of oxidized modified starch wastewater (OMSW). Optimum ranges for important operating variables were experimentally determined and the treated water was tested for reuse in the production process of corn starch. The optimum hydraulic retention time (HRT) of micro-electrolysis, methanation reactor, aerobic process and electrolysis process were 5, 24, 12 and 3 h, respectively. The addition of iron-carbon fillers to the acidification reactor was 200 mg/L while the best current density of electrolysis was 300 A/m2. The biodegradability was improved from 0.12 to 0.34 by micro-electrolysis. The whole treatment was found to be effective with removal of 96 % of the chemical oxygen demand (COD), 0.71 L/day of methane energy recovery. In addition, active chlorine production (15,720 mg/L) was obtained by electrolysis. The advantage of this hybrid process is that, through appropriate control of reaction conditions, effect from high concentration of salt on the treatment was avoided. Moreover, the process also produced the material needed in the production of oxidized starch while remaining emission-free and solved the problem of high process cost.

  15. Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

    PubMed

    Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C; Housecroft, Catherine E; Neuburger, Markus; Zampese, Jennifer A

    2014-08-28

    The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)- in high yield. The single crystal structure of (R)- reveals a tetranuclear copper(ii) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)- and (S,R)- have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)- selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)- exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)- and (S,R)- in controlling the reactivity towards aerobic oxidation reactions is discussed. PMID:24986135

  16. DnaK dependence of mutant ethanol oxidoreductases evolved for aerobic function and protective role of the chaperone against protein oxidative damage in Escherichia coli

    PubMed Central

    Echave, Pedro; Esparza-Cerón, M. Angel; Cabiscol, Elisa; Tamarit, Jordi; Ros, Joaquim; Membrillo-Hernández, Jorge; Lin, E. C. C.

    2002-01-01

    The adhE gene of Escherichia coli encodes a multifunctional ethanol oxidoreductase (AdhE) that catalyzes successive reductions of acetyl-CoA to acetaldehyde and then to ethanol reversibly at the expense of NADH. Mutant JE52, serially selected for acquired and improved ability to grow aerobically on ethanol, synthesized an AdhEA267T/E568K with two amino acid substitutions that sequentially conferred improved catalytic properties and stability. Here we show that the aerobic growth ability on ethanol depends also on protection of the mutant AdhE against metal-catalyzed oxidation by the chaperone DnaK (a member of the Hsp70 family). No DnaK protection of the enzyme is evident during anaerobic growth on glucose. Synthesis of DnaK also protected E. coli from H2O2 killing under conditions when functional AdhE is not required. Our results therefore suggest that, in addition to the known role of protecting cells against heat stress, DnaK also protects numerous kinds of proteins from oxidative damage. PMID:11917132

  17. Nano Pd(0) supported on cellulose: a highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling and aerobic oxidation of benzyl alcohols under liquid phase catalysis.

    PubMed

    Jamwal, Navjot; Sodhi, Ravinderpal Kour; Gupta, Princy; Paul, Satya

    2011-12-01

    Nano palladium(0) supported on cellulose was found to be highly efficient recyclable heterogeneous catalyst for the Suzuki coupling between aryl bromides and phenyl boronic acid in water and aerobic oxidation of benzyl alcohols using air as the source of molecular oxygen in acetonitrile. The Cell-Pd(0) was prepared by stirring commercially available cellulose with Pd(OAc)(2) in ethanol at 25°C followed by reduction with hydrazine hydrate, leading finally to nano Pd(0) particles uniformly distributed on surface of cellulose. This catalytic system provides biaryls and polyaryls in excellent yields with very high turn over numbers via Suzuki coupling; and benzaldehyde derivatives in high yields and selectivity by oxidation in air. Cell-Pd(0) was characterized by X-ray diffraction techniques (XRD), thermal analysis (TGA), scanning electron microscope (SEM) and transmission electron microscope (TEM).

  18. Full-scale sludge liquor treatment for ammonium reduction with low carbon dosage.

    PubMed

    Gustavsson, D J I; Nyberg, U; Jansen, J la Cour

    2011-01-01

    The separate treatment of sludge liquor, produced by dewatering anaerobic digested sludge at wastewater treatment plants, gives rise to extreme environments for nitrogen removal. A full-scale sequencing batch reactor was operated with the aim of introducing and studying denitritation as a supplement to nitritation in order to reduce operating costs. Since the main plant only has problems with ammonium reduction capacity, the initial strategy was to have sufficient ammonium reduction with optimal alkalinity production by denitrifiers, i.e. low carbon dosage and minimum alkalinity and residual oxidized ammonium in the effluent. This strategy led to an unbalanced and sensitive process because the denitrifiers were often inhibited. High dissolved oxygen (DO) readings and no decrease in oxidation-reduction potential (ORP) during anoxic phases with simultaneous ethanol dosage indicated inhibition of denitrifiers, probably by the intermediate product NO, which may have interfered with the DO sensor. Nitric oxide production was believed to be favoured in the beginning of the anoxic phase as a result of low pH and high nitrite concentration. A stable nitritation-denitritation process could be achieved when the aerobic hydraulic retention time (HRT) was decreased to the same length as the anoxic HRT, which resulted in increased unused alkalinity. PMID:21879560

  19. Selective inhibition of ammonium oxidation and nitrification-linked N2O formation by methyl fluoride and dimethyl ether

    USGS Publications Warehouse

    Miller, L.G.; Coutlakis, M.D.; Oremland, R.S.; Ward, B.B.

    1993-01-01

    Methyl fluoride (CH3F) and dimethyl ether (DME) inhibited nitrification in washed-cell suspensions of Nitrosomonas europaea and in a variety of oxygenated soils and sediments. Headspace additions of CH3F (10% [vol/vol]) and DME (25% [vol/vol]) fully inhibited NO2- and N2O production from NH4+ in incubations of N. europaea, while lower concentrations of these gases resulted in partial inhibition. Oxidation of hydroxylamine (NH2OH) by N. europaea and oxidation of NO2- by a Nitrobacter sp. were unaffected by CH3F or DME. In nitrifying soils, CH3F and DME inhibited N2O production. In field experiments with surface flux chambers and intact cores, CH3F reduced the release of N2O from soils to the atmosphere by 20- to 30-fold. Inhibition by CH3F also resulted in decreased NO3- + NO2- levels and increased NH4+ levels in soils. CH3F did not affect patterns of dissimilatory nitrate reduction to ammonia in cell suspensions of a nitrate- respiring bacterium, nor did it affect N2O metabolism in denitrifying soils. CH3F and DME will be useful in discriminating N2O production via nitrification and denitrification when both processes occur and in decoupling these processes by blocking NO2- and NO3- production.

  20. Aerobic degradation of sulfanilic acid using activated sludge.

    PubMed

    Chen, Gang; Cheng, Ka Yu; Ginige, Maneesha P; Kaksonen, Anna H

    2012-01-01

    This paper evaluates the aerobic degradation of sulfanilic acid (SA) by an acclimatized activated sludge. The sludge was enriched for over three months with SA (>500 mg/L) as the sole carbon and energy source and dissolved oxygen (DO, >5mg/L) as the primary electron acceptor. Effects of aeration rate (0-1.74 L/min), DO concentration (0-7 mg/L) and initial SA concentration (104-1085 mg/L) on SA biodegradation were quantified. A modified Haldane substrate inhibition model was used to obtain kinetic parameters of SA biodegradation and oxygen uptake rate (OUR). Positive linear correlations were obtained between OUR and SA degradation rate (R(2)≥ 0.91). Over time, the culture consumed more oxygen per SA degraded, signifying a gradual improvement in SA mineralization (mass ratio of O(2): SA at day 30, 60 and 120 were 0.44, 0.51 and 0.78, respectively). The concomitant release of near stoichiometric quantity of sulphate (3.2 mmol SO(4)(2-) released from 3.3 mmol SA) and the high chemical oxygen demand (COD) removal efficacy (97.1%) indicated that the enriched microbial consortia could drive the overall SA oxidation close to a complete mineralization. In contrast to other pure-culture systems, the ammonium released from the SA oxidation was predominately converted into nitrate, revealing the presence of ammonium-oxidizing bacteria (AOB) in the mixed culture. No apparent inhibitory effect of SA on the nitrification was noted. This work also indicates that aerobic SA biodegradation could be monitored by real-time DO measurement.

  1. Relationship of arsenic concentration with ammonium-nitrogen concentration, oxidation reduction potential and pH of groundwater in arsenic-contaminated areas in Asia

    NASA Astrophysics Data System (ADS)

    Kurosawa, Kiyoshi; Egashira, Kazuhiko; Tani, Masakazu

    This study examines how arsenic (As) concentration is related to ammonium-nitrogen (NH4-N) concentration, oxidation reduction potential (ORP) and pH in groundwater to determine if they have common characteristics in groundwater with high As concentrations in the As-contaminated areas of Bangladesh, Nepal, Cambodia and Vietnam. For the groundwater samples having the three highest As concentrations (top three groundwaters) selected as representatives at each location, As and NH4-N concentrations varied, but ORP and pH did not vary by locations. The ORP value of 30-110 mV, indicating the reducing condition, and the neutral to slightly alkaline pH (pH 7.0-7.6) were presumed to be the key conditions for high As concentrations in groundwater of the study areas. According to the ORP (Eh)-pH diagram, the dominant As species in the top three groundwaters from each location was hydrogen arsenate (HAsO42-). Out of the correlations between the four elements for the top three groundwaters in the areas, only the correlation between As and NH4-N concentrations was positive and significant. Thus, it was identified that NH4-N had an effect on increasing As concentration in groundwater.

  2. Aerobic Production and Utilization of Lactate Satisfy Increased Energy Demands Upon Neuronal Activation in Hippocampal Slices and Provide Neuroprotection Against Oxidative Stress

    PubMed Central

    Schurr, Avital; Gozal, Evelyne

    2012-01-01

    Ever since it was shown for the first time that lactate can support neuronal function in vitro as a sole oxidative energy substrate, investigators in the field of neuroenergetics have been debating the role, if any, of this glycolytic product in cerebral energy metabolism. Our experiments employed the rat hippocampal slice preparation with electrophysiological and biochemical methodologies. The data generated by these experiments (a) support the hypothesis that lactate, not pyruvate, is the end-product of cerebral aerobic glycolysis; (b) indicate that lactate plays a major and crucial role in affording neural tissue to respond adequately to glutamate excitation and to recover unscathed post-excitation; (c) suggest that neural tissue activation is accompanied by aerobic lactate and NADH production, the latter being produced when the former is converted to pyruvate by mitochondrial lactate dehydrogenase (mLDH); (d) imply that NADH can be utilized as an endogenous scavenger of reactive oxygen species (ROS) to provide neuroprotection against ROS-induced neuronal damage. PMID:22275901

  3. Chemoselective Conversion from α-Hydroxy Acids to α-Keto Acids Enabled by Nitroxyl-Radical-Catalyzed Aerobic Oxidation.

    PubMed

    Furukawa, Keisuke; Inada, Haruki; Shibuya, Masatoshi; Yamamoto, Yoshihiko

    2016-09-01

    The chemoselective oxidation of α-hydroxy acids to α-keto acids catalyzed by 2-azaadamantane N-oxyl (AZADO), a nitroxyl radical catalyst, is described. Although α-keto acids are labile and can easily release CO2 under oxidation conditions, the use of molecular oxygen as a cooxidant enables the desired chemoselective oxidation. PMID:27533283

  4. Community structures and distribution of anaerobic ammonium oxidizing and nirS-encoding nitrite-reducing bacteria in surface sediments of the South China Sea.

    PubMed

    Li, Meng; Hong, Yiguo; Cao, Huiluo; Gu, Ji-Dong

    2013-08-01

    Anaerobic ammonium oxidation (anammox) and denitrification are two important processes responsible for nitrogen loss; monitoring of microbial communities carrying out these two processes offers a unique opportunity to understand the microbial nitrogen cycle. The aim of the current study was to characterize community structures and distribution of anammox and nirS-encoding nitrite-reducing bacteria in surface sediments of the northern South China Sea (SCS). The consistent phylogenetic results of three biomarkers of anammox bacteria, including 16S rRNA, hzo, and Scalindua-nirS genes, showed that Scalindua-like bacteria were the only anammox group presenting in surface sediments of the SCS. However, a relatively high micro-diversity was found within this group, including several SCS habitat-specific phylotypes, Candidatus "Scalindua zhenghei". Comparing to 16S rRNA gene, hzo and Scalindua-nirS genes provided a relatively higher resolution to elucidate anammox bacteria. For the nirS-encoding nitrite-reducing bacteria, the detected nirS gene sequences were closely related to various marine nirS denitrifiers, especially those which originated from coastal and estuarine sediments with a much higher diversity than anammox bacteria. Anammox bacterial communities shifted along with the seawater depth, while nirS-encoding nitrite-reducing bacteria did not. Although nirS-encoding nitrite-reducing bacteria have a much higher abundance and diversity than anammox bacteria, they showed similar abundance variation patterns in research sites, suggesting the two microbial groups might be affected by the similar environmental factors. The significant correlations among the abundance of the two microbial groups with the molar ratio of NH4 (+) to (NO2 (-) + NO3 (-)), pH, and organic matters of sediments strongly supported this hypothesis. PMID:23354291

  5. Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts

    PubMed Central

    Jeon, Jong Yeob; Eo, Seong Chan; Varghese, Jobi Kodiyan

    2014-01-01

    Summary The (salen)Co(III) complex 1 tethering four quaternary ammonium salts, which is a highly active catalyst in CO2/epoxide copolymerizations, shows high activity for propylene oxide/phthalic anhydride (PO/PA) copolymerizations and PO/CO2/PA terpolymerizations. In the PO/PA copolymerizations, full conversion of PA was achieved within 5 h, and strictly alternating copolymers of poly(1,2-propylene phthalate)s were afforded without any formation of ether linkages. In the PO/CO2/PA terpolymerizations, full conversion of PA was also achieved within 4 h. The resulting polymers were gradient poly(1,2-propylene carbonate-co-phthalate)s because of the drift in the PA concentration during the terpolymerization. Both polymerizations showed immortal polymerization character; therefore, the molecular weights were determined by the activity (g/mol-1) and the number of chain-growing sites per 1 [anions in 1 (5) + water (present as impurity) + ethanol (deliberately fed)], and the molecular weight distributions were narrow (M w/M n, 1.05–1.5). Because of the extremely high activity of 1, high-molecular-weight polymers were generated (M n up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO2/PA terpolymerization, respectively). The terpolymers bearing a substantial number of PA units (f PA, 0.23) showed a higher glass-transition temperature (48 °C) than the CO2/PO alternating copolymer (40 °C). PMID:25161738

  6. Community structures and distribution of anaerobic ammonium oxidizing and nirS-encoding nitrite-reducing bacteria in surface sediments of the South China Sea.

    PubMed

    Li, Meng; Hong, Yiguo; Cao, Huiluo; Gu, Ji-Dong

    2013-08-01

    Anaerobic ammonium oxidation (anammox) and denitrification are two important processes responsible for nitrogen loss; monitoring of microbial communities carrying out these two processes offers a unique opportunity to understand the microbial nitrogen cycle. The aim of the current study was to characterize community structures and distribution of anammox and nirS-encoding nitrite-reducing bacteria in surface sediments of the northern South China Sea (SCS). The consistent phylogenetic results of three biomarkers of anammox bacteria, including 16S rRNA, hzo, and Scalindua-nirS genes, showed that Scalindua-like bacteria were the only anammox group presenting in surface sediments of the SCS. However, a relatively high micro-diversity was found within this group, including several SCS habitat-specific phylotypes, Candidatus "Scalindua zhenghei". Comparing to 16S rRNA gene, hzo and Scalindua-nirS genes provided a relatively higher resolution to elucidate anammox bacteria. For the nirS-encoding nitrite-reducing bacteria, the detected nirS gene sequences were closely related to various marine nirS denitrifiers, especially those which originated from coastal and estuarine sediments with a much higher diversity than anammox bacteria. Anammox bacterial communities shifted along with the seawater depth, while nirS-encoding nitrite-reducing bacteria did not. Although nirS-encoding nitrite-reducing bacteria have a much higher abundance and diversity than anammox bacteria, they showed similar abundance variation patterns in research sites, suggesting the two microbial groups might be affected by the similar environmental factors. The significant correlations among the abundance of the two microbial groups with the molar ratio of NH4 (+) to (NO2 (-) + NO3 (-)), pH, and organic matters of sediments strongly supported this hypothesis.

  7. Microbial diversity differences within aerobic granular sludge and activated sludge flocs.

    PubMed

    Winkler, M-K H; Kleerebezem, R; de Bruin, L M M; Verheijen, P J T; Abbas, B; Habermacher, J; van Loosdrecht, M C M

    2013-08-01

    In this study, we investigated during 400 days the microbial community variations as observed from 16S DNA gene DGGE banding patterns from an aerobic granular sludge pilot plant as well as the from a full-scale activated sludge treatment plant in Epe, the Netherlands. Both plants obtained the same wastewater and had the same relative hydraulic variations and run stable over time. For the total bacterial population, a similarity analysis was conducted showing that the community composition of both sludge types was very dissimilar. Despite this difference, general bacterial population of both systems had on average comparable species richness, entropy, and evenness, suggesting that different bacteria were sharing the same functionality. Moreover, multi-dimensional scaling analysis revealed that the microbial populations of the flocculent sludge system moved closely around the initial population, whereas the bacterial population in the aerobic granular sludge moved away from its initial population representing a permanent change. In addition, the ammonium-oxidizing community of both sludge systems was studied in detail showing more unevenness than the general bacterial community. Nitrosomonas was the dominant AOB in flocculent sludge, whereas in granular sludge, Nitrosomonas and Nitrosospira were present in equal amounts. A correlation analysis of process data and microbial data from DGGE gels showed that the microbial diversity shift in ammonium-oxidizing bacteria clearly correlated with fluctuations in temperature. PMID:23064482

  8. Copper-catalyzed aerobic oxidative transformation of ketone-derived N-tosyl hydrazones: an entry to alkynes.

    PubMed

    Li, Xianwei; Liu, Xiaohang; Chen, Huoji; Wu, Wanqing; Qi, Chaorong; Jiang, Huanfeng

    2014-12-22

    A novel strategy involving Cu-catalyzed oxidative transformation of ketone-derived hydrazone moiety to various synthetic valuable internal alkynes and diynes has been developed. This method features inexpensive metal catalyst, green oxidant, good functional group tolerance, high regioselectivity and readily available starting materials. Oxidative deprotonation reactions were carried out to form internal alkynes and symmetrical diynes. Cross-coupling reactions of hydrazones with halides and terminal alkynes were performed to afford functionalized alkynes and unsymmetrical conjugated diynes. A mechanism proceeding through a Cu-carbene intermediate is proposed for the CC triple bond formation. PMID:25424976

  9. Aerobic Exercise Training Prevents the Onset of Endothelial Dysfunction via Increased Nitric Oxide Bioavailability and Reduced Reactive Oxygen Species in an Experimental Model of Menopause

    PubMed Central

    Braga, Viviane A. V. N.; Couto, Gisele K.; Lazzarin, Mariana C.; Rossoni, Luciana V.; Medeiros, Alessandra

    2015-01-01

    Objective Previous studies have shown that estrogen deficiency, arising in postmenopause, promotes endothelial dysfunction. This study evaluated the effects of aerobic exercise training on endothelial dependent vasodilation of aorta in ovariectomized rats, specifically investigating the role of nitric oxide (NO) and reactive oxygen species (ROS). Methods Female Wistar rats ovariectomized (OVX – n=20) or with intact ovary (SHAM – n=20) remained sedentary (OVX and SHAM) or performed aerobic exercise training on a treadmill 5 times a week for a period of 8 weeks (OVX-TRA and SHAM-TRA). In the thoracic aorta the endothelium-dependent and –independent vasodilation was assessed by acetylcholine (ACh) and sodium nitroprusside (SNP), respectively. Certain aortic rings were incubated with L-NAME to assess the NO modulation on the ACh-induced vasodilation. The fluorescence to dihydroethidium in aortic slices and plasma nitrite/nitrate concentrations were measured to evaluate ROS and NO bioavailability, respectively. Results ACh-induced vasodilation was reduced in OVX rats as compared SHAM (Rmax: SHAM: 86±3.3 vs. OVX: 57±3.0%, p<0.01). Training prevented this response in OVX-TRA (Rmax: OVX-TRA: 88±2.0%, p<0.01), while did not change it in SHAM-TRA (Rmax: SHAM-TRA: 80±2.2%, p<0.01). The L-NAME incubation abolished the differences in ACh-induced relaxation among groups. SNP-induced vasodilation was not different among groups. OVX reduced nitrite/nitrate plasma concentrations and increased ROS in aortic slices, training as effective to restore these parameters to the SHAM levels. Conclusions Exercise training, even in estrogen deficiency conditions, is able to improve endothelial dependent vasodilation in rat aorta via enhanced NO bioavailability and reduced ROS levels. PMID:25923465

  10. A robust and cost-effective integrated process for nitrogen and bio-refractory organics removal from landfill leachate via short-cut nitrification, anaerobic ammonium oxidation in tandem with electrochemical oxidation.

    PubMed

    Wu, Li-Na; Liang, Da-Wei; Xu, Ying-Ying; Liu, Ting; Peng, Yong-Zhen; Zhang, Jie

    2016-07-01

    A cost-effective process, consisting of a denitrifying upflow anaerobic sludge blanket (UASB), an oxygen-limited anoxic/aerobic (A/O) process for short-cut nitrification, and an anaerobic reactor (ANR) for anaerobic ammonia oxidation (anammox), followed by an electrochemical oxidation process with a Ti-based SnO2-Sb2O5 anode, was developed to remove organics and nitrogen in a sewage diluted leachate. The final chemical oxygen demand (COD), ammonia nitrogen (NH4(+)-N) and total nitrogen (TN) of 70, 11.3 and 39 (all in mg/L), respectively, were obtained. TN removal in UASB, A/O and ANR were 24.6%, 49.6% and 16.1%, respectively. According to the water quality and molecular biology analysis, a high degree of anammox besides short-cut nitrification and denitrification occurred in A/O. Counting for 16.1% of TN removal in ANR, at least 43.2-49% of TN was removed via anammox. The anammox bacteria in A/O and ANR, were in respective titers of (2.5-5.9)×10(9) and 2.01×10(10)copy numbers/(gSS).

  11. A robust and cost-effective integrated process for nitrogen and bio-refractory organics removal from landfill leachate via short-cut nitrification, anaerobic ammonium oxidation in tandem with electrochemical oxidation.

    PubMed

    Wu, Li-Na; Liang, Da-Wei; Xu, Ying-Ying; Liu, Ting; Peng, Yong-Zhen; Zhang, Jie

    2016-07-01

    A cost-effective process, consisting of a denitrifying upflow anaerobic sludge blanket (UASB), an oxygen-limited anoxic/aerobic (A/O) process for short-cut nitrification, and an anaerobic reactor (ANR) for anaerobic ammonia oxidation (anammox), followed by an electrochemical oxidation process with a Ti-based SnO2-Sb2O5 anode, was developed to remove organics and nitrogen in a sewage diluted leachate. The final chemical oxygen demand (COD), ammonia nitrogen (NH4(+)-N) and total nitrogen (TN) of 70, 11.3 and 39 (all in mg/L), respectively, were obtained. TN removal in UASB, A/O and ANR were 24.6%, 49.6% and 16.1%, respectively. According to the water quality and molecular biology analysis, a high degree of anammox besides short-cut nitrification and denitrification occurred in A/O. Counting for 16.1% of TN removal in ANR, at least 43.2-49% of TN was removed via anammox. The anammox bacteria in A/O and ANR, were in respective titers of (2.5-5.9)×10(9) and 2.01×10(10)copy numbers/(gSS). PMID:27115616

  12. Reaction progress kinetic analysis of a copper-catalyzed aerobic oxidative coupling reaction with N-phenyl tetrahydroisoquinoline.

    PubMed

    Scott, Martin; Sud, Abhishek; Boess, Esther; Klussmann, Martin

    2014-12-19

    The results from a kinetic investigation of a Cu-catalyzed oxidative coupling reaction between N-phenyl tetrahydroisoquinoline and a silyl enol ether using elemental oxygen as oxidant are presented. By using reaction progress kinetic analysis as an evaluation method for the obtained data, we discovered information regarding the reaction order of the substrates and catalysts. Based on this information and some additional experiments, a refined model for the initial oxidative activation of the amine substrate and the activation of the nucleophile by the catalyst was developed. The mechanistic information also helped to understand why silyl nucleophiles have previously failed in a related Cu-catalyzed reaction using tert-butyl hydroperoxide as oxidant and how to overcome this limitation. PMID:25203932

  13. Copper-catalyzed aerobic oxidation of hydroxamic acids leads to a mild and versatile acylnitroso ene reaction.

    PubMed

    Frazier, Charles P; Engelking, Jarred R; Read de Alaniz, Javier

    2011-07-13

    A mild formation of transient acylnitroso intermediates using a copper chloride catalyst and 1 atm of air as the terminal oxidant is described. The mild reaction conditions enable the inter- and intramolecular acylnitroso ene reaction with a wide range of functionalized alkene partners, as well as the first asymmetric variant. Notably, this transformation provides a practical and operationally simple method for effecting allylic amidation using an environmentally benign oxidant and a readily abundant transition metal. PMID:21678942

  14. Efficient synthesis of biazoles by aerobic oxidative homocoupling of azoles catalyzed by a copper(I)/2-pyridonate catalytic system.

    PubMed

    Zhu, Mingwen; Fujita, Ken-ichi; Yamaguchi, Ryohei

    2011-12-28

    A highly efficient and convenient CuCl/2-pyridonate catalytic system for oxidative homocoupling of azoles affording a biazole product has been developed. With this system, a variety of biazoles have been effectively synthesized in good to excellent yields in the presence of a very small amount of copper catalyst (1.0 mol%). It was feasible to employ air as a green oxidant. PMID:22076830

  15. Azo dye removal in a membrane-free up-flow biocatalyzed electrolysis reactor coupled with an aerobic bio-contact oxidation reactor.

    PubMed

    Cui, Dan; Guo, Yu-Qi; Cheng, Hao-Yi; Liang, Bin; Kong, Fan-Ying; Lee, Hyung-Sool; Wang, Ai-Jie

    2012-11-15

    Azo dyes that consist of a large quantity of dye wastewater are toxic and persistent to biodegradation, while they should be removed before being discharged to water body. In this study, Alizarin Yellow R (AYR) as a model azo dye was decolorized in a combined bio-system of membrane-free, continuous up-flow bio-catalyzed electrolysis reactor (UBER) and subsequent aerobic bio-contact oxidation reactor (ABOR). With the supply of external power source 0.5 V in the UBER, AYR decolorization efficiency increased up to 94.8±1.5%. Products formation efficiencies of p-phenylenediamine (PPD) and 5-aminosalicylic acid (5-ASA) were above 90% and 60%, respectively. Electron recovery efficiency based on AYR removal in cathode zone was nearly 100% at HRTs longer than 6 h. Relatively high concentration of AYR accumulated at higher AYR loading rates (>780 gm(-3) d(-1)) likely inhibited acetate oxidation of anode-respiring bacteria on the anode, which decreased current density in the UBER; optimal AYR loading rate for the UBER was 680 gm(-3) d(-1) (HRT 2.5 h). The subsequent ABOR further improved effluent quality. Overall the Chroma decreased from 320 times to 80 times in the combined bio-system to meet the textile wastewater discharge standard II in China. PMID:23009797

  16. Enhancement of Bacterial Transport in Aerobic and Anaerobic Environments: Assessing the Effect of Metal Oxide Chemical Heterogeneities

    SciTech Connect

    T.C. Onstott

    2005-09-30

    The goal of our research was to understand the fundamental processes that control microbial transport in physically and chemically heterogeneous aquifers and from this enhanced understanding determine the requirements for successful, field-scale delivery of microorganisms to metal contaminated subsurface sites. Our specific research goals were to determine; (1) the circumstances under which the preferential adsorption of bacteria to Fe, Mn, and Al oxyhydroxides influences field-scale bacterial transport, (2) the extent to which the adhesion properties of bacterial cells affect field-scale bacterial transport, (3) whether microbial Fe(III) reduction can enhance field-scale transport of Fe reducing bacteria (IRB) and other microorganisms and (4) the effect of field-scale physical and chemical heterogeneity on all three processes. Some of the spin-offs from this basic research that can improve biostimulation and bioaugmentation remediation efforts at contaminated DOE sites have included; (1) new bacterial tracking tools for viable bacteria; (2) an integrated protocol which combines subsurface characterization, laboratory-scale experimentation, and scale-up techniques to accurately predict field-scale bacterial transport; and (3) innovative and inexpensive field equipment and methods that can be employed to enhance Fe(III) reduction and microbial transport and to target microbial deposition under both aerobic and anaerobic conditions.

  17. Bench-scale study of the effect of phosphate on an aerobic iron oxidation plant for mine water treatment.

    PubMed

    Tischler, Judith S; Wiacek, Claudia; Janneck, Eberhard; Schlömann, Michael

    2014-01-01

    At the opencast pit Nochten acidic iron- and sulfate-rich mine waters are treated biotechnologically in a mine-water treatment plant by microbial iron oxidation. Due to the low phosphate concentration in such waters the treatment plant was simulated in bench-scale to investigate the influence of addition of potassium dihydrogen phosphate on chemical and biological parameters of the mine-water treatment. As a result of the phosphate addition the number of cells increased, which resulted in an increase of the iron oxidation rate in the reactor with phosphate addition by a factor of 1.7 compared to a reference approach without phosphate addition. Terminal restriction fragment length polymorphism (T-RFLP) analysis during the cultivation revealed a shift of the microbial community depending on the phosphate addition. While almost exclusively iron-oxidizing bacteria related to "Ferrovum" sp. were detected with phosphate addition, the microbial community was more diverse without phosphate addition. In the latter case, iron-oxidizing bacteria ("Ferrovum" sp., Acidithiobacillus spp.) as well as non-iron-oxidizing bacteria (Acidiphilium sp.) were identified.

  18. A novel bacteriohopanepolyol biomarker reveals anaerobic ammonium oxidation has been an important process in Gulf of Alaska nitrogen cycling over the last ~60 ka.

    NASA Astrophysics Data System (ADS)

    Rush, D.; Zindorf, M.; Talbot, H.; Schnetger, B.; Maerz, C.; Crawford, A.

    2015-12-01

    Anaerobic ammonium oxidation (anammox) is one of the major sinks of bio-available nitrogen from the marine system. Anammox is estimated be responsible for ca. 30% of dinitrogen gas produced in modern open oceans [1]. Tracing the anammox process in the past has been temporally-limited by the lability of the lipid biomarkers synthesised by anammox bacteria. These ladderane lipids are highly susceptible to degradation [2,3], and are not well preserved in the sedimentary record [4]. Recently, however, bacteriohopanetetrol stereoisomer (BHT isomer) was identified as a more recalcitrant biomarker for pelagic anammox, expanding the potential to study past anammox activity [5]. Here, we investigate BHT isomer concentration (Fig. 1a) and BHT isomer ratio (Fig. 1b) in sediments from the last ~60 ka in the Gulf of Alaska (IODP Expedition 341, Site U1419) [6]. Our data show increased deposition of pelagic anammox bacteria, paralleled by inorganic proxy records for oxygen-depleted bottom water conditions (total sulfur and pyrite-bound iron to highly reactive iron ratio; Fig. 1, c,d). This indicates that the oxygen minimum zone in the Gulf of Alaska likely fluctuated following past climate changes. [1] Ward, B.B. 2013. Science 341, 352-353. [2] Sinninghe Damsté, et al. 2002. Nature 419, 708-712. [3] Rush et al. 2011. Geochimica et Cosmochimica Acta 75, 1662-1671. [4] Jaeschke et al. 2009. Paleoceanography 24, PA2202, doi:10.1029/2008PA001712. [5] Rush et al. 2014. Geochimica et Cosmochimica Acta 140, 50-64. [6] Jaeger et al., 2015. Proceedings of the Integrated Ocean Drilling Program, Volume 341 [7] Sáenz et al., 2011. Organic Geochemistry 42, 1351-1362. Figure 1. Anammox in the Gulf of ­­Alaska over ~60 ka. (a) bacteriohopanetetrol and bacteriohopanetetrol stereoisomer (BHT isomer) concentrations, (b) BHT isomer ratio with known ranges for sediment and anammox cultures [5,7], (c) S (% weight), and (d) pyrite-Fe over highly reactive Fe.

  19. Rates of N2 production and diversity and abundance of functional genes associated with denitrification and anaerobic ammonium oxidation in the sediment of the Amundsen Sea Polynya, Antarctica

    NASA Astrophysics Data System (ADS)

    Choi, Ayeon; Cho, Hyeyoun; Kim, Sung-Han; Thamdrup, Bo; Lee, SangHoon; Hyun, Jung-Ho

    2016-01-01

    A combination of molecular microbiological analyses and metabolic rate measurements was conducted to elucidate the diversity and abundance of denitrifying and anaerobic ammonium oxidation (anammox) bacteria and the nitrogen gas (N2) production rates in sediment underlying the highly productive polynya (Stns. 10 and 17) and the sea-ice zone on the outer shelf (Stn. 83) of the Amundsen Sea, Antarctica. Despite the high water column productivity, the N2 production rates by denitrification (0.04-0.31 nmol N cm-3sed. h-1) and anammox (0.13-0.26 nmol N cm-3 sed. h-1) were lower than those measured in other polar regions. In contrast, gene copy number (106-107 copies cm-3 of nirS and nosZ genes targeting denitirifiers and 105-107 copies cm-3 of 16S rRNA genes related to anammox bacteria) of the two bacterial groups at Stn. 17 was similar compared to those of other organic-rich environments. The majority of the nirS sequences were affiliated with Gammaproteobacteria (54% and 61% of the total nirS gene at Stns. 17 and 83, respectively), which were closely related to Pseudomonas aeruginosa. Most nosZ sequences (92% and 72% of the total nosZ genes at Stns. 17 and 83, respectively) were related to the Alphaproteobacteria, which were closely related to Ruegeria pomeroyi and Roseobacter denitrificans. Most (98%) of the sequences related to anammox bacteria were affiliated with Candidatus Scalindua at Stn. 17. Consequently, despite the low metabolic activity, the abundance and composition of most denitrifying and anammox bacteria detected from the ASP were similar to those reported from a variety of marine environments. Our results further imply that increased labile organic matter production resulting from a shift of the phytoplankton community from Phaeocystis to diatoms in response to rapid melting of sea ice stimulates metabolic activities of the denitrifying and anammox bacteria, thereby enhancing the N removal process in the ASP.

  20. Aerobic oxidative amidation of aromatic and cinnamic aldehydes with secondary amines by CuI/2-pyridonate catalytic system.

    PubMed

    Zhu, Mingwen; Fujita, Ken-ichi; Yamaguchi, Ryohei

    2012-10-19

    A simple and convenient CuI/2-pyridonate catalytic system for the oxidative amidation of aldehydes with secondary amines has been developed. With this system, a variety of useful arylamides have been synthesized in moderate to good yields in the presence of small amount of copper catalyst and the pyridonate ligand, generating only water as a coproduct. Synthesis of cinnamamides was also achieved by the reactions of cinnamaldehydes with secondary amines in moderate yields. Air was successfully employed as a green oxidant in this catalytic system, achieving a safe and atom-efficient system for the synthesis of amides. PMID:23006061

  1. The Energetics of Aerobic versus Anaerobic Respiration.

    ERIC Educational Resources Information Center

    Champion, Timothy D.; Schwenz, Richard W.

    1990-01-01

    Background information, laboratory procedures, and a discussion of the results of an experiment designed to investigate the difference in energy gained from the aerobic and anaerobic oxidation of glucose are presented. Sample experimental and calculated data are included. (CW)

  2. The aerobic respiratory chain of the acidophilic archaeon Ferroplasma acidiphilum: A membrane-bound complex oxidizing ferrous iron.

    PubMed

    Castelle, Cindy J; Roger, Magali; Bauzan, Marielle; Brugna, Myriam; Lignon, Sabrina; Nimtz, Manfred; Golyshina, Olga V; Giudici-Orticoni, Marie-Thérèse; Guiral, Marianne

    2015-08-01

    The extremely acidophilic archaeon Ferroplasma acidiphilum is found in iron-rich biomining environments and is an important micro-organism in naturally occurring microbial communities in acid mine drainage. F. acidiphilum is an iron oxidizer that belongs to the order Thermoplasmatales (Euryarchaeota), which harbors the most extremely acidophilic micro-organisms known so far. At present, little is known about the nature or the structural and functional organization of the proteins in F. acidiphilum that impact the iron biogeochemical cycle. We combine here biochemical and biophysical techniques such as enzyme purification, activity measurements, proteomics and spectroscopy to characterize the iron oxidation pathway(s) in F. acidiphilum. We isolated two respiratory membrane protein complexes: a 850 kDa complex containing an aa3-type cytochrome oxidase and a blue copper protein, which directly oxidizes ferrous iron and reduces molecular oxygen, and a 150 kDa cytochrome ba complex likely composed of a di-heme cytochrome and a Rieske protein. We tentatively propose that both of these complexes are involved in iron oxidation respiratory chains, functioning in the so-called uphill and downhill electron flow pathways, consistent with autotrophic life. The cytochrome ba complex could possibly play a role in regenerating reducing equivalents by a reverse ('uphill') electron flow. This study constitutes the first detailed biochemical investigation of the metalloproteins that are potentially directly involved in iron-mediated energy conservation in a member of the acidophilic archaea of the genus Ferroplasma.

  3. Comparison of sidestream treatment technologies: post aerobic digestion and Anammox.

    PubMed

    Bauer, Heidi; Johnson, Thomas D; Johnson, Bruce R; Oerke, David; Graziano, Steven

    2016-01-01

    Post aerobic digestion (PAD) and anaerobic ammonium oxidation (Anammox) are sidestream treatment technologies which are both excellent options for the reduction of nitrogen recycled back to the liquid stream without the need for supplemental carbon or alkalinity. However, the achievement of this goal is where the similarities between the two technologies end. PAD is an advanced digestion process where aerobic digestion is designed to follow anaerobic digestion. Other benefits of PAD include volatile solids reduction, odor reduction, and struvite formation reduction. Anammox harnesses a specific species of autotrophic bacteria that can help achieve partial nitritation/deammonification. Other benefits of Anammox include lower energy consumption due to requiring less oxygen compared with conventional nitrification. This manuscript describes the unique benefits and challenges of each technology. Example installations are presented with a narrative of how and why the technology was selected. A whole plant simulator is used to compare and contrast the mass balances and net present value costs on an 'apples to apples' basis. The discussion includes descriptions of conditions under which each technology would potentially be the most beneficial and cost-effective against a baseline facility without sidestream treatment. PMID:27232417

  4. Comparison of sidestream treatment technologies: post aerobic digestion and Anammox.

    PubMed

    Bauer, Heidi; Johnson, Thomas D; Johnson, Bruce R; Oerke, David; Graziano, Steven

    2016-01-01

    Post aerobic digestion (PAD) and anaerobic ammonium oxidation (Anammox) are sidestream treatment technologies which are both excellent options for the reduction of nitrogen recycled back to the liquid stream without the need for supplemental carbon or alkalinity. However, the achievement of this goal is where the similarities between the two technologies end. PAD is an advanced digestion process where aerobic digestion is designed to follow anaerobic digestion. Other benefits of PAD include volatile solids reduction, odor reduction, and struvite formation reduction. Anammox harnesses a specific species of autotrophic bacteria that can help achieve partial nitritation/deammonification. Other benefits of Anammox include lower energy consumption due to requiring less oxygen compared with conventional nitrification. This manuscript describes the unique benefits and challenges of each technology. Example installations are presented with a narrative of how and why the technology was selected. A whole plant simulator is used to compare and contrast the mass balances and net present value costs on an 'apples to apples' basis. The discussion includes descriptions of conditions under which each technology would potentially be the most beneficial and cost-effective against a baseline facility without sidestream treatment.

  5. Aerobic oxidation of primary alcohols catalyzed by copper complexes of 1,10-phenanthroline-derived ligands.

    PubMed

    Das, Oindrila; Paine, Tapan Kanti

    2012-10-01

    Five copper complexes [(L(1))(2)Cu(H(2)O)](ClO(4))(2) (1), [(L(1))Cu(H(2)O)(3)](ClO(4))(2) (1a), [(L(3))(2)Cu(H(2)O)](ClO(4))(2) (2), [(L(5))(2)Cu(H(2)O)](ClO(4))(2) (3) and [(L(6))(2)Cu](ClO(4)) (4) (where L(1) = 1,10-phenanthroline, L(3) = 1,10-phenanthroline-5,6-dione, L(5) = 1,10-phenanthrolinefuroxan and L(6) = 2,9-dimethyl-1,10-phenanthrolinefuroxan), and in situ prepared copper complexes of 2,9-dimethyl-1,10-phenanthroline (L(2)) or 2,9-dimethyl-1,10-phenanthrolinedione (L(4)) were used for aerial oxidation of primary alcohols to the corresponding aldehydes under ambient conditions. The copper catalysts have been found to catalyze a series of primary alcohols including one secondary alcohol with moderate turnover numbers and selectivity towards primary alcohols. Copper(II) complexes 1 (or 1a) and 2 were found to be the better catalysts among all other systems explored in this study. A copper(II)-superoxo species is implicated to initiate the oxidation reaction. Structural and electronic factors of 1,10-phenanthroline-based ligands affecting the catalytic results for aerial oxidation of alcohols are discussed.

  6. Aerobic Alcohol Oxidation Using a Copper(I)/TEMPO Catalyst System: A Green, Catalytic Oxidation Reaction for the Undergraduate Organic Chemistry Laboratory

    ERIC Educational Resources Information Center

    Hill, Nicholas J.; Hoover, Jessica M.; Stahl, Shannon S.

    2013-01-01

    Modern undergraduate organic chemistry textbooks provide detailed discussion of stoichiometric Cr- and Mn-based reagents for the oxidation of alcohols, yet the use of such oxidants in instructional and research laboratories, as well as industrial chemistry, is increasingly avoided. This work describes a laboratory exercise that uses ambient air as…

  7. Attenuation of Ca2+ homeostasis, oxidative stress, and mitochondrial dysfunctions in diabetic rat heart: insulin therapy or aerobic exercise?

    PubMed

    da Silva, Márcia F; Natali, Antônio J; da Silva, Edson; Gomes, Gilton J; Teodoro, Bruno G; Cunha, Daise N Q; Drummond, Lucas R; Drummond, Filipe R; Moura, Anselmo G; Belfort, Felipe G; de Oliveira, Alessandro; Maldonado, Izabel R S C; Alberici, Luciane C

    2015-07-15

    We tested the effects of swimming training and insulin therapy, either alone or in combination, on the intracellular calcium ([Ca(2+)]i) homeostasis, oxidative stress, and mitochondrial functions in diabetic rat hearts. Male Wistar rats were separated into control, diabetic, or diabetic plus insulin groups. Type 1 diabetes mellitus was induced by streptozotocin (STZ). Insulin-treated groups received 1 to 4 UI of insulin daily for 8 wk. Each group was divided into sedentary or exercised rats. Trained groups were submitted to swimming (90 min/day, 5 days/wk, 8 wk). [Ca(2+)]i transient in left ventricular myocytes (LVM), oxidative stress in LV tissue, and mitochondrial functions in the heart were assessed. Diabetes reduced the amplitude and prolonged the times to peak and to half decay of the [Ca(2+)]i transient in LVM, increased NADPH oxidase-4 (Nox-4) expression, decreased superoxide dismutase (SOD), and increased carbonyl protein contents in LV tissue. In isolated mitochondria, diabetes increased Ca(2+) uptake, susceptibility to permeability transition pore (MPTP) opening, uncoupling protein-2 (UCP-2) expression, and oxygen consumption but reduced H2O2 release. Swimming training corrected the time course of the [Ca(2+)]i transient, UCP-2 expression, and mitochondrial Ca(2+) uptake. Insulin replacement further normalized [Ca(2+)]i transient amplitude, Nox-4 expression, and carbonyl content. Alongside these benefits, the combination of both therapies restored the LV tissue SOD and mitochondrial O2 consumption, H2O2 release, and MPTP opening. In conclusion, the combination of swimming training with insulin replacement was more effective in attenuating intracellular Ca(2+) disruptions, oxidative stress, and mitochondrial dysfunctions in STZ-induced diabetic rat hearts. PMID:25997948

  8. Effects of high-intensity interval versus continuous moderate-intensity aerobic exercise on apoptosis, oxidative stress and metabolism of the infarcted myocardium in a rat model.

    PubMed

    Lu, Kai; Wang, Li; Wang, Changying; Yang, Yuan; Hu, Dayi; Ding, Rongjing

    2015-08-01

    The optimal aerobic exercise training (AET) protocol for patients following myocardial infarction (MI) has remained under debate. The present study therefore aimed to compare the effects of continuous moderate-intensity training (CMT) and high-intensity interval training (HIT) on cardiac functional recovery, and to investigate the potential associated mechanisms in a post-MI rat model. Female Sprague Dawley rats (8-10 weeks old) undergoing MI or sham surgery were subsequently submitted to CMT or HIT, or kept sedentary for eight weeks. Prior to and following AET, echocardiographic parameters and exercise capacity of the rats were measured. Western blotting was used to evaluate the levels of apoptosis and associated signaling pathway protein expression. The concentrations of biomarkers of oxidative stress were also determined by ELISA assay. Messenger (m)RNA levels and activity of the key enzymes for glycolysis and fatty acid oxidation, as well as the rate of adenosine triphosphate (ATP) synthesis, were also measured. Compared with the MI group, exercise capacity and cardiac function were significantly improved following AET, particularly following HIT. Left ventricular ejection fraction and fraction shortening were further improved in the MI-HIT group in comparison to that of the MI-CMT group. The two forms of AET almost equally attenuated apoptosis of the post-infarction myocardium. CMT and HIT also alleviated oxidative stress by decreasing the concentration of malondialdehyde and increasing the concentration of superoxide dismutase and glutathione peroxidase (GPx). In particular, HIT induced a greater increase in the concentration of GPx than that of CMT. AET, and HIT in particular, significantly increased the levels of mRNA and the maximal activity of phosphofructokinase-1 and carnitine palmitoyl transferase-1, as well as the maximal ratio of ATP synthesis. In addition, compared with the MI group, the expression of signaling proteins PI3K, Akt, p38mapk and AMPK

  9. Ammonium dichromate poisoning: A rare cause of acute kidney injury

    PubMed Central

    Radhakrishnan, H.; Gopi, M.; Arumugam, A.

    2014-01-01

    Ammonium dichromate is an inorganic compound frequently used in screen and color printing. Being a strong oxidizing agent, it causes oxygen free radical injury resulting in organ failure. We report a 25-year-old female who presented with acute kidney injury after consumption of ammonium dichromate. She was managed successfully with hemodialysis and supportive measures. This case is reported to highlight the toxicity of ammonium dichromate. PMID:25484533

  10. A biomimetic pathway for vanadium-catalyzed aerobic oxidation of alcohols: evidence for a base-assisted dehydrogenation mechanism.

    PubMed

    Wigington, Bethany N; Drummond, Michael L; Cundari, Thomas R; Thorn, David L; Hanson, Susan K; Scott, Susannah L

    2012-11-19

    The first step in the catalytic oxidation of alcohols by molecular O(2), mediated by homogeneous vanadium(V) complexes [LV(V)(O)(OR)], is ligand exchange. The unusual mechanism of the subsequent intramolecular oxidation of benzyl alcoholate ligands in the 8-hydroxyquinolinato (HQ) complexes [(HQ)(2)V(V)(O)(OCH(2)C(6)H(4)-p-X)] involves intermolecular deprotonation. In the presence of triethylamine, complex 3 (X = H) reacts within an hour at room temperature to generate, quantitatively, [(HQ)(2)V(IV)(O)], benzaldehyde (0.5 equivalents), and benzyl alcohol (0.5 equivalents). The base plays a key role in the reaction: in its absence, less than 12% conversion was observed after 72 hours. The reaction is first order in both 3 and NEt(3), with activation parameters ΔH(≠)=(28±4) kJ mol(-1) and ΔS(≠)=(-169±4) J K(-1)  mol(-1). A large kinetic isotope effect, 10.2±0.6, was observed when the benzylic hydrogen atoms were replaced by deuterium atoms. The effect of the para substituent of the benzyl alcoholate ligand on the reaction rate was investigated using a Hammett plot, which was constructed using σ(p). From the slope of the Hammett plot, ρ=+(1.34±0.18), a significant buildup of negative charge on the benzylic carbon atom in the transition state is inferred. These experimental findings, in combination with computational studies, support an unusual bimolecular pathway for the intramolecular redox reaction, in which the rate-limiting step is deprotonation at the benzylic position. This mechanism, that is, base-assisted dehydrogenation (BAD), represents a biomimetic pathway for transition-metal-mediated alcohol oxidations, differing from the previously identified hydride-transfer and radical pathways. It suggests a new way to enhance the activity and selectivity of vanadium catalysts in a wide range of redox reactions, through control of the outer coordination sphere. PMID:23080554

  11. Aerobic SMBR/reverse osmosis system enhanced by Fenton oxidation for advanced treatment of old municipal landfill leachate.

    PubMed

    Zhang, Guoliang; Qin, Lei; Meng, Qin; Fan, Zheng; Wu, Dexin

    2013-08-01

    A novel combined process of Fenton oxidation, submerged membrane bioreactor (SMBR) and reverse osmosis (RO) was applied as an appropriate option for old municipal landfill leachate treatment. Fenton process was designed to intensively solve the problem of non-biodegradable organic pollutant removal and low biodegradability of leachate, although the removal of ammonia-nitrogen was similar to 10%. After SMBR treatment, it not only presented a higher removal efficiency of organics, but also exhibited high ammonia-nitrogen removal of 80% on average. The variation of extracellular polymeric substance (EPS) content, zeta potential, and particle size of flocs after Fenton effluent continually fed in SMBR was found to be benefit for alleviating membrane fouling. Finally, three kinds of RO membranes (RE, CPA, and BW) were applied to treat SMBR effluents and successfully met wastewater re-utilization requirement. Compared with simple RO process, the troublesome membrane fouling can be effectively reduced in the combined process. PMID:23743431

  12. Pd@Cu(II)-MOF-Catalyzed Aerobic Oxidation of Benzylic Alcohols in Air with High Conversion and Selectivity.

    PubMed

    Chen, Gong-Jun; Wang, Jing-Si; Jin, Fa-Zheng; Liu, Ming-Yang; Zhao, Chao-Wei; Li, Yan-An; Dong, Yu-Bin

    2016-03-21

    A new 3D porous Cu(II)-MOF (1) was synthesized based on a ditopic pyridyl substituted diketonate ligand and Cu(OAc)2 in solution, and it features a 3D NbO motif which is determined by the X-ray crystallography. Furthermore, the Pd NPs-loaded hybrid material Pd@Cu(II)-MOF (2) was prepared based on 1 via solution impregnation, and its structure was confirmed by HRTEM, SEM, XRPD, gas adsorption-desorption, and ICP measurement. 2 exhibits excellent catalytic activity (conversion, 93% to >99%) and selectivity (>99% to benzaldehydes) for various benzyl alcohol substrates (benzyl alcohol and its derivatives with electron-withdrawing and electron-donating groups) oxidation reactions in air. In addition, 2 is a typical heterogeneous catalyst, which was confirmed by hot solution leaching experiment, and it can be recycled at least six times without significant loss of its catalytic activity and selectivity. PMID:26959340

  13. Ammonium removal from groundwater using a zeolite permeable reactive barrier: a pilot-scale demonstration.

    PubMed

    Li, Shengpin; Huang, Guoxin; Kong, Xiangke; Yang, Yingzhao; Liu, Fei; Hou, Guohua; Chen, Honghan

    2014-01-01

    In situ remediation of ammonium-contaminated groundwater is possible through a zeolite permeable reactive barrier (PRB); however, zeolite's finite sorption capacity limits the long-term field application of PRBs. In this paper, a pilot-scale PRB was designed to achieve sustainable use of zeolite in removing ammonium (NH(4)(+)-N) through sequential nitrification, adsorption, and denitrification. An oxygen-releasing compound was added to ensure aerobic conditions in the upper layers of the PRB where NH(4)(+)-N was microbially oxidized to nitrate. Any remaining NH(4)(+)-N was removed abiotically in the zeolite layer. Under lower redox conditions, nitrate formed during nitrification was removed by denitrifying bacteria colonizing the zeolite. During the long-term operation (328 days), more than 90% of NH(4)(+)-N was consistently removed, and approximately 40% of the influent NH(4)(+)-N was oxidized to nitrate. As much as 60% of the nitrate formed in the PRB was reduced in the zeolite layer after 300 days of operation. Removal of NH(4)(+)-N from groundwater using a zeolite PRB through bacterial nitrification and abiotic adsorption is a promising approach. The zeolite PRB has the advantage of achieving sustainable use of zeolite and immediate NH(4)(+)-N removal.

  14. Population of Nitrifying Bacteria and Nitrification in Ammonium Saturated Clinoptilolite

    NASA Technical Reports Server (NTRS)

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

    1999-01-01

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

  15. Biases in community structures of ammonia/ammonium-oxidizing microorganisms caused by insufficient DNA extractions from Baijiang soil revealed by comparative analysis of coastal wetland sediment and rice paddy soil.

    PubMed

    Han, Ping; Li, Meng; Gu, Ji-Dong

    2013-10-01

    Repetitive extraction of DNAs from surface sediments of a coastal wetland in Mai Po Nature Reserve (MP) of Hong Kong and surface Baijiang soils from a rice paddy (RP) in Northeast China was conducted to compare the microbial diversity in this study. Community structures of ammonia/ammonium-oxidizing microorganisms in these samples were analyzed by PCR-DGGE technique. The diversity and abundance of ammonia-oxidizing archaea (AOA), ammonia-oxidizing bacteria (AOB), and anaerobic ammonium-oxidizing (anammox) bacteria were also analyzed based on archaeal and bacterial ammonia monooxygenase subunit A encoding (amoA) and anammox bacterial 16S rRNA genes, respectively. DGGE profiles of archaeal and bacterial amoA and anammox bacterial 16S rRNA genes showed a similar pattern among all five repetitively extracted DNA fractions from both MP and RP, except the anammox bacteria in RP, indicating a more diverse anammox community retrieved in the second to the fifth fractions than the first one. Both soil and marine group AOA were detected while soil and coastal group AOB and Scalindua-anammox bacteria were dominant in MP. Soil group AOA and marine group AOB were dominant in RP, while both Scalindua and Kuenenia species were detected in RP. Pearson correlation analysis showed that the abundance of archaeal and bacterial amoA and anammox bacterial 16S rRNA genes was significantly correlated with the DNA concentrations of the five DNA fractions from MP, but not from RP (except the archaeal amoA gene). Results suggest that anammox bacteria diversity may be biased by insufficient DNA extraction of rice paddy soil samples. PMID:23974369

  16. Optimization of operation conditions for the mitigation of nitrous oxide (N2O) emissions from aerobic nitrifying granular sludge system.

    PubMed

    Liu, Rui-Ting; Wang, Xin-Hua; Zhang, Yan; Wang, Ming-Yu; Gao, Ming-Ming; Wang, Shu-Guang

    2016-05-01

    The optimization of operation parameters is a key consideration to minimize nitrous oxide (N2O) emissions in biological nitrogen removal processes. So far, different parameters have only been investigated individually, making it difficult to compare their specific effects and combined influences. In this study, we applied the Plackett-Burman (PB) multifactorial experimental design and response surface methodology (RSM) analysis to find the optimized condition for the mitigation of N2O release in a nitrifying granular sludge system. Seven parameters (temperature, pH, feeding strategy, C/N ratio, aeration rate, Cu(2+) concentration, and aeration mode) were tested in parallel. Five of them (other than chemical oxygen demand/nitrogen (C/N) ratio and Cu(2+) concentration) were selected as influential factors. Since the type of feeding strategies and aeration modes cannot be quantified, continuous feed strategy and anoxic/oxic aeration mode were applied for the following study. Influences of temperature, pH, and aeration rate on N2O emissions were tested with RSM analysis to further investigate the mutual interactions among the parameters and to identify the optimal values that would minimize N2O release. Results showed the minimum emission value could be obtained under the temperature of 22.3 °C, pH of 7.1 and aeration rate of 0.20 m(3)/h. Predicted results were then verified by subsequent validation experiments. The estimated N2O emission value of each design by RSM was also observed in good relationships with experimental result.

  17. Characterization of DMSO Coordination to Palladium(II) in Solution and Insights into the Aerobic Oxidation Catalyst, Pd(DMSO)2(TFA)2

    PubMed Central

    Diao, Tianning; White, Paul; Guzei, Ilia; Stahl, Shannon S.

    2012-01-01

    Recent studies have shown that Pd(DMSO)2(TFA)2 (TFA = trifluoroacetate) is an effective catalyst for a number of different aerobic oxidation reactions. Here, we provide insights into the coordination properties of DMSO to palladium(II) in both the solid state and in solution. A crystal structure of Pd(DMSO)2(TFA)2 confirms that the solid-state structure of this species has one O-bound and one S-bound DMSO ligand, and a crystallographically characterized mono-DMSO complex, trans-Pd(DMSO)(OH2)(TFA)2, exhibits an S-bound DMSO ligand. 1H and 19F NMR spectroscopic studies show that, in EtOAc and THF-d8, Pd(DMSO)2(TFA)2 consists of an equilibrium mixture of Pd(S-DMSO)(O-DMSO)(TFA)2 and Pd(S-DMSO)2(TFA)2. The O-bound DMSO is determined to be more labile than the S-bound DMSO ligand, and both DMSO ligands are more labile in THF relative to EtOAc as the solvent. DMSO coordination to PdII is substantially less favorable when the TFA ligands are replaced with acetate. An analogous carboxylate ligand effect is observed in the coordination of PdII to the bidentate sulfoxide ligand, 1,2-bis(phenylsulfinyl)ethane. DMSO coordination to Pd(TFA)2 is shown to be incomplete in AcOH-d4 and toluene-d8, resulting in PdII/DMSO adducts with < 2:1 DMSO:PdII stoichiometry. Collectively, these results provide useful insights into the coordination properties of DMSO to PdII under catalytically relevant conditions. PMID:23092381

  18. Inhibition of nitric oxide and prostaglandins, but not endothelial-derived hyperpolarizing factors, reduces blood flow and aerobic energy turnover in the exercising human leg.

    PubMed

    Mortensen, Stefan P; González-Alonso, José; Damsgaard, Rasmus; Saltin, Bengt; Hellsten, Ylva

    2007-06-01

    Prostaglandins, nitric oxide (NO) and endothelial-derived hyperpolarizing factors (EDHFs) are substances that have been proposed to be involved in the regulation of skeletal muscle blood flow during physical activity. We measured haemodynamics, plasma ATP at rest and during one-legged knee-extensor exercise (19 +/- 1 W) in nine healthy subjects with and without intra-arterial infusion of indomethacin (Indo; 621 +/- 17 microg min(-1)), Indo + N(G)-monomethyl-L-arginine (L-NMMA; 12.4 +/- 0.3 mg min(-1)) (double blockade) and Indo + L-NMMA + tetraethylammonium chloride (TEA; 12.4 +/- 0.3 mg min(-1)) (triple blockade). Double and triple blockade lowered leg blood flow (LBF) at rest (P<0.05), while it remained unchanged with Indo. During exercise, LBF and vascular conductance were 2.54 +/- 0.10 l min(-1) and 25 +/- 1 mmHg, respectively, in control and they were lower with double (33 +/- 3 and 36 +/- 4%, respectively) and triple (26 +/- 4 and 28 +/- 3%, respectively) blockade (P<0.05), while there was no difference with Indo. The lower LBF and vascular conductance with double and triple blockade occurred in parallel with a lower O(2) delivery, cardiac output, heart rate and plasma [noradrenaline] (P<0.05), while blood pressure remained unchanged and O(2) extraction and femoral venous plasma [ATP] increased. Despite the increased O(2) extraction, leg was 13 and 17% (triple and double blockade, respectively) lower than control in parallel to a lower femoral venous temperature and lactate release (P<0.05). These results suggest that NO and prostaglandins play important roles in skeletal muscle blood flow regulation during moderate intensity exercise and that EDHFs do not compensate for the impaired formation of NO and prostaglandins. Moreover, inhibition of NO and prostaglandin formation is associated with a lower aerobic energy turnover and increased concentration of vasoactive ATP in plasma. PMID:17347273

  19. Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

    NASA Astrophysics Data System (ADS)

    Talbot, Helen M.; Handley, Luke; Spencer-Jones, Charlotte L.; Dinga, Bienvenu Jean; Schefuß, Enno; Mann, Paul J.; Poulsen, John R.; Spencer, Robert G. M.; Wabakanghanzi, Jose N.; Wagner, Thomas

    2014-05-01

    Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30‰ to -40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential

  20. Teaching Aerobic Fitness Concepts.

    ERIC Educational Resources Information Center

    Sander, Allan N.; Ratliffe, Tom

    2002-01-01

    Discusses how to teach aerobic fitness concepts to elementary students. Some of the K-2 activities include location, size, and purpose of the heart and lungs; the exercise pulse; respiration rate; and activities to measure aerobic endurance. Some of the 3-6 activities include: definition of aerobic endurance; heart disease risk factors;…

  1. One-pot synthesis of polypyrrole film on an aluminum oxide layer by electropolymerization in the presence of ammonium borodisalicylate in acetonitrile

    NASA Astrophysics Data System (ADS)

    Toita, Sadamu; Inoue, Kenzo

    This paper describes how one-pot preparation of polypyrrole (PPy) on Al 2O 3 layer in an aluminum solid capacitor could be achieved by electropolymerization of pyrrole (Py) in acetonitrile with small amounts of water, using ammonium borodisalicylate (ABS) as a new electrolyte. The effects of monomer and electrolyte concentrations, current density, and polymerization temperature on the PPy formation on Al 2O 3 layer in aluminum solid are also discussed. Polymerization occurred smoothly to give PPy on the Al 2O 3 layer under the following conditions: [ammonium borodisalicylate] = 0.02 M, [Py] = 0.1 M, and polymerization temperature = -42 °C, current density = 10 mA cm -2. The normalized capacitance, the C p/ C 0 value of capacitor fabricated, reached more than 0.9, indicating that the porosity and surface of the Al 2O 3 layer are filled up and covered with PPy. The Raman spectra of the PPy film showed that the peak assignable to C dbnd C backbone stretching shifted to a lower wave number of 1585 cm -1. This indicates formation of the film with well-conjugated C dbnd C backbone. The SEM micrograph of PPy on Al 2O 3 layer showed a closely packed globular morphology. These results indicate that the new electrolyte, ABS, has an excellent ability to form PPy film directly on Al 2O 3 surface by electropolymerization.

  2. Infrared band intensities in ammonium hydroxide and ammonium salts

    NASA Technical Reports Server (NTRS)

    Sethna, P. P.; Downing, H. D.; Pinkley, L. W.; Williams, D.

    1978-01-01

    We have applied Kramers-Kronig analysis to reflection spectra to determine the optical constants of ammonium hydroxide and of aqueous solutions of ammonium chloride and bromide. From considerations of the absorption indices k(nu) we conclude that ammonium hydroxide consists of a solution of NH3 in water, in which NH3 molecules are hydrogen bonded to neighboring water molecules. The spectrum of ammonium hydroxide differs from the spectra of ammonium salts, in which bands characteristic of NH4(+) ions are prominent. The existence of ammonium hydroxide as an aerosol in planetary atmospheres is briefly discussed

  3. Genetic associations as indices of nitrogen cycling rates in an aerobic denitrification biofilter used for groundwater remediation.

    PubMed

    Zhang, Yan; Ji, Guodong; Wang, Rongjing

    2015-10-01

    An aerobic denitrification biofilter (ADB) for groundwater remediation was developed with high removal efficiencies (total nitrogen (TN): 82.3-95.8%; NO3(-)-N: 93.2-98.2%). Nitrate (NO3(-)-N) transformation rates stabilized between 21.0 and 23.4 g/(m(3) h), whereas nitrite (NO2(-)-N) and ammonium (NH4(+)-N) transformation rates remained less than 6.0 g/(m(3) h) as the dissolved oxygen (DO) level increased from 1.0 mg/L to 6.0 mg/L. Nitric oxide (NO) and nitrous oxide (N2O) accumulated with great fluctuations (NO: 0-1.6×10(-3) g/(m(3) h); N2O: 0.1-1.1g/(m(3)h)) throughout the experiment. This study suggested that gene associations reflect quantitative relationships with aerobic denitrification rates and can provide useful information regarding aerobic denitrification processes in groundwater. Especially, the qnorB/nosZ ratio acts as the main driver for NO3(-)-N and NH4(+)-N transformation, while the qnorB/nosZ ratio followed by the (nirS+nirK)/nosZ ratio serve a dominant role in the accumulation of N2O and NO.

  4. Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate RuII-aqua complex, fac-[RuII(H2O)(dpp)(tppm)]2+.

    PubMed

    Huynh, My Hang V; Witham, Laura M; Lasker, Joanne M; Wetzler, Modi; Mort, Brendan; Jameson, Donald L; White, Peter S; Takeuchi, Kenneth J

    2003-01-15

    fac-[RuII(Cl)(dpp)(L3)]+ (L3 = tris(pyrid-2-yl)methoxymethane (tpmm) = [1A]+ and tris(pyrid-2-yl)pentoxymethane (tppm) = [1B]+ and dpp = di(pyrazol-1-yl)propane) rapidly undergo ligand substitution with water to form fac-[RuII(H2O)(dpp)(L3)]2+ (L3 = tpmm = [2A]2+ and tppm = [2B]2+). In the structure of [2A]2+, the distorted octahedral arrangement of ligands around Ru is evident by a long Ru(1)-O(40) of 2.172(3) A and a large angle O(40)-Ru(1)-N(51) of 96.95(14) degrees . The remarkably short distance between O(40) of H2O and H(45a) of dpp confirms the heteroscorpionate ligand effect of dpp on H2O. [2B]2+ aerobically catalyzes methyl p-tolyl sulfide to methyl p-tolyl sulfoxide in 1,2-dichlorobenzene at 25.0 +/- 0.1 degrees C under 11.4 psi of O2. Experimental facts in support of this aerobic sulfide oxidation are the absence of H2O2 and the oxidative reactivity of the putative Ru(IV)-oxo intermediate toward methyl p-tolyl sulfide, 2-propanol, and allyl alcohol. This study provides the first documented example of aerobic-sulfide oxidation catalyzed by the remarkably labile heteroscorpionate Ru(II)-aqua complex without the formation of a highly reactive peroxide as an intermediate.

  5. 70. INTERIOR VIEW OF AMMONIUM NITRATE HOUSE, LOOKING AT AMMONIUM ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    70. INTERIOR VIEW OF AMMONIUM NITRATE HOUSE, LOOKING AT AMMONIUM NITRATE IN STORAGE. APRIL 18, 1919. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  6. Glufosinate-ammonium

    Integrated Risk Information System (IRIS)

    Glufosinate - ammonium ; CASRN 77182 - 82 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarci

  7. Stable partial nitritation for low-strength wastewater at low temperature in an aerobic granular reactor.

    PubMed

    Isanta, Eduardo; Reino, Clara; Carrera, Julián; Pérez, Julio

    2015-09-01

    Partial nitritation for a low-strength wastewater at low temperature was stably achieved in an aerobic granular reactor. A bench-scale granular sludge bioreactor was operated in continuous mode treating an influent of 70 mg N-NH4(+) L(-1) to mimic pretreated municipal nitrogenous wastewater and the temperature was progressively decreased from 30 to 12.5 °C. A suitable effluent nitrite to ammonium concentrations ratio to a subsequent anammox reactor was maintained stable during 300 days at 12.5 °C. The average applied nitrogen loading rate at 12.5 °C was 0.7 ± 0.3 g N L(-1) d(-1), with an effluent nitrate concentration of only 2.5 ± 0.7 mg N-NO3(-) L(-1). The biomass fraction of nitrite-oxidizing bacteria (NOB) in the granular sludge decreased from 19% to only 1% in 6 months of reactor operation at 12.5 °C. Nitrobacter spp. where found as the dominant NOB population, whereas Nitrospira spp. were not detected. Simulations indicated that: (i) NOB would only be effectively repressed when their oxygen half-saturation coefficient was higher than that of ammonia-oxidizing bacteria; and (ii) a lower specific growth rate of NOB was maintained at any point in the biofilm (even at 12.5 °C) due to the bulk ammonium concentration imposed through the control strategy.

  8. Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: a tool for investigating the role of the polymer host.

    PubMed

    Buonerba, Antonio; Noschese, Annarita; Grassi, Alfonso

    2014-04-25

    The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4-polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea = 57.8±11.5 and 62.7±16.7 kJ mol(-1) for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction. PMID:24644103

  9. Highly efficient direct aerobic oxidative esterification of cinnamyl alcohol with alkyl alcohols catalysed by gold nanoparticles incarcerated in a nanoporous polymer matrix: a tool for investigating the role of the polymer host.

    PubMed

    Buonerba, Antonio; Noschese, Annarita; Grassi, Alfonso

    2014-04-25

    The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi-block copolymer matrix, which consisted of syndiotactic polystyrene-co-cis-1,4-polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base-catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10-45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2-propanol, 1-butanol, 1-hexanol or 1-octanol. The rate constants of the latter reaction are pseudo-zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1-butanol (Ea = 57.8±11.5 and 62.7±16.7 kJ mol(-1) for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2-phenylethanol follows pseudo-first-order kinetics with respect to 2-phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction.

  10. Aerobic and anaerobic nitrogen transformation processes in N2-fixing cyanobacterial aggregates

    PubMed Central

    Klawonn, Isabell; Bonaglia, Stefano; Brüchert, Volker; Ploug, Helle

    2015-01-01

    Colonies of N2-fixing cyanobacteria are key players in supplying new nitrogen to the ocean, but the biological fate of this fixed nitrogen remains poorly constrained. Here, we report on aerobic and anaerobic microbial nitrogen transformation processes that co-occur within millimetre-sized cyanobacterial aggregates (Nodularia spumigena) collected in aerated surface waters in the Baltic Sea. Microelectrode profiles showed steep oxygen gradients inside the aggregates and the potential for nitrous oxide production in the aggregates' anoxic centres. 15N-isotope labelling experiments and nutrient analyses revealed that N2 fixation, ammonification, nitrification, nitrate reduction to ammonium, denitrification and possibly anaerobic ammonium oxidation (anammox) can co-occur within these consortia. Thus, N. spumigena aggregates are potential sites of nitrogen gain, recycling and loss. Rates of nitrate reduction to ammonium and N2 were limited by low internal nitrification rates and low concentrations of nitrate in the ambient water. Presumably, patterns of N-transformation processes similar to those observed in this study arise also in other phytoplankton colonies, marine snow and fecal pellets. Anoxic microniches, as a pre-condition for anaerobic nitrogen transformations, may occur within large aggregates (⩾1 mm) even when suspended in fully oxygenated waters, whereas anoxia in small aggregates (<1 to ⩾0.1 mm) may only arise in low-oxygenated waters (⩽25 μM). We propose that the net effect of aggregates on nitrogen loss is negligible in NO3−-depleted, fully oxygenated (surface) waters. In NO3−-enriched (>1.5 μM), O2-depleted water layers, for example, in the chemocline of the Baltic Sea or the oceanic mesopelagic zone, aggregates may promote N-recycling and -loss processes. PMID:25575306

  11. Aerobic and anaerobic nitrogen transformation processes in N2-fixing cyanobacterial aggregates.

    PubMed

    Klawonn, Isabell; Bonaglia, Stefano; Brüchert, Volker; Ploug, Helle

    2015-06-01

    Colonies of N(2)-fixing cyanobacteria are key players in supplying new nitrogen to the ocean, but the biological fate of this fixed nitrogen remains poorly constrained. Here, we report on aerobic and anaerobic microbial nitrogen transformation processes that co-occur within millimetre-sized cyanobacterial aggregates (Nodularia spumigena) collected in aerated surface waters in the Baltic Sea. Microelectrode profiles showed steep oxygen gradients inside the aggregates and the potential for nitrous oxide production in the aggregates' anoxic centres. (15)N-isotope labelling experiments and nutrient analyses revealed that N(2) fixation, ammonification, nitrification, nitrate reduction to ammonium, denitrification and possibly anaerobic ammonium oxidation (anammox) can co-occur within these consortia. Thus, N. spumigena aggregates are potential sites of nitrogen gain, recycling and loss. Rates of nitrate reduction to ammonium and N(2) were limited by low internal nitrification rates and low concentrations of nitrate in the ambient water. Presumably, patterns of N-transformation processes similar to those observed in this study arise also in other phytoplankton colonies, marine snow and fecal pellets. Anoxic microniches, as a pre-condition for anaerobic nitrogen transformations, may occur within large aggregates (⩾1 mm) even when suspended in fully oxygenated waters, whereas anoxia in small aggregates (<1 to ⩾0.1 mm) may only arise in low-oxygenated waters (⩽25 μM). We propose that the net effect of aggregates on nitrogen loss is negligible in NO(3)(-)-depleted, fully oxygenated (surface) waters. In NO(3)(-)-enriched (>1.5 μM), O(2)-depleted water layers, for example, in the chemocline of the Baltic Sea or the oceanic mesopelagic zone, aggregates may promote N-recycling and -loss processes.

  12. Hydrothermal synthesis of ammonium illite

    USGS Publications Warehouse

    Sucha, V.; Elsass, F.; Eberl, D.D.; Kuchta, L'.; Madejova, J.; Gates, W.P.; Komadel, P.

    1998-01-01

    Synthetic gel and glass of illitic composition, natural kaolinite, and mixed-layer illite-smectite were used as starting materials for hydrothermal synthesis of ammonium illite. Ammonium illite was prepared from synthetic gel by hydrothermal treatment at 300??C. The onset of crystallization began within 3 h, and well-crystallized ammonium illite appeared at 24 h. Increasing reaction time (up to four weeks) led to many illite layers per crystal. In the presence of equivalent proportions of potassium and ammonium, the gel was transformed to illite with equimolar contents of K and NH4. In contrast, synthesis using glass under the same conditions resulted in a mixture of mixed-layer ammonium illite-smectite with large expandability and discrete illite. Hydrothermal treatments of the fine fractions of natural kaolinite and illite-smectite produced ammonium illite from kaolinite but the illite-smectite remained unchanged.

  13. Detonation Properties of Ammonium Dinitramide (ADN)

    NASA Astrophysics Data System (ADS)

    Wätterstam, A.; Östmark, H.; Helte, A.; Karlsson, S.

    1999-06-01

    Ammonium Dinitramide, ADN, has a potential as an oxidizer for underwater high explosives. Pure ADN has a large reaction-zone length and shows a strong non-ideal behaviour. The work presented here is an extension of previous work.(Sensitivity and Performance Characterization of Ammonium Dinitramide (ADN). Presented at 11th International Detonation Symposium, Snowmass, CO, 1998.) Experiments for determining the detonation velocity as a function of inverse charge radius and density, reaction-zone length and curvature, and the detonation pressure are presented. Measurements of pressure indicates that no, or weak von-Neumann spike exists, suggesting an immediate chemical decomposition. Experimental data are compared with predicted using thermochemical codes and ZND-theory.

  14. Aerobic Conditioning Class.

    ERIC Educational Resources Information Center

    Johnson, Neil R.

    1980-01-01

    An aerobic exercise class that focuses on the conditioning of the cardiovascular and muscular systems is presented. Students complete data cards on heart rate, pulse, and exercises to be completed during the forty minute course. (CJ)

  15. UV – INDUCED SYNTHESIS OF AMINO ACIDS FROM AQUEOUS STERILIZED SOLUTION OF AMMONIUM FORMATE AND AMMONIA UNDER HETROGENEOUS CONDITIONS

    PubMed Central

    Bisht, G.; Bisht, L. S.

    1990-01-01

    Irradiation of sterilized aqueous solution of ammonium formate and ammonia with UV light in the presence and or absence of certain inorganic sensitizers for 25 hrs. gave six ninhydrin positive products in appreciable amounts. Out of the six products observed fiver were characterized as lysine, serine, glutemic acid, n-amino butyric acid and leucine. The sensitizing effect of additives on ammonium formate was observed in the order; uranium oxide > ammonium formate > ferric oxide > arsenic oxide. PMID:22556511

  16. Efficient and General Aerobic Oxidative Cross-Coupling of THIQs with Organozinc Reagents Catalyzed by CuCl2: Proof of a Radical Intermediate.

    PubMed

    Wang, Tongtong; Schrempp, Michael; Berndhäuser, Andreas; Schiemann, Olav; Menche, Dirk

    2015-08-21

    A general new method for the highly concise synthesis of C-1-alkylated tetrahydroisoquinolines (THIQ) is reported. The CuCl2-catalyzed procedure is based on a coupling of nonfunctionalized THIQs with organozinc reagents under aerobic conditions. It proceeds in high yields and is broadly applicable to a wide range of substrates. It relies on a regioselective sp(3) C-H bond activation allowing for an sp(3)-sp(3) bond union under mild reaction conditions in a rapid and effective manner. Mechanistically it involves an iminium ion intermediate that is formed via an organic radical involving a single-electron-transfer process. For the first time for this type of reaction a radical intermediate has been proven by EPR spectroscopy. PMID:26252357

  17. Nitrogen Removal over Nitrite by Aeration Control in Aerobic Granular Sludge Sequencing Batch Reactors

    PubMed Central

    Lochmatter, Samuel; Maillard, Julien; Holliger, Christof

    2014-01-01

    This study investigated the potential of aeration control for the achievement of N-removal over nitrite with aerobic granular sludge in sequencing batch reactors. N-removal over nitrite requires less COD, which is particularly interesting if COD is the limiting parameter for nutrient removal. The nutrient removal performances for COD, N and P have been analyzed as well as the concentration of nitrite-oxidizing bacteria in the granular sludge. Aeration phase length control combined with intermittent aeration or alternate high-low DO, has proven to be an efficient way to reduce the nitrite-oxidizing bacteria population and hence achieve N-removal over nitrite. N-removal efficiencies of up to 95% were achieved for an influent wastewater with COD:N:P ratios of 20:2.5:1. The total N-removal rate was 0.18 kgN·m−3·d−1. With N-removal over nitrate the N-removal was only 74%. At 20 °C, the nitrite-oxidizing bacteria concentration decreased by over 95% in 60 days and it was possible to switch from N-removal over nitrite to N-removal over nitrate and back again. At 15 °C, the nitrite-oxidizing bacteria concentration decreased too but less, and nitrite oxidation could not be completely suppressed. However, the combination of aeration phase length control and high-low DO was also at 15 °C successful to maintain the nitrite pathway despite the fact that the maximum growth rate of nitrite-oxidizing bacteria at temperatures below 20 °C is in general higher than the one of ammonium-oxidizing bacteria. PMID:25006970

  18. Batch- and Continuous-Flow Aerobic Oxidation of 14-Hydroxy Opioids to 1,3-Oxazolidines-A Concise Synthesis of Noroxymorphone.

    PubMed

    Gutmann, Bernhard; Weigl, Ulrich; Cox, D Phillip; Kappe, C Oliver

    2016-07-18

    14-Hydroxymorphinone is converted to noroxymorphone, the immediate precursor of important opioid antagonists, such as naltrexone and naloxone, in a three-step reaction sequence. The initial oxidation of the N-methyl group in 14-hydroxymorphinone with in situ generated colloidal palladium(0) as the catalyst and molecular oxygen as the terminal oxidant constitutes the key transformation in this new route. This oxidation results in the formation of an unexpected oxazolidine ring structure. Subsequent hydrolysis of the oxazolidine under reduced pressure followed by hydrogenation in a packed-bed flow reactor using palladium(0) as the catalyst provides noroxymorphone in high purity and good overall yield. To overcome challenges associated with gas-liquid reactions with molecular oxygen, the key oxidation reaction was translated to a continuous-flow process. PMID:27172347

  19. Stabilization of fine fraction from landfill mining in anaerobic and aerobic laboratory leach bed reactors.

    PubMed

    Mönkäre, Tiina J; Palmroth, Marja R T; Rintala, Jukka A

    2015-11-01

    Fine fraction (FF, <20 mm) from mined landfill was stabilized in four laboratory-scale leach bed reactors (LBR) over 180 days. The aim was to study feasibility of biotechnological methods to treat FF and if further stabilization of FF is possible. Four different stabilization methods were compared and their effects upon quality of FF were evaluated. Also during the stabilization experiment, leachate quality as well as gas composition and quantity were analyzed. The methods studied included three anaerobic LBRs (one without water addition, one with water addition, and one with leachate recirculation) and one aerobic LBR (with water addition). During the experiment, the most methane was produced in anaerobic LBR without water addition (18.0 L CH4/kg VS), while water addition and leachate recirculation depressed methane production slightly, to 16.1 and 16.4 L CH4/kg VS, respectively. Organic matter was also removed via the leachate and was measured as chemical oxygen demand (COD). Calculated removal of organic matter in gas and leachate was highest in LBR with water addition (59 g COD/kg VS), compared with LBR without water addition or with leachate recirculation (51 g COD/kg VS). Concentrations of COD, ammonium nitrogen and anions in leachate decreased during the experiment, indicating washout mechanism caused by water additions. Aeration increased sulfate and nitrate concentrations in leachate due to oxidized sulfide and ammonium. Molecular weight distributions of leachates showed that all the size categories decreased, especially low molecular weight compounds, which were reduced the most. Aerobic stabilization resulted in the lowest final VS/TS (13.1%), lowest respiration activity (0.9-1.2 mg O2/g TS), and lowest methane production after treatment (0.0-0.8 L CH4/kg VS), with 29% of VS being removed from FF. Anaerobic stabilization methods also reduced organic matter by 9-20% compared with the initial amount. Stabilization reduced the quantity of soluble nitrogen

  20. Stabilization of fine fraction from landfill mining in anaerobic and aerobic laboratory leach bed reactors.

    PubMed

    Mönkäre, Tiina J; Palmroth, Marja R T; Rintala, Jukka A

    2015-11-01

    Fine fraction (FF, <20 mm) from mined landfill was stabilized in four laboratory-scale leach bed reactors (LBR) over 180 days. The aim was to study feasibility of biotechnological methods to treat FF and if further stabilization of FF is possible. Four different stabilization methods were compared and their effects upon quality of FF were evaluated. Also during the stabilization experiment, leachate quality as well as gas composition and quantity were analyzed. The methods studied included three anaerobic LBRs (one without water addition, one with water addition, and one with leachate recirculation) and one aerobic LBR (with water addition). During the experiment, the most methane was produced in anaerobic LBR without water addition (18.0 L CH4/kg VS), while water addition and leachate recirculation depressed methane production slightly, to 16.1 and 16.4 L CH4/kg VS, respectively. Organic matter was also removed via the leachate and was measured as chemical oxygen demand (COD). Calculated removal of organic matter in gas and leachate was highest in LBR with water addition (59 g COD/kg VS), compared with LBR without water addition or with leachate recirculation (51 g COD/kg VS). Concentrations of COD, ammonium nitrogen and anions in leachate decreased during the experiment, indicating washout mechanism caused by water additions. Aeration increased sulfate and nitrate concentrations in leachate due to oxidized sulfide and ammonium. Molecular weight distributions of leachates showed that all the size categories decreased, especially low molecular weight compounds, which were reduced the most. Aerobic stabilization resulted in the lowest final VS/TS (13.1%), lowest respiration activity (0.9-1.2 mg O2/g TS), and lowest methane production after treatment (0.0-0.8 L CH4/kg VS), with 29% of VS being removed from FF. Anaerobic stabilization methods also reduced organic matter by 9-20% compared with the initial amount. Stabilization reduced the quantity of soluble nitrogen

  1. Formation of a cobalt(III)-phenoxyl radical complex by acetic acid promoted aerobic oxidation of a Co(II)salen complex.

    PubMed

    Vinck, Evi; Murphy, Damien M; Fallis, Ian A; Strevens, Robert R; Van Doorslaer, Sabine

    2010-03-01

    The activation of N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co(II), [Co(II)(1)], by the addition of acetic acid under aerobic conditions has been investigated by a range of spectroscopic techniques including continuous-wave EPR, HYSCORE, pulsed ENDOR, and resonance Raman. These measurements have revealed for the first time the formation of a coordinated cobalt(III)-bound phenoxyl radical labeled [Co(III)(1(*))(OAc)(n)](OAc)(m) (n = m = 1 or n = 2, m = 0). This cobalt(III)-bound phenoxyl radical is characterized by the following spin Hamiltonian parameters: g(x) = 2.0060, g(y) = 2.0031, g(z) = 1.9943, A(x) = 17 MHz, A(y) = 55 MHz, and A(z) = 14 MHz. Although the radical contains coordinated acetate(s), the experiments unambiguously proved that the phenoxyl radical is situated on ligand (1) as opposed to a phenoxyl radical ligated to cobalt in the axial position. Density functional theory computations on different models corroborate the stability of such a phenoxyl radical species and suggest the ligation of one or two acetate molecules to the complex. A mechanism is proposed, which accounts for the formation of this unusual and extremely robust phenoxyl radical, never previously observed for [Co(1)].

  2. Organic and nitrogen removal from landfill leachate in aerobic granular sludge sequencing batch reactors

    SciTech Connect

    Wei Yanjie; Ji Min; Li Ruying; Qin Feifei

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer Aerobic granular sludge SBR was used to treat real landfill leachate. Black-Right-Pointing-Pointer COD removal was analyzed kinetically using a modified model. Black-Right-Pointing-Pointer Characteristics of nitrogen removal at different ammonium inputs were explored. Black-Right-Pointing-Pointer DO variations were consistent with the GSBR performances at low ammonium inputs. - Abstract: Granule sequencing batch reactors (GSBR) were established for landfill leachate treatment, and the COD removal was analyzed kinetically using a modified model. Results showed that COD removal rate decreased as influent ammonium concentration increasing. Characteristics of nitrogen removal at different influent ammonium levels were also studied. When the ammonium concentration in the landfill leachate was 366 mg L{sup -1}, the dominant nitrogen removal process in the GSBR was simultaneous nitrification and denitrification (SND). Under the ammonium concentration of 788 mg L{sup -1}, nitrite accumulation occurred and the accumulated nitrite was reduced to nitrogen gas by the shortcut denitrification process. When the influent ammonium increased to a higher level of 1105 mg L{sup -1}, accumulation of nitrite and nitrate lasted in the whole cycle, and the removal efficiencies of total nitrogen and ammonium decreased to only 35.0% and 39.3%, respectively. Results also showed that DO was a useful process controlling parameter for the organics and nitrogen removal at low ammonium input.

  3. Dance--Aerobic and Anaerobic.

    ERIC Educational Resources Information Center

    Cohen, Arlette

    1984-01-01

    This article defines and explains aerobic exercise and its effects on the cardiovascular system. Various studies on dancers are cited indicating that dance is an anaerobic activity with some small degree of aerobic benefit. (DF)

  4. Selective aerobic oxidation of 5-HMF into 2,5-furandicarboxylic acid with Pt catalysts supported on TiO2 - and ZrO2 -based supports.

    PubMed

    Ait Rass, Hicham; Essayem, Nadine; Besson, Michèle

    2015-04-13

    Pt catalysts prepared over different metallic oxide supports were investigated in the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) in alkaline aqueous solutions with air, to examine the combined effect of the support and base addition. The base (nature and amount) played a significant role in the degradation or oxidation of HMF. Increasing amounts of the weak NaHCO3 base improved significantly the overall catalytic activity of Pt/TiO2 and Pt/ZrO2 by accelerating the oxidation steps, especially for the aldehyde group. This was highlighted by a proposed kinetic model that gave very good concentration-time fittings. Moreover, the promotion of the catalyst with bismuth yielded a PtBi/TiO2 catalytic system with improved activity and stability. Y2 O3  and La2 O3 ZrO2 -supported catalysts exhibited lower activity than Pt/ZrO2 , which suggests no cooperative effect of the weakly basic properties introduced and the homogeneous base. Quantitative oxidation of HMF (0.1 M) and high yields of FDCA (>99 %) were obtained in less than 5 h by using an HMF/Pt molar ratio of 100 and Na2 CO3 as a weak base over PtBi/TiO2 (Bi/Pt=0.22). PMID:25736596

  5. Performance of aerobic granular sludge in a sequencing batch bioreactor exposed to ofloxacin, norfloxacin and ciprofloxacin.

    PubMed

    Amorim, Catarina L; Maia, Alexandra S; Mesquita, Raquel B R; Rangel, António O S S; van Loosdrecht, Mark C M; Tiritan, Maria Elizabeth; Castro, Paula M L

    2014-03-01

    A granular sludge sequencing batch reactor (SBR) was operated for 340 days for treating a synthetic wastewater containing fluoroquinolones (FQs), namely ofloxacin, norfloxacin and ciprofloxacin. The SBR was intermittently fed with FQs, at concentrations of 9 and 32 μM. No evidence of FQ biodegradation was observed but the pharmaceutical compounds adsorbed to the aerobic granular sludge, being gradually released into the medium in successive cycles after stopping the FQ feeding. Overall COD removal was not affected during the shock loadings. Activity of ammonia oxidizing bacteria and nitrite oxidizing bacteria did not seem to be inhibited by the presence of FQs (maximum of 0.03 and 0.01 mM for ammonium and nitrite in the effluent, respectively). However, during the FQs feeding, nitrate accumulation up to 1.7 mM was observed at the effluent suggesting that denitrification was inhibited. The activity of phosphate accumulating organisms was affected, as indicated by the decrease of P removal capacity during the aerobic phase. Exposure to the FQs also promoted disintegration of the granules leading to an increase of the effluent solid content, nevertheless the solid content at the bioreactor effluent returned to normal levels within ca. 1 month after removing the FQs in the feed allowing recovery of the bedvolume. Denaturing gradient gel electrophoresis revealed a dynamic bacterial community with gradual changes due to FQs exposure. Bacterial isolates retrieved from the granules predominantly belonged to α- and γ-branch of the Proteobacteria phylum. The capacity of the system to return to its initial conditions after withdrawal of the FQ compounds in the inlet stream, reinforced its robustness to deal with wastewaters containing organic pollutants.

  6. Copper-TEMPO-catalyzed synthesis of α-ketoamides via tandem sp(3)C-H aerobic oxidation and amination of phenethyl alcohol derivatives.

    PubMed

    Liu, Chengkou; Yang, Zhao; Guo, Shiyu; Zeng, Yu; Zhu, Ning; Li, Xin; Fang, Zheng; Guo, Kai

    2016-09-28

    An efficient copper-TEMPO-catalyzed one-pot synthesis of α-ketoamides from phenethyl alcohol derivatives was developed firstly. Moreover, molecular oxygen in open air was employed as the oxidant with a broad substrate scope, which makes this methodology more practical. Based on some control experiments, a plausible mechanism was proposed. PMID:27548362

  7. Solubility of the Sodium and Ammonium Salts of Oxalic Acid in Water with Ammonium Sulfate.

    PubMed

    Buttke, Lukas G; Schueller, Justin R; Pearson, Christian S; Beyer, Keith D

    2016-08-18

    The solubility of the sodium and ammonium salts of oxalic acid in water with ammonium sulfate present has been studied using differential scanning calorimetry, X-ray crystallography, and infrared spectroscopy. The crystals that form from aqueous mixtures of ammonium sulfate/sodium hydrogen oxalate were determined to be sodium hydrogen oxalate monohydrate under low ammonium sulfate conditions and ammonium hydrogen oxalate hemihydrate under high ammonium sulfate conditions. Crystals from aqueous mixtures of ammonium sulfate/sodium oxalate were determined to be ammonium oxalate monohydrate under moderate to high ammonium sulfate concentrations and sodium oxalate under low ammonium sulfate concentrations. It was also found that ammonium sulfate enhances the solubility of the sodium oxalate salts (salting in effect) and decreases the solubility of the ammonium oxalate salts (salting out effect). In addition, a partial phase diagram for the ammonium hydrogen oxalate/water system was determined.

  8. Solubility of the Sodium and Ammonium Salts of Oxalic Acid in Water with Ammonium Sulfate.

    PubMed

    Buttke, Lukas G; Schueller, Justin R; Pearson, Christian S; Beyer, Keith D

    2016-08-18

    The solubility of the sodium and ammonium salts of oxalic acid in water with ammonium sulfate present has been studied using differential scanning calorimetry, X-ray crystallography, and infrared spectroscopy. The crystals that form from aqueous mixtures of ammonium sulfate/sodium hydrogen oxalate were determined to be sodium hydrogen oxalate monohydrate under low ammonium sulfate conditions and ammonium hydrogen oxalate hemihydrate under high ammonium sulfate conditions. Crystals from aqueous mixtures of ammonium sulfate/sodium oxalate were determined to be ammonium oxalate monohydrate under moderate to high ammonium sulfate concentrations and sodium oxalate under low ammonium sulfate concentrations. It was also found that ammonium sulfate enhances the solubility of the sodium oxalate salts (salting in effect) and decreases the solubility of the ammonium oxalate salts (salting out effect). In addition, a partial phase diagram for the ammonium hydrogen oxalate/water system was determined. PMID:27482644

  9. Effect of oxic and anoxic conditions on nitrous oxide emissions from nitrification and denitrification processes.

    PubMed

    Rassamee, Varit; Sattayatewa, Chakkrid; Pagilla, Krishna; Chandran, Kartik

    2011-09-01

    A lab-scale sequencing batch reactor fed with real municipal wastewater was used to study nitrous oxide (N(2)O) emissions from simulated wastewater treatment processes. The experiments were performed under four different controlled conditions as follows: (1) fully aerobic, (2) anoxic-aerobic with high dissolved oxygen (DO) concentration, (3) anoxic-aerobic with low DO concentration, and 4) intermittent aeration. The results indicated that N(2)O production can occur from both incomplete nitrification and incomplete denitrification. N(2)O production from denitrification was observed in both aerobic and anoxic phases. However, N(2)O production from aerobic conditions occurred only when both low DO concentrations and high nitrite concentration existed simultaneously. The magnitude of N(2) O produced via anoxic denitrification was lower than via oxic denitrification and required the presence of nitrite. Changes in DO, ammonium, and nitrite concentrations influenced the magnitude of N(2)O production through denitrification. The results also suggested that N(2)O can be produced from incomplete denitrification and then released to the atmosphere during aeration phase due to air stripping. Therefore, biological nitrogen removal systems should be optimized to promote complete nitrification and denitrification to minimize N(2)O emissions.

  10. One-Pot Template-Free Synthesis of Cu-MOR Zeolite toward Efficient Catalyst Support for Aerobic Oxidation of 5-Hydroxymethylfurfural under Ambient Pressure.

    PubMed

    Zhang, Wei; Xie, Jingyan; Hou, Wei; Liu, Yangqing; Zhou, Yu; Wang, Jun

    2016-09-01

    Supported catalysts are widely studied, and exploring new promising supports is significant to access more applications. In this work, novel copper-containing MOR-type zeolites Cu-MOR were synthesized in a one-pot template-free route and served as efficient supports for vanadium oxide. In the heterogeneous oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) with molecular oxygen (O2) under ambient pressure, the obtained catalyst demonstrated high yield (91.5%) and good reusability. Even under the ambient air pressure, it gave a DFF yield of 72.1%. Structure-activity relationship analysis indicated that the strong interaction between the framework Cu species and the guest V sites accounted for the remarkable performance. This work reveals that the Cu-MOR zeolite uniquely acts as the robust support toward well-performed non-noble metal heterogeneous catalyst for biomass conversion. PMID:27523255

  11. Genome sequence of Fulvimarina pelagi HTCC2506T, a Mn(II)-oxidizing alphaproteobacterium possessing an aerobic anoxygenic photosynthetic gene cluster and Xanthorhodopsin.

    PubMed

    Kang, Ilnam; Oh, Hyun-Myung; Lim, Seung-Il; Ferriera, Steve; Giovannoni, Stephen J; Cho, Jang-Cheon

    2010-09-01

    Fulvimarina pelagi is a Mn(II)-oxidizing marine heterotrophic bacterium in the order Rhizobiales. Here we announce the draft genome sequence of F. pelagi HTCC2506(T), which was isolated from the Sargasso Sea by using dilution-to-extinction culturing. The genome sequence contained a xanthorhodopsin gene as well as a photosynthetic gene cluster, which suggests the coexistence of two different phototrophic mechanisms in a single microorganism. PMID:20639329

  12. TREATMENT OF AMMONIUM NITRATE SOLUTIONS

    DOEpatents

    Boyer, T.W.; MacHutchin, J.G.; Yaffe, L.

    1958-06-10

    The treatment of waste solutions obtained in the processing of neutron- irradiated uranium containing fission products and ammonium nitrate is described. The object of this process is to provide a method whereby the ammonium nitrate is destroyed and removed from the solution so as to permit subsequent concentration of the solution.. In accordance with the process the residual nitrate solutions are treated with an excess of alkyl acid anhydride, such as acetic anhydride. Preferably, the residual nitrate solution is added to an excess of the acetic anhydride at such a rate that external heat is not required. The result of this operation is that the ammonium nitrate and acetic anhydride react to form N/sub 2/ O and acetic acid.

  13. Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

    PubMed

    Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

    2016-06-01

    The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

  14. Handling of Ammonium Nitrate Mother-Liquid Radiochemical Production - 13089

    SciTech Connect

    Zherebtsov, Alexander; Dvoeglazov, Konstantine; Volk, Vladimir; Zagumenov, Vladimir; Zverev, Dmitriy; Tinin, Vasiliy; Kozyrev, Anatoly; Shamin, Dladimir; Tvilenev, Konstantin

    2013-07-01

    The aim of the work is to develop a basic technology of decomposition of ammonium nitrate stock solutions produced in radiochemical enterprises engaged in the reprocessing of irradiated nuclear fuel and fabrication of fresh fuel. It was necessary to work out how to conduct a one-step thermal decomposition of ammonium nitrate, select and test the catalysts for this process and to prepare proposals for recycling condensation. Necessary accessories were added to a laboratory equipment installation decomposition of ammonium nitrate. It is tested several types of reducing agents and two types of catalyst to neutralize the nitrogen oxides. It is conducted testing of modes of the process to produce condensation, suitable for use in the conversion of a new technological scheme of production. It is studied the structure of the catalysts before and after their use in a laboratory setting. It is tested the selected catalyst in the optimal range for 48 hours of continuous operation. (authors)

  15. Granulation of Non-filamentous Bulking Sludge Directed by pH, ORP and DO in an Anaerobic/Aerobic/Anoxic SBR.

    PubMed

    Zhang, Cuiya; Zhang, Hanmin; Yang, Fenglin

    2016-01-01

    In an anaerobic/aerobic/anoxic (A/O/A) sequencing batch reactor (SBR), non-filamentous bulking sludge granulated after the adjustment of cycle duration and influent composition directed by pH, oxidation-reduction potential (ORP) and dissolved oxygen (DO). The turning points and plateaux of pH, ORP and DO profiles indicated the end of biochemical reactions, such as chemical oxygen demand (COD) consumption, P release, ammonium oxidation, P uptake and denitrification. The difference of nutrient concentration between the beginning and turning points represented the actual treatment capability of the sludge. Non-filamentous bulking with SVI30 of 255 mL g(-1) resulted in a huge biomass loss. After regulation, the cycle duration was shortened from 310 to 195 min without unnecessary energy input. In addition, the settling ability was obviously improved as SVI30 reduced to 28 mL g(-1). Moreover, matured granules with an average diameter of 600 μm were obtained after 45 days, and simultaneous COD, ammonium and phosphate (P) removal was also realized after granulation.

  16. Remarkable effect of bimetallic nanocluster catalysts for aerobic oxidation of alcohols: combining metals changes the activities and the reaction pathways to aldehydes/carboxylic acids or esters.

    PubMed

    Kaizuka, Kosuke; Miyamura, Hiroyuki; Kobayashi, Shū

    2010-11-01

    Selective oxidation of alcohols catalyzed by novel carbon-stabilized polymer-incarcerated bimetallic nanocluster catalysts using molecular oxygen has been developed. The reactivity and the selectivity were strongly dependent on the combination of metals and solvent systems; aldehydes and ketones were obtained by the gold/platinum catalyst in benzotrifluoride, and esters were formed by the gold/palladium catalyst in methanol. To the best of our knowledge, this is the first example that the reaction pathway has been changed dramatically in gold catalysis by combining with a second metal. The differences in the activity and the selectivity are considered to be derived from the difference in the structure of the bimetallic clusters.

  17. The development of copper-catalyzed aerobic oxidative coupling of H-tetrazoles with boronic acids and an insight into the reaction mechanism.

    PubMed

    Liu, Chao-You; Li, Yu; Ding, Jin-Ying; Dong, De-Wen; Han, Fu-She

    2014-02-17

    The development of a highly efficient and practical protocol for the direct C-N coupling of H-tetrazole and boronic acid was presented. A careful and patient optimization of a variety of reaction parameters revealed that this conventionally challenge reaction could indeed proceed efficiently in a very simple system, that is, just by stirring the tetrazoles and boronic acids under oxygen in the presence of different Cu(I) or Cu(II) salts with only 5 mol % loading in DMSO at 100 °C. Most significantly, the reaction could proceed very smoothly in a regiospecific manner to afford the 2,5-disubstituted tetrazoles in high to excellent yields. A mechanistic study revealed that both tetrazole and DMSO are crucial for the generation of catalytically active copper species in the reaction process in addition to their role as reactant and solvent, respectively. It is demonstrated that in the reaction cycle, the Cu(I) catalyst could be oxidized to Cu(II) by oxygen to form a [CuT2D] complex (T = tetrazole anion; D = DMSO) through an oxidative copper amination reaction. The Cu(II) complex thus formed was confirmed to be the real catalytically active copper species. Namely, the Cu(II) complex disproportionates to aryl Cu(III) and Cu(I) in the presence of boronic acid. Facile elimination of the Cu(III) species delivers the C-N-coupled product. The results presented herein not only provide a reliable and efficient protocol for the synthesis of 2,5-disubstituted tetrazoles, but most importantly, the mechanistic results would have broad implications for the de novo design and development of new methods for Cu-catalyzed coupling reactions.

  18. The development of copper-catalyzed aerobic oxidative coupling of H-tetrazoles with boronic acids and an insight into the reaction mechanism.

    PubMed

    Liu, Chao-You; Li, Yu; Ding, Jin-Ying; Dong, De-Wen; Han, Fu-She

    2014-02-17

    The development of a highly efficient and practical protocol for the direct C-N coupling of H-tetrazole and boronic acid was presented. A careful and patient optimization of a variety of reaction parameters revealed that this conventionally challenge reaction could indeed proceed efficiently in a very simple system, that is, just by stirring the tetrazoles and boronic acids under oxygen in the presence of different Cu(I) or Cu(II) salts with only 5 mol % loading in DMSO at 100 °C. Most significantly, the reaction could proceed very smoothly in a regiospecific manner to afford the 2,5-disubstituted tetrazoles in high to excellent yields. A mechanistic study revealed that both tetrazole and DMSO are crucial for the generation of catalytically active copper species in the reaction process in addition to their role as reactant and solvent, respectively. It is demonstrated that in the reaction cycle, the Cu(I) catalyst could be oxidized to Cu(II) by oxygen to form a [CuT2D] complex (T = tetrazole anion; D = DMSO) through an oxidative copper amination reaction. The Cu(II) complex thus formed was confirmed to be the real catalytically active copper species. Namely, the Cu(II) complex disproportionates to aryl Cu(III) and Cu(I) in the presence of boronic acid. Facile elimination of the Cu(III) species delivers the C-N-coupled product. The results presented herein not only provide a reliable and efficient protocol for the synthesis of 2,5-disubstituted tetrazoles, but most importantly, the mechanistic results would have broad implications for the de novo design and development of new methods for Cu-catalyzed coupling reactions. PMID:24449340

  19. Metal-free g-C{sub 3}N{sub 4} photocatalyst by sulfuric acid activation for selective aerobic oxidation of benzyl alcohol under visible light

    SciTech Connect

    Zhang, Ligang; Liu, Di; Guan, Jing; Chen, Xiufang; Guo, Xingcui; Zhao, Fuhua; Hou, Tonggang; Mu, Xindong

    2014-11-15

    Highlights: • A novel visible-light-driven acid-modified g-C{sub 3}N{sub 4} was prepared. • The texture, electronic and surface property were tuned by acid modification. • Acid-modified g-C{sub 3}N{sub 4} shows much higher activity for photocatalytic activity. • Acid sites on the surface of g-C{sub 3}N{sub 4} favor efficient charge separation. - Abstract: In this work, modification of graphitic carbon nitride photocatalyst with acid was accomplished with a facile method through reflux in different acidic substances. The g-C{sub 3}N{sub 4}-based material was found to be a metal-free photocatalyst useful for the selective oxidation of benzyl alcohol with dioxygen as the oxidant under visible light irradiation. Acid modification had a significant influence on the photocatalytic performance of g-C{sub 3}N{sub 4}. Among all acid tested, sulfuric acid-modified g-C{sub 3}N{sub 4} showed the highest catalytic activity and gave benzaldehyde in 23% yield for 4 h under visible light irradiation, which was about 2.5 times higher than that of g-C{sub 3}N{sub 4}. The acid modification effectively improved surface area, reduced structural size, enlarged band gap, enhanced surface chemical state, and facilitated photoinduced charge separation, contributing to the enhanced photocatalytic activity. It is hoped that our work can open promising prospects for the utilization of metal free g-C{sub 3}N{sub 4}-based semiconductor as visible-light photocatalyst for selective organic transformation.

  20. Enhanced aerobic nitrifying granulation by static magnetic field.

    PubMed

    Wang, Xin-Hua; Diao, Mu-He; Yang, Ying; Shi, Yi-Jing; Gao, Ming-Ming; Wang, Shu-Guang

    2012-04-01

    One of the main challenging issues for aerobic nitrifying granules in treating high strength ammonia wastewater is the long granulation time required for activated sludge to transform into aerobic granules. The present study provides a novel strategy for enhancing aerobic nitrifying granulation by applying an intensity of 48.0mT static magnetic field. The element analysis showed that the applied magnetic field could promote the accumulation of iron compounds in the sludge. And then the aggregation of iron decreased the full granulation time from 41 to 25days by enhancing the setting properties of granules and stimulating the secretion of extracellular polymeric substances (EPS). Long-term, cycle experiments and fluorescence in-situ hybridization (FISH) analysis proved that an intensity of 48.0mT magnetic field could enhance the activities and growth of nitrite-oxidizing bacteria (NOB). These findings suggest that magnetic field is helpful and reliable for accelerating the aerobic nitrifying granulation.

  1. Relations of ammonium minerals at several hydrothermal systems in the western U.S.

    USGS Publications Warehouse

    Krohn, M.D.; Kendall, C.; Evans, J.R.; Fries, T.L.

    1993-01-01

    Ammonium bound to silicate and sulfate minerals has recently been located at several major hydrothermal systems in the western U.S. utilizing newly-discovered near-infrared spectral properties. Knowledge of the origin and mineralogic relations of ammonium minerals at known hydrothermal systems is critical for the proper interpretation of remote sensing data and for testing of possible links to mineralization. Submicroscopic analysis of ammonium minerals from two mercury- and gold-bearing hot-springs deposits at Ivanhoe, Nevada and McLaughlin, California shows that the ammonium feldspar, buddingtonite, occurs as fine-grained euhedral crystals coating larger sulfide and quartz crystals. Ammonium feldspar seems to precipitate relatively late in the crystallization sequence and shows evidence for replacement of NH4+ by K+ or other monovalent cations. Some buddingtonite is observed in close association with mercury, but not with gold. Ammonioalunite is found in a variety of isolated crystal forms at both deposits. Nitrogen isotopic values for ammonium-bearing minerals show a 14??? range in composition, precluding assignment of a specific provenance to the nitrogen. The correlations of nitrogen isotopic values with depth and ammonium content suggest some loss of nitrogen in the oxidizing supergene environment, possibly as a metastable mineral. The high ammonium content in these hydrothermal systems, the close association to mercury, and the small crystal size of the ammonium-bearing minerals all suggest that ammonium may be transported in a late-stage vapor phase or as an organic volatile. Such a process could lead to the formation of a non-carbonaceous organic aureole above a buried geothermal source. The discovery of a 10-km outcrop of ammonium minerals confirms that significant substitution of ammonium in minerals is possible over an extensive area and that remote sensing is a feasible means to detect such aureoles. ?? 1993.

  2. 21 CFR 582.1135 - Ammonium bicarbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Additives § 582.1135 Ammonium bicarbonate. (a) Product. Ammonium bicarbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  3. 21 CFR 582.1137 - Ammonium carbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1137 Ammonium carbonate. (a) Product. Ammonium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  4. 21 CFR 582.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1139 Ammonium hydroxide. (a) Product. Ammonium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  5. 21 CFR 582.1135 - Ammonium bicarbonate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1135 Ammonium bicarbonate. (a) Product. Ammonium bicarbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  6. 21 CFR 582.1139 - Ammonium hydroxide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Additives § 582.1139 Ammonium hydroxide. (a) Product. Ammonium hydroxide. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  7. 21 CFR 582.1143 - Ammonium sulfate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... Additives § 582.1143 Ammonium sulfate. (a) Product. Ammonium sulfate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding practice....

  8. 21 CFR 582.1137 - Ammonium carbonate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Additives § 582.1137 Ammonium carbonate. (a) Product. Ammonium carbonate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or...

  9. 21 CFR 582.1143 - Ammonium sulfate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... Additives § 582.1143 Ammonium sulfate. (a) Product. Ammonium sulfate. (b) Conditions of use. This substance is generally recognized as safe when used in accordance with good manufacturing or feeding practice....

  10. 21 CFR 556.375 - Maduramicin ammonium.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... residues of maduramicin ammonium in chickens as follows: (a) A tolerance for maduramicin ammonium (marker... concentration of marker residues in the target tissue used to monitor for total drug residues in the...

  11. Aerobic landfill bioreactor

    DOEpatents

    Hudgins, Mark P; Bessette, Bernard J; March, John C; McComb, Scott T.

    2002-01-01

    The present invention includes a system of decomposing municipal solid waste (MSW) within a landfill by converting the landfill to aerobic degradation in the following manner: (1) injecting air via the landfill leachate collection system (2) injecting air via vertical air injection wells installed within the waste mass; (3) applying leachate to the waste mass using a pressurized drip irrigation system; (4) allowing landfill gases to vent; and (5) adjusting air injection and recirculated leachate to achieve a 40% to 60% moisture level and a temperature between 120.degree. F. and 140.degree. F. in steady state.

  12. Aerobic landfill bioreactor

    DOEpatents

    Hudgins, Mark P; Bessette, Bernard J; March, John; McComb, Scott T.

    2000-01-01

    The present invention includes a method of decomposing municipal solid waste (MSW) within a landfill by converting the landfill to aerobic degradation in the following manner: (1) injecting air via the landfill leachate collection system (2) injecting air via vertical air injection wells installed within the waste mass; (3) applying leachate to the waste mass using a pressurized drip irrigation system; (4) allowing landfill gases to vent; and (5) adjusting air injection and recirculated leachate to achieve a 40% to 60% moisture level and a temperature between 120.degree. F. and 140.degree. F. in steady state.

  13. Aerobic landfill bioreactor

    SciTech Connect

    Hudgins, M.P.; Bessette, B.J.; March, J.; McComb, S.T.

    2000-02-15

    The present invention includes a method of decomposing municipal solid waste (MSW) within a landfill by converting the landfill to aerobic degradation in the following manner: (1) injecting air via the landfill leachate collection system (2) injecting air via vertical air injection wells installed within the waste mass; (3) applying leachate to the waste mass using a pressurized drip irrigation system; (4) allowing landfill gases to vent; and (5) adjusting air injection and recirculated leachate to achieve a 40% to 60% moisture level and a temperature between 120 F and 140 F in steady state.

  14. Human 2-oxoglutarate dehydrogenase complex E1 component forms a thiamin-derived radical by aerobic oxidation of the enamine intermediate.

    PubMed

    Nemeria, Natalia S; Ambrus, Attila; Patel, Hetalben; Gerfen, Gary; Adam-Vizi, Vera; Tretter, Laszlo; Zhou, Jieyu; Wang, Junjie; Jordan, Frank

    2014-10-24

    Herein are reported unique properties of the human 2-oxoglutarate dehydrogenase multienzyme complex (OGDHc), a rate-limiting enzyme in the Krebs (citric acid) cycle. (a) Functionally competent 2-oxoglutarate dehydrogenase (E1o-h) and dihydrolipoyl succinyltransferase components have been expressed according to kinetic and spectroscopic evidence. (b) A stable free radical, consistent with the C2-(C2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (ThDP) cation radical was detected by electron spin resonance upon reaction of the E1o-h with 2-oxoglutarate (OG) by itself or when assembled from individual components into OGDHc. (c) An unusual stability of the E1o-h-bound C2-(2α-hydroxy)-γ-carboxypropylidene thiamin diphosphate (the "ThDP-enamine"/C2α-carbanion, the first postdecarboxylation intermediate) was observed, probably stabilized by the 5-carboxyl group of OG, not reported before. (d) The reaction of OG with the E1o-h gave rise to superoxide anion and hydrogen peroxide (reactive oxygen species (ROS)). (e) The relatively stable enzyme-bound enamine is the likely substrate for oxidation by O2, leading to the superoxide anion radical (in d) and the radical (in b). (f) The specific activity assessed for ROS formation compared with the NADH (overall complex) activity, as well as the fraction of radical intermediate occupying active centers of E1o-h are consistent with each other and indicate that radical/ROS formation is an "off-pathway" side reaction comprising less than 1% of the "on-pathway" reactivity. However, the nearly ubiquitous presence of OGDHc in human tissues, including the brain, makes these findings of considerable importance in human metabolism and perhaps disease.

  15. Low-Impact Aerobics: Better than Traditional Aerobic Dance?

    ERIC Educational Resources Information Center

    Koszuta, Laurie Einstein

    1986-01-01

    A form of dance exercise called low-impact aerobics is being touted as a misery-free form of aerobic dance. Because this activity is relatively new, the exact kinds and frequencies of injuries are not known and the fitness benefits have not been examined. (MT)

  16. Removal of the anti-cancer drug methotrexate from water by advanced oxidation processes: Aerobic biodegradation and toxicity studies after treatment.

    PubMed

    Lutterbeck, Carlos Alexandre; Baginska, Ewelina; Machado, Ênio Leandro; Kümmerer, Klaus

    2015-12-01

    Anti-cancer drugs are discussed as high risk substances in regard to human health and considered as problematic for the environment. They are of potential environmental relevance due to their poor biodegradability and toxicological properties. Methotrexate (MTX) is an antimetabolite that was introduced in the pharmaceutical market in the 40's and still today is one of the most consumed cytotoxic compounds around the world. In the present study MTX was only partially biodegraded in the closed bottle test (CBT). Therefore, it was submitted to three different advanced oxidation processes (AOPs): UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. The irradiation was carried out with a Hg medium-pressure lamp during 256min whereas the analytical monitoring was done through LC-UV-MS/MS and DOC analysis. MTX was easily removed in all the irradiation experiments, while the highest mineralization values and rates were achieved by the UV/Fe(2+)/H2O2 treatment. The lowest resulted from the UV/H2O2 reactions. The UV/H2O2 treatment resulted in little biodegradable transformation products (TPs). However, the same treatment resulted in a reduction of the toxicity of MTX by forming less toxic TPs. Analysis by LC-UV-MS/MS revealed the existence of nine TPs formed during the photo-catalytic treatments. The pH of the solutions decreased from 6.4 (t 0min) to 5.15 in the UV/H2O2 and from 6.4 (t 0min) to 5.9 in the UV/TiO2 at the end of the experiments. The initial pH of the UV/Fe(2+)/H2O2 experiments was adjusted to 5 and after the addition of H2O2 the pH decreased to around 3 and remained in this range until the end of the treatments.

  17. 21 CFR 184.1138 - Ammonium chloride.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... from the filtrate on cooling. Alternatively, hydrogen chloride formed by the burning of hydrogen in... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS...

  18. 21 CFR 184.1138 - Ammonium chloride.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... from the filtrate on cooling. Alternatively, hydrogen chloride formed by the burning of hydrogen in... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS...

  19. 21 CFR 184.1138 - Ammonium chloride.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... from the filtrate on cooling. Alternatively, hydrogen chloride formed by the burning of hydrogen in... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS...

  20. 21 CFR 184.1138 - Ammonium chloride.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... from the filtrate on cooling. Alternatively, hydrogen chloride formed by the burning of hydrogen in... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Ammonium chloride. 184.1138 Section 184.1138 Food... Specific Substances Affirmed as GRAS § 184.1138 Ammonium chloride. (a) Ammonium chloride (NH4Cl, CAS...