Sample records for acceptors oxygen nitrate

  1. Biodegradation of monoaromatic hydrocarbons by aquifer microorganisms using oxygen, nitrate, or nitrous oxide as the terminal electron acceptor.

    PubMed Central

    Hutchins, S R

    1991-01-01

    Microcosms were prepared from aquifer material, spiked with monoaromatic hydrocarbons, and amended with oxygen, nitrate, and nitrous oxide. Benzene and alkylbenzenes were degraded to concentrations below 5 micrograms/liter within 7 days under aerobic conditions, whereas only the alkylbenzenes were degraded when either nitrate or nitrous oxide was used. With limited oxygen, monoaromatic hydrocarbons were degraded but removal ceased once oxygen was consumed. However, when nitrate was also present, biodegradation of the alkylbenzenes continued with no apparent lag. Although benzene was still recalcitrant, levels were reduced compared with levels after treatment with nitrate or limited oxygen alone. PMID:1768110

  2. Controlled field study on the use of nitrate and oxygen for bioremediation of a gasoline source zone

    USGS Publications Warehouse

    Barbaro, J.R.; Barker, J.F.

    2000-01-01

    Controlled releases of unleaded gasoline were utilized to evaluate the biotransformation of the soluble aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene isomers, trimethylbenzene isomers, and naphthalene) within a source zone using nitrate and oxygen as electron acceptors. Experiments were conducted within two 2 m ?? 2 m ?? 3.5 m deep sheet-piling cells. In each treatment cell, a gasoline-contaminated zone was created below the water table. Groundwater amended with electron acceptors was then flushed continuously through the cells for 174 day. Electron-acceptor utilization and hydrocarbon-metabolite formation were noted in both cells, indicating that some microbial activity had been induced in response to flushing. Relative to the cell residence time, nitrate utilization was slow and aromatic-hydrocarbon mass losses in response to microaerophilic dissolved oxygen addition were not obvious under these in situ conditions. There was relatively little biotransformation of the aromatic hydrocarbons over the 2-m flow path monitored in this experiment. A large denitrifying population capable of aromatic hydrocarbon biotransformation failed to develop within the gasoline source zone over a 14-mo period of nitrate exposure.

  3. Nitrate is a preferred electron acceptor for growth of freshwater selenate-respiring bacteria

    USGS Publications Warehouse

    Steinberg, Nisan A.; Blum, Jodi Switzer; Hochstein , Lawrence; Oremland, Ronald S.

    1992-01-01

    An anaerobic, freshwater enrichment grew with either nitrate or selenate as an electron acceptor. With both ions present, nitrate reduction preceded selenate reduction. An isolate from the enrichment grew on either ion, but the presence of nitrate precluded the reduction of selenate. Stock cultures of denitrifiers grew anaerobically on nitrate but not on selenate.

  4. Anaerobic electron acceptor chemotaxis in Shewanella putrefaciens

    NASA Technical Reports Server (NTRS)

    Nealson, K. H.; Moser, D. P.; Saffarini, D. A.

    1995-01-01

    Shewanella putrefaciens MR-1 can grow either aerobically or anaerobically at the expense of many different electron acceptors and is often found in abundance at redox interfaces in nature. Such redox interfaces are often characterized by very strong gradients of electron acceptors resulting from rapid microbial metabolism. The coincidence of S. putrefaciens abundance with environmental gradients prompted an examination of the ability of MR-1 to sense and respond to electron acceptor gradients in the laboratory. In these experiments, taxis to the majority of the electron acceptors that S. putrefaciens utilizes for anaerobic growth was seen. All anaerobic electron acceptor taxis was eliminated by the presence of oxygen, nitrate, nitrite, elemental sulfur, or dimethyl sulfoxide, even though taxis to the latter was very weak and nitrate and nitrite respiration was normal in the presence of dimethyl sulfoxide. Studies with respiratory mutants of MR-1 revealed that several electron acceptors that could not be used for anaerobic growth nevertheless elicited normal anaerobic taxis. Mutant M56, which was unable to respire nitrite, showed normal taxis to nitrite, as well as the inhibition of taxis to other electron acceptors by nitrite. These results indicate that electron acceptor taxis in S. putrefaciens does not conform to the paradigm established for Escherichia coli and several other bacteria. Carbon chemo-taxis was also unusual in this organism: of all carbon compounds tested, the only positive response observed was to formate under anaerobic conditions.

  5. BIODEGRADATION OF MONOAROMATIC HYDROCARBONS BY AQUIFER MICROORGANISMS USING OXYGEN, NITRATE, OR NITROUS OXIDE AS THE TERMINAL ELECTRON ACCEPTOR

    EPA Science Inventory

    Microcosms were prepared from aquifer material, spiked with monoaromatic hydrocarbons, and amended with oxygen, nitrate, and nitrous oxide. Benzene and alkylbenzenes were degraded to concentrations below 5 µg/liter within 7 days under aerobic conditions, whereas only the alkylbe...

  6. [Effects of carbon sources, temperature and electron acceptors on biological phosphorus removal].

    PubMed

    Han, Yun; Xu, Song; Dong, Tao; Wang, Bin-Fan; Wang, Xian-Yao; Peng, Dang-Cong

    2015-02-01

    Effects of carbon sources, temperature and electron acceptors on phosphorus uptake and release were investigated in a pilot-scale oxidation ditch. Phosphorus uptake and release rates were measured with different carbon sources (domestic sewage, sodium acetate, glucose) at 25 degrees C. The results showed that the minimum phosphorus uptake and release rates of glucose were 5.12 mg x (g x h)(-1) and 6.43 mg x (g x h)(-1), respectively, and those of domestic sewage are similar to those of sodium acetate. Phosphorus uptake and release rates increased with the increase of temperature (12, 16, 20 and 25 degrees C) using sodium acetate as carbon sources. Anoxic phosphorus uptake rate decreased with added COD. Electron acceptors (oxygen, nitrate, nitrite) had significant effects on phosphorus uptake rate and their order was in accordance with oxygen > nitrate > nitrite. The mass ratio of anoxic P uptake and N consumption (P(uptake)/N (consumption)) of nitrate and nitrite were 0.96 and 0.65, respectively.

  7. Anaerobic biodegradability of alkylphenols and fuel oxygenates in the presence of alternative electron acceptors.

    PubMed

    Puig-Grajales, L; Tan, N G; van der Zee, F; Razo-Flores, E; Field, J A

    2000-11-01

    Alkylphenols and fuel oxygenates are important environmental pollutants produced by the petrochemical industry. A batch biodegradability test was conducted with selected ortho-substituted alkylphenols (2-cresol, 2,6-dimethylphenol and 2-ethylphenol), fuel oxygenates (methyl tert-butyl ether, ethyl tert-butyl ether and tert-amylmethyl ether) and tert-butyl alcohol (TBA) as model compounds. The ortho-substituted alkylphenols were not biodegraded after 100 days of incubation under methanogenic, sulfate-, or nitrate-reducing conditions. However, biodegradation of 2-cresol and 2-ethylphenol (150 mg l(-1)) was observed in the presence of Mn (IV) as electron acceptor. The biodegradation of these two compounds took place in less than 15 days and more than 90% removal was observed for both compounds. Mineralization was indicated since no UV-absorbing metabolites accumulated after 23 days of incubation. These alkylphenols were also slowly chemically oxidized by Mn (IV). No biodegradation of fuel oxygenates or TBA (1 g l(-1)) was observed after 80 or more days of incubation under methanogenic, Fe (III)-, or Mn (IV)-reducing conditions, suggesting that these compounds are recalcitrant under anaerobic conditions. The fuel oxygenates caused no toxicity towards acetoclastic methanogens activity in anaerobic granular sludge.

  8. The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT).

    PubMed

    Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

    2016-11-22

    The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La 3+ donor-doped, Fe 3+ acceptor-doped and La 3+ /Fe 3+ -co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT.

  9. The Effect of Acceptor and Donor Doping on Oxygen Vacancy Concentrations in Lead Zirconate Titanate (PZT)

    PubMed Central

    Slouka, Christoph; Kainz, Theresa; Navickas, Edvinas; Walch, Gregor; Hutter, Herbert; Reichmann, Klaus; Fleig, Jürgen

    2016-01-01

    The different properties of acceptor-doped (hard) and donor-doped (soft) lead zirconate titanate (PZT) ceramics are often attributed to different amounts of oxygen vacancies introduced by the dopant. Acceptor doping is believed to cause high oxygen vacancy concentrations, while donors are expected to strongly suppress their amount. In this study, La3+ donor-doped, Fe3+ acceptor-doped and La3+/Fe3+-co-doped PZT samples were investigated by oxygen tracer exchange and electrochemical impedance spectroscopy in order to analyse the effect of doping on oxygen vacancy concentrations. Relative changes in the tracer diffusion coefficients for different doping and quantitative relations between defect concentrations allowed estimates of oxygen vacancy concentrations. Donor doping does not completely suppress the formation of oxygen vacancies; rather, it concentrates them in the grain boundary region. Acceptor doping enhances the amount of oxygen vacancies but estimates suggest that bulk concentrations are still in the ppm range, even for 1% acceptor doping. Trapped holes might thus considerably contribute to the charge balancing of the acceptor dopants. This could also be of relevance in understanding the properties of hard and soft PZT. PMID:28774067

  10. Nitrate and Nitrite Reduction by Wolffia arrhiza.

    PubMed

    Swader, J A; Stocking, C R

    1971-02-01

    Nitrate reductase was not found to be present in or associated with partially purified, intact chloroplasts aqueously isolated from Wolffia arrhiza. Such chloroplasts are capable of using nitrite but not nitrate as an electron acceptor during light-stimulated electron transport in the absence of additional cytoplasmic components. When nitrite acts as an electron acceptor under these conditions, on the average 1.5 moles of oxygen are evolved per mole of nitrite reduced by the chloroplasts, indicating a probable reduction of nitrite to ammonia. Chloroplasts ruptured by osmotic shock fail to reduce nitrite in the absence of additional components.

  11. Flexible biological arsenite oxidation utilizing NOx and O2 as alternative electron acceptors.

    PubMed

    Wang, Jie; Wan, Junfeng; Wu, Zihao; Li, Hongli; Li, Haisong; Dagot, Christophe; Wang, Yan

    2017-07-01

    The feasibility of flexible microbial arsenite (As III ) oxidation coupled with the reduction of different electron acceptors was investigated. The results indicated the acclimated microorganisms could oxidize As III with oxygen, nitrate and nitrite as the alternative electron acceptors. A series of batch tests were conducted to measure the kinetic parameters of As III oxidation and to evaluate the effects of environmental conditions including pH and temperature on the activity of biological As III oxidation dependent on different electron acceptors. Kinetic results showed that oxygen-dependent As III oxidation had the highest oxidation rate (0.59 mg As g -1  VSS min -1 ), followed by nitrate- (0.40 mg As g -1  VSS min -1 ) and nitrite-dependent As III oxidation (0.32 mg As g -1  VSS min -1 ). The kinetic data of aerobic As III oxidation were fitted well with the Monod kinetic model, while the Haldane substrate inhibition model was better applicable to describe the inhibition of anoxic As III oxidation. Both aerobic and anoxic As III oxidation performed the optimal activity at the near neutral pH. Besides, the optimal temperature for oxygen-, nitrate- and nitrite-dependent As III oxidation was 30 ± 1 °C, 40 ± 1 °C and 20 ± 1 °C, respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Nitrate and Nitrite Reduction by Wolffia arrhiza1

    PubMed Central

    Swader, J. A.; Stocking, C. R.

    1971-01-01

    Nitrate reductase was not found to be present in or associated with partially purified, intact chloroplasts aqueously isolated from Wolffia arrhiza. Such chloroplasts are capable of using nitrite but not nitrate as an electron acceptor during light-stimulated electron transport in the absence of additional cytoplasmic components. When nitrite acts as an electron acceptor under these conditions, on the average 1.5 moles of oxygen are evolved per mole of nitrite reduced by the chloroplasts, indicating a probable reduction of nitrite to ammonia. Chloroplasts ruptured by osmotic shock fail to reduce nitrite in the absence of additional components. PMID:16657592

  13. Candidatus Accumulibacter phosphatis clades enriched under cyclic anaerobic and microaerobic conditions simultaneously use different electron acceptors

    EPA Science Inventory

    Lab- and pilot-scale simultaneous nitrification, denitrification and phosphorus removal-sequencing batch reactors were operated under cyclic anaerobic and micro-aerobic conditions. The use of oxygen, nitrite, and nitrate as electron acceptors by Candidatus Accumulibacter phosphat...

  14. Is beetroot juice more effective than sodium nitrate? The effects of equimolar nitrate dosages of nitrate-rich beetroot juice and sodium nitrate on oxygen consumption during exercise.

    PubMed

    Flueck, Joelle Leonie; Bogdanova, Anna; Mettler, Samuel; Perret, Claudio

    2016-04-01

    Dietary nitrate has been reported to lower oxygen consumption in moderate- and severe-intensity exercise. To date, it is unproven that sodium nitrate (NaNO3(-); NIT) and nitrate-rich beetroot juice (BR) have the same effects on oxygen consumption, blood pressure, and plasma nitrate and nitrite concentrations or not. The aim of this study was to compare the effects of different dosages of NIT and BR on oxygen consumption in male athletes. Twelve healthy, well-trained men (median [minimum; maximum]; peak oxygen consumption: 59.4 mL·min(-1)·kg(-1) [40.5; 67.0]) performed 7 trials on different days, ingesting different nitrate dosages and placebo (PLC). Dosages were 3, 6, and 12 mmol nitrate as concentrated BR or NIT dissolved in plain water. Plasma nitrate and nitrite concentrations were measured before, 3 h after ingestion, and postexercise. Participants cycled for 5 min at moderate intensity and further 8 min at severe intensity. End-exercise oxygen consumption at moderate intensity was not significantly different between the 7 trials (p = 0.08). At severe-intensity exercise, end-exercise oxygen consumption was ~4% lower in the 6-mmol BR trial compared with the 6-mmol NIT (p = 0.003) trial as well as compared with PLC (p = 0.010). Plasma nitrite and nitrate concentrations were significantly increased after the ingestion of BR and NIT with the highest concentrations in the 12-mmol trials. Plasma nitrite concentration between NIT and BR did not significantly differ in the 6-mmol (p = 0.27) and in the 12-mmol (p = 0.75) trials. In conclusion, BR might reduce oxygen consumption to a greater extent compared with NIT.

  15. Biodegradation of pharmaceuticals and endocrine disruptors with oxygen, nitrate, manganese (IV), iron (III) and sulfate as electron acceptors

    NASA Astrophysics Data System (ADS)

    Schmidt, Natalie; Page, Declan; Tiehm, Andreas

    2017-08-01

    Biodegradation of pharmaceuticals and endocrine disrupting compounds was examined in long term batch experiments for a period of two and a half years to obtain more insight into the effects of redox conditions. A mix including lipid lowering agents (e.g. clofibric acid, gemfibrozil), analgesics (e.g. diclofenac, naproxen), beta blockers (e.g. atenolol, propranolol), X-ray contrast media (e.g. diatrizoic acid, iomeprol) as well as the antiepileptic carbamazepine and endocrine disruptors (e.g. bisphenol A, 17α-ethinylestradiol) was analyzed in batch tests in the presence of oxygen, nitrate, manganese (IV), iron (III), and sulfate. Out of the 23 selected substances, 14 showed a degradation of > 50% of their initial concentrations under aerobic conditions. The beta blockers propranolol and atenolol and the analgesics pentoxifylline and naproxen showed a removal of > 50% under anaerobic conditions. In particular naproxen proved to be degradable with oxygen and under most anaerobic conditions, i.e. with manganese (IV), iron (III), or sulfate. The natural estrogens estriol, estrone and 17β-estradiol showed complete biodegradation under aerobic and nitrate-reducing conditions, with a temporary increase of estrone during transformation of estriol and 17β-estradiol. Transformation of 17β-estradiol under Fe(III)-reducing conditions resulted in an increase of estriol as well. Concentrations of clofibric acid, carbamazepine, iopamidol and diatrizoic acid, known for their recalcitrance in the environment, remained unchanged.

  16. Fungal oxygen exchange between denitrification intermediates and water.

    PubMed

    Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Anette; Wrage-Mönnig, Nicole; Well, Reinhard

    2014-02-28

    Fungi can contribute greatly to N2O production from denitrification. Therefore, it is important to quantify the isotopic signature of fungal N2O. The isotopic composition of N2O can be used to identify and analyze the processes of N2O production and N2O reduction. In contrast to bacteria, information about the oxygen exchange between denitrification intermediates and water during fungal denitrification is lacking, impeding the explanatory power of stable isotope methods. Six fungal species were anaerobically incubated with the electron acceptors nitrate or nitrite and (18)O-labeled water to determine the oxygen exchange between denitrification intermediates and water. After seven days of incubation, gas samples were analyzed for N2O isotopologues by isotope ratio mass spectrometry. All the fungal species produced N2O. N2O production was greater when nitrite was the sole electron acceptor (129 to 6558 nmol N2O g dw(-1)  h(-1)) than when nitrate was the electron acceptor (6 to 47 nmol N2O g dw(-1)  h(-1)). Oxygen exchange was complete with nitrate as electron acceptor in one of five fungi and with nitrite in two of six fungi. Oxygen exchange of the other fungi varied (41 to 89% with nitrite and 11 to 61% with nitrate). This is the first report on oxygen exchange with water during fungal denitrification. The exchange appears to be within the range previously reported for bacterial denitrification. This adds to the difficulty of differentiating N2O producing processes based on the origin of N2O-O. However, the large oxygen exchange repeatedly observed for bacteria and now also fungi could lead to less variability in the δ(18)O values of N2O from soils, which could facilitate the assessment of the extent of N2O reduction. Copyright © 2013 John Wiley & Sons, Ltd.

  17. Comment on Egami's concept of the evolution of nitrate respiration

    NASA Technical Reports Server (NTRS)

    Rambler, M.; Margulis, L.

    1976-01-01

    Recent results suggest that the presence of common nitrogen salts (sodium nitrite and nitrate) in the irradiation medium can markedly protect filamentous blue-green algae from potentially lethal ultraviolet irradiation. The present results as well as general biological arguments of Egami support and extend Egami's original view that anaerobic respiratory pathways using nitrite and nitrate as terminal electron acceptors evolved prior to oxygen requiring aerobic respiratory pathways.

  18. Biodegradation of pharmaceuticals and endocrine disruptors with oxygen, nitrate, manganese (IV), iron (III) and sulfate as electron acceptors.

    PubMed

    Schmidt, Natalie; Page, Declan; Tiehm, Andreas

    2017-08-01

    Biodegradation of pharmaceuticals and endocrine disrupting compounds was examined in long term batch experiments for a period of two and a half years to obtain more insight into the effects of redox conditions. A mix including lipid lowering agents (e.g. clofibric acid, gemfibrozil), analgesics (e.g. diclofenac, naproxen), beta blockers (e.g. atenolol, propranolol), X-ray contrast media (e.g. diatrizoic acid, iomeprol) as well as the antiepileptic carbamazepine and endocrine disruptors (e.g. bisphenol A, 17α-ethinylestradiol) was analyzed in batch tests in the presence of oxygen, nitrate, manganese (IV), iron (III), and sulfate. Out of the 23 selected substances, 14 showed a degradation of >50% of their initial concentrations under aerobic conditions. The beta blockers propranolol and atenolol and the analgesics pentoxifylline and naproxen showed a removal of >50% under anaerobic conditions. In particular naproxen proved to be degradable with oxygen and under most anaerobic conditions, i.e. with manganese (IV), iron (III), or sulfate. The natural estrogens estriol, estrone and 17β-estradiol showed complete biodegradation under aerobic and nitrate-reducing conditions, with a temporary increase of estrone during transformation of estriol and 17β-estradiol. Transformation of 17β-estradiol under Fe(III)-reducing conditions resulted in an increase of estriol as well. Concentrations of clofibric acid, carbamazepine, iopamidol and diatrizoic acid, known for their recalcitrance in the environment, remained unchanged. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  19. An Overview of Electron Acceptors in Microbial Fuel Cells

    PubMed Central

    Ucar, Deniz; Zhang, Yifeng; Angelidaki, Irini

    2017-01-01

    Microbial fuel cells (MFC) have recently received increasing attention due to their promising potential in sustainable wastewater treatment and contaminant removal. In general, contaminants can be removed either as an electron donor via microbial catalyzed oxidization at the anode or removed at the cathode as electron acceptors through reduction. Some contaminants can also function as electron mediators at the anode or cathode. While previous studies have done a thorough assessment of electron donors, cathodic electron acceptors and mediators have not been as well described. Oxygen is widely used as an electron acceptor due to its high oxidation potential and ready availability. Recent studies, however, have begun to assess the use of different electron acceptors because of the (1) diversity of redox potential, (2) needs of alternative and more efficient cathode reaction, and (3) expanding of MFC based technologies in different areas. The aim of this review was to evaluate the performance and applicability of various electron acceptors and mediators used in MFCs. This review also evaluated the corresponding performance, advantages and disadvantages, and future potential applications of select electron acceptors (e.g., nitrate, iron, copper, perchlorate) and mediators. PMID:28469607

  20. Interactions of chloride and formate at the donor and the acceptor side of photosystem II.

    PubMed

    Jajoo, Anjana; Bharti, Sudhakar; Kawamori, Asako

    2005-02-01

    Chloride is required for the maximum activity of the oxygen evolving complex (OEC) while formate inhibits the function of OEC. On the basis of the measurements of oxygen evolution rates and the S(2) state multiline EPR signal, an interaction between the action of chloride and formate at the donor side of PS II has been suggested. Moreover, the Fe(2)+Q-A EPR signals were measured to investigate a common binding site of both these anions at the PS II acceptor side. Other monovalent anions like bromide, nitrate etc. could influence the effects of formate to a small extent at the donor side of PS II, but not significantly at the acceptor side of PS II. The results presented in this paper clearly suggest a competitive binding of formate and chloride at the PS II acceptor side.

  1. Growth of strain SES-3 with arsenate and other diverse electron acceptors

    USGS Publications Warehouse

    Laverman, A.M.; Blum, J.S.; Schaefer, J.K.; Phillips, E.J.P.; Lovley, D.R.; Oremland, R.S.

    1995-01-01

    The selenate-respiring bacterial strain SES-3 was able to use a variety of inorganic electron acceptors to sustain growth. SES-3 grew with the reduction of arsenate to arsenite, Fe(III) to Fe(II), or thiosulfate to sulfide. It also grew in medium in which elemental sulfur, Mn(IV), nitrite, trimethylamine N-oxide, or fumarate was provided as an electron acceptor. Growth on oxygen was microaerophilic. There was no growth with arsenite or chromate. Washed suspensions of cells grown on selenate or nitrate had a constitutive ability to reduce arsenate but were unable to reduce arsenite. These results suggest that strain SES-3 may occupy a niche as an environmental opportunist by being able to take advantage of a diversity of electron acceptors.

  2. BIODEGRADATION OF AROMATIC COMPOUNDS UNDER MIXED OXYGEN/DENITRIFYING CONDITIONS: A REVIEW

    EPA Science Inventory

    Bioremediation of aromatic hydrocarbons in groundwater and sediments is often limited by dissolved oxygen. Many aromatic hydrocarbons degrade very slowly or not at all under anaerobic conditions. Nitrate is a good alternative electron acceptor to oxygen, and denitrifying bacteria...

  3. Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

    PubMed Central

    Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

    2014-01-01

    Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

  4. A modified procedure for measuring oxygen-18 content of nitrate

    NASA Astrophysics Data System (ADS)

    Ahmed, M. A.; Aly, A. I. M.; Abdel Monem, N.; Hanafy, M.; Gomaa, H. E.

    2012-11-01

    SummaryMass spectrometric analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. Through this work, rapid, reliable, precise, broadly applicable, catalyst-free, low-priced and less labor intensive procedure for measuring δ18O of nitrate using Isotope Ratio Mass Spectrometer has been developed and implemented. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing anions and dissolved organic carbon (DOC) without scarifying the isotopic signature of nitrate were investigated. The developed procedure consists of two main parts: (1) wet chemistry train for extraction and purification of nitrate from the liquid matrix; (2) off-line pyrolysis of extracted nitrate salt with activated graphite at 550 °C for 30 min. The conditions necessary to effect complete nitrate recovery and complete removal of other oxygen containing compounds were investigated. Dramatic reduction in processing times needed for analysis of δ18O of nitrate at natural abundance level was achieved. Preservation experiments revealed that chloroform (99.8%) is an effective preservative. Isotopic contents of some selected nitrate salts were measured using the modified procedure and some other well established methods at two laboratories in Egypt and Germany. Performance assessment of the whole developed analytical train was made using internationally distributed nitrate isotopes reference materials and real world sample of initial zero-nitrate content. The uncertainty budget was evaluated using the graphical nested hierarchal approach. The obtained results proved the suitability for handling samples of complicated matrices. Reduction of consumables cost by about 80% was achieved.

  5. Oxygen and Carbon Dioxide Fluxes from Barley Shoots Depend on Nitrate Assimilation 1

    PubMed Central

    Bloom, Arnold J.; Caldwell, Richard M.; Finazzo, John; Warner, Robert L.; Weissbart, Joseph

    1989-01-01

    A custom oxygen analyzer in conjunction with an infrared carbon dioxide analyzer and humidity sensors permitted simultaneous measurements of oxygen, carbon dioxide, and water vapor fluxes from the shoots of intact barley plants (Hordeum vulgare L. cv Steptoe). The oxygen analyzer is based on a calciazirconium sensor and can resolve concentration differences to within 2 microliters per liter against the normal background of 210,000 microliters per liter. In wild-type plants receiving ammonium as their sole nitrogen source or in nitrate reductase-deficient mutants, photosynthetic and respiratory fluxes of oxygen equaled those of carbon dioxide. By contrast, wild-type plants exposed to nitrate had unequal oxygen and carbon dioxide fluxes: oxygen evolution at high light exceeded carbon dioxide consumption by 26% and carbon dioxide evolution in the dark exceeded oxygen consumption by 25%. These results indicate that a substantial portion of photosynthetic electron transport or respiration generates reductant for nitrate assimilation rather than for carbon fixation or mitochondrial electron transport. PMID:16667024

  6. (Per)Chlorate-Reducing Bacteria Can Utilize Aerobic and Anaerobic Pathways of Aromatic Degradation with (Per)Chlorate as an Electron Acceptor

    PubMed Central

    Carlström, Charlotte I.; Loutey, Dana; Bauer, Stefan; Clark, Iain C.; Rohde, Robert A.; Iavarone, Anthony T.; Lucas, Lauren

    2015-01-01

    ABSTRACT The pathways involved in aromatic compound oxidation under perchlorate and chlorate [collectively known as (per)chlorate]-reducing conditions are poorly understood. Previous studies suggest that these are oxygenase-dependent pathways involving O2 biogenically produced during (per)chlorate respiration. Recently, we described Sedimenticola selenatireducens CUZ and Dechloromarinus chlorophilus NSS, which oxidized phenylacetate and benzoate, two key intermediates in aromatic compound catabolism, coupled to the reduction of perchlorate or chlorate, respectively, and nitrate. While strain CUZ also oxidized benzoate and phenylacetate with oxygen as an electron acceptor, strain NSS oxidized only the latter, even at a very low oxygen concentration (1%, vol/vol). Strains CUZ and NSS contain similar genes for both the anaerobic and aerobic-hybrid pathways of benzoate and phenylacetate degradation; however, the key genes (paaABCD) encoding the epoxidase of the aerobic-hybrid phenylacetate pathway were not found in either genome. By using transcriptomics and proteomics, as well as by monitoring metabolic intermediates, we investigated the utilization of the anaerobic and aerobic-hybrid pathways on different electron acceptors. For strain CUZ, the results indicated utilization of the anaerobic pathways with perchlorate and nitrate as electron acceptors and of the aerobic-hybrid pathways in the presence of oxygen. In contrast, proteomic results suggest that strain NSS may use a combination of the anaerobic and aerobic-hybrid pathways when growing on phenylacetate with chlorate. Though microbial (per)chlorate reduction produces molecular oxygen through the dismutation of chlorite (ClO2−), this study demonstrates that anaerobic pathways for the degradation of aromatics can still be utilized by these novel organisms. PMID:25805732

  7. Donor/acceptor nanoparticle pair-based singlet oxygen channeling homogenous chemiluminescence immunoassay for quantitative determination of bisphenol A.

    PubMed

    Hou, Changjiang; Zhao, Lixia; Geng, Fanglan; Wang, Dan; Guo, Liang-Hong

    2016-12-01

    Bisphenol A (BPA) is widely used in consumer products such as plastic bottles and food containers. It has become a ubiquitous environmental contaminant and poses a serious risk to human health. A rapid, sensitive, and high-throughput method for detecting BPA is therefore desirable. Herein, a donor/acceptor nanoparticle pair-based singlet oxygen channeling chemiluminescence homogenous immunoassay is developed for the determination of BPA. The donor nanoparticles were modified with phthalocyanine as a photosensitizer and were then coated with streptavidin. The acceptor nanoparticles were doped with thioxene derivatives and Eu(III) as a chemiluminescence emitter and then coated with anti-BPA antibody. Under light irradiation, oxygen near the donor surface transforms to singlet oxygen ( 1 O 2 ), which migrates to the acceptor and reacts with it, generating luminescence. Because 1 O 2 has a very short lifetime, luminescence is generated only when the donor and acceptor are in close proximity. This occurs when they are brought together by the antigen/antibody and streptavidin/biotin reaction. Based on this singlet oxygen channeling mechanism, a competitive homogenous chemiluminescence immunoassay for BPA was developed on 384 microplates. The assay exhibited linear detection over the range 10-1000 ng/mL and a limit of detection of 2.9 ng/mL. The intra- and inter-assay precisions were both below 5.1 %. The average recoveries of three spiked samples in tap and river water samples were in the range 95.5-121.0 %, in agreement with values obtained using high-performance liquid chromatography. The homogeneous assay is rapid, low cost, sensitive, and allows high-throughput, so is well suited for screening large numbers of environmental samples. Graphical abstract Principle of the singlet oxygen channeling homogenous chemiluminescence competitive immunoassay based on nanoparticle pairs for determination of BPA.

  8. Forensic applications of nitrogen and oxygen isotopes in tracing nitrate sources in urban environments

    USGS Publications Warehouse

    Silva, S.R.; Ging, P.B.; Lee, R.W.; Ebbert, J.C.; Tesoriero, A.J.; Inkpen, E.L.

    2002-01-01

    Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington. In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing ??15N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  9. Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method

    USGS Publications Warehouse

    Casciotti, K.L.; Sigman, D.M.; Hastings, M. Galanter; Böhlke, J.K.; Hilkert, A.

    2002-01-01

    We report a novel method for measurement of the oxygen isotopic composition (18O/16O) of nitrate (NO3-) from both seawater and freshwater. The denitrifier method, based on the isotope ratio analysis of nitrous oxide generated from sample nitrate by cultured denitrifying bacteria, has been described elsewhere for its use in nitrogen isotope ratio (15N/14N) analysis of nitrate.1Here, we address the additional issues associated with 18O/16O analysis of nitrate by this approach, which include (1) the oxygen isotopic difference between the nitrate sample and the N2O analyte due to isotopic fractionation associated with the loss of oxygen atoms from nitrate and (2) the exchange of oxygen atoms with water during the conversion of nitrate to N2O. Experiments with 18O-labeled water indicate that water exchange contributes less than 10%, and frequently less than 3%, of the oxygen atoms in the N2O product for Pseudomonas aureofaciens. In addition, both oxygen isotope fractionation and oxygen atom exchange are consistent within a given batch of analyses. The analysis of appropriate isotopic reference materials can thus be used to correct the measured 18O/16O ratios of samples for both effects. This is the first method tested for 18O/16O analysis of nitrate in seawater. Benefits of this method, relative to published freshwater methods, include higher sensitivity (tested down to 10 nmol and 1 μM NO3-), lack of interference by other solutes, and ease of sample preparation.

  10. [Research advances in identifying nitrate pollution sources of water environment by using nitrogen and oxygen stable isotopes].

    PubMed

    Mao, Wei; Liang, Zhi-wei; Li, Wei; Zhu, Yao; Yanng, Mu-yi; Jia, Chao-jie

    2013-04-01

    Water body' s nitrate pollution has become a common and severe environmental problem. In order to ensure human health and water environment benign evolution, it is of great importance to effectively identify the nitrate pollution sources of water body. Because of the discrepant composition of nitrogen and oxygen stable isotopes in different sources of nitrate in water body, nitrogen and oxygen stable isotopes can be used to identify the nitrate pollution sources of water environment. This paper introduced the fractionation factors of nitrogen and oxygen stable isotopes in the main processes of nitrogen cycling and the composition of these stable isotopes in main nitrate sources, compared the advantages and disadvantages of five pre-treatment methods for analyzing the nitrogen and oxygen isotopes in nitrate, and summarized the research advances in this aspect into three stages, i. e. , using nitrogen stable isotope alone, using nitrogen and oxygen stable isotopes simultaneously, and combining with mathematical models. The future research directions regarding the nitrate pollution sources identification of water environment were also discussed.

  11. Rethinking anaerobic As(III) oxidation in filters: Effect of indigenous nitrate respirers.

    PubMed

    Cui, Jinli; Du, Jingjing; Tian, Haixia; Chan, Tingshan; Jing, Chuanyong

    2018-04-01

    Microorganisms play a key role in the redox transformation of arsenic (As) in aquifers. In this study, the impact of indigenous bacteria, especially the prevailing nitrate respirers, on arsenite (As(III)) oxidation was explored during groundwater filtration using granular TiO 2 and subsequent spent TiO 2 anaerobic landfill. X-ray absorption near edge structure spectroscopy analysis showed As(III) oxidation (46% in 10 days) in the presence of nitrate in the simulated anaerobic landfills. Meanwhile, iron (Fe) species on the spent TiO 2 were dominated by amorphous ferric arsenate, ferrihydrite and goethite. The Fe phase showed no change during the anaerobic landfill incubation. Batch incubation experiments implied that the indigenous bacteria completely oxidized As(III) to arsenate (As(V)) in 10 days using nitrate as the terminal electron acceptor under anaerobic conditions. The bacterial community analysis indicated that various kinds of microbial species exist in groundwater matrix. Phylogenetic tree analysis revealed that Proteobacteria was the dominant phylum, with Hydrogenophaga (34%), Limnohabitans (16%), and Simplicispira (7%) as the major bacterial genera. The nitrate respirers especially from the Hydrogenophaga genus anaerobically oxidized As(III) using nitrate as an electron acceptor instead of oxygen. Our study implied that microbes can facilitate the groundwater As oxidation using nitrate on the adsorptive media. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

    PubMed

    Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

    2012-09-30

    Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

  13. Analysis of Atmospheric Nitrate Deposition in Lake Tahoe Using Multiple Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    McCabe, J. R.; Michalski, G. M.; Hernandez, L. P.; Thiemens, M. H.; Taylor, K.; Kendall, C.; Wankel, S. D.

    2002-12-01

    Lake Tahoe in the Sierra Nevada Mountain Range is world renown for its depth and water clarity bringing 2.2 million visitors per year resulting in annual revenue of \\1.6 billion from tourism. In past decades the lake has suffered from decreased water clarity (from 32 m plate depth to less than 20), which is believed to be largely the result of algae growth initiated by increased nutrient loading. Lake nutrients have also seen a shift from a nitrogen limited to a phosphorous limited system indicating a large increase in the flux of fixed nitrogen. Several sources of fixed nitrogen of have been suggested including surface runoff, septic tank seepage from ground water and deposition from the atmosphere. Bio-available nitrogen in the form of nitrate (NO_{3}$-) is a main component of this system. Recent studies have estimated that approximately 50% of the nitrogen input into the lake is of atmospheric origin (Allison et al. 2000). However, the impact and magnitude of atmospheric deposition is still one of the least understood aspects of the relationship between air and water quality in the Basin (TRPA Threshold Assessment 2002). The utility of stable isotopes as tracers of nitrate reservoirs has been shown in several studies (Bohlke et al. 1997, Kendall and McDonnell 1998, Durka et al. 1994). Stable nitrogen (δ15N) and oxygen (δ18O) isotopes have been implemented in a dual isotope approach to characterize the various nitrate sources to an ecosystem. While δ18O distinguishes between atmospheric and soil sources of nitrate, processes such as denitrification can enrich the residual nitrate in δ18O leaving a misleading atmospheric signature. The benefit of δ15N as a tracer for NO3- sources is the ability to differentiate natural soil, fertilizer, and animal or septic waste, which contain equivalent δ18O values. The recent implementation of multiple oxygen isotopes to measure Δ17O in nitrate has proven to be a more sensitive tracer of atmospheric deposition. The

  14. Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea

    PubMed Central

    2014-01-01

    Background A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report on the anaerobic nitrate metabolism of the fungus Aspergillus terreus (isolate An-4) that was obtained from sediment in the seasonal oxygen minimum zone in the Arabian Sea, a globally important site of oceanic nitrogen loss and nitrous oxide emission. Results Axenic incubations of An-4 in the presence and absence of oxygen and nitrate revealed that this fungal isolate is capable of dissimilatory nitrate reduction to ammonium under anoxic conditions. A 15N-labeling experiment proved that An-4 produced and excreted ammonium through nitrate reduction at a rate of up to 175 nmol 15NH4+ g-1 protein h-1. The products of dissimilatory nitrate reduction were ammonium (83%), nitrous oxide (15.5%), and nitrite (1.5%), while dinitrogen production was not observed. The process led to substantial cellular ATP production and biomass growth and also occurred when ammonium was added to suppress nitrate assimilation, stressing the dissimilatory nature of nitrate reduction. Interestingly, An-4 used intracellular nitrate stores (up to 6–8 μmol NO3- g-1 protein) for dissimilatory nitrate reduction. Conclusions Our findings expand the short list of microbial eukaryotes that store nitrate intracellularly and carry out dissimilatory nitrate reduction when oxygen is absent. In the currently spreading oxygen-deficient zones in the ocean, an as yet unexplored diversity of fungi may recycle nitrate to ammonium and nitrite, the substrates of the major nitrogen loss process anaerobic ammonium oxidation, and the potent greenhouse gas nitrous oxide. PMID:24517718

  15. Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea.

    PubMed

    Stief, Peter; Fuchs-Ocklenburg, Silvia; Kamp, Anja; Manohar, Cathrine-Sumathi; Houbraken, Jos; Boekhout, Teun; de Beer, Dirk; Stoeck, Thorsten

    2014-02-11

    A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report on the anaerobic nitrate metabolism of the fungus Aspergillus terreus (isolate An-4) that was obtained from sediment in the seasonal oxygen minimum zone in the Arabian Sea, a globally important site of oceanic nitrogen loss and nitrous oxide emission. Axenic incubations of An-4 in the presence and absence of oxygen and nitrate revealed that this fungal isolate is capable of dissimilatory nitrate reduction to ammonium under anoxic conditions. A ¹⁵N-labeling experiment proved that An-4 produced and excreted ammonium through nitrate reduction at a rate of up to 175 nmol ¹⁵NH₄⁺ g⁻¹ protein h⁻¹. The products of dissimilatory nitrate reduction were ammonium (83%), nitrous oxide (15.5%), and nitrite (1.5%), while dinitrogen production was not observed. The process led to substantial cellular ATP production and biomass growth and also occurred when ammonium was added to suppress nitrate assimilation, stressing the dissimilatory nature of nitrate reduction. Interestingly, An-4 used intracellular nitrate stores (up to 6-8 μmol NO₃⁻ g⁻¹ protein) for dissimilatory nitrate reduction. Our findings expand the short list of microbial eukaryotes that store nitrate intracellularly and carry out dissimilatory nitrate reduction when oxygen is absent. In the currently spreading oxygen-deficient zones in the ocean, an as yet unexplored diversity of fungi may recycle nitrate to ammonium and nitrite, the substrates of the major nitrogen loss process anaerobic ammonium oxidation, and the potent greenhouse gas nitrous oxide.

  16. Net community production at Ocean Station Papa observed with nitrate and oxygen sensors on profiling floats

    NASA Astrophysics Data System (ADS)

    Plant, Joshua N.; Johnson, Kenneth S.; Sakamoto, Carole M.; Jannasch, Hans W.; Coletti, Luke J.; Riser, Stephen C.; Swift, Dana D.

    2016-06-01

    Six profiling floats equipped with nitrate and oxygen sensors were deployed at Ocean Station P in the Gulf of Alaska. The resulting six calendar years and 10 float years of nitrate and oxygen data were used to determine an average annual cycle for net community production (NCP) in the top 35 m of the water column. NCP became positive in February as soon as the mixing activity in the surface layer began to weaken, but nearly 3 months before the traditionally defined mixed layer began to shoal from its winter time maximum. NCP displayed two maxima, one toward the end of May and another in August with a summertime minimum in June corresponding to the historical peak in mesozooplankton biomass. The average annual NCP was determined to be 1.5 ± 0.6 mol C m-2 yr-1 using nitrate and 1.5 ± 0.7 mol C m-2 yr-1 using oxygen. The results from oxygen data proved to be quite sensitive to the gas exchange model used as well as the accuracy of the oxygen measurement. Gas exchange models optimized for carbon dioxide flux generally ignore transport due to gas exchange through the injection of bubbles, and these models yield NCP values that are two to three time higher than the nitrate-based estimates. If nitrate and oxygen NCP rates are assumed to be related by the Redfield model, we show that the oxygen gas exchange model can be optimized by tuning the exchange terms to reproduce the nitrate NCP annual cycle.

  17. New insight into sludge reduction induced by different substrate allocation strategy between oxygen and nitrate/nitrite as terminal electron acceptor.

    PubMed

    Yan, Peng; Guo, Jin-Song; Xu, Yu-Feng; Chen, You-Peng; Wang, Jing; Liu, Zhi-Ping; Fang, Fang

    2018-06-01

    Sludge reduction based on regulating substrate allocation between catabolism and anabolism as a strategy is proposed to reduce energy and chemicals consumption during wastewater treatment. The results indicated that a sludge reduction of 14.8% and excellent nutrient removal were simultaneously achieved in the low dissolved oxygen (LDO) activated sludge system with a hydraulic retention time of 24 h at 25 °C. Denitrifiers comprised nearly 1/4 of all microorganisms in the system. These denitrifiers converted NO x - to N 2 obtaining a lower biomass yield. The oxidoreductase activity proteins in the LDO sample was more than twice that of the normal DO sample, indicating that catabolism was stimulated by NO x - when replacing O 2 as electron acceptor. Less substrate was used for cell synthesis in the LDO system. Stable sludge reduction without extra energy and chemicals inputs was achieved by regulating the substrate allocation by inducing the bacteria to utilize NO x - instead of O 2 . Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Kinetics of nitrate and sulfate removal using a mixed microbial culture with or without limited-oxygen fed.

    PubMed

    Xu, Xi-Jun; Chen, Chuan; Wang, Ai-Jie; Guo, Hong-Liang; Yuan, Ye; Lee, Duu-Jong; Ren, Nan-Qi

    2014-07-01

    The biological degradation of nitrate and sulfate was investigated using a mixed microbial culture and lactate as the carbon source, with or without limited-oxygen fed. It was found that sulfate reduction was slightly inhibited by nitrate, since after nitrate depletion the sulfate reduction rate increased from 0.37 mg SO4 (2-)/mg VSS d to 0.71 mg SO4 (2-)/mg VSS d, and the maximum rate of sulfate reduction in the presence of nitrate corresponded to 56 % of the non-inhibited sulfate reduction rate determined after nitrate depleted. However, simultaneous but not sequential reduction of both oxy-anions was observed in this study, unlike some literature reports in which sulfate reduction starts only after depletion of nitrate, and this case might be due to the fact that lactate was always kept above the limiting conditions. At limited oxygen, the inhibited effect on sulfate reduction by nitrate was relieved, and the sulfate reduction rate seemed relatively higher than that obtained without limited-oxygen fed, whereas kept almost constant (0.86-0.89 mg SO4 (2-)/mg VSS d) cross the six ROS states. In contrast, nitrate reduction rates decreased substantially with the increase in the initial limited-oxygen fed, showing an inhibited effect on nitrate reduction by oxygen. Kinetic parameters determined for the mixed microbial culture showed that the maximum specific sulfate utilization rate obtained (0.098 ± 0.022 mg SO4 (2-)/(mg VSS h)) was similar to the reported typical value (0.1 mg SO4 (2-)/(mg VSS h)), also indicating a moderate inhibited effect by nitrate.

  19. Contribution of atmospheric nitrate to stream-water nitrate in Japanese coniferous forests revealed by the oxygen isotope ratio of nitrate.

    PubMed

    Tobari, Y; Koba, K; Fukushima, K; Tokuchi, N; Ohte, N; Tateno, R; Toyoda, S; Yoshioka, T; Yoshida, N

    2010-05-15

    Evaluation of the openness of the nitrogen (N) cycle in forest ecosystems is important in efforts to improve forest management because the N supply often limits primary production. The use of the oxygen isotope ratio (delta(18)O) of nitrate is a promising approach to determine how effectively atmospheric nitrate can be retained in a forest ecosystem. We investigated the delta(18)O of nitrate in stream water in order to estimate the contribution of atmospheric NO(3) (-) in stream-water NO(3) (-) (f(atm)) from 26 watersheds with different stand ages (1-87 years) in Japan. The stream-water nitrate concentrations were high in young forests whereas, in contrast, old forests discharged low-nitrate stream water. These results implied a low f(atm) and a closed N cycle in older forests. However, the delta(18)O values of nitrate in stream water revealed that f(atm) values were higher in older forests than in younger forests. These results indicated that even in old forests, where the discharged N loss was small, atmospheric nitrate was not retained effectively. The steep slopes of the studied watersheds (>40 degrees ) which hinder the capturing of atmospheric nitrate by plants and microbes might be responsible for the inefficient utilization of atmospheric nitrate. Moreover, the unprocessed fraction of atmospheric nitrate in the stream-water nitrate in the forest (f(unprocessed)) was high in the young forest (78%), although f(unprocessed) was stable and low for other forests (5-13%). This high f(unprocessed) of the young forest indicated that the young forest retained neither atmospheric NO(3) (-) nor soil NO(3) (-) effectively, engendering high stream-water NO(3) (-) concentrations. Copyright (c) 2010 John Wiley & Sons, Ltd.

  20. Dietary nitrate does not reduce oxygen cost of exercise or improve muscle mitochondrial function in patients with mitochondrial myopathy.

    PubMed

    Nabben, Miranda; Schmitz, Joep P J; Ciapaite, Jolita; le Clercq, Carlijn M P; van Riel, Natal A; Haak, Harm R; Nicolay, Klaas; de Coo, Irenaeus F M; Smeets, Hubert; Praet, Stephan F; van Loon, Luc J; Prompers, Jeanine J

    2017-05-01

    Muscle weakness and exercise intolerance negatively affect the quality of life of patients with mitochondrial myopathy. Short-term dietary nitrate supplementation has been shown to improve exercise performance and reduce oxygen cost of exercise in healthy humans and trained athletes. We investigated whether 1 wk of dietary inorganic nitrate supplementation decreases the oxygen cost of exercise and improves mitochondrial function in patients with mitochondrial myopathy. Ten patients with mitochondrial myopathy (40 ± 5 yr, maximal whole body oxygen uptake = 21.2 ± 3.2 ml·min -1 ·kg body wt -1 , maximal work load = 122 ± 26 W) received 8.5 mg·kg body wt -1 ·day -1 inorganic nitrate (~7 mmol) for 8 days. Whole body oxygen consumption at 50% of the maximal work load, in vivo skeletal muscle oxidative capacity (evaluated from postexercise phosphocreatine recovery using 31 P-magnetic resonance spectroscopy), and ex vivo mitochondrial oxidative capacity in permeabilized skinned muscle fibers (measured with high-resolution respirometry) were determined before and after nitrate supplementation. Despite a sixfold increase in plasma nitrate levels, nitrate supplementation did not affect whole body oxygen cost during submaximal exercise. Additionally, no beneficial effects of nitrate were found on in vivo or ex vivo muscle mitochondrial oxidative capacity. This is the first time that the therapeutic potential of dietary nitrate for patients with mitochondrial myopathy was evaluated. We conclude that 1 wk of dietary nitrate supplementation does not reduce oxygen cost of exercise or improve mitochondrial function in the group of patients tested. Copyright © 2017 the American Physiological Society.

  1. Involvement of Activated Oxygen in Nitrate-Induced Senescence of Pea Root Nodules.

    PubMed Central

    Escuredo, P. R.; Minchin, F. R.; Gogorcena, Y.; Iturbe-Ormaetxe, I.; Klucas, R. V.; Becana, M.

    1996-01-01

    The effect of short-term nitrate application (10 mM, 0-4 d) on nitrogenase (N2ase) activity, antioxidant defenses, and related parameters was investigated in pea (Pisum sativum L. cv Frilene) nodules. The response of nodules to nitrate comprised two stages. In the first stage (0-2 d), there were major decreases in N2ase activity and N2ase-linked respiration and concomitant increases in carbon cost of N2ase and oxygen diffusion resistance of nodules. There was no apparent oxidative damage, and the decline in N2ase activity was, to a certain extent, reversible. The second stage (>2 d) was typical of a senescent, essentially irreversible process. It was characterized by moderate increases in oxidized proteins and catalytic Fe and by major decreases in antioxidant enzymes and metabolites. The restriction in oxygen supply to bacteroids may explain the initial decline in N2ase activity. The decrease in antioxidant protection is not involved in this process and is not specifically caused by nitrate, since it also occurs with drought stress. However, comparison of nitrate- and drought-induced senescence shows an important difference: there is no lipid degradation or lipid peroxide accumulation with nitrate, indicating that lipid peroxidation is not necessarily involved in nodule senescence. PMID:12226252

  2. Anaerobic methanotrophy in tidal wetland: Effects of electron acceptors

    NASA Astrophysics Data System (ADS)

    Lin, Li-Hung; Yu, Zih-Huei; Wang, Pei-Ling

    2016-04-01

    Wetlands have been considered to represent the largest natural source of methane emission, contributing substantially to intensify greenhouse effect. Despite in situ methanogenesis fueled by organic degradation, methanotrophy also plays a vital role in controlling the exact quantity of methane release across the air-sediment interface. As wetlands constantly experience various disturbances of anthropogenic activities, biological burrowing, tidal inundation, and plant development, rapid elemental turnover would enable various electron acceptors available for anaerobic methanotrophy. The effects of electron acceptors on stimulating anaerobic methanotrophy and the population compositions involved in carbon transformation in wetland sediments are poorly explored. In this study, sediments recovered from tidally influenced, mangrove covered wetland in northern Taiwan were incubated under the static conditions to investigate whether anaerobic methanotrophy could be stimulated by the presence of individual electron acceptors. Our results demonstrated that anaerobic methanotrophy was clearly stimulated in incubations amended with no electron acceptor, sulfate, or Fe-oxyhydroxide. No apparent methane consumption was observed in incubations with nitrate, citrate, fumarate or Mn-oxides. Anaerobic methanotrophy in incubations with no exogenous electron acceptor appears to proceed at the greatest rates, being sequentially followed by incubations with sulfate and Fe-oxyhydroxide. The presence of basal salt solution stimulated methane oxidation by a factor of 2 to 3. In addition to the direct impact of electron acceptor and basal salts, incubations with sediments retrieved from low tide period yielded a lower rate of methane oxidation than from high tide period. Overall, this study demonstrates that anaerobic methanotrophy in wetland sediments could proceed under various treatments of electron acceptors. Low sulfate content is not a critical factor in inhibiting methane

  3. Using Nitrogen and Oxygen Isotope Compositions of Nitrate to Distinguish Contaminant Sources in Hanford Soil and Groundwater

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Conrad, Mark; Bill, Markus

    2008-08-01

    The nitrogen ({delta}{sup 15}N) and oxygen ({delta}{sup 18}O) isotopic compositions of nitrate in the environment are primarily a function of the source of the nitrate. The ranges of isotopic compositions for nitrate resulting from common sources are outlined in Figure 1 from Kendall (1998). As noted on Figure 1, processes such as microbial metabolism can modify the isotopic compositions of the nitrate, but the effects of these processes are generally predictable. At Hanford, nitrate and other nitrogenous compounds were significant components of most of the chemical processes used at the site. Most of the oxygen in nitrate chemicals (e.g., nitricmore » acid) is derived from atmospheric oxygen, giving it a significantly higher {delta}{sup 18}O value (+23.5{per_thousand}) than naturally occurring nitrate that obtains most of its oxygen from water (the {delta}{sup 18}O of Hanford groundwater ranges from -14{per_thousand} to -18{per_thousand}). This makes it possible to differentiate nitrate from Hanford site activities from background nitrate at the site (including most fertilizers that might have been used prior to the Department of Energy plutonium production activities at the site). In addition, the extreme thermal and chemical conditions that occurred during some of the waste processing procedures and subsequent waste storage in select single-shell tanks resulted in unique nitrate isotopic compositions that can be used to identify those waste streams in soil and groundwater at the site (Singleton et al., 2005; Christensen et al., 2007). This report presents nitrate isotope data for soil and groundwater samples from the Hanford 200 Areas and discusses the implications of that data for potential sources of groundwater contamination.« less

  4. Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers, nitric acid, and reagent salts.

    PubMed

    Michalski, Greg; Kolanowski, Michelle; Riha, Krystin M

    2015-01-01

    Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ(15)N values of synthetic and natural nitrates were 0 ± 2 ‰ similar to the air N2 from which they are derived. The δ(18)O values of synthetic nitrates were 23 ± 3 ‰, similar to air O2, and natural nitrate fertilizer δ(18)O values (55 ± 5 ‰) were similar to those observed in atmospheric nitrate. The Δ(17)O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ(17)O values of 18 ± 2 ‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.

  5. Enhanced biodegradation of cyclotetramethylenetetranitramine (HMX) under mixed electron-acceptor condition.

    PubMed

    Boopathy, R

    2001-02-01

    The biodegradation of cyclotetramethylenetetranitramine, commonly known as 'high melting explosive' (HMX), under various electron-acceptor conditions was investigated using enrichment cultures developed from the anaerobic digester sludge of Thibodaux sewage treatment plant. The results indicated that the HMX was biodegraded under sulfate reducing, nitrate reducing, fermenting, methanogenic, and mixed electron accepting conditions. However, the rates of degradation varied among the various conditions studied. The fastest removal of HMX (from 22 ppm on day 0 to < 0.05 ppm on day 11) was observed under mixed electron-acceptor conditions, followed in order by sulfate reducing, fermenting, methanogenic, and nitrate reducing conditions. Under aerobic conditions, HMX was not biodegraded, which indicated that HMX degradation takes place under anaerobic conditions via reduction. HMX was converted to methanol and chloroform under mixed electron-acceptor conditions. This study showed evidence for HMX degradation under anaerobic conditions in a mixed microbial population system similar to any contaminated field sites, where a heterogeneous population exists.

  6. Effect of Acute Dietary Nitrate Consumption on Oxygen Consumption During Submaximal Exercise in Hypobaric Hypoxia.

    PubMed

    Carriker, Colin R; Mermier, Christine M; Van Dusseldorp, Trisha A; Johnson, Kelly E; Beltz, Nicholas M; Vaughan, Roger A; McCormick, James J; Cole, Nathan H; Witt, Christopher C; Gibson, Ann L

    2016-08-01

    Reduced partial pressure of oxygen impairs exercise performance at altitude. Acute nitrate supplementation, at sea level, may reduce oxygen cost during submaximal exercise in hypobaric hypoxia. Therefore, we investigated the metabolic response during exercise at altitude following acute nitrate consumption. Ten well-trained (61.0 ± 7.4 ml/kg/min) males (age 28 ± 7 yr) completed 3 experimental trials (T1, T2, T3). T1 included baseline demographics, a maximal aerobic capacity test (VO2max) and five submaximal intensity cycling determination bouts at an elevation of 1600 m. A 4-day dietary washout, minimizing consumption of nitrate-rich foods, preceded T2 and T3. In a randomized, double-blind, placebo-controlled, crossover fashion, subjects consumed either a nitrate-depleted beetroot juice (PL) or ~12.8 mmol nitrate rich (NR) beverage 2.5 hr before T2 and T3. Exercise at 3500 m (T2 and T3) via hypobaric hypoxia consisted of a 5-min warm-up (25% of normobaric VO2max) and four 5-min cycling bouts (40, 50, 60, 70% of normobaric VO2max) each separated by a 4-min rest period. Cycling RPM and watts for each submaximal bout during T2 and T3 were determined during T1. Preexercise plasma nitrite was elevated following NR consumption compared with PL (1.4 ± 1.2 and 0.7 ± 0.3 uM respectively; p < .05). There was no difference in oxygen consumption (-0.5 ± 1.8, 0.1 ± 1.7, 0.7 ± 2.1, and 1.0 ± 3.0 ml/kg/min) at any intensity (40, 50, 60, 70% of VO2max, respectively) between NR and PL. Further, respiratory exchange ratio, oxygen saturation, heart rate and rating of perceived exertion were not different at any submaximal intensity between NR and PL either. Blood lactate, however, was reduced following NR consumption compared with PL at 40 and 60% of VO2max (p < .0.05). Our findings suggest that acute nitrate supplementation before exercise at 3500 m does not reduce oxygen cost but may reduce blood lactate accumulation at lower intensity workloads.

  7. Autotrophic, hydrogen-oxidizing, denitrifying bacteria in groundwater, potential agents for bioremediation of nitrate contamination

    USGS Publications Warehouse

    Smith, R.L.; Ceazan, M.L.; Brooks, M.H.

    1994-01-01

    Addition of hydrogen or formate significantly enhanced the rate of consumption of nitrate in slurried core samples obtained from an active zone of denitrification in a nitrate-contaminated sand and gravel aquifer (Cape Cod, Mass.). Hydrogen uptake by the core material was immediate and rapid, with an apparent K(m) of 0.45 to 0.60 ??M and a V(max) of 18.7 nmol cm-3 h-1 at 30??C. Nine strains of hydrogen-oxidizing denitrifying bacteria were subsequently isolated from the aquifer. Eight of the strains grew autotrophically on hydrogen with either oxygen or nitrate as the electron acceptor. One strain grew mixotrophically. All of the isolates were capable of heterotrophic growth, but none were similar to Paracoccus denitrificans, a well-characterized hydrogen-oxidizing denitrifier. The kinetics for hydrogen uptake during denitrification were determined for each isolate with substrate depletion progress curves; the K(m)s ranged from 0.30 to 3.32 ??M, with V(max)s of 1.85 to 13.29 fmol cell-1 h-1. Because these organisms appear to be common constituents of the in situ population of the aquifer, produce innocuous end products, and could be manipulated to sequentially consume oxygen and then nitrate when both were present, these results suggest that these organisms may have significant potential for in situ bioremediation of nitrate contamination in groundwater.

  8. Microbiological oxidation of antimony(III) with oxygen or nitrate by bacteria isolated from contaminated mine sediments

    USGS Publications Warehouse

    Terry, Lee R.; Kulp, Thomas R.; Wiatrowski, Heather A.; Miller, Laurence G.; Oremland, Ronald S.

    2015-01-01

    Bacterial oxidation of arsenite [As(III)] is a well-studied and important biogeochemical pathway that directly influences the mobility and toxicity of arsenic in the environment. In contrast, little is known about microbiological oxidation of the chemically similar anion antimonite [Sb(III)]. In this study, two bacterial strains, designated IDSBO-1 and IDSBO-4, which grow on tartrate compounds and oxidize Sb(III) using either oxygen or nitrate, respectively, as a terminal electron acceptor, were isolated from contaminated mine sediments. Both isolates belonged to the Comamonadaceae family and were 99% similar to previously described species. We identify these novel strains as Hydrogenophagataeniospiralis strain IDSBO-1 and Variovorax paradoxus strain IDSBO-4. Both strains possess a gene with homology to the aioA gene, which encodes an As(III)-oxidase, and both oxidize As(III) aerobically, but only IDSBO-4 oxidized Sb(III) in the presence of air, while strain IDSBO-1 could achieve this via nitrate respiration. Our results suggest that expression of aioA is not induced by Sb(III) but may be involved in Sb(III) oxidation along with an Sb(III)-specific pathway. Phylogenetic analysis of proteins encoded by the aioA genes revealed a close sequence similarity (90%) among the two isolates and other known As(III)-oxidizing bacteria, particularly Acidovorax sp. strain NO1. Both isolates were capable of chemolithoautotrophic growth using As(III) as a primary electron donor, and strain IDSBO-4 exhibited incorporation of radiolabeled [14C]bicarbonate while oxidizing Sb(III) from Sb(III)-tartrate, suggesting possible Sb(III)-dependent autotrophy. Enrichment cultures produced the Sb(V) oxide mineral mopungite and lesser amounts of Sb(III)-bearing senarmontite as precipitates.

  9. Nitrate reduction in sulfate-reducing bacteria.

    PubMed

    Marietou, Angeliki

    2016-08-01

    Sulfate-reducing bacteria (SRBs) gain their energy by coupling the oxidation of organic substrate to the reduction of sulfate to sulfide. Several SRBs are able to use alternative terminal electron acceptors to sulfate such as nitrate. Nitrate-reducing SRBs have been isolated from a diverse range of environments. In order to be able to understand the significance of nitrate reduction in SRBs, we need to examine the ecology and physiology of the nitrate-reducing SRB isolates. © FEMS 2016. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  10. Transient exposure to oxygen or nitrate reveals ecophysiology of fermentative and sulfate‐reducing benthic microbial populations

    PubMed Central

    Saad, Sainab; Bhatnagar, Srijak; Tegetmeyer, Halina E.; Geelhoed, Jeanine S.; Strous, Marc

    2017-01-01

    Summary For the anaerobic remineralization of organic matter in marine sediments, sulfate reduction coupled to fermentation plays a key role. Here, we enriched sulfate‐reducing/fermentative communities from intertidal sediments under defined conditions in continuous culture. We transiently exposed the cultures to oxygen or nitrate twice daily and investigated the community response. Chemical measurements, provisional genomes and transcriptomic profiles revealed trophic networks of microbial populations. Sulfate reducers coexisted with facultative nitrate reducers or aerobes enabling the community to adjust to nitrate or oxygen pulses. Exposure to oxygen and nitrate impacted the community structure, but did not suppress fermentation or sulfate reduction as community functions, highlighting their stability under dynamic conditions. The most abundant sulfate reducer in all cultures, related to Desulfotignum balticum, appeared to have coupled both acetate‐ and hydrogen oxidation to sulfate reduction. We describe a novel representative of the widespread uncultured candidate phylum Fermentibacteria (formerly candidate division Hyd24‐12). For this strictly anaerobic, obligate fermentative bacterium, we propose the name ‘USabulitectum silens’ and identify it as a partner of sulfate reducers in marine sediments. Overall, we provide insights into the function of fermentative, as well as sulfate‐reducing microbial communities and their adaptation to a dynamic environment. PMID:28836729

  11. Long-Term Observations of Ocean Biogeochemistry with Nitrate and Oxygen Sensors in Apex Profiling Floats

    NASA Astrophysics Data System (ADS)

    Johnson, K. S.; Coletti, L.; Jannasch, H.; Martz, T.; Swift, D.; Riser, S.

    2008-12-01

    Long-term, autonomous observations of ocean biogeochemical cycles are now feasible with chemical sensors in profiling floats. These sensors will enable decadal-scale observations of trends in global ocean biogeochemical cycles. Here, we focus on measurements on nitrate and dissolved oxygen. The ISUS (In Situ Ultraviolet Spectrophotometer) optical nitrate sensor has been adapted to operate in a Webb Research, Apex profiling float. The Apex float is of the type used in the Argo array and is designed for multi-year, expendable deployments in the ocean. Floats park at 1000 m depth and make 60 nitrate and oxygen measurements at depth intervals ranging from 50 m below 400 m to 5 m in the upper 100 m as they profile to the surface. All data are transmitted to shore using the Iridium telemetry system and they are available on the Internet in near-real time. Floats equipped with ISUS and an Aanderaa oxygen sensor are capable of making 280 vertical profiles from 1000 m. At a 5 day cycle time, the floats should have nearly a four year endurance. Three floats have now been deployed at the Hawaii Ocean Time series station (HOT), Ocean Station Papa (OSP) in the Gulf of Alaska and at 50 South, 30 East in the Southern Ocean. Two additional floats are designated for deployment at the Bermuda Atlantic Time Series station (BATS) and in the Drake Passage. The HOT float has made 56 profiles over 260 days and should continue operating for 3 more years. Nitrate concentrations are in excellent agreement with the long-term mean observed at HOT. No significant long-term drift in sensor response has occurred. A variety of features have been observed in the HOT nitrate data that are linked to contemporaneous changes in oxygen production and mesoscale dynamics. The impacts of these features will be briefly described. The Southern Ocean float has operated for 200 days and is now observing reinjection of nitrate into surface waters as winter mixing occurs(surface nitrate > 24 micromolar). We

  12. Effect of nitrate concentration on filamentous bulking under low level of dissolved oxygen in an airlift inner circular anoxic-aerobic incorporate reactor.

    PubMed

    Su, Yiming; Zhang, Yalei; Zhou, Xuefei; Jiang, Ming

    2013-09-01

    This laboratory research investigated a possible cause of filamentous bulking under low level of dissolved oxygen conditions (dissolved oxygen value in aerobic zone maintained between 0.6-0.8 mg O2/L) in an airlift inner-circular anoxic-aerobic reactor. During the operating period, it was observed that low nitrate concentrations affected sludge volume index significantly. Unlike the existing hypothesis, the batch tests indicated that filamentous bacteria (mainly Thiothrix sp.) could store nitrate temporarily under carbon restricted conditions. When nitrate concentration was below 4 mg/L, low levels of carbon substrates and dissolved oxygen in the aerobic zone stimulated the nitrate-storing capacity of filaments. When filamentous bacteria riched in nitrate reached the anoxic zone, where they were exposed to high levels of carbon but limited nitrate, they underwent denitrification. However, when nonfilamentous bacteria were exposed to similar conditions, denitrification was restrained due to their intrinsic nitrate limitation. Hence, in order to avoid filamentous bulking, the nitrate concentration in the return sludge (from aerobic zone to the anoxic zone) should be above 4 mg/L, or alternatively, the nitrate load in the anoxic zone should be kept at levels above 2.7 mg NO(3-)-N/g SS.

  13. Understanding the response of Desulfovibrio desulfuricans ATCC 27774 to the electron acceptors nitrate and sulfate - biosynthetic costs modulate substrate selection.

    PubMed

    Sousa, Joana R; Silveira, Célia M; Fontes, Pedro; Roma-Rodrigues, Catarina; Fernandes, Alexandra R; Van Driessche, Gonzalez; Devreese, Bart; Moura, Isabel; Moura, José J G; Almeida, M Gabriela

    2017-11-01

    Sulfate-reducing bacteria (SRB) are a diverse group of anaerobic microorganisms that obtain their energy from dissimilatory sulfate reduction. Some SRB species have high respiratory versatility due to the possible use of alternative electron acceptors. A good example is Desulfovibrio desulfuricans ATCC 27774, which grows in the presence of nitrate (end product: ammonium) with higher rates and yields to those observed in sulfate containing medium (end product: sulfide). In this work, the mechanisms supporting the respiratory versatility of D. desulfuricans were unraveled through the analysis of the proteome of the bacterium under different experimental conditions. The most remarkable difference in the two-dimensional gel electrophoresis maps is the high number of spots exclusively represented in the nitrate medium. Most of the proteins with increase abundance are involved in the energy metabolism and the biosynthesis of amino acids (or proteins), especially those participating in ammonium assimilation processes. qPCR analysis performed during different stages of the bacterium's growth showed that the genes involved in nitrate and nitrite reduction (napA and nrfA, respectively) have different expressions profiles: while napA did not vary significantly, nrfA was highly expressed at a 6h time point. Nitrite levels measured along the growth curve revealed a peak at 3h. Thus, the initial consumption of nitrate and concomitant production of nitrite must induce nrfA expression. The activation of alternative mechanisms for energy production, aside several N-assimilation metabolisms and detoxification processes, solves potential survival problems in adapting to different environments and contributes to higher bacterial growth rates. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Emerging Technologies for Enhanced In Situ Biodenitrification of Nitrate Contaminated Ground Water

    NASA Astrophysics Data System (ADS)

    Faris, B.; Faris, B.

    2001-05-01

    One of the most pervasive ground water contaminants in the U.S. is nitrate. Traditional technologies for the remediation of nitrate-contaminated ground water are generally costly, lengthy, and often only partly effective. Enhanced in situ biodenitrification (EISBD) is a developing technology for remediating nitrate contaminated ground water and protecting public and domestic supply wells through in situ reduction. Natural denitrification processes have been well understood for some time. However, managing these processes to effectively remediated contaminated ground water in a timely fashion is innovative. EISBD is a remediation technology through which a carbon source (electron donor) is introduced to a nitrate-contaminated aquifer. Since many aquifers are aerobic, indigenous aerobic bacteria utilize the introduced carbon as a food source and oxygen serves as an electron acceptor. Oxygen in the aquifer becomes depleted, forming an anaerobic aquifer. When this occurs and an abundant carbon source is present, indigenous denitrifying bacteria proliferate and reduce nitrate to nitrogen gas through anaerobic respiration. EISBD technology deployments are currently underway for either remediation of sizable nitrate plumes in ground water systems or the reduction of nitrate contaminated ground water around public and/or domestic well fields dedicated to the production of drinking water. Regulatory enforcement of nitrate plumes has been limited. Pollution prevention programs are in place to limit further nitrate contamination, however, once a site becomes contaminated with nitrates above standards, the deployment of remediation technologies is lacking. With the development and further deployment of EISBD technologies, a cost-effective short-term tool is available for nitrate remediation. A multi-disciplinary team of the Interstate Technology Regulatory Cooperation published a Technology Overview guidance document on the emerging technology of EISBD. ITRC is a state

  15. Improvement of a microbial fuel cell performance as a BOD sensor using respiratory inhibitors.

    PubMed

    Chang, In Seop; Moon, Hyunsoo; Jang, Jae Kyung; Kim, Byung Hong

    2005-03-15

    Studies were made to improve the performance of a microbial fuel cell (MFC) as a biochemical oxygen demand (BOD) sensor. The signal from MFCs decreased in the presence of electron acceptors of higher redox potential such as nitrate and oxygen. The addition of azide and cyanide did not change the signal in the absence of the electron acceptors. The respiratory inhibitors eliminated the inhibitory effects of the electron acceptors on the current generation from MFCs. Similar results were obtained using oligotrophic MFCs fed with an environmental sample that contained nitrate. The use of the respiratory inhibitors is therefore recommended for the accurate BOD measurement of environmental samples containing nitrate and/or oxygen with an MFC-type BOD sensor.

  16. Respiratory Nitrate Ammonification by Shewanella oneidensis MR-1▿

    PubMed Central

    Cruz-García, Claribel; Murray, Alison E.; Klappenbach, Joel A.; Stewart, Valley; Tiedje, James M.

    2007-01-01

    Anaerobic cultures of Shewanella oneidensis MR-1 grown with nitrate as the sole electron acceptor exhibited sequential reduction of nitrate to nitrite and then to ammonium. Little dinitrogen and nitrous oxide were detected, and no growth occurred on nitrous oxide. A mutant with the napA gene encoding periplasmic nitrate reductase deleted could not respire or assimilate nitrate and did not express nitrate reductase activity, confirming that the NapA enzyme is the sole nitrate reductase. Hence, S. oneidensis MR-1 conducts respiratory nitrate ammonification, also termed dissimilatory nitrate reduction to ammonium, but not respiratory denitrification. PMID:17098906

  17. Transient exposure to oxygen or nitrate reveals ecophysiology of fermentative and sulfate-reducing benthic microbial populations.

    PubMed

    Saad, Sainab; Bhatnagar, Srijak; Tegetmeyer, Halina E; Geelhoed, Jeanine S; Strous, Marc; Ruff, S Emil

    2017-12-01

    For the anaerobic remineralization of organic matter in marine sediments, sulfate reduction coupled to fermentation plays a key role. Here, we enriched sulfate-reducing/fermentative communities from intertidal sediments under defined conditions in continuous culture. We transiently exposed the cultures to oxygen or nitrate twice daily and investigated the community response. Chemical measurements, provisional genomes and transcriptomic profiles revealed trophic networks of microbial populations. Sulfate reducers coexisted with facultative nitrate reducers or aerobes enabling the community to adjust to nitrate or oxygen pulses. Exposure to oxygen and nitrate impacted the community structure, but did not suppress fermentation or sulfate reduction as community functions, highlighting their stability under dynamic conditions. The most abundant sulfate reducer in all cultures, related to Desulfotignum balticum, appeared to have coupled both acetate- and hydrogen oxidation to sulfate reduction. We describe a novel representative of the widespread uncultured candidate phylum Fermentibacteria (formerly candidate division Hyd24-12). For this strictly anaerobic, obligate fermentative bacterium, we propose the name ' U Sabulitectum silens' and identify it as a partner of sulfate reducers in marine sediments. Overall, we provide insights into the function of fermentative, as well as sulfate-reducing microbial communities and their adaptation to a dynamic environment. © 2017 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

  18. Spectroscopic Study of Deep Level Emissions from Acceptor Defects in ZnO Thin Films with Oxygen Rich Stoichiometry

    NASA Astrophysics Data System (ADS)

    Ilyas, Usman; Rawat, R. S.; Tan, T. L.

    2013-10-01

    This paper reports the tailoring of acceptor defects in oxygen rich ZnO thin films at different post-deposition annealing temperatures (500-800°C) and Mn doping concentrations. The XRD spectra exhibited the nanocrystalline nature of ZnO thin films along with inconsistent variation in lattice parameters suggesting the temperature-dependent activation of structural defects. Photoluminescence emission spectra revealed the temperature dependent variation in deep level emissions (DLE) with the presence of acceptors as dominating defects. The concentration of native defects was estimated to be increased with temperature while a reverse trend was observed for those with increasing doping concentration. A consistent decrease in DLE spectra, with increasing Mn content, revealed the quenching of structural defects in the optical band gap of ZnO favorable for good quality thin films with enhanced optical transparency.

  19. Tracing the Impact of Aviation on the Atmospheric Nitrate With Oxygen Triple Isotopes

    NASA Astrophysics Data System (ADS)

    Shaheen, R.; Jackson, T. L.; Chan, S.; Hill, A.; Chakraborty, S.; Thiemens, M. H.

    2014-12-01

    The aviation industry is responsible for ~ 5% of anthropogenic climate change. Jet emission affects ~ in 25 mile radii from airports produce fine particles and concomitant pulmonary and cardio-vascular diseases. These unregulated emissions are of particular concerns for the health of local residents and environment in general due to rapid increase in worldwide air travel in 21st century. The accurate measurement of emissions from airports therefore requires development of new tools that quantification of aviation related emissions against other road traffic and hence to assess its local and global impacts and provide deeper understanding of nitrate in the environment in general, including the stratosphere where contrails are inadequately detailed Triple oxygen isotopic analysis of particulate nitrate from a DC 8 engine during a controlled experiment in Palmdale, CA documented the emission of nitric acid (~31 ng.m-3) at ~ 1m. The oxygen triple isotopic composition of nitrate emitted directly from the jet had δ18O values (22±1‰) identical to air O2 (δ18O = 23.5‰) with a mass dependent isotopic signature (Δ17O = 0), thus providing a unique isotopic signature of jet nitrate. A year long sampling campaign at one of the world's busiest airports, the Los Angeles International airport showed the contribution of NO3 varies from 60 to 90% in summer and winter with variations largely attributed to the change in road traffic as air traffic remains fairly constant throughout the year at LAX. The next step in this is to detect these contributions at distal sites and use this as a signal carrier of atmospheric nitrate and its transport in general in the global biogeochemical system. These aspects will be discussed in the presentation.

  20. Fractionation of Nitrogen and Oxygen Isotopes and Roles of Bacteria during Denitrification

    NASA Astrophysics Data System (ADS)

    Kang, J.; Buyanjargal, A.; Jeen, S. W.

    2017-12-01

    Nitrate in groundwater can cause health and environmental problems when not properly treated. The purpose of this study was to develop a treatment method for nitrate in groundwater using organic carbon-based reactive mixtures (i.e., wood chips and gravel) through column experiments and to evaluate reaction mechanisms responsible for the treatment. The column experiments were operated for a total of 19 months. The results from the geochemical analyses for the experiments suggest that cultures of denitrifying bacteria used organic carbon while utilizing nitrate as their electron acceptor via denitrification process. Proteobacteria was the most abundant phylum in all samples, accounting for 45.7% of the bacterial reads, followed by Firmicutes (22.6%) and Chlorobi (10.6%). Bacilli, Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, and Actinobacteria_c consisted of 32, 30, 23, 11, and 2% of denitrifying bacteria class. The denitrification process caused fractionation of nitrogen and oxygen isotopes of nitrate while nitrate concentration decreased. When fitted to the Rayleigh's fractionation model, enrichment factors (ɛ) were 11.5‰ and 5.6‰ for 15N and 18O isotopes, respectively. Previous studies suggested that nitrogen isotope enrichment factors of denitrification are within the range of 4.7 to 40‰ and oxygen isotopic enrichment factors are between 8 and 18.3‰. This study shows that nitrate in groundwater can be effectively treated using passive treatment systems, such as permeable reactive barriers (PRBs), and denitrificaton is the dominant process reponsible for the removal of nitrate.

  1. Insights on alterations to the rumen ecosystem by nitrate and nitrocompounds

    USDA-ARS?s Scientific Manuscript database

    Nitrate and certain short chain nitrocompounds are being investigated as dietary supplements to reduce economic and environmental costs associated with ruminal methane emissions. Thermodynamically, nitrate is a preferred electron acceptor in the rumen that consumes electrons at the expense of metha...

  2. Bayesian Nitrate Source Apportionment to Individual Groundwater Wells in the Central Valley by use of Nitrogen, Oxygen, and Boron Isotopic Tracers

    NASA Astrophysics Data System (ADS)

    Lockhart, K.; Harter, T.; Grote, M.; Young, M. B.; Eppich, G.; Deinhart, A.; Wimpenny, J.; Yin, Q. Z.

    2014-12-01

    Groundwater quality is a concern in alluvial aquifers underlying agricultural areas worldwide, an example of which is the San Joaquin Valley, California. Nitrate from land applied fertilizers or from animal waste can leach to groundwater and contaminate drinking water resources. Dairy manure and synthetic fertilizers are the major sources of nitrate in groundwater in the San Joaquin Valley, however, septic waste can be a major source in some areas. As in other such regions around the world, the rural population in the San Joaquin Valley relies almost exclusively on shallow domestic wells (≤150 m deep), of which many have been affected by nitrate. Consumption of water containing nitrate above the drinking water limit has been linked to major health effects including low blood oxygen in infants and certain cancers. Knowledge of the proportion of each of the three main nitrate sources (manure, synthetic fertilizer, and septic waste) contributing to individual well nitrate can aid future regulatory decisions. Nitrogen, oxygen, and boron isotopes can be used as tracers to differentiate between the three main nitrate sources. Mixing models quantify the proportional contributions of sources to a mixture by using the concentration of conservative tracers within each source as a source signature. Deterministic mixing models are common, but do not allow for variability in the tracer source concentration or overlap of tracer concentrations between sources. Bayesian statistics used in conjunction with mixing models can incorporate variability in the source signature. We developed a Bayesian mixing model on a pilot network of 32 private domestic wells in the San Joaquin Valley for which nitrate as well as nitrogen, oxygen, and boron isotopes were measured. Probability distributions for nitrogen, oxygen, and boron isotope source signatures for manure, fertilizer, and septic waste were compiled from the literature and from a previous groundwater monitoring project on several

  3. Bioreactor performance and functional gene analysis of microbial community in a limited-oxygen fed bioreactor for co-reduction of sulfate and nitrate with high organic input.

    PubMed

    Xu, Xi-jun; Chen, Chuan; Wang, Ai-jie; Yu, Hao; Zhou, Xu; Guo, Hong-liang; Yuan, Ye; Lee, Duu-jong; Zhou, Jizhong; Ren, Nan-qi

    2014-08-15

    Limited-oxygen mediated synergistic relationships between sulfate-reducing bacteria (SRB), nitrate-reducing bacteria (NRB) and sulfide-oxidizing bacteria (SOB, including nitrate-reducing, sulfide-oxidizing bacteria NR-SOB) were predicted to simultaneously remove contaminants of nitrate, sulfate and high COD, and eliminate sulfide generation. A lab-scale experiment was conducted to examine the impact of limited oxygen on these oxy-anions degradation, sulfide oxidation and associated microbial functional responses. In all scenarios tested, the reduction of both nitrate and sulfate was almost complete. When limited-oxygen was fed into bioreactors, S(0) formation was significantly improved up to ∼ 70%. GeoChip 4.0, a functional gene microarray, was used to determine the microbial gene diversity and functional potential for nitrate and sulfate reduction, and sulfide oxidation. The diversity of the microbial community in bioreactors was increased with the feeding of limited oxygen. Whereas the intensities of the functional genes involved in sulfate reduction did not show a significant difference, the abundance of the detected denitrification genes decreased in limited oxygen samples. More importantly, sulfide-oxidizing bacteria may alter their populations/genes in response to limited oxygen potentially to function more effectively in sulfide oxidation, especially to elemental sulfur. The genes fccA/fccB from nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB), such as Paracoccus denitrificans, Thiobacillus denitrificans, Beggiatoa sp., Thiomicrospira sp., and Thioalkalivibrio sp., were more abundant under limited-oxygen condition. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Influence of dissolved oxygen conditions on toxicity of ammonium nitrate to larval natterjack toads.

    PubMed

    Ortiz-Santaliestra, Manuel E; Marco, Adolfo

    2015-07-01

    Temporary ponds, where many amphibians from temperate regions breed, show an annual cycle with a maximum water volume in spring followed by a progressive desiccation throughout late spring and summer. This desiccation leads to a decrease in dissolved oxygen and an increase in nitrogen levels, which can additionally increase because of anthropogenic sources such as chemical fertilizers. We analyzed the toxicity posed by environmentally relevant levels of a common nitrogenous fertilizer, ammonium nitrate, at different conditions of oxygen availability to Bufo calamita tadpoles, which typically develop in ephemeral ponds. Ammonium nitrate (90.3 mg N-NO3NH4/l) and hypoxic conditions (initial dissolved oxygen 4.53 ± 0.40 mg/l) caused significant lethal effects after 7 and 12 days of exposure, respectively. At the end of experiment (16 days), mortality rates were 32.5 % in individuals exposed to the fertilizer and 15 % in those growing under hypoxic conditions. When both stressors were combined, they showed an additive effect on tadpole survival. Malformations, such as oedemas and spinal curvatures, and locomotory abnormalities, were detected after 12 days of experiment in >90 % of individuals exposed to 45.2 mg N-NO3NH4/l under hypoxic conditions, whereas none of these stressors by separate related to abnormality rates >35 %. Delayed development was also observed in tadpoles exposed to ammonium nitrate with hypoxia affecting developmental rate only after 12 days of exposure. The results are discussed in terms of potential mechanisms linking negative effects of both factors as well as in terms of potential alterations of the ecological plasticity that often allows amphibians to survive in unpredictable environments.

  5. Cytochrome components of nitrate- and sulfate-respiring Desulfovibrio desulfuricans ATCC 27774.

    PubMed Central

    Liu, M C; Costa, C; Coutinho, I B; Moura, J J; Moura, I; Xavier, A V; LeGall, J

    1988-01-01

    Three multiheme c-type cytochromes--the tetraheme cytochrome c3 (molecular weight [MW] 13,500), a dodecaheme cytochrome c (MW 40,800), and a "split-Soret" cytochrome c (MW 51,540), which is a dimer with 2 hemes per subunit (MW 26,300)--were isolated from the soluble fraction of Desulfovibrio desulfuricans (ATCC 27774) grown under nitrate- or sulfate-respiring conditions. Two of them, the dodecaheme and the split-Soret cytochromes, showed no similarities to any of the c-type cytochromes isolated from other sulfate-reducing bacteria, while the tetraheme cytochrome c3 appeared to be analogous to the cytochrome c3 found in other sulfate-reducing bacteria. For all three multiheme c-type cytochromes isolated, the homologous proteins from nitrate- and sulfate-grown cells were indistinguishable in amino acid composition, physical properties, and spectroscopic characteristics. It therefore appears that the same c-type cytochrome components are present when D. desulfuricans ATCC 27774 cells are grown under either condition. This is in contrast to the considerable difference found in Pseudomonas perfectomarina (Liu et al., J. Bacteriol. 154:278-286, 1983), a marine denitrifier, when the cells are grown on nitrate or oxygen as the terminal electron acceptor. In addition, two spectroscopy methods capable of revealing minute structural variations in proteins provided identical information about the tetraheme cytochrome c3 from nitrate-grown and sulfate-grown cells. PMID:2848008

  6. Description of strain 3CB-1, a genomovar of Thauera aromatica, capable of degrading 3-chlorobenzoate coupled to nitrate reduction.

    PubMed

    Song, B; Palleroni, N J; Häggblom, M M

    2000-03-01

    A Gram-negative bacterium, strain 3CB-1, isolated from a 3-chlorobenzoate enrichment culture inoculated with a sediment sample is capable of degrading various aromatic compounds and halogenated derivatives with nitrate as electron acceptor. Compounds capable of serving as carbon and energy sources include 3-chlorobenzoate, 3-bromobenzoate, 2-fluorobenzoate, 4-fluorobenzoate, benzoate, 3-hydroxybenzoate, 4-hydroxybenzoate, 3-aminobenzoate, protocatechuate, m-cresol and p-cresol. Oxygen, nitrate and nitrite were used as electron acceptors for growth. Cells are Gram-negative short rods with peritrichous flagellation. The predominant fatty acids are cis-9-hexadecenoic acid (16:1 omega 7c), hexadecanoic acid (16:0), octadecanoic acid (18:0), octadecenoic acid (18:1), 3-hydroxydecanoic acid (10:0 3OH) and dodecanoic acid (12:0). The sequence of the 16S rRNA gene, as well as the fatty acid composition, indicate that the strain is a member of the genus Thauera in the beta-subclass of the Proteobacteria and very close to Thauera aromatica. DNA-DNA hybridization and nutrient screening indicate that strain 3CB-1 is a genomovar of Thauera aromatica with the proposed name Thauera aromatica genomovar chlorobenzoica.

  7. Controlled temperature expansion in oxygen production by molten alkali metal salts

    DOEpatents

    Erickson, Donald C.

    1985-06-04

    A continuous process is set forth for the production of oxygen from an oxygen containing gas stream, such as air, by contacting a feed gas stream with a molten solution of an oxygen acceptor to oxidize the acceptor and cyclically regenerating the oxidized acceptor by releasing oxygen from the acceptor wherein the oxygen-depleted gas stream from the contact zone is treated sequentially to temperature reduction by heat exchange against the feed stream so as to condense out entrained oxygen acceptor for recycle to the process, combustion of the gas stream with fuel to elevate its temperature and expansion of the combusted high temperature gas stream in a turbine to recover power.

  8. Controlled temperature expansion in oxygen production by molten alkali metal salts

    DOEpatents

    Erickson, D.C.

    1985-06-04

    A continuous process is set forth for the production of oxygen from an oxygen containing gas stream, such as air, by contacting a feed gas stream with a molten solution of an oxygen acceptor to oxidize the acceptor and cyclically regenerating the oxidized acceptor by releasing oxygen from the acceptor wherein the oxygen-depleted gas stream from the contact zone is treated sequentially to temperature reduction by heat exchange against the feed stream so as to condense out entrained oxygen acceptor for recycle to the process, combustion of the gas stream with fuel to elevate its temperature and expansion of the combusted high temperature gas stream in a turbine to recover power. 1 fig.

  9. A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios

    USGS Publications Warehouse

    Silva, S.R.; Kendall, C.; Wilkison, D.H.; Ziegler, A.C.; Chang, Cecily C.Y.; Avanzino, R.J.

    2000-01-01

    A new method for concentrating nitrate from fresh waters for ??15N and ??18O analysis has been developed and field-tested for four years. The benefits of the method are: (1) elimination of the need to transport large volumes of water to the laboratory for processing; (2) elimination of the need for hazardous preservatives; and (3) the ability to concentrate nitrate from fresh waters. Nitrate is collected by, passing the water-sample through pre-filled, disposable, anion exchanging resin columns in the field. The columns are subsequently transported to the laboratory where the nitrate is extracted, converted to AgNO3 and analyzed for its isotope composition. Nitrate is eluted from the anion exchange columns with 15 ml of 3 M HCl. The nitrate-bearing acid eluant is neutralized with Ag2O, filtered to remove the AgCl precipitate, then freeze-dried to obtain solid AgNO3, which is then combusted to N2 in sealed quartz tubes for ?? 15N analysis. For ?? 18O analysis, aliquots of the neutralized eluant are processed further to remove non-nitrate oxygen-bearing anions and dissolved organic matter. Barium chloride is added to precipitate sulfate and phosphate; the solution is then filtered, passed through a cation exchange column to remove excess Ba2+, re-neutralized with Ag2O, filtered, agitated with activated carbon to remove dissolved organic matter and freeze-dried. The resulting AgNO3 is combusted with graphite in a closed tube to produce CO2, which is cryogenically purified and analyzed for its oxygen isotope composition. The 1?? analytical precisions for ??15N and ??18O are ?? 0.05%o and ??0.5???, respectively, for solutions of KNO3 standard processed through the entire column procedure. High concentrations of anions in solution can interfere with nitrate adsorption on the anion exchange resins, which may result in isotope fractionation of nitrogen and oxygen (fractionation experiments were conducted for nitrogen only; however, fractionation for oxygen is expected

  10. Tracing seasonal nitrate sources and loads in the San Joaquin River using nitrogen and oxygen stable isotopes

    NASA Astrophysics Data System (ADS)

    Young, M. B.; Kendall, C.; Silva, S.; Stringfellow, W. T.; Dahlgren, R. A.

    2007-12-01

    The San Joaquin River (SJR) is a heavily impacted river draining a major agricultural basin in central California. This river receives nitrate inputs from multiple point and non-point sources including agriculture, livestock, waste water treatment plants, septic systems, urban run-off, and natural soil leaching. Nitrate inputs to the SJR may play a significant role in driving algal blooms and reducing overall water quality. The San Joaquin River discharges into the San Francisco Bay-Delta ecosystem, and reduced water quality and large algal blooms in the SJR may play a significant role in driving critically low oxygen levels in the Stockton Deep Water Shipping Channel. Correct identification of the major nitrate sources to the SJR is important for coordinating mitigation efforts throughout the SJR-Delta-San Francisco Bay region. Measurements of the nitrogen and oxygen isotopic composition of nitrate were made monthly to bimonthly from 2005 through 2007 within the Lower SJR, major tributaries, and various other water input sources in order to assess spatial and temporal variations in nitrate inputs and cycling in this heavily impacted watershed. The oxygen and hydrogen isotopic composition of water was also measured to better distinguish water sources and identify changes in water inputs. A very wide range of δ15N-NO3 and δ18O-NO3 values were observed in the main stem SJR and tributaries. The δ15N values ranged from +2 to +17 ‰, and the δ18O values ranged from -1 to +18 ‰. Except for a major agricultural drain site (San Luis Drain), all the sites showed temporal changes in both δ15N-NO3 and δ18O-NO3 much greater than the differences seen between individual sites. In general, the δ15N values of nitrate in the larger tributary rivers (Merced, Tuolumne and Stanislaus) were much lower than those of the main stem SJR from April to May; however, after June the tributary values began to rise toward the values in the main stem river. Some of the highest δ15N-NO3

  11. Nitrate-Containing Beetroot Juice Reduces Oxygen Consumption During Submaximal Exercise in Low but Not High Aerobically Fit Male Runners.

    PubMed

    Carriker, Colin R; Vaughan, Roger A; VanDusseldorp, Trisha A; Johnson, Kelly E; Beltz, Nicholas M; McCormick, James J; Cole, Nathan H; Gibson, Ann L

    2016-12-31

    to examine the effect of a 4-day NO3- loading protocol on the submaximal oxygen cost of both low fit and high fit participants at five different exercise intensities. participants were initially assigned to a placebo (PL; negligible NO3-) or inorganic nitrate-rich (NR; 6.2 mmol nitrate/day) group; double-blind, placebo-controlled, crossover. Participants completed three trials (T1, T2 and T3). T1 included a maximal aerobic capacity (VO2max) treadmill test. A 6-day washout, minimizing nitrate consumption, preceded T2. Each of the four days prior to T2 and T3, participants consumed either PL or NR; final dose 2.5 hours prior to exercise. A 14-day washout followed T2. T2 and T3 consisted of 5-minute submaximal treadmill bouts (45, 60, 70, 80 and 85% VO2max) determined during T1. Low fit nitrate-supplemented participants consumed less oxygen (p<0.05) at lower workloads (45% and 60% VO2max) compared to placebo trials; changes not observed in high fit participants. The two lowest intensity workloads of 45 and 60% VO2max revealed the greatest correlation (r=0.54, p=0.09 and r=0.79, p<0.05; respectively). No differences were found between conditions for heart rate, respiratory exchange ratio or rating of perceived exertion for either fitness group. Nitrate consumption promotes reduced oxygen consumption at lower exercise intensities in low fit, but not high fit males. Lesser fit individuals may receive greater benefit than higher fit participants exercising at intensities <60% VO2max.

  12. Simulating biodegradation of toluene in sand column experiments at the macroscopic and pore-level scale for aerobic and denitrifying conditions

    NASA Astrophysics Data System (ADS)

    Kim, Hyun-su; Jaffé, Peter R.; Young, Lily Y.

    2004-04-01

    Heterotropic bacteria can degrade organic substrates utilizing different terminal electron acceptors. The sequence of electron acceptor utilization depends on the energy yield of the individual reaction pathway, which decreases as the redox potential decreases. Due to these differences in energy yield, and an inhibiting activity of oxygen on some enzymatic processes, the simultaneous utilization of oxygen and nitrate as terminal electron acceptors may not occur for many degradation processes, unless the oxygen concentration falls below a given threshold level (about 0.2 mg/l). Two sand column experiments were conducted, with toluene as the carbon source, and showed an apparent simultaneous utilization of oxygen and nitrate as electron acceptors in regions where the oxygen concentration was significantly higher (⩾1.1 mg/l) than the above mentioned threshold concentration. Results from aerobic and anaerobic plate-count analyses showed growth of both aerobes and denitrifiers in the zone of the column where simultaneous utilization of oxygen and nitrate was observed. From these observations, it was postulated that the porous media contained oxygen-free microlocations where the denitrifiers were able to degrade the toluene. To simulate the observed dynamics, a dual biofilm model was implemented. This model formulation assumes that the biofilm is composed of two distinct layers, where the outer layer is colonized by aerobic bacteria and the inner layer by denitrifying bacteria. The thickness of the aerobic layer is such that oxygen is depleted at the boundary of these two layers, resulting in oxygen-free microlocations that allows denitrification to proceed, even though oxygen is still present in the bulk fluid phase. The model simulations compared well to the experimental profiles. Model analyses indicated that changes in physical, chemical, and hydrologic parameters could change the length and location of the zone where at the macroscopic level, oxygen and nitrate

  13. Nitrate-containing beetroot juice reduces oxygen consumption during submaximal exercise in low but not high aerobically fit male runners

    PubMed Central

    Carriker, Colin R.; Vaughan, Roger A.; VanDusseldorp, Trisha A.; Johnson, Kelly E.; Beltz, Nicholas M.; McCormick, James J.; Cole, Nathan H.; Gibson, Ann L.

    2016-01-01

    [Purpose] To examine the effect of a 4-day NO3- loading protocol on the submaximal oxygen cost of both low fit and high fit participants at five different exercise intensities. [Methods] Eleven (6 high fit, VO2max 60.1 ± 4.6ml/kg/min; 5 low fit, VO2max 42.4 ± 3.2ml/ kg/min) participants were initially assigned to a placebo (PL; negligible NO3-) or inorganic nitrate-rich (NR; 6.2 mmol nitrate/day) group using a double-blind, placebo-controlled, crossover design. Participants completed three trials (T1, T2 and T3). T1 included a maximal aerobic capacity (VO2max) treadmill test. A 6-day washout, minimizing nitrate consumption, preceded T2. Each of the four days prior to T2 and T3, participants consumed either PL or NR with the final dose 2.5 hours prior to exercise. A 14-day washout followed T2. T2 and T3 consisted of 5-minute submaximal treadmill bouts (45, 60, 70, 80 and 85% VO2max) determined during T1. [Results] Low fit nitrate-supplemented participants consumed less oxygen (p<0.05) at lower workloads (45% and 60% VO2max) compared to placebo trials; changes were not observed in high fit participants. The two lowest intensity workloads of 45 and 60% VO2max revealed the greatest correlation (r=0.54, p=0.09 and r=0.79, p<0.05; respectively) between VO2max and change in oxygen consumption. No differences were found between conditions for heart rate, respiratory exchange ratio or rating of perceived exertion for either fitness group. [Conclusion] Nitrate consumption promotes reduced oxygen consumption at lower exercise intensities in low fit, but not high fit males. Lesser fit individuals may receive greater benefit than higher fit participants exercising at intensities <60% VO2max. PMID:28150476

  14. 'Low-acid' sulfide oxidation using nitrate-enriched groundwater

    NASA Astrophysics Data System (ADS)

    Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

    2016-04-01

    where pH remains neutral. The "low-acid" oxidation of sulfides with nitrate as an electron acceptor has been demonstrated at the laboratory scale. In 90-day microcosm respirometry experiments, we exposed a mixture of pulverized quartz and pyrite -rich ore to natural, high-nitrate groundwater and inoculated the microcosms with a culture of aerobic and anaerobic nitrate-dependent iron and sulfur-oxidising microorganisms, which were enriched from ore, groundwater and activated waste water. Incubations were performed under both oxic and anoxic conditions, in addition to abiotic controls. Initial results show that oxidation of the sulfides under nitrate-rich and microbially enhanced conditions does produce less acid than the same material under oxic conditions, and to some degree can match the models as long as oxygen ingress can be controlled. These results are the focus of further research into how this process can be enhanced and whether it can be applied in the field. Nitrate-driven oxidation of sulfides could potentially be used as a new approach to reduce acid generation and leaching of contaminants from waste dumps, in a passive or actively managed process designed to deplete and/or ameliorate (i.e. through surface passivation) the mineralogical hazard. Developing our understanding of biological aspects of these processes may also allow testing of longer-term "bio-caps" for various tailings and dump materials.

  15. Nitrating reactive nitric oxygen species transform acetaminophen to 3-nitroacetaminophen.

    PubMed

    Lakshmi, V M; Hsu, F F; Davis, B B; Zenser, T V

    2000-09-01

    Nitrating reactive nitric oxygen species (RNOS) elicit many of the deleterious effects of the inflammatory response. Their high reactivity and short half-life make RNOS analysis difficult. Reaction of acetaminophen (APAP) with RNOS generated by various conditions was evaluated by HPLC. When [(14)C]APAP was incubated at pH 7.4, the same new product (3NAP) was produced by at least three separate pathways represented by the following conditions: myeloperoxidase oxidation of NO(2)(-), NO(2)Cl, and ONOO(-) or Sin-1. Diethylamine NONO and spermine NONO did not convert APAP to 3NAP. 3NAP was stable at pH 5, 7.4, or 9, and at pH 7.4 with ONOO(-), spermine NONO, Sin-1, or H(2)O(2). HOCl transformed 3NAP, which was prevented by APAP, ascorbic acid, taurine, or NO(2)(-). ONOO(-)-derived 3NAP was identified by (1)H NMR as 3-nitroacetaminophen or 3-nitro-N-acetyl-p-aminophenol, and the product mass was verified by EI/ESI mass spectrometry. Human polymorphonuclear neutrophils incubated with [(14)C]APAP and stimulated with beta-phorbol 12-myristate 13-acetate produced 3NAP in the presence of NO(2)(-). Neutrophil 3NAP formation was verified by mass spectrometry and was consistent with myeloperoxidase oxidation of NO(2)(-). Spermine NONO supported 3NAP formation by stimulated cells in the absence of NO(2)(-). Results demonstrate that 3NAP is a product of nitrating RNOS generated by at least three separate pathways and may be a biomarker for nitrating mediators of inflammation.

  16. CONTROLLED FIELD STUDY ON THE USE OF NITRATE AND OXYGEN FOR BIOREMEDIATION OF A GASOLINE SOURCE ZONE

    EPA Science Inventory

    Controlled releases of unleaded gasoline were used to evaluate the biotransformation of the soluble aromatic hydrocarbons (benzene, toluene, ethylbenzene, xylene isomers, trimethylbenzene isomers, and naphthalene) within a source zone using nitrate and oxygen as electron accepto...

  17. Using rates of oxygen and nitrate reduction to map the subsurface distribution of groundwater denitrification

    NASA Astrophysics Data System (ADS)

    Kolbe, T.; De Dreuzy, J. R.; Abbott, B. W.; Aquilina, L.; Babey, T.; Green, C. T.; Fleckenstein, J. H.; Labasque, T.; Laverman, A.; Marçais, J.; Peiffer, S.; Thomas, Z.; Pinay, G.

    2017-12-01

    Widespread fertilizer application over the last 70 years has caused serious ecological and socioeconomic problems in aquatic and estuarine ecosystems. When surplus nitrogen leaches as nitrate (a major groundwater pollutant) to the aquifer, complex flow dynamics and naturally occurring degradation processes control its transport. Under the conditions of depleted oxygen and abundant electron donors, microorganisms reduce NO3- to N2 (denitrification). Denitrification rates vary over orders of magnitude among sites within the same aquifer, complicating estimation of denitrification capacity at the catchment scale. Because it is impractical or impossible to access the subsurface to directly quantify denitrification rates, reactivity is often assumed to occur continuous along flowlines, potentially resulting in substantial over- or underestimation of denitrification. Here we investigated denitrification in an unconfined crystalline aquifer in western France using a combination of common tracers (chlorofluorocarbons, O2, NO3-, and N2) measured in 16 wells to inform a time-based modeling approach. We found that spatially variable denitrification rates arise from the intersection of nitrate rich water with reactive zones defined by the abundance of electron donors (primarily pyrite). Furthermore, based on observed reaction rates of the sequential reduction of oxygen and nitrate, we present a general framework to estimate the location and intensity of the reactive zone in aquifers. Accounting for the vertical distribution of reaction rates results in large differences in estimations of net denitrification rates that assume homogeneous reactivity. This new framework provides a tractable approach for quantifying catchment and regional groundwater denitrification rates that could be used to improve estimation of groundwater resilience to nitrate pollution and develop more realistic management strategies.

  18. Total electron acceptor loading and composition affect hexavalent uranium reduction and microbial community structure in a membrane biofilm reactor.

    PubMed

    Ontiveros-Valencia, Aura; Zhou, Chen; Ilhan, Zehra Esra; de Saint Cyr, Louis Cornette; Krajmalnik-Brown, Rosa; Rittmann, Bruce E

    2017-11-15

    Molecular microbiology tools (i.e., 16S rDNA gene sequencing) were employed to elucidate changes in the microbial community structure according to the total electron acceptor loading (controlled by influent flow rate and/or medium composition) in a H 2 -based membrane biofilm reactor evaluated for removal of hexavalent uranium. Once nitrate, sulfate, and dissolved oxygen were replaced by U(VI) and bicarbonate and the total acceptor loading was lowered, slow-growing bacteria capable of reducing U(VI) to U(IV) dominated in the biofilm community: Replacing denitrifying bacteria Rhodocyclales and Burkholderiales were spore-producing Clostridiales and Natranaerobiales. Though potentially competing for electrons with U(VI) reducers, homo-acetogens helped attain steady U(VI) reduction, while methanogenesis inhibited U(VI) reduction. U(VI) reduction was reinstated through suppression of methanogenesis by addition of bromoethanesulfonate or by competition from SRB when sulfate was re-introduced. Predictive metagenome analysis further points out community changes in response to alterations in the electron-acceptor loading: Sporulation and homo-acetogenesis were critical factors for strengthening stable microbial U(VI) reduction. This study documents that sporulation was important to long-term U(VI) reduction, whether or not microorganisms that carry out U(VI) reduction mediated by cytochrome c 3 , such as SRB and ferric-iron-reducers, were inhibited. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. 27 CFR 555.220 - Table of separation distances of ammonium nitrate and blasting agents from explosives or blasting...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... distances of ammonium nitrate and blasting agents from explosives or blasting agents. 555.220 Section 555... ammonium nitrate and blasting agents from explosives or blasting agents. Table: Department of Defense... Not over Minimum separation distance of acceptor from donor when barricaded (ft.) Ammonium nitrate...

  20. 27 CFR 555.220 - Table of separation distances of ammonium nitrate and blasting agents from explosives or blasting...

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... distances of ammonium nitrate and blasting agents from explosives or blasting agents. 555.220 Section 555... ammonium nitrate and blasting agents from explosives or blasting agents. Table: Department of Defense... Not over Minimum separation distance of acceptor from donor when barricaded (ft.) Ammonium nitrate...

  1. 27 CFR 555.220 - Table of separation distances of ammonium nitrate and blasting agents from explosives or blasting...

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... distances of ammonium nitrate and blasting agents from explosives or blasting agents. 555.220 Section 555... ammonium nitrate and blasting agents from explosives or blasting agents. Table: Department of Defense... Not over Minimum separation distance of acceptor from donor when barricaded (ft.) Ammonium nitrate...

  2. 27 CFR 555.220 - Table of separation distances of ammonium nitrate and blasting agents from explosives or blasting...

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... distances of ammonium nitrate and blasting agents from explosives or blasting agents. 555.220 Section 555... ammonium nitrate and blasting agents from explosives or blasting agents. Table: Department of Defense... Not over Minimum separation distance of acceptor from donor when barricaded (ft.) Ammonium nitrate...

  3. 27 CFR 555.220 - Table of separation distances of ammonium nitrate and blasting agents from explosives or blasting...

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... distances of ammonium nitrate and blasting agents from explosives or blasting agents. 555.220 Section 555... ammonium nitrate and blasting agents from explosives or blasting agents. Table: Department of Defense... Not over Minimum separation distance of acceptor from donor when barricaded (ft.) Ammonium nitrate...

  4. Nitrate biosensors and biological methods for nitrate determination.

    PubMed

    Sohail, Manzar; Adeloju, Samuel B

    2016-06-01

    The inorganic nitrate (NO3‾) anion is present under a variety of both natural and artificial environmental conditions. Nitrate is ubiquitous within the environment, food, industrial and physiological systems and is mostly present as hydrated anion of a corresponding dissolved salt. Due to the significant environmental and toxicological effects of nitrate, its determination and monitoring in environmental and industrial waters are often necessary. A wide range of analytical techniques are available for nitrate determination in various sample matrices. This review discusses biosensors available for nitrate determination using the enzyme nitrate reductase (NaR). We conclude that nitrate determination using biosensors is an excellent non-toxic alternative to all other available analytical methods. Over the last fifteen years biosensing technology for nitrate analysis has progressed very well, however, there is a need to expedite the development of nitrate biosensors as a suitable alternative to non-enzymatic techniques through the use of different polymers, nanostructures, mediators and strategies to overcome oxygen interference. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. The Periplasmic Nitrate Reductase Nap Is Required for Anaerobic Growth and Involved in Redox Control of Magnetite Biomineralization in Magnetospirillum gryphiswaldense

    PubMed Central

    Li, Yingjie; Katzmann, Emanuel; Borg, Sarah

    2012-01-01

    The magnetosomes of many magnetotactic bacteria consist of membrane-enveloped magnetite crystals, whose synthesis is favored by a low redox potential. However, the cellular redox processes governing the biomineralization of the mixed-valence iron oxide have remained unknown. Here, we show that in the alphaproteobacterium Magnetospirillum gryphiswaldense, magnetite biomineralization is linked to dissimilatory nitrate reduction. A complete denitrification pathway, including gene functions for nitrate (nap), nitrite (nir), nitric oxide (nor), and nitrous oxide reduction (nos), was identified. Transcriptional gusA fusions as reporters revealed that except for nap, the highest expression of the denitrification genes coincided with conditions permitting maximum magnetite synthesis. Whereas microaerobic denitrification overlapped with oxygen respiration, nitrate was the only electron acceptor supporting growth in the entire absence of oxygen, and only the deletion of nap genes, encoding a periplasmic nitrate reductase, and not deletion of nor or nos genes, abolished anaerobic growth and also delayed aerobic growth in both nitrate and ammonium media. While loss of nosZ or norCB had no or relatively weak effects on magnetosome synthesis, deletion of nap severely impaired magnetite biomineralization and resulted in fewer, smaller, and irregular crystals during denitrification and also microaerobic respiration, probably by disturbing the proper redox balance required for magnetite synthesis. In contrast to the case for the wild type, biomineralization in Δnap cells was independent of the oxidation state of carbon substrates. Altogether, our data demonstrate that in addition to its essential role in anaerobic respiration, the periplasmic nitrate reductase Nap has a further key function by participating in redox reactions required for magnetite biomineralization. PMID:22730130

  6. Automated system measuring triple oxygen and nitrogen isotope ratios in nitrate using the bacterial method and N2 O decomposition by microwave discharge.

    PubMed

    Hattori, Shohei; Savarino, Joel; Kamezaki, Kazuki; Ishino, Sakiko; Dyckmans, Jens; Fujinawa, Tamaki; Caillon, Nicolas; Barbero, Albane; Mukotaka, Arata; Toyoda, Sakae; Well, Reinhard; Yoshida, Naohiro

    2016-12-30

    Triple oxygen and nitrogen isotope ratios in nitrate are powerful tools for assessing atmospheric nitrate formation pathways and their contribution to ecosystems. N 2 O decomposition using microwave-induced plasma (MIP) has been used only for measurements of oxygen isotopes to date, but it is also possible to measure nitrogen isotopes during the same analytical run. The main improvements to a previous system are (i) an automated distribution system of nitrate to the bacterial medium, (ii) N 2 O separation by gas chromatography before N 2 O decomposition using the MIP, (iii) use of a corundum tube for microwave discharge, and (iv) development of an automated system for isotopic measurements. Three nitrate standards with sample sizes of 60, 80, 100, and 120 nmol were measured to investigate the sample size dependence of the isotope measurements. The δ 17 O, δ 18 O, and Δ 17 O values increased with increasing sample size, although the δ 15 N value showed no significant size dependency. Different calibration slopes and intercepts were obtained with different sample amounts. The slopes and intercepts for the regression lines in different sample amounts were dependent on sample size, indicating that the extent of oxygen exchange is also dependent on sample size. The sample-size-dependent slopes and intercepts were fitted using natural log (ln) regression curves, and the slopes and intercepts can be estimated to apply to any sample size corrections. When using 100 nmol samples, the standard deviations of residuals from the regression lines for this system were 0.5‰, 0.3‰, and 0.1‰, respectively, for the δ 18 O, Δ 17 O, and δ 15 N values, results that are not inferior to those from other systems using gold tube or gold wire. An automated system was developed to measure triple oxygen and nitrogen isotopes in nitrate using N 2 O decomposition by MIP. This system enables us to measure both triple oxygen and nitrogen isotopes in nitrate with comparable precision

  7. Donor assists acceptor binding and catalysis of human α1,6-fucosyltransferase.

    PubMed

    Kötzler, Miriam P; Blank, Simon; Bantleon, Frank I; Wienke, Martin; Spillner, Edzard; Meyer, Bernd

    2013-08-16

    α1,6-Core-fucosyltransferase (FUT8) is a vital enzyme in mammalian physiological and pathophysiological processes such as tumorigenesis and progress of, among others, non-small cell lung cancer and colon carcinoma. It was also shown that therapeutic antibodies have a dramatically higher efficacy if the α1,6-fucosyl residue is absent. However, specific and potent inhibitors for FUT8 and related enzymes are lacking. Hence, it is crucial to elucidate the structural basis of acceptor binding and the catalytic mechanism. We present here the first structural model of FUT8 in complex with its acceptor and donor molecules. An unusually large acceptor, i.e., a hexasaccharide from the core of N-glycans, is required as minimal structure. Acceptor substrate binding of FUT8 is being dissected experimentally by STD NMR and SPR and theoretically by molecular dynamics simulations. The acceptor binding site forms an unusually large and shallow binding site. Binding of the acceptor to the enzyme is much faster and stronger if the donor is present. This is due to strong hydrogen bonding between O6 of the proximal N-acetylglucosamine and an oxygen atom of the β-phosphate of GDP-fucose. Therefore, we propose an ordered Bi Bi mechanism for FUT8 where the donor molecule binds first. No specific amino acid is present that could act as base during catalysis. Our results indicate a donor-assisted mechanism, where an oxygen of the β-phosphate deprotonates the acceptor. Knowledge of the mechanism of FUT8 is now being used for rational design of targeted inhibitors to address metastasis and prognosis of carcinomas.

  8. Proteomic analysis of nitrate-dependent acetone degradation by Alicycliphilus denitrificans strain BC.

    PubMed

    Oosterkamp, Margreet J; Boeren, Sjef; Atashgahi, Siavash; Plugge, Caroline M; Schaap, Peter J; Stams, Alfons J M

    2015-06-01

    Alicycliphilus denitrificans strain BC grows anaerobically on acetone with nitrate as electron acceptor. Comparative proteomics of cultures of A. denitrificans strain BC grown on either acetone or acetate with nitrate was performed to study the enzymes involved in the acetone degradation pathway. In the proposed acetone degradation pathway, an acetone carboxylase converts acetone to acetoacetate, an AMP-dependent synthetase/ligase converts acetoacetate to acetoacetyl-CoA, and an acetyl-CoA acetyltransferase cleaves acetoacetyl-CoA to two acetyl-CoA. We also found a putative aldehyde dehydrogenase associated with acetone degradation. This enzyme functioned as a β-hydroxybutyrate dehydrogenase catalyzing the conversion of surplus acetoacetate to β-hydroxybutyrate that may be converted to the energy and carbon storage compound, poly-β-hydroxybutyrate. Accordingly, we confirmed the formation of poly-β-hydroxybutyrate in acetone-grown cells of strain BC. Our findings provide insight in nitrate-dependent acetone degradation that is activated by carboxylation of acetone. This will aid studies of similar pathways found in other microorganisms degrading acetone with nitrate or sulfate as electron acceptor. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

  9. Fate of microbial metabolites of hydrocarbons in a coastal plain aquifer: The role of electron acceptors

    USGS Publications Warehouse

    Cozzarelli, I.M.; Herman, J.S.; Baedecker, M. Jo

    1995-01-01

    A combined field and laboratory study was undertaken to understand the distribution and geochemical conditions that influence the prevalence of low molecular weight organic acids in groundwater of a shallow aquifer contaminated with gasoline. Aromatic hydrocarbons from gasoline were degraded by microbially mediated oxidation-reduction reactions, including reduction of nitrate, sulfate, and Fe(III). The biogeochemical reactions changed overtime in response to changes in the hydrogeochemical conditions in the aquifer. Aliphatic and aromatic organic acids were associated with hydrocarbon degradation in anoxic zones of the aquifer. Laboratory microcosms demonstrated that the biogeochemical fate of specific organic acids observed in groundwater varied with the structure of the acid and the availability of electron acceptors. Benzoic and phenylacetic acid were degraded by indigenous aquifer microorganisms when nitrate was supplied as an electron acceptor. Aromatic acids with two or more methyl substituants on the benzene ring persisted under nitrate-reducing conditions. Although iron reduction and sulfate reduction were important processes in situ and occurred in the microcosms, these reactions were not coupled to the biological oxidation of aromatic organic acids that were added to the microcosms as electron donors. ?? 1995 American Chemical Society.

  10. Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism

    PubMed Central

    Price, Alex; Pearson, Victoria K.; Schwenzer, Susanne P.; Miot, Jennyfer; Olsson-Francis, Karen

    2018-01-01

    This work considers the hypothetical viability of microbial nitrate-dependent Fe2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1–3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

  11. Nitrate-Dependent Iron Oxidation: A Potential Mars Metabolism.

    PubMed

    Price, Alex; Pearson, Victoria K; Schwenzer, Susanne P; Miot, Jennyfer; Olsson-Francis, Karen

    2018-01-01

    This work considers the hypothetical viability of microbial nitrate-dependent Fe 2+ oxidation (NDFO) for supporting simple life in the context of the early Mars environment. This draws on knowledge built up over several decades of remote and in situ observation, as well as recent discoveries that have shaped current understanding of early Mars. Our current understanding is that certain early martian environments fulfill several of the key requirements for microbes with NDFO metabolism. First, abundant Fe 2+ has been identified on Mars and provides evidence of an accessible electron donor; evidence of anoxia suggests that abiotic Fe 2+ oxidation by molecular oxygen would not have interfered and competed with microbial iron metabolism in these environments. Second, nitrate, which can be used by some iron oxidizing microorganisms as an electron acceptor, has also been confirmed in modern aeolian and ancient sediment deposits on Mars. In addition to redox substrates, reservoirs of both organic and inorganic carbon are available for biosynthesis, and geochemical evidence suggests that lacustrine systems during the hydrologically active Noachian period (4.1-3.7 Ga) match the circumneutral pH requirements of nitrate-dependent iron-oxidizing microorganisms. As well as potentially acting as a primary producer in early martian lakes and fluvial systems, the light-independent nature of NDFO suggests that such microbes could have persisted in sub-surface aquifers long after the desiccation of the surface, provided that adequate carbon and nitrates sources were prevalent. Traces of NDFO microorganisms may be preserved in the rock record by biomineralization and cellular encrustation in zones of high Fe 2+ concentrations. These processes could produce morphological biosignatures, preserve distinctive Fe-isotope variation patterns, and enhance preservation of biological organic compounds. Such biosignatures could be detectable by future missions to Mars with appropriate

  12. Difference between resistance degradation of fixed valence acceptor (Mg) and variable valence acceptor (Mn)-doped BaTiO3 ceramics

    NASA Astrophysics Data System (ADS)

    Yoon, Seok-Hyun; Randall, Clive A.; Hur, Kang-Heon

    2010-09-01

    The difference in the resistance degradation behavior was investigated between fixed valence acceptor (Mg) and the variable valence acceptor (Mn)-doped BaTiO3 ceramics with an increase of each acceptor concentration. Coarse-grained specimens with uniform grain sizes and different acceptor concentrations were prepared. In the case of Mg-doped BaTiO3, the time to degradation systematically decreased with the increase in Mg concentration. In contrast, there is a systematically increased time to degradation with the increase in Mn concentration in Mn-doped BaTiO3. The fast degradation by the increase in Mg concentration directly corresponded to an increase in the Warburg impedance and ionic transference number (tion) associated with an increase in oxygen vacancy concentration ([VO••]). On the other hand, no distinct Warburg impedance or ionic conduction contribution could be observed with the increase in Mn concentration. It is supposed that the increase in [VO••] is negligible in spite of the increase in acceptor Mn concentration, when it is compared to Mg-doped BaTiO3. The much lower [VO••] and more dominant electron/hole trapping effect due to multivalence nature of Mn are supposed to cause such a contrary degradation behavior between Mg and Mn-doped BaTiO3. Reoxidation in a slightly reducing atmosphere (N2) showed better resistance to degradation behavior than in a oxidizing air atmosphere in both Mg and Mn-doped BaTiO3, which is anticipated to be an increase in the electron/hole trapping sites. All these behaviors could be explained by the low temperature defect chemical model that shows difference in the defect structure between Mg and Mn-doped BaTiO3, and its dependence on the oxygen partial pressure (pO2) during reoxidation and cooling. Not only the [VO••], but also the density of electron/hole trap sites, are believed to be crucial in controlling resistance degradation.

  13. Nitrogen Oxides in Early Earth's Atmosphere as Electron Acceptors for Life's Emergence.

    PubMed

    Wong, Michael L; Charnay, Benjamin D; Gao, Peter; Yung, Yuk L; Russell, Michael J

    2017-10-01

    We quantify the amount of nitrogen oxides (NOx) produced through lightning and photochemical processes in the Hadean atmosphere to be available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO 3 - ) and nitrite (NO 2 - ) are the most attractive high-potential electron acceptors for pulling and enabling crucial redox reactions of autotrophic metabolic pathways at submarine alkaline hydrothermal vents. The Hadean atmosphere, dominated by CO 2 and N 2 , will produce nitric oxide (NO) when shocked by lightning. Photochemical reactions involving NO and H 2 O vapor will then produce acids such as HNO, HNO 2 , HNO 3 , and HO 2 NO 2 that rain into the ocean. There, they dissociate into or react to form nitrate and nitrite. We present new calculations based on a novel combination of early-Earth global climate model and photochemical modeling, and we predict the flux of NOx to the Hadean ocean. In our 0.1-, 1-, and 10-bar pCO 2 models, we calculate the NOx delivery to be 2.4 × 10 5 , 6.5 × 10 8 , and 1.9 × 10 8 molecules cm -2 s -1 . After only tens of thousands to tens of millions of years, these NOx fluxes are expected to produce sufficient (micromolar) ocean concentrations of high-potential electron acceptors for the emergence of life. Key Words: Nitrogen oxides-Nitrate-Nitrite-Photochemistry-Lightning-Emergence of life. Astrobiology 17, 975-983.

  14. Effect of dietary nitrate supplementation on conduit artery blood flow, muscle oxygenation, and metabolic rate during handgrip exercise.

    PubMed

    Craig, Jesse C; Broxterman, Ryan M; Smith, Joshua R; Allen, Jason David; Barstow, Thomas J

    2018-05-03

    Dietary nitrate supplementation has positive effects on mitochondrial and muscle contractile efficiency during large muscle mass exercise in humans, and on skeletal muscle blood flow (Q̇) in rats. However, concurrent measurement of these effects has not been performed in humans. Therefore, we assessed the influence of nitrate supplementation on Q̇ and muscle oxygenation characteristics during moderate (40%peak) and severe (85%peak) intensity handgrip exercise in a randomized, double-blind, crossover-design. Nine healthy men (age: 25{plus minus}2 yrs) completed four constant-power exercise tests (two per intensity) randomly assigned to condition (nitrate-rich (Nitrate) or nitrate-poor (Placebo) beetroot supplementation) and intensity (40%peak or 85%peak). Resting mean arterial pressure was lower after Nitrate compared to Placebo (84{plus minus}4 vs 89{plus minus}4 mmHg; p<0.01). All subjects were able to sustain 10 min of exercise at 40%peak in both conditions. Nitrate had no effect on exercise tolerance during 85%peak (Nitrate: 358{plus minus}29, Placebo: 341{plus minus}34 s; p=0.3). Brachial artery Q̇ was not different after Nitrate at rest or any time during exercise. Deoxygenated-[hemoglobin+myoglobin] was not different for 40%peak (p>0.05), but was elevated throughout 85%peak (p<0.05) after Nitrate. The metabolic cost (V̇O2) was not different at end exercise, however, the V̇O 2 primary amplitude at the onset of exercise was elevated after Nitrate for the 85%peak work rate (96{plus minus}20 vs 72{plus minus}12 ml/min; p<0.05) and had a faster response. These findings suggest that an acute dose of Nitrate reduces resting blood pressure and speeds V̇O 2 kinetics in young adults, but does not augment Q̇ or reduce steady-state V̇O 2 during small muscle mass handgrip exercise.

  15. Sources of nitrate in Xiangshan Bay (China), as identified using nitrogen and oxygen isotopes

    NASA Astrophysics Data System (ADS)

    Yang, Zhi; Chen, Jianfang; Li, Hongliang; Jin, Haiyan; Gao, Shenquan; Ji, Zhongqiang; Zhu, Yong; Ran, Lihua; Zhang, Jingjing; Liao, Yibo; Bai, Youcheng

    2018-07-01

    Eutrophication, mainly caused by the oversupply of nitrate (NO3-) and phosphate, has become a serious environmental problem in Xiangshan Bay (east China), but the sources of the nitrate are poorly understood. In this study, the estuarine distributions of dual stable isotopes (δ15N and δ18O) of NO3- measured in May 2012 were used in combination with concurrent measurements of salinity, pH, dissolved oxygen, and nutrients (nitrate, nitrite, ammonium, and phosphate) to investigate NO3- sources and the processes that control NO3- distributions within the bay. In the lower bay, high concentrations of NO3- (up to 60.6 μmol L-1), an N/P ratio of 52, and low values of nitrate δ15N (δ15NNO3 = 5.7‰-6.7‰) and δ18O (δ18ONO3 = 1.8‰-3.5‰) indicate that NO3- in this area was likely from the Changjiang and Qiantangjiang rivers as well as local nitrification-associated inputs. In the upper bay, constituent concentrations and high values of δ15NNO3 (up to 8.8‰) and δ18ONO3 (up to 6.8‰) suggest that NO3- distributions here were controlled mainly by the mixing of coastal and fresh waters, phytoplankton assimilation, and inputs of riverine NO3-, possibly derived from manure and sewage. Spatial variations of Δ(15,18), the nitrate δ15N-to-δ18O anomaly, is possibly resulted from the different water residence times across the bay, which could in turn lead to different degrees of nitrification or variable amounts of NO3- from atmospheric deposition.

  16. Purification and properties of a dissimilatory nitrate reductase from Haloferax denitrificans

    NASA Technical Reports Server (NTRS)

    Hochstein, L. I.; Lang, F.

    1991-01-01

    A membrane-bound nitrate reductase (nitrite:(acceptor) oxidoreductase, EC 1.7.99.4) from the extremely halophilic bacterium Haloferax denitrificans was solubilized by incubating membranes in buffer lacking NaCl and purified by DEAE, hydroxylapatite, and Sepharose 6B gel filtration chromatography. The purified nitrate reductase reduced chlorate and was inhibited by azide and cyanide. Preincubating the enzyme with cyanide increased the extent of inhibition which in turn was intensified when dithionite was present. Although cyanide was a noncompetitive inhibitor with respect to nitrate, nitrate protected against inhibition. The enzyme, as isolated, was composed of two subunits (Mr 116,000 and 60,000) and behaved as a dimer during gel filtration (Mr 380,000). Unlike other halobacterial enzymes, this nitrate reductase was most active, as well as stable, in the absence of salt.

  17. BIOREMEDIATION AT WOOD-PRESERVING SITES

    EPA Science Inventory

    The removal of organic compounds from ground water during bioremediation at wood-preserving sites is a function of the stoichiometric demand for electron acceptors (oxygen, nitrate, and sulfate) to metabolize the organic contaminants and the supply of the electron acceptors in th...

  18. NITRATE FOR BIORESTORATION OF AN AQUIFER CONTAMINATED WITH JET FUEL

    EPA Science Inventory

    There is little information available in the open literature on the performance of bioremediation at field scale. The report documents the rate and extent of treatment of a spill of JP-4 in a drinking-water aquifer, using nitrate as the primary electron acceptor for microbial res...

  19. Validation Testing a Contaminant Transport and Natural Attenuation Simulation Model Using Field Data.

    DTIC Science & Technology

    1995-12-01

    reactions . The following figure shows the relationship of common electron acceptors with regard to their redox potential. Redox Potential (pH = 7) in...Model 8 Fuel-Spill Plume Profile 8 Hydrocarbon Biodegradation 1° Oxygen 11 Anaerobic Electron Acceptors 12 Redox Potential *4 Contaminants of...Biodegradation Reactions 21 Oxygen Reactions 21 Nitrate 22 Manganese (IV) 22 Iron (III) 23 Sulfate 24 in Page Intrinsic Bioremediation Model

  20. New insights into bioactivation of organic nitrates, nitrate tolerance and cross-tolerance.

    PubMed

    Daiber, A; Wenzel, P; Oelze, M; Münzel, T

    2008-01-01

    Organic nitrates still represent a group of very effective anti-ischemic drugs used for the treatment of patients with stable angina, acute myocardial infarction and chronic congestive heart failure. Long-term therapy with organic nitrates, however, results in a rapid development of nitrate tolerance blunting their hemodynamic and antiischemic efficacy. Recent studies revealed that mitochondrial reactive oxygen species (ROS) formation and a subsequent oxidative inactivation of nitrate reductase, the mitochondrial aldehyde dehydrogenase (ALDH-2), play an important role for the development of nitrate and crosstolerance. The present review focuses firstly on the role of ALDH-2 for organic nitrate bioactivation and secondly on the role of oxidative stress in the development of tolerance and cross-tolerance (endothelial dysfunction) in response to various organic nitrates. Finally, we would like to draw the reader's attention to the protective properties of the organic nitrate pentaerithrityl tetranitrate (PETN), which, in contrast to all other organic nitrates, is able to upregulate enzymes with a strong antioxidative capacity thereby preventing tolerance and the development of endothelial dysfunction.

  1. The environmental controls that govern the end product of bacterial nitrate respiration

    DOE PAGES

    Kraft, Beate; Tegetmeyer, Halina E.; Sharma, Ritin; ...

    2014-08-08

    In the biogeochemical nitrogen cycle, microbial respiration processes compete for nitrate as an electron acceptor. Denitrification converts nitrate into nitrogenous gas and thus removes fixed nitrogen from the biosphere, whereas ammonification converts nitrate into ammonium, which is directly reusable by primary producers. In this paper, we combined multiple parallel long-term incubations of marine microbial nitrate-respiring communities with isotope labeling and metagenomics to unravel how specific environmental conditions select for either process. Microbial generation time, supply of nitrite relative to nitrate, and the carbon/nitrogen ratio were identified as key environmental controls that determine whether nitrite will be reduced to nitrogenous gasmore » or ammonium. Finally, our results define the microbial ecophysiology of a biogeochemical feedback loop that is key to global change, eutrophication, and wastewater treatment.« less

  2. Identification of nitrate sources and discharge-depending nitrate dynamics in a mesoscale catchment

    NASA Astrophysics Data System (ADS)

    Mueller, Christin; Strachauer, Ulrike; Brauns, Mario; Musolff, Andreas; Kunz, Julia Vanessa; Brase, Lisa; Tarasova, Larisa; Merz, Ralf; Knöller, Kay

    2017-04-01

    During the last decades, nitrate concentrations in surface and groundwater have increased due to land use change and accompanying application of fertilizer in agriculture as well as increased atmospheric deposition. To mitigate nutrient impacts on downstream aquatic ecosystems, it is important to quantify potential nitrate sources, instream nitrate processing and its controls in a river system. The objective of this project is to characterize and quantify (regional) scale dynamics and trends in water and nitrogen fluxes of the entire Holtemme river catchment in central Germany making use of isotopic fingerprinting methods. Here we compare two key date sampling campaigns in 2014 and 2015, with spatially highly resolved measurements of discharge at 23 sampling locations including 11 major tributaries and 12 locations at the main river. Additionally, we have data from continuous runoff measurements at 10 locations operated by the local water authorities. Two waste water treatment plants contribute nitrogen to the Holtemme stream. This contribution impacts nitrate loads and nitrate isotopic signatures depending on the prevailing hydrological conditions. Nitrogen isotopic signatures in the catchment are mainly controlled by different sources (nitrified soil nitrogen in the headwater and manure/ effluents from WWTPs in the lowlands) and increase with raising nitrate concentrations along the main river. Nitrate loads at the outlet of the catchment are extremely different between both sampling campaigns (2014: NO3- = 97 t a-1, 2015: NO3- = 5 t a-1) which is associated with various runoff (2014: 0.8 m3 s-1, 2015: 0.2 m3 s-1). In 2015, the inflow from WWTP's raises the NO3- loads and enriches δ18O-NO3 values. Generally, oxygen isotope signatures from nitrate are more variable and are controlled by biogeochemical processes in concert with the oxygen isotopic composition of the ambient water. Elevated δ18O-NO3 in 2015 are most likely due to higher temperatures and lower

  3. Assessing the Role of Land Use in Watershed Nitrate Export Using Triple Oxygen Isotopes

    NASA Astrophysics Data System (ADS)

    Bostic, J.; Nelson, D. M.; Eshleman, K. N.

    2017-12-01

    Quantifying the influence of land-use patterns on the amount and source(s) of nitrate (NO3) exported from watersheds is critical for understanding and mitigating the effects of nutrient pollution on downstream waterbodies. The isotopic composition of NO3 is valuable for fingerprinting of NO3 sources, including manure and atmospheric nitrate. To assess loads, sources, and potential transformations of NO3 in the Chesapeake Bay (CB) watershed, stream samples from fourteen sub-watersheds of the CB were collected semi-monthly and during multiple storm events from October 2015-September 2016 (Water Year 2016). The watersheds range in size (500 - 127,900 ha) and in dominant land-use (forest, urban, agriculture). The samples were analyzed for nitrate concentrations and isotopes (δ15N, as well as the triple oxygen isotope composition, defined as Δ17O ≅ δ17O - 0.52 x δ18O). Stream loads of nitrate were estimated using WRTDS (Weighted Regressions on Time, Discharge, and Season). NO3 deposition (dry and wet) was fairly uniform across all watersheds (2.1 - 3.0 kg NO3-N ha-1), whereas stream NO3 varied greatly (0.6 - 11.8 kg NO3-N ha-1). Stream loads of NO3 were positively related to the percent of agricultural land (r2 = 0.67, p < 0.005) and negatively related to the percent of forested land (r2 = 0.61, p < 0.005). Preliminary isotope data indicate a positive relationship between δ15NNO3 and the proportion of agricultural land (r2 = 0.48, p < 0.0001), which suggests that nitrate inputs in predominantly agricultural watersheds are manure or pools of partially denitrified fertilizer. A positive relationship between Δ17ONO3 and the percent of forested land (r2 = 0.19, p < 0.005) suggests that forests export a greater proportion of atmospheric nitrate than other systems. Full NO3 isotope data for Water Year 2016 ( 400 samples) will be presented from all watersheds to elucidate the amount and sources of NO3 exported from a variety of land-uses.

  4. Mammalian Nitrate Biosynthesis: Incorporation of 15NH3 into Nitrate is Enhanced by Endotoxin Treatment

    NASA Astrophysics Data System (ADS)

    Wagner, David A.; Young, Vernon R.; Tannenbaum, Steven R.

    1983-07-01

    Incorporation of an oral dose of [15N]ammonium acetate into urinary [15N]nitrate has been demonstrated in the rat. Investigation of the regulation of nitrate synthesis has shown that Escherichia coli lipopolysaccharide potently stimulates urinary nitrate excretion (9-fold increase). It was further shown that the enhanced rate of nitrate excretion by lipopolysaccharide was due not to a reduction in nitrate metabolic loss but rather to an increased rate of synthesis. This conclusion was based on finding a proportionally increased incorporation of [15N]ammonium into nitrate nitrogen with lipopolysaccharide treatment. Nitrate biosynthesis was also increased by intraperitoneal injection of carrageenan and subcutaneous injection of turpentine. It is proposed that the pathway of nitrate biosynthesis may be the result of oxidation of reduced nitrogen compounds by oxygen radicals generated by an activated reticuloendothelial system.

  5. Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

    2014-01-28

    The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

  6. Ammonification in Bacillus subtilis Utilizing Dissimilatory Nitrite Reductase Is Dependent on resDE

    PubMed Central

    Hoffmann, Tamara; Frankenberg, Nicole; Marino, Marco; Jahn, Dieter

    1998-01-01

    During anaerobic nitrate respiration Bacillus subtilis reduces nitrate via nitrite to ammonia. No denitrification products were observed. B. subtilis wild-type cells and a nitrate reductase mutant grew anaerobically with nitrite as an electron acceptor. Oxygen-sensitive dissimilatory nitrite reductase activity was demonstrated in cell extracts prepared from both strains with benzyl viologen as an electron donor and nitrite as an electron acceptor. The anaerobic expression of the discovered nitrite reductase activity was dependent on the regulatory system encoded by resDE. Mutation of the gene encoding the regulatory Fnr had no negative effect on dissimilatory nitrite reductase formation. PMID:9422613

  7. The effect of dietary nitrate supplementation on the oxygen cost of cycling, walking performance and resting blood pressure in individuals with chronic obstructive pulmonary disease: A double blind placebo controlled, randomised control trial.

    PubMed

    Shepherd, Anthony I; Wilkerson, Daryl P; Dobson, Lee; Kelly, James; Winyard, Paul G; Jones, Andrew M; Benjamin, Nigel; Shore, Angela C; Gilchrist, Mark

    2015-08-01

    Chronic obstructive pulmonary disease (COPD) results in exercise intolerance. Dietary nitrate supplementation has been shown to lower blood pressure (BP), reduce the oxygen cost of exercise, and enhance exercise tolerance in healthy volunteers. This study assessed the effects of dietary nitrate on the oxygen cost of cycling, walking performance and BP in individuals with mild-moderate COPD. Thirteen patients with mild-moderate COPD were recruited. Participants consumed 70 ml of either nitrate-rich (6.77 mmol nitrate; beetroot juice) or nitrate-depleted beetroot juice (0.002 mmol nitrate; placebo) twice a day for 2.5 days, with the final supplement ~3 hours before testing. BP was measured before completing two bouts of moderate-intensity cycling, where pulmonary gas exchange was measured throughout. The six-minute walk test (6 MWT) was completed 30 minutes subsequent to the second cycling bout. Plasma nitrate concentration was significantly elevated following beetroot juice vs. placebo (placebo; 48 ± 86 vs. beetroot juice; 215 ± 84 µM, P = 0.002). No significant differences were observed between placebo vs. beetroot juice for oxygen cost of exercise (933 ± 323 vs. 939 ± 302 ml: min(-1); P = 0.88), distance covered in the 6 MWT (456 ± 86 vs. 449 ± 79 m; P = 0.37), systolic BP (123 ± 14 vs. 123 ± 14 mmHg; P = 0.91), or diastolic BP (77 ± 9 vs. 79 ± 9 mmHg; P = 0.27). Despite a large rise in plasma nitrate concentration, two days of nitrate supplementation did not reduce the oxygen cost of moderate intensity cycling, increase distance covered in the 6 MWT, or lower BP. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. Nitrogen Oxides in Early Earth's Atmosphere as Electron Acceptors for Life's Emergence

    NASA Astrophysics Data System (ADS)

    Wong, Michael L.; Charnay, Benjamin D.; Gao, Peter; Yung, Yuk L.; Russell, Michael J.

    2017-10-01

    We quantify the amount of nitrogen oxides (NOx) produced through lightning and photochemical processes in the Hadean atmosphere to be available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO3-) and nitrite (NO2-) are the most attractive high-potential electron acceptors for pulling and enabling crucial redox reactions of autotrophic metabolic pathways at submarine alkaline hydrothermal vents. The Hadean atmosphere, dominated by CO2 and N2, will produce nitric oxide (NO) when shocked by lightning. Photochemical reactions involving NO and H2O vapor will then produce acids such as HNO, HNO2, HNO3, and HO2NO2 that rain into the ocean. There, they dissociate into or react to form nitrate and nitrite. We present new calculations based on a novel combination of early-Earth global climate model and photochemical modeling, and we predict the flux of NOx to the Hadean ocean. In our 0.1-, 1-, and 10-bar pCO2 models, we calculate the NOx delivery to be 2.4 × 105, 6.5 × 108, and 1.9 × 108 molecules cm-2 s-1. After only tens of thousands to tens of millions of years, these NOx fluxes are expected to produce sufficient (micromolar) ocean concentrations of high-potential electron acceptors for the emergence of life.

  9. Decomposition of plant materials in marine sediment exposed to different electron acceptors (O 2, NO 3-, and SO 42-), with emphasis on substrate origin, degradation kinetics, and the role of bioturbation

    NASA Astrophysics Data System (ADS)

    Kristensen, Erik; Holmer, Marianne

    2001-02-01

    Carbon mineralization of fresh and aged diatoms ( Skeletonema costatum) and barley hay ( Hordeum vulgare) was followed for 23 to 35 d in sandy and silty sediment. By the use of a thin-layer flow-through technique, it was possible to expose the sediment selectively for oxygen, nitrate or sulfate as electron acceptors in the terminal oxidation of organic carbon. Decomposition took place in two basic stages. Mineralization of the rapidly leachable fraction of the fresh materials occurred rapidly and with the same constant rate regardless of the electron acceptor available, indicating that the dissolved organic carbon released initially was labile and readily available for all heterotrophic respirers. In the case of diatoms, decay of the remaining, more refractory, particulate fraction of fresh and aged diatoms were strikingly similar, although both were degraded 5 to 10 times faster under oxic than anoxic conditions. Most of the particulate remains of diatoms after leaching apparently belong to one fraction, which maintains the same degradability even after prolonged aging. With respect to hay, the late divergence in rates of aerobic and anaerobic decay (a factor of 4 to 5 for aged hay only after 20 d) indicated that the larger hay particles (<500 μm) became exhausted in labile organic matter much slower through time than fine-particulate diatoms (˜20 μm). Anaerobic carbon mineralization rates of diatoms and hay particulates with sulfate and nitrate as electron acceptors were similar or up to two times faster with sulfate. The generally low levels of dissolved organic carbon in all incubations after the initial leaching phase suggest that the limiting step of decomposition under both aerobic and anaerobic decay is the initial hydrolytic attack on the complex particulate remains. Based on a volumetric model, we show that the exposure of anoxic subsurface sediment containing partly degraded organic material to oxygen via irrigated worm burrows or by reworking may

  10. Electrochemical determination of nitrate with nitrate reductase-immobilized electrodes under ambient air.

    PubMed

    Quan, De; Shim, Jun Ho; Kim, Jong Dae; Park, Hyung Soo; Cha, Geun Sig; Nam, Hakhyun

    2005-07-15

    Nitrate monitoring biosensors were prepared by immobilizing nitrate reductase derived from yeast on a glassy carbon electrode (GCE, d = 3 mm) or screen-printed carbon paste electrode (SPCE, d = 3 mm) using a polymer (poly(vinyl alcohol)) entrapment method. The sensor could directly determine the nitrate in an unpurged aqueous solution with the aid of an appropriate oxygen scavenger: the nitrate reduction reaction driven by the enzyme and an electron-transfer mediator, methyl viologen, at -0.85 V (GCE vs Ag/AgCl) or at -0.90 V (SPCE vs Ag/AgCl) exhibited no oxygen interference in a sulfite-added solution. The electroanalytical properties of optimized biosensors were measured: the sensitivity, linear response range, and detection limit of the sensors based on GCE were 7.3 nA/microM, 15-300 microM (r2 = 0.995), and 4.1 microM (S/N = 3), respectively, and those of SPCE were 5.5 nA/microM, 15-250 microM (r2 = 0.996), and 5.5 microM (S/N = 3), respectively. The disposable SPCE-based biosensor with a built-in well- or capillary-type sample cell provided high sensor-to-sensor reproducibility (RSD < 3.4% below 250 microM) and could be used more than one month in normal room-temperature storage condition. The utility of the proposed sensor system was demonstrated by determining nitrate in real samples.

  11. Oxygen Isotopic Composition of Nitrate and Sulfate in Fog and River water in Podocarpus National Forest, Ecuador

    NASA Astrophysics Data System (ADS)

    Brothers, L. A.; Fabian, P.; Thiemens, M. H.

    2006-12-01

    The eastern slopes of the Andean rainforests of Ecuador possess some of the highest plant biodiversity found on the planet; however, these ecosystems are in jeopardy because region is experiences one of the highest deforestation rates in South America. This rainforest characterized by high acidity and low nutrient soils and experiences natural process which are both destabilizing and stabilizing to biodiversity rendering this a unique, though sensitive environment. There is increased concern that anthropogenic activities are affecting rainforests and could lead to higher extinction rates, changes in the biodiversity and far reaching effects on the global troposphere. Measurements of nitrate and sulfate in rain and fog water have shown periods of elevated concentrations in the Podocarpus National Park near Loja, Ecuador. These high episodes contribute to annual deposition rates that are comparable to polluted central Europe. Significant anthropogenic sources near this region are lacking and it is believed that the majority of the nitrate and sulfate pollution can be attributed to biomass burning in the Amazon basin. Concentration measurements do not elucidate the source of high nitrate and sulfate pollution; however, by measuring all three stable isotopes of oxygen in nitrate and sulfate from fog and river water provides a new way to examine the impacts of biomass burning on the region. By using stable isotope techniques atmospheric nitrate and sulfate can be resolved from terrestrial sources. This provides an unique way to trace the contributions from the biomass burning and farming sources. Current research at the field station monitors sulfate and nitrate concentrations in rain and fog water by standard methods to investigate water and nutrient pathways along with data from satellite and ground based remote sensing, in-situ observations and numerical models.

  12. Metagenomic analysis of nitrogen and methane cycling in the Arabian Sea oxygen minimum zone.

    PubMed

    Lüke, Claudia; Speth, Daan R; Kox, Martine A R; Villanueva, Laura; Jetten, Mike S M

    2016-01-01

    Oxygen minimum zones (OMZ) are areas in the global ocean where oxygen concentrations drop to below one percent. Low oxygen concentrations allow alternative respiration with nitrate and nitrite as electron acceptor to become prevalent in these areas, making them main contributors to oceanic nitrogen loss. The contribution of anammox and denitrification to nitrogen loss seems to vary in different OMZs. In the Arabian Sea, both processes were reported. Here, we performed a metagenomics study of the upper and core zone of the Arabian Sea OMZ, to provide a comprehensive overview of the genetic potential for nitrogen and methane cycling. We propose that aerobic ammonium oxidation is carried out by a diverse community of Thaumarchaeota in the upper zone of the OMZ, whereas a low diversity of Scalindua-like anammox bacteria contribute significantly to nitrogen loss in the core zone. Aerobic nitrite oxidation in the OMZ seems to be performed by Nitrospina spp. and a novel lineage of nitrite oxidizing organisms that is present in roughly equal abundance as Nitrospina. Dissimilatory nitrate reduction to ammonia (DNRA) can be carried out by yet unknown microorganisms harbouring a divergent nrfA gene. The metagenomes do not provide conclusive evidence for active methane cycling; however, a low abundance of novel alkane monooxygenase diversity was detected. Taken together, our approach confirmed the genomic potential for an active nitrogen cycle in the Arabian Sea and allowed detection of hitherto overlooked lineages of carbon and nitrogen cycle bacteria.

  13. Metagenomic analysis of nitrogen and methane cycling in the Arabian Sea oxygen minimum zone

    PubMed Central

    Kox, Martine A.R.; Villanueva, Laura; Jetten, Mike S.M.

    2016-01-01

    Oxygen minimum zones (OMZ) are areas in the global ocean where oxygen concentrations drop to below one percent. Low oxygen concentrations allow alternative respiration with nitrate and nitrite as electron acceptor to become prevalent in these areas, making them main contributors to oceanic nitrogen loss. The contribution of anammox and denitrification to nitrogen loss seems to vary in different OMZs. In the Arabian Sea, both processes were reported. Here, we performed a metagenomics study of the upper and core zone of the Arabian Sea OMZ, to provide a comprehensive overview of the genetic potential for nitrogen and methane cycling. We propose that aerobic ammonium oxidation is carried out by a diverse community of Thaumarchaeota in the upper zone of the OMZ, whereas a low diversity of Scalindua-like anammox bacteria contribute significantly to nitrogen loss in the core zone. Aerobic nitrite oxidation in the OMZ seems to be performed by Nitrospina spp. and a novel lineage of nitrite oxidizing organisms that is present in roughly equal abundance as Nitrospina. Dissimilatory nitrate reduction to ammonia (DNRA) can be carried out by yet unknown microorganisms harbouring a divergent nrfA gene. The metagenomes do not provide conclusive evidence for active methane cycling; however, a low abundance of novel alkane monooxygenase diversity was detected. Taken together, our approach confirmed the genomic potential for an active nitrogen cycle in the Arabian Sea and allowed detection of hitherto overlooked lineages of carbon and nitrogen cycle bacteria. PMID:27077014

  14. Biological Redox Cycling Of Iron In Nontronite And Its Potential Application In Nitrate Removal

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.

    2015-05-05

    Redox cycling of structural Fe in phyllosilicates provides a potential method to remediate nitrate contamination in natural environment. Past research has only studied chemical redox cycles or a single biologically mediated redox cycle of Fe in phyllosilicates. The objective of this research was to study three microbially driven redox cycles of Fe in one phyllosilicate, nontronite (NAu-2). During the reduction phase structural Fe(III) in NAu-2 served as electron acceptor, lactate as electron donor, AQDS as electron shuttle, and dissimilatory Fe(III)-reducing bacteria Shewanella putrefaciens CN32 as mediator in bicarbonate-buffered and PIPES-buffered media. During the oxidation phase, biogenic Fe(II) served an electronmore » donor, nitrate as electron acceptor, and nitrate-dependent Fe(II)-oxidizing bacteria Pseudogulbenkiania sp. strain 2002 as mediator in the same media. For all three cycles, structural Fe in NAu-2 was able to reversibly undergo 3 redox cycles without significant reductive or oxidative dissolution. X-ray diffraction and scanning and transmission electron microscopy revealed that NAu-2 was the dominant residual mineral throughout the 3 redox cycles with some dissolution textures but no significant secondary mineralization. Mössbauer spectroscopy revealed that Fe(II) in bio-reduced samples likely occurred in two distinct environments, at edges and the interior of the NAu-2 structure. Nitrate was completely reduced to nitrogen gas under both buffer conditions and this extent and rate did not change with Fe redox cycles. Mössbauer spectroscopy further revealed that nitrate reduction was coupled to predominant/preferred oxidation of edge Fe(II). These results suggest that structural Fe in phyllosilicates may represent a renewable source to continuously remove nitrate in natural environments.« less

  15. Influence of alternative electron acceptors on the anaerobic biodegradability of chlorinated phenols and benzoic acids

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y.

    1993-01-01

    Nitrate, sulfate, and carbonate were used as electron acceptors to examine the anaerobic biodegradability of chlorinated aromatic compounds in estuarine and freshwater sediments. The respective denitrifying, sulfidogenic, and methanogenic enrichment cultures were established on each of the monochlorinated phenol and monochlorinated benzoic acid isomers, using sediment from the upper (freshwater) and lower (estuarine) Hudson River and the East River (estuarine) as source materials. (Copyright (c) 1993 American Society for Microbiology.)

  16. An Integrated Proteomics/Transcriptomics Approach Points to Oxygen as the Main Electron Sink for Methanol Metabolism in Methylotenera mobilis▿†

    PubMed Central

    Beck, David A. C.; Hendrickson, Erik L.; Vorobev, Alexey; Wang, Tiansong; Lim, Sujung; Kalyuzhnaya, Marina G.; Lidstrom, Mary E.; Hackett, Murray; Chistoserdova, Ludmila

    2011-01-01

    Methylotenera species, unlike their close relatives in the genera Methylophilus, Methylobacillus, and Methylovorus, neither exhibit the activity of methanol dehydrogenase nor possess mxaFI genes encoding this enzyme, yet they are able to grow on methanol. In this work, we integrated a genome-wide proteomics approach, shotgun proteomics, and a genome-wide transcriptomics approach, shotgun transcriptome sequencing (RNA-seq), of Methylotenera mobilis JLW8 to identify genes and enzymes potentially involved in methanol oxidation, with special attention to alternative nitrogen sources, to address the question of whether nitrate could play a role as an electron acceptor in place of oxygen. Both proteomics and transcriptomics identified a limited number of genes and enzymes specifically responding to methanol. This set includes genes involved in oxidative stress response systems, a number of oxidoreductases, including XoxF-type alcohol dehydrogenases, a type II secretion system, and proteins without a predicted function. Nitrate stimulated expression of some genes in assimilatory nitrate reduction and denitrification pathways, while ammonium downregulated some of the nitrogen metabolism genes. However, none of these genes appeared to respond to methanol, which suggests that oxygen may be the main electron sink during growth on methanol. This study identifies initial targets for future focused physiological studies, including mutant analysis, which will provide further details into this novel process. PMID:21764938

  17. Mechanisms of electron acceptor utilization: Implications for simulating anaerobic biodegradation

    USGS Publications Warehouse

    Schreiber, M.E.; Carey, G.R.; Feinstein, D.T.; Bahr, J.M.

    2004-01-01

    Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum- contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and

  18. Influence of nitrate, sulfate and operational parameters on the bioreduction of perchlorate using an up-flow packed bed reactor at high salinity.

    PubMed

    Chung, J; Shin, S; Oh, J

    2010-05-01

    In this study we have investigated whether electron acceptors, such as nitrate or sulphate ions, competitively inhibit the reduction of perchlorate in brine in continuous up-flow packed bed bioreactors. The effect of pH and hydraulic retention time (HRT) on the reduction of perchlorate at high salinity has also been examined. Reduction of perchlorate was found to be only moderately influenced by nitrate (under 163 mg N L-'), implying that there was no significant microbial competition for electron acceptors. As a result of microbial diversity, there were few differences between microbial communities fed with a variety of media, suggesting that most nitrate-reducing bacteria are able to reduce perchlorate at high salinity. Reduction of perchlorate was almost complete at relatively high sulfate levels (1000 mg L(-1)), neutral pH (6-8) and relatively long HRTs (> 10 h).

  19. Nitrate sources and sinks in Elkhorn Slough, California: Results from long-term continuous in situ nitrate analyzers

    USGS Publications Warehouse

    Chapin, T.P.; Caffrey, J.M.; Jannasch, H.W.; Coletti, L.J.; Haskins, J.C.; Johnson, K.S.

    2004-01-01

    Nitrate and water quality parameters (temperature, salinity, dissolved oxygen, turbidity, and depth) were measured continuously with in situ NO 3 analyzers and water quality sondes at two sites in Elkhorn Slough in Central California. The Main Channel site near the mouth of Elkhorn Slough was sampled from February to September 2001. Azevedo Pond, a shallow tidal pond bordering agricultural fields further inland, was sampled from December 1999 to July 2001. Nitrate concentrations were recorded hourly while salinity, temperature, depth, oxygen, and turbidity were recorded every 30 min. Nitrate concentrations at the Main Channel site ranged from 5 to 65 ??M. The propagation of an internal wave carrying water from ???100 m depth up the Monterey Submarine Canyon and into the lower section of Elkhorn Slough on every rising tide was a major source of nitrate, accounting for 80-90% of the nitrogen load during the dry summer period. Nitrate concentrations in Azevedo Pond ranged from 0-20 ??M during the dry summer months. Nitrate in Azevedo Pond increased to over 450 ??M during a heavy winter precipitation event, and interannual variability driven by differences in precipitation was observed. At both sites, tidal cycling was the dominant forcing, often changing nitrate concentrations by 5-fold or more within a few hours. Water volume flux estimates were combined with observed nitrate concentrations to obtain nitrate fluxes. Nitrate flux calculations indicated a loss of 4 mmol NO3 m -2 d-1 for the entire Elkhorn Slough and 1 mmol NO 3 m-2 d-1 at Azevedo Pond. These results suggested that the waters of Elkhorn Slough were not a major source of nitrate to Monterey Bay but actually a nitrate sink during the dry season. The limited winter data at the Main Channel site suggest that nitrate was exported from Elkhorn Slough during the wet season. Export of ammonium or dissolved organic nitrogen, which we did not monitor, may balance some or all of the NO 3 flux.

  20. Modeling the long-term fate of agricultural nitrate in groundwater in the San Joaquin Valley, California

    USGS Publications Warehouse

    Chapelle, Francis H.; Campbell, Bruce G.; Widdowson, Mark A.; Landon, Mathew K.

    2013-01-01

    (POC) are the primary electron donors driving active denitrification in groundwater. The purpose of this chapter is to use a numerical mass balance modeling approach to quantitatively compare sources of electron donors (DOC, POC) and electron acceptors (dissolved oxygen, nitrate, and ferric iron) in order to assess the potential for denitrification to attenuate nitrate migration in the Central Valley aquifer.

  1. Reactions of Free Radicals with Nitro-Compounds and Nitrates

    DTIC Science & Technology

    1981-03-31

    PAGE(I/hmm a•Ia ntatemd the fragment derived from the nitrates but not from the nitro-compounds could undergo exothermic rearrangement. Product analyses...compounds could undergo exothermic rearrangement. Product analyses and computer modelling were undertaken, these provided a clear explanation of why the...Nitrate 14 Reaction of Oxygen Atoms with Nitromethane 16 Reaction of Oxygen Atoms with Nitroethane 17 Products from Nitrocompounds 18 Effect of Carbon

  2. Coupling of phonons with excitons bound to different donors and acceptors in hexagonal GaN

    NASA Astrophysics Data System (ADS)

    Korona, K. P.; Wysmoek, A.; Kuhl, J.; Kamiska, M.; Baranowski, J. M.; Look, D. C.; Park, S. S.

    2006-06-01

    Time-resolved measurements of GaN with different donors (oxygen or silicon) and acceptors (zinc or magnesium) showed pronounced bound exciton lines and their phonon replicas. The analysis included three phonon modes characteristic for the wurtzite (hexagonal) phase: A1(LO), E1(TO) and E2H. It was shown that relative amplitudes of replicas depended upon the chemical nature of the defects that the bind excitons. The replicas were stronger for acceptor- than for donor-related features. Huang-Rhys factors S = 0.06 +/- 0.02 and S = 0.025 +/- 0.01, were found for the A0X and the D0X LO replicas, respectively. A significant difference in phonon coupling to silicon and oxygen donor bound excitons has been observed.

  3. Vaccine perception among acceptors and non-acceptors in Sokoto State, Nigeria.

    PubMed

    Murele, Bola; Vaz, Rui; Gasasira, Alex; Mkanda, Pascal; Erbeto, Tesfaye; Okeibunor, Joseph

    2014-05-30

    Vaccine perceptions among acceptors and non-acceptors of childhood vaccination were explored. Seventy-two care givers, among them, acceptors and non-acceptors were interviewed in-depth with an interview guide that assessed vaccine acceptance, social and personality factors, and health belief model (HBM) categories in relation to oral polio vaccine (perceived susceptibility, severity, cost barriers, general barriers, benefits, knowledge, and engagement in preventative health behaviours). Community leaders were purposively selected while parents were selected on the basis of availability while ensuring the different attitude to vaccines was covered. Results showed that the HBM framework was found to be appropriate for identifying and distinguishing vaccine acceptors and non-acceptors. In addition, the HBM categories of benefits and susceptibility were found to influence oral polio vaccine acceptance. Second, the opinion of family members about the oral polio vaccine moderated the relationship between number of social ties and vaccine acceptance. Further, oral polio vaccine acceptance was related to outbreaks of paralysis of any sort, but not aggregate scores of other preventative health behaviours. Implications of this study include the investigation of vaccine acceptance in a high risk population. Research was done to investigate vaccine acceptance. Copyright © 2014 Elsevier Ltd. All rights reserved.

  4. Influence of alternative electron acceptors on the anaerobic biodegradability of chlorinated phenols and benzoic acids

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Haeggblom, M.M.; Rivera, M.D.; Young, L.Y.

    1993-04-01

    Methanogeneic conditions can promote the biodegradation of a number of halogenated aromatic compounds. This study, using sediments from freshwater and estuarine sites, is an evaluation of the anaerobic biodegradability of monochlorinated phenols and benzoic acids coupled to denitrification, sulfidogenesis, and methanogenesis. The results indicate that chlorinated phenols and benzoic acids are biodegradable under at least one set of anaerobic conditions. Metabolism depends both on the electron acceptor available and on the position of the chlorine substituent. Presence of alternative electron acceptors, nitrate, sulfate, and carbonate, can affect degradation rates and substrate specificities. Since contaminated sites usually have mixtures of wastes,more » bioremediation efforts may need to consider the activities of diverse anaerobic communities to carry out effective treatment of all components. 37 refs., 4 figs., 4 tabs.« less

  5. Oxidation and mobilization of selenium by nitrate in irrigation drainage

    USGS Publications Warehouse

    Wright, W.G.

    1999-01-01

    Selenium (Se) can be oxidized by nitrate (NO3-) from irrigation on Cretaceous marine shale in western Colorado. Dissolved Se concentrations are positively correlated with dissolved NO3- concentrations in surface water and ground water samples from irrigated areas. Redox conditions dominate in the mobilization of Se in marine shale hydrogeologic settings; dissolved Se concentrations increase with increasing platinum-electrode potentials. Theoretical calculations for the oxidation of Se by NO3- and oxygen show favorable Gibbs free energies for the oxidation of Se by NO3-, indicating NO3- can act as an electron acceptor for the oxidation of Se. Laboratory batch experiments were performed by adding Mancos Shale samples to zero- dissolved-oxygen water containing 0, 5, 50, and 100 mg/L NO3- as N (mg N/L). Samples were incubated in airtight bottles at 25??C for 188 d; samples collected from the batch experiment bottles show increased Se concentrations over time with increased NO3- concentrations. Pseudo first-order rate constants for NO3- oxidation of Se ranged from 0.0007 to 0.0048/d for 0 to 100 mg N/L NO3- concentrations, respectively. Management of N fertilizer applications in Cretaceous shale settings might help to control the oxidation and mobilization of Se and other trace constituents into the environment.

  6. Photochemical Aging of α-pinene and β-pinene Secondary Organic Aerosol formed from Nitrate Radical Oxidation: New Insights into the Formation and Fates of Highly Oxygenated Gas- and Particle-phase Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Nah, T.; Sanchez, J.; Boyd, C.; Ng, N. L.

    2015-12-01

    The nitrate radical (NO3), one of the most important oxidants in the nocturnal atmosphere, can react rapidly with a variety of biogenic volatile organic compounds (BVOCs) to form high mass concentrations of secondary organic aerosol (SOA) and organic nitrates (ON). Despite its critical importance in aerosol formation, the mechanisms and products from the NO3 oxidation of BVOCs have been largely unexplored, and the fates of their SOA and ON after formation are not well characterized. In this work, we studied the formation of SOA and ON from the NO3 oxidation of α-pinene and β-pinene and investigated for the first time how they evolve during dark and photochemical aging through a series of chamber experiments performed at the Georgia Tech Environmental Chamber (GTEC) facility. The α-pinene and β-pinene SOA are characterized using real-time gas- and particle-phase measurements, which are used to propose mechanisms for SOA and organic nitrate formation and aging. Highly oxygenated gas- and particle-phase ON (containing as many as 9 oxygen atoms) are detected during the NO3 reaction. In addition, the β-pinene SOA and α-pinene SOA exhibited drastically different behavior during photochemical aging. Our results indicate that nighttime ON formed by NO3+monoterpene chemistry can serve as either NOx reservoirs or sinks depending on the monoterpene precursor. Results from this study provide fundamental data for evaluating the contributions of NO3+monoterpene reactions to ambient OA measured in the Southeastern U.S.

  7. Nitrate and Nitrite Variability at the Seafloor of an Oxygen Minimum Zone Revealed by a Novel Microfluidic In-Situ Chemical Sensor

    PubMed Central

    Yücel, Mustafa; Beaton, Alexander D.; Dengler, Marcus; Mowlem, Matthew C.; Sohl, Frank; Sommer, Stefan

    2015-01-01

    Microfluidics, or lab-on-a-chip (LOC) is a promising technology that allows the development of miniaturized chemical sensors. In contrast to the surging interest in biomedical sciences, the utilization of LOC sensors in aquatic sciences is still in infancy but a wider use of such sensors could mitigate the undersampling problem of ocean biogeochemical processes. Here we describe the first underwater test of a novel LOC sensor to obtain in situ calibrated time-series (up to 40 h) of nitrate+nitrite (ΣNOx) and nitrite on the seafloor of the Mauritanian oxygen minimum zone, offshore Western Africa. Initial tests showed that the sensor successfully reproduced water column (160 m) nutrient profiles. Lander deployments at 50, 100 and 170 m depth indicated that the biogeochemical variability was high over the Mauritanian shelf: The 50 m site had the lowest ΣNOx concentration, with 15.2 to 23.4 μM (median=18.3 μM); while at the 100 site ΣNOx varied between 21.0 and 30.1 μM over 40 hours (median = 25.1μM). The 170 m site had the highest median ΣNOx level (25.8 μM) with less variability (22.8 to 27.7 μM). At the 50 m site, nitrite concentration decreased fivefold from 1 to 0.2 μM in just 30 hours accompanied by decreasing oxygen and increasing nitrate concentrations. Taken together with the time series of oxygen, temperature, pressure and current velocities, we propose that the episodic intrusion of deeper waters via cross-shelf transport leads to intrusion of nitrate-rich, but oxygen-poor waters to shallower locations, with consequences for benthic nitrogen cycling. This first validation of an LOC sensor at elevated water depths revealed that when deployed for longer periods and as a part of a sensor network, LOC technology has the potential to contribute to the understanding of the benthic biogeochemical dynamics. PMID:26161958

  8. Respiration-linked proton translocation coupled to anaerobic reduction of manganese(IV) and iron(III) in Shewanella putrefaciens MR-1.

    PubMed Central

    Myers, C R; Nealson, K H

    1990-01-01

    An oxidant pulse technique, with lactate as the electron donor, was used to study respiration-linked proton translocation in the manganese- and iron-reducing bacterium Shewanella putrefaciens MR-1. Cells grown anaerobically with fumarate or nitrate as the electron acceptor translocated protons in response to manganese (IV), fumarate, or oxygen. Cells grown anaerobically with fumarate also translocated protons in response to iron(III) and thiosulfate, whereas those grown with nitrate did not. Aerobically grown cells translocated protons only in response to oxygen. Proton translocation with all electron acceptors was abolished in the presence of the protonophore carbonyl cyanide m-chlorophenylhydrazone (20 microM) and was partially to completely inhibited by the electron transport inhibitor 2-n-heptyl-4-hydroxyquinoline N-oxide (50 microM). PMID:2172208

  9. Engineering of Pyranose Dehydrogenase for Increased Oxygen Reactivity

    PubMed Central

    Krondorfer, Iris; Lipp, Katharina; Brugger, Dagmar; Staudigl, Petra; Sygmund, Christoph; Haltrich, Dietmar; Peterbauer, Clemens K.

    2014-01-01

    Pyranose dehydrogenase (PDH), a member of the GMC family of flavoproteins, shows a very broad sugar substrate specificity but is limited to a narrow range of electron acceptors and reacts extremely slowly with dioxygen as acceptor. The use of substituted quinones or (organo)metals as electron acceptors is undesirable for many production processes, especially of food ingredients. To improve the oxygen reactivity, site-saturation mutagenesis libraries of twelve amino acids around the active site of Agaricus meleagris PDH were expressed in Saccharomyces cerevisiae. We established high-throughput screening assays for oxygen reactivity and standard dehydrogenase activity using an indirect Amplex Red/horseradish peroxidase and a DCIP/D-glucose based approach. The low number of active clones confirmed the catalytic role of H512 and H556. Only one position was found to display increased oxygen reactivity. Histidine 103, carrying the covalently linked FAD cofactor in the wild-type, was substituted by tyrosine, phenylalanine, tryptophan and methionine. Variant H103Y was produced in Pichia pastoris and characterized and revealed a five-fold increase of the oxygen reactivity. PMID:24614932

  10. Alkalilimnicola ehrlichii sp. nov., a novel, arsenite-oxidizing haloalkaliphilic gammaproteobacterium capable of chemoautotrophic or heterotrophic growth with nitrate or oxygen as the electron acceptor

    USGS Publications Warehouse

    Hoeft, S.E.; Blum, J.S.; Stolz, J.F.; Tabita, F.R.; Witte, B.; King, G.M.; Santini, J.M.; Oremland, R.S.

    2007-01-01

    A facultative chemoautotrophic bacterium, strain MLHE-1T, was isolated from Mono Lake, an alkaline hypersaline soda lake in California, USA. Cells of strain MLHE-1T were Gram-negative, short motile rods that grew with inorganic electron donors (arsenite, hydrogen, sulfide or thiosulfate) coupled with the reduction of nitrate to nitrite. No aerobic growth was attained with arsenite or sulfide, but hydrogen sustained both aerobic and anaerobic growth. No growth occurred when nitrite or nitrous oxide was substituted for nitrate. Heterotrophic growth was observed under aerobic and anaerobic (nitrate) conditions. Cells of strain MLHE-1T could oxidize but not grow on CO, while CH4 neither supported growth nor was it oxidized. When grown chemoautotrophically, strain MLHE-1T assimilated inorganic carbon via the Calvin-Benson-Bassham reductive pentose phosphate pathway, with the activity of ribulose 1,5-bisphosphate carboxylase (RuBisCO) functioning optimally at 0.1 M NaCl and at pH 7.3. Strain MLHE-1T grew over broad ranges of pH (7.3-10.0; optimum, 9.3), salinity (115-190 g l-1; optimum 30 g l-1) and temperature (113-40 ??C; optimum, 30 ??C). Phylogenetic analysis of 16S rRNA gene sequences placed strain MLHE-1T in the class Gammaproteobacteria (family Ectothiorhodospiraceae) and most closely related to Alkalispirillum mobile (98.5%) and Alkalilimnicola halodurans (98.6%), although none of these three haloalkaliphilic micro-organisms were capable of photoautotrophic growth and only strain MLHE-1T was able to oxidize As(III). On the basis of physiological characteristics and DNA-DNA hybridization data, it is suggested that strain MLHE-1T represents a novel species within the genus Alkalilimnicola for which the name Alkalilimnicola ehrlichii is proposed. The type strain is MLHE-1T (=DSM 17681T =ATCC BAA-1101T). Aspects of the annotated full genome of Alkalilimnicola ehrlichii are discussed in the light of its physiology. ?? 2007 IUMS.

  11. Organic nitrates and nitrate tolerance--state of the art and future developments.

    PubMed

    Daiber, Andreas; Münzel, Thomas; Gori, Tommaso

    2010-01-01

    The hemodynamic and antiischemic effects of nitroglycerin (GTN) are lost upon chronic administration due to the rapid development of nitrate tolerance. The mechanism of this phenomenon has puzzled several generations of scientists, but recent findings have led to novel hypotheses. The formation of reactive oxygen and nitrogen species in the mitochondria and the subsequent inhibition of the nitrate-bioactivating enzyme mitochondrial aldehyde dehydrogenase (ALDH-2) appear to play a central role, at least for GTN, that is, bioactivated by ALDH-2. Importantly, these findings provide the opportunity to reconcile the two "traditional" hypotheses of nitrate tolerance, that is, the one postulating a decreased bioactivation and the concurrent one suggesting a role of oxidative stress. Furthermore, recent animal and human experimental studies suggest that the organic nitrates are not a homogeneous group but demonstrate a broad diversity with regard to induction of vascular dysfunction, oxidative stress, and other side effects. In the past, attempts to avoid nitrate-induced side effects have focused on administration schedules that would allow a "nitrate-free interval"; in the future, the role of co-therapies with antioxidant compounds and of activation of endogeneous protective pathways such as the heme oxygenase 1 (HO-1) will need to be explored. However, the development of new nitrates, for example, tolerance-free aminoalkyl nitrates or combination of nitrate groups with established cardiovascular drugs like ACE inhibitors or AT(1)-receptor blockers (hybrid molecules) may be of great clinical interest. Copyright © 2010 Elsevier Inc. All rights reserved.

  12. Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

    USGS Publications Warehouse

    Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

    2007-01-01

    Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

  13. Influence of Different Electron Donors and Acceptors on Dehalorespiration of Tetrachloroethene by Desulfitobacterium frappieri TCE1

    PubMed Central

    Gerritse, Jan; Drzyzga, Oliver; Kloetstra, Geert; Keijmel, Mischa; Wiersum, Luit P.; Hutson, Roger; Collins, Matthew D.; Gottschal, Jan C.

    1999-01-01

    Strain TCE1, a strictly anaerobic bacterium that can grow by reductive dechlorination of tetrachloroethene (PCE) and trichloroethene (TCE), was isolated by selective enrichment from a PCE-dechlorinating chemostat mixed culture. Strain TCE1 is a gram-positive, motile, curved rod-shaped organism that is 2 to 4 by 0.6 to 0.8 μm and has approximately six lateral flagella. The pH and temperature optima for growth are 7.2 and 35°C, respectively. On the basis of a comparative 16S rRNA sequence analysis, this bacterium was identified as a new strain of Desulfitobacterium frappieri, because it exhibited 99.7% relatedness to the D. frappieri type strain, strain PCP-1. Growth with H2, formate, l-lactate, butyrate, crotonate, or ethanol as the electron donor depends on the availability of an external electron acceptor. Pyruvate and serine can also be used fermentatively. Electron donors (except formate and H2) are oxidized to acetate and CO2. When l-lactate is the growth substrate, strain TCE1 can use the following electron acceptors: PCE and TCE (to produce cis-1,2-dichloroethene), sulfite and thiosulfate (to produce sulfide), nitrate (to produce nitrite), and fumarate (to produce succinate). Strain TCE1 is not able to reductively dechlorinate 3-chloro-4-hydroxyphenylacetate. The growth yields of the newly isolated bacterium when PCE is the electron acceptor are similar to those obtained for other dehalorespiring anaerobes (e.g., Desulfitobacterium sp. strain PCE1 and Desulfitobacterium hafniense) and the maximum specific reductive dechlorination rates are 4 to 16 times higher (up to 1.4 μmol of chloride released · min−1 · mg of protein−1). Dechlorination of PCE and TCE is an inducible process. In PCE-limited chemostat cultures of strain TCE1, dechlorination is strongly inhibited by sulfite but not by other alternative electron acceptors, such as fumarate or nitrate. PMID:10583967

  14. Skeletal muscle as an endogenous nitrate reservoir

    PubMed Central

    Piknova, Barbora; Park, Ji Won; Swanson, Kathryn M.; Dey, Soumyadeep; Noguchi, Constance Tom; Schechter, Alan N

    2015-01-01

    The nitric oxide synthase (NOS) family of enzymes form nitric oxide (NO) from arginine in the presence of oxygen. At reduced oxygen availability NO is also generated from nitrate in a two step process by bacterial and mammalian molybdopterin proteins, and also directly from nitrite by a variety of five-coordinated ferrous hemoproteins. The mammalian NO cycle also involves direct oxidation of NO to nitrite, and both NO and nitrite to nitrate by oxy-ferrous hemoproteins. The liver and blood are considered the sites of active mammalian NO metabolism and nitrite and nitrate concentrations in the liver and blood of several mammalian species, including human, have been determined. However, the large tissue mass of skeletal muscle had not been generally considered in the analysis of the NO cycle, in spite of its long-known presence of significant levels of active neuronal NOS (nNOS or NOS1). We hypothesized that skeletal muscle participates in the NO cycle and, due to its NO oxidizing heme protein, oxymyoglobin, has high concentrations of nitrate ions. We measured nitrite and nitrate concentrations in rat and mouse leg skeletal muscle and found unusually high concentrations of nitrate but similar levels of nitrite, when compared to the liver. The nitrate reservoir in muscle is easily accessible via the bloodstream and therefore nitrate is available for transport to internal organs where it can be reduced to nitrite and NO. Nitrate levels in skeletal muscle and blood in nNOS−/− mice were dramatically lower when compared with controls, which support further our hypothesis. Although the nitrate reductase activity of xanthine oxidoreductase in muscle is less than that of liver, the residual activity in muscle could be very important in view of its total mass and the high basal level of nitrate. We suggest that skeletal muscle participates in overall NO metabolism, serving as a nitrate reservoir, for direct formation of nitrite and NO, and for determining levels of nitrate

  15. Phenotypic characteristics of nitrate and 3-nitro-1-propionate-respiring enzymes of the obligate respiratory anaerobe Denitrobacterium detoxificans

    USDA-ARS?s Scientific Manuscript database

    Anaerobic respiration consumes reducing equivalents generated during fermentation thereby contributing to the maintenance of hydrogen homoeostasis in gut ecosystems. Nitrate and 3-nitro-1-propionate (NPA) are acceptors used by the nonfermentative, rumen anaerobe, Denitrobacterium detoxificans, whic...

  16. Evaluating the source of streamwater nitrate using d15N and d18O in nitrate in two watersheds in New Hampshire, USA

    Treesearch

    Linda H. Pardo; Carol Kendall; Jennifer Pett-Ridge; Cecily C.Y. Chang; Cecily C.Y. Chang

    2004-01-01

    The natural abundance of nitrogen and oxygen isotopes in nitrate can be a powerful tool for identifying the source of nitrate in streamwater in forested watersheds, because the two main sources of nitrate, atmospheric deposition and microbial nitrification, have distinct d18O values. Using a simple mixing model, we estimated the relative fractions in streamwater...

  17. Nitrogen and Triple Oxygen Isotopic Analyses of Atmospheric Particulate Nitrate over the Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Kamezaki, Kazuki; Hattori, Shohei; Iwamoto, Yoko; Ishino, Sakiko; Furutani, Hiroshi; Miki, Yusuke; Miura, Kazuhiko; Uematsu, Mitsuo; Yoshida, Naohiro

    2017-04-01

    Nitrate plays a significant role in the biogeochemical cycle. Atmospheric nitrate (NO3- and HNO3) are produced by reaction precursor as NOx (NO and NO2) emitted by combustion, biomass burning, lightning, and soil emission, with atmospheric oxidants like ozone (O3), hydroxyl radical (OH), peroxy radical and halogen oxides. Recently, industrial activity lead to increases in the concentrations of nitrogen species (NOx and NHy) throughout the environment. Because of the increase of the amount of atmospheric nitrogen deposition, the oceanic biogeochemical cycle are changed (Galloway et al., 2004; Kim et al., 2011). However, the sources and formation pathways of atmospheric nitrate are still uncertain over the Pacific Ocean because the long-term observation is limited. Stable isotope analysis is useful tool to gain information of sources, sinks and formation pathways. The nitrogen stable isotopic composition (δ15N) of atmospheric particulate NO3- can be used to posses information of its nitrogen sources (Elliott et al., 2007). Triple oxygen isotopic compositions (Δ17O = δ17O - 0.52 ×δ18O) of atmospheric particulate NO3- can be used as tracer of the relative importance of mass-independent oxygen bearing species (e.g. O3, BrO; Δ17O ≠ 0 ‰) and mass-dependent oxygen bearing species (e.g. OH radical; Δ17O ≈ 0 ‰) through the formation processes from NOx to NO3- in the atmosphere (Michalski et al., 2003; Thiemens, 2006). Here, we present the isotopic compositions of atmospheric particulate NO3- samples collected over the Pacific Ocean from 40˚ S to 68˚ N. We observed significantly low δ15N values for atmospheric particulate NO3- on equatorial Pacific Ocean during both cruises. Although the data is limited, combination analysis of δ15N and Δ17O values for atmospheric particulate NO3- showed the possibility of the main nitrogen source of atmospheric particulate NO3- on equatorial Pacific Ocean is ammonia oxidation in troposphere. Furthermore, the Δ17O values

  18. Nitrate ammonification in mangrove soils: a hidden source of nitrite?

    PubMed Central

    Balk, Melike; Laverman, Anniet M.; Keuskamp, Joost A.; Laanbroek, Hendrikus J.

    2015-01-01

    Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests. The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden by the presence of active nitrite-reducing microorganisms under the nitrate-limited conditions of most mangrove forest soils. PMID:25784903

  19. Nitrate ammonification in mangrove soils: a hidden source of nitrite?

    PubMed

    Balk, Melike; Laverman, Anniet M; Keuskamp, Joost A; Laanbroek, Hendrikus J

    2015-01-01

    Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests. The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden by the presence of active nitrite-reducing microorganisms under the nitrate-limited conditions of most mangrove forest soils.

  20. Temperature-Dependent Compensation and Optical Quenching by Thermal Oxygen Donors in Germanium

    NASA Technical Reports Server (NTRS)

    Watson, D.; Guptill, M.; Huffman, J.; Krabach, T.; Raines, S.

    1994-01-01

    Photothermal ionization spectroscopy of germanium, doped in the impurity-band conduction range with gallium acceptors and with thermal oxygen donors, reveals that the donors and acceptors compensate each other at temperatures higher than about 5K, but that the impurities coexist as neutral donors and acceptors at lower temperatures.

  1. Oxygen and life on earth: an anesthesiologist's views on oxygen evolution, discovery, sensing, and utilization.

    PubMed

    Lindahl, Sten G E

    2008-07-01

    The advent of oxygenic photosynthesis and the accumulation of oxygen in our atmosphere opened up new possibilities for the development of life on Earth. The availability of oxygen, the most capable electron acceptor on our planet, allowed the development of highly efficient energy production from oxidative phosphorylation, which shaped the evolutionary development of aerobic life forms from the first multicellular organisms to the vertebrates.

  2. Stimulating hydrogenotrophic denitrification in simulated groundwater containing high dissolved oxygen and nitrate concentrations.

    PubMed

    Schnobrich, Matthew R; Chaplin, Brian P; Semmens, Michael J; Novak, Paige J

    2007-05-01

    In agricultural areas, nitrate (NO3-) is a common groundwater pollutant as a result of extensive fertilizer application. At elevated concentrations, NO3- consumption causes methemoglobinemia in infants and has been linked to several cancers; therefore, its removal from groundwater is important. The addition of hydrogen gas (H2) via gas-permeable membranes has been shown to stimulate denitrification in a laboratory-scale reactor. This research, using large columns packed with aquifer material to which a simulated groundwater was fed, was conducted to further identify the conditions required for the use of membrane-delivered H2 in situ. In this study, we show that this novel technology was capable of treating highly contaminated (25 mg/L NO3- -N) and oxygenated (5.5mg/L dissolved oxygen) water, but that nutrient addition and gas pressure adjustment was required. Complete NO3- reduction was possible without the accumulation of either NO2- or N2O when the H2 lumen pressure was increased to 17 psi and phosphate was added to the groundwater. The total organic carbon content of the effluent, 110 cm downgradient of H2 addition, did not increase. The results from these experiments demonstrate that this technology can be optimized to provide effective NO3- removal in even challenging field applications.

  3. Nitrate Reduction Functional Genes and Nitrate Reduction Potentials Persist in Deeper Estuarine Sediments. Why?

    PubMed Central

    Papaspyrou, Sokratis; Smith, Cindy J.; Dong, Liang F.; Whitby, Corinne; Dumbrell, Alex J.; Nedwell, David B.

    2014-01-01

    Denitrification and dissimilatory nitrate reduction to ammonium (DNRA) are processes occurring simultaneously under oxygen-limited or anaerobic conditions, where both compete for nitrate and organic carbon. Despite their ecological importance, there has been little investigation of how denitrification and DNRA potentials and related functional genes vary vertically with sediment depth. Nitrate reduction potentials measured in sediment depth profiles along the Colne estuary were in the upper range of nitrate reduction rates reported from other sediments and showed the existence of strong decreasing trends both with increasing depth and along the estuary. Denitrification potential decreased along the estuary, decreasing more rapidly with depth towards the estuary mouth. In contrast, DNRA potential increased along the estuary. Significant decreases in copy numbers of 16S rRNA and nitrate reducing genes were observed along the estuary and from surface to deeper sediments. Both metabolic potentials and functional genes persisted at sediment depths where porewater nitrate was absent. Transport of nitrate by bioturbation, based on macrofauna distributions, could only account for the upper 10 cm depth of sediment. A several fold higher combined freeze-lysable KCl-extractable nitrate pool compared to porewater nitrate was detected. We hypothesised that his could be attributed to intracellular nitrate pools from nitrate accumulating microorganisms like Thioploca or Beggiatoa. However, pyrosequencing analysis did not detect any such organisms, leaving other bacteria, microbenthic algae, or foraminiferans which have also been shown to accumulate nitrate, as possible candidates. The importance and bioavailability of a KCl-extractable nitrate sediment pool remains to be tested. The significant variation in the vertical pattern and abundance of the various nitrate reducing genes phylotypes reasonably suggests differences in their activity throughout the sediment column. This

  4. Assessing the Role of Sewers and Atmospheric Deposition as Nitrate Contamination Sources to Urban Surface Waters using Stable Nitrate Isotopes

    NASA Astrophysics Data System (ADS)

    Sikora, M. T.; Elliott, E. M.

    2009-12-01

    Excess nitrate (NO3-) contributes to the overall degraded quality of streams in many urban areas. These systems are often dominated by impervious surfaces and storm sewers that can route atmospherically deposited nitrogen, from both wet and dry deposition, to waterways. Moreover, in densely populated watersheds there is the potential for interaction between urban waterways and sewer systems. The affects of accumulated nitrate in riverine and estuary systems include low dissolved oxygen, loss of species diversity, increased mortality of aquatic species, and general eutrophication of the waterbody. However, the dynamics of nitrate pollution from each source and it’s affect on urban waterways is poorly constrained. The isotopes of nitrogen and oxygen in nitrate have been proven effective in helping to distinguish contamination sources to ground and surface waters. In order to improve our understanding of urban nitrate pollution sources and dynamics, we examined nitrate isotopes (δ15N and δ18O) in base- and stormflow samples collected over a two-year period from a restored urban stream in Pittsburgh, Pennsylvania (USA). Nine Mile Run drains a 1,600 hectare urban watershed characterized by 38% impervious surface cover. Prior work has documented high nitrate export from the watershed (~19 kg NO3- ha-1 yr-1). Potential nitrate sources to the watershed include observed sewer overflows draining directly to the stream, as well as atmospheric deposition (~23 kg NO3- ha-1 yr-1). In this and other urban systems with high percentages of impervious surfaces, there is likely minimal input from nitrate derived from soil or fertilizer. In this presentation, we examine spatial and temporal patterns in nitrate isotopic composition collected at five locations along Nine Mile Run characterized by both sanitary and combined-sewer cross-connections. Preliminary isotopic analysis of low-flow winter streamwater samples suggest nitrate export from Nine Mile Run is primarily influenced by

  5. Organic Nitrate Therapy, Nitrate Tolerance, and Nitrate-Induced Endothelial Dysfunction: Emphasis on Redox Biology and Oxidative Stress.

    PubMed

    Daiber, Andreas; Münzel, Thomas

    2015-10-10

    Organic nitrates, such as nitroglycerin (GTN), isosorbide-5-mononitrate and isosorbide dinitrate, and pentaerithrityl tetranitrate (PETN), when given acutely, have potent vasodilator effects improving symptoms in patients with acute and chronic congestive heart failure, stable coronary artery disease, acute coronary syndromes, or arterial hypertension. The mechanisms underlying vasodilation include the release of •NO or a related compound in response to intracellular bioactivation (for GTN, the mitochondrial aldehyde dehydrogenase [ALDH-2]) and activation of the enzyme, soluble guanylyl cyclase. Increasing cyclic guanosine-3',-5'-monophosphate (cGMP) levels lead to an activation of the cGMP-dependent kinase I, thereby causing the relaxation of the vascular smooth muscle by decreasing intracellular calcium concentrations. The hemodynamic and anti-ischemic effects of organic nitrates are rapidly lost upon long-term (low-dose) administration due to the rapid development of tolerance and endothelial dysfunction, which is in most cases linked to increased intracellular oxidative stress. Enzymatic sources of reactive oxygen species under nitrate therapy include mitochondria, NADPH oxidases, and an uncoupled •NO synthase. Acute high-dose challenges with organic nitrates cause a similar loss of potency (tachyphylaxis), but with distinct pathomechanism. The differences among organic nitrates are highlighted regarding their potency to induce oxidative stress and subsequent tolerance and endothelial dysfunction. We also address pleiotropic effects of organic nitrates, for example, their capacity to stimulate antioxidant pathways like those demonstrated for PETN, all of which may prevent adverse effects in response to long-term therapy. Based on these considerations, we will discuss and present some preclinical data on how the nitrate of the future should be designed.

  6. Organic Nitrate Therapy, Nitrate Tolerance, and Nitrate-Induced Endothelial Dysfunction: Emphasis on Redox Biology and Oxidative Stress

    PubMed Central

    2015-01-01

    Abstract Organic nitrates, such as nitroglycerin (GTN), isosorbide-5-mononitrate and isosorbide dinitrate, and pentaerithrityl tetranitrate (PETN), when given acutely, have potent vasodilator effects improving symptoms in patients with acute and chronic congestive heart failure, stable coronary artery disease, acute coronary syndromes, or arterial hypertension. The mechanisms underlying vasodilation include the release of •NO or a related compound in response to intracellular bioactivation (for GTN, the mitochondrial aldehyde dehydrogenase [ALDH-2]) and activation of the enzyme, soluble guanylyl cyclase. Increasing cyclic guanosine-3′,-5′-monophosphate (cGMP) levels lead to an activation of the cGMP-dependent kinase I, thereby causing the relaxation of the vascular smooth muscle by decreasing intracellular calcium concentrations. The hemodynamic and anti-ischemic effects of organic nitrates are rapidly lost upon long-term (low-dose) administration due to the rapid development of tolerance and endothelial dysfunction, which is in most cases linked to increased intracellular oxidative stress. Enzymatic sources of reactive oxygen species under nitrate therapy include mitochondria, NADPH oxidases, and an uncoupled •NO synthase. Acute high-dose challenges with organic nitrates cause a similar loss of potency (tachyphylaxis), but with distinct pathomechanism. The differences among organic nitrates are highlighted regarding their potency to induce oxidative stress and subsequent tolerance and endothelial dysfunction. We also address pleiotropic effects of organic nitrates, for example, their capacity to stimulate antioxidant pathways like those demonstrated for PETN, all of which may prevent adverse effects in response to long-term therapy. Based on these considerations, we will discuss and present some preclinical data on how the nitrate of the future should be designed. Antioxid. Redox Signal. 23, 899–942. PMID:26261901

  7. Triple Oxygen Isotope Measurement of Nitrate to Analyze Impact of Aircraft Emissions

    NASA Astrophysics Data System (ADS)

    Chan, Sharleen

    With 4.9% of total anthropogenic radiative forcing attributed to aircraft emissions, jet engines combust copious amounts of fuel producing gases including: NOx (NO + NO2), SOx, VOC's and fine particles [IPCC (1999), IPCC (2007), Lee et al., 2009]. The tropospheric non-linear relationships between NOx, OH and O3 contribute uncertainties in the ozone budget amplified by poor understanding of the NOx cycle. In a polluted urban environment, interaction of gases and particles produce various new compounds that are difficult to measure with analytical tools available today [Thiemens, 2006]. Using oxygen triple isotopic measurement of NO3 to investigate gas to particle formation and chemical transformation in the ambient atmosphere, this study presents data obtained from aerosols sampled at NASA's Dryden Aircraft Operations Facility (DAOF) in Palmdale, CA during January and February, 2009 and Los Angeles International Airport (LAX) during Fall 2009, Winter 2010, and Spring 2010. The aerosols collected from jet aircraft exhaust in Palmdale exhibit an oxygen isotope anomaly (Delta17O =delta 17O -0.52 delta18O) increase with photochemical age of particles (-0.22 to 26.41‰) while NO3 concentration decreases from 53.76 - 5.35ppm with a radial distance from the jet dependency. Bulk aerosol samples from LAX exhibit seasonal variation with Delta17 O and NO3 concentration peaking in winter suggesting multiple sources and increased fossil fuel burning. Using oxygen triple isotopes of NO3, we are able to distinguish primary and secondary nitrate by aircraft emissions allowing new insight into a portion of the global nitrogen cycle. This represents a new and potentially important means to uniquely identify aircraft emissions on the basis of the unique isotopic composition of jet aircraft emissions.

  8. Respiration of Nitrate and Nitrite.

    PubMed

    Cole, Jeffrey A; Richardson, David J

    2008-09-01

    Nitrate reduction to ammonia via nitrite occurs widely as an anabolic process through which bacteria, archaea, and plants can assimilate nitrate into cellular biomass. Escherichia coli and related enteric bacteria can couple the eight-electron reduction of nitrate to ammonium to growth by coupling the nitrate and nitrite reductases involved to energy-conserving respiratory electron transport systems. In global terms, the respiratory reduction of nitrate to ammonium dominates nitrate and nitrite reduction in many electron-rich environments such as anoxic marine sediments and sulfide-rich thermal vents, the human gastrointestinal tract, and the bodies of warm-blooded animals. This review reviews the regulation and enzymology of this process in E. coli and, where relevant detail is available, also in Salmonella and draws comparisons with and implications for the process in other bacteria where it is pertinent to do so. Fatty acids may be present in high levels in many of the natural environments of E. coli and Salmonella in which oxygen is limited but nitrate is available to support respiration. In E. coli, nitrate reduction in the periplasm involves the products of two seven-gene operons, napFDAGHBC, encoding the periplasmic nitrate reductase, and nrfABCDEFG, encoding the periplasmic nitrite reductase. No bacterium has yet been shown to couple a periplasmic nitrate reductase solely to the cytoplasmic nitrite reductase NirB. The cytoplasmic pathway for nitrate reduction to ammonia is restricted almost exclusively to a few groups of facultative anaerobic bacteria that encounter high concentrations of environmental nitrate.

  9. Impact of electron acceptor availability on the anaerobic oxidation of methane in coastal freshwater and brackish wetland sediments

    NASA Astrophysics Data System (ADS)

    Segarra, Katherine E. A.; Comerford, Christopher; Slaughter, Julia; Joye, Samantha B.

    2013-08-01

    Methane, a powerful greenhouse gas, is both produced and consumed in anoxic coastal sediments via microbial processes. Although the anaerobic oxidation of methane (AOM) is almost certainly an important process in coastal freshwater and salt marsh sediments, the factors that control the rates and pathways of AOM in these habitats are poorly understood. Here, we present the first direct measurements of AOM activity in freshwater (0 PSU) and brackish (25 PSU) wetland sediments. Despite disparate sulfate concentrations, both environments supported substantial rates of AOM. Higher sulfate reduction (SR) rates were measured in the freshwater site and SR at both sites was of sufficient magnitude to support the observed AOM activity. Laboratory incubations of freshwater and brackish tidal, wetland sediments amended with either nothing [control], sulfate, nitrate, manganese oxide (birnessite) or iron oxide (ferrihydrite) and supplied with a methane headspace were used to evaluate the impact(s) of electron acceptor availability on potential AOM rates. Maximum AOM rates in brackish slurries occurred in the sulfate amendments. In contrast, addition of sulfate and several possible electron acceptors to the freshwater slurries decreased AOM rates relative to the control. High ratios of AOM activity relative to SR activity in the nitrate, birnessite, and ferrihydrite treatments of both the brackish and freshwater slurries provided evidence of AOM decoupled from SR. This study demonstrates that both freshwater and brackish coastal wetland sediments support considerable rates of anaerobic methanotrophy and provides evidence for sulfate-independent AOM that may be coupled to nitrate, iron, or manganese reduction in both environments.

  10. Roles of oxyanions in promoting the partial oxidation of styrene on Ag(110): nitrate, carbonate, sulfite, and sulfate.

    PubMed

    Zhou, Ling; Madix, Robert J

    2010-11-02

    The promotion roles of nitrate, carbonate, sulfite, and sulfate in oxidation of styrene on Ag(110) have been studied by means of temperature-programmed reaction spectroscopy (TPRS) and X-ray photoelectron spectroscopy (XPS). While isolated nitrate leads only to the secondary oxidation of styrene, a surface co-covered by nitrate, oxygen, and 0.1 ML cesium promotes a low-temperature epoxidation pathway. XPS indicates that adsorbed surface oxygen is the oxidant in this selective reaction pathway, and, though it affects the reactivity of the surface oxygen, nitrate is a spectator. Carbonate acts as an oxygen transfer agent and exhibits similar reactivity and selectivity as an oxidant for styrene as does atomic oxygen on Ag(110). The reactivities of sulfite and sulfate are strongly dependent on their surface structures, the c(6 × 2) sulfite showing the capacity to transfer oxygen to styrene.

  11. Iron Corrosion Induced by Nonhydrogenotrophic Nitrate-Reducing Prolixibacter sp. Strain MIC1-1

    PubMed Central

    Ito, Kimio; Wakai, Satoshi; Tsurumaru, Hirohito; Ohkuma, Moriya; Harayama, Shigeaki

    2014-01-01

    Microbiologically influenced corrosion (MIC) of metallic materials imposes a heavy economic burden. The mechanism of MIC of metallic iron (Fe0) under anaerobic conditions is usually explained as the consumption of cathodic hydrogen by hydrogenotrophic microorganisms that accelerates anodic Fe0 oxidation. In this study, we describe Fe0 corrosion induced by a nonhydrogenotrophic nitrate-reducing bacterium called MIC1-1, which was isolated from a crude-oil sample collected at an oil well in Akita, Japan. This strain requires specific electron donor-acceptor combinations and an organic carbon source to grow. For example, the strain grew anaerobically on nitrate as a sole electron acceptor with pyruvate as a carbon source and Fe0 as the sole electron donor. In addition, ferrous ion and l-cysteine served as electron donors, whereas molecular hydrogen did not. Phylogenetic analysis based on 16S rRNA gene sequences revealed that strain MIC1-1 was a member of the genus Prolixibacter in the order Bacteroidales. Thus, Prolixibacter sp. strain MIC1-1 is the first Fe0-corroding representative belonging to the phylum Bacteroidetes. Under anaerobic conditions, Prolixibacter sp. MIC1-1 corroded Fe0 concomitantly with nitrate reduction, and the amount of iron dissolved by the strain was six times higher than that in an aseptic control. Scanning electron microscopy analyses revealed that microscopic crystals of FePO4 developed on the surface of the Fe0 foils, and a layer of FeCO3 covered the FePO4 crystals. We propose that cells of Prolixibacter sp. MIC1-1 accept electrons directly from Fe0 to reduce nitrate. PMID:25548048

  12. Formation, Evaporation, and Hydrolysis of Organic Nitrates from Nitrate Radical Oxidation of Monoterpenes

    NASA Astrophysics Data System (ADS)

    Ng, N. L.; Takeuchi, M.; Eris, G.; Berkemeier, T.; Boyd, C.; Nah, T.; Xu, L.

    2017-12-01

    Organic nitrates play an important role in the cycling of NOx and secondary organic aerosol (SOA) formation, yet their formation mechanisms and fates remain highly uncertain. The interactions of biogenic VOCs with NO3 radicals represent a direct way for positively linking anthropogenic and biogenic emissions. Results from ambient studies suggest that organic nitrates have a relatively short lifetime, though corresponding laboratory data are limited. SOA and organic nitrates produced at night may evaporate the following morning due to increasing temperatures or dilution of semi-volatile compounds. Once formed, organic nitrates can also undergo hydrolysis in the presence of particle water. In this work, we investigate the formation, evaporation, and hydrolysis of organic nitrates generated from the nitrate radical oxidation of a-pinene, b-pinene, and limonene. Experiments are conducted in the Georgia Environmental Chamber facility (GTEC) under dry and humid conditions and different temperatures. Experiments are also designed to probe different peroxy radical pathways (RO2+HO2 vs RO2+NO3). Speciated gas-phase and particle-phase organic nitrates are continuously monitored by a Filter Inlet for Gases and AEROsols High Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (FIGAERO-HR-ToF-CIMS). Bulk aerosol composition is measured by a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). A large suite of highly oxygenated gas- and particle-phase organic nitrates are formed rapidly. We find a resistance to aerosol evaporation when it is heated. The extent of organic nitrate hydrolysis in the humid experiments is evaluated. The dynamics of the speciated organic nitrates over the course of the experiments will also be discussed. Results from this chamber study provide fundamental data for understanding the dynamics of organic nitrate aerosols over its atmospheric lifetime.

  13. Respiration Strategies Utilized by the Gill Endosymbiont from the Host Lucinid Codakia orbicularis (Bivalvia: Lucinidae)

    PubMed Central

    Duplessis, Melinda R.; Ziebis, Wiebke; Gros, Olivier; Caro, Audrey; Robidart, Julie; Felbeck, Horst

    2004-01-01

    The large tropical lucinid clam Codakia orbicularis has a symbiotic relationship with intracellular, sulfide-oxidizing chemoautotrophic bacteria. The respiration strategies utilized by the symbiont were explored using integrative techniques on mechanically purified symbionts and intact clam-symbiont associations along with habitat analysis. Previous work on a related symbiont species found in the host lucinid Lucinoma aequizonata showed that the symbionts obligately used nitrate as an electron acceptor, even under oxygenated conditions. In contrast, the symbionts of C. orbicularis use oxygen as the primary electron acceptor while evidence for nitrate respiration was lacking. Direct measurements obtained by using microelectrodes in purified symbiont suspensions showed that the symbionts consumed oxygen; this intracellular respiration was confirmed by using the redox dye CTC (5-cyano-2,3-ditolyl tetrazolium chloride). In the few intact chemosymbioses tested in previous studies, hydrogen sulfide production was shown to occur when the animal-symbiont association was exposed to anoxia and elemental sulfur stored in the thioautotrophic symbionts was proposed to serve as an electron sink in the absence of oxygen and nitrate. However, this is the first study to show by direct measurements using sulfide microelectrodes in enriched symbiont suspensions that the symbionts are the actual source of sulfide under anoxic conditions. PMID:15240294

  14. Electron acceptors for anaerobic oxidation of methane drive microbial community structure and diversity in mud volcanoes.

    PubMed

    Ren, Ge; Ma, Anzhou; Zhang, Yanfen; Deng, Ye; Zheng, Guodong; Zhuang, Xuliang; Zhuang, Guoqiang; Fortin, Danielle

    2018-04-06

    Mud volcanoes (MVs) emit globally significant quantities of methane into the atmosphere, however, methane cycling in such environments is not yet fully understood, as the roles of microbes and their associated biogeochemical processes have been largely overlooked. Here, we used data from high-throughput sequencing of microbial 16S rRNA gene amplicons from six MVs in the Junggar Basin in northwest China to quantify patterns of diversity and characterize the community structure of archaea and bacteria. We found anaerobic methanotrophs and diverse sulfate- and iron-reducing microbes in all of the samples, and the diversity of both archaeal and bacterial communities was strongly linked to the concentrations of sulfate, iron and nitrate, which could act as electron acceptors in anaerobic oxidation of methane (AOM). The impacts of sulfate/iron/nitrate on AOM in the MVs were verified by microcosm experiments. Further, two representative MVs were selected to explore the microbial interactions based on phylogenetic molecular ecological networks. The sites showed distinct network structures, key species and microbial interactions, with more complex and numerous linkages between methane-cycling microbes and their partners being observed in the iron/sulfate-rich MV. These findings suggest that electron acceptors are important factors driving the structure of microbial communities in these methane-rich environments. © 2018 The Authors. Environmental Microbiology published by Society for Applied Microbiology and John Wiley & Sons Ltd.

  15. Associative Memory Acceptors.

    ERIC Educational Resources Information Center

    Card, Roger

    The properties of an associative memory are examined in this paper from the viewpoint of automata theory. A device called an associative memory acceptor is studied under real-time operation. The family "L" of languages accepted by real-time associative memory acceptors is shown to properly contain the family of languages accepted by one-tape,…

  16. FLAME DENITRATION AND REDUCTION OF URANIUM NITRATE TO URANIUM DIOXIDE

    DOEpatents

    Hedley, W.H.; Roehrs, R.J.; Henderson, C.M.

    1962-06-26

    A process is given for converting uranyl nitrate solution to uranium dioxide. The process comprises spraying fine droplets of aqueous uranyl nitrate solution into a hightemperature hydrocarbon flame, said flame being deficient in oxygen approximately 30%, retaining the feed in the flame for a sufficient length of time to reduce the nitrate to the dioxide, and recovering uranium dioxide. (AEC)

  17. Inorganic Nitrate Promotes the Browning of White Adipose Tissue through the Nitrate-Nitrite-Nitric Oxide Pathway

    PubMed Central

    Roberts, Lee D; Ashmore, Tom; Kotwica, Aleksandra O; Murfitt, Steven A; Fernandez, Bernadette O; Feelisch, Martin; Griffin, Julian L

    2015-01-01

    Inorganic nitrate was once considered an oxidation end-product of nitric oxide metabolism with little biological activity. However, recent studies have demonstrated that dietary nitrate can modulate mitochondrial function in man and is effective in reversing features of the metabolic syndrome in mice. Using a combined histological, metabolomics, and transcriptional and protein analysis approach we mechanistically define that nitrate not only increases the expression of thermogenic genes in brown-adipose tissue but also induces the expression of brown adipocyte-specific genes and proteins in white adipose tissue, substantially increasing oxygen consumption and fatty acid β-oxidation in adipocytes. Nitrate induces these phenotypic changes through a mechanism distinct from known physiological small molecule activators of browning, the recently identified nitrate-nitrite-nitric oxide pathway. The nitrate-induced browning effect was enhanced in hypoxia, a serious co-morbidity affecting white adipose tissue in obese individuals, and corrected impaired brown adipocyte-specific gene expression in white adipose tissue in a murine model of obesity. Since resulting beige/brite cells exhibit anti-obesity and anti-diabetic effects, nitrate may be an effective means of inducing the browning response in adipose tissue to treat the metabolic syndrome. PMID:25249574

  18. Mesophilic, Circumneutral Anaerobic Iron Oxidation as a Remediation Mechanism for Radionuclides, Nitrate and Perchlorate

    NASA Astrophysics Data System (ADS)

    Bose, S.; Thrash, J. C.; Coates, J. D.

    2008-12-01

    Iron oxidation is a novel anaerobic metabolism where microorganisms obtain reducing equivalents from the oxidization of Fe(II) and assimilate carbon from organic carbon compounds or CO2. Recent evidence indicates that in combination with the activity of dissimilatory Fe(III)-reducing bacteria, anaerobic microbial Fe(II) oxidation can also contribute to the global iron redox cycle. Studies have also proved that Fe(II)- oxidation is ubiquitous in diverse environments and produce a broad range of insoluble iron forms as end products. These biogenic Fe(III)-oxides and mixed valence Fe minerals have a very high adsorption capacity of heavy metals and radionuclides. Adsorption and immobilization by these biogenic Fe phases produced at circumneutral pH, is now considered a very effective mode of remediation of radionuclides like Uranium, especially under variable redox conditions. By coupling soluble and insoluble Fe(II) oxidation with nitrate and perchlorate as terminal electron acceptors in-situ, anaerobic Fe-oxidation can also be used for environmental cleanup of Fe through Fe-mineral precipitation, as well as nitrate and perchlorate through reduction. Coupling of Fe as the sole electron and energy source to the reduction of perchlorate or nitrate boosts the metabolism without building up biomass hence also taking care of biofouling. To understand the mechanisms by which microorganisms can grow at circumneutral pH by mesophilic, anaerobic iron oxidation and the ability of microorganisms to reduce nitrate and perchlorate coupled to iron oxidation recent work in our lab involved the physiological characterization of Dechlorospirillum strain VDY which was capable of anaerobic iron-oxidation with either nitrate or perchlorate serving as terminal electron acceptor. Under non-growth conditions, VDY oxidized 3mM Fe(II) coupled to nitrate reduction, and 2mM Fe(II) coupled to perchlorate reduction, in 24 hours. It contained a copy of the RuBisCO cbbM subunit gene which was

  19. Electron paramagnetic resonance study of neutral Mg acceptors in β-Ga2O3 crystals

    NASA Astrophysics Data System (ADS)

    Kananen, B. E.; Halliburton, L. E.; Scherrer, E. M.; Stevens, K. T.; Foundos, G. K.; Chang, K. B.; Giles, N. C.

    2017-08-01

    Electron paramagnetic resonance (EPR) is used to directly observe and characterize neutral Mg acceptors ( M gGa0 ) in a β-Ga2O3 crystal. These acceptors, best considered as small polarons, are produced when the Mg-doped crystal is irradiated at or near 77 K with x rays. During the irradiation, neutral acceptors are formed when holes are trapped at singly ionized Mg acceptors ( M gGa- ). Unintentionally present Fe3+ (3d5) and Cr3+ (3d3) transition-metal ions serve as the corresponding electron traps. The hole is localized in a nonbonding p orbital on a threefold-coordinated oxygen ion adjacent to an Mg ion at a sixfold-coordinated Ga site. These M gGa0 acceptors (S = 1/2) have a slightly anisotropic g matrix (principal values are 2.0038, 2.0153, and 2.0371). There is also partially resolved 69Ga and 71Ga hyperfine structure resulting from unequal interactions with the two Ga ions adjacent to the hole. With the magnetic field along the a direction, hyperfine parameters are 2.61 and 1.18 mT for the 69Ga nuclei at the two inequivalent neighboring Ga sites. The M gGa0 acceptors thermally convert back to their nonparamagnetic M gGa- charge state when the temperature of the crystal is raised above approximately 250 K.

  20. Influence of Oxygen and Nitrate on Fe (Hydr)oxide Mineral Transformation and Soil Microbial Communities during Redox Cycling.

    PubMed

    Mejia, Jacqueline; Roden, Eric E; Ginder-Vogel, Matthew

    2016-04-05

    Oscillations between reducing and oxidizing conditions are observed at the interface of anaerobic/oxic and anaerobic/anoxic environments, and are often stimulated by an alternating flux of electron donors (e.g., organic carbon) and electron acceptors (e.g., O2 and NO3(-)). In iron (Fe) rich soils and sediments, these oscillations may stimulate the growth of both Fe-reducing bacteria (FeRB) and Fe-oxidizing bacteria (FeOB), and their metabolism may induce cycling between Fe(II) and Fe(III), promoting the transformation of Fe (hydr)oxide minerals. Here, we examine the mineralogical evolution of lepidocrocite and ferrihydrite, and the adaptation of a natural microbial community to alternating Fe-reducing (anaerobic with addition of glucose) and Fe-oxidizing (with addition of nitrate or air) conditions. The growth of FeRB (e.g., Geobacter) is stimulated under anaerobic conditions in the presence of glucose. However, the abundance of these organisms depends on the availability of Fe(III) (hydr)oxides. Redox cycling with nitrate results in decreased Fe(II) oxidation thereby decreasing the availability of Fe(III) for FeRB. Additionally, magnetite is detected as the main product of both lepidocrocite and ferrihydrite reduction. In contrast, introduction of air results in increased Fe(II) oxidation, increasing the availability of Fe(III) and the abundance of Geobacter. In the lepidocrocite reactors, Fe(II) oxidation by dissolved O2 promotes the formation of ferrihydrite and lepidocrocite, whereas in the ferrihydrite reactors we observe a decrease in magnetite stoichiometry (e.g., oxidation). Understanding Fe (hydr)oxide transformation under environmentally relevant redox cycling conditions provides insight into nutrient availability and transport, contaminant mobility, and microbial metabolism in soils and sediments.

  1. Ralstonia solanacearum uses inorganic nitrogen metabolism for virulence, ATP production, and detoxification in the oxygen-limited host xylem environment.

    PubMed

    Dalsing, Beth L; Truchon, Alicia N; Gonzalez-Orta, Enid T; Milling, Annett S; Allen, Caitilyn

    2015-03-17

    Genomic data predict that, in addition to oxygen, the bacterial plant pathogen Ralstonia solanacearum can use nitrate (NO3(-)), nitrite (NO2(-)), nitric oxide (NO), and nitrous oxide (N2O) as terminal electron acceptors (TEAs). Genes encoding inorganic nitrogen reduction were highly expressed during tomato bacterial wilt disease, when the pathogen grows in xylem vessels. Direct measurements found that tomato xylem fluid was low in oxygen, especially in plants infected by R. solanacearum. Xylem fluid contained ~25 mM NO3(-), corresponding to R. solanacearum's optimal NO3(-) concentration for anaerobic growth in vitro. We tested the hypothesis that R. solanacearum uses inorganic nitrogen species to respire and grow during pathogenesis by making deletion mutants that each lacked a step in nitrate respiration (ΔnarG), denitrification (ΔaniA, ΔnorB, and ΔnosZ), or NO detoxification (ΔhmpX). The ΔnarG, ΔaniA, and ΔnorB mutants grew poorly on NO3(-) compared to the wild type, and they had reduced adenylate energy charge levels under anaerobiosis. While NarG-dependent NO3(-) respiration directly enhanced growth, AniA-dependent NO2(-) reduction did not. NO2(-) and NO inhibited growth in culture, and their removal depended on denitrification and NO detoxification. Thus, NO3(-) acts as a TEA, but the resulting NO2(-) and NO likely do not. None of the mutants grew as well as the wild type in planta, and strains lacking AniA (NO2(-) reductase) or HmpX (NO detoxification) had reduced virulence on tomato. Thus, R. solanacearum exploits host NO3(-) to respire, grow, and cause disease. Degradation of NO2(-) and NO is also important for successful infection and depends on denitrification and NO detoxification systems. The plant-pathogenic bacterium Ralstonia solanacearum causes bacterial wilt, one of the world's most destructive crop diseases. This pathogen's explosive growth in plant vascular xylem is poorly understood. We used biochemical and genetic approaches to show

  2. Evaluation of Nitrate Sources and Nitrate Management Strategies in California Suburban Growth Areas

    NASA Astrophysics Data System (ADS)

    Singleton, M. J.; Moran, J. E.; Esser, B. K.; Leif, R. N.; McNab, W. W.; Carle, S. F.; Moore, K. B.

    2005-12-01

    Population growth in California has pushed the boundaries of suburban communities into formerly agricultural areas. As a result there is considerable uncertainty as to whether nitrate contamination in groundwater wells results from current sources or is a legacy of agriculture. Fertilizer application for historical agriculture is frequently assumed to be a major source, but septic system leachate, other animal waste, and residential fertilizer application may also contribute. Potential remediation strategies may include improved fertilizer management and/or conversion from septic tanks to sewer systems, but the sources of nitrate and pathways to groundwater must first be identified in order to develop a plan of action. We combine the detection of trace organic compounds that are specific to domestic waste with isotopic compositions of nitrogen and oxygen in nitrate in order to determine nitrate sources. Under anaerobic conditions and in the presence of an electron donor such as organic carbon, microbially mediated denitrification may transform nitrate to harmless nitrogen gas, and fractionate the isotopologues of any residual nitrate. The occurrence of saturated zone denitrification is detected by measuring excess dissolved nitrogen gas with a field-portable membrane inlet mass spectrometer system. Groundwater age dating using the 3H/3He method provides a means of tracking the history of nitrate inputs to groundwater, including changes in nitrate flux after implementation of a remediation program. Groundwater that pre-dates agricultural or suburban activity is used to define natural background levels of nitrate. Study areas in California include Chico, Livermore, and Gilroy. This work was performed under the auspices of the U.S. Department of Energy by University of California, Lawrence Livermore National Laboratory under Contract W-7405-Eng-48.

  3. North American International Society for Microbial Electrochemical Technologies Meeting (Abstracts)

    DTIC Science & Technology

    2016-04-18

    systems. Unlike the well-studied case of dissolved oxygen (D.O.) effects on the facultative metabolic shift between aerobic respiration and nitrate...The Pt catalyst can effectively catalyze oxygen reduction and ensure a healthy operation of bioelectrochemical systems but its high cost limits the... effect of COEs on other species in bioelectrochemical systems. Effects of additional electron acceptors in bio-anodic processes: oxygen and sulfate

  4. Thermovibrio ammonificans sp. nov., a thermophilic, chemolithotrophic, nitrate-ammonifying bacterium from deep-sea hydrothermal vents.

    PubMed

    Vetriani, Costantino; Speck, Mark D; Ellor, Susan V; Lutz, Richard A; Starovoytov, Valentin

    2004-01-01

    A thermophilic, anaerobic, chemolithoautotrophic bacterium was isolated from the walls of an active deep-sea hydrothermal vent chimney on the East Pacific Rise at 9 degrees 50' N. Cells of the organism were Gram-negative, motile rods that were about 1.0 microm in length and 0.6 microm in width. Growth occurred between 60 and 80 degrees C (optimum at 75 degrees C), 0.5 and 4.5% (w/v) NaCl (optimum at 2%) and pH 5 and 7 (optimum at 5.5). Generation time under optimal conditions was 1.57 h. Growth occurred under chemolithoautotrophic conditions in the presence of H2 and CO2, with nitrate or sulfur as the electron acceptor and with concomitant formation of ammonium or hydrogen sulfide, respectively. Thiosulfate, sulfite and oxygen were not used as electron acceptors. Acetate, formate, lactate and yeast extract inhibited growth. No chemoorganoheterotrophic growth was observed on peptone, tryptone or Casamino acids. The genomic DNA G+C content was 54.6 mol%. Phylogenetic analyses of the 16S rRNA gene sequence indicated that the organism was a member of the domain Bacteria and formed a deep branch within the phylum Aquificae, with Thermovibrio ruber as its closest relative (94.4% sequence similarity). On the basis of phylogenetic, physiological and genetic considerations, it is proposed that the organism represents a novel species within the newly described genus Thermovibrio. The type strain is Thermovibrio ammonificans HB-1T (=DSM 15698T=JCM 12110T).

  5. Simultaneous reduction of nitrate and selenate by cell suspensions of selenium-respiring bacteria

    USGS Publications Warehouse

    Oremland, R.S.; Blum, J.S.; Bindi, A.B.; Dowdle, P.R.; Herbel, M.; Stolz, J.F.

    1999-01-01

    Washed-cell suspensions of Sulfurospirillum barnesii reduced selenate [Se(VI)] when cells were cultured with nitrate, thiosulfate, arsenate, or fumarate as the electron acceptor. When the concentration of the electron donor was limiting, Se(VI) reduction in whole cells was approximately fourfold greater in Se(VI)-grown cells than was observed in nitrate-grown cells; correspondingly, nitrate reduction was ~11-fold higher in nitrate-grown cells than in Se(VI)-grown cells. However, a simultaneous reduction of nitrate and Se(VI) was observed in both cases. At nonlimiting electron donor concentrations, nitrate- grown cells suspended with equimolar nitrate and selenate achieved a complete reductive removal of nitrogen and selenium oxyanions, with the bulk of nitrate reduction preceding that of selenate reduction. Chloramphenicol did not inhibit these reductions. The Se(VI)-respiring haloalkaliphile Bacillus arsenicoselenatis gave similar results, but its Se(VI) reductase was not constitutive in nitrate-grown cells. No reduction of Se(VI) was noted for Bacillus selenitireducens, which respires selenite. The results of kinetic experiments with cell membrane preparations of S. barnesii suggest the presence of constitutive selenate and nitrate reduction, as well as an inducible, high- affinity nitrate reductase in nitrate-grown cells which also has a low affinity for selenate. The simultaneous reduction of micromolar Se(VI) in the presence of millimolar nitrate indicates that these organisms may have a functional use in bioremediating nitrate-rich, seleniferous agricultural wastewaters. Results with 75Se-selenate tracer show that these organisms can lower ambient Se(VI) concentrations to levels in compliance with new regulations proposed for release of selenium oxyanions into the environment.

  6. Coupled jump rotational dynamics in aqueous nitrate solutions.

    PubMed

    Banerjee, Puja; Yashonath, Subramanian; Bagchi, Biman

    2016-12-21

    A nitrate ion (NO 3 - ) with its trigonal planar geometry and charges distributed among nitrogen and oxygen atoms can couple to the extensive hydrogen bond network of water to give rise to unique dynamical characteristics. We carry out detailed atomistic simulations and theoretical analyses to investigate these aspects and report certain interesting findings. We find that the nitrate ions in aqueous potassium nitrate solution exhibit large amplitude rotational jump motions that are coupled to the hydrogen bond rearrangement dynamics of the surrounding water molecules. The jump motion of nitrate ions bears certain similarities to the Laage-Hynes mechanism of rotational jump motions of tagged water molecules in neat liquid water. We perform a detailed atomic-level investigation of hydrogen bond rearrangement dynamics of water in aqueous KNO 3 solution to unearth two distinct mechanisms of hydrogen bond exchange that are instrumental to promote these jump motions of nitrate ions. As observed in an earlier study by Xie et al., in the first mechanism, after breaking a hydrogen bond with nitrate ion, water forms a new hydrogen bond with a water molecule, whereas the second mechanism involves just a switching of hydrogen bond between the two oxygen atoms of the same nitrate ion (W. J. Xie et al., J. Chem. Phys. 143, 224504 (2015)). The magnitude as well as nature of the reorientational jump of nitrate ion for the two mechanisms is different. In the first mechanism, nitrate ion predominantly undergoes out-of-plane rotation, while in the second mechanism, in-plane reorientation of NO 3 - is favourable. These have been deduced by computing the torque on the nitrate ion during the hydrogen bond switching event. We have defined and computed the time correlation function for coupled reorientational jump of nitrate and water and obtained the associated relaxation time which is also different for the two mechanisms. These results provide insight into the relation between the

  7. From Nitrate to Nitric Oxide: The Role of Salivary Glands and Oral Bacteria.

    PubMed

    Qu, X M; Wu, Z F; Pang, B X; Jin, L Y; Qin, L Z; Wang, S L

    2016-12-01

    The salivary glands and oral bacteria play an essential role in the conversion process from nitrate (NO 3 - ) and nitrite (NO 2 - ) to nitric oxide (NO) in the human body. NO is, at present, recognized as a multifarious messenger molecule with important vascular and metabolic functions. Besides the endogenous L-arginine pathway, which is catalyzed by complex NO synthases, nitrate in food contributes to the main extrinsic generation of NO through a series of sequential steps (NO 3 - -NO 2 - -NO pathway). Up to 25% of nitrate in circulation is actively taken up by the salivary glands, and as a result, its concentration in saliva can increase 10- to 20-fold. However, the mechanism has not been clearly illustrated until recently, when sialin was identified as an electrogenic 2NO 3 - /H + transporter in the plasma membrane of salivary acinar cells. Subsequently, the oral bacterial species located at the posterior part of the tongue reduce nitrate to nitrite, as catalyzed by nitrate reductase enzymes. These bacteria use nitrate and nitrite as final electron acceptors in their respiration and meanwhile help the host to convert nitrate to NO as the first step. This review describes the role of salivary glands and oral bacteria in the metabolism of nitrate and in the maintenance of NO homeostasis. The potential therapeutic applications of oral inorganic nitrate and nitrite are also discussed. © International & American Associations for Dental Research 2016.

  8. Production of Methane During Anaerobic Degradation of Ethanol in Gasoline

    EPA Science Inventory

    Field and laboratory studies show that the natural biodegradation of benzene may be inhibited by the presence of ethanol. Preferential biodegradation of ethanol can consume electron acceptors such as sulfate, nitrate, or oxygen that are needed for BTEX biodegradation. An additi...

  9. Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

    PubMed

    Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

    2016-07-21

    Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface.

  10. Acceptors in ZnO

    DOE PAGES

    Mccluskey, Matthew D.; Corolewski, Caleb; Lv, Jinpeng; ...

    2015-03-21

    Zinc oxide (ZnO) has potential for a range of applications in the area of optoelectronics. The quest for p-type ZnO has focused much attention on acceptors. In this paper, Cu, N, and Li acceptor impurities are discussed. Experimental evidence shows that these point defects have acceptor levels 3.2, 1.5, and 0.8 eV above the valence-band maximum, respectively. The levels are deep because the ZnO valence band is quite low compared to conventional, non-oxide semiconductors. Using MoO2 contacts, the electrical resistivity of ZnO:Li was measured and showed behavior consistent with bulk hole conduction for temperatures above 400 K. A photoluminescence peakmore » in ZnO nanocrystals has been attributed to an acceptor, which may involve a zinc vacancy. High field (W-band) electron paramagnetic resonance measurements on the nanocrystals revealed an axial center with g = 2.0033 and g = 2.0075, along with an isotropic center at g = 2.0053.« less

  11. Effects of nitrate injection on microbial enhanced oil recovery and oilfield reservoir souring.

    PubMed

    da Silva, Marcio Luis Busi; Soares, Hugo Moreira; Furigo, Agenor; Schmidell, Willibaldo; Corseuil, Henry Xavier

    2014-11-01

    Column experiments were utilized to investigate the effects of nitrate injection on sulfate-reducing bacteria (SRB) inhibition and microbial enhanced oil recovery (MEOR). An indigenous microbial consortium collected from the produced water of a Brazilian offshore field was used as inoculum. The presence of 150 mg/L volatile fatty acids (VFA´s) in the injection water contributed to a high biological electron acceptors demand and the establishment of anaerobic sulfate-reducing conditions. Continuous injection of nitrate (up to 25 mg/L) for 90 days did not inhibit souring. Contrariwise, in nitrogen-limiting conditions, the addition of nitrate stimulated the proliferation of δ-Proteobacteria (including SRB) and the associated sulfide concentration. Denitrification-specific nirK or nirS genes were not detected. A sharp decrease in water interfacial tension (from 20.8 to 14.5 mN/m) observed concomitantly with nitrate consumption and increased oil recovery (4.3 % v/v) demonstrated the benefits of nitrate injection on MEOR. Overall, the results support the notion that the addition of nitrate, at this particular oil reservoir, can benefit MEOR by stimulating the proliferation of fortuitous biosurfactant-producing bacteria. Higher nitrate concentrations exceeding the stoichiometric volatile fatty acid (VFA) biodegradation demands and/or the use of alternative biogenic souring control strategies may be necessary to warrant effective SRB inhibition down gradient from the injection wells.

  12. Effect of nitrate, acetate and hydrogen on native perchlorate-reducing microbial communities and their activity in vadose soil

    PubMed Central

    Nozawa-Inoue, Mamie; Jien, Mercy; Yang, Kun; Rolston, Dennis E.; Hristova, Krassimira R.; Scow, Kate M.

    2011-01-01

    Effect of nitrate, acetate and hydrogen on native perchlorate-reducing bacteria (PRB) was examined by conducting microcosm tests using vadose soil collected from a perchlorate-contaminated site. The rate of perchlorate reduction was enhanced by hydrogen amendment and inhibited by acetate amendment, compared to unamendment. Nitrate was reduced before perchlorate in all amendments. In hydrogen-amended and unamended soils, nitrate delayed perchlorate reduction, suggesting the PRB preferentially use nitrate as an electron acceptor. In contrast, nitrate eliminated the inhibitory effect of acetate amendment on perchlorate reduction and increased the rate and the extent, possibly because the preceding nitrate reduction/denitrification decreased the acetate concentration which was inhibitory to the native PRB. In hydrogen-amended and unamended soils, perchlorate reductase gene (pcrA) copies, representing PRB densities, increased with either perchlorate or nitrate reduction, suggesting either perchlorate or nitrate stimulates growth of the PRB. In contrast, in acetate-amended soil pcrA increased only when perchlorate was depleted: a large portion of the PRB may have not utilized nitrate in this amendment. Nitrate addition did not alter the distribution of the dominant pcrA clones in hydrogen-amended soil, likely because of the functional redundancy of PRB as nitrate-reducers/denitrifiers, whereas acetate selected different pcrA clones from those with hydrogen amendment. PMID:21284679

  13. Algal productivity and nitrate assimilation in an effluent dominated concrete lined stream

    USGS Publications Warehouse

    Kent, Robert; Belitz, Kenneth; Burton, Carmen

    2005-01-01

    This study examined algal productivity and nitrate assimilation in a 2.85 km reach of Cucamonga Creek, California, a concrete lined channel receiving treated municipal wastewater. Stream nitrate concentrations observed at two stations indicated nearly continuous loss throughout the diel study. Nitrate loss in the reach was approximately 11 mg/L/d or 1.0 g/m2/d as N, most of which occurred during daylight. The peak rate of nitrate loss (1.13 mg/l/hr) occurred just prior to an afternoon total CO2 depletion. Gross primary productivity, as estimated by a model using the observed differences in dissolved oxygen between the two stations, was 228 mg/L/d, or 21 g/m2/d as O2. The observed diel variations in productivity, nitrate loss, pH, dissolved oxygen, and CO2indicate that nitrate loss was primarily due to algal assimilation. The observed levels of productivity and nitrate assimilation were exceptionally high on a mass per volume basis compared to studies on other streams; these rates occurred because of the shallow stream depth. This study suggests that concrete‐lined channels can provide an important environmental service: lowering of nitrate concentrations similar to rates observed in biological treatment systems.

  14. Phylogenetic analyses and nitrate-reducing activity of fungal cultures isolated from the permanent, oceanic oxygen minimum zone of the Arabian Sea.

    PubMed

    Manohar, Cathrine Sumathi; Menezes, Larissa Danielle; Ramasamy, Kesava Priyan; Meena, Ram M

    2015-03-01

    Reports on the active role of fungi as denitrifiers in terrestrial ecosystems have stimulated an interest in the study of the role of fungi in oxygen-deficient marine systems. In this study, the culturable diversity of fungi was investigated from 4 stations within the permanent, oceanic, oxygen minimum zone of the Arabian Sea. The isolated cultures grouped within the 2 major fungal phyla Ascomycota and Basidiomycota; diversity estimates in the stations sampled indicated that the diversity of the oxygen-depleted environments is less than that of mangrove regions and deep-sea habitats. Phylogenetic analyses of 18S rRNA sequences revealed a few divergent isolates that clustered with environmental sequences previously obtained by others. This is significant, as these isolates represent phylotypes that so far were known only from metagenomic studies and are of phylogenetic importance. Nitrate reduction activity, the first step in the denitrification process, was recorded for isolates under simulated anoxic, deep-sea conditions showing ecological significance of fungi in the oxygen-depleted habitats. This report increases our understanding of fungal diversity in unique, poorly studied habitats and underlines the importance of fungi in the oxygen-depleted environments.

  15. Distinguishing summertime atmospheric production of nitrate across the East Antarctic Ice Sheet

    NASA Astrophysics Data System (ADS)

    Shi, G.; Buffen, A. M.; Ma, H.; Hu, Z.; Sun, B.; Li, C.; Yu, J.; Ma, T.; An, C.; Jiang, S.; Li, Y.; Hastings, M. G.

    2018-06-01

    Surface snow and atmospheric samples collected along a traverse from the coast to the ice sheet summit (Dome A) are used to investigate summertime atmospheric production of nitrate (NO3-) across East Antarctica. The strong relationship observed between δ15N and δ18O of nitrate in the surface snow suggests a large (lesser) extent of nitrate photolysis in the interior (coastal) region. A linear correlation between the oxygen isotopes of nitrate (δ18O and Δ17O) indicates mixing of various oxidants that react with NOx (NOx = NO + NO2) to produce atmospheric nitrate. On the plateau, the isotopes of snow nitrate are best explained by local reoxidation chemistry of NOx, possibly occurring in both condensed and gas phases. Nitrate photolysis results in redistribution of snow nitrate, and the plateau snow is a net exporter of nitrate and its precursors. Our results suggest that while snow-sourced NOx from the plateau due to photolysis is a significant input to the nitrate budget in coastal snow (up to ∼35%), tropospheric transport from mid-low latitudes dominates (∼65%) coastal snow nitrate. The linear relationship of δ18O vs. Δ17O of the snow nitrate suggests a predominant role of hydroxyl radical (OH) and ozone (O3) in nitrate production, although a high Δ17O(O3) is required to explain the observations. Across Antarctica the oxygen isotope composition of OH appears to be dominated by exchange with water vapor, despite the very dry environment. One of the largest uncertainties in quantifying nitrate production pathways is the limited knowledge of atmospheric oxidant isotopic compositions.

  16. Ammonium Nitrate as an Oxidant for Composite Propellants. Part 1. Preliminary Considerations

    DTIC Science & Technology

    1954-09-01

    obtainable with a sirple amonium nitrate / fucl mixture is about 223 sec. The advantage of using oxygenated fuels is calculated for cases where, because of...Propulsion Laboratory have used ammonium nitrate and mixtures of arnonium nitrate and ammonium perchloratc as the oxidant /in COi IDE ,T )kL/ D ISCRT&T...previously considered are giver and also a curve for amnonium nitrate / polyvinyl alcohol mixtures. Amonium pcrchlorate/polyisobutenc is inclu£cd for

  17. Reactions of atomic oxygen with the chlorate ion and the perchlorate ion

    NASA Astrophysics Data System (ADS)

    Anan'ev, Vladimir; Miklin, Mikhail; Kriger, Ludmila

    2014-06-01

    The reactions of the chlorate ion with atomic oxygen formed under photolysis of the nitrate ion introduced to potassium chlorate crystal by co-crystallization were studied by optical and infrared absorption spectroscopy. The perchlorate ion was found to form in solids as product of addition reaction of singlet atomic oxygen, formed under dissociation of the peroxynitrite ion - the product of isomerization of the excited nitrate ion. Triplet atomic oxygen does not react with the chlorate ion. The atomic oxygen formed under photolysis of the nitrate ion introduced to potassium perchlorate crystal by co-crystallization does not react with the perchlorate ion.

  18. The preservation of long-range transported nitrate in snow at Summit, Greenland (Invited)

    NASA Astrophysics Data System (ADS)

    Hastings, M. G.

    2013-12-01

    Nitrate is one of the major anions found in polar and alpine snow, both today and in the past. Deposition of nitrate to snow surfaces results from reactions of nitrogen oxides (NOx) with oxidants in the atmosphere, resulting in the production of HNO3 that is incorporated into precipitation or reacts on the surface of particles. Several factors motivate studying nitrate concentration in ice cores including reconstructing past levels of NOx, tropospheric oxidant concentrations and natural variability in NOx sources. The link between the atmospheric concentration of NOx and nitrate concentration in ice core records is problematic because post-depositional processing, such as photolysis and evaporation, can impact the concentration of nitrate in snow. Recent work has shown that the isotopic ratios of nitrate (15N/14N, 18O/16O, 17O/16O) can be a powerful tool for tracing post-depositional loss of nitrate from surface snow. The isotopic composition of nitrate has been shown to contain information about the source of the nitrate (i.e, NOx sources) and the oxidation processes that convert NOx to nitrate in the atmosphere prior to deposition. Results from a number of studies at Summit, Greenland reveal limited loss of nitrate from surface snow during highly photoactive periods, and the oxygen isotopic signatures in snow nitrate appear to be representative of atmospheric deposition of nitrate from outside of Summit. Higher than expected oxygen isotope ratios (18O/16O, 17O/16O) found in Summit summertime nitrate were expected to be dependent upon local photochemistry in which nitrate in the snow is photolyzed to NOx that is then oxidized above the snow by BrO to reform nitrate (i.e., BrONO2). However, the oxygen isotopic composition of nitrate collected at high time resolution in surface snow does not show any link to local gas phase concentrations of a number of species, including BrO. Furthermore, the combination of nitrogen and oxygen isotope data reveals interesting

  19. Acceptor Ionization Energies in GaN*

    NASA Astrophysics Data System (ADS)

    Wang, Hao; Ban Chen, An

    2001-03-01

    The k.p Hamiltonian and a model potential are used to deduce the acceptor ionization energies in GaN from a systematic study of the chemical trend in GaAs, GaP, and InP. The acceptors studied include Be, Mg, Ca, Zn, and Cd on the cation sites and C, Si, and Ge on the anion sites. Our calculated acceptor ionization energies are estimated to be accurate to better than ten percent across the board. The ionization energies of C and Be (152 and 187 meV respectively) in wurtzite GaN are found to be lower than that of Mg (224 meV). The C was found to behave like the hydrogenic acceptor in all systems and it has the smallest ionization energy among all the acceptors studied.

  20. Transformation of Nitrate and Toluene in Groundwater by Sulfur Modified Iron(SMI-III)

    NASA Astrophysics Data System (ADS)

    Lee, W.; Park, S.; Lim, J.; Hong, U.; Kwon, S.; Kim, Y.

    2009-12-01

    In Korea, nitrate and benzene, toluene, ethylbenzene, and xylene isomers (BTEX) are frequently detected together as ground water contaminants. Therefore, a system simultaneously treating both nitrate (inorganic compound) and BTEX (organic compounds) is required to utilize groundwater as a water resource. In this study, we investigated the efficiency of Sulfur Modified Iron (SMI-III) in treating both nitrate and BTEX contaminated groundwater. Based on XRD (X-Ray Diffraction) analysis, the SMI-III is mainly composed of Fe3O4, S, and Fe. A series of column tests were conducted at three different empty bed contact times (EBCTs) for each compound. During the experiments, removal efficiency for both nitrate and toluene were linearly correlated with EBCT, suggesting that SMI-III have an ability to transform both nitrate and toluene. The concentration of SO42- and oxidation/reduction potential (ORP) were also measured. After exposed to nitrate contaminated groundwater, the composition of SMI-III was changed to Fe2O3, Fe3O4, Fe, and Fe0.95S1.05. The trends of effluent sulfate concentrations were inversely correlated with effluent nitrate concentrations, while the trends of ORP values, having the minimum values of -480 mV, were highly correlated with effluent nitrate concentrations. XRD analysis before and after exposed to nitrate contaminated groundwater, sulfate production, and nitrite detection as a reductive transformation by-product of nitrate suggest that nitrate is reductively transformed by SMI-III. Interestingly, in the toluene experiments, the trends of ORP values were inversely correlated with effluent toluene concentrations, suggesting that probably degrade through oxidation reaction. Consequently, nitrate and toluene probably degrade through reduction and oxidation reaction, respectively and SMI-III could serve as both electron donor and acceptor.

  1. Negative impacts of elevated nitrate on physiological performance are not exacerbated by low pH.

    PubMed

    Gomez Isaza, Daniel F; Cramp, Rebecca L; Franklin, Craig E

    2018-05-15

    Multiple environmental stressors, including nutrient effluents (i.e. nitrates [NO 3 - ]) and altered pH regimes, influence the persistence of freshwater species in anthropogenically disturbed habitats. Independently, nitrate and low pH affect energy allocation by increasing maintenance costs and disrupting oxygen uptake, which ultimately results in impacts upon whole animal performance. However, the interaction between these two stressors has not been characterised. To address this, the effects of nitrate and pH and their interaction on aerobic scope and physiological performance were investigated in the blueclaw crayfish, Cherax destructor. Crayfish were exposed to a 2 × 3 factorial combination, with two pH levels (pH 5.0 and 7.0) and three nitrate concentrations (0, 50 and 100 mg L -1 NO 3 - ). Crayfish were exposed to experimental conditions for 65 days and growth and survival were monitored. Aerobic scope (i.e. maximal - standard oxygen uptake) was measured at six time points (1, 3, 5, 7, 14, and 21 days) during exposure to experimental treatments. Crayfish performance was assessed after 28 days, by measuring chelae strength and whole animal activity capacity via the righting response. Survival was reduced in crayfish exposed to pH 5.0, but there was no exacerbation of this effect by exposure to high nitrate levels. Aerobic scope was compromised by the interaction between low pH and nitrate and resulted in prolonged elevations of standard oxygen uptake rates. Exposure to nitrate alone affected aerobic scope, causing a 59% reduction in maximum oxygen uptake. Reduced aerobic capacity translated to reduced chelae strength and righting capacity. Together, these data show that low pH and elevated nitrate levels reduce aerobic scope and translate to poorer performance in C. destructor, which may have the potential to affect organismal fitness in disturbed habitats. Copyright © 2018 Elsevier B.V. All rights reserved.

  2. Elevated nitrate alters the metabolic activity of embryonic zebrafish.

    PubMed

    Conlin, Sarah M; Tudor, M Scarlett; Shim, Juyoung; Gosse, Julie A; Neilson, Andrew; Hamlin, Heather J

    2018-04-01

    Nitrate accumulation in aquatic reservoirs from agricultural pollution has often been overlooked as a water quality hazard, yet a growing body of literature suggests negative effects on human and wildlife health following nitrate exposure. This research seeks to understand differences in oxygen consumption rates between different routes of laboratory nitrate exposure, whether via immersion or injection, in zebrafish (Danio rerio) embryos. Embryos were exposed within 1 h post fertilization (hpf) to 0, 10, and 100 mg/L NO 3 -N with sodium nitrate, or to counter ion control (CIC) treatments using sodium chloride. Embryos in the immersion treatments received an injection of 4 nL of appropriate treatment solution into the perivitelline space. At 24 hpf, Oxygen Consumption Rates (OCR) were measured and recorded in vivo using the Agilent Technologies XF e 96 Extracellular Flux Analyzer and Spheroid Microplate. Immersion exposures did not induce significant changes in OCR, yet nitrate induced significant changes when injected through the embryo chorion. Injection of 10 and 100 mg/L NO 3 -N down-regulated OCR compared to the control treatment group. Injection of the 100 mg/L CIC also significantly down-regulated OCR compared to the control treatment group. Interestingly, the 100 mg/L NO 3 -N treatment further down-regulated OCR compared to the 100 mg/L CIC treatment, suggesting the potential for additive effects between the counter ion and the ion of interest. These data support that elevated nitrate exposure can alter normal metabolic activity by changing OCR in 24 hpf embryos. These results highlight the need for regularly examining the counter ion of laboratory nitrate compounds while conducting research with developing zebrafish, and justify examining different routes of laboratory nitrate exposure, as the chorion may act as an effective barrier to nitrate penetration in zebrafish, which may lead to conservative estimates of significant effects in other

  3. Limitations of the isotopic composition of nitrates as a tracer of their origin

    NASA Astrophysics Data System (ADS)

    Kloppmann, Wolfram; Mayer, Bernhard; Otero, Neus; Sebilo, Mathieu; Gooddy, Daren; Lapworth, Dan; Surridge, Ben; Petelet Giraud, Emmanuelle; Flehoc, Christine; Baran, Nicole

    2017-04-01

    Nitrogen and oxygen isotopes are traditionally considered and frequently used as tracers of nitrate sources in watersheds used for drinking water production. The enrichment of synthetic nitrate-containing fertilizers in 18O due to the contribution of atmospheric oxygen in the production process confers a specific isotopic fingerprint to mineral fertilizers. In spite of the still widespread use on nitrate-containing synthetic fertilizers, their characteristic N and O isotope signatures are rarely unambiguously observed in nitrate-contaminated groundwater. We postulate, in line with Mengis et al. (2001), that fertilizer-derived nitrate is not directly and rapidly transferred to groundwater but rather retained in the soil-plant system as organic N and then mineralized and re-oxidized (termed the mineralization-immobilization turnover, MIT) thereby re-setting the oxygen isotope composition of nitrate and also changing its N isotope ratios. We show examples from watersheds on diverse alluvial/clastic and carbonate aquifers in eastern and northern France where, in spite of the use of mineral fertilizers, evidenced also through other isotopic tracers (boron isotopes), both N and O-isotope ratios are very homogeneous and compatible with nitrification of ammonium where 2/3 of oxygen is derived from soil water and 1/3 from atmospheric O2. These field data are corroborated by lysimeter data from Canada. Even if in areas where ammonium is derived from chemical fertilizers, N values still tend to be lower than in areas where ammonium is derived from manure/sewage, this is clearly a limitation to the dual isotope method (N, O) for nitrate source identification, but has important implications for the nitrogen mobility and residence time in soils amended with synthetic fertilizers (Sebilo et al., 2013). Mengis M., Walther U., Bernasconi S. M., Wehrli B. (2001) Limitations of Using δ18O for the Source Identification of Nitrate in Agricultural Soils. Environmental Science

  4. Insights on Alterations to the Rumen Ecosystem by Nitrate and Nitrocompounds

    PubMed Central

    Latham, Elizabeth A.; Anderson, Robin C.; Pinchak, William E.; Nisbet, David J.

    2016-01-01

    Nitrate and certain short chain nitrocompounds and nitro-oxy compounds are being investigated as dietary supplements to reduce economic and environmental costs associated with ruminal methane emissions. Thermodynamically, nitrate is a preferred electron acceptor in the rumen that consumes electrons at the expense of methanogenesis during dissimilatory reduction to an intermediate, nitrite, which is primarily reduced to ammonia although small quantities of nitrous oxide may also be produced. Short chain nitrocompounds act as direct inhibitors of methanogenic bacteria although certain of these compounds may also consume electrons at the expense of methanogenesis and are effective inhibitors of important foodborne pathogens. Microbial and nutritional consequences of incorporating nitrate into ruminant diets typically results in increased acetate production. Unlike most other methane-inhibiting supplements, nitrate decreases or has no effect on propionate production. The type of nitrate salt added influences rates of nitrate reduction, rates of nitrite accumulation and efficacy of methane reduction, with sodium and potassium salts being more potent than calcium nitrate salts. Digestive consequences of adding nitrocompounds to ruminant diets are more variable and may in some cases increase propionate production. Concerns about the toxicity of nitrate's intermediate product, nitrite, to ruminants necessitate management, as animal poisoning may occur via methemoglobinemia. Certain of the naturally occurring nitrocompounds, such as 3-nitro-1-propionate or 3-nitro-1-propanol also cause poisoning but via inhibition of succinate dehydrogenase. Typical risk management procedures to avoid nitrite toxicity involve gradually adapting the animals to higher concentrations of nitrate and nitrite, which could possibly be used with the nitrocompounds as well. A number of organisms responsible for nitrate metabolism in the rumen have been characterized. To date a single rumen bacterium

  5. Using dual-bacterial denitrification to improve δ15N determinations of nitrates containing mass-independent 17O

    USGS Publications Warehouse

    Coplen, T.B.; Böhlke, J.K.; Casciotti, K.L.

    2004-01-01

    The bacterial denitrification method for isotopic analysis of nitrate using N2O generated from Pseudomonas aureofaciens may overestimate δ15N values by as much as 1–2‰ for samples containing atmospheric nitrate because of mass-independent 17O variations in such samples. By analyzing such samples for δ15N and δ18O using the denitrifier Pseudomonas chlororaphis, one obtains nearly correct δ15N values because oxygen in N2O generated by P. chlororaphis is primarily derived from H2O. The difference between the apparent δ15N value determined with P. aureofaciens and that determined with P. chlororaphis, assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent 17O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different δ18O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N2O derived from the nitrate and from water with each denitrifier. This information can be used to improve δ15N values of nitrates having excess 17O. The same analyses also yield estimates of the magnitude of 17O excess in the nitrate (expressed as Δ17O) that may be useful in some environmental studies. The 1-σ uncertainties of δ15N, δ18O and Δ17O measurements are ±0.2, ±0.3 and ±5‰, respectively.

  6. Quantum Dot-Based Luminescent Oxygen Channeling Assay for Potential Application in Homogeneous Bioassays.

    PubMed

    Zhuang, Si-Hui; Guo, Xin-Xin; Wu, Ying-Song; Chen, Zhen-Hua; Chen, Yao; Ren, Zhi-Qi; Liu, Tian-Cai

    2016-01-01

    The unique photoproperties of quantum dots are promising for potential application in bioassays. In the present study, quantum dots were applied to a luminescent oxygen channeling assay. The reaction system developed in this study was based on interaction of biotin with streptavidin. Carboxyl-modified polystyrene microspheres doped with quantum dots were biotinylated and used as acceptors. Photosensitizer-doped carboxyl-modified polystyrene microspheres were conjugated with streptavidin and used as donors. The results indicated that the singlet oxygen that was released from the donor beads diffused into the acceptor beads. The acceptor beads were then exited via thioxene, and were subsequently fluoresced. To avoid generating false positives, a high concentration (0.01 mg/mL) of quantum dots is required for application in homogeneous immunoassays. Compared to a conventional luminescent oxygen channeling assay, this quantum dots-based technique requires less time, and would be easier to automate and miniaturize because it requires no washing to remove excess labels.

  7. Nitrate-Mediated Microbially Enhanced Oil Recovery (N-MEOR) from model upflow bioreactors.

    PubMed

    Gassara, Fatma; Suri, Navreet; Voordouw, Gerrit

    2017-02-15

    Microbially Enhanced Oil Recovery (MEOR) can enhance oil production with less energy input and less costs than other technologies. The present study used different aqueous electron donors (acetate, glucose, molasses) and an aqueous electron acceptor (nitrate) to stimulate growth of heterotrophic nitrate reducing bacteria (hNRB) to improve production of oil. Initial flooding of columns containing heavy oil (viscosity of 3400cP at 20°C) with CSBK (Coleville synthetic brine medium) produced 0.5 pore volume (PV) of oil. Bioreactors were then inoculated with hNRB with 5.8g/L of molasses and 0, 10, 20, 40, 60 or 80mM nitrate, as well as with 17mM glucose or 57mM acetate and 80mM nitrate. During incubations no oil was produced in the bioreactors that received 5.8g/L of molasses and 0, 10, 20, 40 or 60mM nitrate. However, the bioreactors injected with 5.8g/L of molasses, 17mM glucose or 57mM acetate and 80mM nitrate produced 13.9, 11.3±3.1 and 17.8±6.6% of residual oil, respectively. The significant production of oil from these bioreactors may be caused by N 2 -CO 2 gas production. Following continued injection with CSBK without nitrate, subsequent elution of significant residual oil (5-30%) was observed. These results also indicate possible involvement of fermentation products (organic acids, alcohols) to enhance heavy oil recovery. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Effect of sulfate and nitrate on acetate conversion by anaerobic microorganisms in a freshwater sediment.

    PubMed

    Scholten, Johannes C M; Bodegom, Peter M; Vogelaar, Jaap; Ittersum, Alexander; Hordijk, Kees; Roelofsen, Wim; Stams, Alfons J M

    2002-12-01

    Acetate is quantitatively the most important substrate for methane production in a freshwater sediment in The Netherlands. In the presence of alternative electron acceptors the conversion of acetate by methanogens was strongly inhibited. By modelling the results, obtained in experiments with and without (13)C-labelled acetate, we could show that the competition for acetate between methanogens and sulfate reducers is the main cause of inhibition of methanogenesis in the sediment. Although nitrate led to a complete inhibition of methanogenesis, acetate-utilising nitrate-reducing bacteria hardly competed with methanogens for the available acetate in the presence of nitrate. Most-probable-number enumerations showed that methanogens (2x10(8) cells cm(-3) sediment) and sulfate reducers (2x10(8) cells cm(-3) sediment) were the dominant acetate-utilising organisms in the sediment, while numbers of acetate-utilising nitrate reducers were very low (5x10(5) cells cm(-3) sediment). However, high numbers of sulfide-oxidising nitrate reducers were detected. Denitrification might result in the formation of toxic products. We speculate that the accumulation of low concentrations of NO (<0.2 mM) may result in an inhibition of methanogenesis.

  9. Natural organic matter as electron acceptor: experimental evidence for its important role in anaerobic respiration

    NASA Astrophysics Data System (ADS)

    Lau, Maximilian Peter; Sander, Michael; Gelbrecht, Jörg; Hupfer, Michael

    2014-05-01

    Microbial respiration is a key driver of element cycling in oxic and anoxic environments. Upon depletion of oxygen as terminal electron acceptor (TEA), a number of anaerobic bacteria can employ alternative TEA for intracellular energy generation. Redox active quinone moieties in dissolved organic matter (DOM) are well known electron acceptors for microbial respiration. However, it remains unclear whether quinones in adsorbed and particulate OM accept electrons in a same way. In our studies we aim to understand the importance of natural organic matter (NOM) as electron acceptors for microbial energy gain and its possible implications for methanogenesis. Using a novel electrochemical approach, mediated electrochemical reduction and -oxidation, we can directly quantify reduced hydroquinone and oxidized quionone moieties in dissolved and particulate NOM samples. In a mesocosm experiment, we rewetted sediment and peat soil and followed electron transfer to the inorganic and organic electron acceptors over time. We found that inorganic and organic electron acceptor pools were depleted over the same timescales. More importantly, we showed that organic, NOM-associated electron accepting moieties represent as much as 21 40% of total TEA inventories. These findings support earlier studies that propose that the reduction of quinone moieties in particulate organic matter competitively suppresses methanogenesis in wetland soils. Our results indicate that electron transfer to organic, particulate TEA in inundated ecosystems has to be accounted for when establishing carbon budgets in and projecting greenhouse gas emissions from these systems.

  10. Oxygen - Enemy or Friend for Microbial Fuel Cell Anode Performance?

    USDA-ARS?s Scientific Manuscript database

    Until recently, scientists and engineers have held a strong belief that oxygen intrusion into the anode chamber of a bioelectrochemical system (BES) is detrimental to microbial fuel cell (MFC) performance because oxygen acts as an alternate electron acceptor. This would, according to recent beliefs...

  11. Triple oxygen isotopes indicate urbanization affects sources of nitrate in wet and dry atmospheric deposition

    NASA Astrophysics Data System (ADS)

    Nelson, David M.; Tsunogai, Urumu; Ding, Dong; Ohyama, Takuya; Komatsu, Daisuke D.; Nakagawa, Fumiko; Noguchi, Izumi; Yamaguchi, Takashi

    2018-05-01

    Atmospheric nitrate deposition resulting from anthropogenic activities negatively affects human and environmental health. Identifying deposited nitrate that is produced locally vs. that originating from long-distance transport would help inform efforts to mitigate such impacts. However, distinguishing the relative transport distances of atmospheric nitrate in urban areas remains a major challenge since it may be produced locally and/or be transported from upwind regions. To address this uncertainty we assessed spatiotemporal variation in monthly weighted-average Δ17O and δ15N values of wet and dry nitrate deposition during one year at urban and rural sites along the western coast of the northern Japanese island of Hokkaido, downwind of the East Asian continent. Δ17O values of nitrate in wet deposition at the urban site mirrored those of wet and dry deposition at the rural site, ranging between ˜ +23 and +31 ‰ with higher values during winter and lower values in summer, which suggests the greater relative importance of oxidation of NO2 by O3 during winter and OH during summer. In contrast, Δ17O values of nitrate in dry deposition at the urban site were lower (+19 - +25 ‰) and displayed less distinct seasonal variation. Furthermore, the difference between δ15N values of nitrate in wet and dry nitrate deposition was, on average, 3 ‰ greater at the urban than rural site, and Δ17O and δ15N values were correlated for both forms of deposition at both sites with the exception of dry deposition at the urban site. These results suggest that, relative to nitrate in wet and dry deposition in rural environments and wet deposition in urban environments, nitrate in dry deposition in urban environments forms from relatively greater oxidation of NO by peroxy radicals and/or oxidation of NO2 by OH. Given greater concentrations of peroxy radicals and OH in cities, these results imply that dry nitrate deposition results from local NOx emissions more so than wet

  12. Nitrate-dependent iron oxidation limits iron transport in anoxic ocean regions

    NASA Astrophysics Data System (ADS)

    Scholz, Florian; Löscher, Carolin R.; Fiskal, Annika; Sommer, Stefan; Hensen, Christian; Lomnitz, Ulrike; Wuttig, Kathrin; Göttlicher, Jörg; Kossel, Elke; Steininger, Ralph; Canfield, Donald E.

    2016-11-01

    Iron is an essential element for life on Earth and limits primary production in large parts of the ocean. Oxygen-free continental margin sediments represent an important source of bioavailable iron to the ocean, yet little of the iron released from the seabed reaches the productive sea surface. Even in the anoxic water of oxygen minimum zones, where iron solubility should be enhanced, most of the iron is rapidly re-precipitated. To constrain the mechanism(s) of iron removal in anoxic ocean regions we explored the sediment and water in the oxygen minimum zone off Peru. During our sampling campaign the water column featured two distinct redox boundaries separating oxic from nitrate-reducing (i.e., nitrogenous) water and nitrogenous from weakly sulfidic water. The sulfidic water mass in contact with the shelf sediment contained elevated iron concentrations >300 nM. At the boundary between sulfidic and nitrogenous conditions, iron concentrations dropped sharply to <20 nM coincident with a maximum in particulate iron concentration. Within the iron gradient, we found an increased expression of the key functional marker gene for nitrate reduction (narG). Part of this upregulation was related to the activity of known iron-oxidizing bacteria. Collectively, our data suggest that iron oxidation and removal is induced by nitrate-reducing microbes, either enzymatically through anaerobic iron oxidation or by providing nitrite for an abiotic reaction. Given the important role that iron plays in nitrogen fixation, photosynthesis and respiration, nitrate-dependent iron oxidation likely represents a key-link between the marine biogeochemical cycles of nitrogen, oxygen and carbon.

  13. Vulnerability of streams to legacy nitrate sources

    USGS Publications Warehouse

    Tesoriero, Anthony J.; Duff, John H.; Saad, David A.; Spahr, Norman E.; Wolock, David M.

    2013-01-01

    The influence of hydrogeologic setting on the susceptibility of streams to legacy nitrate was examined at seven study sites having a wide range of base flow index (BFI) values. BFI is the ratio of base flow to total streamflow volume. The portion of annual stream nitrate loads from base flow was strongly correlated with BFI. Furthermore, dissolved oxygen concentrations in streambed pore water were significantly higher in high BFI watersheds than in low BFI watersheds suggesting that geochemical conditions favor nitrate transport through the bed when BFI is high. Results from a groundwater-surface water interaction study at a high BFI watershed indicate that decades old nitrate-laden water is discharging to this stream. These findings indicate that high nitrate levels in this stream may be sustained for decades to come regardless of current practices. It is hypothesized that a first approximation of stream vulnerability to legacy nutrients may be made by geospatial analysis of watersheds with high nitrogen inputs and a strong connection to groundwater (e.g., high BFI).

  14. Nitrate supplementation and human exercise performance: too much of a good thing?

    PubMed

    Poortmans, Jacques R; Gualano, Bruno; Carpentier, Alain

    2015-11-01

    Ergogenic supplements in sport events are widely used by popular and competitive athletes to enhance performance and reduce oxygen cost. Beetroot juice and nitrate salts have been increasingly used for the past 5-6 years. The present review discusses the scientific background, the efficiency and potential adverse effects of excessive nitrate supplementation. There is clear evidence that nitrate from different food ingredients (such as beetroot juice and other vegetables) is converted into nitrite and possibly into nitric oxide, which may promote vasodilation, angiogenesis and mitochondrial biogenesis. The high affinity of nitric oxide towards different enzyme pathways inhibits excessive mitochondrial respiration and, therefore, tissue oxygen consumption. In addition, L-arginine supplements are proposed to stimulate nitric oxide synthesis in the endothelium. On the basis of these biochemical properties, nitrate supplementation has been suggested to athletes to enhance exercise performance. The recent publications in human individuals based on L-arginine, beetroot juice or nitrate supplementation revealed either a minor positive effect or no systematic effect on exercise performance, especially in trained athletes. Of note, the sugar content of whole beetroot juice might induce a slightly more pronounced effect. Although reasonable intake of nitrate salts (up to 1 g/day) has no detrimental effect on kidney function, the risk and benefit of higher nitrate intake needs to be evaluated to define the optimal range of supplementation.

  15. Anaerobic Nitrate-Dependent Metal Bio-Oxidation

    NASA Astrophysics Data System (ADS)

    Weber, K.; Knox, T.; Achenbach, L. A.; Coates, J. D.

    2007-12-01

    Direct biological oxidation of reduced metals (Fe(II) and U(IV)) coupled to nitrate reduction at circumneutral pH under anaerobic conditions has been recognized in several environments as well as pure culture. Several phylogentically diverse mesophilic bacteria have been described as capable of anaerobic, nitrate-dependent Fe(II) oxidation (NFOx). Our recent identification of a freshwater mesophilic, lithoautotroph, Ferrutens nitratireducens strain 2002, capable of growth through NFOx presents an opportunity to further study metal bio- oxidation. Continuing physiological studies revealed that in addition to Fe(II) oxidation, strain 2002 is capable of oxidizing U(IV) (4 μM) in washed cell suspensions with nitrate serving as the electron acceptor. Pasteurized cultures exhibited abiotic oxidation of 2 μM U(IV). Under growth conditions, strain 2002 catalyzed the oxidation of 12 μM U(IV) within a two week period. Cultures amended with sodium azide, an electron transport inhibitor, demonstrated limited oxidation (7 μM) similar to pasteurized cultures, supporting the direct role of electron transport in U(IV) bio-oxidation. The oxidation of U(IV) coupled denitrification at circumneutral pH would yield enough energy to support anaerobic microbial growth (ΔG°'= -460.36 kJ/mole). It is currently unknown whether or not strain 2002 can couple this metabolism to growth. The growth of F. nitratireducens strain 2002 utilizing Fe(II) as the sole electron donor was previously demonstrated. The amount of U(IV) (~12 μM) that strain 2002 oxidized under similar autotrophic growth conditions yields 0.0019 kJ, enough energy for the generation of ATP (5.3 x 10-20 kJ ATP-1), but not enough energy for cell replication as calculated for nitrate-dependent Fe(II) oxidizing conditions (0.096 kJ) assuming a similar metabolism. In addition to F. nitratireducens strain 2002, a nitrate-dependent Fe(II) oxidizing bacterium isolated from U contaminated groundwater, Diaphorobacter sp. strain

  16. Effect of dissolved oxygen on biological denitrification using biodegradable plastic as the carbon source

    NASA Astrophysics Data System (ADS)

    Zhang, Xucai; Zhang, Jianmei

    2018-02-01

    Biological denitrification is currently a common approach to remove nitrate from wastewater. This study was conducted to evaluate the influence of dissolved oxygen on denitrification in wastewater treatment using biodegradable plastic as carbon source by designing the aerated, anoxic, and low-oxygen experimental treatment groups. The results showed that the removal rates of nitrate in anoxic and low-oxygen groups were 30.6 g NO3 --Nm-3 d-1 and 30.8 g NO3 --N m-3 d-1 at 83 h, respectively, both of which were higher than that of the aerated group. There was no significant difference between the anoxic and low-oxygen treatment groups for the nitrate removal. Additional, the nitrite accumulated during the experiments, and the nitrite concentrations in anoxic and aerated groups were lower than those in low-oxygen group. No nitrite was detected in all groups at the end of the experiments. These findings indicated that dissolved oxygen has important influence on denitrification, and anoxic and low-oxygen conditions can support completely denitrification when using BP as carbon source in nitrate-polluted wastewater treatment.

  17. Nitrate and periplasmic nitrate reductases

    PubMed Central

    Sparacino-Watkins, Courtney; Stolz, John F.; Basu, Partha

    2014-01-01

    The nitrate anion is a simple, abundant and relatively stable species, yet plays a significant role in global cycling of nitrogen, global climate change, and human health. Although it has been known for quite some time that nitrate is an important species environmentally, recent studies have identified potential medical applications. In this respect the nitrate anion remains an enigmatic species that promises to offer exciting science in years to come. Many bacteria readily reduce nitrate to nitrite via nitrate reductases. Classified into three distinct types – periplasmic nitrate reductase (Nap), respiratory nitrate reductase (Nar) and assimilatory nitrate reductase (Nas), they are defined by their cellular location, operon organization and active site structure. Of these, Nap proteins are the focus of this review. Despite similarities in the catalytic and spectroscopic properties Nap from different Proteobacteria are phylogenetically distinct. This review has two major sections: in the first section, nitrate in the nitrogen cycle and human health, taxonomy of nitrate reductases, assimilatory and dissimilatory nitrate reduction, cellular locations of nitrate reductases, structural and redox chemistry are discussed. The second section focuses on the features of periplasmic nitrate reductase where the catalytic subunit of the Nap and its kinetic properties, auxiliary Nap proteins, operon structure and phylogenetic relationships are discussed. PMID:24141308

  18. Upwelling and isolation in oxygen-depleted anticyclonic modewater eddies and implications for nitrate cycling

    NASA Astrophysics Data System (ADS)

    Karstensen, Johannes; Schütte, Florian; Pietri, Alice; Krahmann, Gerd; Fiedler, Björn; Grundle, Damian; Hauss, Helena; Körtzinger, Arne; Löscher, Carolin R.; Testor, Pierre; Vieira, Nuno; Visbeck, Martin

    2017-04-01

    The temporal evolution of the physical and biogeochemical structure of an oxygen-depleted anticyclonic modewater eddy is investigated over a 2-month period using high-resolution glider and ship data. A weakly stratified eddy core (squared buoyancy frequency N2 ˜ 0.1 × 10-4 s-2) at shallow depth is identified with a horizontal extent of about 70 km and bounded by maxima in N2. The upper N2 maximum (3-5 × 10-4 s-2) coincides with the mixed layer base and the lower N2 maximum (0.4 × 10-4 s-2) is found at about 200 m depth in the eddy centre. The eddy core shows a constant slope in temperature/salinity (T/S) characteristic over the 2 months, but an erosion of the core progressively narrows down the T/S range. The eddy minimal oxygen concentrations decreased by about 5 µmol kg-1 in 2 months, confirming earlier estimates of oxygen consumption rates in these eddies. Separating the mesoscale and perturbation flow components reveals oscillating velocity finestructure ( ˜ 0.1 m s-1) underneath the eddy and at its flanks. The velocity finestructure is organized in layers that align with layers in properties (salinity, temperature) but mostly cross through surfaces of constant density. The largest magnitude in velocity finestructure is seen between the surface and 140 m just outside the maximum mesoscale flow but also in a layer underneath the eddy centre, between 250 and 450 m. For both regions a cyclonic rotation of the velocity finestructure with depth suggests the vertical propagation of near-inertial wave (NIW) energy. Modification of the planetary vorticity by anticyclonic (eddy core) and cyclonic (eddy periphery) relative vorticity is most likely impacting the NIW energy propagation. Below the low oxygen core salt-finger type double diffusive layers are found that align with the velocity finestructure. Apparent oxygen utilization (AOU) versus dissolved inorganic nitrate (NO3-) ratios are about twice as high (16) in the eddy core compared to surrounding waters (8

  19. Isotopic composition of atmospheric nitrate in a tropical marine boundary layer.

    PubMed

    Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D; Vicars, William; Alexander, Becky; Achterberg, Eric P

    2013-10-29

    Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL.

  20. Isotopic composition of atmospheric nitrate in a tropical marine boundary layer

    PubMed Central

    Savarino, Joel; Morin, Samuel; Erbland, Joseph; Grannec, Francis; Patey, Matthew D.; Vicars, William; Alexander, Becky; Achterberg, Eric P.

    2013-01-01

    Long-term observations of the reactive chemical composition of the tropical marine boundary layer (MBL) are rare, despite its crucial role for the chemical stability of the atmosphere. Recent observations of reactive bromine species in the tropical MBL showed unexpectedly high levels that could potentially have an impact on the ozone budget. Uncertainties in the ozone budget are amplified by our poor understanding of the fate of NOx (= NO + NO2), particularly the importance of nighttime chemical NOx sinks. Here, we present year-round observations of the multiisotopic composition of atmospheric nitrate in the tropical MBL at the Cape Verde Atmospheric Observatory. We show that the observed oxygen isotope ratios of nitrate are compatible with nitrate formation chemistry, which includes the BrNO3 sink at a level of ca. 20 ± 10% of nitrate formation pathways. The results also suggest that the N2O5 pathway is a negligible NOx sink in this environment. Observations further indicate a possible link between the NO2/NOx ratio and the nitrogen isotopic content of nitrate in this low NOx environment, possibly reflecting the seasonal change in the photochemical equilibrium among NOx species. This study demonstrates the relevance of using the stable isotopes of oxygen and nitrogen of atmospheric nitrate in association with concentration measurements to identify and constrain chemical processes occurring in the MBL. PMID:23431201

  1. Oxygen Isotope Composition of Nitrate Produced by Freshwater Nitrification

    NASA Astrophysics Data System (ADS)

    Boshers, D.; Granger, J.; Bohlke, J. K.

    2016-12-01

    Measurements of the naturally occurring nitrogen and oxygen stable isotope ratios of nitrate (NO3-), δ15N and δ18O, can be used to determine the source, dispersal, and fate of natural and contaminant NO3- in aquatic environments. To this end, it is necessary to know the extent to which NO3- isotopologues are modified by biological reactions, as heavy and light isotopes have different reaction rates. The purpose of this study was to determine the influence of the δ18O of ambient water on the isotope composition of NO3- produced during nitrification, the biological oxidation of ammonium (NH4+) to nitrite (NO2-) and then NO3-, which is poorly constrained in freshwater systems. To determine the δ18O of NO3- produced by nitrification in freshwater, we collected water from a stream in New England, which we amended with NH4+ and with increments of 18O-enriched water, to monitor the isotope composition of NO3- produced by a natural consortium of nitrifiers. Added NH4+ was completely oxidized to NO3- over 26 days. The final δ18O of nitrified NO3- revealed sensitivity to the δ18O of water mediated by (a) isotopic equilibration between water and NO2- and (b) kinetic isotope fractionation during O-atom incorporation from water into NO2- and NO3-. Our results concur with nitrifying culture experiments that have demonstrated analogous sensitivity of the δ18O of nitrified NO3- to equilibrium and kinetic O isotope effects (Buchwald et al. 2012), as well as show that these dynamics need to be considered to interpret NO3- isotope distribution in freshwater environments.

  2. Non-fullerene electron acceptors for organic photovoltaic devices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jenekhe, Samson A.; Li, Haiyan; Earmme, Taeshik

    Non-fullerene electron acceptors for highly efficient organic photovoltaic devices are described. The non-fullerene electron acceptors have an extended, rigid, .pi.-conjugated electron-deficient framework that can facilitate exciton and charge derealization. The non-fullerene electron acceptors can physically mix with a donor polymer and facilitate improved electron transport. The non-fullerene electron acceptors can be incorporated into organic electronic devices, such as photovoltaic cells.

  3. Tracking nitrate sources in the Chaohu Lake, China, using the nitrogen and oxygen isotopic approach.

    PubMed

    Yu, Qibiao; Wang, Fang; Li, Xinyan; Yan, Weijin; Li, Yanqiang; Lv, Shucong

    2018-05-07

    The Chaohu Lake is highly polluted and suffers from severe eutrophication. Nitrate is a key form of nitrogen that can cause water quality degradation. In this study, hydrochemical and dual isotopic approaches were utilized to identify the seasonal variation of nitrate sources in the Chaohu Lake and its inflowing rivers. The average nitrate concentrations ([NO 3 - ]) of the lake and its inflowing rivers were 89.9 and 140.8 μmol L -1 , respectively. The isotopic values of δ 15 N-NO 3 - and δ 18 O-NO 3 - in the lake ranged from - 1.01 to + 16.67‰ and from - 4.39 to + 22.20‰, respectively. The two major rivers had distinct isotopic compositions, with average δ 15 N-NO 3 - values of + 17.52 and + 3.51‰, and average δ 18 O-NO 3 - values of + 2.71 and + 7.47‰ for the Nanfei River and Hangbu River, respectively. The results show that soil organic ammonium and urban wastewater discharge were the main sources of nitrate in the Chaohu Lake, and nitrate assimilation was an important process affected [NO 3 - ] and isotopic compositions, especially in the western Chaohu Lake. The elevated [NO 3 - ] and δ 15 N-NO 3 - values in the western Chaohu Lake indicate the high influence of human activities. Urban wastewater discharge was the primary nitrate source in the Nanfei River and soil organic ammonium was the main source in the Hangbu River. Although nitrate from direct atmospheric deposition was low, its strong flushing effect can substantially improve riverine [NO 3 - ] and nitrate loading from terrestrial ecosystem. The relatively high nitrate fluxes from the Hangbu River indicate that nitrogen loading from agricultural watershed is unneglectable in watershed nitrogen sources reduction strategies.

  4. Dependence of nitrite oxidation on nitrite and oxygen in low-oxygen seawater

    NASA Astrophysics Data System (ADS)

    Sun, Xin; Ji, Qixing; Jayakumar, Amal; Ward, Bess B.

    2017-08-01

    Nitrite oxidation is an essential step in transformations of fixed nitrogen. The physiology of nitrite oxidizing bacteria (NOB) implies that the rates of nitrite oxidation should be controlled by concentration of their substrate, nitrite, and the terminal electron acceptor, oxygen. The sensitivities of nitrite oxidation to oxygen and nitrite concentrations were investigated using 15N tracer incubations in the Eastern Tropical North Pacific. Nitrite stimulated nitrite oxidation under low in situ nitrite conditions, following Michaelis-Menten kinetics, indicating that nitrite was the limiting substrate. The nitrite half-saturation constant (Ks = 0.254 ± 0.161 μM) was 1-3 orders of magnitude lower than in cultivated NOB, indicating higher affinity of marine NOB for nitrite. The highest rates of nitrite oxidation were measured in the oxygen depleted zone (ODZ), and were partially inhibited by additions of oxygen. This oxygen sensitivity suggests that ODZ specialist NOB, adapted to low-oxygen conditions, are responsible for apparently anaerobic nitrite oxidation.

  5. Nitrative and Oxidative Stress in Toxicology and Disease

    PubMed Central

    Roberts, Ruth A.; Laskin, Debra L.; Smith, Charles V.; Robertson, Fredika M.; Allen, Erin M. G.; Doorn, Jonathan A.; Slikker, William

    2009-01-01

    Persistent inflammation and the generation of reactive oxygen and nitrogen species play pivotal roles in tissue injury during disease pathogenesis and as a reaction to toxicant exposures. The associated oxidative and nitrative stress promote diverse pathologic reactions including neurodegenerative disorders, atherosclerosis, chronic inflammation, cancer, and premature labor and stillbirth. These effects occur via sustained inflammation, cellular proliferation and cytotoxicity and via induction of a proangiogenic environment. For example, exposure to the ubiquitous air pollutant ozone leads to generation of reactive oxygen and nitrogen species in lung macrophages that play a key role in subsequent tissue damage. Similarly, studies indicate that genes involved in regulating oxidative stress are altered by anesthetic treatment resulting in brain injury, most notable during development. In addition to a role in tissue injury in the brain, inflammation, and oxidative stress are implicated in Parkinson's disease, a neurodegenerative disease characterized by the loss of dopamine neurons. Recent data suggest a mechanistic link between oxidative stress and elevated levels of 3,4-dihydroxyphenylacetaldehyde, a neurotoxin endogenous to dopamine neurons. These findings have significant implications for development of therapeutics and identification of novel biomarkers for Parkinson's disease pathogenesis. Oxidative and nitrative stress is also thought to play a role in creating the proinflammatory microenvironment associated with the aggressive phenotype of inflammatory breast cancer. An understanding of fundamental concepts of oxidative and nitrative stress can underpin a rational plan of treatment for diseases and toxicities associated with excessive production of reactive oxygen and nitrogen species. PMID:19656995

  6. A national look at nitrate contamination of ground water

    USGS Publications Warehouse

    Nolan, Bernard T.; Ruddy, Barbara C.; Hitt, Kerie J.; Helsel, Dennis R.

    1998-01-01

    Knowing where and what type of risks to ground water exist can alert water-resource managers and private users of the need to protect water supplies. Although nitrate generally is not an adult public-health threat, ingestion in drinking water by infants can cause low oxygen levels in the blood, a potentially fatal condition (Spalding and Exner, 1993). For this reason, the U.S. Environmental Protection Agency (EPA) has established a drinking-water standard of 10 milligrams per liter (mg/L) nitrate as nitrogen (U.S. Environmental Protection Agency, 1995). Nitrate concentrations in natural ground waters are usually less than 2 mg/L (Mueller and others, 1995).

  7. THE ENVIRONMENTAL CONSEQUENCES OF A RELEASE OF ETHANOL AT A UST SITE

    EPA Science Inventory

    Ethanol from gasoline (E10 and E85) is expected to produce ethanol concentrations in ground water in the range of 4,000 to 15,000 mg/L. In this range of concentrations, ethanol can be expected to deplete the supply of soluble electrons acceptors such as oxygen, nitrate and sulfa...

  8. Fullerene-bisadduct acceptors for polymer solar cells.

    PubMed

    Li, Yongfang

    2013-10-01

    Polymer solar cells (PSCs) have drawn great attention in recent years for their simple device structure, light weight, and low-cost fabrication in comparison with inorganic semiconductor solar cells. However, the power-conversion efficiency (PCE) of PSCs needs to be increased for their future application. The key issue for improving the PCE of PSCs is the design and synthesis of high-efficiency conjugated polymer donors and fullerene acceptors for the photovoltaic materials. For the acceptor materials, several fullerene-bisadduct acceptors with high LUMO energy levels have demonstrated excellent photovoltaic performance in PSCs with P3HT as a donor. In this Focus Review, recent progress in high-efficiency fullerene-bisadduct acceptors is discussed, including the bisadduct of PCBM, indene-C60 bisadduct (ICBA), indene-C70 bisadduct (IC70BA), DMPCBA, NCBA, and bisTOQC. The LUMO levels and photovoltaic performance of these bisadduct acceptors with P3HT as a donor are summarized and compared. In addition, the applications of an ICBA acceptor in new device structures and with other conjugated polymer donors than P3HT are also introduced and discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Synthetic CO.sub.2 acceptor

    DOEpatents

    Lancet, Michael S.; Curran, George P.

    1981-08-18

    A synthetic CO.sub.2 acceptor consisting essentially of at least one compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix, the carrier having the general formula Ca.sub.5 (SiO.sub.4).sub.2 CO.sub.3. A method for producing the synthetic CO.sub.2 acceptor is also disclosed.

  10. Early intervention of tyrosine nitration prevents vaso-obliteration and neovascularization in ischemic retinopathy.

    PubMed

    Abdelsaid, Mohammed A; Pillai, Bindu A; Matragoon, Suraporn; Prakash, Roshini; Al-Shabrawey, Mohamed; El-Remessy, Azza B

    2010-01-01

    Diabetic retinopathy and retinopathy of prematurity are blinding disorders that follow a pathological pattern of ischemic retinopathy and affect premature infants and working-age adults. Yet, the treatment options are limited to laser photocoagulation. The goal of this study is to elucidate the molecular mechanism and examine the therapeutic effects of inhibiting tyrosine nitration on protecting early retinal vascular cell death and late neovascularization in the ischemic retinopathy model. Ischemic retinopathy was developed by exposing neonatal mice to 75% oxygen [postnatal day (p) 7-p12] followed by normoxia (21% oxygen) (p12-p17). Peroxynitrite decomposition catalyst 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrinato iron III chloride (FeTPPS) (1 mg/kg), the nitration inhibitor epicatechin (10 mg/kg) or the thiol donor N-acetylcysteine (NAC, 150 mg/kg) were administered (p7-p12) or (p7-p17). Vascular endothelial cells were incubated at hyperoxia (40% oxygen) or normoxia (21% oxygen) for 48 h. Vascular density was determined in retinal flat mounts labeled with isolectin B4. Expression of vascular endothelial growth factor, caspase-3, and poly(ADP ribose) polymerase (PARP), activation of Akt and p38 mitogen-activated protein kinase (MAPK), and tyrosine nitration of the phosphatidylinositol (PI) 3-kinase p85 subunit were analyzed by Western blot. Hyperoxia-induced peroxynitrite caused endothelial cell apoptosis as indicated by expression of cleaved caspase-3 and PARP leading to vaso-obliteration. These effects were associated with significant tyrosine nitration of the p85 subunit of PI 3-kinase, decreased Akt activation, and enhanced p38 MAPK activation. Blocking tyrosine nitration of PI 3-kinase with epicatechin or NAC restored Akt phosphorylation, and inhibited vaso-obliteration at p12 and neovascularization at p17 comparable with FeTPPS. Early inhibition of tyrosine nitration with use of epicatechin or NAC can represent safe and effective vascular

  11. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, Anthony A.

    1985-01-01

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

  12. Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex.

    PubMed

    Elrod, Lee Taylor; Kim, Eunsuk

    2018-03-05

    The reduction of nitrate (NO 3 - ) to nitrite (NO 2 - ) is of significant biological and environmental importance. While Mo IV (O) and Mo VI (O) 2 complexes that mimic the active site structure of nitrate reducing enzymes are prevalent, few of these model complexes can reduce nitrate to nitrite through oxygen atom transfer (OAT) chemistry. We present a novel strategy to induce nitrate reduction chemistry of a previously known catalyst Mo IV (O)(SN) 2 (2), where SN = bis(4- tert-butylphenyl)-2-pyridylmethanethiolate, that is otherwise incapable of achieving OAT with nitrate. Addition of nitrate with the Lewis acid Sc(OTf) 3 (OTf = trifluoromethanesulfonate) to 2 results in an immediate and clean conversion of 2 to Mo VI (O) 2 (SN) 2 (1). The Lewis acid additive further reacts with the OAT product, nitrite, to form N 2 O and O 2 . This work highlights the ability of Sc 3+ additives to expand the reactivity scope of an existing Mo IV (O) complex together with which Sc 3+ can convert nitrate to stable gaseous molecules.

  13. Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

    NASA Astrophysics Data System (ADS)

    Martin, T. S.; Casciotti, K. L.

    2017-03-01

    The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

  14. Nitrate dynamics within a stream-lake network through time and space

    NASA Astrophysics Data System (ADS)

    Loken, L. C.; Crawford, J. T.; Childress, E. S.; Casson, N. J.; Stanley, E. H.

    2014-12-01

    Nitrate dynamics in streams are governed by biology, hydrology, and geomorphology, and the ability to parse these drivers apart has improved with the development of accurate high-frequency sensors. By combining a stationary Eulerian and a quasi-Lagrangian sensor platform, we investigated the timing of nitrate flushing and identified locations of elevated biogeochemical cycling along a stream-lake network in Northern Wisconsin, USA. Two years of continuous oxygen, carbon dioxide, and discharge measurements were used to compute gross primary production (GPP) and ecosystem respiration (ER) downstream of a wetland reach of Allequash Creek. Metabolic rates and flow patterns were compared with nitrate concentrations measured every 30 minutes using an optical sensor. Additionally, we floated a sensor array from the headwater spring ponds through a heterogeneous stream reach consisting of wetlands, beaver ponds, forested segments, and two lakes. Two distinct temporal patterns of stream nitrate concentrations were observed. During high flow events such as spring snowmelt and summer rain events, nitrate concentrations increased from ~5 μM (baseflow) to 12 μM, suggesting flushing from catchment sources. During baseflow conditions, nitrate followed a diel cycle with a 0.3-1.0 μM daytime draw down. Daily nitrate reduction was positively correlated with GPP calculated from oxygen and carbon dioxide records. Lastly, spatial analyses revealed lowest nitrate concentrations in the wetland reach, approximately 2-3 μM lower than the upstream spring ponds, and downstream lakes and forested reaches. This snapshot implies greater nitrate removal potential in the wetland reach likely driven by denitrification in organic rich sediments and macrophyte uptake in the open canopy stream segment. Taken together the temporal and spatial results show the dynamics of hydrology, geomorphology, and biology to influence nitrate delivery and variability in ecosystem processing through a stream

  15. Effect of bottom water oxygenation on oxygen consumption and benthic biogeochemical processes at the Crimean Shelf (Black Sea)

    NASA Astrophysics Data System (ADS)

    Lichtschlag, A.; Janssen, F.; Wenzhöfer, F.; Holtappels, M.; Struck, U.; Jessen, G.; Boetius, A.

    2012-04-01

    penetrating less than 5 mm into the seafloor. In total oxygen uptake by the seafloor, the fraction of the diffusive flux, which comprises microbial consumption plus re-oxidation of reduced compounds, increased with declining oxygen concentrations. Measurements and modeling of penetration depths and fluxes of the electron acceptors nitrate, iron- and manganese oxides, sulfate suggest that as long as oxygen is available in the oxic and the hypoxic zones of the Crimean shelf, the largest fraction of oxygen is consumed directly during aerobic mineralization of organic matter and re-oxidation processes play only a minor role. Furthermore, the combination of rapid and strong fluctuation of bottom water oxygen concentration and low sedimentation rates appear to repress anaerobic organic matter degradation. This study was carried out within the framework of the EU-funded project HYPOX (www.hypox.net), which is set up to improve our understanding of hypoxia formation and to develop capacities and know-how for hypoxia monitoring.

  16. Synthesis of a new energetic nitrate ester

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chavez, David E

    2008-01-01

    Nitrate esters have been known as useful energetic materials since the discovery of nitroglycerin by Ascanio Sobrero in 1846. The development of methods to increase the safety and utility of nitroglycerin by Alfred Nobel led to the revolutionary improvement in the utility of nitroglycerin in explosive applications in the form of dynamite. Since then, many nitrate esters have been prepared and incorporated into military applications such as double-based propellants, detonators and as energetic plasticizers. Nitrate esters have also been shown to have vasodilatory effects in humans and thus have been studied and used for treatments of ailments such as angina.more » The mechanism of the biological response towards nitrate esters has been elucidated recently. Interestingly, many of the nitrate esters used for military purposes are liquids (ethylene glycol dinitrate, propylene glycol dinitrate, etc). Pentaerythritol tetranitrate (PETN) is one of the only solid nitrate esters, besides nitrocellulose, that is used in any application. Unfortunately, PETN melting point is above 100 {sup o}C, and thus must be pressed as a solid for detonator applications. A more practical material would be a melt-castable explosive, for potential simplification of manufacturing processes. Herein we describe the synthesis of a new energetic nitrate ester (1) that is a solid at ambient temperatures, has a melting point of 85-86 {sup o}C and has the highest density of any known nitrate ester composed only of carbon, hydrogen, nitrogen and oxygen. We also describe the chemical, thermal and sensitivity properties of 1 as well as some preliminary explosive performance data.« less

  17. Molecular Analysis of the Nitrate-Reducing Community from Unplanted and Maize-Planted Soils

    PubMed Central

    Philippot, Laurent; Piutti, Séverine; Martin-Laurent, Fabrice; Hallet, Stéphanie; Germon, Jean Claude

    2002-01-01

    Microorganisms that use nitrate as an alternative terminal electron acceptor play an important role in the global nitrogen cycle. The diversity of the nitrate-reducing community in soil and the influence of the maize roots on the structure of this community were studied. The narG gene encoding the membrane bound nitrate reductase was selected as a functional marker for the nitrate-reducing community. The use of narG is of special interest because the phylogeny of the narG gene closely reflects the 16S ribosomal DNA phylogeny. Therefore, targeting the narG gene provided for the first time a unique insight into the taxonomic composition of the nitrate-reducing community in planted and unplanted soils. The PCR-amplified narG fragments were cloned and analyzed by restriction fragment length polymorphism (RFLP). In all, 60 RFLP types represented by two or more clones were identified in addition to the 58 RFLP types represented by only one clone. At least one clone belonging to each RFLP type was then sequenced. Several of the obtained sequences were not related to the narG genes from cultivated bacteria, suggesting the existence of unidentified nitrate-reducing bacteria in the studied soil. However, environmental sequences were also related to NarG from many bacterial divisions, i.e., Actinobacteria and α, β, and γ Proteobacteria. The presence of the plant roots resulted in a shift in the structure of the nitrate-reducing community between the unplanted and planted soils. Sequencing of RFLP types dominant in the rhizosphere or present only in the rhizosphere revealed that they are related to NarG from the Actinobacteria in an astonishingly high proportion. PMID:12450836

  18. Nitrate-driven urban haze pollution during summertime over the North China Plain

    NASA Astrophysics Data System (ADS)

    Li, Haiyan; Zhang, Qiang; Zheng, Bo; Chen, Chunrong; Wu, Nana; Guo, Hongyu; Zhang, Yuxuan; Zheng, Yixuan; Li, Xin; He, Kebin

    2018-04-01

    Compared to the severe winter haze episodes in the North China Plain (NCP), haze pollution during summertime has drawn little public attention. In this study, we present the highly time-resolved chemical composition of submicron particles (PM1) measured in Beijing and Xinxiang in the NCP region during summertime to evaluate the driving factors of aerosol pollution. During the campaign periods (30 June to 27 July 2015, for Beijing and 8 to 25 June 2017, for Xinxiang), the average PM1 concentrations were 35.0 and 64.2 µg m-3 in Beijing and Xinxiang. Pollution episodes characterized with largely enhanced nitrate concentrations were observed at both sites. In contrast to the slightly decreased mass fractions of sulfate, semivolatile oxygenated organic aerosol (SV-OOA), and low-volatility oxygenated organic aerosol (LV-OOA) in PM1, nitrate displayed a significantly enhanced contribution with the aggravation of aerosol pollution, highlighting the importance of nitrate formation as the driving force of haze evolution in summer. Rapid nitrate production mainly occurred after midnight, with a higher formation rate than that of sulfate, SV-OOA, or LV-OOA. Based on observation measurements and thermodynamic modeling, high ammonia emissions in the NCP region favored the high nitrate production in summer. Nighttime nitrate formation through heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) enhanced with the development of haze pollution. In addition, air masses from surrounding polluted areas during haze episodes led to more nitrate production. Finally, atmospheric particulate nitrate data acquired by mass spectrometric techniques from various field campaigns in Asia, Europe, and North America uncovered a higher concentration and higher fraction of nitrate present in China. Although measurements in Beijing during different years demonstrate a decline in the nitrate concentration in recent years, the nitrate contribution in PM1 still remains high. To effectively alleviate

  19. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOEpatents

    Cassano, A.A.

    1985-07-02

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

  20. Caminibacter mediatlanticus sp. nov., a thermophilic, chemolithoautotrophic, nitrate-ammonifying bacterium isolated from a deep-sea hydrothermal vent on the Mid-Atlantic Ridge.

    PubMed

    Voordeckers, James W; Starovoytov, Valentin; Vetriani, Costantino

    2005-03-01

    A thermophilic, anaerobic, chemolithoautotrophic bacterium, designated strain TB-2(T), was isolated from the walls of an active deep-sea hydrothermal vent chimney on the Mid-Atlantic Ridge at 36 degrees 14' N 33 degrees 54' W. The cells were Gram-negative rods approximately 1.5 microm in length and 0.75 microm in width. Strain TB-2(T) grew between 45 and 70 degrees C (optimum 55 degrees C), 10 and 40 g NaCl l(-1) (optimum 30 g l(-1)) and pH 4.5 and 7.5 (optimum pH 5.5). Generation time under optimal conditions was 50 min. Growth occurred under chemolithoautotrophic conditions with H(2) as the energy source and CO(2) as the carbon source. Nitrate or sulfur was used as the electron acceptor, with resulting production of ammonium and hydrogen sulfide, respectively. Oxygen, thiosulfate, sulfite, selenate and arsenate were not used as electron acceptors. Growth was inhibited by the presence of acetate, lactate, formate and peptone. The G+C content of the genomic DNA was 25.6 mol%. Phylogenetic analysis of the 16S rRNA gene sequence indicated that this organism is closely related to Caminibacter hydrogeniphilus and Caminibacter profundus (95.9 and 96.3 % similarity, respectively). On the basis of phylogenetic, physiological and genetic considerations, it is proposed that the organism represents a novel species within the genus Caminibacter, Caminibacter mediatlanticus sp. nov. The type strain is TB-2(T) (=DSM 16658(T)=JCM 12641(T)).

  1. Metal-catalyzed protein tyrosine nitration in biological systems.

    PubMed

    Campolo, Nicolás; Bartesaghi, Silvina; Radi, Rafael

    2014-11-01

    Protein tyrosine nitration is an oxidative postranslational modification that can affect protein structure and function. It is mediated in vivo by the production of nitric oxide-derived reactive nitrogen species (RNS), including peroxynitrite (ONOO(-)) and nitrogen dioxide ((•)NO₂). Redox-active transition metals such as iron (Fe), copper (Cu), and manganese (Mn) can actively participate in the processes of tyrosine nitration in biological systems, as they catalyze the production of both reactive oxygen species and RNS, enhance nitration yields and provide site-specificity to this process. Early after the discovery that protein tyrosine nitration can occur under biologically relevant conditions, it was shown that some low molecular weight transition-metal centers and metalloproteins could promote peroxynitrite-dependent nitration. Later studies showed that nitration could be achieved by peroxynitrite-independent routes as well, depending on the transition metal-catalyzed oxidation of nitrite (NO₂(-)) to (•)NO₂ in the presence of hydrogen peroxide. Processes like these can be achieved either by hemeperoxidase-dependent reactions or by ferrous and cuprous ions through Fenton-type chemistry. Besides the in vitro evidence, there are now several in vivo studies that support the close relationship between transition metal levels and protein tyrosine nitration. So, the contribution of transition metals to the levels of tyrosine nitrated proteins observed under basal conditions and, specially, in disease states related with high levels of these metal ions, seems to be quite clear. Altogether, current evidence unambiguously supports a central role of transition metals in determining the extent and selectivity of protein tyrosine nitration mediated both by peroxynitrite-dependent and independent mechanisms.

  2. Calculations of acceptor ionization energies in GaN

    NASA Astrophysics Data System (ADS)

    Wang, H.; Chen, A.-B.

    2001-03-01

    The k.p Hamiltonian and a model potential are used to deduce the acceptor ionization energies in GaN from a systematic study of the chemical trend in GaAs, GaP, and InP. The acceptors studied include Be, Mg, Ca, Zn, and Cd on the cation sites and C, Si, and Ge on the anion sites. Our calculated acceptor ionization energies are estimated to be accurate to better than 10% across the board. The ionization energies of C and Be (152 and 187 meV, respectively) in wurtzite GaN are found to be lower than that of Mg (224 meV). The C was found to behave like the hydrogenic acceptor in all systems and it has the smallest ionization energy among all the acceptors studied.

  3. Iodate Reduction by Shewanella oneidensis Does Not Involve Nitrate Reductase

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mok, Jung Kee; Toporek, Yael J.; Shin, Hyun-Dong

    Microbial iodate (IO 3 -) reduction is a major component of the iodine biogeochemical reaction network and is the basis of alternative strategies for remediation of iodine-contaminated environments. The molecular mechanism of microbial IO 3 - reduction, however, is not well understood. In microorganisms displaying IO 3 - and nitrate (NO 3 -) reduction activities, NO 3 - reductase is postulated to reduce IO 3 - as alternate electron acceptor. In the present study, whole genome analyses of 25 NO 3 --reducing Shewanella strains identified various combinations of genes encoding one assimilatory (cytoplasmic Nas) and three dissimilatory (membrane-associated Nar andmore » periplasmic Napα and Napβ) NO 3 - reductases. S. oneidensis was the only Shewanella strain whose genome encoded a single NO 3 - reductase (Napβ). Terminal electron acceptor competition experiments in S. oneidensis batch cultures amended with both NO 3 - and IO 3 - demonstrated that neither NO 3 - nor IO 3 - reduction activities were competitively inhibited by the presence of the competing electron acceptor. The lack of involvement of S. oneidensis Napβ in IO 3 - reduction was confirmed via phenotypic analysis of an in-frame gene deletion mutant lacking napβΑ (encoding the NO 3 --reducing NapβA catalytic subunit). S. oneidensis ΔnapβA was unable to reduce NO 3 -, yet reduced IO 3 - at rates higher than the wild-type strain. Thus, NapβA is required for dissimilatory NO 3 - reduction by S. oneidensis, while neither the assimilatory (Nas) nor dissimilatory (Napα, Napβ, and Nar) NO 3 - reductases are required for IO 3 - reduction. These findings oppose the traditional view that NO 3 - reductase reduces IO 3 - as alternate electron acceptor and indicate that S. oneidensis reduces IO 3 - via an as yet undiscovered enzymatic mechanism.« less

  4. Acceptors in bulk and nanoscale ZnO

    NASA Astrophysics Data System (ADS)

    McCluskey, M. D.

    2012-02-01

    Zinc oxide (ZnO) is a semiconductor that emits bright UV light, with little wasted heat. This intrinsic feature makes it a promising material for energy-efficient white lighting, nano-lasers, and other optical applications. For devices to be competitive, however, it is necessary to develop reliable p-type doping. Although substitutional nitrogen has been considered as a potential p-type dopant for ZnO, theoretical and experimental work indicates that nitrogen is a deep acceptor and will not lead to p-type conductivity. This talk will highlight recent experiments on ZnO:N at low temperatures. A red/near-IR photoluminescence (PL) band is correlated with the presence of deep nitrogen acceptors. PL excitation (PLE) measurements show an absorption threshold of 2.26 eV, in good agreement with theory. Magnetic resonance experiments provide further evidence for this assignment. The results of these studies seem to rule out group-V elements as shallow acceptors in ZnO, contradicting numerous reports in the literature. If these acceptors do not work as advertised, is there a viable alternative? Optical studies on ZnO nanocrystals show some intriguing leads. At liquid-helium temperatures, a series of sharp IR absorption peaks arise from an unknown acceptor impurity. The data are consistent with a hydrogenic acceptor 0.46 eV above the valence band edge. While this binding energy is still too deep for many practical applications, it represents a significant improvement over the ˜ 1.3 eV binding energy for nitrogen acceptors. Nanocrystals present another twist. Due to their high surface-to-volume ratio, surface states are especially important. Specifically, electron-hole recombination at the surface give rises to a red luminescence band. From our PL and IR experiments, we have developed a ``unified'' model that attempts to explain acceptor and surface states in ZnO nanocrystals. This model could provide a useful framework for designing future nanoscale ZnO devices.

  5. Chemical trends for acceptor impurities in GaN

    NASA Astrophysics Data System (ADS)

    Neugebauer, Jörg; Van de Walle, Chris G.

    1999-03-01

    We present a comprehensive investigation of acceptor impurities in GaN, based on first-principles total-energy calculations. Two main factors are identified that determine acceptor incorporation: the strength of chemical bonding between the acceptor and its neighbors (which can be assessed by comparison with existing compounds) and the atomic size match between the acceptor and the host atom for which it substitutes. None of the candidates (Li, Na, K, Be, Zn, and Ca) exhibits characteristics which surpass those of Mg in all respects. Only Be emerges as a potential alternative dopant, although it may suffer from compensation by Be interstitial donors.

  6. Influence of dietary nitrate supplementation on physiological and cognitive responses to incremental cycle exercise.

    PubMed

    Thompson, Kevin G; Turner, Louise; Prichard, Jonathon; Dodd, Fiona; Kennedy, David O; Haskell, Crystal; Blackwell, James R; Jones, Andrew M

    2014-03-01

    Dietary inorganic nitrate supplementation causes physiological effects which may enhance exercise tolerance. However it is not known whether nitrate might alter cognitive function during exercise. In a double-blind, cross-over study, sixteen subjects ingested either nitrate-rich beetroot juice or a placebo and completed a continuous cycle exercise test involving 20min stages at 50% and 70% V˙O2peak and a final stage at 90% V˙O2peak until volitional exhaustion. Cognitive tasks were completed before, during and after exercise. In the dietary nitrate condition: plasma [nitrite] increased (p<0.01), systolic blood pressure decreased (p<0.05) and there was a trend for a reduced oxygen uptake at 50% V˙O2peak. Tissue oxygenation improved across exercise intensities and exercise tolerance was greater at 90% V˙O2peak (p<0.05). Rating of perceived exertion, energy levels and cognitive performance were similar between conditions with mental fatigue being evident from 70% V˙O2peak onwards (p<0.05). Dietary nitrate supplementation enhanced short-term endurance exercise performance with concomitant mental fatigue but did not improve cognitive performance post-fatigue. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

    PubMed Central

    Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

    2016-01-01

    Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

  8. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126..., ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. (a) When any item of ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

  9. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126..., ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. (a) When any item of ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

  10. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126..., ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. (a) When any item of ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

  11. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126..., ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. (a) When any item of ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

  12. 33 CFR 126.28 - Ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. 126.28 Section 126..., ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate; general provisions. (a) When any item of ammonium nitrate, ammonium nitrate fertilizers, fertilizer mixtures, or nitro carbo nitrate...

  13. Molybdenum effector of fumarate reductase repression and nitrate reductase induction in Escherichia coli.

    PubMed Central

    Iuchi, S; Lin, E C

    1987-01-01

    In Escherichia coli the presence of nitrate prevents the utilization of fumarate as an anaerobic electron acceptor. The induction of the narC operon encoding the nitrate reductase is coupled to the repression of the frd operon encoding the fumarate reductase. This coupling is mediated by nitrate as an effector and the narL product as the regulatory protein (S. Iuchi and E. C. C. Lin, Proc. Natl. Acad. Sci. USA 84:3901-3905, 1987). The protein-ligand complex appears to control narC positively but frd negatively. In the present study we found that a molybdenum coeffector acted synergistically with nitrate in the regulation of frd and narC. In chlD mutants believed to be impaired in molybdate transport (or processing), full repression of phi(frd-lac) and full induction of phi(narC-lac) by nitrate did not occur unless the growth medium was directly supplemented with molybdate (1 microM). This requirement was not clearly manifested in wild-type cells, apparently because it was met by the trace quantities of molybdate present as a contaminant in the mineral medium. In chlB mutants, which are known to accumulate the Mo cofactor because of its failure to be inserted as a prosthetic group into proteins such as nitrate reductase, nitrate repression of frd and induction of narC were also intensified by molybdate supplementation. In this case a deficiency of the molybdenum coeffector might have resulted from enhanced feedback inhibition of molybdate transport (or processing) by the elevated level of the unutilized Mo cofactor. In addition, mutations in chlE, which are known to block the synthesis of the organic moiety of the Mo cofactor, lowered the threshold concentration of nitrate (< 1 micromole) necessary for frd repression and narC induction. These changes could be explained simply by the higher intracellular nitrate attainable in cells lacking the ability to destroy the effector. PMID:3301812

  14. Chemolithotrophic nitrate-dependent Fe(II)-oxidizing nature of actinobacterial subdivision lineage TM3.

    PubMed

    Kanaparthi, Dheeraj; Pommerenke, Bianca; Casper, Peter; Dumont, Marc G

    2013-08-01

    Anaerobic nitrate-dependent Fe(II) oxidation is widespread in various environments and is known to be performed by both heterotrophic and autotrophic microorganisms. Although Fe(II) oxidation is predominantly biological under acidic conditions, to date most of the studies on nitrate-dependent Fe(II) oxidation were from environments of circumneutral pH. The present study was conducted in Lake Grosse Fuchskuhle, a moderately acidic ecosystem receiving humic acids from an adjacent bog, with the objective of identifying, characterizing and enumerating the microorganisms responsible for this process. The incubations of sediment under chemolithotrophic nitrate-dependent Fe(II)-oxidizing conditions have shown the enrichment of TM3 group of uncultured Actinobacteria. A time-course experiment done on these Actinobacteria showed a consumption of Fe(II) and nitrate in accordance with the expected stoichiometry (1:0.2) required for nitrate-dependent Fe(II) oxidation. Quantifications done by most probable number showed the presence of 1 × 10(4) autotrophic and 1 × 10(7) heterotrophic nitrate-dependent Fe(II) oxidizers per gram fresh weight of sediment. The analysis of microbial community by 16S rRNA gene amplicon pyrosequencing showed that these actinobacterial sequences correspond to ~0.6% of bacterial 16S rRNA gene sequences. Stable isotope probing using (13)CO2 was performed with the lake sediment and showed labeling of these Actinobacteria. This indicated that they might be important autotrophs in this environment. Although these Actinobacteria are not dominant members of the sediment microbial community, they could be of functional significance due to their contribution to the regeneration of Fe(III), which has a critical role as an electron acceptor for anaerobic microorganisms mineralizing sediment organic matter. To the best of our knowledge this is the first study to show the autotrophic nitrate-dependent Fe(II)-oxidizing nature of TM3 group of uncultured

  15. Effective Tuning of Ketocyanine Derivatives through Acceptor Substitution.

    PubMed

    Poe, Ambata; Della Pelle, Andrea; Byrnes, Sean; Thayumanavan, S

    2015-05-18

    A series of ketocyanine derivatives possessing bis(diarylamino)fluorenyl donors and variable acceptors installed at the bridging carbon atom were synthesized to investigate how the electronic structure of the dye can be systemically tuned through stabilization of the cyanine-like character of the donor by increasing the acceptor strength. Analysis of the (1) H NMR spectra indicates that the "charge-separated" species dominates in these dyes, given that carbons possessing a positive or negative charge in the resonance structures of this state purposefully shift downfield or upfield, respectively, depending on the strength of the acceptor moiety. In DAA-Fl-PI, the acceptor strength and the gain of acceptor aromaticity indicates a predisposition of the separated state, indicated by asymmetry in the (1) H NMR spectrum, as well as uneven distribution of the HOMO on the fluorenyl donor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Safety Testing of Ammonium Nitrate Based Mixtures

    NASA Astrophysics Data System (ADS)

    Phillips, Jason; Lappo, Karmen; Phelan, James; Peterson, Nathan; Gilbert, Don

    2013-06-01

    Ammonium nitrate (AN)/ammonium nitrate based explosives have a lengthy documented history of use by adversaries in acts of terror. While historical research has been conducted on AN-based explosive mixtures, it has primarily focused on detonation performance while varying the oxygen balance between the oxidizer and fuel components. Similarly, historical safety data on these materials is often lacking in pertinent details such as specific fuel type, particle size parameters, oxidizer form, etc. A variety of AN-based fuel-oxidizer mixtures were tested for small-scale sensitivity in preparation for large-scale testing. Current efforts focus on maintaining a zero oxygen-balance (a stoichiometric ratio for active chemical participants) while varying factors such as charge geometry, oxidizer form, particle size, and inert diluent ratios. Small-scale safety testing was conducted on various mixtures and fuels. It was found that ESD sensitivity is significantly affected by particle size, while this is less so for impact and friction. Thermal testing is in progress to evaluate hazards that may be experienced during large-scale testing.

  17. Understanding organic nitrates – a vein hope?

    PubMed Central

    Miller, Mark R; Wadsworth, Roger M

    2009-01-01

    The organic nitrate drugs, such as glyceryl trinitrate (GTN; nitroglycerin), are clinically effective in angina because of their dilator profile in veins and arteries. The exact mechanism of intracellular delivery of nitric oxide (NO), or another NO-containing species, from these compounds is not understood. However, mitochondrial aldehyde dehydrogenase (mtALDH) has recently been identified as an organic nitrate bioactivation enzyme. Nitrate tolerance, the loss of effect of organic nitrates over time, is caused by reduced bioactivation and/or generation of NO-scavenging oxygen-free radicals. In a recent issue of the British Journal of Pharmacology, Wenzl et al. show that guinea-pigs, deficient in ascorbate, also have impaired responsiveness to GTN, but nitrate tolerance was not due to ascorbate deficiency that exhibited divergent changes in mtALDH activity. Thus, the complex function of mtALDH appears to be the key to activation of GTN, the active NO species formed and the induction of tolerance that can limit clinical effectiveness of organic nitrate drugs. British Journal of Pharmacology (2009) 157, 565–567; doi:10.1111/j.1476-5381.2009.00193.x This article is part of a themed section on Endothelium in Pharmacology. For a list of all articles in this section see the end of this paper, or visit: http://www3.interscience.wiley.com/journal/121548564/issueyear?year=2009 The paper by Wenzl et al. is available from http://www3.interscience.wiley.com/cgi-bin/fulltext/122221718/PDFSTART PMID:19630835

  18. Microbial Preference for Soil Organic Carbon Changes Along Redox Gradients as a Function of the Energetic Cost of Respiration

    NASA Astrophysics Data System (ADS)

    Naughton, H.; Keiluweit, M.; Fendorf, S. E.; Farrant, D. N.

    2016-12-01

    Soil organic carbon (SOC) chemistry is known to impact carbon preservation via mineral associations and physical protection, which chemically or physically block SOC from microbial enzymatic access for decomposition. However, SOC decay models that include these processes do not reliably predict SOC dynamics. We propose that the energetics of respiration additionally regulate SOC cycling. Specifically, organic carbon will only be respired if the available electron acceptors yield enough energy for microbial growth when metabolically coupled to the SOC. To test this hypothesis, we constructed dual pore domain reactors in which water flows normal to a column of packed soil, allowing oxygen to diffuse from the upper channel through the soil and establish a redox gradient. With increasing depth into the soil column, the soil experiences a typical redox profile indicative of anaerobic respiration processes: after oxygen is consumed, nitrate, Mn, Fe, and sulfate serve as electron acceptors. We measure porewater and effluent for nitrate, sulfate, Fe(II) and Mn(II) and take microsensor profiles of dissolved oxygen and H2S to characterize the redox gradient and respiration pathways. To this we couple incubations of solid material at each depth post-experiment and quantify CO2 and CH4 production to assess respiration potential along the redox gradient. Porewater SOC chemistry is analyzed via spectroscopy and mass spectrometry to interpret SOC oxidation state and composition and thus test thermodynamic predictions on SOC stability given the available redox acceptors at a given depth in the reactor. Within 0.5 cm of the soil surface, oxygen concentrations drop below detection and signs of anaerobic respiration (Fe(II) production, loss of nitrate) initiate while respiration rates drops precipitously. More oxidized SOC is preferentially utilized with progression along the redox gradient, supporting thermodynamic predictions. This work highlights the potential of SOC chemistry

  19. Oxygen isotope dynamics of atmospheric nitrate over the Antarctic plateau: First combined measurements of ozone and nitrate 17O-excess (Δ17O)

    NASA Astrophysics Data System (ADS)

    Vicars, William; Savarino, Joël; Erbland, Joseph; Preunkert, Susanne; Jourdain, Bruno; Frey, Markus; Gil, Jaime; Legrand, Michel

    2013-04-01

    Variations in the isotopic composition of atmospheric nitrate (NO3-) provide novel indicators for important processes in boundary layer chemistry, often acting as source markers for reactive nitrogen (NOx = NO + NO2) and providing both qualitative and quantitative constraints on the pathways that determine its fate. Stable isotope ratios of nitrate (δ15N, δ17O, δ18O) offer direct insight into the nature and magnitude of the fluxes associated with different processes, thus providing unique information regarding phenomena that are often difficult to quantify from concentration measurements alone. The unique and distinctive 17O-excess (Δ17O = δ17O - 0.52 × δ18O ) of ozone (O3), which is transferred to NOx via oxidation reactions in the atmosphere, has been found to be a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O-excess within the NOx cycle is critical in polar areas where there exists the possibility of extending atmospheric interpretations to the glacial/interglacial time scale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C, Antarctica during December 2011 to January 2012. Sampling was conducted within the framework of the OPALE (Oxidant Production over Antarctic Land and its Export) project, thus providing an opportunity to combine our isotopic observations with a wealth of meteorological and chemical data, including in-situ concentration measurements of the gas-phase precursors involved in nitrate production (NOx, O3, OH, HO2, etc.). Furthermore, nitrate isotope analysis has been combined in this study for the first time with parallel observations of the transferrable Δ17O of surface ozone, which was measured concurrently at Dome C using our recently developed analytical approach. This unique dataset has allowed for a direct comparison of observed Δ17O(NO3-) values to those that are

  20. Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

    PubMed

    Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

    2017-09-01

    The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

  1. Aminoethyl nitrate – the novel super nitrate?

    PubMed Central

    Bauersachs, Johann

    2009-01-01

    Long-term use of most organic nitrates is limited by development of tolerance, induction of oxidative stress and endothelial dysfunction. In this issue of the BJP, Schuhmacher et al. characterized a novel class of organic nitrates with amino moieties (aminoalkyl nitrates). Aminoethyl nitrate was identified as a novel organic mononitrate with high potency but devoid of induction of mitochondrial oxidative stress. Cross-tolerance to nitroglycerin or the endothelium-dependent agonist acetylcholine after in vivo treatment was not observed. Like all nitrates, aminoethyl nitrate induced vasorelaxation by activation of soluble guanylate cyclase. Thus, in contrast to the prevailing view, high potency in an organic nitrate is not necessarily accompanied by induction of oxidative stress or endothelial dysfunction. This work from Daiber's group is an important step forward in the understanding of nitrate bioactivation, tolerance phenomena and towards the development of better organic nitrates for clinical use. PMID:19732062

  2. How localized acceptors limit p-type conductivity in GaN

    NASA Astrophysics Data System (ADS)

    Lyons, John L.

    2013-03-01

    Despite the impressive development of GaN as an optoelectronic material, p-type conductivity is still limited. Only a single acceptor impurity, magnesium, is known to lead to p-type GaN. But Mg is far from a well-behaved acceptor. Hydrogen is known to passivate Mg, necessitating a post-growth anneal for acceptor activation. In addition, the ionization energy is quite large (~ 200 meV in GaN), meaning only a few percent of Mg acceptors are ionized at room temperature. Thus, hole conductivity is limited, and high concentrations of Mg are required to achieve moderately p-type GaN. Other acceptor impurities have not proven to be effective p-type dopants, for reasons that are still unresolved. Using advanced first-principles calculations based on a hybrid functional, we investigate the electrical and optical properties of the isolated Mg acceptor and its complexes with hydrogen in GaN, InN, and AlN.[2] We employ a technique that overcomes the band-gap-problem of traditional density functional theory, and allows for quantitative predictions of acceptor ionization energies and optical transition energies. Our results allow us to explain the deep or shallow nature of the Mg acceptor and its relation to the optical signals observed in Mg-doped GaN. We also revisit the properties of other group-II acceptors in GaN. We find that all cation-site acceptors show behavior similar to MgGa, and lead to highly localized holes. The ZnGa and BeGa acceptors have ionization energies that are even larger than that of Mg, making them ineffective dopants. All acceptors cause large lattice distortions in their neutral charge state, in turn leading to deep, broad luminescence signals that can serve as a means of experimentally verifying the deep nature of these acceptors. This work was performed in collaboration with Audrius Alkauskas, Anderson Janotti, and Chris G. Van de Walle. It was supported by the NSF and by the Solid State Lighting and Energy Center at UCSB.

  3. Lanthanum(III) and Lutetium(III) in Nitrate-Based Ionic Liquids: A Theoretical Study of Their Coordination Shell.

    PubMed

    Bodo, Enrico

    2015-09-03

    By using ab initio molecular dynamics, we investigate the solvent shell structure of La(3+) and Lu(3+) ions immersed in two ionic liquids, ethylammonium nitrate (EAN) and its hydroxy derivative (2-ethanolammonium nitrate, HOEAN). We provide the first study of the coordination properties of these heavy metal ions in such a highly charged nonacqueous environment. We find, as expected, that the coordination in the liquid is mainly due to nitrate anions and that, due to the bidentate nature of the ligand, the complexation shell of the central ion has a nontrivial geometry and a coordination number in terms of nitrate molecules that apparently violates the decrease of ionic radii along the lanthanides series, since the smaller Lu(3+) ion seems to coordinate six nitrate molecules and the La(3+) ion only five. A closer inspection of the structural features obtained from our calculations shows, instead, that the first shell of oxygen atoms is more compact for Lu(3+) than for La(3+) and that the former coordinates 8 oxygen atoms while the latter 10 in accord with the typical lanthanide's trend along the series and that their first solvation shells have a slight irregular and complex geometrical pattern. When moving to the HOEAN solutions, we have found that the solvation of the central ion is possibly also due to the cation itself through the oxygen atom on the side chain. Also, in this liquid, the coordination numbers in terms of oxygen atoms in both solvents is 10 for La(3+) and 8 for Lu(3+).

  4. Shallow versus deep nature of Mg acceptors in nitride semiconductors

    NASA Astrophysics Data System (ADS)

    Lyons, John; Janotti, Anderson; van de Walle, Chris G.

    2012-02-01

    Although Mg doping is the only known method for achieving p-type conductivity in nitride semiconductors, Mg is not a perfect acceptor. Hydrogen is known to passivate the Mg acceptor, necessitating a post-growth anneal for acceptor activation. Furthermore, the acceptor ionization energy of Mg is relatively large (200 meV) in GaN, thus only a few percent of Mg acceptors are ionized at room temperature. Surprisingly, despite the importance of this impurity, open questions remain regarding the nature of the acceptor. Optical and magnetic resonance measurements on Mg-doped GaN indicate intriguing and complex behavior that depends on the growth, doping level, and thermal treatment of the samples. Motivated by these studies, we have revisited this topic by performing first-principles calculations based on a hybrid functional. We investigate the electrical and optical properties of the isolated Mg acceptor and its complexes with hydrogen in GaN, InN, and AlN. With the help of these advanced techniques we explain the deep or shallow nature of the Mg acceptor and its relation to optical signals often seen in Mg-doped GaN. We also explore the properties of the Mg acceptor in InN and AlN, allowing predictions of the behavior of the Mg dopant in ternary nitride alloys.

  5. Spectral, thermal and kinetic studies of charge-transfer complexes formed between the highly effective antibiotic drug metronidazole and two types of acceptors: σ- and π-acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2015-04-01

    Understanding the interaction between drugs and small inorganic or organic molecules is critical in being able to interpret the drug-receptor interactions and acting mechanism of these drugs. A combined solution and solid state study was performed to describe the complexation chemistry of drug metronidazole (MZ) which has a broad-spectrum antibacterial activity with two types of acceptors. The acceptors include, σ-acceptor (i.e., iodine) and π-acceptors (i.e., dichlorodicyanobenzoquinone (DDQ), chloranil (CHL) and picric acid (PA)). The molecular structure, spectroscopic characteristics, the binding modes as well as the thermal stability were deduced from IR, UV-vis, 1H NMR and thermal studies. The binding ratio of complexation (MZ: acceptor) was determined to be 1:2 for the iodine acceptor and 1:1 for the DDQ, CHL or PA acceptor, according to the CHN elemental analyses and spectrophotometric titrations. It has been found that the complexation with CHL and PA acceptors increases the values of enthalpy and entropy, while the complexation with DDQ and iodine acceptors decreases the values of these parameters compared with the free MZ donor.

  6. It is rocket science - why dietary nitrate is hard to 'beet'! Part II: further mechanisms and therapeutic potential of the nitrate-nitrite-NO pathway.

    PubMed

    Mills, Charlotte Elizabeth; Khatri, Jibran; Maskell, Perry; Odongerel, Chimed; Webb, Andrew James

    2017-01-01

    Dietary nitrate (found in green leafy vegetables such as rocket and in beetroot) is now recognized to be an important source of nitric oxide, via the nitrate-nitrite-NO pathway. Dietary nitrate confers several cardiovascular beneficial effects on blood pressure, platelets, endothelial function, mitochondrial efficiency and exercise. Having described key twists and turns in the elucidation of the pathway and the underlying mechanisms in Part I, we explore the more recent developments which have served to confirm mechanisms, extend our understanding, and discover new properties and potential therapeutic uses of the pathway in Part II. Even the established dependency on low oxygen states for bioactivation of nitrite has recently been challenged. Dietary nitrate appears to be an important component of 'healthy diets', such as the DASH diet to lower blood pressure and the Mediterranean diet, with its potential to lower cardiovascular risk, possibly through beneficial interactions with a range of other constituents. The World Cancer Research Foundation report strong evidence for vegetables including spinach and lettuce (high nitrate-containing) decreasing cancer risk (mouth, pharynx, larynx, oesophagus and stomach), summarized in a 'Nitrate-Cancer Risk Veg-Table'. The European Space Agency recommends that beetroot, lettuce, spinach and rocket (high-nitrate vegetables) are grown to provide food for long-term space missions. Nitrate, an ancient component of rocket fuel, could support sustainable crops for healthy humans. © 2016 The British Pharmacological Society.

  7. Inorganic nitrite and nitrate in cardiovascular therapy: A better alternative to organic nitrates as nitric oxide donors?

    PubMed

    Münzel, Thomas; Daiber, Andreas

    2018-03-01

    In 1867 the organic nitrite, amyl nitrite, was introduced as a therapeutic agent in the treatment of angina pectoris and was later substituted by the organic nitrate nitroglycerin (NTG). Despite having a highly potent vasodilator capacity in veins>coronary arteries>arterioles, the vasodilator effects NTG are rapidly attenuated by the development of nitrate tolerance. We and others established that NTG treatment stimulates the production of reactive oxygen species such as superoxide and peroxynitrite with subsequent marked attenuation of the NTG vasodilator potency. The nitrite anion (NO 2 - ) has more recently been characterized to possess novel pharmacotherapeutic actions such as modulation of vasodilation under hypoxic conditions, thereby providing protection in ischemia-reperfusion injury. Administration of NO 2 - /NO 3 - has also been shown to improve myocardial function in heart failure and to lower blood pressure. Despite these positive aspects there is still a great need to study inorganic nitrate and nitrite therapy in various cardiovascular diseases in prospective outcome directed studies. In case being successful, this kind of therapy would indeed represent a cheap, therefore affordable, effective cardiovascular therapy without major side effects as observed in response to therapy with organic nitrates. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

  8. Inhibitory Effects of Sulfate and Nitrate Reduction on Reductive Dechlorination of PCP in a Flooded Paddy Soil

    PubMed Central

    Xu, Yan; Xue, Lili; Ye, Qi; Franks, Ashley E.; Zhu, Min; Feng, Xi; Xu, Jianming; He, Yan

    2018-01-01

    Pentachlorophenol (PCP) is highly toxic and persistent in soils. Bioreduction of PCP often co-occurs with varying concentrations of sulfate and nitrate in flooded paddy soils where each can act as an electron acceptor. Anaerobic soil microcosms were constructed to evaluate the influence of sulfate and nitrate amendments and their redox processes. Microcosms with varying sulfate and nitrate concentrations demonstrated an inhibitory effect on reductive dechlorination of PCP compared to an untreated control. Compared to nitrate, sulfate exhibited a more significant impact on PCP dechlorination, as evidenced by a lower maximum reaction rate and a longer time to reach the maximum reaction rate. Dechlorination of PCP was initiated at the ortho-position, and then at the para- and meta-positions to form 3-CP as the final product in all microcosms. Deep sequencing of microbial communities in the microcosms revealed a strong variation in bacterial taxon among treatments. Specialized microbial groups, such as the genus of Desulfovibrio responding to the addition of sulfate, had a potential to mediate the competitive microbial dechlorination of PCP. Our results provide an insight into the competitive microbial-mediated reductive dechlorination of PCP in natural flooded soil or sediment environments. PMID:29643842

  9. Spectral, thermal, XRD and SEM studies of charge-transfer complexation of hexamethylenediamine and three types of acceptors: π-, σ- and vacant orbital acceptors that include quinol, picric acid, bromine, iodine, SnCl4 and ZnCl2 acceptors

    NASA Astrophysics Data System (ADS)

    Adam, Abdel Majid A.; Refat, Moamen S.; Saad, Hosam A.

    2013-11-01

    In this work, structural, thermal, morphological and pharmacological characterization was performed on the interactions between a hexamethylenediamine (HMDA) donor and three types of acceptors to understand the complexation behavior of diamines. The three types of acceptors include π-acceptors (i.e., quinol (QL) and picric acid (PA)), σ-acceptors (i.e., bromine and iodine) and vacant orbital acceptors (i.e., tin(IV) tetrachloride (SnCl4) and zinc chloride (ZnCl2)). The characterization of the obtained CT complexes was performed using elemental analysis, infrared (IR), Raman, 1H NMR and electronic absorption spectroscopy, powder X-ray diffraction (XRD) and thermogravimetric (TG) analysis. Their morphologies were studied using scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). The biological activities of the obtained CT complexes were tested for their antibacterial activities. The complex containing the QL acceptor exhibited a remarkable electronic spectrum with a strong, broad absorption band, which had an observed λmax that was at a much longer wavelength than those of the free reactants. In addition, this complex exhibited strong antimicrobial activities against various bacterial and fungal strains compared to standard drugs. The complexes containing the PA, iodine, Sn(IV) and Zn(II) acceptors exhibited good thermal stability up to 240, 330, 275 and 295 °C, respectively. The complexes containing bromine, Sn(IV) and Zn(II) acceptors exhibited good crystallinity. In addition to its good crystallinity properties, the complex containing the bromine acceptor exhibits a remarkable morphology feature.

  10. The location of dissimilatory nitrite reductase and the control of dissimilatory nitrate reductase by oxygen in Paracoccus denitrificans.

    PubMed Central

    Alefounder, P R; Ferguson, S J

    1980-01-01

    1. A method is described for preparing spheroplasts from Paracoccus denitrificans that are substantially depleted of dissimilatory nitrate reductase (cytochrome cd) activity. Treatment of cells with lysozyme + EDTA together with a mild osmotic shock, followed by centrifugation, yielded a pellet of spheroplasts and a supernatant that contained d-type cytochrome. The spheroplasts were judged to have retained an intact plasma membrane on the basis that less than 1% of the activity of a cytoplasmic marker protein, malate dehydrogenase, was released from the spheroplasts. In addition to a low activity towards added nitrite, the suspension of spheroplasts accumulated the nitrite that was produced by respiratory chain-linked reduction of nitrate. It is concluded that nitrate reduction occurs at the periplasmic side of the plasma membrane irrespective of whether nitrite is generated by nitrate reduction or is added exogenously. 2. Further evidence for the integrity of the spheroplasts was that nitrate reduction was inhibited by O2, and that chlorate was reduced at a markedly lower rate than nitrate. These data are taken as evidence for an intact plasma membrane because it was shown that cells acquire the capability to reduce nitrate under aerobic conditions after addition of low amounts of Triton X-100 which, with the same titre, also overcame the permeability barrier to chlorate reduction by intact cells. The close relationship between the appearance of chlorate reduction and the loss of the inhibitory effect of O2 on nitrate reduction also suggests that the later feature of nitrate respiration is due to a control on the accessibility of nitrate to its reductase rather than on the flow of electrons to nitrate reductase. PMID:7197918

  11. Nitrate in groundwater of the United States, 1991-2003

    USGS Publications Warehouse

    Burow, Karen R.; Nolan, Bernard T.; Rupert, Michael G.; Dubrovsky, Neil M.

    2010-01-01

    An assessment of nitrate concentrations in groundwater in the United States indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high N inputs. During 1991-2003, 5101 wells were sampled in 51 study areas throughout the U.S. as part of the U.S. Geological Survey National Water-Quality Assessment (NAWQA) program. The well networks reflect the existing used resource represented by domestic wells in major aquifers (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations were highest in shallow groundwater beneath agricultural land use in areas with well-drained soils and oxic geochemical conditions. Nitrate concentrations were lowest in deep groundwater where groundwater is reduced, or where groundwater is older and hence concentrations reflect historically low N application rates. Classification and regression tree analysis was used to identify the relative importance of N inputs, biogeochemical processes, and physical aquifer properties in explaining nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that dissolved iron concentrations explained most of the variation in groundwater nitrate concentration, followed by manganese, calcium, farm N fertilizer inputs, percent well-drained soils, and dissolved oxygen. Overall, nitrate concentrations in groundwater are most significantly affected by redox conditions, followed by nonpoint-source N inputs. Other water-quality indicators and physical variables had a secondary influence on nitrate concentrations.

  12. The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

    NASA Astrophysics Data System (ADS)

    Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

    2014-05-01

    Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between

  13. Contrasting performance of donor-acceptor copolymer pairs in ternary blend solar cells and two-acceptor copolymers in binary blend solar cells.

    PubMed

    Khlyabich, Petr P; Rudenko, Andrey E; Burkhart, Beate; Thompson, Barry C

    2015-02-04

    Here two contrasting approaches to polymer-fullerene solar cells are compared. In the first approach, two distinct semi-random donor-acceptor copolymers are blended with phenyl-C61-butyric acid methyl ester (PC61BM) to form ternary blend solar cells. The two poly(3-hexylthiophene)-based polymers contain either the acceptor thienopyrroledione (TPD) or diketopyrrolopyrrole (DPP). In the second approach, semi-random donor-acceptor copolymers containing both TPD and DPP acceptors in the same polymer backbone, termed two-acceptor polymers, are blended with PC61BM to give binary blend solar cells. The two approaches result in bulk heterojunction solar cells that have the same molecular active-layer components but differ in the manner in which these molecular components are mixed, either by physical mixing (ternary blend) or chemical "mixing" in the two-acceptor (binary blend) case. Optical properties and photon-to-electron conversion efficiencies of the binary and ternary blends were found to have similar features and were described as a linear combination of the individual components. At the same time, significant differences were observed in the open-circuit voltage (Voc) behaviors of binary and ternary blend solar cells. While in case of two-acceptor polymers, the Voc was found to be in the range of 0.495-0.552 V, ternary blend solar cells showed behavior inherent to organic alloy formation, displaying an intermediate, composition-dependent and tunable Voc in the range from 0.582 to 0.684 V, significantly exceeding the values achieved in the two-acceptor containing binary blend solar cells. Despite the differences between the physical and chemical mixing approaches, both pathways provided solar cells with similar power conversion efficiencies, highlighting the advantages of both pathways toward highly efficient organic solar cells.

  14. Bacterial Community Morphogenesis Is Intimately Linked to the Intracellular Redox State

    PubMed Central

    Okegbe, Chinweike; Price-Whelan, Alexa; Sakhtah, Hassan; Hunter, Ryan C.; Newman, Dianne K.

    2013-01-01

    Many microbial species form multicellular structures comprising elaborate wrinkles and concentric rings, yet the rules governing their architecture are poorly understood. The opportunistic pathogen Pseudomonas aeruginosa produces phenazines, small molecules that act as alternate electron acceptors to oxygen and nitrate to oxidize the intracellular redox state and that influence biofilm morphogenesis. Here, we show that the depth occupied by cells within colony biofilms correlates well with electron acceptor availability. Perturbations in the environmental provision, endogenous production, and utilization of electron acceptors affect colony development in a manner consistent with redox control. Intracellular NADH levels peak before the induction of colony wrinkling. These results suggest that redox imbalance is a major factor driving the morphogenesis of P. aeruginosa biofilms and that wrinkling itself is an adaptation that maximizes oxygen accessibility and thereby supports metabolic homeostasis. This type of redox-driven morphological change is reminiscent of developmental processes that occur in metazoans. PMID:23292774

  15. Energy bands and acceptor binding energies of GaN

    NASA Astrophysics Data System (ADS)

    Xia, Jian-Bai; Cheah, K. W.; Wang, Xiao-Liang; Sun, Dian-Zhao; Kong, Mei-Ying

    1999-04-01

    The energy bands of zinc-blende and wurtzite GaN are calculated with the empirical pseudopotential method, and the pseudopotential parameters for Ga and N atoms are given. The calculated energy bands are in agreement with those obtained by the ab initio method. The effective-mass theory for the semiconductors of wurtzite structure is established, and the effective-mass parameters of GaN for both structures are given. The binding energies of acceptor states are calculated by solving strictly the effective-mass equations. The binding energies of donor and acceptor are 24 and 142 meV for the zinc-blende structure, 20 and 131, and 97 meV for the wurtzite structure, respectively, which are consistent with recent experimental results. It is proposed that there are two kinds of acceptor in wurtzite GaN. One kind is the general acceptor such as C, which substitutes N, which satisfies the effective-mass theory. The other kind of acceptor includes Mg, Zn, Cd, etc., the binding energy of these acceptors is deviated from that given by the effective-mass theory. In this report, wurtzite GaN is grown by the molecular-beam epitaxy method, and the photoluminescence spectra were measured. Three main peaks are assigned to the donor-acceptor transitions from two kinds of acceptors. Some of the transitions were identified as coming from the cubic phase of GaN, which appears randomly within the predominantly hexagonal material.

  16. Distant electric coupling between nitrate reduction and sulphide oxidation investigated by an improved nitrate microscale biosensor

    NASA Astrophysics Data System (ADS)

    Marzocchi, U.; Revsbech, N. P.; Nielsen, L. P.; Risgaard-Petersen, N.

    2012-04-01

    Bacteria are apparently able to transmit electrons to other bacteria (Summers et al. 2010) or to electrodes (Malvankar et al. 2011) by some kind of nanowires (Reguera et al. 2005, Gorbi et al. 2006). Lately it has been shown that such transfer may occur over distances of centimetres in sediments, thereby coupling sulphide oxidation in deeper layers with oxygen reduction near the surface (Nielsen 2011). The finding of these long-distance electrical connections originated from analysis of O2, H2S, and pH profiles measured with microsensors. Nitrate is thermodynamically almost as good an electron acceptor as O2, and we therefore set up an experiment to investigate whether long-distance electron transfer also happens with NO3-. Aquaria were filled with sulphidic marine sediment from Aarhus Bay that was previously used to show long-distance electron transfer to O2. The aquaria were equipped with a lid so that they could be completely filled without a gas phase. Anoxic seawater with 300 μM NO3- was supplied at a constant rate resulting in a steady state concentration in the aquatic phase of 250 μM NO3-. The reservoir with the nitrate-containing water was kept anoxic by bubbling it with a N2/CO2 mixture and was kept at an elevated temperature. The water was cooled on the way to the aquaria to keep the water in the aquaria undersaturated with gasses, so that bubble formation by denitrification in the sediment could be minimised. Profiles of NO3-, H2S, and pH were measured as a function of time (2 months) applying commercial sensors for H2S and pH and an improved microscale NO3- biosensor developed in our laboratory. The penetration of NO3- in the sediment was 4-5 mm after 2 months, whereas sulphide only could be detected below 8-9 mm depth. The electron acceptor and electron donor were thus separated by 4-5 mm, indicating long distance electron transfer. A pH maximum of about 8.6 pH units at the NO3- reduction zone similar to a pH maximum observed in the O2 reduction

  17. Goethite promoted biodegradation of 2,4-dinitrophenol under nitrate reduction condition.

    PubMed

    Tang, Ting; Yue, Zhengbo; Wang, Jin; Chen, Tianhu; Qing, Chengsong

    2018-02-05

    Iron oxide may interact with other pollutants in the aquatic environments and further influence their toxicity, transport and fate. The current study was conducted to investigate the biodegradation of 2,4-dinitrophenol (2,4-DNP) in the presence of iron oxide of goethite under anoxic condition using nitrate as the electron acceptor. Experiment results showed that the degradation rate of 2,4-DNP was improved by goethite. High performance liquid chromatography-mass spectra analysis results showed that goethite promoted degradation and transformation of 2,4-diaminophenol and 2-amino-4-nitrophenol (2-nitro-4-aminophenol). Microbial community analysis results showed that the abundance of Actinobacteria, which have the potential ability to degrade PAHs, was increased when goethite was available. This might partially explain the higher degradation of 2,4-DNP. Furthermore, another bacterium of Desulfotomaculum reducens which could reduce soluble Fe(III) and nitrate was also increased. Results further confirmed that nanomaterials in the aquatic environment will influence the microbial community and further change the transformation process of toxic pollutants. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Organic solar cells based on non-fullerene acceptors

    NASA Astrophysics Data System (ADS)

    Hou, Jianhui; Inganäs, Olle; Friend, Richard H.; Gao, Feng

    2018-02-01

    Organic solar cells (OSCs) have been dominated by donor:acceptor blends based on fullerene acceptors for over two decades. This situation has changed recently, with non-fullerene (NF) OSCs developing very quickly. The power conversion efficiencies of NF OSCs have now reached a value of over 13%, which is higher than the best fullerene-based OSCs. NF acceptors show great tunability in absorption spectra and electron energy levels, providing a wide range of new opportunities. The coexistence of low voltage losses and high current generation indicates that new regimes of device physics and photophysics are reached in these systems. This Review highlights these opportunities made possible by NF acceptors, and also discuss the challenges facing the development of NF OSCs for practical applications.

  19. Nitrate Reduction to Nitrite, Nitric Oxide and Ammonia by Gut Bacteria under Physiological Conditions

    PubMed Central

    Tiso, Mauro; Schechter, Alan N.

    2015-01-01

    The biological nitrogen cycle involves step-wise reduction of nitrogen oxides to ammonium salts and oxidation of ammonia back to nitrites and nitrates by plants and bacteria. Neither process has been thought to have relevance to mammalian physiology; however in recent years the salivary bacterial reduction of nitrate to nitrite has been recognized as an important metabolic conversion in humans. Several enteric bacteria have also shown the ability of catalytic reduction of nitrate to ammonia via nitrite during dissimilatory respiration; however, the importance of this pathway in bacterial species colonizing the human intestine has been little studied. We measured nitrite, nitric oxide (NO) and ammonia formation in cultures of Escherichia coli, Lactobacillus and Bifidobacterium species grown at different sodium nitrate concentrations and oxygen levels. We found that the presence of 5 mM nitrate provided a growth benefit and induced both nitrite and ammonia generation in E.coli and L.plantarum bacteria grown at oxygen concentrations compatible with the content in the gastrointestinal tract. Nitrite and ammonia accumulated in the growth medium when at least 2.5 mM nitrate was present. Time-course curves suggest that nitrate is first converted to nitrite and subsequently to ammonia. Strains of L.rhamnosus, L.acidophilus and B.longum infantis grown with nitrate produced minor changes in nitrite or ammonia levels in the cultures. However, when supplied with exogenous nitrite, NO gas was readily produced independently of added nitrate. Bacterial production of lactic acid causes medium acidification that in turn generates NO by non-enzymatic nitrite reduction. In contrast, nitrite was converted to NO by E.coli cultures even at neutral pH. We suggest that the bacterial nitrate reduction to ammonia, as well as the related NO formation in the gut, could be an important aspect of the overall mammalian nitrate/nitrite/NO metabolism and is yet another way in which the microbiome

  20. Regulation of nitrate reductase by nitric oxide in Chinese cabbage pakchoi (Brassica chinensis L.).

    PubMed

    Du, Shaoting; Zhang, Yongsong; Lin, Xianyong; Wang, Yue; Tang, Caixian

    2008-02-01

    Nitrate reductase (NR), a committed enzyme in nitrate assimilation, involves generation of nitric oxide (NO) in plants. Here we show that the NR activity was significantly enhanced by the addition of NO donors sodium nitroprusside (SNP) and NONOate (diethylamine NONOate sodium) to the culturing solution, whereas it was decreased by NO scavenger 2-(4-carboxyphenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide (cPTIO). Interestingly, both NO gas and SNP directly enhanced but cPTIO inhibited the NR activities of crude enzyme extracts and purified NR enzyme. The cPTIO terminated the interaction between NR-generated NO and the NR itself. Furthermore, the NR protein content was not affected by the SNP treatment. The investigation of the partial reactions catalysed by purified NR using various electron donors and acceptors indicated that the haem and molybdenum centres in NR were the two sites activated by NO. The results suggest that the activation of NR activity by NO is regulated at the post-translational level, probably via a direct interaction mechanism. Accordingly, the concentration of nitrate both in leaves and roots was decreased after 2 weeks of cultivation with SNP. The present study identifies a new mechanism of NR regulation and nitrate assimilation, which provides important new insights into the complex regulation of N-metabolism in plants.

  1. Protein Tyrosine Nitration: Role in Aging.

    PubMed

    Chakravarti, Bulbul; Chakravarti, Deb N

    2017-01-01

    Aging is the inevitable fate of all living organisms, but the molecular basis of physiological aging is poorly understood. Oxidative stress is believed to play a key role in the aging process. In addition to Reactive Oxygen Species (ROS), Reactive Nitrogen Species (RNS) are generated during aerobic metabolism in living organisms. Although protein damage and functional modification by ROS have been demonstrated in details, fewer studies have been reported on protein damage by RNS and its implication in the aging process. Proteins undergoing tyrosine nitration are associated with pathophysiology of several diseases, as well as physiological aging. The purpose of the current review article is to provide a brief summary of the biochemical mechanisms of tyrosine nitration, methodologies used for the detection of these modified proteins, effect of RNS induced post translational modification on biological functions and the putative role of tyrosine nitrated proteins in the aging process. Published studies on the role of RNS in age related functional alteration of various organs/ tissues were critically reviewed and evaluated. Covalent modification of various proteins by tyrosine nitration is associated with modification of biological functions of various organs/tissues such as skeletal muscle, heart, brain and liver due to aging. This information will be helpful to further investigate the interplay of different biochemical pathways and networks involved in the tyrosine nitration of various proteins due to aging with the ultimate goal to prevent the detrimental effects of RNS on the functional activities of these proteins. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  2. Nitrate and pesticides in ground water in the eastern San Joaquin Valley, California : occurrence and trends

    USGS Publications Warehouse

    Burow, Karen R.; Stork, Sylvia V.; Dubrovsky, N.M.

    1998-01-01

    The occurrence of nitrate and pesticides in ground water in California's eastern San Joaquin Valley may be greatly influenced by the long history of intensive farming and irrigation and the generally permeable sediments. This study, which is part of the U.S. Geological Survey National Water-Quality Assessment Program, was done to assess the quality of the ground water and to do a preliminary evaluation of the temporal trends in nitrate and pesticides in the alluvial fans of the eastern San Joaquin Valley. Ground-water samples were collected from 30 domestic wells in 1995 (each well was sampled once during 1995). The results of the analyses of these samples were related to various physical and chemical factors in an attempt to understand the processes that control the occurrence and the concentrations of nitrate and pesticides. A preliminary evaluation of the temporal trends in the occurrence and the concentration of nitrate and pesticides was done by comparing the results of the analyses of the 1995 ground-water samples with the results of the analyses of the samples collected in 1986-87 as part of the U.S. Geological Survey Regional Aquifer-System Analysis Program. Nitrate concentrations (dissolved nitrate plus nitrite, as nitrogen) in ground water sampled in 1995 ranged from less than 0.05 to 34 milligrams per liter, with a median concentration of 4.6 milligrams per liter. Nitrate concentrations exceeded the maximum contaminant level of 10 milligrams per liter (as nitrogen) in 5 of the 30 ground-water samples (17 percent), whereas 12 of the 30 samples (40 percent) had nitrate concentrations less than 3.0 milligrams per liter. The high nitrate concentrations were associated with recently recharged, well-oxygenated ground water that has been affected by agriculture (indicated by the positive correlations between nitrate, dissolved-oxygen, tritium, and specific conductance). Twelve pesticides were detected in 21 of the 30 ground-water samples (70 percent) in 1995

  3. Nitrate uptake and nitrite release by tomato roots in response to anoxia.

    PubMed

    Morard, Philippe; Silvestre, Jérôme; Lacoste, Ludovic; Caumes, Edith; Lamaze, Thierry

    2004-07-01

    Excised root systems of tomato plants (early fruiting stage, 2nd flush) were subjected to a gradual transition from normoxia to anoxia by seating the hydroponic root medium while aeration was stopped. Oxygen level in the medium and respiration rate decreased and reached very low values after 12 h of treatment, indicating that the tissues were anoxic thereafter. Nitrate loss from the nutrient solution was strongly stimulated by anoxia (after 26 h) concomitantly with a release of nitrite starting only after 16 h of treatment. This effect was not observed in the absence of roots or in the presence of tungstate, but occurred with whole plants or with sterile in vitro cultured root tissues. These results indicate that biochemical processes in the root involve nitrate reductase. NR activity assayed in tomato roots increased during anoxia. This phenomenon appeared in intact plants and in root tissues of detopped plants. The stimulating effect of oxygen deprivation on nitrate uptake was specific; anoxia simultaneously entailed a release of orthophosphate, sulfate, and potassium by the roots. Anoxia enhanced nitrate reduction by root tissues, and nitrite ions were released into xylem sap and into medium culture. In terms of the overall balance, the amount of nitrite recovered represented only half of the amount of nitrate utilized. Nitrite reduction into nitric oxide and perhaps into nitrogen gas could account for this discrepancy. These results appear to be the first report of an increase in nitrate uptake by plant roots under anoxia of tomato at the early fruiting stage, and the rates of nitrite release in nutrient medium by the asphyxiated roots are the fastest yet reported.

  4. Determination of the total oxygen isotopic composition of nitrate and the calibration of a Δ17Ο nitrate reference material

    USGS Publications Warehouse

    Michalski, Greg; Savarino, Joel; Böhlke, J.K.; Thiemens , Mark

    2002-01-01

    A thermal decomposition method was developed and tested for the simultaneous determination of δ18O and δ17Ο in nitrate. The thermal decomposition of AgNO3 allows for the rapid and accurate determination of 18O/16O and 17O/16O isotopic ratios with a precision of ±1.5‰ for δ18O and ±0.11‰ for Δ17Ο (Δ17Ο = δ17Ο − 0.52 × δ18O). The international nitrate isotope reference material IAEA-NO3 yielded a δ18O value of +23.6‰ and Δ17Ο of −0.2‰, consistent with normal terrestrial mass-dependent isotopic ratios. In contrast, a large sample of NaNO3 from the Atacama Desert, Chile, was found to have Δ17Ο = 21.56 ± 0.11‰ and δ18O = 54.9 ± 1.5‰, demonstrating a substantial mass-independent isotopic composition consistent with the proposed atmospheric origin of the desert nitrate. It is suggested that this sample (designated USGS-35) can be used to generate other gases (CO2, CO, N2O, O2) with the same Δ17Ο to serve as measurement references for a variety of applications involving mass-independent isotopic compositions in environmental studies.

  5. Analysis of nitrate in near-surface aquifers in the midcontinental United States: An application of the inverse hyperbolic sine Tobit model

    USGS Publications Warehouse

    Yen, Steven T.; Liu, Shiping; Kolpin, Dana W.

    1996-01-01

    A nonnormal and heteroscedastic Tobit model is used to determine the primary factors that affect nitrate concentrations in near-surface aquifers, using data from the U.S. Geological Survey collected in 1991. Both normality and homoscedasticity of errors are rejected, justifying the use of a nonnormal and heteroscedastic model. The following factors are found to have significant impacts on nitrate concentrations in groundwater: well screen interval, depth to top of aquifers, percentages of urban residential, forest land, and pasture within 3.2 km, dissolved oxygen concentration level, and presence of a chemical facility and feedlot. The effects of explanatory variables on nitrate concentration are explored further by calculating elasticities. Dissolved oxygen concentration level has more notable effects on nitrate concentrations in groundwater than other variables.

  6. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources of...

  7. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources of...

  8. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium nitrate and potassium nitrate. 181.33... nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions issued... potassium nitrite, in the production of cured red meat products and cured poultry products. [48 FR 1705, Jan...

  9. Rise-Time of FRET-Acceptor Fluorescence Tracks Protein Folding

    PubMed Central

    Lindhoud, Simon; Westphal, Adrie H.; van Mierlo, Carlo P. M.; Visser, Antonie J. W. G.; Borst, Jan Willem

    2014-01-01

    Uniform labeling of proteins with fluorescent donor and acceptor dyes with an equimolar ratio is paramount for accurate determination of Förster resonance energy transfer (FRET) efficiencies. In practice, however, the labeled protein population contains donor-labeled molecules that have no corresponding acceptor. These FRET-inactive donors contaminate the donor fluorescence signal, which leads to underestimation of FRET efficiencies in conventional fluorescence intensity and lifetime-based FRET experiments. Such contamination is avoided if FRET efficiencies are extracted from the rise time of acceptor fluorescence upon donor excitation. The reciprocal value of the rise time of acceptor fluorescence is equal to the decay rate of the FRET-active donor fluorescence. Here, we have determined rise times of sensitized acceptor fluorescence to study the folding of double-labeled apoflavodoxin molecules and show that this approach tracks the characteristics of apoflavodoxinʼs complex folding pathway. PMID:25535076

  10. Ipso Nitration. Regiospecific Nitration via Ipso Nitration Products.

    DTIC Science & Technology

    1985-05-20

    products of nitration of alkylbenzenes and alkylphenol derivatives. The general pattern envisioned is shown in Scheme 1. In order to realize this...we have also explored solid state nitration of various alkylphenols . This procedure involves adsorbing concentrated nitric acid on alumina, followed

  11. Long-term use of short- and long-acting nitrates in stable angina pectoris.

    PubMed

    Kosmicki, Marek Antoni

    2009-05-01

    Long-acting nitrates are effective antianginal drugs during initial treatment. However, their therapeutic value is compromised by the rapid development of tolerance during sustained therapy, which means that their clinical efficacy is decreased during long-term use. Sublingual nitroglycerin (NTG), a short-acting nitrate, is suitable for the immediate relief of angina. In patients with stable angina treated with oral long-acting nitrates, NTG maintains its full anti-ischemic effect both after initial oral ingestion and after intermittent long-term oral administration. However, NTG attenuates this effect during continuous treatment, when tolerance to oral nitrates occurs, and this is called cross-tolerance. In stable angina long-acting nitrates are considered third-line therapy because a nitrate-free interval is required to avoid the development of tolerance. Nitrates vary in their potential to induce the development of tolerance. During long-lasting nitrate therapy, except pentaerythritol tetranitrate (PETN), one can observe the development of reactive oxygen species (ROS) inside the muscular cell of a vessel wall, and these bind with nitric oxide (NO). This leads to decreased NO activity, thus, nitrate tolerance. PETN has no tendency to form ROS, and therefore during long-term PETN therapy, there is probably no tolerance or cross-tolerance, as during treatment with other nitrates.

  12. A study of acceptors and non-acceptors of family planning methods among three tribal communities.

    PubMed

    Mutharayappa, R

    1995-03-01

    Primary data were collected from 399 currently married women of the Marati, Malekudiya, and Koraga tribes in the Dakshina Kannada district of Karnataka State in this study of the implementation of family planning programs in tribal areas. The Marati, Malekudiya, and Koraga tribes are three different endogamous tribal populations living in similar ecological conditions. Higher levels of literacy and a high rate of acceptance of family planning methods, however, have been observed among these tribes compared to the rest of the tribal population in the state. 46.4% of currently married women aged 15-49 years in the tribes were acceptors of family planning methods, having a mean 3.7 children. The majority of acceptors opted for tubectomy and vasectomy. The adoption of spacing methods is less common among tribal people. Most acceptors received their operations through government health facilities. They were motivated mainly by female health workers and received both cash and other incentives to accept family planning. The main reason for non-acceptance of family planning among non-acceptors was the desire to conceive and bear more children. The data indicate that most of the tribal households are nuclear families with household size more or less similar to that of the general population. They have a higher literacy rate than the rest of the tribal population in the state, with literacy levels between males and females and between the three tribes being quite different; the school enrollment ratio is relatively higher for both boys and girls.

  13. Nitrite oxidation in the Namibian oxygen minimum zone

    PubMed Central

    Füssel, Jessika; Lam, Phyllis; Lavik, Gaute; Jensen, Marlene M; Holtappels, Moritz; Günter, Marcel; Kuypers, Marcel MM

    2012-01-01

    Nitrite oxidation is the second step of nitrification. It is the primary source of oceanic nitrate, the predominant form of bioavailable nitrogen in the ocean. Despite its obvious importance, nitrite oxidation has rarely been investigated in marine settings. We determined nitrite oxidation rates directly in 15N-incubation experiments and compared the rates with those of nitrate reduction to nitrite, ammonia oxidation, anammox, denitrification, as well as dissimilatory nitrate/nitrite reduction to ammonium in the Namibian oxygen minimum zone (OMZ). Nitrite oxidation (⩽372 nM NO2− d−1) was detected throughout the OMZ even when in situ oxygen concentrations were low to non-detectable. Nitrite oxidation rates often exceeded ammonia oxidation rates, whereas nitrate reduction served as an alternative and significant source of nitrite. Nitrite oxidation and anammox co-occurred in these oxygen-deficient waters, suggesting that nitrite-oxidizing bacteria (NOB) likely compete with anammox bacteria for nitrite when substrate availability became low. Among all of the known NOB genera targeted via catalyzed reporter deposition fluorescence in situ hybridization, only Nitrospina and Nitrococcus were detectable in the Namibian OMZ samples investigated. These NOB were abundant throughout the OMZ and contributed up to ∼9% of total microbial community. Our combined results reveal that a considerable fraction of the recently recycled nitrogen or reduced NO3− was re-oxidized back to NO3− via nitrite oxidation, instead of being lost from the system through the anammox or denitrification pathways. PMID:22170426

  14. Nitrite oxidation in the Namibian oxygen minimum zone.

    PubMed

    Füssel, Jessika; Lam, Phyllis; Lavik, Gaute; Jensen, Marlene M; Holtappels, Moritz; Günter, Marcel; Kuypers, Marcel M M

    2012-06-01

    Nitrite oxidation is the second step of nitrification. It is the primary source of oceanic nitrate, the predominant form of bioavailable nitrogen in the ocean. Despite its obvious importance, nitrite oxidation has rarely been investigated in marine settings. We determined nitrite oxidation rates directly in (15)N-incubation experiments and compared the rates with those of nitrate reduction to nitrite, ammonia oxidation, anammox, denitrification, as well as dissimilatory nitrate/nitrite reduction to ammonium in the Namibian oxygen minimum zone (OMZ). Nitrite oxidation (≤372 nM NO(2)(-) d(-1)) was detected throughout the OMZ even when in situ oxygen concentrations were low to non-detectable. Nitrite oxidation rates often exceeded ammonia oxidation rates, whereas nitrate reduction served as an alternative and significant source of nitrite. Nitrite oxidation and anammox co-occurred in these oxygen-deficient waters, suggesting that nitrite-oxidizing bacteria (NOB) likely compete with anammox bacteria for nitrite when substrate availability became low. Among all of the known NOB genera targeted via catalyzed reporter deposition fluorescence in situ hybridization, only Nitrospina and Nitrococcus were detectable in the Namibian OMZ samples investigated. These NOB were abundant throughout the OMZ and contributed up to ~9% of total microbial community. Our combined results reveal that a considerable fraction of the recently recycled nitrogen or reduced NO(3)(-) was re-oxidized back to NO(3)(-) via nitrite oxidation, instead of being lost from the system through the anammox or denitrification pathways.

  15. Method for producing and regenerating a synthetic CO.sub.2 acceptor

    DOEpatents

    Lancet, Michael S [Pittsburgh, PA; Curran, George P [Pittsburgh, PA; Gorin, Everett [San Rafael, CA

    1982-01-01

    A method for producing a synthetic CO.sub.2 acceptor by feeding a mixture of finely divided silica and at least one finely divided calcium compound selected from the group consisting of calcium oxide and calcium carbonate to a fluidized bed; operating the fluidized bed at suitable conditions to produce pellets of synthetic CO.sub.2 acceptor and recovering the pellets of synthetic CO.sub.2 acceptor from the fluidized bed. Optionally, spent synthetic CO.sub.2 acceptor can be charged to the fluidized bed to produce regenerated pellets of synthetic CO.sub.2 acceptor.

  16. Assessment of a New Type of Coin Acceptor

    DOT National Transportation Integrated Search

    1983-04-01

    An assessment of the Mars Money Systems Model CD 540-1 coin acceptor associated with farecard vendors was conducted at the Port Authority Transit Corp. as part of an appraisal of automatic fare collection (AFC) equipment. The Mars acceptor consistent...

  17. Nitrate removal in deep sediments of a nitrogen-rich river network: A test of a conceptual model

    USGS Publications Warehouse

    Stelzer, Robert S.; Bartsch, Lynn

    2012-01-01

    Many estimates of nitrogen removal in streams and watersheds do not include or account for nitrate removal in deep sediments, particularly in gaining streams. We developed and tested a conceptual model for nitrate removal in deep sediments in a nitrogen-rich river network. The model predicts that oxic, nitrate-rich groundwater will become depleted in nitrate as groundwater upwelling through sediments encounters a zone that contains buried particulate organic carbon, which promotes redox conditions favorable for nitrate removal. We tested the model at eight sites in upwelling reaches of lotic ecosystems in the Waupaca River Watershed that varied by three orders of magnitude in groundwater nitrate concentration. We measured denitrification potential in sediment core sections to 30 cm and developed vertical nitrate profiles to a depth of about 1 m with peepers and piezometer nests. Denitrification potential was higher, on average, in shallower core sections. However, core sections deeper than 5 cm accounted for 70%, on average, of the depth-integrated denitrification potential. Denitrification potential increased linearly with groundwater nitrate concentration up to 2 mg NO3-N/L but the relationship broke down at higher concentrations (> 5 mg NO3-N/L), a pattern that suggests nitrate saturation. At most sites groundwater nitrate declined from high concentrations at depth to much lower concentrations prior to discharge into the surface water. The profiles suggested that nitrate removal occurred at sediment depths between 20 and 40 cm. Dissolved oxygen concentrations were much higher in deep sediments than in pore water at 5 cm sediment depth at most locations. The substantial denitrification potential in deep sediments coupled with the declines in nitrate and dissolved oxygen concentrations in upwelling groundwater suggest that our conceptual model for nitrate removal in deep sediments is applicable to this river network. Our results suggest that nitrate removal rates

  18. Isotopic and Chemical Analysis of Nitrate Sources and Cycling in the San Joaquin River Near Stockton, California

    NASA Astrophysics Data System (ADS)

    Silva, S. R.; Kendall, C.; Bemis, B.; Wankel, S.; Bergamaschi, B.; Kratzer, C.; Dileanis, P.; Erickson, D.; Avery, E.; Paxton, K.

    2002-12-01

    Fish migration through the deep-water channel in the San Joaquin River at Stockton, California is inhibited by low oxygen concentrations during the summer months. The cause for this condition appears to be stagnation and decomposition of algae with attendant oxygen consumption. Algae growth in the San Joaquin River is promoted by nutrients entering the river mainly in the form of nitrate. Possible significant sources of nitrate include soil, fertilizer from agriculture, manure from dairy operations, and N derived from municipal sewage. A 2000 CALFED pilot study investigated the sources and cycling of nitrate at four sites along the San Joaquin River upstream of Stockton using the carbon and nitrogen isotopes of total dissolved and particulate organic matter, together with hydrological measurements and various concentration data, including chlorophyll-a. The nitrate source, its relationship to phytoplankton, and the effect of the nitrate source and cycling on the N isotopic composition of dissolved and particulate organic matter were the primary concerns of the study. The d15N values of dissolved organic nitrogen (DON) were used as a proxy for nitrate d15N because nitrate comprised about 90% of DON. Chlorophyll-a and C:N ratios indicated that the particulate organic matter (POM) consisted largely of plankton and therefore the d15N of POM was used as a proxy for the d15N of plankton. A tentative interpretation of the pilot study was that nitrate was a major nutrient for the plankton and the nitrate was of anthropogenic origin, possibly sewage or animal waste. To test these assumptions and interpretations, we are currently analyzing a set of samples collected in 2001. In addition to the previous sample types, a subset of samples will be measured directly for nitrate d15N to assess the validity of using d15N of DON as a proxy for nitrate.

  19. Isotope chemistry of an extensively nitrate-contaminated urban aquifer

    NASA Astrophysics Data System (ADS)

    Kracht, O.; de Souza, L. C.; de Queiros, M. A.; Stegemann, C.; Hunziker, J.

    2003-04-01

    The supply of drinking water for the approximately 800.000 inhabitants of the city of Natal (Rio Grande do Norte, Brazil) is strongly dependent on the use of local groundwater from the Barreiras Aquifer. Over 70 % of the public production are served by a system of about 130 tubular wells, that are distributed all over the urban area. Yet, no groundwater protection zones have been declared. In addition, a comparable number of private wells also depend on the cities underground water resources. Depending on the local topography, the groundwater table is located several tens of meters below surface. Useable groundwater occurrences are bound to an up to hundred meters thick series of unconsolidated clastic sediments from the younger tertiary (Barreiras Formation), that is underlain by less permeable cretaceous carbonates. Natals topography is dominated by impressive quaternary dunes formations, that play an important role for the infiltration of rain as the only source of recharge for the local groundwater. During the last decades, an extensive and rapidly growing groundwater-contamination with up to over 100 mg/l nitrate was observed by the local authorities. Hydrochemical data indicate this deterioration to be due to a massive spill of sanitary effluents over septic pits, as only 20 % of the city is yet served by a sewer system. The isotopic composition of Natals groundwater shows only small variations, with an average δ18O value of -2,3 per mill and δ2H value of -10,5 per mill vs. SMOW. Its origin from recent local precipitation is revealed by a good correspondence with the annual weighted means for precipitation in Ceara Mirim (nearest GNIP station, situated 45 km NE of Natal). In contrast, a set of samples from different regional surface waters indicated a strong evaporation trend with systematic enrichment in the oxygen and hydrogen isotopic composition. Samples from 33 production wells with a wide variation of nitrate concentrations were investigated for their

  20. Growth of Iron(III)-Reducing Bacteria on Clay Minerals as the Sole Electron Acceptor and Comparison of Growth Yields on a Variety of Oxidized Iron Forms†

    PubMed Central

    Kostka, Joel E.; Dalton, Dava D.; Skelton, Hayley; Dollhopf, Sherry; Stucki, Joseph W.

    2002-01-01

    Smectite clay minerals are abundant in soils and sediments worldwide and are typically rich in Fe. While recent investigations have shown that the structural Fe(III) bound in clay minerals is reduced by microorganisms, previous studies have not tested growth with clay minerals as the sole electron acceptor. Here we have demonstrated that a pure culture of Shewanella oneidensis strain MR-1 as well as enrichment cultures of Fe(III)-reducing bacteria from rice paddy soil and subsurface sediments are capable of conserving energy for growth with the structural Fe(III) bound in smectite clay as the sole electron acceptor. Pure cultures of S. oneidensis were used for more detailed growth rate and yield experiments on various solid- and soluble-phase electron acceptors [smectite, Fe(III) oxyhydroxide FeOOH, Fe(III) citrate, and oxygen] in the same minimal medium. Growth was assessed as direct cell counts or as an increase in cell carbon (measured as particulate organic carbon). Cell counts showed that similar growth of S. oneidensis (108 cells ml−1) occurred with smectitic Fe(III) and on other Fe forms [amorphous Fe(III) oxyhydroxide, and Fe citrate] or oxygen as the electron acceptor. In contrast, cell yields of S. oneidensis measured as the increase in cell carbon were similar on all Fe forms tested while yields on oxygen were five times higher, in agreement with thermodynamic predictions. Over a range of particle loadings (0.5 to 4 g liter−1), the increase in cell number was highly correlated to the amount of structural Fe in smectite reduced. From phylogenetic analysis of the complete 16S rRNA gene sequences, a predominance of clones retrieved from the clay mineral-reducing enrichment cultures were most closely related to the low-G+C gram-positive members of the Bacteria (Clostridium and Desulfitobacterium) and the δ-Proteobacteria (members of the Geobacteraceae). Results indicate that growth with smectitic Fe(III) is similar in magnitude to that with Fe

  1. Oxygen-17 anomaly in soil nitrate: A new precipitation proxy for desert landscapes

    NASA Astrophysics Data System (ADS)

    Wang, Fan; Ge, Wensheng; Luo, Hao; Seo, Ji-Hye; Michalski, Greg

    2016-03-01

    The nitrogen cycle in desert soil ecosystems is particularly sensitive to changes in precipitation, even of relatively small magnitude and short duration, because it is already under water stress. This suggests that desert soils may have preserved past evidence of small variations in continental precipitation. We have measured nitrate (NO3-) concentrations in soils from the Atacama (Chile), Kumtag (China), Mojave (US), and Thar (India) deserts, and stable nitrogen and oxygen isotope (15N, 17O, and 18O) abundances of the soil NO3-. 17O anomalies (Δ17O), the deviations from the mass-independent isotopic fractionation, were detected in soil NO3- from almost all sites of these four deserts. There was a strong negative correlation between the mean annual precipitation (MAP) and soil NO3- Δ17O values (Δ

  2. Use of diverse geochemical data sets to determine sources and sinks of nitrate and methane in groundwater, Garfield County, Colorado, 2009

    USGS Publications Warehouse

    McMahon, P.B.; Thomas, J.C.; Hunt, A.G.

    2011-01-01

    Previous water-quality assessments reported elevated concentrations of nitrate and methane in water from domestic wells screened in shallow zones of the Wasatch Formation, Garfield County, Colorado. In 2009, the U.S. Geological Survey, in cooperation with the Colorado Department of Public Health and Environment, analyzed samples collected from 26 domestic wells for a diverse set of geochemical tracers for the purpose of determining sources and sinks of nitrate and methane in groundwater from the Wasatch Formation. Nitrate concentrations ranged from less than 0.04 to 6.74 milligrams per liter as nitrogen (mg/L as N) and were significantly lower in water samples with dissolved-oxygen concentrations less than 0.5 mg/L than in samples with dissolved-oxygen concentrations greater than or equal to 0.5 mg/L. Chloride/bromide mass ratios and tracers of groundwater age (tritium, chlorofluorocarbons, and sulfur hexafluoride) indicate that septic-system effluent or animal waste was a source of nitrate in some young groundwater (less than 50 years), although other sources such as fertilizer also may have contributed nitrate to the groundwater. Nitrate and nitrogen gas (N2) concentrations indicate that denitrification was the primary sink for nitrate in anoxic groundwater, removing 99 percent of the original nitrate content in some samples that had nitrate concentrations greater than 10 mg/L as N at the time of recharge. Methane concentrations ranged from less than 0.0005 to 32.5 mg/L and were significantly higher in water samples with dissolved-oxygen concentrations less than 0.5 mg/L than in samples with dissolved-oxygen concentrations greater than or equal to 0.5 mg/L. High methane concentrations (greater than 1 mg/L) in some samples were biogenic in origin and appeared to be derived from a relatively deep source on the basis of helium concentrations and isotopic data. One such sample had water-isotopic and major-ion compositions similar to that of produced water from the

  3. Nitrate removal by Fe0/Pd/Cu nano-composite in groundwater.

    PubMed

    Liu, Hongyuan; Guo, Min; Zhang, Yan

    2014-01-01

    Nitrate pollution in groundwater shows a great threat to the safety of drinking water. Chemical reduction by zero-valent iron is being considered as a promising technique for nitrate removal from contaminated groundwater. In this paper, Fe0/Pd/Cu nano-composites were prepared by the liquid-phase reduction method, and batch experiments of nitrate reduction by the prepared Fe0/Pd/Cu nano-composites under various operating conditions were carried out. It has been found that nano-Fe0/Pd/Cu composites processed dual functions: catalytic reduction and chemical reduction. The introduction of Pd and Cu not only improved nitrate removal rate, but also reduced the generation of ammonia. Nitrate removal rate was affected by the amount of Fe0/Pd/Cu, initial nitrate concentration, solution pH, dissolved oxygen (DO), reaction temperature, the presence of anions, and organic pollutant. Moreover, nitrate reduction by Fe0/Pd/Cu composites followed the pseudo-first-order reaction kinetics. The removal rate of nitrate and total nitrogen were about 85% and 40.8%, respectively, under the reaction condition of Fe-6.0%Pd-3.0%Cu amount of 0.25 g/L, pH value of 7.1, DO of 0.42 mg/L, and initial nitrate concentration of 100 mg/L. Compared with the previous studies with Fe0 alone or Fe-Cu, nano-Fe-6%Pd-3%Cu composites showed a better selectivity to N2.

  4. Substrate binding site for nitrate reductase of Escherichia coli is on the inner aspect of the membrane.

    PubMed Central

    Kristjansson, J K; Hollocher, T C

    1979-01-01

    Escherichia coli grown anaerobically on nitrate exhibited the same transport barrier to reduction of chlorate, relative to nitrate, as that exhibited by Paracoccus denitrificans. This establishes that the nitrate binding site of nitrate reductase (EC 1.7.99.4) in E. coli must also lie on the cell side of the nitrate transporter which is associated with the plasma membrane. Because nitrate reductase is membrane bound, the nitrate binding site is thus located on the inner aspect of the membrane. Nitrate pulse studies on E. coli in the absence of valinomycin showed a small transient alkalinization (leads to H+/NO3- congruent to --0.07) which did not occur with oxygen pulses. By analogy with P. denitrificans, the alkaline transient is interpreted to arise from proton-linked nitrate uptake which is closely followed by nitrite efflux. The result is consistent with internal reduction of nitrate, whereas external reduction would be expected to give leads to H+/NO3-ratios approaching --2. PMID:374343

  5. Evaluation of the Origin and Fate of Nitrate in the Aquifer System of Southern Baldwin County, Alabama Using Multi-isotopic Data

    NASA Astrophysics Data System (ADS)

    Murgulet, D.; Tick, G. R.

    2008-12-01

    Continued and extensive residential and agricultural development of near-shore areas in southern Baldwin County, Alabama has led to increased inputs of nitrogen (N) to groundwater and to the Gulf of Mexico. Nitrate (NO3-) concentrations in several groundwater wells exceeded the regulatory drinking water standards (10 mg/L nitrate-N). Groundwater and surface water samples were analyzed for nitrate, phosphate, salinity, chloride, and total dissolved solids concentrations to assess the extent of nitrate contamination. Nitrogen and oxygen isotopes of nitrate (e.g., δ15N and δ18O of nitrate) were used in conjunction with other isotopic data (e.g., 13C, and 14C, and hydrogen and oxygen isotopes of groundwater) and hydrogeochemical data to place constraints on potential sources of nitrate. The δ15N and δ18O of groundwater nitrate values ranged between +3.1 and +9.6‰ and +4.2 and +8.7‰, respectively. This range of values suggests that nitrate is primarily derived from nitrification of reduced N compounds (primarily ammonia) from fertilizer and manure or septic waste. However, an overwhelming number of samples show isotopic signatures which indicate that the predominant source of nitrate in these aguifers is the fertilizer and to some extent, for deeper wells with older groundwater, the atmospheric nitrate. The narrow range of δ18O values further confirms the primary nitrate sources. The δ15N and δ18O of nitrate data indicate that denitrification was not an important processes in these aquifers. This conclusion is also supported by the 114C data which revealed relatively young groundwaters with sufficiently high oxygen levels. In the absence of denitrification and the presence of a permanent source, it is expected that the elevated groundwater nitrate concentrations will not be readily attenuated posing a potential contamination and degradation problem of coastal discharge zones into the future. The δ13C and δ18O of groundwater data indicates that water in the

  6. Alternansucrase acceptor reactions with D-tagatose and L-glucose.

    PubMed

    Côté, Gregory L; Dunlap, Christopher A; Appell, Michael; Momany, Frank A

    2005-02-07

    Alternansucrase (EC 2.4.1.140) is a d-glucansucrase that synthesizes an alternating alpha-(1-->3), (1-->6)-linked d-glucan from sucrose. It also synthesizes oligosaccharides via d-glucopyranosyl transfer to various acceptor sugars. Two of the more efficient monosaccharide acceptors are D-tagatose and L-glucose. In the presence of d-tagatose, alternansucrase produced the disaccharide alpha-d-glucopyranosyl-(1-->1)-beta-D-tagatopyranose via glucosyl transfer. This disaccharide is analogous to trehalulose. We were unable to isolate a disaccharide product from L-glucose, but the trisaccharide alpha-D-glucopyranosyl-(1-->6)-alpha-d-glucopyranosyl-(1-->4)-l-glucose was isolated and identified. This is analogous to panose, one of the structural units of pullulan, in which the reducing-end D-glucose residue has been replaced by its L-enantiomer. The putative L-glucose disaccharide product, produced by glucoamylase hydrolysis of the trisaccharide, was found to be an acceptor for alternansucrase. The disaccharide, alpha-D-glucopyranosyl-(1-->4)-L-glucose, was a better acceptor than maltose, previously the best known acceptor for alternansucrase. A structure comparison of alpha-D-glucopyranosyl-(1-->4)-L-glucose and maltose was performed through computer modeling to identify common features, which may be important in acceptor affinity by alternansucrase.

  7. Effect of Dietary Nitrate Supplementation on Swimming Performance in Trained Swimmers.

    PubMed

    Lowings, Sam; Shannon, Oliver Michael; Deighton, Kevin; Matu, Jamie; Barlow, Matthew John

    2017-08-01

    Nitrate supplementation appears to be most ergogenic when oxygen availability is restricted and subsequently may be particularly beneficial for swimming performance due to the breath-hold element of this sport. This represents the first investigation of nitrate supplementation and swimming time-trial (TT) performance. In a randomized double-blind repeated-measures crossover study, ten (5 male, 5 female) trained swimmers ingested 140ml nitrate-rich (~12.5mmol nitrate) or nitrate-depleted (~0.01mmol nitrate) beetroot juice. Three hours later, subjects completed a maximal effort swim TT comprising 168m (8 × 21m lengths) backstroke. Preexercise fractional exhaled nitric oxide concentration was significantly elevated with nitrate compared with placebo, Mean (SD): 17 (9) vs. 7 (3)p.p.b., p = .008. Nitrate supplementation had a likely trivial effect on overall swim TT performance (mean difference 1.22s; 90% CI -0.18-2.6s; 0.93%; p = .144; d = 0.13; unlikely beneficial (22.6%), likely trivial (77.2%), most unlikely negative (0.2%)). The effects of nitrate supplementation during the first half of the TT were trivial (mean difference 0.29s; 90% CI -0.94-1.5s; 0.46%; p = .678; d = 0.05), but there was a possible beneficial effect of nitrate supplementation during the second half of the TT (mean difference 0.93s; 90% CI 0.13-1.70s; 1.36%; p = .062; d = 0.24; possibly beneficial (63.5%), possibly trivial (36.3%), most unlikely negative (0.2%)). The duration and speed of underwater swimming within the performance did not differ between nitrate and placebo (both p > .30). Nitrate supplementation increased nitric oxide bioavailability but did not benefit short-distance swimming performance or the underwater phases of the TT. Further investigation into the effects of nitrate supplementation during the second half of performance tests may be warranted.

  8. Method for producing and regenerating a synthetic CO[sub 2] acceptor

    DOEpatents

    Lancet, M. S.; Curran, G. P.; Gorin, E.

    1982-05-18

    A method is described for producing a synthetic CO[sub 2] acceptor by feeding a mixture of finely divided silica and at least one finely divided calcium compound selected from the group consisting of calcium oxide and calcium carbonate to a fluidized bed; operating the fluidized bed at suitable conditions to produce pellets of synthetic CO[sub 2] acceptor and recovering the pellets of synthetic CO[sub 2] acceptor from the fluidized bed. Optionally, spent synthetic CO[sub 2] acceptor can be charged to the fluidized bed to produce regenerated pellets of synthetic CO[sub 2] acceptor. 1 fig.

  9. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products and...

  10. 21 CFR 181.33 - Sodium nitrate and potassium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium nitrate and potassium nitrate. 181.33...-Sanctioned Food Ingredients § 181.33 Sodium nitrate and potassium nitrate. Sodium nitrate and potassium... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products and...

  11. Deep donor state of the copper acceptor as a source of green luminescence in ZnO

    NASA Astrophysics Data System (ADS)

    Lyons, J. L.; Alkauskas, A.; Janotti, A.; Van de Walle, C. G.

    2017-07-01

    Copper impurities have long been linked with green luminescence (GL) in ZnO. Copper is known to introduce an acceptor level close to the conduction band of ZnO, and the GL has conventionally been attributed to transitions involving an excited state which localizes holes on neighboring oxygen atoms. To date, a theoretical description of the optical properties of such deep centers has been difficult to achieve due to the limitations of functionals in the density functional theory. Here, we employ a screened hybrid density functional to calculate the properties of Cu in ZnO. In agreement with the experiment, we find that CuZn features an acceptor level near the conduction band of ZnO. However, we find that CuZn also gives rise to a deep donor level 0.46 eV above the valence band of ZnO; the calculated optical transitions involving this state agree well with the GL observed in ZnO:Cu.

  12. Developmental stage- and concentration-specific sodium nitroprusside application results in nitrate reductase regulation and the modification of nitrate metabolism in leaves of Medicago truncatula plants

    PubMed Central

    Antoniou, Chrystalla; Filippou, Panagiota; Mylona, Photini; Fasoula, Dionysia; Ioannides, Ioannis; Polidoros, Alexios; Fotopoulos, Vasileios

    2013-01-01

    Nitric oxide (NO) is a bioactive molecule involved in numerous biological events that has been reported to display both pro-oxidant and antioxidant properties in plants. Several reports exist which demonstrate the protective action of sodium nitroprusside (SNP), a widely used NO donor, which acts as a signal molecule in plants responsible for the expression regulation of many antioxidant enzymes. This study attempts to provide a novel insight into the effect of application of low (100 μΜ) and high (2.5 mM) concentrations of SNP on the nitrosative status and nitrate metabolism of mature (40 d) and senescing (65 d) Medicago truncatula plants. Higher concentrations of SNP resulted in increased NO content, cellular damage levels and reactive oxygen species (ROS) concentration, further induced in older tissues. Senescing M. truncatula plants demonstrated greater sensitivity to SNP-induced oxidative and nitrosative damage, suggesting a developmental stage-dependent suppression in the plant’s capacity to cope with free oxygen and nitrogen radicals. In addition, measurements of the activity of nitrate reductase (NR), a key enzyme involved in the generation of NO in plants, indicated a differential regulation in a dose and time-dependent manner. Furthermore, expression levels of NO-responsive genes (NR, nitrate/nitrite transporters) involved in nitrogen assimilation and NO production revealed significant induction of NR and nitrate transporter during long-term 2.5 mM SNP application in mature plants and overall gene suppression in senescing plants, supporting the differential nitrosative response of M. truncatula plants treated with different concentrations of SNP. PMID:23838961

  13. Mapping the Relationship between Glycosyl Acceptor Reactivity and Glycosylation Stereoselectivity.

    PubMed

    van der Vorm, Stefan; van Hengst, Jacob M A; Bakker, Marloes; Overkleeft, Herman S; van der Marel, Gijsbert A; Codée, Jeroen D C

    2018-03-30

    The reactivity of both coupling partners-the glycosyl donor and acceptor-is decisive for the outcome of a glycosylation reaction, in terms of both yield and stereoselectivity. Where the reactivity of glycosyl donors is well understood and can be controlled through manipulation of the functional/protecting-group pattern, the reactivity of glycosyl acceptor alcohols is poorly understood. We here present an operationally simple system to gauge glycosyl acceptor reactivity, which employs two conformationally locked donors with stereoselectivity that critically depends on the reactivity of the nucleophile. A wide array of acceptors was screened and their structure-reactivity/stereoselectivity relationships established. By systematically varying the protecting groups, the reactivity of glycosyl acceptors can be adjusted to attain stereoselective cis-glucosylations. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Evaluating the source of streamwater nitrate using δ15N and δ18O in nitrate in two watersheds in New Hampshire, USA

    USGS Publications Warehouse

    Pardo, Linda H.; Kendall, Carol; Pett-Ridge, Jennifer; Chang, Cecily C.Y.

    2004-01-01

    The natural abundance of nitrogen and oxygen isotopes in nitrate can be a powerful tool for identifying the source of nitrate in streamwater in forested watersheds, because the two main sources of nitrate, atmospheric deposition and microbial nitrification, have distinct δ18O values. Using a simple mixing model, we estimated the relative fractions in streamwater derived from these sources for two forested watersheds with markedly different streamwater nitrate outputs. In this study, we monitored δ15N and δ18O of nitrate biweekly in atmospheric deposition and in streamwater for 20 months at the Hubbard Brook Experimental Forest, New Hampshire, USA (moderate nitrogen export), and monthly in streamwater at the Bowl Research Natural Area, New Hampshire, USA (high nitrogen export). For rain, δ18O values ranged from +47 to +77‰ (mean: +58‰) and δ15N from −5 to +1‰ (mean: −3‰); for snow, δ18O values ranged from +52 to +75‰ (mean: +67‰) and δ15N from −3 to +2‰ (mean: −1‰). Streamwater nitrate, in contrast to deposition, had δ18O values between +12 and +33‰ (mean: +18‰) and δ15N between −3 and +6‰ (mean: 0‰). Since nitrate produced by nitrification typically has δ18O values ranging from −5 to +15‰, our field data suggest that most of the nitrate lost from the watersheds in streamflow was nitrified within the catchment. Our results confirm the importance of microbial nitrogen transformations in regulating nitrogen losses from forested ecosystems and suggest that hydrologic storage may be a factor in controlling catchment nitrate losses.

  15. Defining donor and acceptor strength in conjugated copolymers

    NASA Astrophysics Data System (ADS)

    Hedström, Svante; Wang, Ergang; Persson, Petter

    2017-03-01

    The progress in efficiency of organic photovoltaic devices is largely driven by the development of new donor-acceptor (D-A) copolymers. The number of possible D-A combinations escalates rapidly with the ever-increasing number of donor and acceptor units, and the design process often involves a trial-and-error approach. We here present a computationally efficient methodology for the prediction of optical and electronic properties of D-A copolymers based on density functional theory calculations of donor- and acceptor-only homopolymers. Ten donors and eight acceptors are studied, as well as all of their 80 D-A copolymer combinations, showing absorption energies of 1.3-2.3 eV, and absorption strengths varying by up to a factor of 2.5. Focus lies on exhibited trends in frontier orbital energies, optical band gaps, and absorption intensities, as well as their relation to the molecular structure. Based on the results, we define the concept of donor and acceptor strength, and calculate this quantity for all investigated units. The light-harvesting capabilities of the 80 D-A copolymers were also assessed. This gives a valuable theoretical guideline to the design of D-A copolymers with the potential to reduce the synthesis efforts in the development of new polymers.

  16. Nitrogen Starvation Acclimation in Synechococcus elongatus: Redox-Control and the Role of Nitrate Reduction as an Electron Sink

    PubMed Central

    Klotz, Alexander; Reinhold, Edgar; Doello, Sofía; Forchhammer, Karl

    2015-01-01

    Nitrogen starvation acclimation in non-diazotrophic cyanobacteria is characterized by a process termed chlorosis, where the light harvesting pigments are degraded and the cells gradually tune down photosynthetic and metabolic activities. The chlorosis response is governed by a complex and poorly understood regulatory network, which converges at the expression of the nblA gene, the triggering factor for phycobiliprotein degradation. This study established a method that allows uncoupling metabolic and redox-signals involved in nitrogen-starvation acclimation. Inhibition of glutamine synthetase (GS) by a precise dosage of l-methionine-sulfoximine (MSX) mimics the metabolic situation of nitrogen starvation. Addition of nitrate to such MSX-inhibited cells eliminates the associated redox-stress by enabling electron flow towards nitrate/nitrite reduction and thereby, prevents the induction of nblA expression and the associated chlorosis response. This study demonstrates that nitrogen starvation is perceived not only through metabolic signals, but requires a redox signal indicating over-reduction of PSI-reduced electron acceptors. It further establishes a cryptic role of nitrate/nitrite reductases as electron sinks to balance conditions of over-reduction. PMID:25780959

  17. Nanographenes as electron-deficient cores of donor-acceptor systems.

    PubMed

    Liu, Yu-Min; Hou, Hao; Zhou, Yan-Zhen; Zhao, Xin-Jing; Tang, Chun; Tan, Yuan-Zhi; Müllen, Klaus

    2018-05-15

    Conjugation of nanographenes (NGs) with electro-active molecules can establish donor-acceptor π-systems in which the former generally serve as the electron-donating moieties due to their electronic-rich nature. In contrast, here we report a series of reversed donor-acceptor structures are obtained by C-N coupling of electron-deficient perchlorinated NGs with electron-rich anilines. Selective amination at the vertexes of the NGs is unambiguously shown through X-ray crystallography. By varying the donating ability of the anilino groups, the optical and assembly properties of donor-acceptor NGs can be finely modulated. The electron-deficient concave core of the resulting conjugates can host electron-rich guest molecules by intermolecular donor-acceptor interactions and gives rise to charge-transfer supramolecular architectures.

  18. Production and consumption of nitrous oxide in nitrate-ammonifying Wolinella succinogenes cells.

    PubMed

    Luckmann, Monique; Mania, Daniel; Kern, Melanie; Bakken, Lars R; Frostegård, Asa; Simon, Jörg

    2014-08-01

    Global warming is moving more and more into the public consciousness. Besides the commonly mentioned carbon dioxide and methane, nitrous oxide (N2O) is a powerful greenhouse gas in addition to its contribution to depletion of stratospheric ozone. The increasing concern about N2O emission has focused interest on underlying microbial energy-converting processes and organisms harbouring N2O reductase (NosZ), such as denitrifiers and ammonifiers of nitrate and nitrite. Here, the epsilonproteobacterial model organism Wolinella succinogenes is investigated with regard to its capacity to produce and consume N2O during growth by anaerobic nitrate ammonification. This organism synthesizes an unconventional cytochrome c nitrous oxide reductase (cNosZ), which is encoded by the first gene of an atypical nos gene cluster. However, W. succinogenes lacks a nitric oxide (NO)-producing nitrite reductase of the NirS- or NirK-type as well as an NO reductase of the Nor-type. Using a robotized incubation system, the wild-type strain and suitable mutants of W. succinogenes that either produced or lacked cNosZ were analysed as to their production of NO, N2O and N2 in both nitrate-sufficient and nitrate-limited growth medium using formate as electron donor. It was found that cells growing in nitrate-sufficient medium produced small amounts of N2O, which derived from nitrite and, most likely, from the presence of NO. Furthermore, cells employing cNosZ were able to reduce N2O to N2. This reaction, which was fully inhibited by acetylene, was also observed after adding N2O to the culture headspace. The results indicate that W. succinogenes cells are competent in N2O and N2 production despite being correctly grouped as respiratory nitrate ammonifiers. N2O production is assumed to result from NO detoxification and nitrosative stress defence, while N2O serves as a terminal electron acceptor in anaerobic respiration. The ecological implications of these findings are discussed. © 2014 The Authors.

  19. Inhibition of bacterial adhesion on PVC endotracheal tubes by RF-oxygen glow discharge, sodium hydroxide and silver nitrate treatments.

    PubMed

    Balazs, D J; Triandafillu, K; Wood, P; Chevolot, Y; van Delden, C; Harms, H; Hollenstein, C; Mathieu, H J

    2004-05-01

    Medical-grade poly(vinyl chloride) (PVC) was chemically modified to study how the incorporation of monovalent silver influences Pseudomonas aeruginosa adhesion and colonization. The modification investigated consisted of a radio frequency-oxygen (RF-O(2)) glow discharge pre-functionalization, followed by a two-step wet-treatment in sodium hydroxide and silver nitrate solutions. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurements were used to investigate the chemical nature and surface wettability of the films following each step of the modification. XPS analysis proved that the RF-O(2) plasma pre-functionalization of native PVC reproducibly increased the amount of functional groups representative of PVC additives, including ether/alcohol, esters and carboxyl groups. More specifically, we demonstrated that the O-C=O groups representative of the phthalic ester and zinc carboxylate additives identified for native PVC increased by two-fold following the RF-O(2) plasma pre-functionalization step. Although RF-O(2) pre-functionalization did not have an effect on the silver content of the NaOH/AgNO(3) treated substrates, such a modification was necessary for biomaterial products that did not have reproducible surfaces amongst production lots. XPS analysis also demonstrated that saponification with sodium hydroxide (NaOH) of esters, like those of the phthalic ester additives of PVC is a simple, irreversible method of hydrolysis, which produced sodium carboxylate and sodium phthalate salts. Exposure of native PVC to NaOH resulted in an increased surface hydrophilicity (from ca 90 degrees to ca 60 degrees ) due to dechlorination. XPS analysis following further incubation in silver nitrate demonstrated that silver ions can be trapped when the sodium of sodium carboxylate is replaced by silver after performing a second treatment with a monovalent silver-containing solution. The creation of silver salt on native PVC resulted in an ultra

  20. A Metagenomics-Based Metabolic Model of Nitrate-Dependent Anaerobic Oxidation of Methane by Methanoperedens-Like Archaea

    PubMed Central

    Arshad, Arslan; Speth, Daan R.; de Graaf, Rob M.; Op den Camp, Huub J. M.; Jetten, Mike S. M.; Welte, Cornelia U.

    2015-01-01

    Methane oxidation is an important process to mitigate the emission of the greenhouse gas methane and further exacerbating of climate forcing. Both aerobic and anaerobic microorganisms have been reported to catalyze methane oxidation with only a few possible electron acceptors. Recently, new microorganisms were identified that could couple the oxidation of methane to nitrate or nitrite reduction. Here we investigated such an enrichment culture at the (meta) genomic level to establish a metabolic model of nitrate-driven anaerobic oxidation of methane (nitrate-AOM). Nitrate-AOM is catalyzed by an archaeon closely related to (reverse) methanogens that belongs to the ANME-2d clade, tentatively named Methanoperedens nitroreducens. Methane may be activated by methyl-CoM reductase and subsequently undergo full oxidation to carbon dioxide via reverse methanogenesis. All enzymes of this pathway were present and expressed in the investigated culture. The genome of the archaeal enrichment culture encoded a variety of enzymes involved in an electron transport chain similar to those found in Methanosarcina species with additional features not previously found in methane-converting archaea. Nitrate reduction to nitrite seems to be located in the pseudoperiplasm and may be catalyzed by an unusual Nar-like protein complex. A small part of the resulting nitrite is reduced to ammonium which may be catalyzed by a Nrf-type nitrite reductase. One of the key questions is how electrons from cytoplasmically located reverse methanogenesis reach the nitrate reductase in the pseudoperiplasm. Electron transport in M. nitroreducens probably involves cofactor F420 in the cytoplasm, quinones in the cytoplasmic membrane and cytochrome c in the pseudoperiplasm. The membrane-bound electron transport chain includes F420H2 dehydrogenase and an unusual Rieske/cytochrome b complex. Based on genome and transcriptome studies a tentative model of how central energy metabolism of nitrate-AOM could work is

  1. Optimization of enhanced bioelectrical reactor with electricity from microbial fuel cells for groundwater nitrate removal.

    PubMed

    Liu, Ye; Zhang, Baogang; Tian, Caixing; Feng, Chuanping; Wang, Zhijun; Cheng, Ming; Hu, Weiwu

    2016-01-01

    Factors influencing the performance of a continual-flow bioelectrical reactor (BER) intensified by microbial fuel cells for groundwater nitrate removal, including nitrate load, carbon source and hydraulic retention time (HRT), were investigated and optimized by response surface methodology (RSM). With the target of maximum nitrate removal and minimum intermediates accumulation, nitrate load (for nitrogen) of 60.70 mg/L, chemical oxygen demand (COD) of 849.55 mg/L and HRT of 3.92 h for the BER were performed. COD was the dominant factor influencing performance of the system. Experimental results indicated the undistorted simulation and reliable optimized values. These demonstrate that RSM is an effective method to evaluate and optimize the nitrate-reducing performance of the present system and can guide mathematical models development to further promote its practical applications.

  2. Isotopic signals from precipitation and denitrification in nitrate in a northern hardwood forest

    NASA Astrophysics Data System (ADS)

    Goodale, C. L.; Wexller, S.

    2012-12-01

    Denitrification can represent an important term in the nitrogen budget of small catchments; however, this process varies greatly over space and time and is notoriously difficult to quantify. Measurements of the natural abundance of stable isotopes of nitrogen and oxygen in dissolved nitrate in stream- and river water can sometimes provide evidence of denitrification, particularly in large river basins or agriculturally impacted catchments. To date, however, this approach has provided little to no evidence of denitrification in catchments in temperate forests. Here, we examined d15N and d18O of nitrate in water samples collected during summer 2011 not only from streams and precipitation, but also from groundwater from the hydrologic reference watershed (W3) drained by Paradise Brook, at the Hubbard Brook Experimental Forest, in the White Mountains, New Hampshire. Despite low nitrate concentrations (< 0.5 to 8.8 uM nitrate) dual-isotopic signals of nitrate sources and nitrogen cycle processes were clearly distinguishable, including sources from atmospheric deposition, and from nitrification of atmospheric ammonium and from or soil organic nitrogen, as well as nitrate affected by soil denitrification. An atmospheric signal from nitrate in precipitation (enriched with 18O) was observed immediately following a precipitation event in mid-July contributing roughly 22% of stream nitrate export on this date. Stream samples the day following this and other storms showed this export of event nitrate to be short-lived. Hillslope piezometers showed low nitrate concentrations and high d15N- and d18O-nitrate values (averaging 12 and 18 per mil, repectively) indicating denitrification, which preferentially removes isotopically light N and O in N gases and leaves isotopically heavy nitrate behind. These samples showed a positive relationship between nitrogen and oxygen isotopic composition with a regression line slope of 0.76 (R2 = 0.68), and an isotope enrichment factor -12.7 per

  3. Molecular Signals Controlling the Inhibition of Nodulation by Nitrate in Medicago truncatula

    PubMed Central

    van Noorden, Giel E.; Verbeek, Rob; Dinh, Quy Dung; Jin, Jian; Green, Alexandra; Ng, Jason Liang Pin; Mathesius, Ulrike

    2016-01-01

    The presence of nitrogen inhibits legume nodule formation, but the mechanism of this inhibition is poorly understood. We found that 2.5 mM nitrate and above significantly inhibited nodule initiation but not root hair curling in Medicago trunatula. We analyzed protein abundance in M. truncatula roots after treatment with either 0 or 2.5 mM nitrate in the presence or absence of its symbiont Sinorhizobium meliloti after 1, 2 and 5 days following inoculation. Two-dimensional gel electrophoresis combined with mass spectrometry was used to identify 106 differentially accumulated proteins responding to nitrate addition, inoculation or time point. While flavonoid-related proteins were less abundant in the presence of nitrate, addition of Nod gene-inducing flavonoids to the Sinorhizobium culture did not rescue nodulation. Accumulation of auxin in response to rhizobia, which is also controlled by flavonoids, still occurred in the presence of nitrate, but did not localize to a nodule initiation site. Several of the changes included defense- and redox-related proteins, and visualization of reactive oxygen species indicated that their induction in root hairs following Sinorhizobium inoculation was inhibited by nitrate. In summary, the presence of nitrate appears to inhibit nodulation via multiple pathways, including changes to flavonoid metabolism, defense responses and redox changes. PMID:27384556

  4. Tyrosine oxidation and nitration in transmembrane peptides is connected to lipid peroxidation.

    PubMed

    Bartesaghi, Silvina; Herrera, Daniel; Martinez, Débora M; Petruk, Ariel; Demicheli, Verónica; Trujillo, Madia; Martí, Marcelo A; Estrín, Darío A; Radi, Rafael

    2017-05-15

    Tyrosine nitration is an oxidative post-translational modification that can occur in proteins associated to hydrophobic bio-structures such as membranes and lipoproteins. In this work, we have studied tyrosine nitration in membranes using a model system consisting of phosphatidylcholine liposomes with pre-incorporated tyrosine-containing 23 amino acid transmembrane peptides. Tyrosine residues were located at positions 4, 8 or 12 of the amino terminal, resulting in different depths in the bilayer. Tyrosine nitration was accomplished by exposure to peroxynitrite and a peroxyl radical donor or hemin in the presence of nitrite. In egg yolk phosphatidylcholine liposomes, nitration was highest for the peptide with tyrosine at position 8 and dramatically increased as a function of oxygen levels. Molecular dynamics studies support that the proximity of the tyrosine phenolic ring to the linoleic acid peroxyl radicals contributes to the efficiency of tyrosine oxidation. In turn, α-tocopherol inhibited both lipid peroxidation and tyrosine nitration. The mechanism of tyrosine nitration involves a "connecting reaction" by which lipid peroxyl radicals oxidize tyrosine to tyrosyl radical and was fully recapitulated by computer-assisted kinetic simulations. Altogether, this work underscores unique characteristics of the tyrosine oxidation and nitration process in lipid-rich milieu that is fueled via the lipid peroxidation process. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Impact of Thermal Annealing on Organic Photovoltaic Cells Using Regioisomeric Donor-Acceptor-Acceptor Molecules.

    PubMed

    Zhang, Tao; Han, Han; Zou, Yunlong; Lee, Ying-Chi; Oshima, Hiroya; Wong, Ken-Tsung; Holmes, Russell J

    2017-08-02

    We report a promising set of donor-acceptor-acceptor (D-A-A) electron-donor materials based on coplanar thieno[3,2-b]/[2,3-b]indole, benzo[c][1,2,5]thiadiazole, and dicyanovinylene, which are found to show broadband absorption with high extinction coefficients. The role of the regioisomeric electron-donating thienoindole moiety on the physical and structural properties is examined. Bulk heterojunction (BHJ) organic photovoltaic cells (OPVs) based on the thieno[2,3-b]indole-based electron donor NTU-2, using C 70 as an electron acceptor, show a champion power conversion efficiency of 5.2% under AM 1.5G solar simulated illumination. This efficiency is limited by a low fill factor (FF), as has previously been the case in D-A-A systems. In order to identify the origin of the limited FF, further insight into donor layer charge-transport behavior is realized by examining planar heterojunction OPVs, with emphasis on the evolution of film morphology with thermal annealing. Compared to as-deposited OPVs that exhibit insufficient donor crystallinity, crystalline OPVs based on annealed thin films show an increase in the short-circuit current density, FF, and power conversion efficiency. These results suggest that that the crystallization of D-A-A molecules might not be realized spontaneously at room temperature and that further processing is needed to realize efficient charge transport in these materials.

  6. Toward the development of the direct and selective detection of nitrates by a bioinspired Mo-Cu system.

    PubMed

    Marom, Hanit; Popowski, Yanay; Antonov, Svetlana; Gozin, Michael

    2011-10-21

    The development of a new platform for the direct and selective detection of nitrates is described. Two thioether-based chemosensors and the corresponding sulfoxides and sulfones were prepared, and their photophysical properties were evaluated. Upon selective sulfoxidation of these thioethers with nitrates via an oxygen-transfer reaction promoted by a bioinspired Mo-Cu system, significant fluorescence shifts were measured. A selective response of these systems, discriminating between nitrate salts and H(2)O(2), was also shown. © 2011 American Chemical Society

  7. Expression of denitrification enzymes in response to the dissolved oxygen level and respiratory substrate in continuous culture of Pseudomonas stutzeri.

    PubMed Central

    Körner, H; Zumft, W G

    1989-01-01

    The onset and cessation of the synthesis of denitrification enzymes of Pseudomonas stutzeri were investigated by using continuous culture and defined dissolved oxygen levels covering the full range of transition from air saturation to complete anaerobiosis. Expression of nitrate reductase, nitrite reductase (cytochrome cd1), and N2O reductase was controlled by discrete oxygen levels and by the nature of the nitrogenous oxide available for respiration. N2O reductase was synthesized constitutively at a low level; for enhanced expression, oxygen concentrations were required to decrease below 5 mg of O2 per liter. The threshold values for synthesis of nitrate reductase and cytochrome cd1 in the presence of nitrate were ca. 5 and ca. 2.5 mg of O2 per liter, respectively. With nitrous oxide as the respiratory substrate, nitrite reductase was again the most sensitive to oxygen concentration; however, thresholds for all denitrification enzymes shifted to lower oxygen levels. Whereas the presence of nitrate resulted in maximum expression and nearly uniform induction of all reductases, nitrite and nitrous oxide stimulated preferably the respective enzyme catalyzing reduction. In the absence of a nitrogenous oxide, anaerobiosis did not induce enzyme synthesis to any significant degree. The accumulation of nitrite seen during both the aerobic-anaerobic and anaerobic-aerobic transition phases was caused by the differences in onset or cessation of synthesis of nitrate and nitrite reductases and an inhibitory effect of nitrate on nitrite reduction. Images PMID:2764573

  8. Satisfied IUD acceptors as family planning motivators in Sri Lanka.

    PubMed

    Fisher, A A; de Silva, V

    1986-01-01

    In this study, government midwives were teamed with currently satisfied IUD acceptors to strengthen field motivational and recruitment efforts. The objective was to increase the number of new IUD acceptors. In the experimental study areas, a total of 3,019 new IUD acceptors were recruited. Time series regression analysis revealed a significant difference between the experimental and comparison areas that was over and above what might be expected on the basis of the past history of differences between these two areas. These and other findings suggest that teaming currently satisfied acceptors with government field-workers can have a substantial impact on the recruitment of new family planning users.

  9. Effect of oral nitrate supplementation on pulmonary hemodynamics during exercise and time trial performance in normoxia and hypoxia: a randomized controlled trial

    PubMed Central

    Bourdillon, Nicolas; Fan, Jui-Lin; Uva, Barbara; Müller, Hajo; Meyer, Philippe; Kayser, Bengt

    2015-01-01

    Background: Hypoxia-induced pulmonary vasoconstriction increases pulmonary arterial pressure (PAP) and may impede right heart function and exercise performance. This study examined the effects of oral nitrate supplementation on right heart function and performance during exercise in normoxia and hypoxia. We tested the hypothesis that nitrate supplementation would attenuate the increase in PAP at rest and during exercise in hypoxia, thereby improving exercise performance. Methods: Twelve trained male cyclists [age: 31 ± 7 year (mean ± SD)] performed 15 km time-trial cycling (TT) and steady-state submaximal cycling (50, 100, and 150 W) in normoxia and hypoxia (11% inspired O2) following 3-day oral supplementation with either placebo or sodium nitrate (0.1 mmol/kg/day). We measured TT time-to-completion, muscle tissue oxygenation during TT and systolic right ventricle to right atrium pressure gradient (RV-RA gradient: index of PAP) during steady state cycling. Results: During steady state exercise, hypoxia elevated RV-RA gradient (p > 0.05), while oral nitrate supplementation did not alter RV-RA gradient (p > 0.05). During 15 km TT, hypoxia lowered muscle tissue oxygenation (p < 0.05). Nitrate supplementation further decreased muscle tissue oxygenation during 15 km TT in hypoxia (p < 0.05). Hypoxia impaired time-to-completion during TT (p < 0.05), while no improvements were observed with nitrate supplementation in normoxia or hypoxia (p > 0.05). Conclusion: Our findings indicate that oral nitrate supplementation does not attenuate acute hypoxic pulmonary vasoconstriction nor improve performance during time trial cycling in normoxia and hypoxia. PMID:26528189

  10. A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater

    USGS Publications Warehouse

    Sigman, D.M.; Casciotti, K.L.; Andreani, M.; Barford, C.; Galanter, M.; Böhlke, J.K.

    2001-01-01

    We report a new method for measurement of the isotopic composition of nitrate (NO3-) at the natural-abundance level in both seawater and freshwater. The method is based on the isotopic analysis of nitrous oxide (N2O) generated from nitrate by denitrifying bacteria that lack N2O-reductase activity. The isotopic composition of both nitrogen and oxygen from nitrate are accessible in this way. In this first of two companion manuscripts, we describe the basic protocol and results for the nitrogen isotopes. The precision of the method is better than 0.2‰ (1 SD) at concentrations of nitrate down to 1 μM, and the nitrogen isotopic differences among various standards and samples are accurately reproduced. For samples with 1 μM nitrate or more, the blank of the method is less than 10% of the signal size, and various approaches may reduce it further.

  11. Bacterial transformations of inorganic nitrogen in the oxygen-deficient waters of the Eastern Tropical South Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Lipschultz, F.; Wofsy, S. C.; Ward, B. B.; Codispoti, L. A.; Friedrich, G.; Elkins, J. W.

    1990-10-01

    Rates of transformations of inorganic nitrogen were measured in the low oxygen, subsurface waters (50-450 m) of the Eastern Tropical South Pacific during February 1985, using 15N tracer techniques. Oxygen concentrations over the entire region were in a range (O 2 < 2.5 μM) that allowed both oxidation and reduction of nitrogen to occur. A wide range of rates was observed for the lowest oxygen levels, indicating that observed oxygen concentration was not a primary factor regulating nitrogen metabolism. High values for subsurface metabolic rates correspond with high levels for surface primary production, both apparently associated with mesoscale features observed in satellite imagery and with mesoscale features of the current field. Measured rates of nitrate reduction and estimated rates of denitrification were sufficient to respire nearly all of the surface primary production that might be transported into the oxygen deficient zone. These results imply that the supply of labile organic material, especially from the surface, was more important than oxygen concentration in modulating the rates of nitrogen transformations within the low oxygen water mass of the Eastern Tropical South Pacific. The pattern of nitrite oxidation and nitrite reduction activities in the oxygen minimum zone supports the hypothesis ( ANDERSONet al., 1982, Deep-Sea Research, 29, 1113-1140) that nitrite, produced from nitrate reduction, can be recycled by oxidation at the interface between low and high oxygen waters. Rates for denitrification, estimated from nitrate reduction rates, were in harmony with previous estimates based on electron transport system (ETS) measurements and analysis of the nitrate deficit and water residence times. Assimilation rates of NH 4+ were substantial, providing evidence for heterotrophic bacterial growth in low oxygen waters. Ambient concentrations of ammonium were maintained at low values primarily by assimilation; ammonium oxidation was an important mechanism at

  12. Pseudo-constitutivity of nitrate-responsive genes in nitrate reductase mutants

    PubMed Central

    Schinko, Thorsten; Gallmetzer, Andreas; Amillis, Sotiris; Strauss, Joseph

    2013-01-01

    In fungi, transcriptional activation of genes involved in NO3- assimilation requires the presence of an inducer (nitrate or nitrite) and low intracellular concentrations of the pathway products ammonium or glutamine. In Aspergillus nidulans, the two transcription factors NirA and AreA act synergistically to mediate nitrate/nitrite induction and nitrogen metabolite derepression, respectively. In all studied fungi and in plants, mutants lacking nitrate reductase (NR) activity express nitrate-metabolizing enzymes constitutively without the addition of inducer molecules. Based on their work in A. nidulans, Cove and Pateman proposed an “autoregulation control” model for the synthesis of nitrate metabolizing enzymes in which the functional nitrate reductase molecule would act as co-repressor in the absence and as co-inducer in the presence of nitrate. However, NR mutants could simply show “pseudo-constitutivity” due to induction by nitrate which accumulates over time in NR-deficient strains. Here we examined this possibility using strains which lack flavohemoglobins (fhbs), and are thus unable to generate nitrate internally, in combination with nitrate transporter mutations (nrtA, nrtB) and a GFP-labeled NirA protein. Using different combinations of genotypes we demonstrate that nitrate transporters are functional also in NR null mutants and show that the constitutive phenotype of NR mutants is not due to nitrate accumulation from intracellular sources but depends on the activity of nitrate transporters. However, these transporters are not required for nitrate signaling because addition of external nitrate (10 mM) leads to standard induction of nitrate assimilatory genes in the nitrate transporter double mutants. We finally show that NR does not regulate NirA localization and activity, and thus the autoregulation model, in which NR would act as a co-repressor of NirA in the absence of nitrate, is unlikely to be correct. Results from this study instead suggest

  13. Influence of acceptor on charge mobility in stacked π-conjugated polymers

    NASA Astrophysics Data System (ADS)

    Sun, Shih-Jye; Menšík, Miroslav; Toman, Petr; Gagliardi, Alessio; Král, Karel

    2018-02-01

    We present a quantum molecular model to calculate mobility of π-stacked P3HT polymer layers with electron acceptor dopants coupled next to side groups in random position with respect to the linear chain. The hole density, the acceptor LUMO energy and the hybridization transfer integral between the acceptor and polymer were found to be very critical factors to the final hole mobility. For a dopant LUMO energy close and high above the top of the polymer valence band we have found a significant mobility increase with the hole concentration and with the dopant LUMO energy approaching the top of the polymer valence band. Higher mobility was achieved for small values of hybridization transfer integral between polymer and the acceptor, corresponding to the case of weakly bound acceptor. Strong couplings between the polymer and the acceptor with Coulomb repulsion interactions induced from the electron localizations was found to suppress the hole mobility.

  14. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of uniform...

  15. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of uniform...

  16. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of uniform...

  17. 46 CFR 148.205 - Ammonium nitrate and ammonium nitrate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ammonium nitrate and ammonium nitrate fertilizers. 148... Materials § 148.205 Ammonium nitrate and ammonium nitrate fertilizers. (a) This section applies to the stowage and transportation in bulk of ammonium nitrate and the following fertilizers composed of uniform...

  18. Characteristics of ovulation method acceptors: a cross-cultural assessment.

    PubMed

    Klaus, H; Labbok, M; Barker, D

    1988-01-01

    Five programs of instruction in the ovulation method (OM) in diverse geographic and cultural settings are described, and characteristics of approximately 200 consecutive OM acceptors in each program are examined. Major findings include: the religious background and family size of acceptors are variable, as is the level of previous contraceptive use. Acceptors are drawn from a wide range of socioeconomic and religious backgrounds; however, family planning intention was similarly distributed in all five countries. In sum, the ovulation method is accepted by persons from a variety of backgrounds within and between cultural setting.

  19. Bioactivation of organic nitrates and the mechanism of nitrate tolerance.

    PubMed

    Klemenska, Emila; Beresewicz, Andrzej

    2009-01-01

    Organic nitrates, such as nitroglycerin, are commonly used in the therapy of cardiovascular disease. Long-term therapy with these drugs, however, results in the rapid development of nitrate tolerance, limiting their hemodynamic and anti-ischemic efficacy. In addition, nitrate tolerance is associated with the expression of potentially deleterious modifications such as increased oxidative stress, endothelial dysfunction, and sympathetic activation. In this review we discuss current concepts regarding the mechanisms of organic nitrate bioactivation, nitrate tolerance, and nitrate-mediated oxidative stress and endothelial dysfunction. We also examine how hydralazine may prevent nitrate tolerance and related endothelial dysfunction.

  20. Transcriptional analysis of Shewanella oneidensis MR-1 with an electrode compared to Fe(III)citrate or oxygen as terminal electron acceptor

    USDA-ARS?s Scientific Manuscript database

    Background. Shewanella oneidensis is a target of extensive research efforts in the fields of bioelectrochemical systems and bioremediation because of its versatile metabolic capabilities, especially in regards to the respiration with extracellular electron acceptors. Here, we took a global approach ...

  1. Effect of sudden addition of PCE and bioreactor coupling to ZVI filters on performance of fluidized bed bioreactors operated in simultaneous electron acceptor modes.

    PubMed

    Moreno-Medina, C U; Poggi-Varaldo, Hector M; Breton-Deval, L; Rinderknecht-Seijas, N

    2017-11-01

    The present work evaluated the effects of (i) feeding a water contaminated with 80 mg/L PCE to bioreactors seeded with inoculum not acclimated to PCE, (ii) coupling ZVI side filters to bioreactors, and (iii) working in different biological regimes, i.e., simultaneous methanogenic aeration and simultaneous methanogenic-denitrifying regimes, on fluidized bed bioreactor performance. Simultaneous electron acceptors refer to the simultaneous presence of two compounds operating as final electron acceptors in the biological respiratory chain (e.g., use of either O 2 or NO 3 - in combination with a methanogenic environment) in a bioreactor or environmental niche. Four lab-scale, mesophilic, fluidized bed bioreactors (bioreactors) were implemented. Two bioreactors were operated as simultaneous methanogenic-denitrifying (MD) units, whereas the other two were operated in partially aerated methanogenic (PAM) mode. In the first period, all bioreactors received a wastewater with 1 g chemical oxygen demand of methanol per liter (COD-methanol/L). In a second period, all the bioreactors received the wastewater plus 80 mg perchloroethylene (PCE)/L; at the start of period 2, one MD and one PAM were coupled to side sand-zero valent iron filters (ZVI). All bioreactors were inoculated with a microbial consortium not acclimated to PCE. In this work, the performance of the full period 1 and the first 60 days of period 2 is reported and discussed. The COD removal efficiency and the nitrate removal efficiency of the bioreactors essentially did not change between period 1 and period 2, i.e., upon PCE addition. On the contrary, specific methanogenic activity in PAM bioreactors (both with and without coupled ZVI filter) significantly decreased. This was consistent with a sharp fall of methane productivity in those bioreactors in period 2. During period 2, PCE removals in the range 86 to 97 % were generally observed; the highest removal corresponded to PAM bioreactors along with the

  2. Thermophilic nitrate-reducing microorganisms prevent sulfate reduction in cold marine sediments incubated at high temperature

    NASA Astrophysics Data System (ADS)

    Nepomnyashchaya, Yana; Rezende, Julia; Hubert, Casey

    2014-05-01

    Hydrogen sulphide produced during metabolism of sulphate-reducing microorganisms (SRM) is toxic, corrosive and causes detrimental oil reservoir souring. During secondary oil recovery, injecting oil reservoirs with seawater that is rich in sulphate and that also cools high temperature formations provides favourable growth conditions for SRM. Nitrate addition can prevent metabolism of SRM by stimulating nitrate-reducing microorganisms (NRM). The investigations of thermophilic NRM are needed to develop mechanisms to control the metabolism of SRM in high temperature oil field ecosystems. We therefore established a model system consisting of enrichment cultures of cold surface marine sediments from the Baltic Sea (Aarhus Bay) that were incubated at 60°C. Enrichments contained 25 mM nitrate and 40 mM sulphate as potential electron acceptors, and a mixture of the organic substrates acetate, lactate, propionate, butyrate (5 mM each) and yeast extract (0.01%) as potential carbon sources and electron donors. Slurries were incubated at 60°C both with and without initial pasteurization at 80°C for 2 hours. In the enrichments containing both nitrate and sulphate, the concentration of nitrate decreased indicating metabolic activity of NRM. After a four-hour lag phase the rate of nitrate reduction increased and the concentration of nitrate dropped to zero after 10 hours of incubation. The concentration of nitrite increased as the reduction of nitrate progressed and reached 16.3 mM after 12 hours, before being consumed and falling to 4.4 mM after 19-day of incubation. No evidence for sulphate reduction was observed in these cultures during the 19-day incubation period. In contrast, the concentration of sulphate decreased up to 50% after one week incubation in controls containing only sulphate but no nitrate. Similar sulfate reduction rates were seen in the pasteurized controls suggesting the presence of heat resistant SRM, whereas nitrate reduction rates were lower in the

  3. NO3- anions can act as Lewis acid in the solid state

    NASA Astrophysics Data System (ADS)

    Bauzá, Antonio; Frontera, Antonio; Mooibroek, Tiddo J.

    2017-02-01

    Identifying electron donating and accepting moieties is crucial to understanding molecular aggregation, which is of pivotal significance to biology. Anions such as NO3- are typical electron donors. However, computations predict that the charge distribution of NO3- is anisotropic and minimal on nitrogen. Here we show that when the nitrate's charge is sufficiently dampened by resonating over a larger area, a Lewis acidic site emerges on nitrogen that can interact favourably with electron rich partners. Surveys of the Cambridge Structural Database and Protein Data Bank reveal geometric preferences of some oxygen and sulfur containing entities around a nitrate anion that are consistent with this `π-hole bonding' geometry. Computations reveal donor-acceptor orbital interactions that confirm the counterintuitive Lewis π-acidity of nitrate.

  4. Hydrogeologic controls on nitrate transport in a small agricultural catchment, Iowa

    USGS Publications Warehouse

    Schilling, K.E.; Tomer, M.D.; Zhang, Y.-K.; Weisbrod, T.; Jacobson, P.; Cambardella, C.A.

    2007-01-01

    Effects of subsurface deposits on nitrate loss in stream riparian zones are recognized, but little attention has been focused on similar processes occurring in upland agricultural settings. In this paper, we evaluated hydrogeologic controls on nitrate transport processes occurring in a small 7.6 ha Iowa catchment. Subsurface deposits in the catchment consisted of upland areas of loess overlying weathered pre-Illinoian till, drained by two ephemeral drainageways that consisted of Holocene-age silty and organic rich alluvium. Water tables in upland areas fluctuated more than 4 m per year compared to less than 0.3 m in the drainageway. Water quality patterns showed a distinct spatial pattern, with groundwater in the drainageways having lower nitrate concentrations (10 mg L-1) as wells as lower pH, dissolved oxygen and redox, and higher ammonium and dissolved organic carbon levels. Several lines of evidence suggested that conditions are conducive for denitrification of groundwater flowing from uplands through the drainageways. Field-measured nitrate decay rates in the drainageways (???0.02 day-1) were consistent with other laboratory studies and regional patterns. Results from MODFLOW and MT3DMS simulations indicated that soils in the ephemeral drainageways could process all upland groundwater nitrate flowing through them. However, model-simulated tile drainage increased both water flux and nitrate loss from the upland catchment. Study results suggest that ephemeral drainageways can provide a natural nitrate treatment system in our upland glaciated catchments, offering management opportunities to reduce nitrate delivery to streams. Copyright 2007 by the American Geophysical Union.

  5. Oxygen-Dependent Cell-to-Cell Variability in the Output of the Escherichia coli Tor Phosphorelay.

    PubMed

    Roggiani, Manuela; Goulian, Mark

    2015-06-15

    Escherichia coli senses and responds to trimethylamine-N-oxide (TMAO) in the environment through the TorT-TorS-TorR signal transduction system. The periplasmic protein TorT binds TMAO and stimulates the hybrid kinase TorS to phosphorylate the response regulator TorR through a phosphorelay. Phosphorylated TorR, in turn, activates transcription of the torCAD operon, which encodes the proteins required for anaerobic respiration via reduction of TMAO to trimethylamine. Interestingly, E. coli respires TMAO in both the presence and absence of oxygen, a behavior that is markedly different from the utilization of other alternative electron acceptors by this bacterium. Here we describe an unusual form of regulation by oxygen for this system. While the average level of torCAD transcription is the same for aerobic and anaerobic cultures containing TMAO, the behavior across the population of cells is strikingly different under the two growth conditions. Cellular levels of torCAD transcription in aerobic cultures are highly heterogeneous, in contrast to the relatively homogeneous distribution in anaerobic cultures. Thus, oxygen regulates the variance of the output but not the mean for the Tor system. We further show that this oxygen-dependent variability stems from the phosphorelay. Trimethylamine-N-oxide (TMAO) is utilized by numerous bacteria as an electron acceptor for anaerobic respiration. In E. coli, expression of the proteins required for TMAO respiration is tightly regulated by a signal transduction system that is activated by TMAO. Curiously, although oxygen is the energetically preferred electron acceptor, TMAO is respired even in the presence of oxygen. Here we describe an interesting and unexpected form of regulation for this system in which oxygen produces highly variable expression of the TMAO utilization proteins across a population of cells without affecting the mean expression of these proteins. To our knowledge, this is the first reported example of a stimulus

  6. Anaerobic ammonium oxidation mediated by Mn-oxides: from sediment to strain level.

    PubMed

    Javanaud, Cedric; Michotey, Valerie; Guasco, Sophie; Garcia, Nicole; Anschutz, Pierre; Canton, Mathieu; Bonin, Patricia

    2011-11-01

    Nitrite and (29)N(2) productions in slurry incubations of anaerobically sediment after (15)NO(3) or (15)NH(4) labelling in the presence of Mn-oxides suggested that anaerobic Mn-oxides mediated nitrification coupled with denitrification in muddy intertidal sediments of Arcachon Bay (SW Atlantic French coast). From this sediment, bacterial strains were isolated and physiologically characterized in terms of Mn-oxides and nitrate reduction as well as potential anaerobic nitrification. One of the isolated strain, identified as Marinobacter daepoensis strain M4AY14, was a denitrifier. Nitrous oxide production by this strain was demonstrated in the absence of nitrate and with Mn-oxides and NH(4) amendment, giving indirect proof of anaerobic nitrate or nitrite production. Anaerobic Mn-oxide-mediated nitrification was confirmed by (29)N(2) production in the presence of (15)NO(3) and (14)NH(4) under denitrifying conditions. Anaerobic nitrification by M4AY14 seemed to occur only in the absence of nitrate, or at nitrate levels lower than that of Mn-oxides. Most of the other isolates were affiliated with the Shewanella genus and were able to use both nitrate and Mn-oxides as electron acceptors. When both electron acceptors were present, whatever their concentrations, nitrate and Mn-oxide reduction co-occurred. These data indicate that bacterial Mn-oxide reduction could be an important process in marine sediments with low oxygen concentrations, and demonstrate for the first time the role of bacteria in anaerobic Mn-mediated nitrification. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  7. Characteristics of contraceptive acceptors in an urban Nigerian setting.

    PubMed

    Ayangade, O

    1984-02-01

    Intensive efforts in promoting family planning concepts and contraceptive delivery in the Third World over the past two- and one-half decades have yielded only token dividends . This has occurred in Nigeria, despite the favorable government attitude. A study of the characteristics of current contraceptive acceptors showed an overwhelming percentage of acceptors are uneducated , married and from the lower socioeconomic class, a striking departure from usual expectations. Most acceptors prefer oral contraceptives. The status of acceptance of modern contraception by the educated population is still undetermined. Contraceptives appeared to be used primarily by women aged 30 and older in our population.

  8. Nitrite and Nitrate Concentrations and Metabolism in Breast Milk, Infant Formula, and Parenteral Nutrition

    PubMed Central

    Jones, Jesica A.; Ninnis, Janet R.; Hopper, Andrew O.; Ibrahim, Yomna; Merritt, T. Allen; Wan, Kim-Wah; Power, Gordon G.; Blood, Arlin B.

    2015-01-01

    Dietary nitrate and nitrite are sources of gastric NO, which modulates blood flow, mucus production, and microbial flora. However, the intake and importance of these anions in infants is largely unknown. Nitrate and nitrite levels were measured in breast milk of mothers of preterm and term infants, infant formulas, and parenteral nutrition. Nitrite metabolism in breast milk was measured after freeze-thawing, at different temperatures, varying oxygen tensions, and after inhibition of potential nitrite-metabolizing enzymes. Nitrite concentrations averaged 0.07 ± 0.01 μM in milk of mothers of preterm infants, less than that of term infants (0.13 ± 0.02 μM) (P < .01). Nitrate concentrations averaged 13.6 ± 3.7 μM and 12.7 ± 4.9 μM, respectively. Nitrite and nitrate concentrations in infant formulas varied from undetectable to many-fold more than breast milk. Concentrations in parenteral nutrition were equivalent to or lower than those of breast milk. Freeze-thawing decreased nitrite concentration ∼64%, falling with a half-life of 32 minutes at 37°C. The disappearance of nitrite was oxygen-dependent and prevented by ferricyanide and 3 inhibitors of lactoperoxidase. Nitrite concentrations in breast milk decrease with storage and freeze-thawing, a decline likely mediated by lactoperoxidase. Compared to adults, infants ingest relatively little nitrite and nitrate, which may be of importance in the modulation of blood flow and the bacterial flora of the infant GI tract, especially given the protective effects of swallowed nitrite. PMID:23894175

  9. Nitrite and nitrate concentrations and metabolism in breast milk, infant formula, and parenteral nutrition.

    PubMed

    Jones, Jesica A; Ninnis, Janet R; Hopper, Andrew O; Ibrahim, Yomna; Merritt, T Allen; Wan, Kim-Wah; Power, Gordon G; Blood, Arlin B

    2014-09-01

    Dietary nitrate and nitrite are sources of gastric NO, which modulates blood flow, mucus production, and microbial flora. However, the intake and importance of these anions in infants is largely unknown. Nitrate and nitrite levels were measured in breast milk of mothers of preterm and term infants, infant formulas, and parenteral nutrition. Nitrite metabolism in breast milk was measured after freeze-thawing, at different temperatures, varying oxygen tensions, and after inhibition of potential nitrite-metabolizing enzymes. Nitrite concentrations averaged 0.07 ± 0.01 μM in milk of mothers of preterm infants, less than that of term infants (0.13 ± 0.02 μM) (P < .01). Nitrate concentrations averaged 13.6 ± 3.7 μM and 12.7 ± 4.9 μM, respectively. Nitrite and nitrate concentrations in infant formulas varied from undetectable to many-fold more than breast milk. Concentrations in parenteral nutrition were equivalent to or lower than those of breast milk. Freeze-thawing decreased nitrite concentration ~64%, falling with a half-life of 32 minutes at 37°C. The disappearance of nitrite was oxygen-dependent and prevented by ferricyanide and 3 inhibitors of lactoperoxidase. Nitrite concentrations in breast milk decrease with storage and freeze-thawing, a decline likely mediated by lactoperoxidase. Compared to adults, infants ingest relatively little nitrite and nitrate, which may be of importance in the modulation of blood flow and the bacterial flora of the infant GI tract, especially given the protective effects of swallowed nitrite. © 2013 American Society for Parenteral and Enteral Nutrition.

  10. Optically (solar) pumped oxygen-iodine lasers

    NASA Astrophysics Data System (ADS)

    Danilov, O. B.; Zhevlakov, A. P.; Yur'ev, M. S.

    2014-07-01

    We present the results of theoretical and experimental studies demonstrating the possibility of developing an oxygen-iodine laser (OIL) with direct optical pumping of molecular oxygen involving inter-molecular interaction with charge transfer from donor molecule (buffer gas) to acceptor molecule (oxygen). This interaction lifts degeneracy of the lower energy states of molecular oxygen and increases its absorption cross section in the visible spectral region and the UV Herzberg band, where high quantum yield of singlet oxygen is achieved (QY ˜ 1 and QY ˜ 2, respectively) at the same time. A pulse-periodic optical pump sources with pulse energy of ˜50 kJ, pulse duration of ˜25 μs, and repetition rate of ˜10 Hz, which are synchronized with the mechanism of singlet oxygen generation, are developed. This allows implementation of a pulse-periodic oxygen-iodine laser with an efficiency of ˜25%, optical efficiency of ˜40%, and parameter L/ T ˜ 1/1.5, where T is the thermal energy released in the laser active medium upon generation of energy L. It is demonstrated that, under direct solar pumping of molecular oxygen, the efficiency parameter of the OIL can reach L/ T ˜ 1/0.8 in a wide range of scaling factors.

  11. Nitrate reduction

    DOEpatents

    Dziewinski, Jacek J.; Marczak, Stanislaw

    2000-01-01

    Nitrates are reduced to nitrogen gas by contacting the nitrates with a metal to reduce the nitrates to nitrites which are then contacted with an amide to produce nitrogen and carbon dioxide or acid anions which can be released to the atmosphere. Minor amounts of metal catalysts can be useful in the reduction of the nitrates to nitrites. Metal salts which are formed can be treated electrochemically to recover the metals.

  12. Control of Sulfide Production in High Salinity Bakken Shale Oil Reservoirs by Halophilic Bacteria Reducing Nitrate to Nitrite.

    PubMed

    An, Biwen A; Shen, Yin; Voordouw, Gerrit

    2017-01-01

    Microbial communities in shale oil fields are still poorly known. We obtained samples of injection, produced and facility waters from a Bakken shale oil field in Saskatchewan, Canada with a resident temperature of 60°C. The injection water had a lower salinity (0.7 Meq of NaCl) than produced or facility waters (0.6-3.6 Meq of NaCl). Salinities of the latter decreased with time, likely due to injection of low salinity water, which had 15-30 mM sulfate. Batch cultures of field samples showed sulfate-reducing and nitrate-reducing bacteria activities at different salinities (0, 0.5, 0.75, 1.0, 1.5, and 2.5 M NaCl). Notably, at high salinity nitrite accumulated, which was not observed at low salinity, indicating potential for nitrate-mediated souring control at high salinity. Continuous culture chemostats were established in media with volatile fatty acids (a mixture of acetate, propionate and butyrate) or lactate as electron donor and nitrate or sulfate as electron acceptor at 0.5 to 2.5 M NaCl. Microbial community analyses of these cultures indicated high proportions of Halanaerobium, Desulfovermiculus, Halomonas , and Marinobacter in cultures at 2.5 M NaCl, whereas Desulfovibrio, Geoalkalibacter , and Dethiosulfatibacter were dominant at 0.5 M NaCl. Use of bioreactors to study the effect of nitrate injection on sulfate reduction showed that accumulation of nitrite inhibited SRB activity at 2.5 M but not at 0.5 M NaCl. High proportions of Halanaerobium and Desulfovermiculus were found at 2.5 M NaCl in the absence of nitrate, whereas high proportions of Halomonas and no SRB were found in the presence of nitrate. A diverse microbial community dominated by the SRB Desulfovibrio was observed at 0.5 M NaCl both in the presence and absence of nitrate. Our results suggest that nitrate injection can prevent souring provided that the salinity is maintained at a high level. Thus, reinjection of high salinity produced water amended with nitrate maybe be a cost effective method

  13. Fluorescent and colorimetric molecular recognition probe for hydrogen bond acceptors.

    PubMed

    Pike, Sarah J; Hunter, Christopher A

    2017-11-22

    The association constants for formation of 1 : 1 complexes between a H-bond donor, 1-naphthol, and a diverse range of charged and neutral H-bond acceptors have been measured using UV/vis absorption and fluorescence emission titrations. The performance of 1-naphthol as a dual colorimetric and fluorescent molecular recognition probe for determining the H-bond acceptor (HBA) parameters of charged and neutral solutes has been investigated in three solvents. The data were employed to establish self-consistent H-bond acceptor parameters (β) for benzoate, azide, chloride, thiocyanate anions, a series of phosphine oxides, phosphate ester, sulfoxide and a tertiary amide. The results demonstrate both the transferability of H-bond parameters between different solvents and the utility of the naphthol-based dual molecular recognition probe to exploit orthogonal spectroscopic techniques to determine the HBA properties of neutral and charged solutes. The benzoate anion is the strongest HBA studied with a β parameter of 15.4, and the neutral tertiary amide is the weakest H-bond acceptor investigated with a β parameter of 8.5. The H-bond acceptor strength of the azide anion is higher than that of chloride (12.8 and 12.2 respectively), and the thiocyanate anion has a β value of 10.8 and thus is a significantly weaker H-bond acceptor than both the azide and chloride anions.

  14. The Measurement of Hot-Spots in Granulated Ammonium Nitrate

    NASA Astrophysics Data System (ADS)

    Proud, W. G.

    2002-07-01

    Ammonium Nitrate (AN) is one of the components of the most widely used explosive in the world namely, ammonium nitrate: fuel oil mixtures (ANFO). By itself, it is an oxygen positive explosive with a large critical diameter. Hot-spots are produced in explosives by various means including gas space collapse, localised shear or friction. If these hot-spots reach critical conditions of size, temperature and duration reaction can grow. This deflagration stage may eventually transition to detonation. This paper describes high-speed image-intensified photography study in which the number and growth of hot spots in granular AN are monitored for a range of different impact pressures. The results can be used in detonation codes to provide a more accurate and realistic description of the initiation process.

  15. Anaerobic biodegradation of nonylphenol in river sediment under nitrate- or sulfate-reducing conditions and associated bacterial community.

    PubMed

    Wang, Zhao; Yang, Yuyin; Dai, Yu; Xie, Shuguang

    2015-04-09

    Nonylphenol (NP) is a commonly detected pollutant in aquatic ecosystem and can be harmful to aquatic organisms. Anaerobic degradation is of great importance for the clean-up of NP in sediment. However, information on anaerobic NP biodegradation in the environment is still very limited. The present study investigated the shift in bacterial community structure associated with NP degradation in river sediment microcosms under nitrate- or sulfate-reducing conditions. Nearly 80% of NP (100 mg kg(-1)) could be removed under these two anaerobic conditions after 90 or 110 days' incubation. Illumina MiSeq sequencing analysis indicated that Proteobacteria, Firmicutes, Bacteroidetes and Chloroflexi became the dominant phylum groups with NP biodegradation. The proportion of Gammaproteobacteria, Deltaproteobacteria and Choloroflexi showed a marked increase in nitrate-reducing microcosm, while Gammaproteobacteria and Firmicutes in sulfate-reducing microcosm. Moreover, sediment bacterial diversity changed with NP biodegradation, which was dependent on type of electron acceptor. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Evidence on Anaerobic Methane Oxidation (AOM) in a boreal cultivated peatland with natural and added electron acceptors

    NASA Astrophysics Data System (ADS)

    Dorodnikov, Maxim; Silvennoinen, Hanna; Martikainen, Pertti; Dörsch, Peter

    2015-04-01

    Anaerobic oxidation of methane (AOM) is a process of methane (CH4) consumption under anoxic conditions driven by microorganisms, which oxidize CH4 with various alternate electron acceptors (AEA): sulfate, nitrate, nitrite, metals-(Fe, Mn, Cu), organic compounds. AOM is common in marine ecosystems, where microbial sulfate reduction (SR) consumes most of the CH4 produced in sediments. Despite the global significance of AOM, the exact mechanisms and relevance of the process in terrestrial ecosystems are almost unknown. In the current study the occurrence of AOM was tested for two organic soil horizons (30 and 40 cm depth) and one mineral sub-soil (sand, 50 cm depth) of a cultivated boreal peatland (Linnansuo, Eastern Finland, energy crop Phalaris arundinacea - reed canarygrass) under controlled conditions with the addition of 13C-labeled CH4 and two common AEAs - SO4-2 and Fe+3. Concentrations of CH4, CO2 and O2 were continuously measured during 10 days of incubation and CO2 was sampled periodically under anaerobic conditions for stable 13C analysis. Oxygen dynamics revealed negligible O2 contamination during incubation and its trace amounts (0.05-0.8% from the atmospheric) were accounted in the net CH4 uptake. Application of 13C-enriched CH4 (4.9 atom%) allowed to track the label in CO2 as the end-product of AOM. The highest 13CO2 enrichment (up to 60‰) was observed in mineral sub-soil, however AOM was quantitatively more pronounced in the upper 30 cm horizon (2.1 vs. 0.2 μg CO2 g soil DW-1 in the 50 cm sub-soil). The highest AOM rate of 8.9 ng CO2 g soil DW-1 h-1 was estimated for the control treatment where no AEAs were added indicating sufficient amount of naturally available AEAs, likely organic compounds. This rate was 50 times more intensive (on the C basis) than the CH4 production potential of the same soil. In contrast, external AEAs decreased AOM rates but added Fe+3 stimulated decomposition of native SOM (as seen from the most depleted 13CO2 signatures

  17. The Impact of Acceptor-Acceptor Homocoupling on the Optoelectronic Properties and Photovoltaic Performance of PDTSQxff Low Bandgap Polymers.

    PubMed

    Pirotte, Geert; Kesters, Jurgen; Cardeynaels, Tom; Verstappen, Pieter; D'Haen, Jan; Lutsen, Laurence; Champagne, Benoît; Vanderzande, Dirk; Maes, Wouter

    2018-04-22

    Push-pull-type conjugated polymers applied in organic electronics do not always contain a perfect alternation of donor and acceptor building blocks. Misscouplings can occur, which have a noticeable effect on the device performance. In this work, the influence of homocoupling on the optoelectronic properties and photovoltaic performance of PDTSQx ff polymers is investigated, with a specific focus on the quinoxaline acceptor moieties. A homocoupled biquinoxaline segment is intentionally inserted in specific ratios during the polymerization. These homocoupled units cause a gradually blue-shifted absorption, while the highest occupied molecular orbital energy levels decrease only significantly upon the presence of 75-100% of homocouplings. Density functional theory calculations show that the homocoupled acceptor unit generates a twist in the polymer backbone, which leads to a decreased conjugation length and a reduced aggregation tendency. The virtually defect-free PDTSQx ff affords a solar cell efficiency of 5.4%, which only decreases substantially upon incorporating a homocoupling degree over 50%. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Spatial structure of single and interacting Mn acceptors in GaAs

    NASA Astrophysics Data System (ADS)

    Koenraad, Paul

    2005-03-01

    Ferromagnetic semiconductors such as Ga1-xMnxAs are receiving a lot of attention at the moment because of their application in spintronic devices. However, despite intense study of deep acceptors in III-V semiconductors such as MnGa, little information has been obtained on their electronic properties at the atomic scale. Yet the spatial shape of the Mn acceptor state will influence the hole-mediated Mn-Mn coupling and thus all of the magnetic properties of ferromagnetic semiconductors such as Ga1-xMnxAs. This study presents an experimental and theoretical description of the spatial symmetry of the Mn acceptor wave-function in GaAs. We present measurements of the spatial mapping of the anisotropic wavefunction of a hole localized at a Mn acceptor. To achieve this, we have used the STM tip not only to image the Mn acceptor but also to manipulate its charge state A^0/A^- at room temperature. Within an envelope function effective mass model (EFM) the anisotropy in the acceptor wave-function can be traced to the influence of the cubic symmetry of the GaAs crystal which selects specific d-states that mix into the ground state due to the spin-orbit interaction in the valence band. Comparison with calculations based on a tight-binding model (TBM) for the Mn acceptor structure supports this conclusion. Using the same experimental and theoretical approach we furthermore explored the interaction between Mn acceptors directly by analyzing close Mn-Mn pairs, which were separated by less than 2 nm. We will discuss some implications of these results for Mn delta-doped layers grown on differently oriented growth surfaces.

  19. Evaluation of Sources of Nitrate Beneath Food Processing Wastewater-Application Sites near Umatilla, Oregon

    USGS Publications Warehouse

    Frans, Lonna; Paulson, Anthony; Richerson, Phil; Striz, Elise; Black, Curt

    2009-01-01

    Water samples from wells were collected beneath and downgradient of two food-processing wastewater-application sites near Umatilla, Oregon. These samples were analyzed for nitrate stable isotopes, nutrients, major ions, and age-dating constituents to determine if nitrate-stable isotopes can be used to differentiate food-processing waste from other potential sources of nitrate. Major-ion data from each site were used to determine which samples were associated with the recharge of the food-processing wastewater. End-member mixing analysis was used to determine the relative amounts of each identified end member within the samples collected from the Terrace Farm site. The delta nitrogen-15 (delta 15N) of nitrate generally ranged between +2 and +9 parts per thousand and the delta oxygen-18 (delta 18O) of nitrate generally ranged between -2 and -7 parts per thousand. None of the samples that were determined to be associated with the wastewater were different from the samples that were not affected by the wastewater. The nitrate isotope values measured in this study are also characteristic of ammonium fertilizer, animal and human waste, and soil nitrate; therefore, it was not possible to differentiate between food-processing wastewater and the other nitrate sources. Values of delta 15N and delta 18O of nitrate provided no more information about the sources of nitrate in the Umatilla River basin than did a hydrologic and geochemical understanding of the ground-water system derived from interpreting water-level and major-ion chemistry data.

  20. Next-generation organic photovoltaics based on non-fullerene acceptors

    NASA Astrophysics Data System (ADS)

    Cheng, Pei; Li, Gang; Zhan, Xiaowei; Yang, Yang

    2018-03-01

    Over the past three years, a particularly exciting and active area of research within the field of organic photovoltaics has been the use of non-fullerene acceptors (NFAs). Compared with fullerene acceptors, NFAs possess significant advantages including tunability of bandgaps, energy levels, planarity and crystallinity. To date, NFA solar cells have not only achieved impressive power conversion efficiencies of 13-14%, but have also shown excellent stability compared with traditional fullerene acceptor solar cells. This Review highlights recent progress on single-junction and tandem NFA solar cells and research directions to achieve even higher efficiencies of 15-20% using NFA-based organic photovoltaics are also proposed.

  1. Concurrent microbial reduction of high concentrations of nitrate and perchlorate in an ion exchange membrane bioreactor.

    PubMed

    Fox, Shalom; Bruner, Tali; Oren, Yoram; Gilron, Jack; Ronen, Zeev

    2016-09-01

    acceptors. Such a mechanism has important implications for controlling the bio-reduction reaction in the IEMB when using glycerol as a carbon source and allowing treating a complex contamination of high concentrations of perchlorate and nitrating in groundwater and successfully biodegrading them to non-hazardous components. Biotechnol. Bioeng. 2016;113: 1881-1891. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  2. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells

    DOE PAGES

    Yu M. Zhong; Nam, Chang -Yong; Trinh, M. Tuan; ...

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealedmore » both electron and hole transfer processes at the donor–acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. As a result, this study describes a new motif for designing highly efficient acceptors for organic solar cells.« less

  3. Molecular helices as electron acceptors in high-performance bulk heterojunction solar cells.

    PubMed

    Zhong, Yu; Trinh, M Tuan; Chen, Rongsheng; Purdum, Geoffrey E; Khlyabich, Petr P; Sezen, Melda; Oh, Seokjoon; Zhu, Haiming; Fowler, Brandon; Zhang, Boyuan; Wang, Wei; Nam, Chang-Yong; Sfeir, Matthew Y; Black, Charles T; Steigerwald, Michael L; Loo, Yueh-Lin; Ng, Fay; Zhu, X-Y; Nuckolls, Colin

    2015-09-18

    Despite numerous organic semiconducting materials synthesized for organic photovoltaics in the past decade, fullerenes are widely used as electron acceptors in highly efficient bulk-heterojunction solar cells. None of the non-fullerene bulk heterojunction solar cells have achieved efficiencies as high as fullerene-based solar cells. Design principles for fullerene-free acceptors remain unclear in the field. Here we report examples of helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometres in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells.

  4. Uranium(VI) Reduction by Anaeromyxobacter dehalogenans Strain 2CP-C

    PubMed Central

    Wu, Qingzhong; Sanford, Robert A.; Löffler, Frank E.

    2006-01-01

    Previous studies demonstrated growth of Anaeromyxobacter dehalogenans strain 2CP-C with acetate or hydrogen as the electron donor and Fe(III), nitrate, nitrite, fumarate, oxygen, or ortho-substituted halophenols as electron acceptors. In this study, we explored and characterized U(VI) reduction by strain 2CP-C. Cell suspensions of fumarate-grown 2CP-C cells reduced U(VI) to U(IV). More-detailed growth studies demonstrated that hydrogen was the required electron donor for U(VI) reduction and could not be replaced by acetate. The addition of nitrate to U(VI)-reducing cultures resulted in a transitory increase in U(VI) concentration, apparently caused by the reoxidation of reduced U(IV), but U(VI) reduction resumed following the consumption of N-oxyanions. Inhibition of U(VI) reduction occurred in cultures amended with Fe(III) citrate, or citrate. In the presence of amorphous Fe(III) oxide, U(VI) reduction proceeded to completion but the U(VI) reduction rates decreased threefold compared to control cultures. Fumarate and 2-chlorophenol had no inhibitory effects on U(VI) reduction, and both electron acceptors were consumed concomitantly with U(VI). Since cocontaminants (e.g., nitrate, halogenated compounds) and bioavailable ferric iron are often encountered at uranium-impacted sites, the metabolic versatility makes Anaeromyxobacter dehalogenans a promising model organism for studying the complex interaction of multiple electron acceptors in U(VI) reduction and immobilization. PMID:16672509

  5. Investigating charge generation in polymer:non-fullerene acceptor bulk heterojunction films

    DOE PAGES

    Stoltzfus, Dani M.; Larson, Bryon W.; Zarrabi, Nasim; ...

    2018-01-31

    Non-fullerene acceptors are now capable of being used in high efficiency bulk heterojunction (BHJ) donor-acceptor organic solar cells. Acceptors comprising single or multiple linked chromophores have been used. We have developed a new non-fullerene molecular acceptor as well as two non-polymeric macromolecular materials that contain four equivalents of a similar chromophore, but can adopt different spatial arrangements of the chromophores. We compare the effect of having single and multiple chromophores within a macromolecule on the charge generation processes in P3HT:non-fullerene acceptor BHJ films using Transient Absorption Spectroscopy (TAS) and Time Resolved Microwave Conductivity (TRMC) measurements. It was found from themore » TAS measurements that at low weight percent (5 wt%) the single chromophore formed more polarons than the acceptors in which chromophores were linked, due to it having a more even distribution within the film. At higher concentrations (50 wt%) the trend was reversed due to the single chromophore forming crystalline domains, which reduced the interface area with the P3HT donor. The TRMC measurements showed that more mobile carriers were formed in the macromolecular acceptors when used at low concentrations in the blend and, independent of concentration, mobile carriers had a longer lifetime when compared to films containing the molecular material, which we ascribe to the charges being able to sample more than one chromophore and thus reduce recombination events.« less

  6. Reduction of nitrate in aquifer microcosms by carbon additions

    USGS Publications Warehouse

    Obenhuber, Donald C.; Lowrance , Richard

    1991-01-01

    Aquifer microcosms were used to examine the effects of NO−3 and C amendments on groundwater from the Claiborne aquifer. Nitrate concentrations of 12.17 mg L−1 in aquifer microcosms were reduced 0.92%/d to 5.84 mg L−1 by the addition of 10 mg C L−1 for 35 d. Nitrate disappearance correlated with increases in number of denitrifiers and dissolved N2O concentration and decreases in dissolved oxygen, suggesting biological denitrification. Nitrate/chloride ratios decreased in microcosms with 10 mg C L−1 added and then increased when the C addition was removed. Carbon additions of 0.4 mg C L−1 had no effect on the microbial or chemical properties of the microcosms. Nitrous oxide levels in wells sampling the Claiborne aquifer showed an increase with depth, indicating N2O production within the aquifer. Microcosms are useful tools to examine biological transformations of chemical contaminants in unconsolidated aquifer material. The remediation of NO−3 contaminated aquifers by organic infusion is possible and appears to be a function of microbial denitrification.

  7. Vertical segregation among pathways mediating nitrogen loss (N2 and N2O production) across the oxygen gradient in a coastal upwelling ecosystem

    NASA Astrophysics Data System (ADS)

    Galán, Alexander; Thamdrup, Bo; Saldías, Gonzalo S.; Farías, Laura

    2017-10-01

    particles, which are a source of organic matter and the fuel for the production of other electron donors (i.e. ammonium) and acceptors (i.e. nitrate and nitrite) after its remineralization. These results highlight the links between several pathways involved in N loss. They also establish that different mechanisms supported by alternative N substrates are responsible for substantial accumulation of N2O, which are frequently observed as hotspots in the oxycline and bottom waters. Considering the extreme variation in oxygen observed in several coastal upwelling systems, these findings could help to understand the ecological and biogeochemical implications due to global warming where intensification and/or expansion of the oceanic OMZs is projected.

  8. [The action of quaternary ammonium derivatives on respiration and nitrate reduction in Pseudomonas aeruginosa].

    PubMed

    Bievskiĭ, A N

    1994-01-01

    It was revealed that the same dosages of quaternary ammonium derivatives, such as decamethoxin and cetyltrimethylammonium bromide, inhibited the respiratory chains and caused destruction of Pseudomonas aeruginosa under aerobic conditions more effectively than under anaerobic ones when anions of nitric acid were the terminal acceptors of electrons. It was also registered that Pseudomonas were able to dissimilatory nitrate reduction in the media under the polysaccharide layer that was produced by these bacteria: this fact possibly proves the possibility of survival of denitrifying bacteria in solutions with high concentrations of quaternary ammonium salts. The data obtained permit supposing that inhibitors of respiratory chains and oxidizers may be used as potentiators of the antimicrobial action of quaternary ammonium derivatives.

  9. Effects of a Short-Term High-Nitrate Diet on Exercise Performance

    PubMed Central

    Porcelli, Simone; Pugliese, Lorenzo; Rejc, Enrico; Pavei, Gaspare; Bonato, Matteo; Montorsi, Michela; La Torre, Antonio; Rasica, Letizia; Marzorati, Mauro

    2016-01-01

    It has been reported that nitrate supplementation can improve exercise performance. Most of the studies have used either beetroot juice or sodium nitrate as a supplement; there is lack of data on the potential ergogenic benefits of an increased dietary nitrate intake from a diet based on fruits and vegetables. Our aim was to assess whether a high-nitrate diet increases nitric oxide bioavailability and to evaluate the effects of this nutritional intervention on exercise performance. Seven healthy male subjects participated in a randomized cross-over study. They were tested before and after 6 days of a high (HND) or control (CD) nitrate diet (~8.2 mmol∙day−1 or ~2.9 mmol∙day−1, respectively). Plasma nitrate and nitrite concentrations were significantly higher in HND (127 ± 64 µM and 350 ± 120 nM, respectively) compared to CD (23 ± 10 µM and 240 ± 100 nM, respectively). In HND (vs. CD) were observed: (a) a significant reduction of oxygen consumption during moderate-intensity constant work-rate cycling exercise (1.178 ± 0.141 vs. 1.269 ± 0.136 L·min−1); (b) a significantly higher total muscle work during fatiguing, intermittent sub-maximal isometric knee extension (357.3 ± 176.1 vs. 253.6 ± 149.0 Nm·s·kg−1); (c) an improved performance in Repeated Sprint Ability test. These findings suggest that a high-nitrate diet could be a feasible and effective strategy to improve exercise performance. PMID:27589795

  10. Modeling the Current and Future Roles of Particulate Organic Nitrates in the Southeastern United States.

    PubMed

    Pye, Havala O T; Luecken, Deborah J; Xu, Lu; Boyd, Christopher M; Ng, Nga L; Baker, Kirk R; Ayres, Benjamin R; Bash, Jesse O; Baumann, Karsten; Carter, William P L; Edgerton, Eric; Fry, Juliane L; Hutzell, William T; Schwede, Donna B; Shepson, Paul B

    2015-12-15

    Organic nitrates are an important aerosol constituent in locations where biogenic hydrocarbon emissions mix with anthropogenic NOx sources. While regional and global chemical transport models may include a representation of organic aerosol from monoterpene reactions with nitrate radicals (the primary source of particle-phase organic nitrates in the Southeast United States), secondary organic aerosol (SOA) models can underestimate yields. Furthermore, SOA parametrizations do not explicitly take into account organic nitrate compounds produced in the gas phase. In this work, we developed a coupled gas and aerosol system to describe the formation and subsequent aerosol-phase partitioning of organic nitrates from isoprene and monoterpenes with a focus on the Southeast United States. The concentrations of organic aerosol and gas-phase organic nitrates were improved when particulate organic nitrates were assumed to undergo rapid (τ = 3 h) pseudohydrolysis resulting in nitric acid and nonvolatile secondary organic aerosol. In addition, up to 60% of less oxidized-oxygenated organic aerosol (LO-OOA) could be accounted for via organic nitrate mediated chemistry during the Southern Oxidants and Aerosol Study (SOAS). A 25% reduction in nitrogen oxide (NO + NO2) emissions was predicted to cause a 9% reduction in organic aerosol for June 2013 SOAS conditions at Centreville, Alabama.

  11. Relative rates of nitric oxide and nitrous oxide production by nitrifiers, denitrifiers, and nitrate respirers

    NASA Technical Reports Server (NTRS)

    Anderson, I. C.; Levine, J. S.

    1986-01-01

    An account is given of the atmospheric chemical and photochemical effects of biogenic nitric and nitrous oxide emissions. The magnitude of the biogenic emission of NO is noted to remain uncertain. Possible soil sources of NO and N2O encompass nitrification by autotropic and heterotropic nitrifiers, denitrification by nitrifiers and denitrifiers, nitrate respiration by fermenters, and chemodenitrification. Oxygen availability is the primary determinant of these organisms' relative rates of activity. The characteristics of this major influence are presently investigated in light of the effect of oxygen partial pressure on NO and N2O production by a wide variety of common soil-nitrifying, denitrifying, and nitrate-respiring bacteria under laboratory conditions. The results obtained indicate that aerobic soils are primary sources only when there is sufficient moisture to furnish anaerobic microsites for denitrification.

  12. Design and conduct of 'Xtreme Alps': a double-blind, randomised controlled study of the effects of dietary nitrate supplementation on acclimatisation to high altitude.

    PubMed

    Martin, Daniel S; Gilbert-Kawai, Edward T; Meale, Paula M; Fernandez, Bernadette O; Cobb, Alexandra; Khosravi, Maryam; Mitchell, Kay; Grocott, Michael P W; Levett, Denny Z H; Mythen, Michael G; Feelisch, Martin

    2013-11-01

    The study of healthy human volunteers ascending to high altitude provides a robust model of the complex physiological interplay that emulates human adaptation to hypoxaemia in clinical conditions. Nitric oxide (NO) metabolism may play an important role in both adaptation to high altitude and response to hypoxaemia during critical illness at sea level. Circulating nitrate and nitrite concentrations can be augmented by dietary supplementation and this is associated with improved exercise performance and mitochondrial efficiency. We hypothesised that the administration of a dietary substance (beetroot juice) rich in nitrate would improve oxygen efficiency during exercise at high altitude by enhancing tissue microcirculatory blood flow and oxygenation. Furthermore, nitrate supplementation would lead to measurable increases in NO bioactivity throughout the body. This methodological manuscript describes the design and conduct of the 'Xtreme Alps' expedition, a double-blind randomised controlled trial investigating the effects of dietary nitrate supplementation on acclimatisation to hypobaric hypoxia at high altitude in healthy human volunteers. The primary outcome measure was the change in oxygen efficiency during exercise at high altitude between participants allocated to receive nitrate supplementation and those receiving a placebo. A number of secondary measures were recorded, including exercise capacity, peripheral and microcirculatory blood flow and tissue oxygenation. Results from this study will further elucidate the role of NO in adaption to hypoxaemia and guide clinical trials in critically ill patients. Improved understanding of hypoxaemia in critical illness may provide new therapeutic avenues for interventions that will improve survival in critically ill patients. © 2013. Published by Elsevier Inc. All rights reserved.

  13. Three holes bound to a double acceptor - Be(+) in germanium

    NASA Technical Reports Server (NTRS)

    Haller, E. E.; Mcmurray, R. E., Jr.; Falicov, L. M.; Haegel, N. M.; Hansen, W. L.

    1983-01-01

    A double acceptor binding three holes has been observed for the first time with photoconductive far-infrared spectroscopy in beryllium-doped germanium single crystals. This new center, Be(+), has a hole binding energy of about 5 meV and is only present when free holes are generated by ionization of either neutral shallow acceptors or neutral Be double acceptors. The Be(+) center thermally ionizes above 4 K. It disappears at a uniaxial stress higher than about a billion dyn/sq cm parallel to (111) as a result of the lifting of the valence-band degeneracy.

  14. Improving Photoconductance of Fluorinated Donors with Fluorinated Acceptors

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Garner, Logan E.; Larson, Bryon; Oosterhout, Stefan

    2016-11-21

    This work investigates the influence of fluorination of both donor and acceptor materials on the generation of free charge carriers in small molecule donor/fullerene acceptor BHJ OPV active layers. A fluorinated and non-fluorinated small molecule analogue were synthesized and their optoelectronic properties characterized. The intrinsic photoconductance of blends of these small molecule donors was investigated using time-resolved microwave conductivity. Blends of the two donor molecules with a traditional non-fluorinated fullerene (PC70BM) as well as a fluorinated fullerene (C60(CF3)2-1) were investigated using 5% and 50% fullerene loading. We demonstrate for the first time that photoconductance in a 50:50 donor:acceptor BHJ blendmore » using a fluorinated fullerene can actually be improved relative to a traditional non-fluorinated fullerene by fluorinating the donor molecule as well.« less

  15. Acceptor binding energies in GaN and AlN

    NASA Astrophysics Data System (ADS)

    Mireles, Francisco; Ulloa, Sergio E.

    1998-08-01

    We employ effective-mass theory for degenerate hole bands to calculate the acceptor binding energies for Be, Mg, Zn, Ca, C, and Si substitutional acceptors in GaN and AlN. The calculations are performed through the 6×6 Rashba-Sheka-Pikus and the Luttinger-Kohn matrix Hamiltonians for wurtzite (WZ) and zinc-blende (ZB) crystal phases, respectively. An analytic representation for the acceptor pseudopotential is used to introduce the specific nature of the impurity atoms. The energy shift due to polaron effects is also considered in this approach. The ionization energy estimates are in very good agreement with those reported experimentally in WZ GaN. The binding energies for ZB GaN acceptors are all predicted to be shallower than the corresponding impurities in the WZ phase. The binding-energy dependence upon the crystal-field splitting in WZ GaN is analyzed. Ionization levels in AlN are found to have similar ``shallow'' values to those in GaN, but with some important differences which depend on the band structure parametrizations, especially the value of the crystal-field splitting used.

  16. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    NASA Astrophysics Data System (ADS)

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

    2017-01-01

    Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several weeks

  17. Plasma nitrate and nitrite are increased by a high nitrate supplement, but not by high nitrate foods in older adults

    PubMed Central

    Miller, Gary D.; Marsh, Anthony P.; Dove, Robin W.; Beavers, Daniel; Presley, Tennille; Helms, Christine; Bechtold, Erika; King, S. Bruce; Kim-Shapiro, Daniel

    2012-01-01

    Little is known about the effect of dietary nitrate on the nitrate/nitrite/NO (nitric oxide) cycle in older adults. We examined the effect of a 3-day control diet vs. high nitrate diet, with and without a high nitrate supplement (beetroot juice), on plasma nitrate and nitrite kinetics, and blood pressure using a randomized four period cross-over controlled design. We hypothesized that the high nitrate diet would show higher levels of plasma nitrate/nitrite and blood pressure compared to the control diet, which would be potentiated by the supplement. Participants were eight normotensive older men and women (5 female, 3 male, 72.5±4.7 yrs) with no overt disease or medications that affect NO metabolism. Plasma nitrate and nitrite levels and blood pressure were measured prior to and hourly for 3 hours after each meal. The mean daily changes in plasma nitrate and nitrite were significantly different from baseline for both control diet+supplement (p<0.001 and =0.017 for nitrate and nitrite, respectively) and high nitrate diet+supplement (p=0.001 and 0.002), but not for control diet (p=0.713 and 0.741) or high nitrate diet (p=0.852 and 0.500). Blood pressure decreased from the morning baseline measure to the three 2 hr post-meal follow-up time-points for all treatments, but there was no main effect for treatment. In healthy older adults, a high nitrate supplement consumed at breakfast elevated plasma nitrate and nitrite levels throughout the day. This observation may have practical utility for the timing of intake of a nitrate supplement with physical activity for older adults with vascular dysfunction. PMID:22464802

  18. Impact on electronic structure of donor/acceptor blend in organic photovoltaics by decontamination of molybdenum-oxide surface

    NASA Astrophysics Data System (ADS)

    Ito, Yuta; Akaike, Kouki; Fukuda, Takeshi; Sato, Daisuke; Fuse, Takuya; Iwahashi, Takashi; Ouchi, Yukio; Kanai, Kaname

    2018-05-01

    Molybdenum oxide (MoOx) is widely used as the hole-transport layer in bulk-heterojunction organic photovoltaics (BHJ-OPVs). During the fabrication of solution-processed BHJ-OPVs on vacuum-deposited MoOx film, the film must be exposed to N2 atmosphere in a glove box, where the donor/acceptor blends are spin-coated from a mixed solution. Employing photoelectron spectroscopy, we reveal that the exposure of the MoOx film to such atmosphere contaminates the MoOx surface. Annealing the contaminated MoOx film at 160 °C for 5 min, prior to spin-coating the blend film, can partially remove the carbon and oxygen adsorbed on the MoOx surface during the exposure of MoOx. However, the contamination layer on the MoOx surface does not affect the energy-level alignment at the interface between MoOx and the donor/acceptor blend. Hence, significant improvement in the performance of BHJ-OPVs by mildly annealing the MoOx layer, which was previously reported, can be explained by the reduction of undesired contamination.

  19. Dietary nitrate restores compensatory vasodilation and exercise capacity in response to a compromise in oxygen delivery in the noncompensator phenotype.

    PubMed

    Bentley, Robert F; Walsh, Jeremy J; Drouin, Patrick J; Velickovic, Aleksandra; Kitner, Sarah J; Fenuta, Alyssa M; Tschakovsky, Michael E

    2017-09-01

    Recently, dietary nitrate supplementation has been shown to improve exercise capacity in healthy individuals through a potential nitrate-nitrite-nitric oxide pathway. Nitric oxide has been shown to play an important role in compensatory vasodilation during exercise under hypoperfusion. Previously, we established that certain individuals lack a vasodilation response when perfusion pressure reductions compromise exercising muscle blood flow. Whether this lack of compensatory vasodilation in healthy, young individuals can be restored with dietary nitrate supplementation is unknown. Six healthy (21 ± 2 yr), recreationally active men completed a rhythmic forearm exercise. During steady-state exercise, the exercising arm was rapidly transitioned from an uncompromised (below heart) to a compromised (above heart) position, resulting in a reduction in local pressure of -31 ± 1 mmHg. Exercise was completed following 5 days of nitrate-rich (70 ml, 0.4 g nitrate) and nitrate-depleted (70 ml, ~0 g nitrate) beetroot juice consumption. Forearm blood flow (in milliliters per minute; brachial artery Doppler and echo ultrasound), mean arterial blood pressure (in millimeters of mercury; finger photoplethysmography), exercising forearm venous effluent (ante-cubital vein catheter), and plasma nitrite concentrations (chemiluminescence) revealed two distinct vasodilatory responses: nitrate supplementation increased (plasma nitrite) compared with placebo (245 ± 60 vs. 39 ± 9 nmol/l; P < 0.001), and compensatory vasodilation was present following nitrate supplementation (568 ± 117 vs. 714 ± 139 ml ⋅ min -1 ⋅ 100 mmHg -1 ; P = 0.005) but not in placebo (687 ± 166 vs. 697 ± 171 min -1 ⋅ 100 mmHg -1 ; P = 0.42). As such, peak exercise capacity was reduced to a lesser degree (-4 ± 39 vs. -39 ± 27 N; P = 0.01). In conclusion, dietary nitrate supplementation during a perfusion pressure challenge is an effective means of restoring exercise capacity and enabling

  20. The Measurement of Hot-spots in Granulated Ammonium Nitrate

    NASA Astrophysics Data System (ADS)

    Proud, William; Field, John

    2001-06-01

    Ammonium Nitrate (AN) is one of the components of the most widely used explosive in the world ammonium nitrate: fuel oil mixtures (ANFO). By itself, it is an oxygen negative explosive with a large critical diameter. Hot-spots are produced in explosives by various means including gas space collapse, localised shear or friction. If these hot-spots reach critical conditions of size, temperature and duration size reaction can grow. This deflagration stage may eventually transition to detonation. This paper describes a system and presents results where high-speed image intensified photography is used to monitor the number and growth of hot spots in granular AN under a range of different impact pressures. The results can be used in detonation codes to provide a more accurate and realistic description of the initiation process.

  1. Anaerobic production of magnetite by a dissimilatory iron-reducing microorganism

    USGS Publications Warehouse

    Lovley, D.R.; Stolz, J.F.; Nord, G.L.; Phillips, E.J.P.

    1987-01-01

    The potential contribution of microbial metabolism to the magnetization of sediments has only recently been recognized. In the presence of oxygen, magnetotactic bacteria can form intracellular chains of magnetite while using oxygen or nitrate as the terminal electron acceptor for metabolism1. The production of ultrafine-grained magnetite by magnetotactic bacteria in surficial aerobic sediments may contribute significantly to the natural remanent magnetism of sediments2-4. However, recent studies on iron reduction in anaerobic sediments suggested that bacteria can also generate magnetite in the absence of oxygen5. We report here on a sediment organism, designated GS-15, which produces copious quantities of ultrafine-grained magnetite under anaerobic conditions. GS-15 is not magnetotactic, but reduces amorphic ferric oxide to extracellular magnetite during the reduction of ferric iron as the terminal electron acceptor for organic matter oxidation. This novel metabolism may be the mechanism for the formation of ultrafine-grained magnetite in anaerobic sediments, and couldaccount for the accumulation of magnetite in ancient iron formations and hydrocarbon deposits. ?? 1987 Nature Publishing Group.

  2. 2012 Gordon Research Conference, Electron donor-acceptor interactions, August 5-10 2012

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    McCusker, James

    The upcoming incarnation of the Gordon Research Conference on Electron Donor Acceptor Interactions will feature sessions on classic topics including proton-coupled electron transfer, dye-sensitized solar cells, and biological electron transfer, as well as emerging areas such as quantum coherence effects in donor-acceptor interactions, spintronics, and the application of donor-acceptor interactions in chemical synthesis.

  3. Dietary nitrate increases arginine availability and protects mitochondrial complex I and energetics in the hypoxic rat heart

    PubMed Central

    Ashmore, Tom; Fernandez, Bernadette O; Branco-Price, Cristina; West, James A; Cowburn, Andrew S; Heather, Lisa C; Griffin, Julian L; Johnson, Randall S; Feelisch, Martin; Murray, Andrew J

    2014-01-01

    Hypoxic exposure is associated with impaired cardiac energetics in humans and altered mitochondrial function, with suppressed complex I-supported respiration, in rat heart. This response might limit reactive oxygen species generation, but at the cost of impaired electron transport chain (ETC) activity. Dietary nitrate supplementation improves mitochondrial efficiency and can promote tissue oxygenation by enhancing blood flow. We therefore hypothesised that ETC dysfunction, impaired energetics and oxidative damage in the hearts of rats exposed to chronic hypoxia could be alleviated by sustained administration of a moderate dose of dietary nitrate. Male Wistar rats (n = 40) were given water supplemented with 0.7 mmol l−1 NaCl (as control) or 0.7 mmol l−1 NaNO3, elevating plasma nitrate levels by 80%, and were exposed to 13% O2 (hypoxia) or normoxia (n = 10 per group) for 14 days. Respiration rates, ETC protein levels, mitochondrial density, ATP content and protein carbonylation were measured in cardiac muscle. Complex I respiration rates and protein levels were 33% lower in hypoxic/NaCl rats compared with normoxic/NaCl controls. Protein carbonylation was 65% higher in hearts of hypoxic rats compared with controls, indicating increased oxidative stress, whilst ATP levels were 62% lower. Respiration rates, complex I protein and activity, protein carbonylation and ATP levels were all fully protected in the hearts of nitrate-supplemented hypoxic rats. Both in normoxia and hypoxia, dietary nitrate suppressed cardiac arginase expression and activity and markedly elevated cardiac l-arginine concentrations, unmasking a novel mechanism of action by which nitrate enhances tissue NO bioavailability. Dietary nitrate therefore alleviates metabolic abnormalities in the hypoxic heart, improving myocardial energetics. PMID:25172947

  4. Nitrate in ground water and spring water near four dairy farms in North Florida, 1990-93

    USGS Publications Warehouse

    Andrews, W.J.

    1994-01-01

    pastures and wastewater spray fields at dairy farms and in water discharging from three nearby springs. Although denitrifying bacteria were present in counts sometimes exceeding 240,000 colonies/100mL in water from dairy-farm monitoring wells, ground water in the uppermost aquifers in Lafayette and Suwannee Counties generally contained too much oxygen for denitrification to remove nitrate from shallow ground water. Denitrification was more likely to occur in deeper ground water, which typically has lower dissolved oxygen concentrations.

  5. Non-Fullerene Electron Acceptors for Use in Organic Solar Cells

    PubMed Central

    2015-01-01

    Conspectus The active layer in a solution processed organic photovoltaic device comprises a light absorbing electron donor semiconductor, typically a polymer, and an electron accepting fullerene acceptor. Although there has been huge effort targeted to optimize the absorbing, energetic, and transport properties of the donor material, fullerenes remain as the exclusive electron acceptor in all high performance devices. Very recently, some new non-fullerene acceptors have been demonstrated to outperform fullerenes in comparative devices. This Account describes this progress, discussing molecular design considerations and the structure–property relationships that are emerging. The motivation to replace fullerene acceptors stems from their synthetic inflexibility, leading to constraints in manipulating frontier energy levels, as well as poor absorption in the solar spectrum range, and an inherent tendency to undergo postfabrication crystallization, resulting in device instability. New acceptors have to address these limitations, providing tunable absorption with high extinction coefficients, thus contributing to device photocurrent. The ability to vary and optimize the lowest unoccupied molecular orbital (LUMO) energy level for a specific donor polymer is also an important requirement, ensuring minimal energy loss on electron transfer and as high an internal voltage as possible. Initially perylene diimide acceptors were evaluated as promising acceptor materials. These electron deficient aromatic molecules can exhibit good electron transport, facilitated by close packed herringbone crystal motifs, and their energy levels can be synthetically tuned. The principal drawback of this class of materials, their tendency to crystallize on too large a length scale for an optimal heterojunction nanostructure, has been shown to be overcome through introduction of conformation twisting through steric effects. This has been primarily achieved by coupling two units together

  6. Distribution and fate of selected oxygenated organic species in the troposphere and lower stratosphere over the Atlantic

    NASA Astrophysics Data System (ADS)

    Singh, H.; Chen, Y.; Tabazadeh, A.; Fukui, Y.; Bey, I.; Yantosca, R.; Jacob, D.; Arnold, F.; Wohlfrom, K.; Atlas, E.; Flocke, F.; Blake, D.; Blake, N.; Heikes, B.; Snow, J.; Talbot, R.; Gregory, G.; Sachse, G.; Vay, S.; Kondo, Y.

    2000-02-01

    A large number of oxygenated organic chemicals (peroxyacyl nitrates, alkyl nitrates, acetone, formaldehyde, methanol, methylhydroperoxide, acetic acid and formic acid) were measured during the 1997 Subsonic Assessment (SASS) Ozone and Nitrogen Oxide Experiment (SONEX) airborne field campaign over the Atlantic. In this paper, we present a first picture of the distribution of these oxygenated organic chemicals (Ox-organic) in the troposphere and the lower stratosphere, and assess their source and sink relationships. In both the troposphere and the lower stratosphere, the total atmospheric abundance of these oxygenated species (ΣOx-organic) nearly equals that of total nonmethane hydrocarbons (ΣNMHC), which have been traditionally measured. A sizable fraction of the reactive nitrogen (10-30%) is present in its oxygenated organic form. The organic reactive nitrogen fraction is dominated by peroxyacetyl nitrate (PAN), with alkyl nitrates and peroxypropionyl nitrate (PPN) accounting for <5% of total NOy. Comparison of observations with the predictions of the Harvard three-dimensional global model suggests that in many key areas (e.g., formaldehyde and peroxides) substantial differences between measurements and theory are present and must be resolved. In the case of CH3OH, there appears to be a large mismatch between atmospheric concentrations and estimated sources, indicating the presence of major unknown removal processes. Instrument intercomparisons as well as disagreements between observations and model predictions are used to identify needed improvements in key areas. The atmospheric chemistry and sources of this group of chemicals is poorly understood even though their fate is intricately linked with upper tropospheric NOx and HOx cycles.

  7. Impact of Seasonal Hypoxia on Activity and Community Structure of Chemolithoautotrophic Bacteria in a Coastal Sediment

    PubMed Central

    Lipsewers, Yvonne A.; Vasquez-Cardenas, Diana; Seitaj, Dorina; Schauer, Regina; Hidalgo-Martinez, Silvia; Meysman, Filip J. R.

    2017-01-01

    ABSTRACT Seasonal hypoxia in coastal systems drastically changes the availability of electron acceptors in bottom water, which alters the sedimentary reoxidation of reduced compounds. However, the effect of seasonal hypoxia on the chemolithoautotrophic community that catalyzes these reoxidation reactions is rarely studied. Here, we examine the changes in activity and structure of the sedimentary chemolithoautotrophic bacterial community of a seasonally hypoxic saline basin under oxic (spring) and hypoxic (summer) conditions. Combined 16S rRNA gene amplicon sequencing and analysis of phospholipid-derived fatty acids indicated a major temporal shift in community structure. Aerobic sulfur-oxidizing Gammaproteobacteria (Thiotrichales) and Epsilonproteobacteria (Campylobacterales) were prevalent during spring, whereas Deltaproteobacteria (Desulfobacterales) related to sulfate-reducing bacteria prevailed during summer hypoxia. Chemolithoautotrophy rates in the surface sediment were three times higher in spring than in summer. The depth distribution of chemolithoautotrophy was linked to the distinct sulfur oxidation mechanisms identified through microsensor profiling, i.e., canonical sulfur oxidation, electrogenic sulfur oxidation by cable bacteria, and sulfide oxidation coupled to nitrate reduction by Beggiatoaceae. The metabolic diversity of the sulfur-oxidizing bacterial community suggests a complex niche partitioning within the sediment, probably driven by the availability of reduced sulfur compounds (H2S, S0, and S2O32−) and electron acceptors (O2 and NO3−) regulated by seasonal hypoxia. IMPORTANCE Chemolithoautotrophic microbes in the seafloor are dependent on electron acceptors, like oxygen and nitrate, that diffuse from the overlying water. Seasonal hypoxia, however, drastically changes the availability of these electron acceptors in the bottom water; hence, one expects a strong impact of seasonal hypoxia on sedimentary chemolithoautotrophy. A

  8. Impact of Seasonal Hypoxia on Activity and Community Structure of Chemolithoautotrophic Bacteria in a Coastal Sediment.

    PubMed

    Lipsewers, Yvonne A; Vasquez-Cardenas, Diana; Seitaj, Dorina; Schauer, Regina; Hidalgo-Martinez, Silvia; Sinninghe Damsté, Jaap S; Meysman, Filip J R; Villanueva, Laura; Boschker, Henricus T S

    2017-05-15

    Seasonal hypoxia in coastal systems drastically changes the availability of electron acceptors in bottom water, which alters the sedimentary reoxidation of reduced compounds. However, the effect of seasonal hypoxia on the chemolithoautotrophic community that catalyzes these reoxidation reactions is rarely studied. Here, we examine the changes in activity and structure of the sedimentary chemolithoautotrophic bacterial community of a seasonally hypoxic saline basin under oxic (spring) and hypoxic (summer) conditions. Combined 16S rRNA gene amplicon sequencing and analysis of phospholipid-derived fatty acids indicated a major temporal shift in community structure. Aerobic sulfur-oxidizing Gammaproteobacteria ( Thiotrichales ) and Epsilonproteobacteria ( Campylobacterales ) were prevalent during spring, whereas Deltaproteobacteria ( Desulfobacterales ) related to sulfate-reducing bacteria prevailed during summer hypoxia. Chemolithoautotrophy rates in the surface sediment were three times higher in spring than in summer. The depth distribution of chemolithoautotrophy was linked to the distinct sulfur oxidation mechanisms identified through microsensor profiling, i.e., canonical sulfur oxidation, electrogenic sulfur oxidation by cable bacteria, and sulfide oxidation coupled to nitrate reduction by Beggiatoaceae The metabolic diversity of the sulfur-oxidizing bacterial community suggests a complex niche partitioning within the sediment, probably driven by the availability of reduced sulfur compounds (H 2 S, S 0 , and S 2 O 3 2- ) and electron acceptors (O 2 and NO 3 - ) regulated by seasonal hypoxia. IMPORTANCE Chemolithoautotrophic microbes in the seafloor are dependent on electron acceptors, like oxygen and nitrate, that diffuse from the overlying water. Seasonal hypoxia, however, drastically changes the availability of these electron acceptors in the bottom water; hence, one expects a strong impact of seasonal hypoxia on sedimentary chemolithoautotrophy. A

  9. Cetia pacifica gen. nov., sp. nov., a chemolithoautotrophic, thermophilic, nitrate-ammonifying bacterium from a deep-sea hydrothermal vent.

    PubMed

    Grosche, Ashley; Sekaran, Hema; Pérez-Rodríguez, Ileana; Starovoytov, Valentin; Vetriani, Costantino

    2015-04-01

    A thermophilic, anaerobic, chemolithoautotrophic bacterium, strain TB-6(T), was isolated from a deep-sea hydrothermal vent located on the East Pacific Rise at 9° N. The cells were Gram-staining-negative and rod-shaped with one or more polar flagella. Cell size was approximately 1-1.5 µm in length and 0.5 µm in width. Strain TB-6(T) grew between 45 and 70 °C (optimum 55-60 °C), 0 and 35 g NaCl l(-1) (optimum 20-30 g l(-1)) and pH 4.5 and 7.5 (optimum pH 5.5-6.0). Generation time under optimal conditions was 2 h. Growth of strain TB-6(T) occurred with H2 as the energy source, CO2 as the carbon source and nitrate or sulfur as electron acceptors, with formation of ammonium or hydrogen sulfide, respectively. Acetate, (+)-d-glucose, Casamino acids, sucrose and yeast extract were not used as carbon and energy sources. Inhibition of growth occurred in the presence of lactate, peptone and tryptone under a H2/CO2 (80 : 20; 200 kPa) gas phase. Thiosulfate, sulfite, arsenate, selenate and oxygen were not used as electron acceptors. The G+C content of the genomic DNA was 36.8 mol%. Phylogenetic analysis of the 16S rRNA gene of strain TB-6(T) showed that this organism branched separately from the three most closely related genera, Caminibacter , Nautilia and Lebetimonas , within the family Nautiliaceae . Strain TB-6(T) contained several unique fatty acids in comparison with other members of the family Nautiliaceae . Based on experimental evidence, it is proposed that the organism represents a novel species and genus within the family Nautiliaceae , Cetia pacifica, gen. nov., sp. nov. The type strain is TB-6(T) ( = DSM 27783(T) = JCM 19563(T)). © 2015 IUMS.

  10. Positive and negative effects of oxygen in thermal annealing of p-type GaN

    NASA Astrophysics Data System (ADS)

    Wu, L. L.; Zhao, D. G.; Jiang, D. S.; Chen, P.; Le, L. C.; Li, L.; Liu, Z. S.; Zhang, S. M.; Zhu, J. J.; Wang, H.; Zhang, B. S.; Yang, H.

    2012-08-01

    The effect of oxygen on ambient gas on activating p-GaN by rapid thermal annealing was investigated. When the ratio of N2 to O2 is 4:1, the sample activated after annealing at 750 °C exhibits the best electrical properties with respect to resistivity. It is confirmed that the concentration of hydrogen which passivates Mg acceptors in GaN decreases more efficiently when oxygen is introduced into N2 ambient gas. Although oxygen-involved annealing at higher temperature may further reduce the concentration of hydrogen, the resistivity of p-GaN may increase due to the negative effect caused by too much incorporation of oxygen-related donors.

  11. Short-term effects of a high nitrate diet on nitrate metabolism in healthy individuals.

    PubMed

    Bondonno, Catherine P; Liu, Alex H; Croft, Kevin D; Ward, Natalie C; Puddey, Ian B; Woodman, Richard J; Hodgson, Jonathan M

    2015-03-12

    Dietary nitrate, through the enterosalivary nitrate-nitrite-NO pathway, can improve blood pressure and arterial stiffness. How long systemic nitrate and nitrite remain elevated following cessation of high nitrate intake is unknown. In 19 healthy men and women, the time for salivary and plasma nitrate and nitrite to return to baseline after 7 days increased nitrate intake from green leafy vegetables was determined. Salivary and plasma nitrate and nitrite was measured at baseline [D0], end of high nitrate diet [D7], day 9 [+2D], day 14 [+7D] and day 21 [+14D]. Urinary nitrite and nitrate was assessed at D7 and +14D. Increased dietary nitrate for 7 days resulted in a more than fourfold increase in saliva and plasma nitrate and nitrite (p < 0.001) measured at [D7]. At [+2D] plasma nitrite and nitrate had returned to baseline while saliva nitrate and nitrite were more than 1.5 times higher than at baseline levels. By [+7D] all metabolites had returned to baseline levels. The pattern of response was similar between men and women. Urinary nitrate and nitrate was sevenfold higher at D7 compared to +14D. These results suggest that daily ingestion of nitrate may be required to maintain the physiological changes associated with high nitrate intake.

  12. Short-Term Effects of a High Nitrate Diet on Nitrate Metabolism in Healthy Individuals

    PubMed Central

    Bondonno, Catherine P.; Liu, Alex H.; Croft, Kevin D.; Ward, Natalie C.; Puddey, Ian B.; Woodman, Richard J.; Hodgson, Jonathan M.

    2015-01-01

    Dietary nitrate, through the enterosalivary nitrate-nitrite-NO pathway, can improve blood pressure and arterial stiffness. How long systemic nitrate and nitrite remain elevated following cessation of high nitrate intake is unknown. In 19 healthy men and women, the time for salivary and plasma nitrate and nitrite to return to baseline after 7 days increased nitrate intake from green leafy vegetables was determined. Salivary and plasma nitrate and nitrite was measured at baseline [D0], end of high nitrate diet [D7], day 9 [+2D], day 14 [+7D] and day 21 [+14D]. Urinary nitrite and nitrate was assessed at D7 and +14D. Increased dietary nitrate for 7 days resulted in a more than fourfold increase in saliva and plasma nitrate and nitrite (p < 0.001) measured at [D7]. At [+2D] plasma nitrite and nitrate had returned to baseline while saliva nitrate and nitrite were more than 1.5 times higher than at baseline levels. By [+7D] all metabolites had returned to baseline levels. The pattern of response was similar between men and women. Urinary nitrate and nitrate was sevenfold higher at D7 compared to +14D. These results suggest that daily ingestion of nitrate may be required to maintain the physiological changes associated with high nitrate intake. PMID:25774606

  13. Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer.

    PubMed

    Spence, Michael J; Bottrell, Simon H; Thornton, Steven F; Richnow, Hans H; Spence, Keith H

    2005-09-01

    Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has

  14. Challenges with nitrate therapy and nitrate tolerance: prevalence, prevention, and clinical relevance.

    PubMed

    Thadani, Udho

    2014-08-01

    Nitrate therapy has been an effective treatment for ischemic heart disease for over 100 years. The anti-ischemic and exercise-promoting benefits of sublingually administered nitrates are well established. Nitroglycerin is indicated for the relief of an established attack of angina and for prophylactic use, but its effects are short lived. In an effort to increase the duration of beneficial effects, long-acting orally administered and topical applications of nitrates have been developed; however, following their continued or frequent daily use, patients soon develop tolerance to these long-acting nitrate preparations. Once tolerance develops, patients begin losing the protective effects of the long-acting nitrate therapy. By providing a nitrate-free interval, or declining nitrate levels at night, one can overcome or reduce the development of tolerance, but cannot provide 24-h anti-anginal and anti-ischemic protection. In addition, patients may be vulnerable to occurrence of rebound angina and myocardial ischemia during periods of absent nitrate levels at night and early hours of the morning, and worsening of exercise capacity prior to the morning dose of the medication. This has been a concern with nitroglycerin patches but not with oral formulations of isosorbide-5 mononitrates, and has not been adequately studied with isosorbide dinitrate. This paper describes problems associated with nitrate tolerance, reviews mechanisms by which nitrate tolerance and loss of efficacy develop, and presents strategies to avoid nitrate tolerance and maintain efficacy when using long-acting nitrate formulations.

  15. Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions.

    PubMed

    van der Waals, Marcelle J; Pijls, Charles; Sinke, Anja J C; Langenhoff, Alette A M; Smidt, Hauke; Gerritse, Jan

    2018-04-01

    The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl alcohol (TBA, a possible oxygenate metabolite), was studied at an industrially contaminated site and in the laboratory. Analysis of groundwater samples indicated that in the field MtBE was degraded, yielding TBA as major product. In batch microcosms, MtBE was degraded under different conditions: unamended control, with medium without added electron acceptors, or with ferrihydrite or sulfate (with or without medium) as electron acceptor, respectively. Degradation of EtBE was not observed under any of these conditions tested. TBA was partially depleted in parallel with MtBE. Results of microcosm experiments with MtBE substrate analogues, i.e., syringate, vanillate, or ferulate, were in line with the hypothesis that the observed TBA degradation is a cometabolic process. Microcosms with ferulate, syringate, isopropanol, or diethyl ether showed EtBE depletion up to 86.5% of the initial concentration after 83 days. Benzene was degraded in the unamended controls, with medium without added electron acceptors and with ferrihydrite, sulfate, or chlorate as electron acceptor, respectively. In the presence of nitrate, benzene was only degraded after addition of an anaerobic benzene-degrading community. Nitrate and chlorate hindered MtBE, EtBE, and TBA degradation.

  16. Small molecule BODIPY dyes as non-fullerene acceptors in bulk heterojunction organic photovoltaics.

    PubMed

    Poe, Ambata M; Della Pelle, Andrea M; Subrahmanyam, Ayyagari V; White, William; Wantz, Guillaume; Thayumanavan, S

    2014-03-18

    A series of acceptor-donor-acceptor molecules containing terminal BODIPY moieties conjugated through the meso position were synthesized. Deep LUMO energy levels and good visible absorption led to their use as acceptors in bulk heterojunction solar cells. Inverted devices were fabricated, reaching efficiencies as high as 1.51%.

  17. Non-fullerene acceptors for organic solar cells

    NASA Astrophysics Data System (ADS)

    Yan, Cenqi; Barlow, Stephen; Wang, Zhaohui; Yan, He; Jen, Alex K.-Y.; Marder, Seth R.; Zhan, Xiaowei

    2018-03-01

    Non-fullerene acceptors (NFAs) are currently a major focus of research in the development of bulk-heterojunction organic solar cells (OSCs). In contrast to the widely used fullerene acceptors (FAs), the optical properties and electronic energy levels of NFAs can be readily tuned. NFA-based OSCs can also achieve greater thermal stability and photochemical stability, as well as longer device lifetimes, than their FA-based counterparts. Historically, the performance of NFA OSCs has lagged behind that of fullerene devices. However, recent developments have led to a rapid increase in power conversion efficiencies for NFA OSCs, with values now exceeding 13%, demonstrating the viability of using NFAs to replace FAs in next-generation high-performance OSCs. This Review discusses the important work that has led to this remarkable progress, focusing on the two most promising NFA classes to date: rylene diimide-based materials and materials based on fused aromatic cores with strong electron-accepting end groups. The key structure-property relationships, donor-acceptor matching criteria and aspects of device physics are discussed. Finally, we consider the remaining challenges and promising future directions for the NFA OSCs field.

  18. An overview of molecular acceptors for organic solar cells

    NASA Astrophysics Data System (ADS)

    Hudhomme, Piétrick

    2013-07-01

    Organic solar cells (OSCs) have gained serious attention during the last decade and are now considered as one of the future photovoltaic technologies for low-cost power production. The first dream of attaining 10% of power coefficient efficiency has now become a reality thanks to the development of new materials and an impressive work achieved to understand, control and optimize structure and morphology of the device. But most of the effort devoted to the development of new materials concerned the optimization of the donor material, with less attention for acceptors which to date remain dominated by fullerenes and their derivatives. This short review presents the progress in the use of non-fullerene small molecules and fullerene-based acceptors with the aim of evaluating the challenge for the next generation of acceptors in organic photovoltaics.

  19. Control of Sulfide Production in High Salinity Bakken Shale Oil Reservoirs by Halophilic Bacteria Reducing Nitrate to Nitrite

    PubMed Central

    An, Biwen A.; Shen, Yin; Voordouw, Gerrit

    2017-01-01

    Microbial communities in shale oil fields are still poorly known. We obtained samples of injection, produced and facility waters from a Bakken shale oil field in Saskatchewan, Canada with a resident temperature of 60°C. The injection water had a lower salinity (0.7 Meq of NaCl) than produced or facility waters (0.6–3.6 Meq of NaCl). Salinities of the latter decreased with time, likely due to injection of low salinity water, which had 15–30 mM sulfate. Batch cultures of field samples showed sulfate-reducing and nitrate-reducing bacteria activities at different salinities (0, 0.5, 0.75, 1.0, 1.5, and 2.5 M NaCl). Notably, at high salinity nitrite accumulated, which was not observed at low salinity, indicating potential for nitrate-mediated souring control at high salinity. Continuous culture chemostats were established in media with volatile fatty acids (a mixture of acetate, propionate and butyrate) or lactate as electron donor and nitrate or sulfate as electron acceptor at 0.5 to 2.5 M NaCl. Microbial community analyses of these cultures indicated high proportions of Halanaerobium, Desulfovermiculus, Halomonas, and Marinobacter in cultures at 2.5 M NaCl, whereas Desulfovibrio, Geoalkalibacter, and Dethiosulfatibacter were dominant at 0.5 M NaCl. Use of bioreactors to study the effect of nitrate injection on sulfate reduction showed that accumulation of nitrite inhibited SRB activity at 2.5 M but not at 0.5 M NaCl. High proportions of Halanaerobium and Desulfovermiculus were found at 2.5 M NaCl in the absence of nitrate, whereas high proportions of Halomonas and no SRB were found in the presence of nitrate. A diverse microbial community dominated by the SRB Desulfovibrio was observed at 0.5 M NaCl both in the presence and absence of nitrate. Our results suggest that nitrate injection can prevent souring provided that the salinity is maintained at a high level. Thus, reinjection of high salinity produced water amended with nitrate maybe be a cost effective

  20. Nitrate transport is independent of NADH and NAD(P)H nitrate reductases in barley seedlings

    NASA Technical Reports Server (NTRS)

    Warner, R. L.; Huffaker, R. C.

    1989-01-01

    Barley (Hordeum vulgare L.) has NADH-specific and NAD(P)H-bispecific nitrate reductase isozymes. Four isogenic lines with different nitrate reductase isozyme combinations were used to determine the role of NADH and NAD(P)H nitrate reductases on nitrate transport and assimilation in barley seedlings. Both nitrate reductase isozymes were induced by nitrate and were required for maximum nitrate assimilation in barley seedlings. Genotypes lacking the NADH isozyme (Az12) or the NAD(P)H isozyme (Az70) assimilated 65 or 85%, respectively, as much nitrate as the wild type. Nitrate assimilation by genotype (Az12;Az70) which is deficient in both nitrate reductases, was only 13% of the wild type indicating that the NADH and NAD(P)H nitrate reductase isozymes are responsible for most of the nitrate reduction in barley seedlings. For all genotypes, nitrate assimilation rates in the dark were about 55% of the rates in light. Hypotheses that nitrate reductase has direct or indirect roles in nitrate uptake were not supported by this study. Induction of nitrate transporters and the kinetics of net nitrate uptake were the same for all four genotypes indicating that neither nitrate reductase isozyme has a direct role in nitrate uptake in barley seedlings.

  1. Do nitrates differ?

    PubMed Central

    Fung, H.-L.

    1992-01-01

    1 The organic nitrates all share a common biochemical and physiological mechanism of action. 2 The organic nitrates differ substantially in their pharmacologic potency and pharmacokinetics. In vitro potency differences appear larger than the corresponding in vivo activities. 3 The duration of action of organic nitrates, after a single immediate-release dose, is governed by the pharmacokinetics of the drug. However, the duration of action of available sustained-release preparations, whatever the nitrate or formulation, is limited to about 12 h, due to the development of pharmacologic tolerance. 4 Nitrates do not appear to differ in their production of undesirable effects. PMID:1633079

  2. Simulation study on the effects of chemical structure and molecular size on the acceptor strength in poly(3-hexylthiophene)-based copolymer with alternating donor and acceptor for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Rassamesard, Areefen; Pengpan, Teparksorn

    2017-02-01

    This research assessed the effects of various chemical structures and molecular sizes on the simulated geometric parameters, electron structures, and spectroscopic properties of single-chain complex alternating donor-acceptor (D-A) monomers and copolymers that are intended for use as photoactive layer in a polymer solar cell by using Kohn-Sham density functional theory with B3LYP exchange-correlation functional. The 3-hexylthiophene (3HT) was selected for electron donor, while eight chemicals, namely thiazole (Z), thiadiazole (D), thienopyrazine (TP), thienothiadiazole (TD), benzothiadiazole (BT), thiadiazolothieno-pyrazine (TPD), oxadiazole (OXD) and 5-diphenyl-1,2,4-triazole (TAZ), were employed as electron acceptor functional groups. The torsional angle, bridge bond length, intramolecular charge transfer, energy levels, and molecular orbitals were analyzed. The simulation results reveal that the geometry and electron structure of donor-acceptor monomer and copolymer are significantly impacted by heterocyclic rings, heteroatoms, fused rings, degree of steric hindrance and coplanarity of the acceptor molecular structure. Planar conformation was obtained from the D copolymer, and a pseudo-planar structure with the TD copolymer. The TAZ acceptor exhibited strong steric hindrance due to its bulky structure and non-planarity of its structure. An analysis of the electron structures indicated that the degree of intramolecular electron-withdrawing capability had the rank order TAZ  <  Z  <  D  <  TPD  <  OXD  <  TP  <  BT  <  TD. The TD is indicated as the most effective acceptor among those that were simulated. However, the small energy gaps of TD as well as TPD copolymer indicate that these two copolymers can be used in transparent conducting materials. The copolymer based on BT acceptor exhibited good intramolecular charge transfer and absorbed at 656 nm wavelength which is close to the maximum flux of solar

  3. Kinetic hindrance of Fe(II) oxidation at alkaline pH and in the presence of nitrate and oxygen in a facultative wastewater stabilization pond.

    PubMed

    Rockne, Karl J

    2007-02-15

    To better understand the dynamics of Fe2 + oxidation in facultative wastewater stabilization ponds, water samples from a three-pond system were taken throughout the period of transition from anoxic conditions with high aqueous Fe2 + levels in the early spring to fully aerobic conditions in late spring. Fe2 + levels showed a highly significant correlation with pH but were not correlated with dissolved oxygen (DO). Water column Fe2 + levels were modeled using the kinetic rate law for Fe2 + oxidation of Sung and Morgan.[5] The fitted kinetic coefficients were 5 +/- 3 x 10(6) M(- 2) atm(-1) min(-1); more than six orders of magnitude lower than typically reported. Comparison of four potential Fe redox couples demonstrated that the rhoepsilon was at least 3-4 orders of magnitude higher than would be expected based on internal equilibrium. Surprisingly, measured nitrate and DO (when present) were typically consistent with both nitrate (from denitrification) and DO levels (from aerobic respiration) predicted from equilibrium. Although the hydrous Fe oxide/FeCO3 couple was closest to equilibrium and most consistent with the observed pH dependence (in contrast to predicted lepidocrocite), Fe2 + oxidation is kinetically hindered, resulting in up to 10(7)-fold higher levels than expected based on both kinetic and equilibrium analyses.

  4. Effect of oxygen on the per‐cell extracellular electron transfer rate of Shewanella oneidensis MR‐1 explored in bioelectrochemical systems

    PubMed Central

    Lu, Mengqian; Chan, Shirley; Babanova, Sofia

    2016-01-01

    ABSTRACT Extracellular electron transfer (EET) is a mechanism that enables microbes to respire solid‐phase electron acceptors. These EET reactions most often occur in the absence of oxygen, since oxygen can act as a competitive electron acceptor for many facultative microbes. However, for Shewanella oneidensis MR‐1, oxygen may increase biomass development, which could result in an overall increase in EET activity. Here, we studied the effect of oxygen on S. oneidensis MR‐1 EET rates using bioelectrochemical systems (BESs). We utilized optically accessible BESs to monitor real‐time biomass growth, and studied the per‐cell EET rate as a function of oxygen and riboflavin concentrations in BESs of different design and operational conditions. Our results show that oxygen exposure promotes biomass development on the electrode, but significantly impairs per‐cell EET rates even though current production does not always decrease with oxygen exposure. Additionally, our results indicated that oxygen can affect the role of riboflavin in EET. Under anaerobic conditions, both current density and per‐cell EET rate increase with the riboflavin concentration. However, as the dissolved oxygen (DO) value increased to 0.42 mg/L, riboflavin showed very limited enhancement on per‐cell EET rate and current generation. Since it is known that oxygen can promote flavins secretion in S. oneidensis, the role of riboflavin may change under anaerobic and aerobic conditions. Biotechnol. Bioeng. 2017;114: 96–105. © 2016 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc. PMID:27399911

  5. High nitrate concentrations in some Midwest United States streams in 2013 after the 2012 drought

    USGS Publications Warehouse

    Van Metre, Peter C.; Frey, Jeffrey W.; Musgrove, MaryLynn; Nakagaki, Naomi; Qi, Sharon L.; Mahler, Barbara J.; Wieczorek, Michael; Button, Daniel T.

    2016-01-01

    Nitrogen sources in the Mississippi River basin have been linked to degradation of stream ecology and to Gulf of Mexico hypoxia. In 2013, the USGS and the USEPA characterized water quality stressors and ecological conditions in 100 wadeable streams across the midwestern United States. Wet conditions in 2013 followed a severe drought in 2012, a weather pattern associated with elevated nitrogen concentrations and loads in streams. Nitrate concentrations during the May to August 2013 sampling period ranged from <0.04 to 41.8 mg L−1 as N (mean, 5.31 mg L−1). Observed mean May to June nitrate concentrations at the 100 sites were compared with May to June concentrations predicted from a regression model developed using historical nitrate data. Observed concentrations for 17 sites, centered on Iowa and southern Minnesota, were outside the 95% confidence interval of the regression-predicted mean, indicating that they were anomalously high. The sites with a nitrate anomaly had significantly higher May to June nitrate concentrations than sites without an anomaly (means, 19.8 and 3.6 mg L−1, respectively) and had higher antecedent precipitation indices, a measure of the departure from normal precipitation, in 2012 and 2013. Correlations between nitrate concentrations and watershed characteristics and nitrogen and oxygen isotopes of nitrate indicated that fertilizer and manure used in crop production, principally corn, were the dominant sources of nitrate. The anomalously high nitrate levels in parts of the Midwest in 2013 coincide with reported higher-than-normal nitrate loads in the Mississippi River.

  6. The Nitrite-Scavenging Properties of Catechol, Resorcinol, and Hydroquinone: A Comparative Study on Their Nitration and Nitrosation Reactions.

    PubMed

    Lu, Yunhao; Dong, Yanzuo; Li, Xueli; He, Qiang

    2016-10-14

    The nitration and nitrosation reactions of catechol, resorcinol, and hydroquinone (0.05 mmol/L) with sodium nitrite (0.05 mmol/L) at pH 3 and 37 °C were studied by using liquid chromatography and mass spectrometry (LC-MS) and atom charge analysis, which was aimed to provide chemical insight into the nitrite-scavenging behavior of polyphenols. The 3 benzenediols showed different mechanisms to scavenge nitrite due to their differences in hydroxyl position. Catechol was nitrated with 1 NO 2 group at the hydroxyl oxygen, and resorcinol was nitrosated with 2 NO groups at the C 2 and C 4 (or C 6 ) positions of the benzene ring. Hydroquinone could scavenge nitrite through both nitration and nitrosation mechanisms. The nitrated hydroquinone had 1 NO 2 group at the hydroxyl oxygen in the molecule, while the nitrosated 1 containing 2 NO groups at the benzene ring might have 3 structure probabilities. The results may provide a structure-activity understanding on the nitrite-scavenging property of polyphenols, so as to promote their application in the food industry for the removal of possibly toxic nitrites found in many vegetables and often in processed meat products. © 2016 Institute of Food Technologists®.

  7. Nitrate behaviors and its transportation time scale in unsaturated zone under farmlands with different fertilization log in Kumamoto region, southern Japan

    NASA Astrophysics Data System (ADS)

    Okumura, Azusa; Hosono, Takahiro; Shimada, Jun

    2017-04-01

    An application of fertilizers and manure often caused an increase of nitrate concentration in groundwater in the agricultural area. The study area, Kumamoto, is the field facing this type of problem. Previous studies using nitrogen-oxygen isotope ratios in nitrate showed that accumulation of chemical fertilizers is the major factor for observed nitrate contamination. However, once it loaded nitrogen compounds may change its form and isotopic composition during transportation within unsaturation zone prior to reach the aquifer. However, such kind of knowledge is still rarely accumulated. To clarify the behavior and transportation manner of nitrogen in the unsaturated zone, we analyzed the nitrogen-oxygen isotope ratios of the extracted soil water of the unsaturated zone soils from the farmland having different fertilization logs. In addition, we attempted to verify the origin of nitrate in soil water by comparing with previous isotopic results. The plateaus-like topography of the study area is consists of the pyroclastic flow deposits. Land use is mainly farmland and this area is a major source of nitrogen load and transport route into the aquifer. Nitrate concentration in groundwater at terraces recharge area has been reported about 40 mg/L. Drilling survey carried out in the unsaturated zone soil on 4 farmlands with the different land use logs in such terraces. Drilling points S1 and S2 were treated by both slurry and chemical fertilizers, on the other hand, point C1 and C2 were applied chemical fertilizers only. The drilling depth was up to 14-15 m, and soil samples were kept on evacuated condition after sectioning into 10 cm interval. The soil water was extracted using a centrifuge machine. The extracted soil water was measured for the nitrogen-oxygen isotope ratios in nitrate and major ions concentrations. All cores showed high nitrate concentrations in the surface layer (260, 440, 172 and 244 mg/L for S1, S2, C1, and C2 respectively). The concentrations became

  8. Photochemical behavior of carbon nanotubes in natural waters: reactive oxygen species production and effects on •OH generation by Suwannee River fulvic acid, nitrate, and Fe (III).

    PubMed

    Zhou, Lei; Zhang, Ya; Wang, Qi; Ferronato, Corinne; Yang, Xi; Chovelon, Jean-Marc

    2016-10-01

    The photochemical activities of three kinds of carbon nanotubes (CNTs) were investigated in the present study. Efficient procedures of dispersing the three kinds of carbon nanotubes in water were established, and the quantitative analysis methods were also developed by TOC-absorbance method. High pH value or low ionic strength of the colloidal solutions facilitated the dispersion of CNTs. The suspensions of three kinds of CNTs could generate singlet oxygen ((1)O2) and hydroxyl radical (•OH) under irradiation of simulated sunlight, while superoxide radical (O2 (•-)) was not detected. The steady-state concentrations of (1)O2 and •OH generated by these CNTs were also determined. The presence of CNTs in natural waters can affect the photochemical behavior of water constituents, such as nitrate, dissolved organic matter, and Fe(3+). Specifically, in nitrate solution, the presence of CNTs could inhibit the generation of •OH by nitrate through light screening effect, while the quenching effect of hydroxyl radicals by CNTs was not observed. Besides light screening effect, the three kinds of CNTs used in the experiments also have a strong inhibiting effect on the ability of DOM to produce •OH by binding to the active sites. Moreover, the adsorption of Fe(3+) on MWCNT-OH and MWCNT-COOH could lead to its inactivation of formation of •OH in acidic conditions. However, the presence of the three kinds of CNTs did not affect the ligand-to-metal charge transfer (LMCT) reaction of DOM-Fe (III) complex.

  9. Effect of dissolved oxygen on nitrate removal using polycaprolactone as an organic carbon source and biofilm carrier in fixed-film denitrifying reactors.

    PubMed

    Luo, Guozhi; Xu, Guimei; Gao, Jinfang; Tan, Hongxin

    2016-05-01

    Nitrate-nitrogen (NO3(-)-N) always accumulates in commercial recirculating aquaculture systems (RASs) with aerobic nitrification units. The ability to reduce NO3(-)-N consistently and confidently could help RASs to become more sustainable. The rich dissolved oxygen (DO) content and sensitive organisms stocked in RASs increase the difficulty of denitrifying technology. A denitrifying process using biologically degradable polymers as an organic carbon source and biofilm carrier was proposed because of its space-efficient nature and strong ability to remove NO3(-)-N from RASs. The effect of dissolved oxygen (DO) levels on heterotrophic denitrification in fixed-film reactors filled with polycaprolactone (PCL) was explored in the current experiment. DO conditions in the influent of the denitrifying reactors were set up as follows: the anoxic treatment group (Group A, average DO concentration of 0.28±0.05mg/L), the low-oxygen treatment DO group (Group B, average DO concentration of 2.50±0.24mg/L) and the aerated treatment group (Group C, average DO concentration of 5.63±0.57mg/L). Feeding with 200mg/L of NO3(-)-N, the NO3(-)-N removal rates were 1.53, 1.60 and 1.42kg/m(3) PCL/day in Groups A, B and C, respectively. No significant difference in NO3(-)-N removal rates was observed among the three treatments. It was concluded that the inhibitory effects of DO concentrations lower than 6mg/L on heterotrophic denitrification in the fixed-film reactors filled with PCL can be mitigated. Copyright © 2015. Published by Elsevier B.V.

  10. Nitrate-to-nitrite-to-nitric oxide conversion modulated by nitrate-containing {Fe(NO)2}9 dinitrosyl iron complex (DNIC).

    PubMed

    Tsai, Fu-Te; Lee, Yu-Ching; Chiang, Ming-Hsi; Liaw, Wen-Feng

    2013-01-07

    Nitrosylation of high-spin [Fe(κ(2)-O(2)NO)(4)](2-) (1) yields {Fe(NO)}(7) mononitrosyl iron complex (MNIC) [(κ(2)-O(2)NO)(κ(1)-ONO(2))(3)Fe(NO)](2-) (2) displaying an S = 3/2 axial electron paramagnetic resonance (EPR) spectrum (g(⊥) = 3.988 and g(∥) = 2.000). The thermally unstable nitrate-containing {Fe(NO)(2)}(9) dinitrosyl iron complex (DNIC) [(κ(1)-ONO(2))(2)Fe(NO)(2)](-) (3) was exclusively obtained from reaction of HNO(3) and [(OAc)(2)Fe(NO)(2)](-) and was characterized by IR, UV-vis, EPR, superconducting quantum interference device (SQUID), X-ray absorption spectroscopy (XAS), and single-crystal X-ray diffraction (XRD). In contrast to {Fe(NO)(2)}(9) DNIC [(ONO)(2)Fe(NO)(2)](-) constructed by two monodentate O-bound nitrito ligands, the weak interaction between Fe(1) and the distal oxygens O(5)/O(7) of nitrato-coordinated ligands (Fe(1)···O(5) and Fe(1)···O(7) distances of 2.582(2) and 2.583(2) Å, respectively) may play important roles in stabilizing DNIC 3. Transformation of nitrate-containing DNIC 3 into N-bound nitro {Fe(NO)}(6) [(NO)(κ(1)-NO(2))Fe(S(2)CNEt(2))(2)] (7) triggered by bis(diethylthiocarbamoyl) disulfide ((S(2)CNEt(2))(2)) implicates that nitrate-to-nitrite conversion may occur via the intramolecular association of the coordinated nitrate and the adjacent polarized NO-coordinate ligand (nitrosonium) of the proposed {Fe(NO)(2)}(7) intermediate [(NO)(2)(κ(1)-ONO(2))Fe(S(2)CNEt(2))(2)] (A) yielding {Fe(NO)}(7) [(NO)Fe(S(2)CNEt(2))(2)] (6) along with the release of N(2)O(4) (·NO(2)) and the subsequent binding of ·NO(2) to complex 6. The N-bound nitro {Fe(NO)}(6) complex 7 undergoes Me(2)S-promoted O-atom transfer facilitated by imidazole to give {Fe(NO)}(7) complex 6 accompanied by release of nitric oxide. This result demonstrates that nitrate-containing DNIC 3 acts as an active center to modulate nitrate-to-nitrite-to-nitric oxide conversion.

  11. Hexamethoxylated Monocarbonyl Analogues of Curcumin Cause G2/M Cell Cycle Arrest in NCI-H460 Cells via Michael Acceptor-Dependent Redox Intervention.

    PubMed

    Li, Yan; Zhang, Li-Ping; Dai, Fang; Yan, Wen-Jing; Wang, Hai-Bo; Tu, Zhi-Shan; Zhou, Bo

    2015-09-09

    Curcumin, derived from the dietary spice turmeric, holds promise for cancer prevention. This prompts much interest in investigating the action mechanisms of curcumin and its analogues. Two symmetrical hexamethoxy-diarylpentadienones (1 and 2) as cucumin analogues were reported to possess significantly enhanced cytotoxicity compared with the parent molecule. However, the detailed mechanisms remain unclear. In this study, compounds 1 and 2 were identified as the G2/M cell cycle arrest agents to mediate the cytotoxicity toward NCI-H460 cells via Michael acceptor-dependent redox intervention. Compared with curcumin, they could more easily induce a burst of reactive oxygen species (ROS) and collapse of the redox buffering system. One possible reason is that they could more effectively target intracellular TrxR to convert this antioxidant enzyme into a ROS promoter. Additionally, they caused up-regulation of p53 and p21 and down-regulation of redox-sensitive Cdc25C along with cyclin B1/Cdk1 in a Michael acceptor- and ROS-dependent fashion. Interestingly, in comparison with compound 2, compound 1 displayed a relatively weak ability to generate ROS but increased cell cycle arrest activity and cytotoxicity probably due to its Michael acceptor-dependent microtubule-destabilizing effect and greater GST-inhibitory activity, as well as its enhanced cellular uptake. This work provides useful information for understanding Michael acceptor-dependent and redox-mediated cytotoxic mechanisms of curcumin and its active analogues.

  12. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    USGS Publications Warehouse

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

    2017-01-01

    Nitrate has become an increasingly abundant potential electron acceptor for Fe(II) oxidation in groundwater, but this redox couple has not been well characterized within aquifer settings. To investigate this reaction and some of its implications for redox-sensitive groundwater contaminants, we conducted an in situ field study in a wastewater-contaminated aquifer on Cape Cod. Long-term (15 year) geochemical monitoring within the contaminant plume indicated interacting zones with variable nitrate-, Fe(II)-, phosphate-, As(V)-, and As(III)-containing groundwater. Nitrate and phosphate were derived predominantly from wastewater disposal, whereas Fe(II), As(III), and As(V) were mobilized from the aquifer sediments. Multiple natural gradient, anoxic tracer tests were conducted in which nitrate and bromide were injected into nitrate-free, Fe(II)-containing groundwater. Prior to injection, aqueous Fe(II) concentrations were approximately 175 μM, but sorbed Fe(II) accounted for greater than 90% of the total reactive Fe(II) in the aquifer. Nitrate reduction was stimulated within 1 m of transport for 100 μM and 1000 μM nitrate additions, initially producing stoichiometric quantities of nitrous oxide (>300 μM N). In subsequent injections at the same site, nitrate was reduced even more rapidly and produced less nitrous oxide, especially over longer transport distances. Fe(II) and nitrate concentrations decreased together and were accompanied by Fe(III) oxyhydroxide precipitation and decreases in dissolved phosphate, As(III), and As(V) concentrations. Nitrate N and O isotope fractionation effects during nitrate reduction were approximately equal (ε15N/ε18O = 1.11) and were similar to those reported for laboratory studies of biological nitrate reduction, including denitrification, but unlike some reported effects on nitrate by denitrification in aquifers. All constituents affected by the in situ tracer experiments returned to pre-injection levels after several

  13. Hybrid respiration in the denitrifying mitochondria of Fusarium oxysporum.

    PubMed

    Takaya, Naoki; Kuwazaki, Seigo; Adachi, Yoshiaki; Suzuki, Sawako; Kikuchi, Tomoko; Nakamura, Hiro; Shiro, Yoshitsugu; Shoun, Hirofumi

    2003-04-01

    Induction of the mitochondrial nitrate-respiration (denitrification) system of the fungus Fusarium oxysporum requires the supply of low levels of oxygen (O(2)). Here we show that O(2) and nitrate (NO(3)(-)) respiration function simultaneously in the mitochondria of fungal cells incubated under hypoxic, denitrifying conditions in which both O(2) and NO(3)(-) act as the terminal electron acceptors. The NO(3)(-) and nitrite (NO(2)(-)) reductases involved in fungal denitrification share the mitochondrial respiratory chain with cytochrome oxidase. F. oxysporum cytochrome c(549) can serve as an electron donor for both NO(2)(-) reductase and cytochrome oxidase. We are the first to demonstrate hybrid respiration in respiring eukaryotic mitochondria.

  14. Arabidopsis Nitrate Transporter NRT1.9 Is Important in Phloem Nitrate Transport[W][OA

    PubMed Central

    Wang, Ya-Yun; Tsay, Yi-Fang

    2011-01-01

    This study of the Arabidopsis thaliana nitrate transporter NRT1.9 reveals an important function for a NRT1 family member in phloem nitrate transport. Functional analysis in Xenopus laevis oocytes showed that NRT1.9 is a low-affinity nitrate transporter. Green fluorescent protein and β-glucuronidase reporter analyses indicated that NRT1.9 is a plasma membrane transporter expressed in the companion cells of root phloem. In nrt1.9 mutants, nitrate content in root phloem exudates was decreased, and downward nitrate transport was reduced, suggesting that NRT1.9 may facilitate loading of nitrate into the root phloem and enhance downward nitrate transport in roots. Under high nitrate conditions, the nrt1.9 mutant showed enhanced root-to-shoot nitrate transport and plant growth. We conclude that phloem nitrate transport is facilitated by expression of NRT1.9 in root companion cells. In addition, enhanced root-to-shoot xylem transport of nitrate in nrt1.9 mutants points to a negative correlation between xylem and phloem nitrate transport. PMID:21571952

  15. Minimizing the effects of oxygen interference on l-lactate sensors by a single amino acid mutation in Aerococcus viridansl-lactate oxidase.

    PubMed

    Hiraka, Kentaro; Kojima, Katsuhiro; Lin, Chi-En; Tsugawa, Wakako; Asano, Ryutaro; La Belle, Jeffrey T; Sode, Koji

    2018-04-30

    l-lactate biosensors employing l-lactate oxidase (LOx) have been developed mainly to measure l-lactate concentration for clinical diagnostics, sports medicine, and the food industry. Some l-lactate biosensors employ artificial electron mediators, but these can negatively impact the detection of l-lactate by competing with the primary electron acceptor: molecular oxygen. In this paper, a strategic approach to engineering an AvLOx that minimizes the effects of oxygen interference on sensor strips was reported. First, we predicted an oxygen access pathway in Aerococcus viridans LOx (AvLOx) based on its crystal structure. This was subsequently blocked by a bulky amino acid substitution. The resulting Ala96Leu mutant showed a drastic reduction in oxidase activity using molecular oxygen as the electron acceptor and a small increase in dehydrogenase activity employing an artificial electron acceptor. Secondly, the Ala96Leu mutant was immobilized on a screen-printed carbon electrode using glutaraldehyde cross-linking method. Amperometric analysis was performed with potassium ferricyanide as an electron mediator under argon or atmospheric conditions. Under argon condition, the response current increased linearly from 0.05 to 0.5mM l-lactate for both wild-type and Ala96Leu. However, under atmospheric conditions, the response of wild-type AvLOx electrode was suppressed by 9-12% due to oxygen interference. The Ala96Leu mutant maintained 56-69% of the response current at the same l-lactate level and minimized the relative bias error to -19% from -49% of wild-type. This study provided significant insight into the enzymatic reaction mechanism of AvLOx and presented a novel approach to minimize oxygen interference in sensor applications, which will enable accurate detection of l-lactate concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Theoretical Study of the Mechanism Behind the para-Selective Nitration of Toluene in Zeolite H-Beta

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Andersen, Amity; Govind, Niranjan; Subramanian, Lalitha

    Periodic density functional theory calculations were performed to investigate the origin of the favorable para-selective nitration of toluene exhibited by zeolite H-beta with acetyl nitrate nitration agent. Energy calculations were performed for each of the 32 crystallographically unique Bronsted acid sites of a beta polymorph B zeolite unit cell with multiple Bronsted acid sites of comparable stability. However, one particular aluminum T-site with three favorable Bronsted site oxygens embedded in a straight 12-T channel wall provides multiple favorable proton transfer sites. Transition state searches around this aluminum site were performed to determine the barrier to reaction for both para andmore » ortho nitration of toluene. A three-step process was assumed for the nitration of toluene with two organic intermediates: the pi- and sigma-complexes. The rate limiting step is the proton transfer from the sigma-complex to a zeolite Bronsted site. The barrier for this step in ortho nitration is shown to be nearly 2.5 times that in para nitration. This discrepancy appears to be due to steric constraints imposed by the curvature of the large 12-T pore channels of beta and the toluene methyl group in the ortho approach that are not present in the para approach.« less

  17. A survey of acceptor dopants for β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Lyons, John L.

    2018-05-01

    With a wide band gap, high critical breakdown voltage and commercially available substrates, Ga2O3 is a promising material for next-generation power electronics. Like most wide-band-gap semiconductors, obtaining better control over its electrical conductivity is critically important, but has proven difficult to achieve. Although efficient p-type doping in Ga2O3 is not expected, since theory and experiment indicate the self-trapping of holes, the full development of this material will require a better understanding of acceptor dopants. Here the properties of group 2, group 5 and group 12 acceptor impurities in β-Ga2O3 are explored using hybrid density functional calculations. All impurities are found to exhibit acceptor transition levels above 1.3 eV. After examining formation energies as a function of chemical potential, Mg (followed closely by Be) is determined to be the most stable acceptor species.

  18. Nitrate fertilisation does not enhance CO2 responses in two tropical seagrass species

    NASA Astrophysics Data System (ADS)

    Ow, Y. X.; Vogel, N.; Collier, C. J.; Holtum, J. A. M.; Flores, F.; Uthicke, S.

    2016-03-01

    Seagrasses are often considered “winners” of ocean acidification (OA); however, seagrass productivity responses to OA could be limited by nitrogen availability, since nitrogen-derived metabolites are required for carbon assimilation. We tested nitrogen uptake and assimilation, photosynthesis, growth, and carbon allocation responses of the tropical seagrasses Halodule uninervis and Thalassia hemprichii to OA scenarios (428, 734 and 1213 μatm pCO2) under two nutrients levels (0.3 and 1.9 μM NO3-). Net primary production (measured as oxygen production) and growth in H. uninervis increased with pCO2 enrichment, but were not affected by nitrate enrichment. However, nitrate enrichment reduced whole plant respiration in H. uninervis. Net primary production and growth did not show significant changes with pCO2 or nitrate by the end of the experiment (24 d) in T. hemprichii. However, nitrate incorporation in T. hemprichii was higher with nitrate enrichment. There was no evidence that nitrogen demand increased with pCO2 enrichment in either species. Contrary to our initial hypothesis, nutrient increases to levels approximating present day flood plumes only had small effects on metabolism. This study highlights that the paradigm of increased productivity of seagrasses under ocean acidification may not be valid for all species under all environmental conditions.

  19. Nitrate fertilisation does not enhance CO2 responses in two tropical seagrass species.

    PubMed

    Ow, Y X; Vogel, N; Collier, C J; Holtum, J A M; Flores, F; Uthicke, S

    2016-03-15

    Seagrasses are often considered "winners" of ocean acidification (OA); however, seagrass productivity responses to OA could be limited by nitrogen availability, since nitrogen-derived metabolites are required for carbon assimilation. We tested nitrogen uptake and assimilation, photosynthesis, growth, and carbon allocation responses of the tropical seagrasses Halodule uninervis and Thalassia hemprichii to OA scenarios (428, 734 and 1213 μatm pCO2) under two nutrients levels (0.3 and 1.9 μM NO3(-)). Net primary production (measured as oxygen production) and growth in H. uninervis increased with pCO2 enrichment, but were not affected by nitrate enrichment. However, nitrate enrichment reduced whole plant respiration in H. uninervis. Net primary production and growth did not show significant changes with pCO2 or nitrate by the end of the experiment (24 d) in T. hemprichii. However, nitrate incorporation in T. hemprichii was higher with nitrate enrichment. There was no evidence that nitrogen demand increased with pCO2 enrichment in either species. Contrary to our initial hypothesis, nutrient increases to levels approximating present day flood plumes only had small effects on metabolism. This study highlights that the paradigm of increased productivity of seagrasses under ocean acidification may not be valid for all species under all environmental conditions.

  20. Benthic metabolism and nitrogen dynamics in an urbanised tidal creek: Domination of DNRA over denitrification as a nitrate reduction pathway

    NASA Astrophysics Data System (ADS)

    Dunn, Ryan J. K.; Robertson, David; Teasdale, Peter R.; Waltham, Nathan J.; Welsh, David T.

    2013-10-01

    Benthic oxygen and nutrient fluxes and nitrate reduction rates were determined seasonally under light and dark conditions at three sites in a micro-tidal creek within an urbanised catchment (Saltwater Creek, Australia). It was hypothesized that stormwater inputs of organic matter and inorganic nitrogen would stimulate rates of benthic metabolism and nutrient recycling and preferentially stimulate dissimilatory nitrate reduction to ammonium (DNRA) over denitrification as a pathway for nitrate reduction. Stormwaters greatly influenced water column dissolved inorganic nitrogen (DIN) and suspended solids concentrations with values following a large rainfall event being 5-20-fold greater than during the preceding dry period. Seasonally, maximum and minimum water column total dissolved nitrogen (TDN) and DIN concentrations occurred in the summer (wet) and winter (dry) seasons. Creek sediments were highly heterotrophic throughout the year, and strong sinks for oxygen, and large sources of dissolved organic and inorganic nitrogen during both light and dark incubations, although micro-phytobenthos (MPB) significantly decreased oxygen consumption and N-effluxes during light incubations due to photosynthetic oxygen production and photoassimilation of nutrients. Benthic denitrification rates ranged from 3.5 to 17.7 μmol N m2 h-1, denitrification efficiencies were low (<1-15%) and denitrification was a minor process compared to DNRA, which accounted for ˜75% of total nitrate reduction. Overall, due to the low denitrification efficiencies and high rates of N-regeneration, Saltwater Creek sediments would tend to increase rather than reduce dissolved nutrient loads to the downstream Gold Coast Broadwater and Moreton Bay systems. This may be especially true during wet periods when increased inputs of particulate organic nitrogen (PON) and suspended solids could respectively enhance rates of N-regeneration and decrease light availability to MPB, reducing their capacity to

  1. Hybrid coconut seedlings, scholarships, and discount cards for family planning acceptors.

    PubMed

    Sumarsono

    1989-10-01

    Having learned from failed family planning (FP) incentive schemes in other countries, Indonesia implemented a reward system designed to popularize FP in the community. In order to overcome cultural opposition to FP, many countries in the 1970s opted to give incentives--money, materials, etc.--to new contraceptive acceptors and the FP workers who successfully recruited them. These countries, which oftentimes spent up to 1/4 of their program budget on incentives, saw rapid increases in the number of new acceptors. The results, however, only reflected a superficial acceptance of FP. When the incentives stopped, the number of acceptors dropped considerably. Recognizing this, the Indonesian government set out to increase FP acceptance by making the small family the norm in the community. And one of the approaches for doing so was a reward system. The goals of the reward program were: 1) to raise awareness of the recognition given to individuals or groups that have accepted FP; 2) to create pride among FP workers and new acceptors; and 3) to generate leadership in the community. Villages with high FP acceptance receive rewards such as deep-wells that provide clean water or income generating projects. Individuals also receive rewards that sometimes include hybrid coconut seedlings which, after 3 years, can yield up to 700 coconuts, which can provide a family with a significant supplemental income. The government also gives scholarships to children of FP acceptors. Also, the president of Indonesia publicly recognized family planning acceptors. In 1989, over 800,000 couples received awards for practicing contraception over the past 5-16 years.

  2. Acceptor Products of Alternansucrase with Gentiobiose

    USDA-ARS?s Scientific Manuscript database

    In the presence of suitable acceptor molecules, dextransucrase makes a homologous series of oligosaccharides in which the isomers differ by a single glucosyl unit, whereas alternansucrase synthesizes one trisaccharide, two tetrasaccharides, etc. Previously, we showed that alternansucrase only forms...

  3. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(-)-myrtenol nitrate.

    PubMed

    Bew, Sean P; Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Here we report the chemoselective synthesis of several important, climate relevant isoprene nitrates using silver nitrate to mediate a 'halide for nitrate' substitution. Employing readily available starting materials, reagents and Horner-Wadsworth-Emmons chemistry the synthesis of easily separable, synthetically versatile 'key building blocks' (E)- and (Z)-3-methyl-4-chlorobut-2-en-1-ol as well as (E)- and (Z)-1-((2-methyl-4-bromobut-2-enyloxy)methyl)-4-methoxybenzene has been achieved using cheap, 'off the shelf' materials. Exploiting their reactivity we have studied their ability to undergo an 'allylic halide for allylic nitrate' substitution reaction which we demonstrate generates (E)- and (Z)-3-methyl-4-hydroxybut-2-enyl nitrate, and (E)- and (Z)-2-methyl-4-hydroxybut-2-enyl nitrates ('isoprene nitrates') in 66-80% overall yields. Using NOESY experiments the elucidation of the carbon-carbon double bond configuration within the purified isoprene nitrates has been established. Further exemplifying our 'halide for nitrate' substitution chemistry we outline the straightforward transformation of (1R,2S)-(-)-myrtenol bromide into the previously unknown monoterpene nitrate (1R,2S)-(-)-myrtenol nitrate.

  4. Nitrate Transport Is Independent of NADH and NAD(P)H Nitrate Reductases in Barley Seedlings 1

    PubMed Central

    Warner, Robert L.; Huffaker, Ray C.

    1989-01-01

    Barley (Hordeum vulgare L.) has NADH-specific and NAD(P)H-bispecific nitrate reductase isozymes. Four isogenic lines with different nitrate reductase isozyme combinations were used to determine the role of NADH and NAD(P)H nitrate reductases on nitrate transport and assimilation in barley seedlings. Both nitrate reductase isozymes were induced by nitrate and were required for maximum nitrate assimilation in barley seedlings. Genotypes lacking the NADH isozyme (Az12) or the NAD(P)H isozyme (Az70) assimilated 65 or 85%, respectively, as much nitrate as the wild type. Nitrate assimilation by genotype (Az12;Az70) which is deficient in both nitrate reductases, was only 13% of the wild type indicating that the NADH and NAD(P)H nitrate reductase isozymes are responsible for most of the nitrate reduction in barley seedlings. For all genotypes, nitrate assimilation rates in the dark were about 55% of the rates in light. Hypotheses that nitrate reductase has direct or indirect roles in nitrate uptake were not supported by this study. Induction of nitrate transporters and the kinetics of net nitrate uptake were the same for all four genotypes indicating that neither nitrate reductase isozyme has a direct role in nitrate uptake in barley seedlings. PMID:11537465

  5. Bioelectrode-based approach for enhancing nitrate and nitrite removal and electricity generation from eutrophic lakes.

    PubMed

    Zhang, Yifeng; Angelidaki, Irini

    2012-12-01

    Nitrate and nitrite contamination of surface waters (e.g. lakes) has become a severe environmental and health problem, especially in developing countries. The recent demonstration of nitrate reduction at the cathode of microbial fuel cell (MFC) provides an opportunity to develop a new technology for nitrogen removal from surface waters. In this study, a sediment-type MFC based on two pieces of bioelectrodes was employed as a novel in situ applicable approach for nitrogen removal, as well as electricity production from eutrophic lakes. Maximum power density of 42 and 36 mW/m(2) was produced respectively from nitrate- and nitrite-rich synthetic lake waters at initial concentration of 10 mg-N/L. Along with the electricity production a total nitrogen removal of 62% and 77% was accomplished, for nitrate and nitrite, respectively. The nitrogen removal was almost 4 times higher under close-circuit condition with biocathode, compared to either the open-circuit operation or with abiotic cathode. The mass balance on nitrogen indicates that most of the removed nitrate and nitrite (84.7 ± 0.1% and 81.8 ± 0.1%, respectively) was reduced to nitrogen gas. The nitrogen removal and power generation was limited by the dissolved oxygen (DO) level in the water and acetate level injected to the sediment. Excessive oxygen resulted in dramatically decrease of nitrogen removal efficiency and only 7.8% removal was obtained at DO level of 7.8 mg/l. The power generation and nitrogen removal increased with acetate level and was nearly saturated at 0.84 mg/g-sediment. This bioelectrode-based in situ approach is attractive not only due to the electricity production, but also due to no need of extra reactor construction, which may broaden the application possibilities of sediment MFC technology. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Enhanced thermoelectric property of oxygen deficient nickel doped SnO2 for high temperature application

    NASA Astrophysics Data System (ADS)

    Paulson, Anju; Sabeer, N. A. Muhammad; Pradyumnan, P. P.

    2018-04-01

    Motivated by the detailed investigation on the thermoelectric performance of oxide materials our work concentrated on the influence of acceptor dopants and defect density in the lattice plane for the enhancement of thermoelectric power. The series of Sn1‑x Nix O2 (0.01 ≤ x ≤ 0.05) compositions were prepared by solid state reaction mechanism and found that 3 atomic percentage Ni doped SnO2 can be considered as a good candidate due to its promising electrical and transport properties. Defect lattices were introduced in the sample and the deviation from oxygen stochiometry was ensured using photoluminescence measurement. High power factor was obtained for the 3 atomic percentage nickel doped SnO2 due to the effective number of charge carrier concentration and the depletion of oxygen rich layers. Defect centered and acceptor doped SnO2 lattice opens a new door for energy harvesting at higher temperatures.

  7. Nitrated carbon nanoblisters for high-performance glucose dehydrogenase bioanodes.

    PubMed

    de Souza, João C P; Iost, Rodrigo M; Crespilho, Frank N

    2016-03-15

    Recently, many strategies are being explored for efficiently wiring glucose dehydrogenase (GDh) enzymes capable of glucose (fuel) oxidation. For instance, the use of GDh NAD(+)-dependent for glucose oxidation is of great interest in biofuel cell technology because the enzyme are unaffected by the presence of molecular oxygen commonly present in electrolyte. Here we present the fabrication of flexible carbon fibers modified with nitrated carbon nanoblisters and their application as high-performance GDh bioanodes. These bioelectrodes could electro-oxidize glucose at -360 mV (vs. Ag/AgClsat) in the presence of a molecular oxygen saturated electrolyte with current densities higher than 1.0 mAcm(-2) at 0.0 V. It is corroborated by open circuit potential, where a potential stabilization occurs at -150 mV in a long term stability current-transient experiment. This value is in agreement with the quasi-steady current obtained at very low scan rate (0.1 mVs(-1)), where the onset potential for glucose oxidation is -180 mV. X-ray photoelectron spectroscopy and scanning electron microscopy revealed that the nitrated blisters and edge-like carbon structures, enabling highly efficient enzyme immobilization and low overpotential for electron transfer, allowing for glucose oxidation with potential values close to the thermodynamic cofactor. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Particulate Pyrite Autotrophic Denitrification (PPAD) for Remediation of Nitrate-contaminated Groundwater

    NASA Astrophysics Data System (ADS)

    Tong, S.; Rodriguez-Gonzalez, L. C.; Henderson, M.; Feng, C.; Ergas, S. J.

    2015-12-01

    The rapid movement of human civilization towards urbanization, industrialization, and increased agricultural activities has introduced a large amount of nitrate into groundwater. Nitrate is a toxic substance discharged from groundwater to rivers and leads to decreased dissolved oxygen and eutrophication. For this experiment, an electron donor is needed to convert nitrate into non-toxic nitrogen gas. Pyrite is one of the most abundant minerals in the earth's crust making it an ideal candidate as an electron donor. The overall goal of this research was to investigate the potential for pyrite to be utilized as an electron donor for autotrophic denitrification of nitrate-contaminated groundwater. Batch studies of particulate pyrite autotrophic denitrification (PPAD) of synthetic groundwater (100 mg NO3--N L-1) were set up with varying biomass concentration, pyrite dose, and pyrite particle size. Reactors were seeded with mixed liquor volatile suspended solids (VSS) from a biological nitrogen removal wastewater treatment facility. PPAD using small pyrite particles (<0.45mm) resulted in a favorable nitrate removal. The nitrate removal rate increased from 0.26 to 0.34 mg L-1h-1 and then to 0.86 mg L-1h-1, approaching that of the sulfur oxidizing denitrification (SOD) rate of 1.19 mg L-1h-1. Based on Box-Behnken design (BBD) and response surface methodology (RSM), the optimal amount of biomass concentration, pyrite dose, and pyrite particle size were 1,250 mg VSS L-1, 125 g L-1, and 0.815-1.015 mm, respectively. PPAD exhibited substantial nitrate removal rate, lower sulfate accumulation (5.46 mg SO42-/mg NO3--N) and lower alkalinity consumption (1.70 mg CaCO3/mg NO3--N) when compared to SOD (7.54 mg SO42-/mg NO3--N, 4.57 mg CaCO3/mg NO3--N based on stoichiometric calculation). This research revealed that the PPAD process is a promising technique for nitrate-contaminated groundwater treatment and promoted the utilization of pyrite in the field of environmental remediation.

  9. Donor-Acceptor-Collector Ternary Crystalline Films for Efficient Solid-State Photon Upconversion.

    PubMed

    Ogawa, Taku; Hosoyamada, Masanori; Yurash, Brett; Nguyen, Thuc-Quyen; Yanai, Nobuhiro; Kimizuka, Nobuo

    2018-06-25

    It is pivotal to achieve efficient triplet-triplet annihilation based photon upconversion (TTA-UC) in the solid-state for enhancing potentials of renewable energy production devices. However, the UC efficiency of solid materials is largely limited by low fluorescence quantum yields that originate from the aggregation of TTA-UC chromophores, and also by severe back energy transfer from the acceptor singlet state to the singlet state of the triplet donor in the condensed state. In this work, to overcome these issues, we introduce a highly fluorescent singlet energy collector as the third component of donor-doped acceptor crystalline films, in which dual energy migration, i.e., triplet energy migration for TTA-UC and succeeding singlet energy migration for transferring energy to a collector, takes place. To demonstrate this scheme, a highly fluorescent singlet energy collector was added as the third component of donor-doped acceptor crystalline films. An anthracene-based acceptor containing alkyl chains and a carboxylic moiety is mixed with the triplet donor Pt(II) octaethylporphyrin (PtOEP) and the energy collector 2,5,8,11-tetra- tert-butylperylene (TTBP) in solution, and spin-coating of the mixed solution gives acceptor films of nanofibrous crystals homogeneously doped with PtOEP and TTBP. Interestingly, delocalized singlet excitons in acceptor crystals are found to diffuse effectively over the distance of ~37 nm. Thanks to this high diffusivity, only 0.5 mol% of doped TTBP can harvest most of the singlet excitons, which successfully doubles the solid-state fluorescent quantum yield of acceptor/TTBP blend films to 76%. Furthermore, since the donor PtOEP and the collector TTBP are separately isolated in the nanofibrous acceptor crystals, the singlet back energy transfer from the collector to the donor is effectively avoided. Such efficient singlet energy collection and inhibited back energy transfer processes result in a large increase of UC efficiency up to 9

  10. Photoinduced electron transfer in fixed distance chlorophyll-quinone donor-acceptor molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.

    1987-01-01

    A series of fixed distance chlorophyll-quinone donor-acceptor molecules have been prepared. The donor consists of either methyl pyropheophorbide a or methyl pyrochlorophyllide a, while the acceptor is either benzoquinone or naphthoquinone. The acceptors are fused to a triptycene spacer group, which in turn is attached to the donors at their vinyl groups. Picosecond transient absorption measurements have been used to identify electron transfer from the lowest excited singlet state of the donor to the acceptor as the mechanism of fluorescence quenching in these molecules. The charge separation rate constants increase from 2 x 10/sup 10/ s/sup -1/ to 4 xmore » 10/sup 11/ s/sup -1/ as the free energy of charge separation increases, while the radical pair recombination rate constants decrease from 1.2 x 10/sup 11/ s/sup -1/ to 2 x 10/sup 9/ s/sup -1/ as the free energy of recombination increases. The resulting total reorganization energy lambda = 0.9 eV.« less

  11. The use and control of nitrate and nitrite for the processing of meat products.

    PubMed

    Honikel, Karl-Otto

    2008-01-01

    Nitrate and nitrite are used for the purpose of curing meat products. In most countries the use of both substances, usually added as potassium or sodium salts, is limited. Either the ingoing or the residual amounts are regulated by laws. The effective substance is nitrite acting primarily as an inhibitor for some microorganisms. Nitrite added to a batter of meat is partially oxidized to nitrate by sequestering oxygen - thus it acts as an antioxidant - a part of nitrite is bound to myoglobin, forming the heat stable NO-myoglobin, a part is bound to proteins or other substances in meat. Nitrate may be reduced to nitrite in raw meat products by microorganisms. As oxidation and reduction may occur the concentrations of nitrite plus nitrate in a product has to be controlled and measured especially if the residual amounts are regulated. This sum of both compounds is important for the human body. Intake of nitrate with food leads to its absorption over the digestive tract into the blood. In the oral cavity nitrate appears again where it is reduced to nitrite. With the saliva the nitrite is mixed with food, having the same effect as nitrite in a batter (inhibiting growth of some pathogenic microorganisms) and swallowed. In the stomach nitrite can eventually form carcinogenic nitrosamines in the acidic environment.

  12. An unexpected truth: increasing nitrate loading can decrease nitrate export from watersheds

    NASA Astrophysics Data System (ADS)

    Askarizadeh Bardsiri, A.; Grant, S. B.; Rippy, M.

    2015-12-01

    The discharge of anthropogenic nitrate (e.g., from partially treated sewage, return flows from agricultural irrigation, and runoff from animal feeding operations) to streams can negatively impact both human and ecosystem health. Managing these many point and non-point sources to achieve some specific end-point—for example, reducing the annual mass of nitrate exported from a watershed—can be a challenge, particularly in rapidly growing urban areas. Adding to this complexity is the fact that streams are not inert: they too can add or remove nitrate through assimilation (e.g., by stream-associated plants and animals) and microbially-mediated biogeochemical reactions that occur in streambed sediments (e.g., respiration, ammonification, nitrification, denitrification). By coupling a previously published correlation for in-stream processing of nitrate [Mulholland et al., Nature, 2008, 452, 202-205] with a stream network model of the Jacksons Creek watershed (Victoria, Australia) I demonstrate that managing anthropogenic sources of stream nitrate without consideration of in-stream processing can result in a number of non-intuitive "surprises"; for example, wastewater effluent discharges that increase nitrate loading but decrease in-stream nitrate concentrations can reduce the mass of nitrate exported from a watershed.

  13. Nitration of naphthalene and remarks on the mechanism of electrophilic aromatic nitration.

    PubMed

    Olah, G A; Narang, S C; Olah, J A

    1981-06-01

    Naphthalene was nitrated with a variety of nitrating agents. Comparison of data with Perrin's electrochemical nitration [Perrin, C. L. (1977) J. Am. Chem. Soc. 99, 5516-5518] shows that nitration of naphthalene gives an alpha-nitronaphthalene to beta-nitronaphthalene ratio that varies between 9 and 29 and is thus not constant. Perrin's data, therefore, are considered to be inconclusive evidence for the proposed one-electron transfer mechanism for the nitration of naphthalene and other reactive aromatics. Moodie and Schoefield [Hoggett, J. G., Moodie, R. B., Penton, J. R. & Schoefield, K. (1971) Nitration and Aromatic Reactivity (Cambridge Univ. Press, London)], as well as Perrin, independently concluded that, in the general scheme of nitration of reactive aromatics, there is the necessity to introduce into the classical Ingold mechanism an additional step involving a distinct intermediate preceding the formation of the Wheland intermediate (sigma complexes). This view coincides with our two-step mechanistic picture [Kuhn, S. J. & Olah, G. A. (1961) J. Am. Chem. Soc. 83, 4564-4571] of the nitronium salt nitration of aromatic hydrocarbons (including benzene and toluene), in which low substrate selectivity but high positional selectivity was found, indicating the independence of substrate from positional selectivity.

  14. Nitration of naphthalene and remarks on the mechanism of electrophilic aromatic nitration*

    PubMed Central

    Olah, George A.; Narang, Subhash C.; Olah, Judith A.

    1981-01-01

    Naphthalene was nitrated with a variety of nitrating agents. Comparison of data with Perrin's electrochemical nitration [Perrin, C. L. (1977) J. Am. Chem. Soc. 99, 5516-5518] shows that nitration of naphthalene gives an α-nitronaphthalene to β-nitronaphthalene ratio that varies between 9 and 29 and is thus not constant. Perrin's data, therefore, are considered to be inconclusive evidence for the proposed one-electron transfer mechanism for the nitration of naphthalene and other reactive aromatics. Moodie and Schoefield [Hoggett, J. G., Moodie, R. B., Penton, J. R. & Schoefield, K. (1971) Nitration and Aromatic Reactivity (Cambridge Univ. Press, London)], as well as Perrin, independently concluded that, in the general scheme of nitration of reactive aromatics, there is the necessity to introduce into the classical Ingold mechanism an additional step involving a distinct intermediate preceding the formation of the Wheland intermediate (σ complexes). This view coincides with our two-step mechanistic picture [Kuhn, S. J. & Olah, G. A. (1961) J. Am. Chem. Soc. 83, 4564-4571] of the nitronium salt nitration of aromatic hydrocarbons (including benzene and toluene), in which low substrate selectivity but high positional selectivity was found, indicating the independence of substrate from positional selectivity. PMID:16593026

  15. Alkali metal nitrate purification

    DOEpatents

    Fiorucci, Louis C.; Morgan, Michael J.

    1986-02-04

    A process is disclosed for removing contaminants from impure alkali metal nitrates containing them. The process comprises heating the impure alkali metal nitrates in solution form or molten form at a temperature and for a time sufficient to effect precipitation of solid impurities and separating the solid impurities from the resulting purified alkali metal nitrates. The resulting purified alkali metal nitrates in solution form may be heated to evaporate water therefrom to produce purified molten alkali metal nitrates suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of purified alkali metal nitrates.

  16. Tracing Nitrate Deposition Using Δ 17O

    NASA Astrophysics Data System (ADS)

    Michalski, G m; Hernandez, L.; Meixner, T.; Fenn, M.; Thiemens, M.

    2001-12-01

    Assessing the impact of atmospheric deposition of fixed nitrogen on local, regional, and global biogeochemical cycles has received much attention in recent years. Local and regional ecosystems can suffer from eutrophication and shrinking biodiversity from the increased nitrogen flux, in addition to degradation associated with acid rain ( an increasing proportion of which is as HNO3 ). On a global scale, the effect of nitrogen fertilization on CO2 uptake rates is one of the biggest unknowns in global warming research. This renewed interest has led to new attempts to utilize current, and in the development of new, analytical techniques in order to better understand the source, sink and transport mechanisms of atmospheric nitrogen deposition. Its role as the primary sink of the NOx cycle makes atmospheric nitrate (as particulate nitrate or nitric acid ) the primary source of nitrogen deposition. Stable isotopes of nitrogen and oxygen have been used by several researchers to trace atmospheric nitrate through the biogeochemical system. 15N ratios have been problematic due to the lack of large fractionations and an overlap of 15N ratios between sources. Initial studies of 18O ratios showed promise due to the large enrichment (60 ‰ ) in atmospheric nitrate. However, subsequent studies showed an δ 18O spread of 25 - 80 ‰ and have made quantitative analysis of mixing reservoirs difficult. No studies of δ 17O nitrates have been published. For δ 17O, thermodynamic, kinetic, and equilibrium isotope effects dictate that δ 17O = .52 x δ 18O . Certain photochemical processes violate this rule due to quantum effects and are quantified by Δ 17O = δ 17O -.52 x δ 18O which are called mass independent fractionations (MIF). Atmospheric nitrates have now been measured and have been found to have a large MIF; Δ 17O ~ 25 ‰ and a small range +/- 4‰ . The large variations in δ 18O of atmospheric nitrate are due to mass dependent fractions from transport and source ratios

  17. Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

    NASA Astrophysics Data System (ADS)

    Fang, Y. T.; Koba, K.; Wang, X. M.; Wen, D. Z.; Li, J.; Takebayashi, Y.; Liu, X. Y.; Yoh, M.

    2010-09-01

    Nitric acid (HNO3) or nitrate (NO3-) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we used the denitrifier method to measure nitrogen (N) and oxygen (O) isotopic composition of NO3- in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3- formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3- (versus air N2) ranged from -4.9 to +10.1‰, and averaged +3.9‰ in 2008 and +3.3‰ in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3- were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5‰ (average +65.0‰ and +67.0‰ in 2008 and 2009, respectively), a range being lower than those reported for high altitude and polar areas. Several δ18O values were observed lower than the expected minimum of 50‰ at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3-. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3- in a N-polluted city.

  18. Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China

    NASA Astrophysics Data System (ADS)

    Fang, Y. T.; Koba, K.; Wang, X. M.; Wen, D. Z.; Li, J.; Takebayashi, Y.; Liu, X. Y.; Yoh, M.

    2011-02-01

    Nitric acid (HNO3) or nitrate (NO3-) is the dominant sink for reactive nitrogen oxides (NOx = NO + NO2) in the atmosphere. In many Chinese cities, HNO3 is becoming a significant contributor to acid deposition. In the present study, we measured nitrogen (N) and oxygen (O) isotopic composition of NO3- in 113 precipitation samples collected from Guangzhou City in southern China over a two-year period (2008 and 2009). We attempted to better understand the spatial and seasonal variability of atmospheric NOx sources and the NO3- formation pathways in this N-polluted city in the Pearl River Delta region. The δ15N values of NO3- (versus air N2) ranged from -4.9 to +10.1‰, and averaged +3.9‰ in 2008 and +3.3‰ in 2009. Positive δ15N values were observed throughout the year, indicating the anthropogenic contribution of NOx emissions, particularly from coal combustion. Different seasonal patterns of δ15N-NO3- were observed between 2008 and 2009, which might reflect different human activities associated with the global financial crisis and the intensive preparations for the 16th Asian Games. Nitrate δ18O values (versus Vienna Standard Mean Ocean Water) varied from +33.4 to +86.5‰ (average +65.0‰ and +67.0‰ in 2008 and 2009, respectively), a range being lower than those reported for high latitude and polar areas. Sixteen percent of δ18O values was observed lower than the expected minimum of +55‰ at our study site. This was likely caused by the reaction of NO with peroxy radicals; peroxy radicals can compete with O3 to convert NO to NO2, thereby donate O atoms with much lower δ18O value than that of O3 to atmospheric NO3-. Our results highlight that the influence of human activities on atmospheric chemistry can be recorded by the N and O isotopic composition of atmospheric NO3- in a N-polluted city.

  19. Degradation of TCE, Cr(VI), sulfate, and nitrate mixtures by granular iron in flow-through columns under different microbial conditions.

    PubMed

    Gandhi, Sumeet; Oh, Byung-Taek; Schnoor, Jerald L; Alvarez, Pedro J J

    2002-04-01

    Flow-through aquifer columns packed with a middle layer of granular iron (Fe0) were used to study the applicability and limitations of bio-enhanced Fe0 barriers for the treatment of contaminant mixtures in groundwater. Concentration profiles along the columns showed extensive degradation of hexavalent chromium Cr(VI), nitrate, sulfate, and trichloroethene (TCE), mainly in the Fe0 layer. One column was bioaugmented with Shevanella algae BRY, an iron-reducing bacterium that could enhance Fe0 reactivity by reductive dissolution of passivating iron oxides. This strain did not enhance Cr(VI), which was rapidly reduced by iron, leaving little room for improvement by microbial participation. Nevertheless, BRY-enhanced nitrate removal (from 15% to 80%), partly because this strain has a wide range of electron acceptors, including nitrate. Sulfate was removed (55%) only in a column that was bioaugmented with a mixed culture containing sulfate-reducing bacteria. Apparently, these bacteria used H2 (produced by Fe0 corrosion) as electron donor to respire sulfate. Most of the TCE was degraded in the zone containing Fe0 (50-70%), and bioaugmentation with BRY slightly increased the removal efficiency to about 80%. Microbial colonization of the Fe0 surface was confirmed by scanning electron microscopy.

  20. Reduction of bromate to bromide coupled to acetate oxidation by anaerobic mixed microbial cultures.

    PubMed

    van Ginkel, C G; van Haperen, A M; van der Togt, B

    2005-01-01

    Bromate, a weakly mutagenic oxidizing agent, exists in surface waters. The biodegradation of bromate was investigated by assessing the ability of mixed cultures of micro-organisms for utilization of bromate as electron acceptor and acetate as electron donor. Reduction of bromate was only observed at relatively low concentrations (<3.0 mM) in the absence of molecular oxygen. Under these conditions bromate was reduced stoichiometrically to bromide. Unadapted sludge from an activated sludge treatment plant and a digester reduced bromate without lag period at a constant rate. Using an enrichment culture adapted to bromate, it was demonstrated that bromate was a terminal electron acceptor for anaerobic growth. Approximately 50% of the acetate was utilized for growth with bromate by the enrichment culture. A doubling of 20 h was estimated from a logarithmic growth curve. Other electron acceptors, like perchlorate, chlorate and nitrate, were not reduced or at negligible rates by bromate-utilizing microorganisms.

  1. Process for gasification using a synthetic CO.sub.2 acceptor

    DOEpatents

    Lancet, Michael S.; Curran, George P.

    1980-01-01

    A gasification process is disclosed using a synthetic CO.sub.2 acceptor consisting essentially of at least one compound selected from the group consisting of calcium oxide and calcium carbonate supported in a refractory carrier matrix, the carrier having the general formula Ca.sub.5 (SiO.sub.4).sub.2 CO.sub.3. A method for producing the synthetic CO.sub.2 acceptor is also disclosed.

  2. Effects of oxygen vacancy on the photoconductivity in BaSnO3

    NASA Astrophysics Data System (ADS)

    Park, Jisung; Char, Kookrin; Institute of Applied Physics, Department of Physics; Astronomy, Seoul National University Team

    We have found the photoconductive behavior of BaSnO3, especially their magnitude and time dependence, is very sensitive to the oxygen vacancy concentration. We made epitaxial BaSnO3 film with BaHfO3 buffer layer by pulsed laser deposition. As we had reported before, MgO substrate with its large band gap size about 7.8 eV was used to exclude any photoconductance from the substrate. BaHfO3 layer was used to reduce the threading dislocation density in BaSnO3 film. To control the oxygen vacancy concentration in the BaSnO3 film, we annealed the sample in Ar or O2 atmosphere with varying annealing conditions. After each annealing process, photoconductivity of BaSnO3 was measured during illumination of UV light. The result showed that the magnitude of photoconductivity of BaSnO3 increased after annealing at higher temperature in Ar atmosphere, while the changes in the dark current remains minimal. The result can be explained by a hole trap mechanism. Higher Fermi level due to the increased oxygen vacancy concentration can cause occupation of deep acceptor levels in dislocations of the BaSnO3 film. These occupied deep acceptor levels in turn trap photo-generated holes so that the recombination of electron-hole pair is deterred. Samsung Science and Technology Foundation.

  3. Dye-Incorporated Polynaphthalenediimide Acceptor for Additive-Free High-Performance All-Polymer Solar Cells.

    PubMed

    Chen, Dong; Yao, Jia; Chen, Lie; Yin, Jingping; Lv, Ruizhi; Huang, Bin; Liu, Siqi; Zhang, Zhi-Guo; Yang, Chunhe; Chen, Yiwang; Li, Yongfang

    2018-04-16

    All-polymer solar cells (all-PSCs) can offer unique advantages for applications in flexible devices, and naphthalene diimide (NDI)-based polymer acceptors are the widely used polymer acceptors. However, their power conversion efficiency (PCE) still lags behind that of state-of-the-art polymer solar cells, due to low light absorption, suboptimal energy levels and the strong aggregation of the NDI-based polymer acceptor. Herein, a rhodanine-based dye molecule was introduced into the NDI-based polymer acceptor by simple random copolymerization and showed an improved light absorption coefficient, an up-shifted lowest unoccupied molecular orbital level and reduced crystallization. Consequently, additive-free all-PSCs demonstrated a high PCE of 8.13 %, which is one of the highest performance characteristics reported for all-PSCs to date. These results indicate that incorporating a dye into the n-type polymer gives insight into the precise design of high-performance polymer acceptors for all-PSCs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Analysis of large oxygenated and nitrated polycyclic aromatic hydrocarbons formed under simulated diesel engine exhaust conditions (by compound fingerprints with SPE/LC-API-MS)

    PubMed Central

    Adelhelm, Christoph; Niessner, Reinhard; Pöschl, Ulrich

    2008-01-01

    The analysis of organic compounds in combustion exhaust particles and the chemical transformation of soot by nitrogen oxides are key aspects of assessment and mitigation of the climate and health effects of aerosol emissions from fossil fuel combustion and biomass burning. In this study we present experimental and analytical techniques for efficient investigation of oxygenated and nitrated derivatives of large polycyclic aromatic hydrocarbons (PAHs), which can be regarded as well-defined soot model substances. For coronene and hexabenzocoronene exposed to nitrogen dioxide under simulated diesel exhaust conditions, several reaction products with high molecular mass could be characterized by liquid chromatography-atmospheric pressure chemical (and photo) ionization-mass spectrometry (LC-APCI-MS and LC-APPI-MS). The main products of coronene contained odd numbers of nitrogen atoms (m/z 282, 256, 338), whereas one of the main products of hexabenzocoronene exhibited an even number of nitrogen atoms (m/z 391). Various reaction products containing carbonyl and nitro groups could be tentatively identified by combining chromatographic and mass spectrometric information, and changes of their relative abundance were observed to depend on the reaction conditions. This analytical strategy should highlight a relatively young technique for the characterization of various soot-contained, semi-volatile, and semi-polar reaction products of large PAHs. Figure LC-APCI-MS analysis of nitrated coronene (and HBC): Total-Ion-Chromatogram (TIC), Extracted Ion Chromatograms (EICs) and corresponding mass spectrum (top). PMID:18560812

  5. Modeling chlorophyll-a and dissolved oxygen concentration in tropical floodplain lakes (Paraná River, Brazil).

    PubMed

    Rocha, R R A; Thomaz, S M; Carvalho, P; Gomes, L C

    2009-06-01

    The need for prediction is widely recognized in limnology. In this study, data from 25 lakes of the Upper Paraná River floodplain were used to build models to predict chlorophyll-a and dissolved oxygen concentrations. Akaike's information criterion (AIC) was used as a criterion for model selection. Models were validated with independent data obtained in the same lakes in 2001. Predictor variables that significantly explained chlorophyll-a concentration were pH, electrical conductivity, total seston (positive correlation) and nitrate (negative correlation). This model explained 52% of chlorophyll variability. Variables that significantly explained dissolved oxygen concentration were pH, lake area and nitrate (all positive correlations); water temperature and electrical conductivity were negatively correlated with oxygen. This model explained 54% of oxygen variability. Validation with independent data showed that both models had the potential to predict algal biomass and dissolved oxygen concentration in these lakes. These findings suggest that multiple regression models are valuable and practical tools for understanding the dynamics of ecosystems and that predictive limnology may still be considered a powerful approach in aquatic ecology.

  6. Benzothiadiazole Versus Thiophene: Influence of the Auxiliary Acceptor on the Photovoltaic Properties of Donor-Acceptor-Based Copolymers.

    PubMed

    Li, Zongbo; Weng, Kangkang; Chen, Aihua; Sun, Xiaobo; Wei, Donghui; Yu, Mingming; Huo, Lijun; Sun, Yanming

    2018-01-01

    Two donor-acceptor (D-A) type conjugated copolymers, P1 and P2, are designed and synthesized. A classical benzothiadiazole acceptor is used to replace a thiophene unit in the polymer chain of P1 to obtain P2 terpolymer. Compared with P1, P2 exhibits broader absorption spectra, higher absorption coefficient, deeper lowest unoccupied molecular orbital level, and a relatively lower band gap. As a result, the P2-based solar cell exhibits a high power conversion efficiency (PCE) of 6.60%, with a short-circuit current (J sc ) of 12.43 mA cm -2 , and a fill factor (FF) of 73.1%, which are higher than those of the P1-based device with a PCE of 4.70%, a J sc of 9.43 mA cm -2 , and an FF of 61.6%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Exogenous pyruvate facilitates cancer cell adaptation to hypoxia by serving as an oxygen surrogate.

    PubMed

    Yin, Chengqian; He, Dan; Chen, Shuyang; Tan, Xiaoling; Sang, Nianli

    2016-07-26

    Molecular oxygen is the final electron acceptor in cellular metabolism but cancer cells often become adaptive to hypoxia, which promotes resistance to chemotherapy and radiation. The reduction of endogenous glycolytic pyruvate to lactate is known as an adaptive strategy for hypoxic cells. Whether exogenous pyruvate is required for hypoxic cell proliferation by either serving as an electron acceptor or a biosynthetic substrate remains unclear. By using both hypoxic and ρ0 cells defective in electron transfer chain, we show that exogenous pyruvate is required to sustain proliferation of both cancer and non-cancer cells that cannot utilize oxygen. Particularly, we show that absence of pyruvate led to glycolysis inhibition and AMPK activation along with decreased NAD+ levels in ρ0 cells; and exogenous pyruvate increases lactate yield, elevates NAD+/NADH ratio and suppresses AMPK activation. Knockdown of lactate dehydrogenase significantly inhibits the rescuing effects of exogenous pyruvate. In contrast, none of pyruvate-derived metabolites tested (including acetyl-CoA, α-ketoglutarate, succinate and alanine) can replace pyruvate in supporting ρ0 cell proliferation. Knockdown of pyruvate carboxylase, pyruvate dehydrogenase and citrate synthase do not impair exogenous pyruvate to rescue ρ0 cells. Importantly, we show that exogenous pyruvate relieves ATP insufficiency and mTOR inhibition and promotes proliferation of hypoxic cells, and that well-oxygenated cells release pyruvate, providing a potential in vivo source of pyruvate. Taken together, our data support a novel pyruvate cycle model in which oxygenated cells release pyruvate for hypoxic cells as an oxygen surrogate. The pyruvate cycle may be targeted as a new therapy of hypoxic cancers.

  8. Sphaerotilus natans encrusted with nanoball-shaped Fe(III) oxide minerals formed by nitrate-reducing mixotrophic Fe(II) oxidation

    PubMed Central

    Park, Sunhwa; Kim, Dong-Hun; Lee, Ji-Hoon; Hur, Hor-Gil

    2014-01-01

    Ferrous iron has been known to function as an electron source for iron-oxidizing microorganisms in both anoxic and oxic environments. A diversity of bacteria has been known to oxidize both soluble and solid-phase Fe(II) forms coupled to the reduction of nitrate. Here, we show for the first time Fe(II) oxidation by Sphaerotilus natans strain DSM 6575T under mixotrophic condition. Sphaerotilus natans has been known to form a sheath structure enclosing long chains of rod-shaped cells, resulting in a thick biofilm formation under oxic conditions. Here, we also demonstrate that strain DSM 6575T grows mixotrophically with pyruvate, Fe(II) as electron donors and nitrate as an electron acceptor and single cells of strain DSM 6575T are dominant under anoxic conditions. Furthermore, strain DSM 6575T forms nanoball-shaped amorphous Fe(III) oxide minerals encrusting on the cell surfaces through the mixotrophic iron oxidation reaction under anoxic conditions. We propose that cell encrustation results from the indirect Fe(II) oxidation by biogenic nitrite during nitrate reduction and that causes the bacterial morphological change to individual rod-shaped single cells from filamentous sheath structures. This study extends the group of existing microorganisms capable of mixotrophic Fe(II) oxidation by a new strain, S. natans strain DSM 6575T, and could contribute to biogeochemical cycles of Fe and N in the environment. PMID:24965827

  9. Thermochemical nitrate destruction

    DOEpatents

    Cox, John L.; Hallen, Richard T.; Lilga, Michael A.

    1992-01-01

    A method is disclosed for denitrification of nitrates and nitrates present in aqueous waste streams. The method comprises the steps of (1) identifying the concentration nitrates and nitrites present in a waste stream, (2) causing formate to be present in the waste stream, (3) heating the mixture to a predetermined reaction temperature from about 200.degree. C. to about 600.degree. C., and (4) holding the mixture and accumulating products at heated and pressurized conditions for a residence time, thereby resulting in nitrogen and carbon dioxide gas, and hydroxides, and reducing the level of nitrates and nitrites to below drinking water standards.

  10. Targeting ideal acceptor-donor materials based on hexabenzocoronene

    NASA Astrophysics Data System (ADS)

    Santos Silva, H.; Metz, Sebastian; Hiorns, Roger C.; Bégué, D.

    2018-06-01

    A series of new hybrid donor-acceptor materials based on hexabenzocoronenes (HBC) functionalized with electron donors is investigated by combining a variety of quantum mechanical and molecular dynamic methodologies for use in organic photovoltaic (OPV) devices. Segments of a low band gap alternating copolymer constructed of benzo[1,2-b;3,4-b]dithiophene and thieno[3,4-c]pyrrole-4,6-dione were attached to the conjugated HBC core. The copolymer was chosen for its known high performance in OPVs, and both moieties were singled out due to their exceptional resistance to photo-oxidation, an important requirement for such applications. The macromolecular topology of these systems are expected to induce supra-molecular columns, such as those common to discotic liquid crystals, conducive to the effective percolation of electrons in OPV devices. A challenge with these systems, that of the mixing of the electronic structures of the donor and acceptor moieties that result in excitonic losses and charge recombination, was diminished by trialling a range of linking units. It was found possible to propose ideal donor-acceptor structures with enhanced charge dissociations and transfers in the π-stacking direction for use in OPV and other organic electronic devices.

  11. Stainless steel corrosion by molten nitrates : analysis and lessons learned.

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kruizenga, Alan Michael

    2011-09-01

    A secondary containment vessel, made of stainless 316, failed due to severe nitrate salt corrosion. Corrosion was in the form of pitting was observed during high temperature, chemical stability experiments. Optical microscopy, scanning electron microscopy and energy dispersive spectroscopy were all used to diagnose the cause of the failure. Failure was caused by potassium oxide that crept into the gap between the primary vessel (alumina) and the stainless steel vessel. Molten nitrate solar salt (89% KNO{sub 3}, 11% NaNO{sub 3} by weight) was used during chemical stability experiments, with an oxygen cover gas, at a salt temperature of 350-700 C.more » Nitrate salt was primarily contained in an alumina vessel; however salt crept into the gap between the alumina and 316 stainless steel. Corrosion occurred over a period of approximately 2000 hours, with the end result of full wall penetration through the stainless steel vessel; see Figures 1 and 2 for images of the corrosion damage to the vessel. Wall thickness was 0.0625 inches, which, based on previous data, should have been adequate to avoid corrosion-induced failure while in direct contact with salt temperature at 677 C (0.081-inch/year). Salt temperatures exceeding 650 C lasted for approximately 14 days. However, previous corrosion data was performed with air as the cover gas. High temperature combined with an oxygen cover gas obviously drove corrosion rates to a much higher value. Corrosion resulted in the form of uniform pitting. Based on SEM and EDS data, pits contained primarily potassium oxide and potassium chromate, reinforcing the link between oxides and severe corrosion. In addition to the pitting corrosion, a large blister formed on the side wall, which was mainly composed of potassium, chromium and oxygen. All data indicated that corrosion initiated internally and moved outward. There was no evidence of intergranular corrosion nor were there any indication of fast pathways along grain boundaries. Much

  12. Evaluation of Nitrate Concentrations and Sources in the Elk Creek Watershed, Southwestern Ohio, 2003-2004

    USGS Publications Warehouse

    Schumann, Thomas L.; Pletsch, Bruce A.

    2006-01-01

    Nitrate concentrations exceeding the U.S. Environmental Protection Agency maximum contaminant level of 10 milligrams per liter have been reported in ground water near the City of Trenton, Ohio, in the southern part of the Elk Creek watershed. A study of nitrate concentrations and sources in surface and ground water within the Elk Creek watershed was conducted during 2003 and 2004. Nitrate concentrations in the Elk Creek watershed range from less than 0.06 to 11 milligrams per liter. The likely sources of elevated nitrate in the ground water near the City of Trenton appear to be soil organic matter and ammonia fertilizer. Land use is predominantly (93 percent) agricultural, with no identified point sources of nitrate. Likely sources of nitrate in the surface water appear to be manure and septic system effluent, soil organic matter, and ammonia fertilizer. Water-quality constituents, including nitrate, were sampled in water from 38 wells and at 6 surface-water sites. The wells were all shallow (less than 105 feet deep), with open intervals in aquifers of glacial origin, that include tills, outwash, and alluvium. Nitrate concentrations (median of 0.06 milligrams per liter) in the ground water of the upper section of the watershed were lower than those in the lower section of the watershed (median of 4.2 milligrams per liter). Nitrate was analyzed for nitrogen and oxygen isotope values. The d15N and d18O range from -22.36 to +32.29 per mil, and -6.27 to +17.72 per mil, respectively. A positive correlation of d15N and d18O enrichment indicates that denitrification is a prevalent process within the watershed.

  13. Non-hemodynamic effects of organic nitrates and the distinctive characteristics of pentaerithrityl tetranitrate.

    PubMed

    Gori, Tommaso; Daiber, Andreas

    2009-01-01

    Organic nitrates are among the oldest and yet most commonly employed drugs in the long-term therapy of coronary artery disease and congestive heart failure. While they have long been used in clinical practice, our understanding of their mechanism of action and side effects remains incomplete. For instance, recent findings provide evidence of previously unanticipated, non-hemodynamic properties that include potentially beneficial mechanisms (such as the induction of a protective phenotype that mimics ischemic preconditioning), but also toxic effects (such as endothelial and autonomic dysfunction, rebound angina, tolerance). To date, the most commonly employed organic nitrates are isosorbide mononitrate, isosorbide dinitrate, and nitroglycerin (glyceryl trinitrate). Another organic nitrate, pentaerithrityl tetranitrate (PETN), has long been employed in eastern European countries and is currently being reintroduced in Western countries. In light of their wide use, and of the (re)introduction of PETN in Western markets, the present review focuses on the novel effects of organic nitrates, describing their potential clinical implications and discussing differences among different compounds. We believe that these recent findings have important clinical implications. Since the side effects of organic nitrates such as nitroglycerin and isosorbides appear to be mediated by reactive oxygen species, care should be taken that drugs with antioxidant properties are co-administered. On the other hand, efforts should be made to clinically exploit the preconditioning effects of these drugs.

  14. Nitrate fertilisation does not enhance CO2 responses in two tropical seagrass species

    PubMed Central

    Ow, Y. X.; Vogel, N.; Collier, C. J.; Holtum, J. A. M.; Flores, F.; Uthicke, S.

    2016-01-01

    Seagrasses are often considered “winners” of ocean acidification (OA); however, seagrass productivity responses to OA could be limited by nitrogen availability, since nitrogen-derived metabolites are required for carbon assimilation. We tested nitrogen uptake and assimilation, photosynthesis, growth, and carbon allocation responses of the tropical seagrasses Halodule uninervis and Thalassia hemprichii to OA scenarios (428, 734 and 1213 μatm pCO2) under two nutrients levels (0.3 and 1.9 μM NO3−). Net primary production (measured as oxygen production) and growth in H. uninervis increased with pCO2 enrichment, but were not affected by nitrate enrichment. However, nitrate enrichment reduced whole plant respiration in H. uninervis. Net primary production and growth did not show significant changes with pCO2 or nitrate by the end of the experiment (24 d) in T. hemprichii. However, nitrate incorporation in T. hemprichii was higher with nitrate enrichment. There was no evidence that nitrogen demand increased with pCO2 enrichment in either species. Contrary to our initial hypothesis, nutrient increases to levels approximating present day flood plumes only had small effects on metabolism. This study highlights that the paradigm of increased productivity of seagrasses under ocean acidification may not be valid for all species under all environmental conditions. PMID:26976685

  15. Aerosol-spray diverse mesoporous metal oxides from metal nitrates.

    PubMed

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-04-21

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances.

  16. Aerosol-spray diverse mesoporous metal oxides from metal nitrates

    PubMed Central

    Kuai, Long; Wang, Junxin; Ming, Tian; Fang, Caihong; Sun, Zhenhua; Geng, Baoyou; Wang, Jianfang

    2015-01-01

    Transition metal oxides are widely used in solar cells, batteries, transistors, memories, transparent conductive electrodes, photocatalysts, gas sensors, supercapacitors, and smart windows. In many of these applications, large surface areas and pore volumes can enhance molecular adsorption, facilitate ion transfer, and increase interfacial areas; the formation of complex oxides (mixed, doped, multimetallic oxides and oxide-based hybrids) can alter electronic band structures, modify/enhance charge carrier concentrations/separation, and introduce desired functionalities. A general synthetic approach to diverse mesoporous metal oxides is therefore very attractive. Here we describe a powerful aerosol-spray method for synthesizing various mesoporous metal oxides from low-cost nitrate salts. During spray, thermal heating of precursor droplets drives solvent evaporation and induces surfactant-directed formation of mesostructures, nitrate decomposition and oxide cross-linking. Thirteen types of monometallic oxides and four groups of complex ones are successfully produced, with mesoporous iron oxide microspheres demonstrated for photocatalytic oxygen evolution and gas sensing with superior performances. PMID:25897988

  17. Cardiorespiratory function associated with dietary nitrate supplementation

    PubMed Central

    Bond, Vernon; Curry, Bryan H.; Adams, Richard G.; Millis, Richard M.; Haddad, Georges E.

    2014-01-01

    The advent of medical nutrition therapy and nutritional physiology affords the opportunity to link diet to specific cardiovascular mechanisms, suggesting novel treatments for cardiovascular disease. This study tests the hypothesis that beetroot juice increases the plasma nitric oxide (NO) concentration, which is associated with improvements in cardiorespiratory function at rest and during submaximal aerobic exercise. The subjects were 12 healthy, young adult, normotensive African-American females, with a body mass of 61 ± 2 kg, body fat of 28% ± 4%, and peak oxygen consumption of 26 ± 3 mL·kg−1·min−1. The subjects were studied at rest and during cycle ergometer exercise at 40%, 60%, and 80% of peak oxygen consumption. Plasma NO concentration, respiratory quotient (RQ), minute ventilation, systolic and diastolic blood pressure (SBP and DBP), heart rate, and oxygen consumption were compared between isocaloric, isovolumetric placebo control orange juice and experimental beetroot juice treatments on separate days. The beetroot juice treatment increased plasma NO concentration and decreased oxygen consumption, SBP, and the heart rate-SBP product at rest and at 40%, 60%, and 80% of peak oxygen consumption in the absence of significant effects on RQ, minute ventilation, heart rate, and DBP. These findings suggest that, in healthy subjects, beetroot juice treatments increase plasma NO concentration and decrease cardiac afterload and myocardial oxygen demand at rest and during 3 submaximal levels of aerobic exercise. Future studies should determine the cellular and molecular mechanisms responsible for the improvement in cardiorespiratory function associated with dietary nitrate supplementation and whether they translate into better cardiovascular function and exercise tolerance in individuals with a compromised cardiovascular system. PMID:24476472

  18. Tetrahydrothiophene 1-oxide as an electron acceptor for Escherichia coli.

    PubMed Central

    Meganathan, R; Schrementi, J

    1987-01-01

    Escherichia coli used tetrahydrothiophene 1-oxide (THTO) as an electron acceptor for anaerobic growth with glycerol as a carbon source; the THTO was reduced to tetrahydrothiophene. Cell extracts also reduced THTO to tetrahydrothiophene in the presence of a variety of electron donors. Chlorate-resistant (chl) mutants (chlA, chlB, chlD, and chlE) were unable to grow with THTO as the electron acceptor. However, growth and THTO reduction by the chlD mutant were restored by high concentrations of molybdate. Similarly, mutants of E. coli that are blocked in the menaquinone (vitamin K2) biosynthetic pathway, i.e., menB, menC, and menD mutants, did not grow with THTO as an electron acceptor. Growth and THTO reduction were restored in these mutants by the presence of appropriate intermediates of the vitamin K biosynthetic pathway. PMID:3294808

  19. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed with...

  20. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed with...

  1. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed with...

  2. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures. 176.410 Section 176.410 Transportation Other Regulations Relating to... nitrate and ammonium nitrate mixtures. (a) This section prescribes requirements to be observed with...

  3. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Simulating nitrate response functions in watersheds: Case studies in the United States and New Zealand

    NASA Astrophysics Data System (ADS)

    Gusyev, Maksym; Abrams, Daniel; Morgenstern, Uwe; Stewart, Michael

    2016-04-01

    Non-point sources of nitrate contamination are a common concern in different parts of the world and are difficult to characterize. Due to the solubility of nitrate, it easily enters groundwater and may take years or decades to completely flush to a stream. During this time, it may undergo denitrification, in particular if dissolved oxygen levels are low, requiring a representation of spatially distributed nitrate input as well as detailed hydrogeology. In this presentation, nitrate response functions are generated with four different methodologies that are listed in the order of decreasing degrees of freedom: groundwater flow and chemical transport (MODFLOW/MT3D), groundwater flow with solute particle tracing (MODFLOW/MODPATH), cross-sectional groundwater flow model (MODFLOW), and lumped parameter models (LPMs). We tested these approaches in selected watersheds in the Eastern and Midwestern United States as well as New Zealand and found similar nitrate results in all cases despite different model complexities. It is noted that only the fully three dimensional MODFLOW models with MT3D or MODPATH could account for detailed patterns of land use and nitrate applications; the cross-sectional models and lumped parameter models could only do so approximately. Denitrification at depth could also be explicitly accounted for in all four approaches, although this was not a major factor in any of the watersheds investigated.

  5. Perylene-Diimide Based Donor-Acceptor-Donor Type Small-Molecule Acceptors for Solution-Processable Organic Solar Cells

    NASA Astrophysics Data System (ADS)

    Ganesamoorthy, Ramasamy; Vijayaraghavan, Rajagopalan; Sakthivel, Pachagounder

    2017-12-01

    Development of nonfullerene acceptors plays an important role in the commercial availability of plastic solar cells. We report herein synthesis of bay-substituted donor-acceptor-donor (D-A-D)-type perylene diimide (PDI)-based small molecules (SM-1 to SM-4) by Suzuki coupling method and their use as acceptors in bulk heterojunction organic solar cells (BHJ-OSCs) with poly(3-hexylthiophene) (P3HT) polymer donor. We varied the number of electron-rich thiophene units and the solubilizing side chains and also evaluated the optical and electrochemical properties of the small molecules. The synthesized small molecules were confirmed by Fourier-transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and high-resolution mass spectroscopy (HR-MS). The small molecules showed extensive and strong absorption in the ultraviolet-visible (UV-Vis) region up to 750 nm, with bandgap (E_{{g}}^{{opt}} ) reduced below <2 eV. The energy levels of small molecules SM-1 to SM-4 were suitable for use as electron-accepting materials. The small molecules showed good thermal stability up to 300°C. BHJ-OSCs with SM-1 and P3HT polymer donor showed maximum power conversion efficiency (PCE) of 0.19% with V oc of 0.30 V, J sc of 1.72 mA cm-2, and fill factor (FF) of 37%. The PCE decreased with the number of thiophene units. The PCE of SM-2 was lower than that of SM-1. This difference in PCE can be explained by the higher aggregation tendency of the bithiophene compared with the thiophene unit. Introduction of the solubilizing group in the bay position increased the aggregation property, leading to much lower PCE than for the small molecules without solubilizing group.

  6. Cylodextrin Polymer Nitrate

    NASA Technical Reports Server (NTRS)

    Kosowski, Bernard; Ruebner, Anja; Statton, Gary; Robitelle, Danielle; Meyers, Curtis

    2000-01-01

    The development of the use of cyclodextrin nitrates as possible components of insensitive, high-energy energetics is outlined over a time period of 12 years. Four different types of cyclodextrin polymers were synthesized, nitrated, and evaluated regarding their potential use for the military and aerospace community. The synthesis of these novel cyclodextrin polymers and different nitration techniques are shown and the potential of these new materials is discussed.

  7. Isolation and characterization of Sulfurospirillum carboxydovorans sp. nov., a new microaerophilic carbon monoxide oxidizing epsilon Proteobacterium.

    PubMed

    Jensen, Anders; Finster, Kai

    2005-05-01

    A new microaerophilic, Gram-negative, motile, 2-3 microm long and 0.3 microm wide, vibrioid to spirillum-shaped, CO oxidizing bacterium, designated strain MV, isolated from marine sediment (The North Sea) is described. Strain MV was able to couple the oxidation of CO to the reduction of elemental sulphur, DMSO and thiosulphate. Growth occurred with up to 100% (v/v) CO in the headspace. Acetate was needed as carbon source. No growth on CO was observed with nitrate and selenate as electron acceptor. Sulphite, elemental sulphur, DMSO, thiosulphate, nitrate, nitrite, perchloroethylene, arsenate and selenate were used as electron acceptors with pyruvate as energy and carbon source. Microaerophilic growth was observed. In non-agitated cultures growth occurred at atmospheric oxygen concentrations in the headspace. Hydrogen (with acetate as carbon source), formate (with acetate as carbon source), pyruvate, lactate, succinate, fumarate, malate alpha-ketoglutaric acid, aspartate and yeast extract (1% (w/v)) supported growth with nitrate as electron acceptor. Fumarate and malate were fermented. Vitamins were not required for growth. The strain was cytochrome C oxidase and catalase positive. The DNA mol G+C content was 30.5%. 16S rRNA gene sequence comparison showed that strain MV grouped within the genus Sulfurospirillum with Sulfurospirillum arcachonense (sequence similarity 98.3%) as closest relative. The relative DNA-DNA relatedness between strain MV and S. arcachonense was 33.1%. Based on a detailed phenotypic and phylogenetic analysis, inclusion of strain MV in the genus Sulfurospirillum as a well separated new species is proposed. As species name we propose Sulfurospirillum carboxydovorans. The type strain is strain MV (ATCC BAA-937 = DSM 16295, GenBank accession number: AY740528).

  8. Electron-Transfer Dynamics for a Donor-Bridge-Acceptor Complex in Ionic Liquids.

    PubMed

    DeVine, Jessalyn A; Labib, Marena; Harries, Megan E; Rached, Rouba Abdel Malak; Issa, Joseph; Wishart, James F; Castner, Edward W

    2015-08-27

    Intramolecular photoinduced electron transfer from an N,N-dimethyl-p-phenylenediamine donor bridged by a diproline spacer to a coumarin 343 acceptor was studied using time-resolved fluorescence measurements in three ionic liquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amide anion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium, and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-proline donor-bridge-acceptor complex are compared to those observed for the same donor and acceptor connected by a single proline bridge, studied previously by Lee et al. (J. Phys. Chem. C 2012, 116, 5197). The increased conformational freedom afforded by the second bridging proline resulted in multiple energetically accessible conformations. The multiple conformations have significant variations in donor-acceptor electronic coupling, leading to dynamics that include both adiabatic and nonadiabatic contributions. In common with the single-proline bridged complex, the intramolecular electron transfer in the two-proline system was found to be in the Marcus inverted regime.

  9. A matrix-isolation-infrared spectroscopic study of the reactions of nitric oxide with oxygen and ozone

    NASA Technical Reports Server (NTRS)

    Bhatia, S. C.; Hall, J. H., Jr.

    1980-01-01

    An investigation of the oxidation of NO to NO2 by trapping the products of the gas-phase reactions with excess oxygen and ozone identified the transient species by their infrared spectra. The primary products of the NO + NO2 reactions were NO2, N2O3(A), N2O3(B), N2O4, and peroxy nitrate (OONO). The primary products of the NO + O3 reactions were NO2 and peroxy NO3 with the higher nitric oxides in low concentrations compared with the NO + O2 reactions. Isotopic oxygen and ozone were used to identify the infrared absorption frequency of the peroxy nitrate.

  10. The nature of electron acceptor (MnIV/NO3) triggers differential expression of genes associated with stress and ammonium limitation responses in Shewanella algae C6G3.

    PubMed

    Aigle, Axel; Bonin, Patricia; -Nunez, Nicolas Fernandez; Loriod, Béatrice; Guasco, Sophie; Bergon, Aurélie; Armougom, Fabrice; Iobbi-Nivol, Chantal; Imbert, Jean; Michotey, Valérie

    2018-03-16

    Shewanella algae C6G3 can reduce dissimilatively nitrate into ammonium and manganese-oxide (MnIV) into MnII. It has the unusual ability to produce anaerobically nitrite from ammonium in the presence of MnIV. To gain insight into their metabolic capabilities, global mRNA expression patterns were investigated by RNA-seq and qRT-PCR in cells growing with lactate and ammonium as carbon and nitrogen sources and with either MnIV or nitrate as electron acceptors. Gene exhibiting higher expression levels in the presence of MnIV belonged to functional categories of carbohydrate, coenzyme, lipid metabolisms and inorganic ion transport. Comparative transcriptomic pattern between MnIV and NO3 revealed that the strain presented an ammonium limitation status with MnIV, despite the presence of non-limiting concentration of ammonium under both culture conditions. In addition, in presence of MnIV, ntrB/nrtC regulators, ammonium channel, nitrogen regulatory protein P-II, glutamine synthetase and asparagine synthetase glutamine dependent genes were over-represented. Under nitrate condition, the expression of genes involved in the synthesis of several amino acids was increased. Finally, expression level of genes associated with the general stress response was also amplified and among them, katE, a putative catalase/peroxidase present on several Shewanella genomes, was highly expressed with a relative median value higher in MnIV condition.

  11. Methods for the synthesis of donor-acceptor cyclopropanes

    NASA Astrophysics Data System (ADS)

    Tomilov, Yu V.; Menchikov, L. G.; Novikov, R. A.; Ivanova, O. A.; Trushkov, I. V.

    2018-03-01

    The interest in cyclopropane derivatives is caused by the facts that, first, the three-carbon ring is present in quite a few natural and biologically active compounds and, second, compounds with this ring are convenient building blocks for the synthesis of diverse molecules (acyclic, alicyclic and heterocyclic). The carbon–carbon bonds in cyclopropane are kinetically rather inert; hence, they need to be activated to be involved in reactions. An efficient way of activation is to introduce vicinal electron-donating and electron-withdrawing substituents into the ring; these substrates are usually referred to as donor-acceptor cyclopropanes. This review gives a systematic account of the key methods for the synthesis of donor-acceptor cyclopropanes. The most important among them are reactions of nucleophilic alkenes with diazo compounds and iodonium ylides and approaches based on reactions of electrophilic alkenes with sulfur ylides (the Corey–Chaykovsky reaction). Among other methods used for this purpose, noteworthy are cycloalkylation of CH-acids, addition of α-halocarbonyl compounds to alkenes, cyclization via 1,3-elimination, reactions of alkenes with halocarbenes followed by reduction, the Simmons–Smith reaction and some other. The scope of applicability and prospects of various methods for the synthesis of donor-acceptor cyclopropanes are discussed. The bibliography includes 530 references.

  12. Vulnerability of recently recharged groundwater in principal aquifers of the United States to nitrate contamination

    USGS Publications Warehouse

    Gurdak, Jason J.; Qi, Sharon L.

    2012-01-01

    Recently recharged water (defined here as <60 years old) is generally the most vulnerable part of a groundwater resource to nonpoint-source nitrate contamination. Understanding at the appropriate scale the interactions of natural and anthropogenic controlling factors that influence nitrate occurrence in recently recharged groundwater is critical to support best management and policy decisions that are often made at the aquifer to subaquifer scale. New logistic regression models were developed using data from the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) program and National Water Information System for 17 principal aquifers of the U.S. to identify important source, transport, and attenuation factors that control nonpoint source nitrate concentrations greater than relative background levels in recently recharged groundwater and were used to predict the probability of detecting elevated nitrate in areas beyond the sampling network. Results indicate that dissolved oxygen, crops and irrigated cropland, fertilizer application, seasonally high water table, and soil properties that affect infiltration and denitrification are among the most important factors in predicting elevated nitrate concentrations. Important differences in controlling factors and spatial predictions were identified in the principal aquifer and national-scale models and support the conclusion that similar spatial scales are needed between informed groundwater management and model development.

  13. Toluene degradation by Cupriavidus metallidurans CH34 in nitrate-reducing conditions and in Bioelectrochemical Systems.

    PubMed

    Tofalos, Anna Espinoza; Daghio, Matteo; González, Myriam; Papacchini, Maddalena; Franzetti, Andrea; Seeger, Michael

    2018-05-16

    Bioelectrochemical remediation of hydrocarbons is a technology that exploits the ability of specific microorganisms to use as electron acceptor an electrode, thus potentially lowering the operational costs related to classical bioremediation. Several well-characterized hydrocarbonoclastic strains might be electroactive, thus their biodegradation performances in Bioelectrochemical Systems should be studied. Cupriavidus metallidurans CH34 is a model metal-resistant strain whose capacity to degrade benzene aerobically has recently been described. In this study, toluene degradation under anaerobic conditions and the exoelectrogenic capacity of Cupriavidus metallidurans CH34 were determined. Strain CH34 was grown anaerobically with toluene as sole carbon source in sealed serum bottles and then inoculated in a Microbial Electrolysis Cell (MEC) to assess its exoelectrogenic capacity. It was demonstrated for the first time that strain CH34 is able to degrade toluene under nitrate-reducing conditions (up to 45 mgtoluene/L were removed within 17 days, corresponding to 73% of toluene amended). Nitrate consumption and cellular growth were observed during toluene removal. In the MEC, toluene degradation was linked to current production, showing current peaks after every toluene addition (maximum current density 48 mA/m2). Coulombic efficiency of the toluene biodegradation process increased with time, from 11% (first batch cycle), up to 77% (last batch cycle).

  14. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more than...

  15. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more than...

  16. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more than...

  17. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... nitrates, and certain ammonium nitrate fertilizers. 176.415 Section 176.415 Transportation Other... requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers. (a) Except as... Captain of the Port (COTP). (1) Ammonium nitrate UN1942, ammonium nitrate fertilizers containing more than...

  18. Chemical catalysis of nitrate reduction by iron (II)

    NASA Astrophysics Data System (ADS)

    Ottley, C. J.; Davison, W.; Edmunds, W. M.

    1997-05-01

    Experiments have been conducted to investigate the chemical reduction of nitrate under conditions relevant to the often low organic carbon environment of groundwaters. At pH 8 and 20 ± 2°C, in the presence of Cu(II), NO 3- was chemically reduced by Fe(II) to NH 4+ with an average stoichiometric liberation of 8 protons. The rate of the reaction systematically increased with pH in the range pH 7-8.5. The half-life for nitrate reduction, t 1/2, was inversely related to the total molar copper concentration, [Cu T], by the equation log t 1/2 = -1.35 log [Cu T] -2.616, for all measured values of t 1/2 from 23 min to 15 days. At the Cu(II) concentrations used of 7 × 10 -6 -10 -3 M, Cu was present mainly as a solid phase, either adsorbed to the surfaces of precipitated iron oxides or as a saturated solid. It is this solid phase copper rather than CU 2+ in solution which is catalytically active. Neither magnetite, which was formed as a product of the reaction, nor freshly prepared lepidocrocite catalysed the reaction, but goethite did. Although traces of oxygen accelerated the reaction, at higher partial pressures (>0.01 atm) the reduction of nitrate was inhibited, probably due to competition between NO 3- and O 2 for Fe(II). Appreciable catalytic effects were also observed for solid phase forms of Ag(I), Cd(H), Ni(H), Hg(II), and Pb(II). Mn(II) enhanced the rate slightly, and there was evidence for slow abiotic reduction in the absence of any added metal catalysts. These results suggest that the chemical reduction of nitrate at catalytic concentrations and temperatures appropriate to groundwater conditions is feasible on a timescale of months to years.

  19. Intensity dependence and transient dynamics of donor-acceptor pair recombination in ZnO thin films grown on (001) silicon

    NASA Astrophysics Data System (ADS)

    Guo, Bing; Qiu, Z. R.; Wong, K. S.

    2003-04-01

    We report room-temperature time-integrated and time-resolved photoluminescence (PL) measurements on a nominally undoped wurtzite ZnO thin film grown on (001) silicon. A linear and sublinear excitation intensity Iex dependence of the PL intensity were observed for the 379.48-nm exciton line and the weak broad green band (˜510 nm), respectively. The green luminescence was found to decay as hyperbolic t-1, and its peak energy was observed to increase nearly logarithmically with increased Iex. These results are in an excellent agreement with the tunnel-assisted donor-deep-acceptor pair (DAP) model so that its large blueshifts of about 25 meV per decade increase in Iex can be accounted for by the screening of the fluctuating impurity potential. Also, the 30-ps fast decay of the exciton emission was attributed to the rapid trapping of carriers at luminescent impurities, while the short lifetime of τ1/e=200 ps for the green luminescence may be due to an alternative trapping by deeper centers in the ZnO. Finally, singly ionized oxygen and zinc vacancies have been tentatively invoked to act as donor-deep-acceptor candidates for the DAP luminescence, respectively.

  20. Exogenous pyruvate facilitates cancer cell adaptation to hypoxia by serving as an oxygen surrogate

    PubMed Central

    Yin, Chengqian; He, Dan; Chen, Shuyang; Tan, Xiaoling; Sang, Nianli

    2016-01-01

    Molecular oxygen is the final electron acceptor in cellular metabolism but cancer cells often become adaptive to hypoxia, which promotes resistance to chemotherapy and radiation. The reduction of endogenous glycolytic pyruvate to lactate is known as an adaptive strategy for hypoxic cells. Whether exogenous pyruvate is required for hypoxic cell proliferation by either serving as an electron acceptor or a biosynthetic substrate remains unclear. By using both hypoxic and ρ0 cells defective in electron transfer chain, we show that exogenous pyruvate is required to sustain proliferation of both cancer and non-cancer cells that cannot utilize oxygen. Particularly, we show that absence of pyruvate led to glycolysis inhibition and AMPK activation along with decreased NAD+ levels in ρ0 cells; and exogenous pyruvate increases lactate yield, elevates NAD+/NADH ratio and suppresses AMPK activation. Knockdown of lactate dehydrogenase significantly inhibits the rescuing effects of exogenous pyruvate. In contrast, none of pyruvate-derived metabolites tested (including acetyl-CoA, α-ketoglutarate, succinate and alanine) can replace pyruvate in supporting ρ0 cell proliferation. Knockdown of pyruvate carboxylase, pyruvate dehydrogenase and citrate synthase do not impair exogenous pyruvate to rescue ρ0 cells. Importantly, we show that exogenous pyruvate relieves ATP insufficiency and mTOR inhibition and promotes proliferation of hypoxic cells, and that well-oxygenated cells release pyruvate, providing a potential in vivo source of pyruvate. Taken together, our data support a novel pyruvate cycle model in which oxygenated cells release pyruvate for hypoxic cells as an oxygen surrogate. The pyruvate cycle may be targeted as a new therapy of hypoxic cancers. PMID:27374086

  1. Origin and roles of oxygen impurities in hexagonal boron nitride epilayers

    NASA Astrophysics Data System (ADS)

    Grenadier, S. J.; Maity, A.; Li, J.; Lin, J. Y.; Jiang, H. X.

    2018-04-01

    Photoluminescence emission spectroscopy and electrical transport measurements have been employed to study the origin and roles of oxygen impurities in hexagonal boron nitride (h-BN) epilayers grown on sapphire substrates. The temperature dependence of the electrical resistivity revealed the presence of a previously unnoticed impurity level of about 0.6 eV in h-BN epilayers grown at high temperatures. The results suggested that in addition to the common nitrogen vacancy (VN) shallow donors in h-BN, oxygen impurities diffused from sapphire substrates during high temperature growth also act as substitutional donors (ON). The presence of ON gives rise to an additional emission peak in the photoluminescence spectrum, corresponding to a donor-acceptor pair recombination involving the ON donor and the CN (carbon occupying nitrogen site) deep level acceptor. Moreover, due to the presence of ON donors, the majority charge carrier type changed to electrons in epilayers grown at high temperatures, in contrast to typical h-BN epilayers which naturally exhibit "p-type" character. The results provided a more coherent picture for common impurities/defects in h-BN as well as a better understanding of the growth mediated impurities in h-BN epilayers, which will be helpful for finding possible ways to further improve the quality and purity of this emerging material.

  2. Immunoglobulins against Tyrosine Nitrated Epitopes in Coronary Artery Disease

    PubMed Central

    Thomson, Leonor; Tenopoulou, Margarita; Lightfoot, Richard; Tsika, Epida; Parastatidis, Ioannis; Martinez, Marissa; Greco, Todd M.; Doulias, Paschalis-Thomas; Wu, Yuping; Tang, W. H. Wilson; Hazen, Stanley L.; Ischiropoulos, Harry

    2012-01-01

    Background Several lines of evidence support a pathophysiological role of immunity in atherosclerosis. Tyrosine nitrated proteins, a footprint of oxygen and nitrogen derived oxidants generated by cells of the immune system, are enriched in atheromatous lesions and in circulation of coronary artery disease (CAD) subjects. However, the consequences of possible immune reactions triggered by the presence of nitrated proteins in subjects with clinically documented atherosclerosis have not been explored. Methods and Results Specific immunoglobulins that recognize 3-nitrotyrosine epitopes were identified in human lesions, as well as in circulation of CAD subjects. The levels of circulating immunoglobulins against 3-nitrotyrosine epitopes were quantified in CAD patients (n=374) and subjects without CAD (non CAD controls, n=313). A ten-fold increase in the mean level of circulating immunoglobulins against protein-bound 3-nitrotyrosine was documented in the CAD subjects (3.75 ± 1.8 μg antibody Eq/mL plasma vs. 0.36 ± 0.8 μg antibody Eq/mL plasma), and was strongly associated with angiographic evidence of significant CAD. Conclusions The results of this cross sectional study suggest that post-translational modification of proteins via nitration within atherosclerotic plaque-laden arteries and in circulation serve as neoepitopes for elaboration of immunoglobulins, thereby providing an association between oxidant production and the activation of the immune system in CAD. PMID:23081989

  3. Exploring the formation pathways of donor-acceptor catenanes in aqueous dynamic combinatorial libraries.

    PubMed

    Cougnon, Fabien B L; Au-Yeung, Ho Yu; Pantoş, G Dan; Sanders, Jeremy K M

    2011-03-09

    The discovery through dynamic combinatorial chemistry (DCC) of a new generation of donor-acceptor [2]catenanes highlights the power of DCC to access unprecedented structures. While conventional thinking has limited the scope of donor-acceptor catenanes to strictly alternating stacks of donor (D) and acceptor (A) aromatic units, DCC is demonstrated in this paper to give access to unusual DAAD, DADD, and ADAA stacks. Each of these catenanes has specific structural requirements, allowing control of their formation. On the basis of these results, and on the observation that the catenanes represent kinetic bottlenecks in the reaction pathway, we propose a mechanism that explains and predicts the structures formed. Furthermore, the spontaneous assembly of catenanes in aqueous dynamic systems gives a fundamental insight into the role played by hydrophobic effect and donor-acceptor interactions when building such complex architectures.

  4. Pyrosequencing analysis yields comprehensive assessment of microbial communities in pilot-scale two-stage membrane biofilm reactors.

    PubMed

    Ontiveros-Valencia, Aura; Tang, Youneng; Zhao, He-Ping; Friese, David; Overstreet, Ryan; Smith, Jennifer; Evans, Patrick; Rittmann, Bruce E; Krajmalnik-Brown, Rosa

    2014-07-01

    We studied the microbial community structure of pilot two-stage membrane biofilm reactors (MBfRs) designed to reduce nitrate (NO3(-)) and perchlorate (ClO4(-)) in contaminated groundwater. The groundwater also contained oxygen (O2) and sulfate (SO4(2-)), which became important electron sinks that affected the NO3(-) and ClO4(-) removal rates. Using pyrosequencing, we elucidated how important phylotypes of each "primary" microbial group, i.e., denitrifying bacteria (DB), perchlorate-reducing bacteria (PRB), and sulfate-reducing bacteria (SRB), responded to changes in electron-acceptor loading. UniFrac, principal coordinate analysis (PCoA), and diversity analyses documented that the microbial community of biofilms sampled when the MBfRs had a high acceptor loading were phylogenetically distant from and less diverse than the microbial community of biofilm samples with lower acceptor loadings. Diminished acceptor loading led to SO4(2-) reduction in the lag MBfR, which allowed Desulfovibrionales (an SRB) and Thiothrichales (sulfur-oxidizers) to thrive through S cycling. As a result of this cooperative relationship, they competed effectively with DB/PRB phylotypes such as Xanthomonadales and Rhodobacterales. Thus, pyrosequencing illustrated that while DB, PRB, and SRB responded predictably to changes in acceptor loading, a decrease in total acceptor loading led to important shifts within the "primary" groups, the onset of other members (e.g., Thiothrichales), and overall greater diversity.

  5. Group III Acceptors with Shallow and Deep Levels in Silicon Carbide: ESR and ENDOR Studies

    NASA Astrophysics Data System (ADS)

    Il'in, I. V.; Uspenskaya, Yu. A.; Kramushchenko, D. D.; Muzafarova, M. V.; Soltamov, V. A.; Mokhov, E. N.; Baranov, P. G.

    2018-04-01

    Results of investigations of Group III acceptors (B, Al, and Ga) in crystals of silicon carbide using the most informative electron spin resonance and electron nuclear double resonance methods are presented. Structural models of the acceptors with shallow and deep levels are considered. In addition to the data obtained earlier, studies using high-frequency magnetic resonance were obtained, which allowed revealing orthorhombic deviations from the axial symmetry for the deep acceptors; theoretical analysis explains experimentally found shifts of g factors for the deep acceptors arising due to the orthorhombic deviations, which appear probably due to the Jahn-Teller effect.

  6. High-Performance All-Polymer Solar Cells Achieved by Fused Perylenediimide-Based Conjugated Polymer Acceptors.

    PubMed

    Yin, Yuli; Yang, Jing; Guo, Fengyun; Zhou, Erjun; Zhao, Liancheng; Zhang, Yong

    2018-05-09

    We report three n-type polymeric electron acceptors (PFPDI-TT, PFPDI-T, and PFPDI-Se) based on the fused perylene diimide (FPDI) and thieno[3,2- b]thiophene, thiophene, or selenophene units for all-polymer solar cells (all-PSCs). These FPDI-based polymer acceptors exhibit strong absorption between 350 and 650 nm with wide optical bandgap of 1.86-1.91 eV, showing good absorption compensation with the narrow bandgap polymer donor. The lowest unoccupied molecular orbital (LUMO) energy levels were located at around -4.11 eV, which are comparable with those of the fullerene derivatives and other small molecular electron acceptors. The conventional all-PSCs based on the three polymer acceptors and PTB7-Th as polymer donor gave remarkable power conversion efficiencies (PCEs) of >6%, and the PFPDI-Se-based all-PSC achieved the highest PCE of 6.58% with a short-circuit current density ( J sc ) of 13.96 mA/cm 2 , an open-circuit voltage ( V oc ) of 0.76 V, and a fill factor (FF) of 62.0%. More interestingly, our results indicate that the photovoltaic performances of the FPDI-based polymer acceptors are mainly determined by the FPDI unit with a small effect from the comonomers, which is quite different from the others reported rylenediimide-based polymer acceptors. This intriguing phenomenon is speculated as the huge geometry configuration of the FPDI unit, which minimizes the effect of the comonomer. These results highlight a promising future for the application of the FPDI-based polymer acceptors in the highly efficient all-PSCs.

  7. Study on the laser irradiation characteristics of NEPE propellant in different oxygen concentrations

    NASA Astrophysics Data System (ADS)

    Xiang, Hengsheng; Chen, Xiong; Zhou, Changsheng

    2016-01-01

    The ignition and combustion characteristics of nitrate ester plasticized polyether (NEPE) propellant in different oxygen concentrations ambient gases were studied by the application of CO2 laser, infrared thermometer and high speed camera. The flame intensity data of the propellant was collected by the photodiode; propellant flame temperature was measured by infrared thermometer. The experimental results show that the time which NEPE propellant spend to be stable combustion will get shorter with the increase of oxygen concentration; the flame peak temperature measured by infrared thermometer increases with the increase of oxygen concentration when the oxygen concentration is less than 30% by volume, then decreases with the increase of oxygen concentration.

  8. Coupling of oceanic carbon and nitrogen: A window to spatially resolved quantitative reconstruction of nitrate inventories

    NASA Astrophysics Data System (ADS)

    Glock, N.; Liebetrau, V.; Gorb, S.; Wallmann, K. J. G.; Erdem, Z.; Schönfeld, J.; Eisenhauer, A.

    2017-12-01

    Anthropogenic impact has led to a severe acceleration of the global nitrogen cycle. Every second nitrogen atom in the biosphere may now originate from anthropogenic sources such as chemical fertilizers and the burning of fossil fuels. A quantitative reconstruction of past reactive nitrogen inventories is invaluable to facilitate projections for future scenarios and calibrations for such paleoproxies should be done as long the natural signature is still visible. Here we present a first quantitative reconstruction of nitrate concentrations in intermediate water depths of the Peruvian oxygen minimum zone over the last deglaciation using the pore density in the benthic foraminiferal species Bolivina spissa. A comparison of the nitrate reconstruction to the stable carbon isotope (δ13C) record reveals a strong coupling between the carbon and nitrogen cycles. The linear correlation between δ13C and nitrate availability remained stable over the last 22,000 years, facilitating the use of δ13C records as a quantitative nitrate proxy. The combination of the pore density record with δ13C records shows an elevated oceanic nitrate inventory during the Last Glacial Maximum as compared to the Holocene. Our novel proxy approach is consistent with the results of previous δ15N-based biogeochemical modeling studies, and thus provides sound estimates of the nitrate inventory in the glacial and deglacial ocean.

  9. REDUCTION OF NITRATE THROUGH THE USE OF NITRATE REDUCTASE FOR THE SMARTCHEM AUTOANALYZER

    EPA Science Inventory

    The standard method for the determination of nitrate in drinking water, USEPA Method 353.2 “Determination of Nitrate-Nitrite by Automated Colorimetry,” employs cadmium as the reductant for the conversion of nitrate to nitrite. The nitrite is then analyzed colorimetrically by way ...

  10. A dark green fluorescent protein as an acceptor for measurement of Förster resonance energy transfer.

    PubMed

    Murakoshi, Hideji; Shibata, Akihiro C E; Nakahata, Yoshihisa; Nabekura, Junichi

    2015-10-15

    Measurement of Förster resonance energy transfer by fluorescence lifetime imaging microscopy (FLIM-FRET) is a powerful method for visualization of intracellular signaling activities such as protein-protein interactions and conformational changes of proteins. Here, we developed a dark green fluorescent protein (ShadowG) that can serve as an acceptor for FLIM-FRET. ShadowG is spectrally similar to monomeric enhanced green fluorescent protein (mEGFP) and has a 120-fold smaller quantum yield. When FRET from mEGFP to ShadowG was measured using an mEGFP-ShadowG tandem construct with 2-photon FLIM-FRET, we observed a strong FRET signal with low cell-to-cell variability. Furthermore, ShadowG was applied to a single-molecule FRET sensor to monitor a conformational change of CaMKII and of the light oxygen voltage (LOV) domain in HeLa cells. These sensors showed reduced cell-to-cell variability of both the basal fluorescence lifetime and response signal. In contrast to mCherry- or dark-YFP-based sensors, our sensor allowed for precise measurement of individual cell responses. When ShadowG was applied to a separate-type Ras FRET sensor, it showed a greater response signal than did the mCherry-based sensor. Furthermore, Ras activation and translocation of its effector ERK2 into the nucleus could be observed simultaneously. Thus, ShadowG is a promising FLIM-FRET acceptor.

  11. Selective simplification and reinforcement of microbial community in autothermal thermophilic aerobic digestion to enhancing stabilization process of sewage sludge by conditioning with ferric nitrate.

    PubMed

    Jin, Ningben; Shou, Zongqi; Yuan, Haiping; Lou, Ziyang; Zhu, Nanwen

    2016-03-01

    The effect of ferric nitrate on microbial community and enhancement of stabilization process for sewage sludge was investigated in autothermal thermophilic aerobic digestion. The disinhibition of volatile fatty acids (VFA) was obtained with alteration of individual VFA concentration order. Bacterial taxonomic identification by 454 high-throughput pyrosequencing found the dominant phylum Proteobacteria in non-dosing group was converted to phylum Firmicutes in dosing group after ferric nitrate added and simplification of bacteria phylotypes was achieved. The preponderant Tepidiphilus sp. vanished, and Symbiobacterium sp. and Tepidimicrobium sp. were the most advantageous phylotypes with conditioning of ferric nitrate. Consequently, biodegradable substances in dissolved organic matters increased, which contributed to the favorable environment for microbial metabolism and resulted in acceleration of sludge stabilization. Ultimately, higher stabilization level was achieved as ratio of soluble chemical oxygen demand to total chemical oxygen demand (TCOD) decreased while TCOD reduced as well in dosing group comparing to non-dosing group. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Microbially catalyzed nitrate-dependent metal/radionuclide oxidation in shallow subsurface sediments

    NASA Astrophysics Data System (ADS)

    Weber, K.; Healy, O.; Spanbauer, T. L.; Snow, D. D.

    2011-12-01

    Anaerobic, microbially catalyzed nitrate-dependent metal/radionuclide oxidation has been demonstrated in a variety of sediments, soils, and groundwater. To date, studies evaluating U bio-oxidation and mobilization have primarily focused on anthropogenically U contaminated sites. In the Platte River Basin U originating from weathering of uranium-rich igneous rocks in the Rocky Mountains was deposited in shallow alluvial sediments as insoluble reduced uranium minerals. These reduced U minerals are subject to reoxidation by available oxidants, such nitrate, in situ. Soluble uranium (U) from natural sources is a recognized contaminant in public water supplies throughout the state of Nebraska and Colorado. Here we evaluate the potential of anaerobic, nitrate-dependent microbially catalyzed metal/radionuclide oxidation in subsurface sediments near Alda, NE. Subsurface sediments and groundwater (20-64ft.) were collected from a shallow aquifer containing nitrate (from fertilizer) and natural iron and uranium. The reduction potential revealed a reduced environment and was confirmed by the presence of Fe(II) and U(IV) in sediments. Although sediments were reduced, nitrate persisted in the groundwater. Nitrate concentrations decreased, 38 mg/L to 30 mg/L, with increasing concentrations of Fe(II) and U(IV). Dissolved U, primarily as U(VI), increased with depth, 30.3 μg/L to 302 μg/L. Analysis of sequentially extracted U(VI) and U(IV) revealed that virtually all U in sediments existed as U(IV). The presence of U(IV) is consistent with reduced Fe (Fe(II)) and low reduction potential. The increase in aqueous U concentrations with depth suggests active U cycling may occur at this site. Tetravalent U (U(IV)) phases are stable in reduced environments, however the input of an oxidant such as oxygen or nitrate into these systems would result in oxidation. Thus co-occurrence of nitrate suggests that nitrate could be used by bacteria as a U(IV) oxidant. Most probable number

  13. Electrophilic and free radical nitration of benzene and toluene with various nitrating agents*

    PubMed Central

    Olah, George A.; Lin, Henry C.; Olah, Judith A.; Narang, Subhash C.

    1978-01-01

    Electrophilic nitration of toluene and benzene was studied under various conditions with several nitrating systems. It was found that high orthopara regioselectivity is prevalent in all reactions and is independent of the reactivity of the nitrating agent. The methyl group of toluene is predominantly ortho-para directing under all reaction conditions. Steric factors are considered to be important but not the sole reason for the variation in the ortho/para ratio. The results reinforce our earlier views that, in electrophilic aromatic nitrations with reactive nitrating agents, substrate and positional selectivities are determined in two separate steps. The first step involves a π-aromatic-NO2+ ion complex or encounter pair, whereas the subsequent step is of arenium ion nature (separate for the ortho, meta, and para positions). The former determines substrate selectivity, whereas the latter determines regioselectivity. Thermal free radical nitration of benzene and toluene with tetranitromethane in sharp contrast gave nearly statistical product distributions. PMID:16592503

  14. The effect of peroxynitrite decomposition catalyst MnTBAP on aldehyde dehydrogenase-2 nitration by organic nitrates: role in nitrate tolerance.

    PubMed

    Mollace, Vincenzo; Muscoli, Carolina; Dagostino, Concetta; Giancotti, Luigino Antonio; Gliozzi, Micaela; Sacco, Iolanda; Visalli, Valeria; Gratteri, Santo; Palma, Ernesto; Malara, Natalia; Musolino, Vincenzo; Carresi, Cristina; Muscoli, Saverio; Vitale, Cristiana; Salvemini, Daniela; Romeo, Francesco

    2014-11-01

    Bioconversion of glyceryl trinitrate (GTN) into nitric oxide (NO) by aldehyde dehydrogenase-2 (ALDH-2) is a crucial mechanism which drives vasodilatory and antiplatelet effect of organic nitrates in vitro and in vivo. Oxidative stress generated by overproduction of free radical species, mostly superoxide anions and NO-derived peroxynitrite, has been suggested to play a pivotal role in the development of nitrate tolerance, though the mechanism still remains unclear. Here we studied the free radical-dependent impairment of ALDH-2 in platelets as well as vascular tissues undergoing organic nitrate ester tolerance and potential benefit when using the selective peroxynitrite decomposition catalyst Mn(III) tetrakis (4-Benzoic acid) porphyrin (MnTBAP). Washed human platelets were made tolerant to nitrates via incubation with GTN for 4h. This was expressed by attenuation of platelet aggregation induced by thrombin (40U/mL), an effect accompanied by GTN-related induction of cGMP levels in platelets undergoing thrombin-induced aggregation. Both effects were associated to attenuated GTN-induced nitrite formation in platelets supernatants and to prominent nitration of ALDH-2, the GTN to NO metabolizing enzyme, suggesting that GTN tolerance was associated to reduced NO formation via impairment of ALDH-2. These effects were all antagonized by co-incubation of platelets with MnTBAP, which restored GTN-induced responses in tolerant platelets. Comparable effect was found under in in vivo settings. Indeed, MnTBAP (10mg/kg, i.p.) significantly restored the hypotensive effect of bolus injection of GTN in rats made tolerants to organic nitrates via chronic administration of isosorbide-5-mononitrate (IS-5-MN), thus confirming the role of peroxynitrite overproduction in the development of tolerance to vascular responses induced by organic nitrates. In conclusion, oxidative stress subsequent to prolonged use of organic nitrates, which occurs via nitration of ALDH-2, represents a key event

  15. Metatranscriptome of an Anaerobic Benzene-Degrading, Nitrate-Reducing Enrichment Culture Reveals Involvement of Carboxylation in Benzene Ring Activation

    PubMed Central

    Luo, Fei; Gitiafroz, Roya; Devine, Cheryl E.; Gong, Yunchen; Hug, Laura A.; Raskin, Lutgarde

    2014-01-01

    The enzymes involved in the initial steps of anaerobic benzene catabolism are not known. To try to elucidate this critical step, a metatranscriptomic analysis was conducted to compare the genes transcribed during the metabolism of benzene and benzoate by an anaerobic benzene-degrading, nitrate-reducing enrichment culture. RNA was extracted from the mixed culture and sequenced without prior mRNA enrichment, allowing simultaneous examination of the active community composition and the differential gene expression between the two treatments. Ribosomal and mRNA sequences attributed to a member of the family Peptococcaceae from the order Clostridiales were essentially only detected in the benzene-amended culture samples, implicating this group in the initial catabolism of benzene. Genes similar to each of two subunits of a proposed benzene-carboxylating enzyme were transcribed when the culture was amended with benzene. Anaerobic benzoate degradation genes from strict anaerobes were transcribed only when the culture was amended with benzene. Genes for other benzoate catabolic enzymes and for nitrate respiration were transcribed in both samples, with those attributed to an Azoarcus species being most abundant. These findings indicate that the mineralization of benzene starts with its activation by a strict anaerobe belonging to the Peptococcaceae, involving a carboxylation step to form benzoate. These data confirm the previously hypothesized syntrophic association between a benzene-degrading Peptococcaceae strain and a benzoate-degrading denitrifying Azoarcus strain for the complete catabolism of benzene with nitrate as the terminal electron acceptor. PMID:24795366

  16. Nitrate radical oxidation of γ-terpinene: hydroxy nitrate, total organic nitrate, and secondary organic aerosol yields

    NASA Astrophysics Data System (ADS)

    Slade, Jonathan H.; de Perre, Chloé; Lee, Linda; Shepson, Paul B.

    2017-07-01

    Polyolefinic monoterpenes represent a potentially important but understudied source of organic nitrates (ONs) and secondary organic aerosol (SOA) following oxidation due to their high reactivity and propensity for multi-stage chemistry. Recent modeling work suggests that the oxidation of polyolefinic γ-terpinene can be the dominant source of nighttime ON in a mixed forest environment. However, the ON yields, aerosol partitioning behavior, and SOA yields from γ-terpinene oxidation by the nitrate radical (NO3), an important nighttime oxidant, have not been determined experimentally. In this work, we present a comprehensive experimental investigation of the total (gas + particle) ON, hydroxy nitrate, and SOA yields following γ-terpinene oxidation by NO3. Under dry conditions, the hydroxy nitrate yield = 4(+1/-3) %, total ON yield = 14(+3/-2) %, and SOA yield ≤ 10 % under atmospherically relevant particle mass loadings, similar to those for α-pinene + NO3. Using a chemical box model, we show that the measured concentrations of NO2 and γ-terpinene hydroxy nitrates can be reliably simulated from α-pinene + NO3 chemistry. This suggests that NO3 addition to either of the two internal double bonds of γ-terpinene primarily decomposes forming a relatively volatile keto-aldehyde, reconciling the small SOA yield observed here and for other internal olefinic terpenes. Based on aerosol partitioning analysis and identification of speciated particle-phase ON applying high-resolution liquid chromatography-mass spectrometry, we estimate that a significant fraction of the particle-phase ON has the hydroxy nitrate moiety. This work greatly contributes to our understanding of ON and SOA formation from polyolefin monoterpene oxidation, which could be important in the northern continental US and the Midwest, where polyolefinic monoterpene emissions are greatest.

  17. Sedimentary denitrification: Isotope fractionation and its impact on water column nitrate isotopes

    NASA Astrophysics Data System (ADS)

    Dähnke, K.; Thamdrup, B.

    2012-04-01

    The global marine nitrogen cycle is constrained by one major source and two processes that act as nitrogen sinks: nitrogen fixation on the one side and denitrification or anammox on the other. These processes with their respective isotope effecst set the marine nitrate 15N-isotope value to a relatively constant average of 5 per mil. This value can be used to better assess the magnitude of these source and sink terms, but the underlying assumption at present is that sedimentary denitrification, a process responsible for approximately one third of global nitrogen removal, has little to no isotope effect on the water column. We tested this hypothesis in sediment incubations, measuring net denitrification and nitrogen and oxygen stable isotope fractionation in surface sediments from the coastal Baltic Sea (Boknis Eck, Northern Germany). We found tremendously high denitrification rates, and regardless of current paradigms assuming little fractionation during sediment denitrification, we measured fractionation factors of 19 per mil for nitrogen and 11 per mil for oxygen in nitrate. These results potentially challenge the current view of fractionation during sedimentary denitrification and imply that nitrogen budget calculation may need to consider this variability. Furthermore, the ratio of fractionation factors for nitrogen and oxygen is distinct from the 1 : 1 ratio otherwise found in marine systems, and suggests that isotope kinetics of sedimentary denitrification might be entirely different from water column denitrification. Acknowledgements: This work was funded by the German Research Foundation (DFG) and in parts by the Danish National Research Foundation.

  18. Solvent as electron donor: Donor/acceptor electronic coupling is a dynamical variable

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Castner, E.W. Jr.; Kennedy, D.; Cave, R.J.

    2000-04-06

    The authors combine analysis of measurements by femtosecond optical spectroscopy, computer simulations, and the generalized Mulliken-Hush (GMH) theory in the study of electron-transfer reactions and electron donor-acceptor interactions. The study focus is on ultrafast photoinduced electron-transfer reactions from aromatic amine solvent donors to excited-state acceptors. The experimental results from femtosecond dynamical measurements fall into three categories: six coumarin acceptors reductively quenched by N,N-dimethylaniline (DMA), eight electron-donating amine solvents reductively quenching coumarin 152 (7-(dimethylamino)-4-(trifluoromethyl)-coumarin), and reductive quenching dynamics of two coumarins by DMA as a function of dilution in the nonreactive solvents toluene and chlorobenzene. Applying a combination of molecular dynamicsmore » trajectories, semiempirical quantum mechanical calculations (of the relevant adiabatic electronic states), and GMH theory to the C152/DMA photoreaction, the authors calculate the electron donor/acceptor interaction parameter H{sub DA} at various time frames, H{sub DA} is strongly modulated by both inner-sphere and outer-sphere nuclear dynamics, leading us to conclude that H{sub DA} must be considered as a dynamical variable.« less

  19. Transferable Denitrification Capability of Thermus thermophilus

    PubMed Central

    Alvarez, Laura; Bricio, Carlos; Blesa, Alba; Hidalgo, Aurelio

    2014-01-01

    Laboratory-adapted strains of Thermus spp. have been shown to require oxygen for growth, including the model strains T. thermophilus HB27 and HB8. In contrast, many isolates of this species that have not been intensively grown under laboratory conditions keep the capability to grow anaerobically with one or more electron acceptors. The use of nitrogen oxides, especially nitrate, as electron acceptors is one of the most widespread capabilities among these facultative strains. In this process, nitrate is reduced to nitrite by a reductase (Nar) that also functions as electron transporter toward nitrite and nitric oxide reductases when nitrate is scarce, effectively replacing respiratory complex III. In many T. thermophilus denitrificant strains, most electrons for Nar are provided by a new class of NADH dehydrogenase (Nrc). The ability to reduce nitrite to NO and subsequently to N2O by the corresponding Nir and Nor reductases is also strain specific. The genes encoding the capabilities for nitrate (nar) and nitrite (nir and nor) respiration are easily transferred between T. thermophilus strains by natural competence or by a conjugation-like process and may be easily lost upon continuous growth under aerobic conditions. The reason for this instability is apparently related to the fact that these metabolic capabilities are encoded in gene cluster islands, which are delimited by insertion sequences and integrated within highly variable regions of easily transferable extrachromosomal elements. Together with the chromosomal genes, these plasmid-associated genetic islands constitute the extended pangenome of T. thermophilus that provides this species with an enhanced capability to adapt to changing environments. PMID:24141123

  20. NOx in the Atmosphere of Early Earth as Electron Acceptors for Life

    NASA Astrophysics Data System (ADS)

    Wong, M. L.; Charnay, B.; Gao, P.; Yung, Y. L.; Russell, M. J.

    2015-12-01

    We quantify the amount of NOx produced in the Hadean atmosphere and available in the Hadean ocean for the emergence of life. Atmospherically generated nitrate (NO3-) and nitrite (NO2-) are the most attractive high-potential electron acceptors for driving the highly endergonic reactions at the entry points to autotrophic metabolic pathways at submarine alkaline hydrothermal vents (Ducluzeau, 2008; Russell, 2014). The Hadean atmosphere, dominated by CO2 and N2, will produce nitric oxide (NO) when shocked by lightning and impacts (Ducluzeau, 2008; Nna Mvondo, 2001). Photochemical reactions involving NO and H2O vapor will then produce acids such as HNO3 and HNO2 that rain into the ocean and dissociate into NO3- and NO2-. Previous work suggests that 1018 g of NOx can be produced in a million years or so, satisfying the need for micromolar concentrations of NO3- and NO2- in the ocean (Ducluzeau, 2008). But because this number is controversial, we present new calculations based on a novel combination of early-Earth GCM and photochemical modeling, calculating the sources and sinks for fixed nitrogen. Finally, it is notable that lightning has been detected on Venus and Mars along with evidence of atmospheric NO; in the distant past, could NOx have been created and available for the emergence of life on numerous wet, rocky worlds?

  1. Single molecule-level study of donor-acceptor interactions and nanoscale environment in blends

    NASA Astrophysics Data System (ADS)

    Quist, Nicole; Grollman, Rebecca; Rath, Jeremy; Robertson, Alex; Haley, Michael; Anthony, John; Ostroverkhova, Oksana

    2017-02-01

    Organic semiconductors have attracted considerable attention due to their applications in low-cost (opto)electronic devices. The most successful organic materials for applications that rely on charge carrier generation, such as solar cells, utilize blends of several types of molecules. In blends, the local environment strongly influences exciton and charge carrier dynamics. However, relationship between nanoscale features and photophysics is difficult to establish due to the lack of necessary spatial resolution. We use functionalized fluorinated pentacene (Pn) molecule as single molecule probes of intermolecular interactions and of the nanoscale environment in blends containing donor and acceptor molecules. Single Pn donor (D) molecules were imaged in PMMA in the presence of acceptor (A) molecules using wide-field fluorescence microscopy. Two sample configurations were realized: (i) a fixed concentration of Pn donor molecules, with increasing concentration of acceptor molecules (functionalized indenflouorene or PCBM) and (ii) a fixed concentration of acceptor molecules with an increased concentration of the Pn donor. The D-A energy transfer and changes in the donor emission due to those in the acceptor- modified polymer morphology were quantified. The increase in the acceptor concentration was accompanied by enhanced photobleaching and blinking of the Pn donor molecules. To better understand the underlying physics of these processes, we modeled photoexcited electron dynamics using Monte Carlo simulations. The simulated blinking dynamics were then compared to our experimental data, and the changes in the transition rates were related to the changes in the nanoscale environment. Our study provides insight into evolution of nanoscale environment during the formation of bulk heterojunctions.

  2. Sterilisation: characteristics of vasectomy acceptors in Delhi.

    PubMed

    Sarkar, N N

    1993-01-01

    The place of vasectomy within the sterilisation programme in Delhi over the period 1983-88 is reviewed and data on vasectomy acceptance and characteristics of acceptors are analysed. Findings suggest a need to improve the strategy for the promotion of vasectomy within the metropolis.

  3. Purification of alkali metal nitrates

    DOEpatents

    Fiorucci, Louis C.; Gregory, Kevin M.

    1985-05-14

    A process is disclosed for removing heavy metal contaminants from impure alkali metal nitrates containing them. The process comprises mixing the impure nitrates with sufficient water to form a concentrated aqueous solution of the impure nitrates, adjusting the pH of the resulting solution to within the range of between about 2 and about 7, adding sufficient reducing agent to react with heavy metal contaminants within said solution, adjusting the pH of the solution containing reducing agent to effect precipitation of heavy metal impurities and separating the solid impurities from the resulting purified aqueous solution of alkali metal nitrates. The resulting purified solution of alkali metal nitrates may be heated to evaporate water therefrom to produce purified molten alkali metal nitrate suitable for use as a heat transfer medium. If desired, the purified molten form may be granulated and cooled to form discrete solid particles of alkali metal nitrates.

  4. Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

  5. Threshold-like complexation of conjugated polymers with small molecule acceptors in solution within the neighbor-effect model.

    PubMed

    Sosorev, Andrey Yu; Parashchuk, Olga D; Zapunidi, Sergey A; Kashtanov, Grigoriy S; Golovnin, Ilya V; Kommanaboyina, Srikanth; Perepichka, Igor F; Paraschuk, Dmitry Yu

    2016-02-14

    In some donor-acceptor blends based on conjugated polymers, a pronounced charge-transfer complex (CTC) forms in the electronic ground state. In contrast to small-molecule donor-acceptor blends, the CTC concentration in polymer:acceptor solution can increase with the acceptor content in a threshold-like way. This threshold-like behavior was earlier attributed to the neighbor effect (NE) in the polymer complexation, i.e., next CTCs are preferentially formed near the existing ones; however, the NE origin is unknown. To address the factors affecting the NE, we record the optical absorption data for blends of the most studied conjugated polymers, poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV) and poly(3-hexylthiophene) (P3HT), with electron acceptors of fluorene series, 1,8-dinitro-9,10-antraquinone (), and 7,7,8,8-tetracyanoquinodimethane () in different solvents, and then analyze the data within the NE model. We have found that the NE depends on the polymer and acceptor molecular skeletons and solvent, while it does not depend on the acceptor electron affinity and polymer concentration. We conclude that the NE operates within a single macromolecule and stems from planarization of the polymer chain involved in the CTC with an acceptor molecule; as a result, the probability of further complexation with the next acceptor molecules at the adjacent repeat units increases. The steric and electronic microscopic mechanisms of NE are discussed.

  6. Protein Tyrosine Nitration: Biochemical Mechanisms and Structural Basis of its Functional Effects

    PubMed Central

    Radi, Rafael

    2012-01-01

    CONSPECTUS The nitration of protein tyrosine residues to 3-nitrotyrosine represents an oxidative postranslational modification that unveils the disruption of nitric oxide (•NO) signaling and metabolism towards pro-oxidant processes. Indeed, excess levels of reactive oxygen species in the presence of •NO or •NO-derived metabolites lead to the formation of nitrating species such as peroxynitrite. Thus, protein 3-nitrotyrosine has been established as a biomarker of cell, tissue and systemic “nitroxidative stress”. Moreover, tyrosine nitration modifies key properties of the amino acid (i.e. phenol group pKa, redox potential, hydrophobicity and volume). Thus, the incorporation of a nitro group (−NO2) to protein tyrosines can lead to profound structural and functional changes, some of which contribute to altered cell and tissue homeostasis. In this Account, I describe our current efforts to define 1) biologically-relevant mechanisms of protein tyrosine nitration and 2) how this modification can cause changes in protein structure and function at the molecular level. First, the relevance of protein tyrosine nitration via free radical-mediated reactions (in both peroxynitrite-dependent or independent pathways) involving the intermediacy of tyrosyl radical (Tyr•) will be underscored. This feature of the nitration process becomes critical as Tyr• can take variable fates, including the formation of 3-nitrotyrosine. Fast kinetic techniques, electron paramagnetic resonance (EPR) studies, bioanalytical methods and kinetic simulations have altogether assisted to characterize and fingerprint the reactions of tyrosine with peroxynitrite and one-electron oxidants and its further evolution to 3-nitrotyrosine. Recent findings show that nitration of tyrosines in proteins associated to biomembranes is linked to the lipid peroxidation process via a connecting reaction that involves the one-electron oxidation of tyrosine by lipid peroxyl radicals (LOO•). Second

  7. Long-term fertilization alters the relative importance of nitrate reduction pathways in salt marsh sediments

    NASA Astrophysics Data System (ADS)

    Peng, Xuefeng; Ji, Qixing; Angell, John H.; Kearns, Patrick J.; Yang, Hannah J.; Bowen, Jennifer L.; Ward, Bess B.

    2016-08-01

    Salt marshes provide numerous valuable ecological services. In particular, nitrogen (N) removal in salt marsh sediments alleviates N loading to the coastal ocean. N removal reduces the threat of eutrophication caused by increased N inputs from anthropogenic sources. It is unclear, however, whether chronic nutrient overenrichment alters the capacity of salt marshes to remove anthropogenic N. To assess the effect of nutrient enrichment on N cycling in salt marsh sediments, we examined important N cycle pathways in experimental fertilization plots in a New England salt marsh. We determined rates of nitrification, denitrification, and dissimilatory nitrate reduction to ammonium (DNRA) using sediment slurry incubations with 15N labeled ammonium or nitrate tracers under oxic headspace (20% oxygen/80% helium). Nitrification and denitrification rates were more than tenfold higher in fertilized plots compared to control plots. By contrast, DNRA, which retains N in the system, was high in control plots but not detected in fertilized plots. The relative contribution of DNRA to total nitrate reduction largely depends on the carbon/nitrate ratio in the sediment. These results suggest that long-term fertilization shifts N cycling in salt marsh sediments from predominantly retention to removal.

  8. Phase Stabilization of Ammonium Nitrate

    DTIC Science & Technology

    2008-11-04

    substance into the ammonium nitrate crystal structure. Salts containing ions larger or smaller than either ammonium or nitrate ions have been used...introducing another substance into the ammonium nitrate crystal structure. Salts containing ions larger or smaller than either ammonium or nitrate...two ionic attachment points should yield a nonmigrating salt due to difficulty of having simultaneous dissociation of two ionic structures

  9. Biological nitrate transport in sediments on the Peruvian margin mitigates benthic sulfide emissions and drives pelagic N loss during stagnation events

    NASA Astrophysics Data System (ADS)

    Dale, A. W.; Sommer, S.; Lomnitz, U.; Bourbonnais, A.; Wallmann, K.

    2016-06-01

    Benthic N cycling in the Peruvian oxygen minimum zone (OMZ) was investigated at ten stations along 12 °S from the middle shelf (74 m) to the upper slope (1024 m) using in situ flux measurements, sediment biogeochemistry and modeling. Middle shelf sediments were covered by mats of the filamentous bacteria Thioploca spp. and contained a large 'hidden' pool of nitrate that was not detectable in the porewater. This was attributed to a biological nitrate reservoir stored within the bacteria to oxidize sulfide during 'dissimilatory nitrate reduction to ammonium' (DNRA). The extremely high rates of DNRA on the shelf (15.6 mmol m-2 d-1 of N), determined using an empirical steady-state model, could easily supply all the ammonium requirements for anammox in the water column. The model further showed that denitrification by foraminifera may account for 90% of N2 production at the lower edge of the OMZ. At the time of sampling, dissolved oxygen was below detection limit down to 400 m and the water body overlying the shelf had stagnated, resulting in complete depletion of nitrate and nitrite. A decrease in the biological nitrate pool was observed on the shelf during fieldwork concomitant with a rise in porewater sulfide levels in surface sediments to 2 mM. Using a non-steady state model to simulate this natural anoxia experiment, these observations were shown to be consistent with Thioploca surviving on a dwindling intracellular nitrate reservoir to survive the stagnation period. The model shows that sediments hosting Thioploca are able to maintain high ammonium fluxes for many weeks following stagnation, potentially sustaining pelagic N loss by anammox. In contrast, sulfide emissions remain low, reducing the economic risk to the Peruvian fishery by toxic sulfide plume development.

  10. Triplet Tellurophene-Based Acceptors for Organic Solar Cells.

    PubMed

    Yang, Lei; Gu, Wenxing; Lv, Lei; Chen, Yusheng; Yang, Yufei; Ye, Pan; Wu, Jianfei; Hong, Ling; Peng, Aidong; Huang, Hui

    2018-01-22

    Triplet materials have been employed to achieve high-performing organic solar cells (OSCs) by extending the exciton lifetime and diffusion distances, while the triplet non-fullerene acceptor materials have never been reported for bulk heterojunction OSCs. Herein, for the first time, three triplet molecular acceptors based on tellurophene with different degrees of ring fusing were designed and synthesized for OSCs. Significantly, these molecules have long exciton lifetime and diffusion lengths, leading to efficient power conversion efficiency (7.52 %), which is the highest value for tellurophene-based OSCs. The influence of the extent of ring fusing on molecular geometry and OSCs performance was investigated to show the power conversion efficiencies (PCEs) continuously increased along with increasing the extent of ring fusing. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Characterization of organic nitrate constituents of secondary organic aerosol (SOA) from nitrate-radical-initiated oxidation of limonene using high-resolution chemical ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Faxon, Cameron; Hammes, Julia; Le Breton, Michael; Kant Pathak, Ravi; Hallquist, Mattias

    2018-04-01

    The gas-phase nitrate radical (NO3⚫) initiated oxidation of limonene can produce organic nitrate species with varying physical properties. Low-volatility products can contribute to secondary organic aerosol (SOA) formation and organic nitrates may serve as a NOx reservoir, which could be especially important in regions with high biogenic emissions. This work presents the measurement results from flow reactor studies on the reaction of NO3⚫ with limonene using a High-Resolution Time-of-Flight Chemical Ionization Mass Spectrometer (HR-ToF-CIMS) combined with a Filter Inlet for Gases and AEROsols (FIGAERO). Major condensed-phase species were compared to those in the Master Chemical Mechanism (MCM) limonene mechanism, and many non-listed species were identified. The volatility properties of the most prevalent organic nitrates in the produced SOA were determined. Analysis of multiple experiments resulted in the identification of several dominant species (including C10H15NO6, C10H17NO6, C8H11NO6, C10H17NO7, and C9H13NO7) that occurred in the SOA under all conditions considered. Additionally, the formation of dimers was consistently observed and these species resided almost completely in the particle phase. The identities of these species are discussed, and formation mechanisms are proposed. Cluster analysis of the desorption temperatures corresponding to the analyzed particle-phase species yielded at least five distinct groupings based on a combination of molecular weight and desorption profile. Overall, the results indicate that the oxidation of limonene by NO3⚫ produces a complex mixture of highly oxygenated monomer and dimer products that contribute to SOA formation.

  12. Identification of groundwater nitrate sources in pre-alpine catchments: a multi-tracer approach

    NASA Astrophysics Data System (ADS)

    Stoewer, Myriam; Stumpp, Christine

    2014-05-01

    Porous aquifers in pre-alpine areas are often used as drinking water resources due to their good water quality status and water yield. Maintaining these resources requires knowledge about possible sources of pollutants and a sustainable management practice in groundwater catchment areas. Of particular interest in agricultural areas, like in pre-alpine regions, is limiting nitrate input as main groundwater pollutant. Therefore, the objective of the presented study is i) to identify main nitrate sources in a pre-alpine groundwater catchment with current low nitrate concentration using stable isotopes of nitrate (d18O and d15N) and ii) to investigate seasonal dynamics of nitrogen compounds. The groundwater catchment areas of four porous aquifers are located in Southern Germany. Most of the land use is organic grassland farming as well as forestry and residential area. Thus, potential sources of nitrate mainly are mineral fertilizer, manure/slurry, leaking sewage system and atmospheric deposition of nitrogen compounds. Monthly freshwater samples (precipitation, river water and groundwater) are analysed for stable isotope of water (d2H, d18O), the concentration of major anions and cations, electrical conductivity, water temperature, pH and oxygen. In addition, isotopic analysis of d18O-NO3- and d15N-NO3- for selected samples is carried out using the denitrifier method. In general, all groundwater samples were oxic (10.0±2.6mg/L) and nitrate concentrations were low (0.2 - 14.6mg/L). The observed nitrate isotope values in the observation area compared to values from local precipitation, sewage, manure and mineral fertilizer as well as to data from literature shows that the nitrate in freshwater samples is of microbial origin. Nitrate derived from ammonium in fertilizers and precipitation as well as from soil nitrogen. It is suggested that a major potential threat to the groundwater quality is ammonia and ammonium at a constant level mainly from agriculture activities as

  13. Energetic Ionic Liquids Based on Anionic Rare Earth Nitrate Complexes (Preprint)

    DTIC Science & Technology

    2008-07-10

    a glass transition temperature (Tg) at -46 oC. However, it is only stable in dry air, and thus must be protected from water. At 75 oC, clear weight...involved highly toxic and corrosive chemicals, N2O4 and NOCl. Ligands which coordinate via oxygen atoms to a rare earth metal ion give rise to stable...complexes. Thus higher air and thermal stabilities may be obtained by introducing rare earth metal nitrates as main components of ionic liquids. We

  14. Organic Donor-Acceptor Complexes as Novel Organic Semiconductors.

    PubMed

    Zhang, Jing; Xu, Wei; Sheng, Peng; Zhao, Guangyao; Zhu, Daoben

    2017-07-18

    Organic donor-acceptor (DA) complexes have attracted wide attention in recent decades, resulting in the rapid development of organic binary system electronics. The design and synthesis of organic DA complexes with a variety of component structures have mainly focused on metallicity (or even superconductivity), emission, or ferroelectricity studies. Further efforts have been made in high-performance electronic investigations. The chemical versatility of organic semiconductors provides DA complexes with a great number of possibilities for semiconducting applications. Organic DA complexes extend the semiconductor family and promote charge separation and transport in organic field-effect transistors (OFETs) and organic photovoltaics (OPVs). In OFETs, the organic complex serves as an active layer across extraordinary charge pathways, ensuring the efficient transport of induced charges. Although an increasing number of organic semiconductors have been reported to exhibit good p- or n-type properties (mobilities higher than 1 or even 10 cm 2 V -1 s -1 ), critical scientific challenges remain in utilizing the advantages of existing semiconductor materials for more and wider applications while maintaining less complicated synthetic or device fabrication processes. DA complex materials have revealed new insight: their unique molecular packing and structure-property relationships. The combination of donors and acceptors could offer practical advantages compared with their unimolecular materials. First, growing crystals of DA complexes with densely packed structures will reduce impurities and traps from the self-assembly process. Second, complexes based on the original structural components could form superior mixture stacking, which can facilitate charge transport depending on the driving force in the coassembly process. Third, the effective use of organic semiconductors can lead to tunable band structures, allowing the operation mode (p- or n-type) of the transistor to be

  15. Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures.

    PubMed

    Vavilin, V A; Rytov, S V

    2015-09-01

    A kinetic analysis of nitrate denitrification by a single or two species of denitrifying bacteria with glucose or ethanol as a carbon source and nitrite or nitrous oxide as intermediate products was performed using experimental data published earlier (Menyailo and Hungate, 2006; Vidal-Gavilan et al., 2013). Modified Monod kinetics was used in the dynamic biological model. The special equations were added to the common dynamic biological model to describe how isotopic fractionation between N species changes. In contrast to the generally assumed first-order kinetics, in this paper, the traditional Rayleigh equation describing stable nitrogen and oxygen isotope fractionation in nitrate was derived from the dynamic isotopic equations for any type of kinetics. In accordance with the model, in Vidal-Gavilan's experiments, the maximum specific rate of nitrate reduction was proved to be less for ethanol compared to glucose. Conversely, the maximum specific rate of nitrite reduction was proved to be much less for glucose compared to ethanol. Thus, the intermediate nitrite concentration was negligible for the ethanol experiment, while it was significant for the glucose experiment. In Menyailo's and Hungate's experiments, the low value of maximum specific rate of nitrous oxide reduction gives high intermediate value of nitrous oxide concentration. The model showed that the dynamics of nitrogen and oxygen isotope signatures are responding to the biological dynamics. Two microbial species instead of single denitrifying bacteria are proved to be more adequate to describe the total process of nitrate denitrification to dinitrogen. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. Nitrate addition to groundwater impacted by ethanol-blended fuel accelerates ethanol removal and mitigates the associated metabolic flux dilution and inhibition of BTEX biodegradation

    NASA Astrophysics Data System (ADS)

    Corseuil, Henry Xavier; Gomez, Diego E.; Schambeck, Cássio Moraes; Ramos, Débora Toledo; Alvarez, Pedro J. J.

    2015-03-01

    A comparison of two controlled ethanol-blended fuel releases under monitored natural attenuation (MNA) versus nitrate biostimulation (NB) illustrates the potential benefits of augmenting the electron acceptor pool with nitrate to accelerate ethanol removal and thus mitigate its inhibitory effects on BTEX biodegradation. Groundwater concentrations of ethanol and BTEX were measured 2 m downgradient of the source zones. In both field experiments, initial source-zone BTEX concentrations represented less than 5% of the dissolved total organic carbon (TOC) associated with the release, and measurable BTEX degradation occurred only after the ethanol fraction in the multicomponent substrate mixture decreased sharply. However, ethanol removal was faster in the nitrate amended plot (1.4 years) than under natural attenuation conditions (3.0 years), which led to faster BTEX degradation. This reflects, in part, that an abundant substrate (ethanol) can dilute the metabolic flux of target pollutants (BTEX) whose biodegradation rate eventually increases with its relative abundance after ethanol is preferentially consumed. The fate and transport of ethanol and benzene were accurately simulated in both releases using RT3D with our general substrate interaction module (GSIM) that considers metabolic flux dilution. Since source zone benzene concentrations are relatively low compared to those of ethanol (or its degradation byproduct, acetate), our simulations imply that the initial focus of cleanup efforts (after free-product recovery) should be to stimulate the degradation of ethanol (e.g., by nitrate addition) to decrease its fraction in the mixture and speed up BTEX biodegradation.

  17. Direct Analysis in Real Time Mass Spectrometry of Potential By-Products from Homemade Nitrate Ester Explosive Synthesis

    PubMed Central

    Sisco, Edward; Forbes, Thomas P.

    2016-01-01

    This work demonstrates the coupling of direct analysis in real time (DART) ionization with time-of-flight mass spectrometry (MS) in an off-axis configuration for the trace detection and analysis of potential partially nitrated and dimerized by-products of homemade nitrate ester explosive synthesis. Five compounds relating to the synthesis of nitroglycerin (NG) and pentaerythritol tetranitrate (PETN) were examined. Deprotonated ions and adducts with molecular oxygen, nitrite, and nitrate were observed in the mass spectral responses of these compounds. A global optimum temperature of 350 °C for the by-products investigated here, enabled single nanogram to sub nanogram trace detection. Matrix effects were examined through a series of mixtures containing one or more compounds (sugar alcohol precursors, by-products, and/or explosives) across a range of mass loadings. The explosives MS responses experienced competitive ionization in the presence of all by-products. The magnitude of this influence corresponded to both the degree of by-product nitration and the relative mass loading of the by-product to the explosive. This work provides a characterization of potential by-products from homemade nitrate ester synthesis, including matrix effects and potential challenges that might arise from the trace detection of homemade explosives (HMEs) containing impurities. Detection and understanding of HME impurities and complex mixtures may provide valuable information for the screening and sourcing of homemade nitrate ester explosives. PMID:26838397

  18. Direct analysis in real time mass spectrometry of potential by-products from homemade nitrate ester explosive synthesis.

    PubMed

    Sisco, Edward; Forbes, Thomas P

    2016-04-01

    This work demonstrates the coupling of direct analysis in real time (DART) ionization with time-of-flight mass spectrometry (MS) in an off-axis configuration for the trace detection and analysis of potential partially nitrated and dimerized by-products of homemade nitrate ester explosive synthesis. Five compounds relating to the synthesis of nitroglycerin (NG) and pentaerythritol tetranitrate (PETN) were examined. Deprotonated ions and adducts with molecular oxygen, nitrite, and nitrate were observed in the mass spectral responses of these compounds. A global optimum temperature of 350 °C for the by-products investigated here enabled single nanogram to sub nanogram trace detection. Matrix effects were examined through a series of mixtures containing one or more compounds (sugar alcohol precursors, by-products, and/or explosives) across a range of mass loadings. The explosives MS responses experienced competitive ionization in the presence of all by-products. The magnitude of this influence corresponded to both the degree of by-product nitration and the relative mass loading of the by-product to the explosive. This work provides a characterization of potential by-products from homemade nitrate ester synthesis, including matrix effects and potential challenges that might arise from the trace detection of homemade explosives (HMEs) containing impurities. Detection and understanding of HME impurities and complex mixtures may provide valuable information for the screening and sourcing of homemade nitrate ester explosives. Published by Elsevier B.V.

  19. Microbial Reduction of Chromate in the Presence of Nitrate by Three Nitrate Respiring Organisms

    PubMed Central

    Chovanec, Peter; Sparacino-Watkins, Courtney; Zhang, Ning; Basu, Partha; Stolz, John F.

    2012-01-01

    A major challenge for the bioremediation of toxic metals is the co-occurrence of nitrate, as it can inhibit metal transformation. Geobacter metallireducens, Desulfovibrio desulfuricans, and Sulfurospirillum barnesii are three soil bacteria that can reduce chromate [Cr(VI)] and nitrate, and may be beneficial for developing bioremediation strategies. All three organisms respire through dissimilatory nitrate reduction to ammonia (DNRA), employing different nitrate reductases but similar nitrite reductase (Nrf). G. metallireducens reduces nitrate to nitrite via the membrane bound nitrate reductase (Nar), while S. barnesii and D. desulfuricans strain 27774 have slightly different forms of periplasmic nitrate reductase (Nap). We investigated the effect of DNRA growth in the presence of Cr(VI) in these three organisms and the ability of each to reduce Cr(VI) to Cr(III), and found that each organisms responded differently. Growth of G. metallireducens on nitrate was completely inhibited by Cr(VI). Cultures of D. desulfuricans on nitrate media was initially delayed (48 h) in the presence of Cr(VI), but ultimately reached comparable cell yields to the non-treated control. This prolonged lag phase accompanied the transformation of Cr(VI) to Cr(III). Viable G. metallireducens cells could reduce Cr(VI), whereas Cr(VI) reduction by D. desulfuricans during growth, was mediated by a filterable and heat stable extracellular metabolite. S. barnesii growth on nitrate was not affected by Cr(VI), and Cr(VI) was reduced to Cr(III). However, Cr(VI) reduction activity in S. barnesii, was detected in both the cell free spent medium and cells, indicating both extracellular and cell associated mechanisms. Taken together, these results have demonstrated that Cr(VI) affects DNRA in the three organisms differently, and that each have a unique mechanism for Cr(VI) reduction. PMID:23251135

  20. The Arabidopsis NRG2 Protein Mediates Nitrate Signaling and Interacts with and Regulates Key Nitrate Regulators[OPEN

    PubMed Central

    Zhao, Lufei; Zhang, Chengfei; Li, Zehui; Lei, Zhao; Liu, Fei; Guan, Peizhu; Crawford, Nigel M.

    2016-01-01

    We show that NITRATE REGULATORY GENE2 (NRG2), which we identified using forward genetics, mediates nitrate signaling in Arabidopsis thaliana. A mutation in NRG2 disrupted the induction of nitrate-responsive genes after nitrate treatment by an ammonium-independent mechanism. The nitrate content in roots was lower in the mutants than in the wild type, which may have resulted from reduced expression of NRT1.1 (also called NPF6.3, encoding a nitrate transporter/receptor) and upregulation of NRT1.8 (also called NPF7.2, encoding a xylem nitrate transporter). Genetic and molecular data suggest that NRG2 functions upstream of NRT1.1 in nitrate signaling. Furthermore, NRG2 directly interacts with the nitrate regulator NLP7 in the nucleus, but nuclear retention of NLP7 in response to nitrate is not dependent on NRG2. Transcriptomic analysis revealed that genes involved in four nitrogen-related clusters including nitrate transport and response to nitrate were differentially expressed in the nrg2 mutants. A nitrogen compound transport cluster containing some members of the NRT/PTR family was regulated by both NRG2 and NRT1.1, while no nitrogen-related clusters showed regulation by both NRG2 and NLP7. Thus, NRG2 plays a key role in nitrate regulation in part through modulating NRT1.1 expression and may function with NLP7 via their physical interaction. PMID:26744214