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Sample records for cerium nitrates

  1. [Determination of silver and cerium in the liver and the kidney from a severely burned infant treated with silver sulfadiazine and cerium nitrate].

    PubMed

    Hirakawa, K

    1983-02-01

    Silver and cerium in the liver and the kidney from severely burned infant were analyzed by neutron activation method. The patient was treated topically with cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for 3 months. Then, the treatment with these drugs was stopped because of abdominal distention. The patient died 1 month after the cessation of the treatment with these drugs. The tissue specimens, blank liver sample and reference standards were irradiated with TRIGA MARK II Reactor of Rikkyo University. About 1 month after the irradiation, the activities were measured with a Ge(Li) detector coupled to a 4096 channel pulse height analyzer. A large amount of silver was detected both in the liver and in the kidney and a trace of cerium only in the liver. A considerable amount of silver was detected in the liver and its quantity was about 1600 times more than that of normal livers reported by Hamilton, Minski and Cleary (1972-73). Neither silver nor cerium were detected in the blank liver. These results suggest that prolonged topical chemotherapy of cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for the extensive burn injuries causes considerable absorption of silver and cerium into the liver and the kidney. PMID:6867381

  2. Application of cerium nitrate-silver sulphadiazine allows for postponement of excision and grafting.

    PubMed

    Vehmeyer-Heeman, M; Tondu, T; Van den Kerckhove, E; Boeckx, W

    2006-02-01

    Early excision and grafting cannot always be performed due to patient's medical status, and the lack of adequate donor sites. The use of cerium nitrate-silver sulphadiazine cream, which causes the formation of a leather-like eschar with excellent resistance to infection, is an alternative method. In order to postpone operations by using cerium nitrate-silver sulphadiazine, we compared the differences in contamination of the grafted areas between early and delayed excision. Eighteen patients underwent excision and grafting within 5 days post burn and nineteen patients were surgically treated after 5 days. Twelve months later the grafted areas were evaluated. Contamination of the grafted area occurred in 17 patients. No differences in contamination occurred between the early and delayed excision group, 8 versus 9. Also no differences in type of organism cultured and follow-up results were found between the early and delayed excision group. Cerium nitrate-silver sulphadiazine allows surgical treatment to be delayed without an increase of contamination of the grafted area and does not adversely affect the long-term outcome.

  3. Falsely raised whole blood chloride caused by systemic absorption of cerium nitrate cream for burns.

    PubMed

    Ha, Leah Y; Woollard, Gerald A; Chiu, Weldon W

    2015-03-01

    Whole blood, serum or plasma chloride is almost exclusively measured by potentiometry with an ion-selective chloride electrode which utilizes membrane selectivity to chloride ions. Other anions such as bromide, iodide and thiosulphate can interfere but usually are not present in high enough concentration to cause significant cross reactivity. A patient from our burns unit had serial chloride measurements on a Radiometer ABL800 blood gas analyser. The results were higher in contrast to plasma measurements on the Abbott Architect Ci8200, which were within reference intervals and in line with the patient's pathophysiological status. This indicated a likely interference with the blood gas analyser chloride estimation. The chloride results on the ABL800 for 3rd, 4th and 5th day after the burn accident were 170, 137 and 119 mmol/L. Corresponding plasma chloride results on the Ci8200 were all around 105 mmol/L. Nitrate was found to be markedly elevated in these samples, and the results were 6.7, 4.9 and 1.1 mmol/L, respectively (reference limit < 0.08 mmol/L). To further demonstrate nitrate was the causative agent, pooled plasma spiked with 7 mmol/L of sodium nitrate caused a rise in the ABL800 chloride from 105 to 202 mmol/L. Later we confirmed that the patient was topically medicated with cerium nitrate cream (Flammacerium®, Sinclair IS Pharma, UK) for his burns. In summary, the results clearly indicated nitrate was the interferent with the ABL800 chloride estimation and the source was the topical burns cerium nitrate cream.

  4. Cerium(IV) ammonium nitrate mediated 5-endo-dig cyclization of α-amino allenylphosphonates to spirodienones.

    PubMed

    Adler, Pauline; Fadel, Antoine; Rabasso, Nicolas

    2015-02-28

    α-Amino allenylphosphonates were treated with cerium(iv) ammonium nitrate under various conditions to form spirodienones in good to excellent yields. The 5-endo-dig cyclization proceeds through the formation of a key iminium intermediate. A comprehensive study on the nature of the solvent used for this reaction was undertaken resulting in the formation of three types of spirodienone scaffolds. PMID:25634577

  5. Topical application of cerium nitrate prevents burn edema after burn plasma transfer.

    PubMed

    Kremer, Thomas; Hernekamp, F; Riedel, K; Peter, Ch; Gebhardt, M M; Germann, G; Heitmann, Ch; Walther, Andreas

    2009-12-01

    Thermal injuries of more than 20% body surface area (BSA) result in systemic capillary leakage with subsequent edema. This can similarly be induced by burn plasma transfer (BPT) from burned individuals to healthy rats. We evaluated if cerium nitrate (CN) bathing can prevent edema after BPT. Therefore, donor rats (DR) underwent thermal injury (100 degrees C water, 30%BSA, 12 s) for positive controls and were additionally bathed in CN (0.05M, at 10 and 120 min) for study groups. For negative controls DR underwent shamburn (37 degrees C water, 30%BSA, 12 s). DR-plasma (harvested 4 h post trauma) was transferred to healthy individuals. Intravital microscopy was performed in mesenteric venules (0/60/120 min). Edema was assessed by FITC-albumin extravasation. Additionally, leukocyte sticking (cells/mm(2)) and micro hemodynamic parameters were assessed. Significant systemic capillary leakage was observed after BPT at 120 min. Edema formation was significantly lower in negative controls. Topical CN application after 10 and 120 min reduced FITC-efflux to baseline levels. Adherent leukocytes increased slightly in all groups. Leukocyte-sticking tended to be reduced after CN bathing. In conclusion, BPT induces burn edema in healthy individuals. CN bathing after 10 and 120 min reduces mediator levels in burned individuals. Therefore, BPT after CN application does not induce burn shock anymore. Burn edema is partially independent from leukocyte activation because CN significantly influences macromolecular leakage whereas leukocyte activation is not significantly altered.

  6. Cerium(IV) ammonium nitrate is an excellent, general catalyst for the Friedländer and Friedländer-Borsche quinoline syntheses: very efficient access to the antitumor alkaloid luotonin A.

    PubMed

    Sridharan, Vellaisamy; Ribelles, Pascual; Ramos, Ma Teresa; Menéndez, J Carlos

    2009-08-01

    The use of cerium(IV) ammonium nitrate as a catalyst of the Friedländer reaction allows the synthesis of polysubstituted quinoline derivatives in excellent yields, avoiding the traditional harshly basic or acidic conditions. Unlike most other previously known reagents, CAN allows double condensations and is also an excellent catalyst for the Borsche variation of the Friedländer reaction, which has been applied to the very efficient synthesis of the antitumor alkaloid luotonin A.

  7. Cerium Oxide and Cerium Compounds

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 08 / 002F www.epa.gov / iris TOXICOLOGICAL REVIEW OF Cerium Oxide and Cerium Compounds ( CAS No . 1306 - 38 - 3 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) September 2009 U.S . Environmental Protection Agency Washington , DC ii DISCLAIMER Th

  8. Nitrate

    Integrated Risk Information System (IRIS)

    Nitrate ; CASRN 14797 - 55 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects

  9. PLUTONIUM-CERIUM ALLOY

    DOEpatents

    Coffinberry, A.S.

    1959-01-01

    An alloy is presented for use as a reactor fuel. The binary alloy consists essentially of from about 5 to 90 atomic per cent cerium and the balance being plutonium. A complete phase diagram for the cerium--plutonium system is given.

  10. Studies of Solution Deposited Cerium Oxide Thin Films on Textured Ni-Alloy Substractes for YBCO Superconductor

    SciTech Connect

    Stewart, Erin L; Bhuiyan, Md S; Sathyamurthy, Srivatsan; Paranthaman, Mariappan Parans

    2006-01-01

    Cerium oxide (CeO2) buffer layers play an important role for the development of YBa2Cu3O7-x (YBCO) based superconducting tapes using the rolling assisted biaxially textured substrates (RABiTS) approach. The chemical solution deposition (CSD) approach has been used to grow epitaxial CeO2 films on textured Ni-3 a 4% W alloy substrates with various starting precursors of ceria. Precursors such as cerium acetate, cerium acetylacetonate, cerium 2-ethylhexanoate, cerium nitrate, and cerium trifluoroacetate were prepared in suitable solvents. The optimum growth conditions for these cerium precursors were Ar-4% H2 gas processing atmosphere, solution concentration levels of 0.2-0.5 M, a dwell time of 15 min, and a process temperature range of 1050-1150 degrees C. X-ray diffraction, AFM, SEM, and optical microscopy were used to characterize the CeO2 films. Highly textured CeO2 layers were obtained on Ni-W substrates with both cerium acetate and cerium acetylacetonate as starting precursors. YBCO films with a Jc of 1.5 MA/cm2 were obtained on cerium acetylacetonate-based CeO2 films with sputtered YSZ and CeO2 cap layers.

  11. Cerium compounds as scintillators

    SciTech Connect

    Wojtowicz, A.J.; Berman, E.; Koepke, C.; Lempicki, A.

    1991-01-01

    Stoichiometric Ce-materials with negligible Ce-Ce interactions should have superior scintillator properties. We present two materials: CeF{sub 3} and Ce{sub x}La{sub 1-x}P{sub 5}O{sub 14}. While cerium trifluoride is a known scintillator, pentaphosphate is of a limited usefulness, except as a remarkable model material. We show that quenching in fluoride is responsible for loss of 50% of the light output and is the cause of the, so-called, ultra fast component (2 ns). Light output of fluoride (about 50% of BGO) could be significantly improved. Deeper understanding of Ce-systems is needed to fully exploit their potentials. 10 figs., 6 refs.

  12. Cerium compounds as scintillators

    SciTech Connect

    Wojtowicz, A.J.; Berman, E.; Koepke, C.; Lempicki, A.

    1991-12-31

    Stoichiometric Ce-materials with negligible Ce-Ce interactions should have superior scintillator properties. We present two materials: CeF{sub 3} and Ce{sub x}La{sub 1-x}P{sub 5}O{sub 14}. While cerium trifluoride is a known scintillator, pentaphosphate is of a limited usefulness, except as a remarkable model material. We show that quenching in fluoride is responsible for loss of 50% of the light output and is the cause of the, so-called, ultra fast component (2 ns). Light output of fluoride (about 50% of BGO) could be significantly improved. Deeper understanding of Ce-systems is needed to fully exploit their potentials. 10 figs., 6 refs.

  13. Synthesis and catalytic properties of microemulsion-derived cerium oxide nanoparticles

    SciTech Connect

    Kockrick, Emanuel; Schrage, Christian; Grigas, Anett; Geiger, Dorin; Kaskel, Stefan

    2008-07-15

    The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated. Cerium hydroxide nanoparticles were synthesized by adding diluted ammonia to n-heptane-surfactant-cerium nitrate system. The micelle and particle size in the range of 5-12 nm were controlled by varying the molar water to surfactant ratio and analyzed by dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM). Cerium hydroxide nanoparticles were isolated and subsequently treated at 100-600 deg. C to obtain nanoscale ceria. Crystallite sizes of cerium dioxide in the range of 6-16 nm were estimated by Scherrer analysis by X-ray diffraction (XRD) and HRTEM. The catalytic activity of particles annealed at 400 and 600 deg. C in soot combustion reactions was characterized by temperature-programmed oxidation (TPO) indicating a size-dependant activity. Crystallite sizes and catalytic stability of elevated ceria systems were tested in second combustion cycles. - Graphical abstract: The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated using small angle X-ray scattering, dynamic light scattering and high-resolution transmission electron microscopy. Catalytic activity of ceria nanoparticles was tested in soot combustion reaction indicating size-dependent reactivity.

  14. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  15. PLUTONIUM-CERIUM-COBALT AND PLUTONIUM-CERIUM-NICKEL ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-08-25

    >New plutonium-base teroary alloys useful as liquid reactor fuels are described. The alloys consist of 10 to 20 atomic percent cobalt with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 88 atomic percent; or, of from 10 to 25 atomic percent nickel (or mixture of nickel and cobalt) with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 86 atomic percent. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are a lower melting point and a wide range of permissible plutonium dilution.

  16. Cerium ion conducting solid electrolyte

    NASA Astrophysics Data System (ADS)

    Hasegawa, Yasunori; Imanaka, Nobuhito; Adachi, Gin-ya

    2003-02-01

    A cerium ion conducting solid electrolyte, (Ce xZr 1- x) 4/4- xNb(PO 4) 3, was successfully realized with the NASICON-type structure which possesses a three-dimensional network, especially suitable for bulky ion migration. The cerium ion conductivity exceeds approximately one order of magnitude in comparison to that of the rare-earth ion conducting R2(WO 4) 3 and R1/3Zr 2(PO 4) 3 ( R=Sc, Y, Eu-Lu) series and the value is in the range between typical oxide anion conductors of yttria stabilized zirconia (YSZ) and calcia stabilized zirconia (CSZ). Since cerium ion has been demonstrated to be another migrating ion species in solid electrolyte field, a promising application for various functional materials is greatly expected.

  17. Green synthesized cerium oxide nanoparticle: A prospective drug against oxidative harm.

    PubMed

    Dutta, Debanjan; Mukherjee, Riya; Patra, Mousumi; Banik, Milon; Dasgupta, Rakhi; Mukherjee, Manabendra; Basu, Tarakdas

    2016-11-01

    Cerium oxide nanoparticle (CeONP) of size 2-3nm was synthesized by a new, simple and green method at ambient temperature, using cerium nitrate as prime precursor and Aloe vera leaf extract as stabilizing agent. Of the two oxidation states (+3) and (+4) of cerium, it was dominantly present in (+3) state in CeONP and cyclic conversion of Ce(III)O→Ce(IV)O→Ce(III)O by reaction with H2O2 implied uninterrupted antioxidant property of CeONP. Moreover, the higher oxygen defect in the crystal lattice produced particles with higher antioxidant activity. CeONP was found to neutralize the deleterious effects of H2O2 viz., cell death, generation of intracellular reactive oxygen species and loss of connectivity in mouse neural cells. Therefore, CeONP might have potential use in future as an anti-oxidant drug.

  18. Green synthesized cerium oxide nanoparticle: A prospective drug against oxidative harm.

    PubMed

    Dutta, Debanjan; Mukherjee, Riya; Patra, Mousumi; Banik, Milon; Dasgupta, Rakhi; Mukherjee, Manabendra; Basu, Tarakdas

    2016-11-01

    Cerium oxide nanoparticle (CeONP) of size 2-3nm was synthesized by a new, simple and green method at ambient temperature, using cerium nitrate as prime precursor and Aloe vera leaf extract as stabilizing agent. Of the two oxidation states (+3) and (+4) of cerium, it was dominantly present in (+3) state in CeONP and cyclic conversion of Ce(III)O→Ce(IV)O→Ce(III)O by reaction with H2O2 implied uninterrupted antioxidant property of CeONP. Moreover, the higher oxygen defect in the crystal lattice produced particles with higher antioxidant activity. CeONP was found to neutralize the deleterious effects of H2O2 viz., cell death, generation of intracellular reactive oxygen species and loss of connectivity in mouse neural cells. Therefore, CeONP might have potential use in future as an anti-oxidant drug. PMID:27478962

  19. Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

    PubMed

    Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

    2005-12-01

    This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

  20. Fungus mediated synthesis of biomedically important cerium oxide nanoparticles

    SciTech Connect

    Khan, Shadab Ali; Ahmad, Absar

    2013-10-15

    Graphical abstract: - Highlights: • First time biological synthesis of cerium oxide oxide nanoparticles using fungus Humicola sp. • Complete characterization of cerium oxide nanoparticles. • Biosynthesis of naturally protein capped, luminescent and water dispersible CeO{sub 2} nanoparticles. • Biosynthesized CeO{sub 2} nanoparticles can be used for many biomedical applications. - Abstract: Nanomaterials can be synthesized by chemical, physical and the more recently discovered biological routes. The biological routes are advantageous over the chemical and physical ones as unlike these, the biological synthesis protocols occur at ambient conditions, are cheap, non-toxic and eco-friendly. Although purely biological and bioinspired methods for the synthesis of nanomaterials are environmentally benign and energy conserving processes, their true potential has not been explored yet and attempts are being made to extend the formation of technologically important nanoparticles using microorganisms like fungi. Though there have been reports on the biosynthesis of oxide nanoparticles by our group in the past, no attempts have been made to employ fungi for the synthesis of nanoparticles of rare earth metals or lanthanides. Here we report for the first time, the bio-inspired synthesis of biomedically important cerium oxide (CeO{sub 2}) nanoparticles using the thermophilic fungus Humicola sp. The fungus Humicola sp. when exposed to aqueous solutions of oxide precursor cerium (III) nitrate hexahydrate (CeN{sub 3}O{sub 9}·6H{sub 2}O) results in the extracellular formation of CeO{sub 2} nanoparticles containing Ce (III) and Ce (IV) mixed oxidation states, confirmed by X-ray Photoemission Spectroscopy (XPS). The formed nanoparticles are naturally capped by proteins secreted by the fungus and thus do not agglomerate, are highly stable, water dispersible and are highly fluorescent as well. The biosynthesized nanoparticles were characterized by UV–vis spectroscopy

  1. PLUTONIUM-CERIUM-COPPER ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-05-12

    A low melting point plutonium alloy useful as fuel is a homogeneous liquid metal fueled nuclear reactor is described. Vessels of tungsten or tantalum are useful to contain the alloy which consists essentially of from 10 to 30 atomic per cent copper and the balance plutonium and cerium. with the plutontum not in excess of 50 atomic per cent.

  2. IRIS Toxicological Review of Cerium Oxide and Cerium Compounds (External Review Draft)

    EPA Science Inventory

    EPA conducted a peer review of the scientific basis supporting the human health hazard and dose-response assessment of cerium oxide and cerium compounds that will appear on the Integrated Risk Information System (IRIS) database.

  3. Nanoparticle cerium oxide and mixed cerium oxides for improved fuel cell lifetime

    NASA Astrophysics Data System (ADS)

    Stewart, Stephen Michael

    While there is a rich body of literature concerning of properties of bulk cerium oxide and cerium cations in solution, the discussion has been inappropriately applied to nanoscale cerium oxide resulting in many unexpected or unexplained results. In particular, there is very limited understanding about the properties of cerium oxide and its potential use as a radical scavenger, and how the catalytic properties of cerium oxide change as the particle size approaches the nanoscale. For example, the involvement of Ce+4 and Ce+3 cations in reactions such as hydrogen peroxide decomposition have been investigated for both cerium cations and bulk cerium oxide. However, while both are assumed to decompose hydrogen peroxide through the same mechanism, whereby Ce+4 is involved in peroxide decomposition while Ce +3 is involved in radical scavenging, there has been very little done to address how the selectivity and activity of these reactions are affected by changing the majority cation population, as cerium cations in solution are predominantly in the +3 oxidation state while cerium cations are predominantly in the +4 oxidation state in cerium oxide. This matter is further complicated in cerium oxide nanoparticles where the surface concentration of Ce +3 cations is increased due to particle curvature effects. Due to the potential of controlling the surface cerium oxidation state using particle size and using this control to change the catalytic properties, this project investigated the effect of particle size and composition and the activity and selectivity of cerium oxide nanoparticles, and has served to expand the understanding of the properties of pure and mixed nanoparticle cerium oxide. This work explains the metric developed for measuring the catalytic properties of pure and mixed cerium oxide nanoparticles, which is also good at predicting the immediate and long-term behavior of nanoparticles in hydrogen fuel cells. This work also directly demonstrates praseodymium

  4. 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.

  5. 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

  6. Grain Growth in Cerium Metal

    NASA Astrophysics Data System (ADS)

    Cooley, Jason; Katz, Martha; Mielke, Charles; Montalvo, Joel

    We report on grain growth in forged and rolled cerium plate for temperatures from 350 to 700 degrees C and times from 30 to 120 minutes. The cerium was made by arc-melting into a 25 mm deep by 80 mm diameter copper mold. The resulting disk was forged at room temperature to a 25% reduction of thickness four times with a 350 degree C strain relief heat treatment for 60 minutes between forging steps. The resulting 8 mm thick plate was clock rolled at room temperature to a 25% reduction of thickness three times with a 350 C strain relief heat treatment between steps resulting in a plate approximately 3 mm thick. 5 x 10 mm coupons were cut from the plate for the grain growth study.

  7. ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

    DOEpatents

    Roberts, F.P.

    1963-08-13

    Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

  8. Formulation and method for preparing gels comprising hydrous cerium oxide

    DOEpatents

    Collins, Jack L; Chi, Anthony

    2013-05-07

    Formulations useful for preparing hydrous cerium oxide gels contain a metal salt including cerium, an organic base, and a complexing agent. Methods for preparing gels containing hydrous cerium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including cerium, an organic base, and a complexing agent.

  9. Determination of Ideal Broth Formulations Needed to Prepare Hydrous Cerium Oxide Microspheres via the Internal Gelation Process

    SciTech Connect

    Collins, Jack Lee; Chi, Anthony

    2009-02-01

    A simple test tube methodology was used to determine optimum process parameters for preparing hydrous cerium oxide microspheres via the internal gelation process.1 Broth formulations of cerium ammonium nitrate [(NH4)2Ce(NO3)6], hexamethylenetetramine, and urea were found that can be used to prepare hydrous cerium oxide gel spheres in the temperature range of 60 to 90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations to be able to equate the test-tube gelation times to actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broth formulations.

  10. Virus removal by biogenic cerium.

    PubMed

    De Gusseme, Bart; Du Laing, Gijs; Hennebel, Tom; Renard, Piet; Chidambaram, Dev; Fitts, Jeffrey P; Bruneel, Els; Van Driessche, Isabel; Verbeken, Kim; Boon, Nico; Verstraete, Willy

    2010-08-15

    The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups of the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L(-1) bio-Ce. Given the fact that virus removal with 50 mg L(-1) Ce(III) as CeNO(3) was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal. PMID:20704235

  11. Virus Removal by Biogenic Cerium

    SciTech Connect

    De Gusseme, B.; Du Laing, G; Hennebel, T; Renard, P; Chidambaram, D; Fitts, J; Bruneel, E; Van Driessche, I; Verbeken, K; et. al.

    2010-01-01

    The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups of the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L{sup -1} bio-Ce. Given the fact that virus removal with 50 mg L{sup -1} Ce(III) as CeNO{sub 3} was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.

  12. Induction of early bolting in Arabidopsis thaliana by triacontanol, cerium and lanthanum is correlated with increased endogenous concentration of isopentenyl adenosine (iPAdos).

    PubMed

    He, Ya-Wen; Loh, Chiang-Shiong

    2002-03-01

    The effects of triacontanol (TRIA), applied singly or in combination with cerium nitrate and lanthanum nitrate, on bolting of Arabidopsis thaliana were studied. Triacontanol (0.1 to 0.6 microM) added to the culture medium induced early bolting. TRIA (0.3 microM) applied with low concentrations of cerium and lanthanum caused a synergistic stimulation of bolting. In medium containing 0.3 microM TRIA, 0.1 microM cerium nitrate and 0.1 mM lanthanum nitrate, 82% of the plants bolted 20 d after seed sowing compared to only 8.6% in basal medium and 47.8% in medium with TRIA only. The changes in the endogenous concentrations of total cytokinins of the isopentenyl adenine (IP) subfamily in the leaf and root tissues were correlated with TRIA-induced early bolting. The combined treatment of TRIA (0.3 microM), cerium nitrate (0.1 microM) and lanthanum nitrate (0.1 mM) resulted in a significant increase in the endogenous concentrations of total cytokinins of the IP subfamily in the root and leaf tissues compared to plants growing in the basal medium and medium with TRIA. The exogenous application of six natural cytokinins to the plants revealed that only isopentenyl adenosine (iPAdos) was as effective as TRIA on floral bud formation. iPAdos was also found to have similar effects as TRIA on root growth and reproductive growth. These results suggest a correlation between the early bolting induced by TRIA, cerium and lanthanum and the production of higher concentrations of endogenous iPAdos.

  13. Pharmacological potential of cerium oxidenanoparticles

    NASA Astrophysics Data System (ADS)

    Celardo, Ivana; Pedersen, Jens Z.; Traversa, Enrico; Ghibelli, Lina

    2011-04-01

    Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxidenanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles between the Ce3+ and Ce4+oxidation states allow nanoceria to react catalytically with superoxide and hydrogen peroxide, mimicking the behavior of two key antioxidant enzymes, superoxide dismutase and catalase, potentially abating all noxious intracellularreactive oxygen species (ROS) via a self-regenerating mechanism. Hence nanoceria, apparently well tolerated by the organism, might fight chronic inflammation and the pathologies associated with oxidative stress, which include cancer and neurodegeneration. Here we review the biological effects of nanoceria as they emerge from in vitro and in vivo studies, considering biocompatibility and the peculiar antioxidant mechanisms.

  14. Cerium anomaly at microscale in fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

    2015-09-01

    Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

  15. Cerium anomaly at microscale in fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

    2015-09-01

    Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies. PMID:26239283

  16. α-Radioactivity of cerium-142

    USGS Publications Warehouse

    Senftle, F.E.; Stern, T.W.; Alekna, V.P.

    1959-01-01

    JOHNSON AND NIER1 have measured the atomic masses of some of the rare-earth isotopes and have shown that the mass difference cerium-142—(barium-138 + helium-4) is equivalent to 1.68 ± 0.10 MeV. Similar results for the naturally occurring samarium and neodymium isotopes show that the α-active isotope of each element is the one having the largest possible decay energy. Rasmussen and others2 suggest that the two or three neutrons just beyond the closed shell of 82 neutrons have decreased binding energies and hence the α-energy has a maximum about 84 neutrons. Johnson and Nier suggest that the α-decay of cerium-142 may take place with enough energy to be experimentally observable. Porschen and Riezler3 examined a sample of un-enriched cerium ammonium citrate using nuclear track plates sensitive to α-particles. No α-activity was observed after a 30-day exposure of 1.2 mgm. of the cerium salt. In 1957 Riezler and Kauw4 reported an alpha activity for an enriched sample of cerium-142. From their results they calculated a half-life of 5.1 × 1015 years with an uncertainty factor of 2.

  17. Nanocrystalline cerium oxide materials for solid fuel cell systems

    SciTech Connect

    Brinkman, Kyle S

    2015-05-05

    Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

  18. Divalent fluoride doped cerium fluoride scintillator

    DOEpatents

    Anderson, David F.; Sparrow, Robert W.

    1991-01-01

    The use of divalent fluoride dopants in scintillator materials comprising cerium fluoride is disclosed. The preferred divalent fluoride dopants are calcium fluoride, strontium fluoride, and barium fluoride. The preferred amount of divalent fluoride dopant is less than about two percent by weight of the total scintillator. Cerium fluoride scintillator crystals grown with the addition of a divalent fluoride have exhibited better transmissions and higher light outputs than crystals grown without the addition of such dopants. These scintillators are useful in radiation detection and monitoring applications, and are particularly well suited for high-rate applications such as positron emission tomography (PET).

  19. Cerium migration during PEM fuel cell accelerated stress testing

    SciTech Connect

    Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; Spernjak, Dusan; Judge, Elizabeth J.; Advani, Suresh G.; Prasad, Ajay K.

    2016-01-01

    Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humidity cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.

  20. Cerium migration during PEM fuel cell accelerated stress testing

    DOE PAGESBeta

    Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; Spernjak, Dusan; Judge, Elizabeth J.; Advani, Suresh G.; Prasad, Ajay K.

    2016-01-01

    Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humiditymore » cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.« less

  1. An investigation of the continuum resonance effect in cerium and cerium oxide

    NASA Astrophysics Data System (ADS)

    Roberts, Mark W.

    1998-10-01

    Large x-ray emission resonances associated with the M shell in cerium and cerium oxide were investigated. The device used in this investigation consisted of an energy dispersive x-ray detector and a double-pass cylindrical mirror electron analyzer within an ultra-high vacuum system. Observations were made of the x-ray and electron emissions from samples bombarded by mono-energetic electrons from an electron gun. The x-ray and electron data were recorded with the system pressure in the low 10-9 torr range. X-ray data were obtained using incident electron energies from 865 eV to 925 eV; the binding energies of the cerium M5 and M4 subshells and the x-ray continuum resonances are contained within this energy range. The x- ray detector was set to count x-rays in a fixed energy window 120 eV wide, centered on 900 eV. Differentiated electron spectra from the samples were recorded using a lock-in amplifier. Vacuum evaporation and condensation were used to deposit cerium metal samples onto a wheel which was then rotated to position a given sample in front of the electron gun. Cerium oxide samples were obtained by exposing cerium metal deposits to room air at atmospheric pressure and then repumping the system. The x-ray yield spectra from the cerium and cerium oxide samples show large resonances for incident electron energies near the M5 and M4 level ionization energies. There are no features in the electron spectra which correspond to the large resonances observed in the x-ray yield spectra. These findings are in agreement with results previously obtained by Chamberlain et al. and by Mason. The maxima in the x-ray resonances for cerium oxide occur at slightly lower incident electron energy than those for cerium metal. There is also a large increase in the intensity of the x-ray continuum resonance yield in cerium oxide above that in the metal. Possible explanations for these observations are presented.

  2. Study on cerium-doped nano-TiO2 coatings for corrosion protection of 316 L stainless steel

    NASA Astrophysics Data System (ADS)

    Li, Suning; Wang, Qian; Chen, Tao; Zhou, Zhihua; Wang, Ying; Fu, Jiajun

    2012-04-01

    Many methods have been reported on improving the photogenerated cathodic protection of nano-TiO2 coatings for metals. In this work, nano-TiO2 coatings doped with cerium nitrate have been developed by sol-gel method for corrosion protection of 316 L stainless steel. Surface morphology, structure, and properties of the prepared coatings were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. The corrosion protection performance of the prepared coatings was evaluated in 3 wt% NaCl solution by using electrochemical techniques in the presence and absence of simulated sunlight illumination. The results indicated that the 1.2% Ce-TiO2 coating with three layers exhibited an excellent photogenerated cathodic protection under illumination attributed to the higher separation efficiency of electron-hole pairs and higher photoelectric conversion efficiency. The results also showed that after doping with an appropriate concentration of cerium nitrate, the anti-corrosion performance of the TiO2 coating was improved even without irradiation due to the self-healing property of cerium ions.

  3. Correlation of the oxidation state of cerium in sol?gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies

    NASA Astrophysics Data System (ADS)

    Assefa, Zerihun; Haire, R. G.; Caulder, D. L.; Shuh, D. K.

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce 3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 °C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 °C and up to ˜1000 °C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 °C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  4. Uptake and accumulation of bulk and nanosized cerium oxide particles and ionic cerium by radish (Raphanus sativus L.).

    PubMed

    Zhang, Weilan; Ebbs, Stephen D; Musante, Craig; White, Jason C; Gao, Cunmei; Ma, Xingmao

    2015-01-21

    The potential toxicity and accumulation of engineered nanomaterials (ENMs) in agricultural crops has become an area of great concern and intense investigation. Interestingly, although below-ground vegetables are most likely to accumulate the highest concentrations of ENMs, little work has been done investigating the potential uptake and accumulation of ENMs for this plant group. The overall objective of this study was to evaluate how different forms of cerium (bulk cerium oxide, cerium oxide nanoparticles, and the cerium ion) affected the growth of radish (Raphanus sativus L.) and accumulation of cerium in radish tissues. Ionic cerium (Ce(3+)) had a negative effect on radish growth at 10 mg CeCl3/L, whereas bulk cerium oxide (CeO2) enhanced plant biomass at the same concentration. Treatment with 10 mg/L cerium oxide nanoparticles (CeO2 NPs) had no significant effect on radish growth. Exposure to all forms of cerium resulted in the accumulation of this element in radish tissues, including the edible storage root. However, the accumulation patterns and their effect on plant growth and physiological processes varied with the characteristics of cerium. This study provides a critical frame of reference on the effects of CeO2 NPs versus their bulk and ionic counterparts on radish growth.

  5. Synthesis of Cerium-Doped Titania Nanoparticles and Nanotubes.

    PubMed

    Cao, Wei; Suzuki, Takuya; Elsayed-Ali, Hani E; Abdel-Fattah, Tarek M

    2015-03-01

    Cerium-doped titania nanoparticles and nanotubes were synthesized via hydrothermal processes. X-Ray Diffraction revealed that cerium-doped titania nanoparticles have an anatase crystal structure, while cerium-doped titania nanotubes have an H2Ti3O7-type structure. Scanning electron microscopy and high resolution transmission electron microscopy showed that both types of titania are well crystallized with relatively uniform size distribution. The photocatalytic degradation of methylthioninium chloride known as methylene blue dye was tested and both cerium-doped titania nanoparticles and nanotubes. The preliminary photocatalytic degradation of Methylene Blue data showed significantly improved visible light photocatalytic activities as compared to commercial titania powders.

  6. Antimony promoted bismuth cerium molybdate catalysts

    SciTech Connect

    Brazdil, J.F.; Glaeser, L.C.; Grasselli, R.K.

    1990-05-01

    This patent describes an improvement in antimony-promoted bismuth cerium molybdate whereby the tendency of the catalyst to lose efectiveness over time is significantly reduced. This patent describes new catalysts which are also useful in other oxidation-type reactions such as the oxidation of acrolein and methacrolein to produce the corresponding unsaturated aldehydes and acids and the oxydehydrogenation of various olefins such as isoamylenes to produce the corresponding diolefins such as isoprene.

  7. Atomic Transition Probabilities for Neutral Cerium

    NASA Astrophysics Data System (ADS)

    Lawler, J. E.; den Hartog, E. A.; Wood, M. P.; Nitz, D. E.; Chisholm, J.; Sobeck, J.

    2009-10-01

    The spectra of neutral cerium (Ce I) and singly ionized cerium (Ce II) are more complex than spectra of other rare earth species. The resulting high density of lines in the visible makes Ce ideal for use in metal halide (MH) High Intensity Discharge (HID) lamps. Inclusion of cerium-iodide in a lamp dose can improve both the Color Rendering Index and luminous efficacy of a MH-HID lamp. Basic spectroscopic data including absolute atomic transition probabilities for Ce I and Ce II are needed for diagnosing and modeling these MH-HID lamps. Recent work on Ce II [1] is now being augmented with similar work on Ce I. Radiative lifetimes from laser induced fluorescence measurements [2] on neutral Ce are being combined with emission branching fractions from spectra recorded using a Fourier transform spectrometer. A total of 14 high resolution spectra are being analyzed to determine branching fractions for 2000 to 3000 lines from 153 upper levels in neutral Ce. Representative data samples and progress to date will be presented. [4pt] [1] J. E. Lawler, C. Sneden, J. J. Cowan, I. I. Ivans, and E. A. Den Hartog, Astrophys. J. Suppl. Ser. 182, 51-79 (2009). [0pt] [2] E. A. Den Hartog, K. P. Buettner, and J. E. Lawler, J. Phys. B: Atomic, Molecular & Optical Physics 42, 085006 (7pp) (2009).

  8. Local Structure of Cerium in Aluminophosphate and Silicophosphate Glasses

    SciTech Connect

    Rygel, Jennifer L.; Chen, Yongsheng; Pantano, Carlo G.; Shibata, Tomohiro; Du, Jincheng; Kokou, Leopold; Woodman, Robert; Belcher, James

    2011-09-20

    The local structure of cerium in two systematic compositional series of glasses, nominally CeP{sub 3}O{sub 9}-AlP{sub 3}O{sub 9} and CeP{sub 3}O{sub 9}-SiP{sub 2}O{sub 7}, was interrogated using X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy. XPS revealed that, for glasses melted in air, {>=}95% of cerium ions are Ce{sup 3+}. This was independently confirmed using X-ray absorption near edge spectroscopy (XANES). Ce K-edge extended X-ray absorption fine structure (EXAFS) has been used to determine the local structure of Ce{sup 3+}. Near the metaphosphate composition, cerium was found to have an average cerium coordination number of {approx}7.0 and an average cerium-oxygen bond length of 2.41 {angstrom}. The average cerium coordination number and average cerium-oxygen bond distance were found to increase with decreasing cerium concentration in both compositional series. Rare-earth clustering is suggested based on numerical calculations for glasses containing {>=}14 and {>=}15 mol% Ce{sub 2}O{sub 3} for the aluminophosphate and silicophosphate series, respectively.

  9. Study of the cerium(IV)-picrate system in acetonitrile.

    PubMed

    Kratochvil, B; Tipler, M; McKay, B

    1966-07-01

    A potentiometric and spectrophotometric study has been made of the reaction between hexanitratocerate and picrate in dry acetonitrile. Several cerium(IV)-picrate complexes are formed; the formation constant for the first is estimated to be 4 from spectrophotometric measurements. The catalytic effect of picrate on hydroquinone oxidation by nitratocerate is postulated to be due to more rapid electron transfer by cerium picrate complexes.

  10. RECOVERY OF Pu FROM CERIUM TRIFLUORIDE BY FLUORINATION

    DOEpatents

    Brown, H.S.; Bohlmann, E.G.

    1959-02-10

    An improved process is prcsented for selectively recovering plutonium from a solution containing fission products comprising precipitating cerium trifluoride in the solution for effccting carrier precipitation of plutonium. The resulting carrier precipitate is dried and subjected to fluorination at about 600 C. The plutonium forms a volatile fiuoridc and is so separated from the nonvolatile cerium fluoride.

  11. Cerium migration during PEM fuel cell assembly and operation

    SciTech Connect

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-10-02

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane cerium gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.

  12. Cerium migration during PEM fuel cell assembly and operation

    SciTech Connect

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-09-14

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane cerium gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.

  13. Ultrathin, epitaxial cerium dioxide on silicon

    NASA Astrophysics Data System (ADS)

    Flege, Jan Ingo; Kaemena, Björn; Höcker, Jan; Bertram, Florian; Wollschläger, Joachim; Schmidt, Thomas; Falta, Jens

    2014-03-01

    It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce2O3 film may very effectively be converted at room temperature to almost fully oxidized CeO2 by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

  14. Ultrathin, epitaxial cerium dioxide on silicon

    SciTech Connect

    Flege, Jan Ingo Kaemena, Björn; Höcker, Jan; Schmidt, Thomas; Falta, Jens; Bertram, Florian; Wollschläger, Joachim

    2014-03-31

    It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce{sub 2}O{sub 3} film may very effectively be converted at room temperature to almost fully oxidized CeO{sub 2} by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

  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. Sorptive separation of yttrium and cerium on a weakly basic anionite

    NASA Astrophysics Data System (ADS)

    Cheremisina, O. V.; Ponomareva, M. A.; Chirkst, D. E.; Lobacheva, O. L.; Shul'gin, I. A.

    2015-01-01

    The sorption of complex yttrium ions with Trilon B onto the weakly basic anionite D-403 in nitrate form from an acidic medium at pH 3 with constant ionic strength (NaNO3, 1 mol/kg) is investigated. A thermodynamic evaluation of the sorption isotherm of anionic yttrium complexes is performed using a method based on the linearization of the equation of the law of active mass, modified for ionic exchange reactions. The ionic exchange constant, the Gibbs free energy of ionic exchange, the capacity of the anionite, and the sorption limit of ethylenediaminetetraacetatoyttrate ions (EDTA yttrate ions) are calculated. Using a frontal version of ion exchange chromatography, cerium and yttrium are separated on D-403 anionite with a fraction of pure yttrium at the column outlet of no less than 30%.

  17. Photodissociation of Cerium Oxide Nanocluster Cations.

    PubMed

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A

    2016-04-21

    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)). PMID:27035210

  18. The surface chemistry of cerium oxide

    SciTech Connect

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  19. The surface chemistry of cerium oxide

    DOE PAGESBeta

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focusmore » of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.« less

  20. The surface chemistry of cerium oxide

    NASA Astrophysics Data System (ADS)

    Mullins, David R.

    2015-03-01

    This review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water-gas shift reaction. Ceria's acid-base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. Most surface science studies have been conducted on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  1. Microstructure of surface cerium hydride growth sites

    SciTech Connect

    Brierley, Martin; Knowles, John; Montgomery, Neil; Preuss, Michael

    2014-05-15

    Samples of cerium were exposed to hydrogen under controlled conditions causing cerium hydride sites to nucleate and grow on the surface. The hydriding rate was measured in situ, and the hydrides were characterised using secondary ion mass spectrometry, scanning electron microscopy, and optical microscopy. The results show that the hydriding rate proceeded more quickly than earlier studies. Characterisation confirmed that the hydrogen is confined to the sites. The morphology of the hydrides was confirmed to be oblate, and stressed material was observed surrounding the hydride, in a number of cases lathlike features were observed surrounding the hydride sites laterally with cracking in the surface oxide above them. It is proposed that during growth the increased lattice parameter of the CeH{sub 2} induces a lateral compressive stress around the hydride, which relieves by the ca. 16% volume collapse of the γ-Ce to α-Ce pressure induced phase transition. Cracking of the surface oxide above the laths reduces the diffusion barrier to hydrogen reaching the metal/oxide interface surrounding the hydride site and contributes to the anisotropic growth of the hydrides.

  2. Optical properties of cerium-codoped high power laser fibers

    NASA Astrophysics Data System (ADS)

    Unger, S.; Schwuchow, A.; Jetschke, S.; Grimm, S.; Scheffel, A.; Kirchhof, J.

    2013-03-01

    The photodarkening resistivity of ytterbium doped alumosilicate fibers can be remarkably improved by cerium codoping. Here we report on systematical investigations of the influence of cerium on an optimized fiber design. Fibers with different ytterbium, aluminium and cerium contents have been prepared both under reducing and oxydizing conditions and characterized concerning refractive index, absorption and emission from UV to NIR. Typical spectral features in the UV and visible range have been analysed with respect to the ratio of Ce3+ / Ce4+. Photodarkening tests have been accomplished in order to correlate the power stability with the Ce content and valency state.

  3. Antibacterial activity of cerium colloids against opportunistic microorganisms in vitro.

    PubMed

    Babenko, L P; Zholobak, N M; Shcherbakov, A B; Voychuk, S I; Lazarenko, L M; Spivak, M Ya

    2012-01-01

    The CeO2 sol with the size of nanoparticles 2-4 nm has been synthesized. It has been determined that the synthesized nanocrystalline cerium has antibacterial activity in vitro against different groups of opportunistic microorganisms: clinical strains of Escherichia coli, Staphylococcus aureus and Candida albicans. The rate of viability depression of test-cultures depends on the concentration of cerium dioxide nanoparticles and time of incubation. It is shown that the sol interacts with the bacterial cell surface. It is suggested that the observed differences of antibacterial action of nanocrystalline cerium dioxide can be related to the structural characteristics of the cell surface.

  4. Study on cerium-doped nano-TiO2 coatings for corrosion protection of 316 L stainless steel.

    PubMed

    Li, Suning; Wang, Qian; Chen, Tao; Zhou, Zhihua; Wang, Ying; Fu, Jiajun

    2012-04-19

    Many methods have been reported on improving the photogenerated cathodic protection of nano-TiO2 coatings for metals. In this work, nano-TiO2 coatings doped with cerium nitrate have been developed by sol-gel method for corrosion protection of 316 L stainless steel. Surface morphology, structure, and properties of the prepared coatings were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive X-ray spectroscopy. The corrosion protection performance of the prepared coatings was evaluated in 3 wt% NaCl solution by using electrochemical techniques in the presence and absence of simulated sunlight illumination. The results indicated that the 1.2% Ce-TiO2 coating with three layers exhibited an excellent photogenerated cathodic protection under illumination attributed to the higher separation efficiency of electron-hole pairs and higher photoelectric conversion efficiency. The results also showed that after doping with an appropriate concentration of cerium nitrate, the anti-corrosion performance of the TiO2 coating was improved even without irradiation due to the self-healing property of cerium ions.

  5. 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...

  6. 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 Section 181.33 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES... nitrate and potassium nitrate. Sodium nitrate and potassium nitrate are subject to prior sanctions...

  7. 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 nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources...

  8. 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 nitrate are subject to prior sanctions issued by the U.S. Department of Agriculture for use as sources...

  9. Optical glass surfaces polishing by cerium oxide particles

    NASA Astrophysics Data System (ADS)

    Bouzid, D.; Belkhie, N.; Aliouane, T.

    2012-02-01

    The use of powders in metallic oxides as means of grinding and polishing of the optical glass components have seen recently a large application in optical industry. In fact, cerium oxide abrasive is more used in the optical glass polishing. It is used as grains abrasive in suspension or fixed abrasive (pellets); these pellets are manufactured from a mixture made of cerium oxide abrasive and a organic binder. The cerium oxide used in the experiments is made by (Logitech USA) of 99 % purity, the average grain size of the particle is 300 nm, the density being 6,74 g /cm3 and the specific surface is 3,3042 m2/g. In this study, we are interested in the surfaces quality of the optical glass borosilicate crown (BK7) polished by particles in cerium oxide bounded by epoxy. The surfaces of the optical glass treated are characterized by the roughness, the flatness by using the microscope Zygo and the SEM.

  10. Cerium migration during PEM fuel cell assembly and operation

    DOE PAGESBeta

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-09-14

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane ceriummore » gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.« less

  11. Effects of the Rare Earth Cerium on Escherichia coli

    PubMed Central

    Sobek, Joseph M.; Talburt, Dwight E.

    1968-01-01

    The rare earth cerium was found to bind rapidly to Escherichia coli. Cerium inhibited oxygen uptake in the presence of glucose as well as the endogenous respiration of glucose-grown cells. For a cell concentration of 4 mg per ml, maximal inhibition was obtained at 120 μg per ml. Greater concentrations did not increase the inhibitory effect. Cerium inhibited 14CO2 evolution and 14C uptake from uniformly labeled glucose. Marked changes in the distribution of 14C incorporated into different chemical fractions of the cell were noted. The most striking changes occurred in the alcohol- and alcohol ether-soluble fractions, in which the 14C activity was increased 5- to 20-fold in the presence of cerium. PMID:4866102

  12. Heteroaggregation of cerium oxide nanoparticles and nanoparticles of pyrolyzed biomass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heteroaggregation with indigenous particles is an important process controlling the mobility of engineered nanomaterials in the environment. We studied heteroaggregation of cerium oxide nanoparticles (n-CeO2), which are widely used commercially, with nanoparticles of pyrogenic carbonaceous material ...

  13. Method of applying a cerium diffusion coating to a metallic alloy

    DOEpatents

    Jablonski, Paul D.; Alman, David E.

    2009-06-30

    A method of applying a cerium diffusion coating to a preferred nickel base alloy substrate has been discovered. A cerium oxide paste containing a halide activator is applied to the polished substrate and then dried. The workpiece is heated in a non-oxidizing atmosphere to diffuse cerium into the substrate. After cooling, any remaining cerium oxide is removed. The resulting cerium diffusion coating on the nickel base substrate demonstrates improved resistance to oxidation. Cerium coated alloys are particularly useful as components in a solid oxide fuel cell (SOFC).

  14. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGESBeta

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  15. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  16. 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.

  17. 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... nitrite, with or without sodium or potassium nitrite, in the production of cured red meat products...

  18. 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.

  19. Gallium nitrate revisited.

    PubMed

    Chitambar, Christopher R

    2003-04-01

    Gallium nitrate, the nitrate salt of the "near-metal" element gallium, is highly effective in the treatment of cancer-related hypercalcemia. Unlike bisphosphonates, gallium nitrate is effective in both parathyroid hormone-related protein-mediated and non-parathyroid hormone-related protein-mediated hypercalcemia. Gallium nitrate's effects on bone are clearly different from those of bisphosphonates. Gallium nitrate enhances calcium and phosphate content of bone and has direct, noncytotoxic effects on osteoclasts at markedly lower doses than those used for the treatment of cancer-related hypercalcemia. The drug may have clinical application in a variety of disorders associated with accelerated bone loss, including multiple myeloma. Gallium nitrate was originally evaluated as an antitumor agent. Its antitumor activity occurs at somewhat higher doses than those used in the treatment of cancer-related hypercalcemia. Gallium nitrate has substantial single-agent activity in the treatment of advanced lymphoma, particularly diffuse large cell lymphoma, small lymphocytic lymphoma, and follicular lymphoma. Because of its profile, including a different mechanism of action and minimal myelosuppression, the drug merits further evaluation in the treatment of advanced lymphoma. Gallium nitrate also has activity in advanced bladder cancer and may be useful in patients with metastatic or unresectable disease failing first-line chemotherapy regimens. Gallium nitrate exhibits a range of dose-dependent pharmacologic actions that provide a basis for its therapeutic potential in a variety of diseases and warrants further investigational evaluation as an antiresorptive and antitumor agent. PMID:12776253

  20. IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR CERIUM OXIDE (STABLE) AND COMPOUNDS

    EPA Science Inventory

    Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is ...

  1. Potential for recovery of cerium contained in automotive catalytic converters

    USGS Publications Warehouse

    Bleiwas, Donald I.

    2013-01-01

    Catalytic converters (CATCONs) are required by Federal law to be installed in nearly all gasoline- and diesel-fueled onroad vehicles used in the United States. About 85 percent of the light-duty vehicles and trucks manufactured worldwide are equipped with CATCONs. Portions of the CATCONs (called monoliths) are recycled for their platinum-group metal (PGM) content and for the value of the stainless steel they contain. The cerium contained in the monoliths, however, is disposed of along with the slag produced from the recycling process. Although there is some smelter capacity in the United States to treat the monoliths in order to recover the PGMs, a great percentage of monoliths is exported to Europe and South Africa for recycling, and a lesser amount is exported to Japan. There is presently no commercial-scale capacity in place domestically to recover cerium from the monoliths. Recycling of cerium or cerium compounds from the monoliths could help ensure against possible global supply shortages by increasing the amount that is available in the supply chain as well as the number and geographic distribution of the suppliers. It could also reduce the amount of material that goes into landfills. Also, the additional supply could lower the price of the commodity. This report analyzes how much cerium oxide is contained in CATCONs and how much could be recovered from used CATCONs.

  2. Mechanical and Thermophysical Properties of Cerium Monopnictides

    NASA Astrophysics Data System (ADS)

    Bhalla, Vyoma; Singh, Devraj; Jain, S. K.

    2016-03-01

    The ultrasonic attenuation due to phonon-phonon interaction, thermoelastic relaxation and dislocation damping mechanisms has been investigated in cerium monopnictides CeX (X: N, P, As, Sb and Bi) for longitudinal and shear waves along {< }100{rangle }, {< }110{rangle } and {< }111{rangle } directions. The second- and third-order elastic constants of CeX have also been computed in the temperature range 0 K to 500 K using Coulomb and Born-Mayer potential upto second nearest neighbours. The computed values of these elastic constants have been applied to find out Young's moduli, bulk moduli, Breazeale's non-linearity parameters, Zener anisotropy, ultrasonic velocity, ultrasonic Grüneisen parameter, thermal relaxation time, acoustic coupling constants and ultrasonic attenuation. The fracture/toughness ratio is less than 1.75, which shows that the chosen materials are brittle in nature as found for other monopnictides. The drag coefficient acting on the motion of screw and edge dislocations due to shear and compressional phonon viscosities of the lattice have also been evaluated for both the longitudinal and shear waves. The thermoelastic loss and dislocation damping loss are negligible in comparison to loss due to Akhieser damping (phonon-phonon interaction). The obtained results for CeX are in qualitative agreement with other semi-metallic monopnictides.

  3. Characterization of cerium fluoride nanocomposite scintillators

    SciTech Connect

    Stange, Sy; Esch, Ernst I; Brown, Leif O; Couture, Aaron J; Mckigney, Edward A; Muenchausen, Ross E; Del Sesto, Rico E; Gilbertson, Robert D; Mccleskey, T Mark; Reifarth, Rene

    2009-01-01

    Measurement of the neutron capture cross-sections of a number of short-lived isotopes would advance both pure and applied scientific research. These cross-sections are needed for calculation of criticality and waste production estimates for the Advanced Fuel Cycle Initiative, for analysis of data from nuclear weapons tests, and to improve understanding of nucleosynthesis. However, measurement of these cross-sections would require a detector with a faster signal decay time than those used in existing neutron capture experiments. Crystals of faster detector materials are not available in sufficient sizes and quantities to supply these large-scale experiments. Instead, we propose to use nanocomposite detectors, consisting of nanoscale particles of a scintillating material dispersed in a matrix material. We have successfully fabricated cerium fluoride (CeF{sub 3}) nanoparticles and dispersed them in a liquid matrix. We have characterized this scintillator and have measured its response to neutron capture. Results of the optical, structural, and radiation characterization will be presented.

  4. Environmental Geochemistry of Cerium: Applications and Toxicology of Cerium Oxide Nanoparticles

    PubMed Central

    Dahle, Jessica T.; Arai, Yuji

    2015-01-01

    Cerium is the most abundant of rare-earth metals found in the Earth’s crust. Several Ce-carbonate, -phosphate, -silicate, and -(hydr)oxide minerals have been historically mined and processed for pharmaceutical uses and industrial applications. Of all Ce minerals, cerium dioxide has received much attention in the global nanotechnology market due to their useful applications for catalysts, fuel cells, and fuel additives. A recent mass flow modeling study predicted that a major source of CeO2 nanoparticles from industrial processing plants (e.g., electronics and optics manufactures) is likely to reach the terrestrial environment such as landfills and soils. The environmental fate of CeO2 nanoparticles is highly dependent on its physcochemical properties in low temperature geochemical environment. Though there are needs in improving the analytical method in detecting/quantifying CeO2 nanoparticles in different environmental media, it is clear that aquatic and terrestrial organisms have been exposed to CeO2 NPs, potentially yielding in negative impact on human and ecosystem health. Interestingly, there has been contradicting reports about the toxicological effects of CeO2 nanoparticles, acting as either an antioxidant or reactive oxygen species production-inducing agent). This poses a challenge in future regulations for the CeO2 nanoparticle application and the risk assessment in the environment. PMID:25625406

  5. Thermodynamic Calculation among Cerium, Oxygen, and Sulfur in Liquid Iron

    PubMed Central

    Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Su, Yen-Hao; Hwang, Weng-Sing

    2016-01-01

    Thermodynamic calculation has been applied to predict the inclusion formation in molten SS400 steel. When the Cerium addition in liquid iron is 70 ppm and the initial Oxygen and Sulphur are both 110 ppm, the formation of oxides containing Cerium would experience the transformation from Ce2O3 to CeO2 and also the formation of sulfides containing Cerium would experience the transformation from CeS to Ce2S3 and then to Ce3S4. Below 2000 K the most thermodynamic stable matter is CeO2 and the less thermodynamic stable inclusion is CeS. Only when the amount of [O] is extremely low and the amount of [S] and [Ce] is relatively high, Ce2S3 has the possibility to form. PMID:27767092

  6. Dehydrogenation of isopropanol on a cerium-nickel catalyst

    NASA Astrophysics Data System (ADS)

    Platonov, E. A.; Naumkin, A. V.; Maslakov, K. I.; Yagodovskii, V. D.

    2012-12-01

    The effect of a cerium additive on the catalytic activity of a 2 wt % Ni/SiO2 catalyst is studied. It found that under both flow and static conditions the activity of (2 wt % Ni + 0.2 wt % Ce)/SiO2 catalyst is higher than that of the original sample; the increase in activity results from a sharp increase in the number of active sites. A change in the composition of the surface layer of the catalysts is analyzed by X-ray photoelectron spectroscopy. It was found that the fraction of nickel decreases and the fraction of carbon increases in cerium-containing catalyst. An explanation of the change in the elemental composition of the catalytic active sites of a nickel catalyst in the presence of cerium is proposed on the basis of XPS data and previous quantum chemical calculations.

  7. A shear viscosity study of cerium (III) nitrate in concentrated aqueous solutions at different temperatures

    NASA Astrophysics Data System (ADS)

    Ouerfelli, N.; Bouanz, M.

    1996-04-01

    Kinematic viscosities and densities of 0953-8984/8/16/005/img1 in aqueous solutions, from pure water to very concentrated solutions, were determined at different temperatures. Shear viscosity data for this asymmetrical 3:1 electrolyte were calculated. For the low concentrations 0953-8984/8/16/005/img2, the Jones - Dole coefficients A and B were determined for this rare-earth salt by fitting the quadratic behaviour of the square root of the molar concentration with the least-squares method. At concentrations above 1 mol 0953-8984/8/16/005/img3, the logarithm of viscosity can be fitted by a third-order polynomial, where the coefficients exhibit a linear dependence on the reciprocal of the absolute temperature. This phenomenon is due to the strong ion - solvent correlation.

  8. Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Kumari, Monika; Kumar, Mintu; Kumar, Sacheen; Kumar, Dinesh

    2016-05-01

    Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO2 was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

  9. In situ growth of epitaxial cerium tungstate (100) thin films.

    PubMed

    Skála, Tomáš; Tsud, Nataliya; Orti, Miguel Ángel Niño; Menteş, Tevfik Onur; Locatelli, Andrea; Prince, Kevin Charles; Matolín, Vladimír

    2011-04-21

    The deposition of ceria on a preoxidized W(110) crystal at 870 K has been studied in situ by photoelectron spectroscopy and low-energy electron diffraction. Formation of an epitaxial layer of crystalline cerium tungstate Ce(6)WO(12)(100), with the metals in the Ce(3+) and W(6+) chemical states, has been observed. The interface between the tungsten substrate and the tungstate film consists of WO suboxide. At thicknesses above 0.89 nm, cerium dioxide grows on the surface of Ce(6)WO(12), favoured by the limited diffusion of tungsten from the substrate. PMID:21399780

  10. Optical and electrical studies of cerium mixed oxides

    SciTech Connect

    Sherly, T. R.; Raveendran, R.

    2014-10-15

    The fast development in nanotechnology makes enthusiastic interest in developing nanomaterials having tailor made properties. Cerium mixed oxide materials have received great attention due to their UV absorption property, high reactivity, stability at high temperature, good electrical property etc and these materials find wide applications in solid oxide fuel cells, solar control films, cosmetics, display units, gas sensors etc. In this study cerium mixed oxide compounds were prepared by co-precipitation method. All the samples were doped with Zn (II) and Fe (II). Preliminary characterizations such as XRD, SEM / EDS, TEM were done. UV - Vis, Diffuse reflectance, PL, FT-IR, Raman and ac conductivity studies of the samples were performed.

  11. The effective thermal conductivity of an adsorbent - Praseodymium cerium oxide

    NASA Technical Reports Server (NTRS)

    Secary, J. J.; Tong, T. W.

    1992-01-01

    The results of an experimental study to determine the effective thermal conductivity of praseodymium cerium oxide are reported. Praseodymium cerium oxide is an adsorbent used in the development of adsorption compressors for spaceborne refrigeration systems. A guarded-hot-plate apparatus was built for this study. Measurements were carried out for mean temperatures ranging from 300 to 600 C under a vacuum of 10 exp -5 torr. For the temperature range studied, the effective thermal conductivity increased from 0.14 to 0.76 W/m per C with increasing temperature, while displaying a cubic temperature dependency.

  12. Cerium phosphate nanotubes: synthesis, characterization and biosensing

    NASA Astrophysics Data System (ADS)

    Meng, Ling; Yang, Lige; Zhou, Bo; Cai, Chenxin

    2009-01-01

    Cerium phosphate (CeP) nanotubes have been synthesized and confirmed by x-ray diffraction (XRD) and transmission electron microscopy (TEM). The 1D nanomaterial has a monoclinic crystal structure with a mean width of 15-20 nm and a length up to several micrometers. The nanotubes have been employed as electrode substrates for immobilization and direct electrochemistry of heme proteins/enzymes with myoglobin (Mb) as a model. The electrochemical characteristics of the Mb-CeP/GC electrode were studied by voltammetry. After being immobilized on the nanotubes, Mb can keep its natural structure and undergo effective direct electron transfer reaction with a pair of well-defined redox peaks at -(367 ± 3) mV (pH 7.5). The apparent electron transfer rate constant is (9.1 ± 1.4) s-1. The electrode displays good features in the electrocatalytic reduction of H2O2, and thus can be used as a biosensor for detecting the substrate with a low detection limit (0.5 ± 0.05 µM), a wide linear range (0.01-2 mM), high sensitivity (14.4 ± 1.2 µA mM-1), as well as good stability and reproducibility. CeP nanotubes can become a simple and effective biosensing platform for the integration of heme proteins/enzymes and electrodes, which can provide analytical access to a large group of enzymes for a wide range of bioelectrochemical applications.

  13. Effect of ultrasound treatment on the morpho-structural and luminescent characteristics of cerium doped yttrium silicate phosphors

    SciTech Connect

    Muresan, L.E.; Cadis, A.I.; Perhaita, I.; Silipas, D.T.; Tudoran, L. Barbu

    2015-08-15

    Highlights: • Y{sub 2}SiO{sub 5}:Ce is prepared by gel combustion in ultrasound conditions (US). • Morpho-structural characteristics are revealed based on FTIR, SEM, XRD, BET. • Incorporation of Ce{sup 3+} in X1/X2 type centers depends on preparative conditions. • US treatment increases the luminescent performances up to 151%. - Abstract: Cerium activated yttrium silicate (Y{sub 2}SiO{sub 5}:Ce) phosphors were prepared by gel-combustion, using yttrium–cerium nitrate as oxidizer, aspartic acid as fuel and TEOS as source of silicon. Two modalities for samples preparation were approached namely: the classical gel-combustion and sonication gel-combustion. The ultrasound treatment during the gelling stage has a positive effect on the structural and luminescent characteristics of the final product. Therefore, a well crystallized single X2–Y{sub 2}SiO{sub 5} phase phosphor was obtained at 1200 °C. Based on FT-IR and XRD investigations, conversion of X1 to X2–Y{sub 2}SiO{sub 5} phases is observed as the firing temperature is varied (1100 °C, 1200 °C, 1300 °C 1400 °C). The ultrasound treatment leads to smaller particle size and enhances the luminescent performances up to 151% in comparison with samples prepared by classical way.

  14. Characterization and activity of visible-light-driven TiO 2 photocatalyst codoped with nitrogen and cerium

    NASA Astrophysics Data System (ADS)

    Liu, Chao; Tang, Xinhu; Mo, Cehui; Qiang, Zhimin

    2008-04-01

    Nitrogen and cerium codoped TiO 2 photocatalysts were prepared by a modified sol-gel process with doping precursors of cerium nitrate and urea, and characterized by X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TG-DSC), X-ray photoelectron spectra (XPS) and ultraviolet-visible light diffuse reflectance spectra (UV-vis DRS). Results indicate that anatase TiO 2 is the dominant crystalline type in as-prepared samples, and CeO 2 crystallites appear as the doping ratio of Ce/Ti reaches to 3.0 at%. The TiO 2 starts to transform from amorphous phase to anatase at 987.1 K during calcination, according to the TG-DSC curves. The XPS show that three major metal ions of Ce 3+, Ce 4+, Ti 4+ and one minor metal ion of Ti 3+ coexist on the surface. The codoped TiO 2 exhibits significant absorption within the range of 400-500 nm compared to the non-doped and only nitrogen-doped TiO 2. The enhanced photocatalytic activity of the codoped TiO 2 is demonstrated through degradation of methyl orange under visible light irradiation.

  15. The effect of lanthanum(III) and cerium(III) ions between layers of manganese oxide on water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Hołyńska, Małgorzata; Shen, Jian-Ren; Allakhverdiev, Suleyman I; Allakhverdiev, Suleyman

    2015-12-01

    Manganese oxide structure with lanthanum(III) or cerium(III) ions between the layers was synthesized by a simple method. The ratio of Mn to Ce or La in samples was 0.00, 0.04, 0.08, 0.16, 0.32, 0.5, 0.82, or 1.62. The compounds were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction studies, and atomic absorption spectroscopy. The compounds show efficient catalytic activity of water oxidation in the presence of cerium(IV) ammonium nitrate with a turnover frequency of 1.6 mmol O2/mol Mn.s. In contrast to the water-oxidizing complex in Photosystem II, calcium(II) has no specific role to enhance the water-oxidizing activity of the layered manganese oxides and other cations can be replaced without any significant decrease in water-oxidizing activities of these layered Mn oxides. Based on this and previously reported results from oxygen evolution in the presence of H 2 (18) O, we discuss the mechanism and the important factors influencing the water-oxidizing activities of the manganese oxides. PMID:25701552

  16. Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Qureshi, Uzma; Dunnill, Charles W.; Parkin, Ivan P.

    2009-11-01

    Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO 2 nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.

  17. Thermochemical nitrate destruction

    DOEpatents

    Cox, J.L.; Hallen, R.T.; Lilga, M.A.

    1992-06-02

    A method is disclosed for denitrification of nitrates and nitrites 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 C to about 600 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.

  18. Hydrothermal preparation of fractal dendrites: Cerium carbonate hydroxide and cerium oxide

    SciTech Connect

    Wu Mingzai; Zhang Qihua; Liu Yanmei; Fang Qingqing; Liu Xiansong

    2009-06-03

    The surfactant-assisted hydrothermal route was used to prepare fractal dendrite cerium carbonate hydroxide (CeOHCO{sub 3}) microstructures. After annealing at 600 deg. C for 4 h, the products were transformed to CeO{sub 2}. The crystal structures of the two compounds were determined by X-ray diffraction (XRD). The morphologies and microstructures were characterized by field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). Room temperature photoluminescence (PL) showed that a strong ultraviolet emission at 336 nm was observed for CeOHCO{sub 3}, and that centered at 415 nm for CeO{sub 2} microstructures. Both of these emission peaks are different from those reported for CeOHCO{sub 3} and CeO{sub 2} with other shapes. In addition, the possible growth mechanism of dendrite CeOHCO{sub 3} microstructures and the role of surfactant polyvinyl pyrrolidone (PVP) were also investigated in this paper.

  19. Determination of intracellular nitrate.

    PubMed Central

    Romero, J M; Lara, C; Guerrero, M G

    1989-01-01

    A sensitive procedure has been developed for the determination of intracellular nitrate. The method includes: (i) preparation of cell lysates in 2 M-H3PO4 after separation of cells from the outer medium by rapid centrifugation through a layer of silicone oil, and (ii) subsequent nitrate analysis by ion-exchange h.p.l.c. with, as mobile phase, a solution containing 50 mM-H3PO4 and 2% (v/v) tetrahydrofuran, adjusted to pH 1.9 with NaOH. The determination of nitrate is subjected to interference by chloride and sulphate when present in the samples at high concentrations. Nitrite also interferes, but it is easily eliminated by treatment of the samples with sulphamic acid. The method has been successfully applied to the study of nitrate transport in the unicellular cyanobacterium Anacystis nidulans. PMID:2497740

  20. Purification of cerium, neodymium and gadolinium for low background experiments

    NASA Astrophysics Data System (ADS)

    Boiko, R. S.; Barabash, A. S.; Belli, P.; Bernabei, R.; Cappella, F.; Cerulli, R.; Danevich, F. A.; Incicchitti, A.; Laubenstein, M.; Mokina, V. M.; Nisi, S.; Poda, D. V.; Polischuk, O. G.; Tretyak, V. I.

    2014-01-01

    Cerium, neodymium and gadolinium contain double beta active isotopes. The most interesting are 150Nd and 160Gd (promising for 0ν2β search), 136Ce (2β+ candidate with one of the highest Q2β). The main problem of compounds containing lanthanide elements is their high radioactive contamination by uranium, radium, actinium and thorium. The new generation 2β experiments require development of methods for a deep purification of lanthanides from the radioactive elements. A combination of physical and chemical methods was applied to purify cerium, neodymium and gadolinium. Liquid-liquid extraction technique was used to remove traces of Th and U from neodymium, gadolinium and for purification of cerium from Th, U, Ra and K. Co-precipitation and recrystallization methods were utilized for further reduction of the impurities. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe gamma spectrometry. As a result of the purification procedure the radioactive contamination of gadolinium oxide (a similar purification efficiency was reached also with cerium and neodymium oxides) was decreased from 0.12 Bq/kg to 0.007 Bq/kg in 228Th, from 0.04 Bq/kg to <0.006 Bq/kg in 226Ra, and from 0.9 Bq/kg to 0.04 Bq/kg in 40K. The purification methods are much less efficient for chemically very similar radioactive elements like actinium, lanthanum and lutetium.

  1. Cerium; crystal structure and position in the periodic table.

    PubMed

    Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

    2014-09-17

    The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized [rlhar2 ] delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table.

  2. Cerium; Crystal Structure and Position in The Periodic Table

    PubMed Central

    Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

    2014-01-01

    The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized ⇌ delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table. PMID:25227991

  3. 40 CFR 721.8657 - Cerium, hydroxy oleate propionate complexes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... complexes. 721.8657 Section 721.8657 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.8657 Cerium, hydroxy oleate propionate complexes. (a) Chemical substance..., hydroxy oleate propionate complexes (PMN P-99-0026) is subject to reporting under this section for...

  4. Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

    DOEpatents

    Borglum, Brian P.; Bessette, Norman F.

    2000-01-01

    An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

  5. Protein tyrosine nitration

    PubMed Central

    Chaki, Mounira; Leterrier, Marina; Barroso, Juan B

    2009-01-01

    Nitric oxide metabolism in plant cells has a relative short history. Nitration is a chemical process which consists of introducing a nitro group (-NO2) into a chemical compound. in biological systems, this process has been found in different molecules such as proteins, lipids and nucleic acids that can affect its function. This mini-review offers an overview of this process with special emphasis on protein tyrosine nitration in plants and its involvement in the process of nitrosative stress. PMID:19826215

  6. Thermochemical nitrate reduction

    SciTech Connect

    Cox, J.L.; Lilga, M.A.; Hallen, R.T.

    1992-09-01

    A series of preliminary experiments was conducted directed at thermochemically converting nitrate to nitrogen and water. Nitrates are a major constituent of the waste stored in the underground tanks on the Hanford Site, and the characteristics and effects of nitrate compounds on stabilization techniques must be considered before permanent disposal operations begin. For the thermochemical reduction experiments, six reducing agents (ammonia, formate, urea, glucose, methane, and hydrogen) were mixed separately with {approximately}3 wt% NO{sub 3}{sup {minus}} solutions in a buffered aqueous solution at high pH (13); ammonia and formate were also mixed at low pH (4). Reactions were conducted in an aqueous solution in a batch reactor at temperatures of 200{degrees}C to 350{degrees}C and pressures of 600 to 2800 psig. Both gas and liquid samples were analyzed. The specific components analyzed were nitrate, nitrite, nitrous oxide, nitrogen, and ammonia. Results of experimental runs showed the following order of nitrate reduction of the six reducing agents in basic solution: formate > glucose > urea > hydrogen > ammonia {approx} methane. Airnmonia was more effective under acidic conditions than basic conditions. Formate was also effective under acidic conditions. A more thorough, fundamental study appears warranted to provide additional data on the mechanism of nitrate reduction. Furthermore, an expanded data base and engineering feasibility study could be used to evaluate conversion conditions for promising reducing agents in more detail and identify new reducing agents with improved performance characteristics.

  7. Cerium as a surrogate in the plutonium immobilization waste form

    NASA Astrophysics Data System (ADS)

    Marra, James Christopher

    In the aftermath of the Cold War, approximately 50 tonnes (MT) of weapons useable plutonium (Pu) has been identified as excess. The U.S. Department of Energy (DOE) has decided that at least a portion of this material will be immobilized in a titanate-based ceramic for final disposal in a geologic repository. The baseline formulation was designed to produce a ceramic consisting primarily of a highly substituted pyrochlore with minor amounts of brannerite and hafnia-substituted rutile. Since development studies with actual actinide materials is difficult, surrogates have been used to facilitate testing. Cerium has routinely been used as an actinide surrogate in actinide chemistry and processing studies. Although cerium appeared as an adequate physical surrogate for powder handling and general processing studies, cerium was found to act significantly different from a chemical perspective in the Pu ceramic form. The reduction of cerium at elevated temperatures caused different reaction paths toward densification of the respective forms resulting in different phase assemblages and microstructural features. Single-phase fabrication studies and cerium oxidation state analyses were performed to further quantify these behavioral differences. These studies indicated that the major phases in the final phase assemblages contained point defects likely leading to their stability. Additionally, thermochemical arguments predicted that the predominant pyrochlore phase in the ceramic was metastable. The apparent metastabilty associated with primary phase in the Pu ceramic form indicated that additional studies must be performed to evaluate the thermodynamic properties of these compounds. Moreover, the metastability of this predominant phase must be considered in assessment of long-term behavior (e.g. radiation stability) of this ceramic.

  8. Fundamental aspects of regenerative cerium oxide nanoparticles and their applications in nanobiotechnology

    NASA Astrophysics Data System (ADS)

    Patil, Swanand D.

    Cerium oxide has been used extensively for various applications over the past two decades. The use of cerium oxide nanoparticles is beneficial in present applications and can open avenues for future applications. The present study utilizes the microemulsion technique to synthesize uniformly distributed cerium oxide nanoparticles. The same technique was also used to synthesize cerium oxide nanoparticles doped with trivalent elements (La and Nd). The fundamental study of cerium oxide nanoparticles identified variations in properties as a function of particle size and also due to doping with trivalent elements (La and Nd). It was found that the lattice parameter of cerium oxide nanoparticles increases with decrease in particle size. Also Raman allowed mode shift to lower energies and the peak at 464 cm-1 becomes broader and asymmetric. The size dependent changes in cerium oxide were correlated to increase in oxygen vacancy concentration in the cerium oxide lattice. The doping of cerium oxide nanoparticles with trivalent elements introduces more oxygen vacancies and expands the cerium oxide lattice further (in addition to the lattice expansion due to the size effect). The lattice expansion is greater for La-doped cerium oxide nanoparticles compared to Nd-doping due to the larger ionic radius of La compared to Nd, the lattice expansion is directly proportional to the dopant concentration. The synthesized cerium oxide nanoparticles were used to develop an electrochemical biosensor of hydrogen peroxide (H2O2). The sensor was useful to detect H2O2 concentrations as low as 1muM in water. Also the preliminary testing of the sensor on tomato stem and leaf extracts indicated that the sensor can be used in practical applications such as plant physiological studies etc. The nanomolar concentrations of cerium oxide nanoparticles were also found to be useful in decreasing ROS (reactive oxygen species) mediated cellular damages in various in vitro cell cultures. Cerium oxide

  9. Study of cerium diffusion in undoped lithium-6 enriched glass with Rutherford backscattering spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaodong; Moore, Michael E.; Lee, Kyung-Min; Lukosi, Eric D.; Hayward, Jason P.

    2016-07-01

    Undoped lithium-6 enriched glasses coated with pure cerium (99.9%) with a gold protection layer on top were heated at three different temperatures (500, 550, and 600 °C) for varied durations (1, 2, and 4 h). Diffusion profiles of cerium in such glasses were obtained with the conventional Rutherford backscattering technique. Through fitting the diffusion profiles with the thin-film solution of Fick's second law, diffusion coefficients of cerium with different annealing temperatures and durations were solved. Then, the activation energy of cerium for the diffusion process in the studied glasses was found to be 114 kJ/mol with the Arrhenius equation.

  10. Isomorphic phase transformation in shocked cerium using molecular dynamics

    SciTech Connect

    Dupont, Virginie; Germann, Timothy C; Chen, Shao - Ping

    2010-08-12

    Cerium (Ce) undergoes a significant ({approx}16%) volume collapse associated with an isomorphic fcc-fcc phase transformation when subject to compressive loading. We present here a new Embedded Atom Method (EAM) potential for Cerium that models two minima for the two fcc phases. We show results from its use in Molecular Dynamics (MD) simulations of Ce samples subjected to shocks with pressures ranging from 0.5 to 25 GPa. A split wave structure is observed, with an elastic precursor followed by a plastic wave. The plastic wave causes the expected fcc-fcc phase transformation. Comparisons to experiments and MD simulations on Cesium (Cs) indicate that three waves could be observed. The construction of the EAM potential may be the source of the difference.

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

    SciTech Connect

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

    1990-05-01

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

  12. Engineered cerium oxide nanoparticles: Effects on bacterial growth and viability

    SciTech Connect

    Pelletier, Dale A; Suresh, Anil K; Holton, Gregory A; McKeown, Catherine K; Wang, Wei; Gu, Baohua; Mortensen, Ninell P; Allison, David P; Joy, David Charles; Allison, Martin R; Brown, Steven D; Phelps, Tommy Joe; Doktycz, Mitchel John

    2010-01-01

    Interest in engineered nanostructures has risen in recent years due to their use in energy conservation strategies and biomedicine. To ensure prudent development and use of nanomaterials, the fate and effects of such engineered structures on the environment should be understood. Interactions of nanomaterials with environmental microorganisms are inevitable, but the general consequences of such interactions remain unclear. Further, standardized methods for assessing such interactions are lacking. Therefore, we have initiated a multianalytical approach to understand the interactions of synthesized nanoparticles with bacterial systems. These efforts are focused initially on cerium oxide nanoparticles and model bacteria in order to evaluate characterization procedures and the possible fate of such materials in the environment. In this study the effects of cerium oxide nanoparticles on the growth and viability of Gram-negative Escherichia coli and Shewanella oneidensis, a metal-reducing bacteria, and Gram-positive Bacillus subtilis were examined relative to particle size, growth media, pH, and dosage. A hydrothermal based synthesis procedure was used to prepare cerium oxide nanoparticles of defined sizes in order to eliminate complications originating from the use of organic solvents and surfactants. Bactericidal effects were determined by minimum inhibitory concentration, colony forming units, disc diffusion tests and Live/Dead assays. In growth inhibition experiments involving E. coli and B. subtilis, a clear strain and size-dependent inhibition was observed. S. oneidensis appeared to be unaffected by the cerium oxide nanoparticles. Transmission electron microscopy along with microarray-based transcriptional profiling have been used to understand the response mechanism of the bacteria. The use of multiple analytical approaches adds confidence to toxicity assessments while the use of different bacterial systems highlights the potential wide-ranging effects of

  13. Monomers, Dimers, and Helices: Complexities of Cerium and Plutonium Phenanthrolinecarboxylates.

    PubMed

    Cary, Samantha K; Ferrier, Maryline G; Baumbach, Ryan E; Silver, Mark A; Lezama Pacheco, Juan; Kozimor, Stosh A; La Pierre, Henry S; Stein, Benjamin W; Arico, Alexandra A; Gray, Danielle L; Albrecht-Schmitt, Thomas E

    2016-05-01

    The reaction of Ce(III) or Pu(III) with 1,10-phenanthroline-2,9-dicarboxylic acid (PDAH2) results in the formation of new f-element coordination complexes. In the case of cerium, Ce(PDA)(H2O)2Cl·H2O (1) or [Ce(PDAH)(PDA)]2[Ce(PDAH)(PDA)] (2) was isolated depending on the Ce/ligand ratio in the reaction. The structure of 2 is composed of two distinct substructures that are constructed from the same monomer. This monomer is composed of a Ce(III) cation bound by one PDA(2-) dianionic ligand and one PDAH(-) monoanionic ligand, both of which are tetradentate. Bridging by the carboxylate moieties leads to either [Ce(PDAH)(PDA)]2 dimers or [Ce(PDAH)(PDA)]1∞ helical chains. For plutonium, Pu(PDA)2 (3) was the only product isolated regardless of the Pu/ligand ratio employed in the reaction. During the reaction of plutonium with PDAH2, Pu(III) is oxidized to Pu(IV), generating 3. This assignment is consistent with structural metrics and the optical absorption spectrum. Ambiguity in the assignment of the oxidation state of cerium in 1 and 2 from UV-vis-near-IR spectra invoked the use of Ce L3,2-edge X-ray absorption near-edge spectroscopy, magnetic susceptibility, and heat capacity measurements. These experiments support the assignment of Ce(III) in both compounds. The bond distances and coordination numbers are also consistent with these assignments. 3 contains 8-coordinate Pu(IV), whereas the cerium centers in 1 and 2 are 9- and/or 10-coordinate, which correlates with the increased size of Ce(III) versus Pu(IV). Taken together, these data provide an example of a system where the differences in the redox behavior between these f elements creates more complex chemistry with cerium than with plutonium. PMID:27070401

  14. Optical Response of Shocked Cerium-Doped Lutetium Oxyorthosilicate

    SciTech Connect

    G. D. Stevens

    2003-03-01

    Shock experiments were performed in order to characterize the triboluminescent signature of cerium-doped lutetium oxyorthosilicate (LSO:Ce). This material shows prompt, nano-second timescale light emission when driven by explosive detonation. When properly applied to a surface, it may be used as a shock arrival sensor, and also for imaging the propagation of a shock front. Triboluminescent rise times, spectral content, and spatial resolution measurements are presented.

  15. Antibacterial Activity of Polymer Coated Cerium Oxide Nanoparticles

    PubMed Central

    Shah, Vishal; Shah, Shreya; Shah, Hirsh; Rispoli, Fred J.; McDonnell, Kevin T.; Workeneh, Selam; Karakoti, Ajay; Kumar, Amit; Seal, Sudipta

    2012-01-01

    Cerium oxide nanoparticles have found numerous applications in the biomedical industry due to their strong antioxidant properties. In the current study, we report the influence of nine different physical and chemical parameters: pH, aeration and, concentrations of MgSO4, CaCl2, KCl, natural organic matter, fructose, nanoparticles and Escherichia coli, on the antibacterial activity of dextran coated cerium oxide nanoparticles. A least-squares quadratic regression model was developed to understand the collective influence of the tested parameters on the anti-bacterial activity and subsequently a computer-based, interactive visualization tool was developed. The visualization allows us to elucidate the effect of each of the parameters in combination with other parameters, on the antibacterial activity of nanoparticles. The results indicate that the toxicity of CeO2 NPs depend on the physical and chemical environment; and in a majority of the possible combinations of the nine parameters, non-lethal to the bacteria. In fact, the cerium oxide nanoparticles can decrease the anti-bacterial activity exerted by magnesium and potassium salts. PMID:23110109

  16. Synthesis and characterization of polyvinylpyrrolidone coated cerium oxide nanoparticles.

    PubMed

    Merrifield, Ruth C; Wang, Zhi Wei; Palmer, Richard E; Lead, Jamie R

    2013-01-01

    There is a pressing need for the development of standard and reference nanomaterials for environmental nanoscience and nanotoxicology. To that aim, suspensions of polyvinylpyrrolidone (PVP)-coated ceria nanoparticles (NPs) were produced. Four differently sized monodispersed samples were produced by using different PVP chain lengths. The chemical and physical properties of these NPs were characterized as prepared and in different ecotoxicology exposure media. Dynamic light scattering analysis showed that the samples were monodispersed, with an unchanged size when suspended in the different media over a 72 h period. Electron microscopy confirmed this and revealed that the larger (ca. 20 nm) particles were aggregates composed of the smaller individual particles (4-5 nm). Electron energy loss spectroscopy (EELS) showed that the smallest and largest samples were composed almost entirely of cerium(III) oxide, with only small amounts of cerium(IV) present in the largest sample. Dissolved cerium concentrations in media were low and constant, showing that the NPs did not dissolve over time. The simple synthesis of the these NPs and their physical and chemical stability in different environmental conditions make them potentially suitable for use as reference materials for (eco)toxicology and surface water environmental studies.

  17. Jet formation in cerium metal to examine material strength

    SciTech Connect

    Jensen, B. J. Cherne, F. J.; Prime, M. B.; Yeager, J. D.; Ramos, K. J.; Hooks, D. E.; Cooley, J. C.; Dimonte, G.; Fezzaa, K.; Iverson, A. J.; Carlson, C. A.

    2015-11-21

    Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solid phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. From these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. The data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.

  18. Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics

    SciTech Connect

    Guo, Xiaofeng; Tavakoli, Amir H.; Sutton, Steve; Kukkadapu, Ravi K.; Qi, Liang; Lanzirotti, Anthony; Newville, Mathew; Asta, Mark D.; Navrotsky, Alexandra

    2014-01-28

    The garnet structure is a promising nuclear waste form because it can accommodate various actinide elements. Y3Fe5O12 (YIG) is a model composition for such substitutions. Since cerium (Ce) can be considered an analogue of actinide elements such as thorium (Th), plutonium (Pu), and uranium (U), studying the local structure and thermodynamic stability of Ce-substituted YIG (Ce:YIG) can provide insights into the structural and energetic aspects of large ion substitution in garnets. Single phases of yttrium iron garnet with Ce substitution up to 20 mol % (Y3-xCexFe5O12 with 0 ≤ x ≤ 0.2) were synthesized through a citrate-nitrate combustion method. The oxidation state of cerium was examined by X-ray absorption near edge structure spectroscopy (XANES); the oxidation state and site occupancy of Fe as a function of Ce loading also was monitored by 57Fe-Mössbauer spectroscopy. These measurements establish that Ce is predominantly in the trivalent state at low substitution levels, while a mixture of trivalent and tetravalent states are observed at higher concentrations. Fe was predominately trivalent and exists in multiple environments. High temperature oxide melt solution calorimetry was used to determine the enthalpy of formation of these Ce-substituted YIG garnets. The thermodynamic analysis demonstrated that, although there is an entropic driving force for the substitution of Ce for Y, the substitution reaction is enthalpically unfavorable. The experimental results are complemented by electronic structure calculations performed within the framework of density functional theory (DFT) with Hubbard-U corrections, which reproduce the observed increase in the tendency for tetravalent Ce to be present with higher loading of Ce. The DFT+U results suggest that the energetics underlying the formation of tetravalent Ce involves a competition between an unfavorable energy to oxidize Ce and reduce Fe, and a favorable contribution due to strain-energy reduction. The structural

  19. Effect of nano-sized cerium-zirconium oxide solid solution on far-infrared emission properties of tourmaline powders

    NASA Astrophysics Data System (ADS)

    Guo, Bin; Yang, Liqing; Hu, Weijie; Li, Wenlong; Wang, Haojing

    2015-10-01

    Far-infrared functional nanocomposites were prepared by the co-precipitation method using natural tourmaline (XY3Z6Si6O18(BO3)3V3W, where X is Na+, Ca2+, K+, or vacancy; Y is Mg2+, Fe2+, Mn2+, Al3+, Fe3+, Mn3+, Cr3+, Li+, or Ti4+; Z is Al3+, Mg2+, Cr3+, or V3+; V is O2-, OH-; and W is O2-, OH-, or F-) powders, ammonium cerium(IV) nitrate and zirconium(IV) nitrate pentahydrate as raw materials. The reference sample, tourmaline modified with ammonium cerium(IV) nitrate alone was also prepared by a similar precipitation route. The results of Fourier transform infrared spectroscopy show that tourmaline modified with Ce and Zr has a better far-infrared emission property than tourmaline modified with Ce alone. Through characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), the mechanism for oxygen evolution during the heat process in the two composite materials was systematically studied. The XPS spectra show that Fe3+ ratio inside tourmaline modified with Ce alone can be raised by doping Zr. Moreover, it is showed that there is a higher Ce3+ ratio inside the tourmaline modified with Ce and Zr than tourmaline modified with Ce alone. In addition, XRD results indicate the formation of CeO2 and Ce1-xZrxO2 crystallites during the heat treatment and further TEM observations show they exist as nanoparticles on the surface of tourmaline powders. Based on these results, we attribute the improved far-infrared emission properties of Ce-Zr doped tourmaline to the enhanced unit cell shrinkage of the tourmaline arisen from much more oxidation of Fe2+ to Fe3+ inside the tourmaline caused by the change in the catalyst redox properties of CeO2 brought about by doping with Zr4+. In all samples, tourmaline modified with 7.14 wt.% Ce and 1.86 wt.% Zr calcined at 800∘C for 5 h has the best far-infrared emission property with the maximum emissivity value of 98%.

  20. Induction of pulmonary fibrosis by cerium oxide nanoparticles

    SciTech Connect

    Ma, Jane Y.; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Scabilloni, James; Ma, Joseph K.; Castranova, Vincent

    2012-08-01

    Cerium compounds have been used as a diesel engine catalyst to lower the mass of diesel exhaust particles, but are emitted as cerium oxide (CeO{sub 2}) nanoparticles in the diesel exhaust. In a previous study, we have demonstrated a wide range of CeO{sub 2}-induced lung responses including sustained pulmonary inflammation and cellular signaling that could lead to pulmonary fibrosis. In this study, we investigated the fibrogenic responses induced by CeO{sub 2} in a rat model at various time points up to 84 days post-exposure. Male Sprague Dawley rats were exposed to CeO{sub 2} by a single intratracheal instillation. Alveolar macrophages (AM) were isolated by bronchial alveolar lavage (BAL). AM-mediated cellular responses, osteopontin (OPN) and transform growth factor (TGF)-β1 in the fibrotic process were investigated. The results showed that CeO{sub 2} exposure significantly increased fibrotic cytokine TGF-β1 and OPN production by AM above controls. The collagen degradation enzymes, matrix metalloproteinase (MMP)-2 and -9 and the tissue inhibitor of MMP were markedly increased in the BAL fluid at 1 day- and subsequently declined at 28 days after exposure, but remained much higher than the controls. CeO{sub 2} induced elevated phospholipids in BAL fluid and increased hydroxyproline content in lung tissue in a dose- and time-dependent manner. Immunohistochemical analysis showed MMP-2, MMP-9 and MMP-10 expressions in fibrotic regions. Morphological analysis noted increased collagen fibers in the lungs exposed to a single dose of 3.5 mg/kg CeO{sub 2} and euthanized at 28 days post-exposure. Collectively, our studies show that CeO{sub 2} induced fibrotic lung injury in rats, suggesting it may cause potential health effects. -- Highlights: ► Cerium oxide exposure significantly affected the following parameters in the lung. ► Induced fibrotic cytokine OPN and TGF-β1 production and phospholipidosis. ► Caused imbalance of the MMP-9/ TIMP-1 ratio that favors fibrosis

  1. Equation of state of quartz glass and cerium in their abnormal compressibility range

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.

    2016-09-01

    In this work, the semiempirical equation of state of quartz glass and polycrystalline γ-cerium are plotted and verified at the compressive pressures to 3 GPa. The proposed equations are shown to uniformly describe the thermophysical and physicomechanical properties of quartz glass and polycrystalline γ-cerium at their abnormal compressibility in compression. The room isotherms of these materials are discussed, as well.

  2. Cerium doped red mud catalytic ozonation for bezafibrate degradation in wastewater: Efficiency, intermediates, and toxicity.

    PubMed

    Xu, Bingbing; Qi, Fei; Sun, Dezhi; Chen, Zhonglin; Robert, Didier

    2016-03-01

    In this study, the performance of bezafibrate (BZF) degradation and detoxification in the aqueous phase using cerium-modified red mud (RM) catalysts prepared using different cerium sources and synthesis methods were evaluated. Experimental results showed that the surface cerium modification was responsible for the development of the catalytic activity of RM and this was influenced by the cerium source and the synthesis method. Catalyst prepared from cerium (IV) by precipitation was found to show the best catalytic activity in BZF degradation and detoxification. Reactive oxygen species including peroxides, hydroxyl radicals, and super oxide ions were identified in all reactions and we proposed the corresponding catalytic reaction mechanism for each catalyst that prepared from different cerium source and method. This was supported by the intermediates profiles that were generated upon BZF degradation. The surface and the structural properties of cerium-modified RM were characterized in detail by several analytical methods. Two interesting findings were made: (1) the surface texture (specific surface area and mesoporous volume) influenced the catalytic reaction pathway; and (2) Ce(III) species and oxygen vacancies were generated on the surface of the catalyst after cerium modification. This plays an important role in the development of the catalytic activity. PMID:26706928

  3. Reactions of carbonyl compounds with Grignard reagents in the presence of cerium chloride

    SciTech Connect

    Imamoto, Tsuneo; Takiyama, Nobuyuki; Nakamura, Kimikazu; Hatajima, Toshihiko; Kamiya, Yasuo )

    1989-06-07

    The addition of Grignard reagents to ketones is significantly enhanced by cerium chloride with remarkable suppression of side reactions, particularly enolization. Some esters, which are prone to side reactions, also react readily with Grignard reagents in the presence of cerium chloride to give normal reaction products in reasonable to high yields.

  4. 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.

  5. Ammonium nitrate explosive systems

    DOEpatents

    Stinecipher, Mary M.; Coburn, Michael D.

    1981-01-01

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

  6. Nitrate Storage and Dissimilatory Nitrate Reduction by Eukaryotic Microbes.

    PubMed

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils; Stief, Peter

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described. A first compilation of intracellular nitrate inventories in various marine sediments is presented, indicating that intracellular nitrate pools vastly exceed porewater nitrate pools. The relative contribution by foraminifers to total sedimentary denitrification is estimated for different marine settings, suggesting that eukaryotes may rival prokaryotes in terms of dissimilatory nitrate reduction. Finally, this review article sketches some evolutionary perspectives of eukaryotic nitrate metabolism and identifies open questions that need to be addressed in future investigations. PMID:26734001

  7. Nitrate Storage and Dissimilatory Nitrate Reduction by Eukaryotic Microbes.

    PubMed

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils; Stief, Peter

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described. A first compilation of intracellular nitrate inventories in various marine sediments is presented, indicating that intracellular nitrate pools vastly exceed porewater nitrate pools. The relative contribution by foraminifers to total sedimentary denitrification is estimated for different marine settings, suggesting that eukaryotes may rival prokaryotes in terms of dissimilatory nitrate reduction. Finally, this review article sketches some evolutionary perspectives of eukaryotic nitrate metabolism and identifies open questions that need to be addressed in future investigations.

  8. Nitrate Storage and Dissimilatory Nitrate Reduction by Eukaryotic Microbes

    PubMed Central

    Kamp, Anja; Høgslund, Signe; Risgaard-Petersen, Nils; Stief, Peter

    2015-01-01

    The microbial nitrogen cycle is one of the most complex and environmentally important element cycles on Earth and has long been thought to be mediated exclusively by prokaryotic microbes. Rather recently, it was discovered that certain eukaryotic microbes are able to store nitrate intracellularly and use it for dissimilatory nitrate reduction in the absence of oxygen. The paradigm shift that this entailed is ecologically significant because the eukaryotes in question comprise global players like diatoms, foraminifers, and fungi. This review article provides an unprecedented overview of nitrate storage and dissimilatory nitrate reduction by diverse marine eukaryotes placed into an eco-physiological context. The advantage of intracellular nitrate storage for anaerobic energy conservation in oxygen-depleted habitats is explained and the life style enabled by this metabolic trait is described. A first compilation of intracellular nitrate inventories in various marine sediments is presented, indicating that intracellular nitrate pools vastly exceed porewater nitrate pools. The relative contribution by foraminifers to total sedimentary denitrification is estimated for different marine settings, suggesting that eukaryotes may rival prokaryotes in terms of dissimilatory nitrate reduction. Finally, this review article sketches some evolutionary perspectives of eukaryotic nitrate metabolism and identifies open questions that need to be addressed in future investigations. PMID:26734001

  9. Hydrocarbon-based polymer electrolyte cerium composite membranes for improved proton exchange membrane fuel cell durability

    NASA Astrophysics Data System (ADS)

    Lee, Hyejin; Han, Myungseong; Choi, Young-Woo; Bae, Byungchan

    2015-11-01

    Hydrocarbon-based cerium composite membranes were prepared for proton exchange membrane fuel cell applications to increase oxidative stability. Different amounts of cerium ions were impregnated in sulfonated poly(arylene ether sulfone) (SPES) membranes and their physicochemical properties were investigated according to the cerium content. Field-emission scanning electron microscopy and inductively coupled plasma analyses confirmed the presence of cerium ions in the composite membranes and 1H NMR indicated the successful coordination of sulfonic acid groups with the metal ions. Increasing amounts of cerium ions resulted in decreases in the proton conductivity and water uptake, but enhanced oxidative stability. The oxidative stability of the composite membranes was proven via a hydrogen peroxide exposure experiment which mimicked fuel cell operating conditions. In addition, more than 2200 h was achieved with the composite membrane under in situ accelerated open circuit voltage (OCV) durability testing (DOE protocol), whereas the corresponding pristine SPES membrane attained only 670 h.

  10. Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

    SciTech Connect

    Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.; Carroll, Patrick J.; Walsh, Patrick J.; Schelter, Eric J.

    2014-06-24

    Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.

  11. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants.

    PubMed

    Barrios, Ana Cecilia; Rico, Cyren M; Trujillo-Reyes, Jesica; Medina-Velo, Illya A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-09-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO2, CA+nCeO2) bulk cerium oxide (bCeO2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500mg/kg, both the uncoated and CA+nCeO2 increased shoot length by ~9 and ~13%, respectively, while bCeO2 and CeAc decreased shoot length by ~48 and ~26%, respectively, compared with MPW (p≤0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA+nCeO2 at 250mg/kg, but reduced by bCeO2 at 62.5mg/kg, compared with MPW. At 250 and 500mg/kg, nCeO2 increased Ce in roots by 10 and 7 times, compared to CA+nCeO2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO2 nor CA+nCeO2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO2 at 62.5mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO2 on tomato plants.

  12. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants.

    PubMed

    Barrios, Ana Cecilia; Rico, Cyren M; Trujillo-Reyes, Jesica; Medina-Velo, Illya A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-09-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO2, CA+nCeO2) bulk cerium oxide (bCeO2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500mg/kg, both the uncoated and CA+nCeO2 increased shoot length by ~9 and ~13%, respectively, while bCeO2 and CeAc decreased shoot length by ~48 and ~26%, respectively, compared with MPW (p≤0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA+nCeO2 at 250mg/kg, but reduced by bCeO2 at 62.5mg/kg, compared with MPW. At 250 and 500mg/kg, nCeO2 increased Ce in roots by 10 and 7 times, compared to CA+nCeO2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO2 nor CA+nCeO2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO2 at 62.5mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO2 on tomato plants. PMID:26672385

  13. Thermal Signatures of The Kondo Volume Collapse in Cerium

    SciTech Connect

    Lipp, M; Jackson, D; Cynn, H; Aracne, C; Evans, W; McMahan, A

    2008-05-23

    X-ray diffraction measurements of cerium in the vicinity of the isostructural {gamma}-{alpha} transition have been performed with high precision and accuracy from room temperature to almost 800 K. The disputed location of the critical point has been found to occur at 1.5 {+-} 0.1 GPa and 480 {+-} 10 K. The data is well fit by the Kondo volume collapse model plus a quasiharmonic representation of the phonons. The resultant free energy is validated against data for the thermodynamic Grueneisen parameter, and beyond the dominant spin fluctuation contribution, indicates a dramatic change in the lattice Grueneisen parameter across the transition.

  14. Identification of the Charge Carriers in Cerium Phosphate Ceramics

    SciTech Connect

    Ray, Hannah L.; Jonghe, Lutgard C. De

    2010-06-02

    The total conductivity of Sr-doped cerium orthophosphate changes by nearly two orders of magnitude depending on the oxygen and hydrogen content of the atmosphere. The defect model for the system suggests that this is because the identity of the dominant charge carrier can change from electron holes to protons when the sample is in equilibrium with air vs. humidified hydrogen. In this work are presented some preliminary measurements that can help to clarify this exchange between carriers. The conduction behavior of a 2percent Sr-doped CePO4 sample under symmetric atmospheric conditions is investigated using several techniques, including AC impedance, H/D isotope effects, and chronoamperometry.

  15. Properties of hot liquid cerium by LDA + U molecular dynamics.

    PubMed

    Siberchicot, Bruno; Clérouin, Jean

    2012-11-14

    We present ab initio simulations of liquid cerium in the framework of the LDA + U formulation. The liquid density has been determined self-consistently by searching for the zero pressure equilibrium state at 1320 K with the same set of parameters (U and J) and occupation matrices as those optimized for the γ phase. We have computed static and transport properties. The liquid produced by the simulations appears more structured than the available measurements. This raises questions regarding the ability of the theory to describe such a complex liquid. Conductivity calculations and temperature dependences are nevertheless in reasonable agreement with data.

  16. Glycine lithium nitrate crystals

    NASA Astrophysics Data System (ADS)

    González-Valenzuela, R.; Hernández-Paredes, J.; Medrano-Pesqueira, T.; Esparza-Ponce, H. E.; Jesús-Castillo, S.; Rodriguez-Mijangos, R.; Terpugov, V. S.; Alvarez-Ramos, M. E.; Duarte-Möller, A.

    Crystals of glycine lithium nitrate with non-linear optical properties have been grown in a solution by slow evaporation at room temperature. The crystal shows a good thermal stability from room temperature to 175 °C where the crystal begins to degrade. This property is desirable for future technological applications. Also, a good performance on the second harmonic generation was found, characterizing the emitted dominant wavelength by a customized indirect procedure using luminance and chromaticity measured data based on the CIE-1931 standard. Additionally, the 532 nm signal was detected by using a variant to the Kurtz and Perry method.

  17. Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Trujillo-Reyes, Jesica; Sun, Youping; Barrios, Ana C; Niu, Genhua; Margez, Juan P Flores-; Gardea-Torresdey, Jorge L

    2016-11-01

    Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0-500mg/kg cerium oxide nanoparticles (nano-CeO2) under greenhouse condition. After 52days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO2 exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65-111% with increasing nano-CeO2 concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5-250mg/kg nano-CeO2 led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25-28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250mg/kg nano-CeO2. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO2 exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment.

  18. Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Trujillo-Reyes, Jesica; Sun, Youping; Barrios, Ana C; Niu, Genhua; Margez, Juan P Flores-; Gardea-Torresdey, Jorge L

    2016-11-01

    Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0-500mg/kg cerium oxide nanoparticles (nano-CeO2) under greenhouse condition. After 52days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO2 exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65-111% with increasing nano-CeO2 concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5-250mg/kg nano-CeO2 led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25-28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250mg/kg nano-CeO2. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO2 exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment. PMID:27343939

  19. Hydrothermal synthesis of cerium titanate nanorods and its application in visible light photocatalysis

    SciTech Connect

    Pei, L.Z. Liu, H.D.; Lin, N.; Yu, H.Y.

    2015-01-15

    Highlights: • Cerium titanate nanorods have been synthesized by a simple hydrothermal process. • The size of the cerium titanate nanorods can be controlled by growth conditions. • Cerium titanate nanorods exhibit good photocatalytic activities for methyl blue. - Abstract: Cerium titanate nanorods have been prepared via a hydrothermal process using sodium dodecyl sulfate (SDS) as the surfactant. The cerium titanate nanorods have been analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and ultraviolet–visible (UV–vis) diffuse reflectance spectrum. XRD shows that the nanorods are composed of CeTi{sub 21}O{sub 38} phase. Electron microscopy observations indicate that the nanorods have good single crystalline nature. The diameter and length of the nanorods are about 50–200 nm and 1–2 μm, respectively. Cerium titanate nanorods have a band gap of 2.65 eV. The photocatalytic activities of the nanorods have been investigated by degrading methylene blue (MB) under visible light irradiation. MB solution with the concentration of 10 mg L{sup −1} can be degraded totally with the irradiation time increasing to 240 min. Cerium titanate nanorods exhibit great potential in photocatalytic degradation of MB under visible light irradiation.

  20. Altering properties of cerium oxide thin films by Rh doping

    SciTech Connect

    Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír; and others

    2015-07-15

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.

  1. Pulmonary toxicity in mice following exposure to cerium chloride.

    PubMed

    Hong, Jie; Yu, Xiaohong; Pan, Xiaoyu; Zhao, Xiaoyang; Sheng, Lei; Sang, Xuezi; Lin, Anan; Zhang, Chi; Zhao, Yue; Gui, Suxin; Sun, Qingqing; Wang, Ling; Hong, Fashui

    2014-06-01

    The widespread application of lanthanoids (Lns) in manufacturing industries has raised occupational and environmental health concerns about the possible increased health risks to humans exposed to Lns in their working and living environments. Numerous studies have shown that exposures to Ln cause pulmonary injury in animals, but very little is known about the molecular mechanisms of the pulmonary inflammation caused by cerium chloride (CeCl3) exposure. In this study, we evaluated the oxidative stress and molecular mechanism underlying with the pulmonary inflammation associated with chronic lung toxicity in mice treated with nasally instilled CeCl3 for 90 consecutive days. Our findings suggest that significant cerium accumulated in the lung, leading the obvious increase of the lung indices, significant increases in inflammatory cells and levels of lactate dehydrogenase, alkaline phosphate, and total protein, overproduction of reactive oxygen species and peroxidation of lipids, reduced antioxidant capacity, and pulmonary inflammation. CeCl3 exposure also activated nuclear factor κB, increased the expression of tumor necrosis factor α, cyclooxygenase-2, heme oxygenase 1, interleukin 2, interleukin 4, interleukin 6, interleukin 8, interleukin 10, interleukin 18, interleukin 1β, and CYP1A1. However, CeCl3 reduced the expression of nuclear factor κB (NF-κB)-inhibiting factor and heat shock protein 70. These findings suggest that the pulmonary inflammation caused by CeCl3 in mice is closely associated with oxidative stress and inflammatory cytokine expression. PMID:24736977

  2. Regulation of Nitrate Assimilation and Nitrate Respiration in Aerobacter aerogenes

    PubMed Central

    Van 'T Riet, J.; Stouthamer, A. H.; Planta, R. J.

    1968-01-01

    The influence of growth conditions on assimilatory and respiratory nitrate reduction in Aerobacter aerogenes was studied. The level of nitrate reductase activity in cells, growing in minimal medium with nitrate as the sole nitrogen source, was much lower under aerobic than anaerobic conditions. Further, the enzyme of the aerobic cultures was very sensitive to sonic disintegration, as distinct from the enzyme of anaerobic cultures. When a culture of A. aerogenes was shifted from anaerobic growth in minimal medium with nitrate and NH4+ to aerobiosis in the same medium, but without NH4+, the production of nitrite stopped instantaneously and the total activity of nitrate reductase decreased sharply. Moreover, there was a lag in growth of about 3 hr after such a shift. After resumption of growth, the total enzymatic activity increased again slowly and simultaneously became gradually sensitive to sonic disintegration. These findings show that oxygen inactivates the anaerobic nitrate reductase and represses its further formation; only after a de novo synthesis of nitrate reductase with an assimilatory function will growth be resumed. The enzyme in aerobic cultures was not significantly inactivated by air, only by pure oxygen. The formation of the assimilatory enzyme complex was repressed, however, by NH4+, under both aerobic and anaerobic conditions. The results indicate that the formation of the assimilatory enzyme complex and that of the respiratory enzyme complex are regulated differently. We suggest that both complexes have a different composition, but that the nitrate reductase in both cases is the same protein. PMID:5726295

  3. Serum ornithine carbamoyltransferase (OCT) in rats poisoned with lanthanum, cerium and praseodymium.

    PubMed

    Marciniak, M; Bałtrukiewicz, Z

    1977-01-01

    Serum ornithine carbamoyltransferase (OCT) in rats poisoned with lanthanum, cerium and praseodymium. Acta Physiol. Pol., 1977, 28 (6): 589-594. The serum ornithine carbamoyltransferase in relation to doses of lanthanum, cerium and praseodymium, administered intravenously as chlorides, was investigated. A directly proportional relationship was found between the doses of these compounds and the serum enzyme level in rats. The lowest doses at which a rise in the serum OCT level occured were determined. They were: lanthanum - 0.75 mg/kg of body weight, cerium - 1.5 mg/kg, and praseodymium - 3 mh/kg. A decreasing toxicity of these elements with increasing value of atomic number was observed.

  4. Cerium-Based Magnets: Novel High Energy Permanent Magnet Without Critical Elements

    SciTech Connect

    2012-01-01

    REACT Project: Ames Laboratory will develop a new class of permanent magnets based on the more commonly available element cerium for use in both EVs and renewable power generators. Cerium is 4 times more abundant and significantly less expensive than the rare earth element neodymium, which is frequently used in today’s most powerful magnets. Ames Laboratory will combine other metal elements with cerium to create a new magnet that can remain stable at the high temperatures typically found in electric motors. This new magnetic material will ultimately be demonstrated in a prototype electric motor, representing a cost-effective and efficient alternative to neodymium-based motors.

  5. Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

    NASA Astrophysics Data System (ADS)

    Kato, Tetsuya; Usami, Tsuyoshi; Tsukada, Takeshi; Shibata, Yuki; Kodama, Takashi

    2016-10-01

    In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO3)3) dissolved in nitric acid (HNO3), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO4) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO3, nitrogen dioxide (NO2), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO4 seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO3 decreases. More volatilization of RuO4 was observed from the HNO3 solution containing not only Ru(NO)(NO3)3 but also cerium nitrate (Ce(NO3)3·6H2O) which was added for extra supply of nitrate ion, compared with that from the HNO3 solution containing only Ru(NO)(NO3)3. These experimental results suggest that Ru could be oxidized to form RuO4 by the nitrate ion as well as HNO3.

  6. Some History of Nitrates

    NASA Astrophysics Data System (ADS)

    Barnum, Dennis W.

    2003-12-01

    The history of saltpeter is an interesting combination of chemistry, world trade, technology, politics, and warfare. Originally it was obtained from the dirt floors of stables, sheep pens, pigeon houses, caverns, and even peasants' cottages; any place manure and refuse accumulated in soil under dry conditions. When these sources became inadequate to meet demand it was manufactured on saltpeter plantations, located in dry climates, where piles of dirt, limestone, and manure were allowed to stand for three to five years while soil microbes oxidized the nitrogen to nitrate—an example of early bioengineering. Extensive deposits of sodium nitrate were mined in the Atacama Desert in northern Chile from 1830 until the mid 1920s when the mines were displaced by the Haber Ostwald process.

  7. Nitrate reductase from Rhodopseudomonas sphaeroides.

    PubMed Central

    Kerber, N L; Cardenas, J

    1982-01-01

    The facultative phototroph Rhodopseudomonas sphaeroides DSM158 was incapable of either assimilating or dissimilating nitrate, although the organism could reduce it enzymatically to nitrite either anaerobically in the light or aerobically in the dark. Reduction of nitrate was mediated by a nitrate reductase bound to chromatophores that could be easily solubilized and functioned with chemically reduced viologens or photochemically reduced flavins as electron donors. The enzyme was solubilized, and some of its kinetic and molecular parameters were determined. It seemed to be nonadaptive, ammonia did not repress its synthesis, and its activity underwent a rapid decline when the cells entered the stationary growth phase. Studies with inhibitors and with metal antagonists indicated that molybdenum and possibly iron participate in the enzymatic reduction of nitrate. The conjectural significance of this nitrate reductase in phototrophic bacteria is discussed. PMID:6978883

  8. TREATMENT OF AMMONIUM NITRATE SOLUTIONS

    DOEpatents

    Boyer, T.W.; MacHutchin, J.G.; Yaffe, L.

    1958-06-10

    The treatment of waste solutions obtained in the processing of neutron- irradiated uranium containing fission products and ammonium nitrate is described. The object of this process is to provide a method whereby the ammonium nitrate is destroyed and removed from the solution so as to permit subsequent concentration of the solution.. In accordance with the process the residual nitrate solutions are treated with an excess of alkyl acid anhydride, such as acetic anhydride. Preferably, the residual nitrate solution is added to an excess of the acetic anhydride at such a rate that external heat is not required. The result of this operation is that the ammonium nitrate and acetic anhydride react to form N/sub 2/ O and acetic acid.

  9. Mortality of nitrate fertiliser workers.

    PubMed

    Al-Dabbagh, S; Forman, D; Bryson, D; Stratton, I; Doll, R

    1986-08-01

    An epidemiological cohort study was conducted to investigate the mortality patterns among a group of workers engaged in the production of nitrate based fertilisers. This study was designed to test the hypothesis that individuals exposed to high concentrations of nitrates might be at increased risk of developing cancers, particularly gastric cancer. A total of 1327 male workers who had been employed in the production of fertilisers between 1946 and 1981 and who had been occupationally exposed to nitrates for at least one year were followed up until 1 March 1981. In total, 304 deaths were observed in this group and these were compared with expected numbers calculated from mortality rates in the northern region of England, where the factory was located. Analysis was also carried out separately for a subgroup of the cohort who had been heavily exposed to nitrates--that is, working in an environment likely to contain more than 10 mg nitrate/m3 for a year or longer. In neither the entire cohort nor the subgroup was any significant excess observed for all causes of mortality or for mortality from any of five broad categories of cause or from four specific types of cancer. A small excess of lung cancer was noted more than 20 years after first exposure in men heavily exposed for more than 10 years. That men were exposed to high concentrations of nitrate was confirmed by comparing concentrations of nitrates in the saliva of a sample of currently employed men with control men, employed at the same factory but not in fertiliser production. The men exposed to nitrate had substantially raised concentrations of nitrate in their saliva compared with both controls within the industry and with men in the general population and resident nearby. The results of this study therefore weight against the idea that exposure to nitrates in the environment leads to the formation in vivo of material amounts of carcinogens. PMID:3015194

  10. Nitrate Transport System in Neurospora crassa

    PubMed Central

    Schloemer, Robert H.; Garrett, Reginald H.

    1974-01-01

    Nitrate uptake in Neurospora crassa has been investigated under various conditions of nitrogen nutrition by measuring the rate of disappearance of nitrate from the medium and by determining mycelial nitrate accumulation. The nitrate transport system is induced by either nitrate or nitrite, but is not present in mycelia grown on ammonia or Casamino Acids. The appearance of nitrate uptake activity is prevented by cycloheximide, puromycin, or 6-methyl purine. The induced nitrate transport system displays a Km for nitrate of 0.25 mM. Nitrate uptake is inhibited by metabolic poisons such as 2,4-dinitrophenol, cyanide, and antimycin A. Furthermore, mycelia can concentrate nitrate 50-fold. Ammonia and nitrite are non-competitive inhibitors with respect to nitrate, with Ki values of 0.13 and 0.17 mM, respectively. Ammonia does not repress the formation of the nitrate transport system. In contrast, the nitrate uptake system is repressed by Casamino Acids. All amino acids individually prevent nitrate accumulation, with the exception of methionine, glutamine, and alanine. The influence of nitrate reduction and the nitrate reductase protein on nitrate transport was investigated in wild-type Neurospora lacking a functional nitrate reductase and in nitrate non-utilizing mutants, nit-1, nit-2, and nit-3. These mycelia contain an inducible nitrate transport system which displays the same characteristics as those found in the wild-type mycelia having the functional nitrate reductase. These findings suggest that nitrate transport is not dependent upon nitrate reduction and that these two processes are separate events in the assimilation of nitrate. PMID:4274457

  11. Correction: Single-molecule magnet behaviour in polynuclear assembly of trivalent cerium ions with polyoxomolybdates.

    PubMed

    Khélifa, A Ben; Belkhiria, M Salah; Huang, G; Freslon, S; Guillou, O; Bernot, K

    2016-06-01

    Correction for 'Single-molecule magnet behaviour in polynuclear assembly of trivalent cerium ions with polyoxomolybdates' by A. Ben Khélifa, et al., Dalton Trans., 2015, 44, 16458-16464. PMID:27161299

  12. Calculation of a volume effect accompanying an electronic topological transition in pure cerium

    NASA Astrophysics Data System (ADS)

    Ponomaryova, S. O.; Koval', Yu. M.; Ponomaryov, O. P.

    2012-10-01

    An analytic expression for estimating the volume effect accompanying an electronic topological transition (ETT) in pure cerium is derived on the basis of the microscopic Falikov-Ramirez-Kimball model.

  13. Recent advances (2010-2015) in studies of cerium oxide nanoparticles' health effects.

    PubMed

    Li, Yan; Li, Peng; Yu, Hua; Bian, Ying

    2016-06-01

    Cerium oxide nanoparticles, widespread applied in our life, have attracted much concern for their human health effects. However, most of the works addressing cerium oxide nanoparticles toxicity have only used in vitro models or in vivo intratracheal instillation methods. The toxicity studies have varied results and not all are conclusive. The information about risk assessments derived from epidemiology studies is severely lacking. The knowledge of occupational safety and health (OSH) for exposed workers is very little. Thus this review focuses on recent advances in studies of toxicokinetics, antioxidant activity and toxicity. Additionally, aim to extend previous health effects assessments of cerium oxide nanoparticles, we summarize the epidemiology studies of engineered cerium oxide nanoparticles used as automotive diesel fuel additive, aerosol particulate matter in air pollution, other industrial ultrafine and nanoparticles (e.g., fumes particles generated in welding and flame cutting processes). PMID:27088851

  14. Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

    NASA Astrophysics Data System (ADS)

    Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo; Kim, Dong Rip

    2015-06-01

    Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields.

  15. Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

    EPA Science Inventory

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe res...

  16. Antioxidant properties of cerium oxide nanocrystals as a function of nanocrystal diameter and surface coating.

    PubMed

    Lee, Seung Soo; Song, Wensi; Cho, Minjung; Puppala, Hema L; Nguyen, Phuc; Zhu, Huiguang; Segatori, Laura; Colvin, Vicki L

    2013-11-26

    This work examines the effect of nanocrystal diameter and surface coating on the reactivity of cerium oxide nanocrystals with H2O2 both in chemical solutions and in cells. Monodisperse nanocrystals were formed in organic solvents from the decomposition of cerium precursors, and subsequently phase transferred into water using amphiphiles as nanoparticle coatings. Quantitative analysis of the antioxidant capacity of CeO2-x using gas chromatography and a luminol test revealed that 2 mol of H2O2 reacted with every mole of cerium(III), suggesting that the reaction proceeds via a Fenton-type mechanism. Smaller diameter nanocrystals containing more cerium(III) were found to be more reactive toward H2O2. Additionally, the presence of a surface coating did not preclude the reaction between the nanocrystal surface cerium(III) and hydrogen peroxide. Taken together, the most reactive nanoparticles were the smallest (e.g., 3.8 nm diameter) with the thinnest surface coating (e.g., oleic acid). Moreover, a benchmark test of their antioxidant capacity revealed these materials were 9 times more reactive than commercial antioxidants such as Trolox. A unique feature of these antioxidant nanocrystals is that they can be applied multiple times: over weeks, cerium(IV) rich particles slowly return to their starting cerium(III) content. In nearly all cases, the particles remain colloidally stable (e.g., nonaggregated) and could be applied multiple times as antioxidants. These chemical properties were also observed in cell culture, where the materials were able to reduce oxidative stress in human dermal fibroblasts exposed to H2O2 with efficiency comparable to their solution phase reactivity. These data suggest that organic coatings on cerium oxide nanocrystals do not limit the antioxidant behavior of the nanocrystals, and that their redox cycling behavior can be preserved even when stabilized. PMID:24079896

  17. Static and dynamic high pressure experiments on cerium

    SciTech Connect

    Jensen, Brian J; Velisavljevic, Nenad; Cherne, Frank J; Stevens, Gerald; Tschauner, Oliver

    2011-01-25

    There is a scientific need to obtain dynamic data to develop and validate multi phase equation-of-state (EOS) models for metals. Experiments are needed to examine the relevant pure phases, to locate phase boundaries and the associated transition kinetics, and other material properties such as strength. Cerium is an ideal material for such work because it exhibits a complex multiphase diagram at relatively moderate pressures readily accessible using standard shock wave methods. In the current work, shock wave (dynamic) and diamond anvil cell (static) experiments were performed to examine the high pressure, low temperature region of the phase diagram to obtain EOS data and to search for the {alpha}-{var_epsilon} boundary. Past work examining the shock-melt transition and the low-pressure {gamma}-{alpha} transition will be presented in brief followed by details of recent results obtained from DAC and double-shock experiments.

  18. The Spin Glass-Kondo Competition in Disordered Cerium Systems

    NASA Astrophysics Data System (ADS)

    Magalhaes, S. G.; Zimmer, F.; Coqblin, B.

    2013-10-01

    We discuss the competition between the Kondo effect, the spin glass state and a magnetic order observed in disordered Cerium systems. We present firstly the experimental situation of disordered alloys such as CeNi1 - xCux and then the different theoretical approaches based on the Kondo lattice model, with different descriptions of the intersite exchange interaction for the spin glass. After the gaussian approach of the Sherrington-Kirkpatrick model, we discuss the Mattis and the van Hemmen models. Then, we present simple cluster calculations in order to describe the percolative evolution of the clusters from the cluster spin glass to the inhomogeneous ferromagnetic order recently observed in CeNi1 - xCux disordered alloys and finally we discuss the effect of random and transverse magnetic field.

  19. Growth of transition metals on cerium tungstate model catalyst layers

    NASA Astrophysics Data System (ADS)

    Skála, T.; Tsud, N.; Stetsovych, V.; Mysliveček, J.; Matolín, V.

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed.

  20. Characterization of a zinc-cerium flow battery

    NASA Astrophysics Data System (ADS)

    Leung, P. K.; Ponce-de-León, C.; Low, C. T. J.; Shah, A. A.; Walsh, F. C.

    The performance of a divided, parallel-plate zinc-cerium redox flow battery using methanesulfonic acid electrolytes was studied. Eight two and three-dimensional electrodes were tested under both constant current density and constant cell voltage discharge. Carbon felt and the three-dimensional platinised titanium mesh electrodes exhibited superior performance over the 2-dimensional electrodes. The charge and discharge characteristics of the redox flow battery were studied under different operating conditions and Zn/Ce reactant, as well as methansulfonic acid concentration. The cell performance improved at higher operating temperatures and faster electrolyte flow velocities. The number of possible cycles increased at reduced states of charge. During 15 min charge/discharge per cycle experiment, 57 cycles were obtained and the zinc reaction was found to be the limiting process during long term operation.

  1. Redox reactivity of cerium oxide nanoparticles against dopamine.

    PubMed

    Hayat, Akhtar; Andreescu, Daniel; Bulbul, Gonca; Andreescu, Silvana

    2014-03-15

    The interaction between dopamine and the redox active cerium oxide nanoparticles, or nanoceria was studied using a suite of spectroscopic and surface characterization methods. Changes in the chemical reactivity and concentration of dopamine upon exposure to nanoceria was assessed in aqueous solutions and a human physiological fluid--human serum. The results indicate strong attachment of dopamine to the nanoparticle surface through oxidation followed by chemisorption of the oxidative product with formation of a charge transfer complex. Such oxidation/surface adsorption processes between nanoceria and dopamine lead to a reduction of the concentration of free dopamine in aqueous environments. These findings suggest that the redox reactivity of nanoceria may alter dopamine levels in biological systems exposed to these particles and indicate the need for a comprehensive assessment of the potential neurological consequences that might result from intended or unintended exposure to these particles. PMID:24461841

  2. Growth of transition metals on cerium tungstate model catalyst layers.

    PubMed

    Skála, T; Tsud, N; Stetsovych, V; Mysliveček, J; Matolín, V

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed. PMID:27494195

  3. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  4. Nitrate concentrations under irrigated agriculture

    USGS Publications Warehouse

    Zaporozec, A.

    1983-01-01

    In recent years, considerable interest has been expressed in the nitrate content of water supplies. The most notable toxic effect of nitrate is infant methemoglobinemia. The risk of this disease increases significantly at nitrate-nitrogen levels exceeding 10 mg/l. For this reason, this concentration has been established as a limit for drinking water in many countries. In natural waters, nitrate is a minor ionic constituent and seldom accounts for more than a few percent of the total anions. However, nitrate in a significant concentration may occur in the vicinity of some point sources such as septic tanks, manure pits, and waste-disposal sites. Non-point sources contributing to groundwater pollution are numerous and a majority of them are related to agricultural activities. The largest single anthropogenic input of nitrate into the groundwater is fertilizer. Even though it has not been proven that nitrogen fertilizers are responsible for much of nitrate pollution, they are generally recognized as the main threat to groundwater quality, especially when inefficiently applied to irrigated fields on sandy soils. The biggest challenge facing today's agriculture is to maintain the balance between the enhancement of crop productivity and the risk of groundwater pollution. ?? 1982 Springer-Verlag New York Inc.

  5. Role of nanocrystalline cerium oxide coatings on austenitic stainless steels

    NASA Astrophysics Data System (ADS)

    Zhang, Haiying

    Protective nanocrystalline cerium oxide coating has been applied to ASTM grade 304L and 304 austenitic stainless steels to improve its oxidation resistance at elevated temperatures. Experimentally, the selected alloy was exposed to 800°C/1000°C under dry air conditions. Weight changes (DeltaW/A) were monitored as a function of time and the results were compared with uncoated alloys tested under similar conditions. It was found that the oxidation resistances of 304L and 304 stainless steels were significantly improved. A comparison of the oxidation rates indicated that the nanocrystalline cerium oxide coating reduced the rate of oxidation by more than two orders of magnitude. Nevertheless, a comprehensive understanding of the mechanisms responsible for the reduction in the oxidation rate is not clear. Consequently, this work is aimed at investigating the mechanisms involved during scale growth in the presence or absence of nanocrystalline coatings. For this purpose, density functional theory was carried out in order to predict oxygen and iron diffusion microscopic activation energies and reveal the intrinsic characteristics of nanocrystalline coatings. A numerical simulation of corrosion process has also been conducted to predict the corrosion rates of alloys with and without coatings. Hence, the results from simulations are compared with the experimental outcome, and possible explanations are given to account for the reduction in the exhibited oxidation rates. The simulation results will provide a highly valuable tool for the realization of functional nanostructures and architectures "by design", particularly in the development of novel coatings, and a new approach of life assessment.

  6. Induction of pulmonary fibrosis by cerium oxide nanoparticles

    PubMed Central

    Ma, Jane Y.; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Scabilloni, James; Ma, Joseph K.; Castranova, Vincent

    2015-01-01

    Cerium compounds have been used as a diesel engine catalyst to lower the mass of diesel exhaust particles, but are emitted as cerium oxide (CeO2) nanoparticles in the diesel exhaust. In a previous study, we have demonstrated a wide range of CeO2-induced lung responses including sustained pulmonary inflammation and cellular signaling that could lead to pulmonary fibrosis. In this study, we investigated the fibrogenic responses induced by CeO2 in a rat model at various time points up to 84 days post-exposure. Male Sprague Dawley rats were exposed to CeO2 by a single intratracheal instillation. Alveolar macrophages (AM) were isolated by bronchial alveolar lavage (BAL). AM-mediated cellular responses, osteopontin (OPN) and transform growth factor (TGF)-β1 in the fibrotic process were investigated. The results showed that CeO2 exposure significantly increased fibrotic cytokine TGF-β1 and OPN production by AM above controls. The collagen degradation enzymes, matrix metalloproteinase (MMP)-2 and -9 and the tissue inhibitor of MMP were markedly increased in the BAL fluid at 1 day- and subsequently declined at 28 days after exposure, but remained much higher than the controls. CeO2 induced elevated phospholipids in BAL fluid and increased hydroxyproline content in lung tissue in a dose- and time-dependent manner. Immunohistochemical analysis showed MMP-2, MMP-9 and MMP-10 expressions in fibrotic regions. Morphological analysis noted increased collagen fibers in the lungs exposed to a single dose of 3.5 mg/kg CeO2 and euthanized at 28 days post-exposure. Collectively, our studies show that CeO2 induced fibrotic lung injury in rats, suggesting it may cause potential health effects. PMID:22613087

  7. Vasodilator Therapy: Nitrates and Nicorandil.

    PubMed

    Tarkin, Jason M; Kaski, Juan Carlos

    2016-08-01

    Nitrates have been used to treat symptoms of chronic stable angina for over 135 years. These drugs are known to activate nitric oxide (NO)-cyclic guanosine-3',-5'-monophasphate (cGMP) signaling pathways underlying vascular smooth muscle cell relaxation, albeit many questions relating to how nitrates work at the cellular level remain unanswered. Physiologically, the anti-angina effects of nitrates are mostly due to peripheral venous dilatation leading to reduction in preload and therefore left ventricular wall stress, and, to a lesser extent, epicardial coronary artery dilatation and lowering of systemic blood pressure. By counteracting ischemic mechanisms, short-acting nitrates offer rapid relief following an angina attack. Long-acting nitrates, used commonly for angina prophylaxis are recommended second-line, after beta-blockers and calcium channel antagonists. Nicorandil is a balanced vasodilator that acts as both NO donor and arterial K(+) ATP channel opener. Nicorandil might also exhibit cardioprotective properties via mitochondrial ischemic preconditioning. While nitrates and nicorandil are effective pharmacological agents for prevention of angina symptoms, when prescribing these drugs it is important to consider that unwanted and poorly tolerated hemodynamic side-effects such as headache and orthostatic hypotension can often occur owing to systemic vasodilatation. It is also necessary to ensure that a dosing regime is followed that avoids nitrate tolerance, which not only results in loss of drug efficacy, but might also cause endothelial dysfunction and increase long-term cardiovascular risk. Here we provide an update on the pharmacological management of chronic stable angina using nitrates and nicorandil.

  8. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... sablefish, smoked, cured salmon, and smoked, cured shad, so that the level of sodium nitrate does not...

  9. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... sablefish, smoked, cured salmon, and smoked, cured shad, so that the level of sodium nitrate does not...

  10. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... sablefish, smoked, cured salmon, and smoked, cured shad, so that the level of sodium nitrate does not...

  11. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified... sablefish, smoked, cured salmon, and smoked, cured shad, so that the level of sodium nitrate does not...

  12. Nitrate Utilization by the Diatom Skeletonema costatum

    PubMed Central

    Serra, Juan L.; Llama, Maria J.; Cadenas, Eduardo

    1978-01-01

    Nitrate utilization has been characterized in nitrogen-deficient cells of the marine diatom Skeletonema costatum. In order to separate nitrate uptake from nitrate reduction, nitrate reductase activity was suppressed with tungstate. Neither nitrite nor the presence of amino acids in the external medium or darkness affects nitrate uptake kinetics. Ammonium strongly inhibits carrier-mediated nitrate uptake, without affecting diffusion transfer. A model is proposed for the uptake and assimilation of nitrate in S. costatum and their regulation by ammonium ions. PMID:16660653

  13. Copper, Boron, and Cerium Additions in Type 347 Austenitic Steel to Improve Creep Rupture Strength

    NASA Astrophysics Data System (ADS)

    Laha, Kinkar; Kyono, J.; Shinya, Norio

    2012-04-01

    Type 347 austenitic stainless steel (18Cr-12Ni-Nb) was alloyed with copper (3 wt pct), boron (0.01 to 0.06 wt pct), and cerium (0.01 wt pct) with an aim to increase the creep rupture strength of the steel through the improved deformation and cavitation resistance. Short-term creep rupture strength was found to increase with the addition of copper in the 347 steel, but the long-term strength was inferior. Extensive creep cavitation deprived the steel of the beneficial effect of creep deformation resistance induced by nano-size copper particles. Boron and cerium additions in the copper-containing steel increased its creep rupture strength and ductility, which were more for higher boron content. Creep deformation, grain boundary sliding, and creep cavity nucleation and growth in the steel were found to be suppressed by microalloying the copper-containing steel with boron and cerium, and the suppression was more for higher boron content. An auger electron spectroscopic study revealed the segregation of boron instead of sulfur on the cavity surface of the boron- and cerium-microalloyed steel. Cerium acted as a scavenger for soluble sulfur in the steels through the precipitation of cerium sulfide (CeS). This inhibited the segregation of sulfur and facilitated the segregation of boron on cavity surface. Boron segregation on the nucleated cavity surface reduced its growth rate. Microalloying the copper-containing 347 steel with boron and cerium thus enabled to use the full extent of creep deformation resistance rendered by copper nano-size particle by increase in creep rupture strength and ductility.

  14. Low Temperature Constrained Sintering of Cerium Gadolinium OxideFilms for Solid Oxide Fuel Cell Applications

    SciTech Connect

    Nicholas, Jason Dale

    2007-01-01

    Cerium gadolinium oxide (CGO) has been identified as an acceptable solid oxide fuel cell (SOFC) electrolyte at temperatures (500-700 C) where cheap, rigid, stainless steel interconnect substrates can be used. Unfortunately, both the high sintering temperature of pure CGO, >1200 C, and the fact that constraint during sintering often results in cracked, low density ceramic films, have complicated development of metal supported CGO SOFCs. The aim of this work was to find new sintering aids for Ce0.9Gd0.1O1.95, and to evaluate whether they could be used to produce dense, constrained Ce0.9Gd0.1O1.95 films at temperatures below 1000 C. To find the optimal sintering aid, Ce0.9Gd0.1O1.95 was doped with a variety of elements, of which lithium was found to be the most effective. Dilatometric studies indicated that by doping CGO with 3mol% lithium nitrate, it was possible to sinter pellets to a relative density of 98.5% at 800 C--a full one hundred degrees below the previous low temperature sintering record for CGO. Further, it was also found that a sintering aid's effectiveness could be explained in terms of its size, charge and high temperature mobility. A closer examination of lithium doped Ce0.9Gd0.1O1.95 indicated that lithium affects sintering by producing a Li2O-Gd2O3-CeO2 liquid at the CGO grain boundaries. Due to this liquid phase sintering, it was possible to produce dense, crack-free constrained films of CGO at the record low temperature of 950 C using cheap, colloidal spray deposition processes. This is the first time dense constrained CGO films have been produced below 1000 C and could help commercialize metal supported ceria based solid oxide fuel cells.

  15. EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS

    DOEpatents

    Furman, N.H.; Mundy, R.J.

    1957-12-10

    An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.

  16. Exposure and Health Effects Review of Engineered Nanoscale Cerium and Cerium Dioxide Associated with its Use as a Fuel Additive - NOW IN PRINT IN THE JOURNAL

    EPA Science Inventory

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels that are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (Ce02) has recently gained a wide range of applications which includes coatin...

  17. Exposure, Health and Ecological Effects Review of Engineered Nanoscale Cerium and Cerium Oxide Associated with its Use as a Fuel Additive

    EPA Science Inventory

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels which are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (CeO(2)) has recently gained a wide range of applications which includes coa...

  18. Thermochemical Modeling of the Uranium-Cerium-Oxygen System

    SciTech Connect

    Voit, Stewart L; Besmann, Theodore M

    2010-10-01

    with actinide materials, fundamental studies with uranium are performed using surrogate materials as stand-ins for transuranic elements. In most cases, cerium can be used as a suitable substitute for plutonium when performing O:M and sintering kinetics studies because of identical valence states. Differences exist between the magnitude of reported thermodynamic data of (U,Pu)O{sub x} and (U,Ce)O{sub x}, however the change in oxygen potential versus O:M follows the same trend for both systems. Cerium is also a major fission product element, and thus understanding its behavior in fuel is an important issue as well.

  19. 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.

  20. Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

    NASA Astrophysics Data System (ADS)

    Cervini-Silva, Javiera; Gilbert, Benjamin; Fakra, Sirine; Friedlich, Stephan; Banfield, Jillian

    2008-05-01

    Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca5(PO4)3.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO4·H2O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic-anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce3+ ions oxidizing to CeO2. Reaction product analysis shows the formation of CO2, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M4,5 and C-K absorption edges on reacted CePO4·H2O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO4·H2O and O2 but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π∗ resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ∗ region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent

  1. Reduction of nitrate in Shewanella

    SciTech Connect

    Gao, Haichun; Yang, Zamin Koo; Barua, Sumitra; Reed, SB; Nealson, Kenneth H.; Fredrikson, JK; Tiedje, James; Zhou, Jizhong

    2009-01-01

    In the genome of Shewanella oneidensis, a napDAGHB gene cluster encoding periplasmic nitrate reductase (NapA) and accessory proteins and an nrfA gene encoding periplasmic nitrite reductase (NrfA) have been identified. These two systems seem to be atypical because the genome lacks genes encoding cytoplasmic membrane electron transport proteins, NapC for NAP and NrfBCD/NrfH for NRF, respectively. Here, we present evidence that reduction of nitrate to ammonium in S. oneidensis is carried out by these atypical systems in a two-step manner. Transcriptional and mutational analyses suggest that CymA, a cytoplasmic membrane electron transport protein, is likely to be the functional replacement of both NapC and NrfH in S. oneidensis. Surprisingly, a strain devoid of napB encoding the small subunit of nitrate reductase exhibited the maximum cell density sooner than the wild type. Further characterization of this strain showed that nitrite was not detected as a free intermediate in its culture and NapB provides a fitness gain for S. oneidensis to compete for nitrate in the environments. On the basis results from mutational analyses of napA, napB, nrfA and napBnrfA in-frame deletion mutants, we propose that NapB is able to favor nitrate reduction by routing electrons to NapA exclusively.

  2. A new class of homogeneous visible-light photocatalysts: molecular cerium vanadium oxide clusters.

    PubMed

    Seliverstov, Andrey; Streb, Carsten

    2014-07-28

    The first systematic access to molecular cerium vanadium oxides is presented. A family of structurally related, di-cerium-functionalized vanadium oxide clusters and their use as visible-light-driven photooxidation catalysts is reported. Comparative analyses show that photocatalytic activity is controlled by the cluster architecture. Increased photoreactivity of the cerium vanadium oxides in the visible range compared with nonfunctionalized vanadates is observed. Based on the recent discovery of the first molecular cerium vanadate cluster, (nBu4 N)2 [(Ce(dmso)3 )2 V12 O33 Cl]⋅2 DMSO (1), two new di-cerium-containing vanadium oxide clusters [(Ce(dmso)4 )2 V11 O30 Cl]⋅DMSO (2) and [(Ce(nmp)4 )2 V12 O32 Cl]⋅NMP⋅Me2 CO (3; NMP=N-methyl-2-pyrrolidone) were obtained by using a novel fragmentation and reassembly route. Pentagonal building units {(V)M5 } (M=V, Ce) reminiscent of "Müller-type" pentagons are observed in 2 and 3. Compounds 1-3 feature high visible-light photooxidative activity, and quantum efficiencies >10 % for indigo photooxidation are observed. Photocatalytic performance increases in the order 1<3<2. Mechanistic studies show that the irradiation wavelength and the presence of oxygen strongly affect photoreactivity. Initial findings suggest that the photooxidation mechanism proceeds by intermediate formation of hydroxyl radicals. The findings open new avenues for the bottom-up design of sunlight-driven photocatalysts.

  3. Exposure of cerium oxide nanoparticles to kidney bean shows disturbance in the plant defense mechanisms.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Bandyopadhyay, Susmita; Castillo-Michel, Hiram; Hernandez-Viezcas, Jose-Angel; Sahi, Shivendra; Gardea-Torresdey, Jorge L

    2014-08-15

    Overwhelming use of engineered nanoparticles demands rapid assessment of their environmental impacts. The transport of cerium oxide nanoparticles (nCeO2) in plants and their impact on cellular homeostasis as a function of exposure duration is not well understood. In this study, kidney bean plants were exposed to suspensions of ∼ 8 ± 1 nm nCeO2 (62.5 to 500 mg/L) for 15 days in hydroponic conditions. Plant parts were analyzed for cerium accumulation after one, seven, and 15 days of nCeO2 exposure. The primary indicators of stress like lipid peroxidation, antioxidant enzyme activities, total soluble protein and chlorophyll contents were studied. Cerium in tissues was localized using scanning electron microscopy and synchrotron μ-XRF mapping, and the chemical forms were identified using μ-XANES. In the root epidermis, cerium was primarily shown to exist as nCeO2, although a small fraction (12%) was biotransformed to Ce(III) compound. Cerium was found to reach the root vascular tissues and translocate to aerial parts with time. Upon prolonged exposure to 500 mg nCeO2/L, the root antioxidant enzyme activities were significantly reduced, simultaneously increasing the root soluble protein by 204%. In addition, leaf's guaiacol peroxidase activity was enhanced with nCeO2 exposure in order to maintain cellular homeostasis. PMID:24981679

  4. Catalysts with Cerium in a Membrane Reactor for the Removal of Formaldehyde Pollutant from Water Effluents.

    PubMed

    Gutiérrez-Arzaluz, Mirella; Noreña-Franco, Luis; Ángel-Cuevas, Saúl; Mugica-Álvarez, Violeta; Torres-Rodríguez, Miguel

    2016-01-01

    We report the synthesis of cerium oxide, cobalt oxide, mixed cerium, and cobalt oxides and a Ce-Co/Al₂O₃ membrane, which are employed as catalysts for the catalytic wet oxidation (CWO) reaction process and the removal of formaldehyde from industrial effluents. Formaldehyde is present in numerous waste streams from the chemical industry in a concentration low enough to make its recovery not economically justified but high enough to create an environmental hazard. Common biological degradation methods do not work for formaldehyde, a highly toxic but refractory, low biodegradability substance. The CWO reaction is a recent, promising alternative that also permits much lower temperature and pressure conditions than other oxidation processes, resulting in economic benefits. The CWO reaction employing Ce- and Co-containing catalysts was carried out inside a slurry batch reactor and a membrane reactor. Experimental results are reported. Next, a mixed Ce-Co oxide film was supported on an γ-alumina membrane used in a catalytic membrane reactor to compare formaldehyde removal between both types of systems. Catalytic materials with cerium and with a relatively large amount of cerium favored the transformation of formaldehyde. Cerium was present as cerianite in the catalytic materials, as indicated by X-ray diffraction patterns. PMID:27231888

  5. Precipitation-Redispersion of Cerium Oxide Nanoparticles with Poly(acrylic acid): Toward Stable Dispersions

    SciTech Connect

    Sehgal,A.; Lalatonne, Y.; Berret, J.; Morvan, M.

    2005-01-01

    We exploit a precipitation-redispersion mechanism for complexation of short chain polyelectrolytes with cerium oxide nanoparticles to extend their stability ranges. As synthesized, cerium oxide sols at pH 1.4 consist of monodisperse cationic nanocrystalline particles having a hydrodynamic diameter of 10 nm and a molecular weight of 400 000 g mol{sup -1}. We show that short chain uncharged poly(acrylic acid) at low pH when added to a cerium oxide sols leads to macroscopic precipitation. As the pH is increased, the solution spontaneously redisperses into a clear solution of single particles with an anionic poly(acrylic acid) corona. The structure and dynamics of cerium oxide nanosols and their hybrid polymer-inorganic complexes in solution are investigated by static and dynamic light scattering, X-ray scattering, and chemical analysis. Quantitative analysis of the redispersed sol gives rise to an estimate of 40-50 polymer chains per particle for stable suspension. This amount represents 20% of the mass of the polymer-nanoparticle complexes. This complexation adds utility to the otherwise unstable cerium oxide dispersions by extending the range of stability of the sols in terms of pH, ionic strength, and concentration.

  6. Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine

    PubMed Central

    Nelson, Bryant C.; Johnson, Monique E.; Walker, Marlon L.; Riley, Kathryn R.; Sims, Christopher M.

    2016-01-01

    Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine. PMID:27196936

  7. Deposition and investigation of lanthanum-cerium hexaboride thin films

    SciTech Connect

    Kuzanyan, A.S. . E-mail: akuzan@ipr.sci.am; Harutyunyan, S.R.; Vardanyan, V.O.; Badalyan, G.R.; Petrosyan, V.A.; Kuzanyan, V.S.; Petrosyan, S.I.; Karapetyan, V.E.; Wood, K.S.; Wu, H.-D.

    2006-09-15

    Thin films of lanthanum-cerium hexaboride, the promising thermoelectric material for low-temperature applications, are deposited on various substrates by the electron-beam evaporation, pulsed laser deposition and magnetron sputtering. The influence of the deposition conditions on the films X-ray characteristics, composition, microstructure and physical properties, such as the resistivity and Seebeck coefficient, is studied. The preferred (100) orientation of all films is obtained from XRD traces. In the range of 780-800 deg. C deposition temperature the highest intensity of diffractions peaks and the highest degree of the preferred orientation are observed. The temperature dependence of the resistivity and the Seebeck coefficient of films are investigated in the temperature range of 4-300 K. The features appropriate to Kondo effect in the dependences {rho}(T) and S(T) are detected at temperatures below 20 K. Interplay between the value of the Seebeck coefficient, metallic parameters and Kondo scattering of investigated films is discussed. - Graphical abstract: Kondo scattering in (La,Ce)B{sub 6} films: temperature dependence of the resistivity of (La,Ce)B{sub 6} films on various substrates and the ceramics La{sub 0.99}Ce{sub 0.01}B{sub 6}.

  8. Toxicity of Cerium Oxide Nanoparticles in Human Lung Cancer Cells

    SciTech Connect

    Weisheng, Lin; Huang, Yue-wern; Zhou, Xiao Dong; Ma, Yinfa

    2006-12-31

    With the fast development of nanotechnology, the nanomaterials start to cause people's attention for potential toxic effect. In this paper, the cytotoxicity and oxidative stress caused by 20-nm cerium oxide (CeO2) nanoparticles in cultured human lung cancer cells was investigated. The sulforhodamine B method was employed to assess cell viability after exposure to 3.5, 10.5, and 23.3 μg/ml of CeO2 nanoparticles for 24, 48, and 72 h. Cell viability decreased significantly as a function of nanoparticle dose and exposure time. Indicators of oxidative stress and cytotoxicity, including total reactive oxygen species, glutathione, malondialdehyde, α-tocopherol, and lactate dehydrogenase, were quantitatively assessed. It is concluded from the results that free radicals generated by exposure to 3.5 to 23.3 μg/ml CeO2 nanoparticles produce significant oxidative stress in the cells, as reflected by reduced glutathione and α-tocopherol levels; the toxic effects of CeO2 nanoparticles are dose dependent and time dependent; elevated oxidative stress increases the production of malondialdehyde and lactate dehydrogenase, which are indicators of lipid peroxidation and cell membrane damage, respectively.

  9. Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine.

    PubMed

    Nelson, Bryant C; Johnson, Monique E; Walker, Marlon L; Riley, Kathryn R; Sims, Christopher M

    2016-05-17

    Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine.

  10. Antioxidant cerium oxide nanoparticle hydrogels for cellular encapsulation.

    PubMed

    Weaver, Jessica D; Stabler, Cherie L

    2015-04-01

    Oxidative stress and the resulting radical by-products cause significant toxicity and graft loss in cellular transplantation. Here, the engineering of an auto-catalytic, antioxidant, self-renewing cerium oxide nanoparticle (CONP)-composite hydrogel is reported. This enzyme-mimetic material ubiquitously scavenges ambient free radicals, with the potential to provide indefinite antioxidant protection. The potential of this system to enhance the protection of encapsulated beta cells was evaluated. Co-incubation of CONPs free in solution with beta cells demonstrated potent cytoprotection from superoxide exposure; however, phagocytosis of the CONPs by the beta cells resulted in cytotoxicity at concentrations as low as 1mM. When CONPs were embedded within alginate hydrogels, the composite hydrogel provided cytoprotection to encapsulated beta cells from free radical attack without cytotoxicity, even up to 10mM. This nanocomposite hydrogel has wide applicability in cellular transplantation, with the unique advantage of localization of these potent antioxidant CONPs and their capacity for sustained, long-term scavenging. PMID:25620795

  11. Catalytic Properties and Biomedical Applications of Cerium Oxide Nanoparticles

    PubMed Central

    Walkey, Carl; Das, Soumen; Seal, Sudipta; Erlichman, Joseph; Heckman, Karin; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William T.

    2014-01-01

    Cerium oxide nanoparticles (Nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of Nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of Nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of Nanoceria in animal studies? 2) What are the considerations to develop Nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials? PMID:26207185

  12. Antioxidant Cerium Oxide Nanoparticle Hydrogels for Cellular Encapsulation

    PubMed Central

    Weaver, Jessica D; Stabler, Cherie L

    2015-01-01

    Oxidative stress and the resulting radical by-products cause significant toxicity and graft loss in cellular transplantation. Here, the engineering of an auto-catalytic, antioxidant, self-renewing cerium oxide nanoparticle (CONP)-composite hydrogel is reported. This enzyme-mimetic material ubiquitously scavenges ambient free radicals, with the potential to provide indefinite antioxidant protection. Here, we evaluated the potential of this system to enhance the protection of encapsulated beta cells. Co-incubation of CONPs, free in solution with beta cells, demonstrated potent cytoprotection from superoxide exposure; however, phagocytosis of the CONPs by the beta cells resulted in cytotoxicity at concentrations as low as 1 mM. When CONPs were embedded within alginate hydrogels, the composite hydrogel provided cytoprotection to encapsulated beta cells from free radical attack without cytotoxicity, even up to 10 mM concentrations. This nanocomposite hydrogel has wide applicability in cellular transplantation, with the unique advantage of localization of these potent antioxidant CONPs and their capacity for sustained, long-term scavenging. PMID:25620795

  13. Nitrate Trends in Minnesota Rivers

    USGS Publications Warehouse

    Wall, Dave; Christopherson, Dave; Lorenz, Dave; Martin, Gary

    2013-01-01

    The objective of this study was to assess long-term trends (30 to 35 years) of flow-adjusted concentrations of nitrite+nitrate-N (hereinafter referred to as nitrate) in a way that would allow us to discern changing trends. Recognizing that these trends are commonly different from one river to another river and from one part of the state to another, our objective was to examine as many river monitoring sites across the state as possible for which sufficient long term streamflow and concentration data were available.

  14. THERMAL EFFECTS ON MASS AND SPATIAL RESOLUTION DURING LASER PULSE ATOM PROBE TOMOGRAPHY OF CERIUM OXIDE

    SciTech Connect

    Rita Kirchhofer; Melissa C. Teague; Brian P. Gorman

    2013-05-01

    Cerium oxide (CeO2) is an ideal surrogate material for trans-uranic elements and fission products found in nuclear fuels due to similarities in their thermal properties; therefore, cerium oxide was used to determine the best run condition for atom probe tomography (APT). Laser pulse APT is a technique that allows for spatial resolution in the nm scale and isotopic/elemental chemical identification. A systematic study of the impact of laser pulse energy and specimen base temperature on the mass resolution, measurement of stoichiometry, multiples, and evaporation mechanisms are reported in this paper. It was demonstrated that using laser pulse APT stoichiometric field evaporation of cerium oxide was achieved at 1 pJ laser pulse energy and 20 K specimen base temperature.

  15. Synthesis and characterization of cerium and yttrium alkoxide complexes supported by ferrocene-based chelating ligands.

    PubMed

    Broderick, Erin M; Thuy-Boun, Peter S; Guo, Neng; Vogel, Carola S; Sutter, Jörg; Miller, Jeffrey T; Meyer, Karsten; Diaconescu, Paula L

    2011-04-01

    Two series of Schiff base metal complexes were investigated, where each series was supported by an ancillary ligand incorporating a ferrocene backbone and different N=X functionalities. One ligand is based on an imine, while the other is based on an iminophosphorane group. Cerium(IV), cerium(III), and yttrium(III) alkoxide complexes supported by the two ligands were synthesized. All metal complexes were characterized by cyclic voltammetry. Additionally, NMR, Mössbauer, X-ray absorption near-edge structure (XANES), and absorption spectroscopies were used. The experimental data indicate that iron remains in the +2 oxidation state and that cerium(IV) does not engage in a redox behavior with the ancillary ligand.

  16. Photoemission of the Oxidation of Cerium Overlayers on GaSb(110) Surface

    NASA Astrophysics Data System (ADS)

    Liang, Qi; Wu, Jian-xin; Ji, Ming-rong; Ma, Mao-sheng; Liu, Xian-ming; Zhang, Yu-heng

    1997-10-01

    We have used x-ray photoelectron spectroscopy to study the oxidation of cerium overlayers on a semiconductor GaSb(110) surface. A GaSb(110) sample covered with 10 monolayers Ce was used to adsorb oxygen. When the exposure of O2 was up to 50 L, the oxide of cerium, Ce2O3, began to change into unstable CeO2. The dissociation of CeO2 resulted in strong oxidation of the substrate. The main products are Ga2O3, Sb2O3, and then Sb2O5. After annealing, a part of the oxygen atoms transferred from cerium dioxide toward Ga and Sb.

  17. Excitation induced spectroscopic study and quenching effect in cerium samarium codoped lithium aluminoborate glasses

    NASA Astrophysics Data System (ADS)

    Kaur, Parvinder; Kaur, Simranpreet; Singh, Gurinder Pal; Arora, Deepawali; Kumar, Sunil; Singh, D. P.

    2016-08-01

    Lithium aluminium borate host has been codoped with cerium and samarium to prepare glass by conventional melt quench technique. Their structural and spectroscopic investigation has been carried out using XRD, FTIR and density measurements. The UV-Vis absorption spectra and fluorescence spectra (λexc.=380 nm and 400 nm) have been studied for spectroscopic analysis. The amorphous nature of the prepared samples is shown by XRD. The density is increasing with addition of cerium at the expense of aluminium, keeping other components constant. FTIR study also shows the presence of compact and stable tetrahedral BO4 units thus supporting the density results. The UV- Vis absorption spectra show a shift of optical absorption edge towards longer wavelength along with an increase in intensity of peaks with rising samarium concentration. The fluorescence spectra show a blue shift and subsequent suppression of cerium peaks with addition of samarium.

  18. Development of graphene-nanometre-sized cerium oxide-incorporated aluminium and its electrochemical evaluation

    NASA Astrophysics Data System (ADS)

    Ashraf, P. Muhamed; Thomas, Saly N.; Edwin, Leela

    2016-02-01

    Graphene-nanometre-sized cerium oxide-incorporated aluminium was prepared and its electrochemical and surface morphological characteristics were studied. The atomic force micrographs and scanning electron micrographs evaluation highlighted that the graphene and nanometre-sized cerium oxide in aluminium had decreased the surface roughness and improved the surface morphological characteristics. The graphene: nanometre-sized cerium oxide (ratios 1:2 or 2:1) with lesser amounts of particle in the matrix showed excellent corrosion resistance in the marine environment as evidenced by linear polarization, electrochemical impedance and weight loss studies. Introduction of graphene in the aluminium matrix showed a barrier separation between the outermost layer and inner layer, increased roughness and increased corrosion. The material is found to be a potential candidate for use in marine environment.

  19. Fabrication of Cerium Oxide and Uranium Oxide Microspheres for Space Nuclear Power Applications

    SciTech Connect

    Jeffrey A. Katalenich; Michael R. Hartman; Robert C. O'Brien

    2013-02-01

    Cerium oxide and uranium oxide microspheres are being produced via an internal gelation sol-gel method to investigate alternative fabrication routes for space nuclear fuels. Depleted uranium and non-radioactive cerium are being utilized as surrogates for plutonium-238 (Pu-238) used in radioisotope thermoelectric generators and for enriched uranium required by nuclear thermal rockets. While current methods used to produce Pu-238 fuels at Los Alamos National Laboratory (LANL) involve the generation of fine powders that pose a respiratory hazard and have a propensity to contaminate glove boxes, the sol-gel route allows for the generation of oxide microsphere fuels through an aqueous route. The sol-gel method does not generate fine powders and may require fewer processing steps than the LANL method with less operator handling. High-quality cerium dioxide microspheres have been fabricated in the desired size range and equipment is being prepared to establish a uranium dioxide microsphere production capability.

  20. Eucalyptus tolerance mechanisms to lanthanum and cerium: subcellular distribution, antioxidant system and thiol pools.

    PubMed

    Shen, Yichang; Zhang, Shirong; Li, Sen; Xu, Xiaoxun; Jia, Yongxia; Gong, Guoshu

    2014-12-01

    Guanglin 9 (Eucalyptus grandis × Eucalyptus urophlla) and Eucalyptus grandis 5 are two eucalyptus species which have been found to grow normally in soils contaminated with lanthanum and cerium, but the tolerance mechanisms are not clear yet. In this study, a pot experiment was conducted to investigate the tolerance mechanisms of the eucalyptus to lanthanum and cerium. Cell walls stored 45.40-63.44% of the metals under lanthanum or cerium stress. Peroxidase and catalase activities enhanced with increasing soil La or Ce concentrations up to 200 mg kg(-1), while there were no obvious changes in glutathione and ascorbate concentrations. Non-protein thiols concentrations increased with increasing treatment levels up to 200 mg kg(-1), and then decreased. Phytochelatins concentrations continued to increase under La or Ce stress. Therefore, the two eucalyptus species are La and Ce tolerant plants, and the tolerance mechanisms include cell wall deposition, antioxidant system response, and thiol compound synthesis. PMID:25303462

  1. Synthesis and photocatalytic activity of mesoporous cerium doped TiO{sub 2} as visible light sensitive photocatalyst

    SciTech Connect

    Aman, Noor; Satapathy, P.K.; Mishra, T.; Mahato, M.; Das, N.N.

    2012-02-15

    Graphical abstract: Cerium doped titania having optimum 5 wt% of cerium can decompose methylene blue and reduce selenium (IV) efficiently under visible light. Highlights: Black-Right-Pointing-Pointer Effect of cerium doping on the surface properties and visible light mediated photocatalytic reaction is studied. Black-Right-Pointing-Pointer Cerium doping increases the anatase phase stability, surface area (up to 137 m{sup 2}/g) and visible light absorption. Black-Right-Pointing-Pointer Importance of Ce{sup 3+}/Ce{sup 4+}, oxygen vacancy, surface area and crystallinity is correlated with improved catalytic activity. Black-Right-Pointing-Pointer Material with 5 wt% Ce is found to be most active photocatalyst for methylene blue decomposition and Se (IV) reduction. -- Abstract: Cerium doped titania materials were synthesized varying the cerium concentration from 0 to 10 wt%. Materials are characterised by XRD, TEM, XPS and N{sub 2} adsorption desorption method. Surface area and visible light absorption substantially increases and crystallite size decreases with the increasing cerium content. Cerium doping stabilizes the anatase phase and surface area even at 600 Degree-Sign C calcination. Photocatalytic activity towards methylene blue decomposition and selenium (IV) reduction is found to increase with the cerium content up to 5 wt% and then decreases. Materials calcined at 600 Degree-Sign C shows better activity than that calcined at 400 Degree-Sign C, even though surface area decreases. Anatase crystallinity mostly decides the photocatalytic activity rather than only surface area. It can be concluded that the optimum visible light absorption and oxygen vacancy with 5% cerium doping enhances the photocatalytic activity. In addition photocatalytic performance is found to depend on the presence of Ce{sup 4+}/Ce{sup 3+} rather than only visible light absorption.

  2. Ab initio studies of anisotropic magnetism in uranium and cerium monopnictides and monochalcogenides

    NASA Astrophysics Data System (ADS)

    Collins, Eric Mason

    We have applied two ab initio based methods to investigate the origin in the electronic structure of the unusual magnetic behavior of the cerium and uranium monopnictides and monochalcogenides. First, we have carried out spin-polarized electronic structure calculations, based on the full potential linear muffin tin (FPLMTO) method, with spin polarization (orbital polarization only via spin-orbit coupling) and also with orbital polarization correction. Second, we have carried out ab initio based calculations synthesizing (1) a phenomenological theory of orbitally driven magnetism based on the Anderson and Kondo, lattice model which incorporates explicitly the hybridization induced and the Coulomb exchange interactions on an equal footing, and (2) FPLMTO electronic structure calculations allowing a first principles evaluation of all the parameters entering the model Hamiltonian. For the cerium compounds, we also include the crystal field interactions on an equal footing with the hybridization and Coulomb exchange interactions with a scaling determined by experiment. The results for the uranium compound calculations show that both methods are limited to the extremes to which they are best suited. The pure band structure calculations provide the best agreement for the lighter uranium compounds, while the model hamiltonian approach provides better agreement for the heavier uranium compounds. In the case of the cerium compounds, while the pure FPLMTO calculations yield values for the magnetic moment in agreement with experiment for the lighter cerium chalcogenides, they fail to give, even qualitatively, the magnetic properties for all other systems. On the other hand, the ab initio based model Hamiltonian calculations reveal for the first time the interplay of hybridization, Coulomb exchange, and crystal field interactions across the cerium series, and give results for the low-temperature moment and ordering temperature in excellent agreement with experiment, for the

  3. The investigation of cerium as a cathodic inhibitor for aluminum-copper alloys

    SciTech Connect

    Aldykewicz, A.J. Jr.; Isaacs, H.S.; Davenport, A.J.

    1995-10-01

    In situ current density mapping, scanning electron microscopy , and energy dispersive spectroscopy were used to study the effects of cerium as a corrosion inhibitor for an aluminum copper alloy (Al 2024-T4) in chloride containing solutions. It was found that cerium inhibits corrosion of this alloy by reducing the rate of the cathodic reaction. This was due to the carried out on an aluminum/copper galvanic couple, which was used to simulate the electrochemical behavior of the copper containing intermetallics, showed that corrosion inhibition was associated with the formation of a Ce-rich film over the copper in agreement with that observed for the alloy.

  4. Synthesis and characterization of two dimensional metal organic framework of cerium with tetraaza macrocyclic

    SciTech Connect

    Bt Safiin, Nurul Atikah; Yarmo, Ambar; Yamin, Bohari M.

    2013-11-27

    A two dimensional metal organic framework containing cerium sufate layers and ethylenediaminium between layers was obtained by refluxing the mixture of cerium sulphate and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7, 14-diene bromide. The complex was characterized by infrared spectroscopy and microelemental analysis. X-ray study showed that the complex adopts eleven coordination environments about the central atom. Thermogravimetric study showed the removal of water molecules at about 70°C followed by a gradual mass loss until the whole structure collapsed at about 400°C.

  5. METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

    DOEpatents

    Duffield, R.B.; Stoughton, R.W.

    1959-02-01

    A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

  6. Systematic variation of rare-earth elements in cerium-earth minerals

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J.; Carron, M.K.; Glass, J.J.

    1957-01-01

    In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (???), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ??? for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ??? for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ??? is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ??? greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements-efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ??? in one crystal and a slightly smaller value of ??? in the outer part of the other crystal compared to the inner part. The ??? of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ??? of monazites in the intruded host rock. These results indicate that the fractionation of the

  7. Dietary nitrate and cardiovascular health

    USGS Publications Warehouse

    Ahluwalia, A.; Gladwin, M.T.; Harman, Jane L.; Ward, M.H.; Nolan, Bernard T.

    2014-01-01

    The National Heart, Lung, and Blood Institute convened this workshop to discuss the results of recent research on the effects of inorganic nitrate and nitrite on the cardiovascular system, possible long term effects of these compounds in the diet and drinking water, and future research needs including population-wide effects examined through epidemiological studies.

  8. Biological denitrification of high concentration nitrate waste

    DOEpatents

    Francis, Chester W.; Brinkley, Frank S.

    1977-01-01

    Biological denitrification of nitrate solutions at concentrations of greater than one kilogram nitrate per cubic meter is accomplished anaerobically in an upflow column having as a packing material a support for denitrifying bacteria.

  9. Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide

    SciTech Connect

    Mullins, David R; Albrecht, Peter M; Calaza, Florencia C

    2013-01-01

    Cerium oxide is a principal component in many heterogeneous catalytic processes. One of its key characteristics is the ability to provide or remove oxygen in chemical reactions. The different crystallographic faces of ceria present significantly different surface structures and compositions that may alter the catalytic reactivity. The structure and composition determine the number of coordination vacancies surrounding surface atoms, the availability of adsorption sites, the spacing between adsorption sites and the ability to remove O from the surface. To investigate the role of surface orientation on reactivity, CeO2 films were grown with two different orientations. CeO2(100) films were grown ex situ by pulsed laser deposition on Nb-doped SrTiO3(100). CeO2(111) films were grown in situ by thermal deposition of Ce metal onto Ru(0001) in an oxygen atmosphere. The chemical reactivity was characterized by the adsorption and decomposition of various molecules such as alcohols, aldehydes and organic acids. In general the CeO2(100) surface was found to be more active, i.e. molecules adsorbed more readily and reacted to form new products, especially on a fully oxidized substrate. However the CeO2(100) surface was less selective with a greater propensity to produce CO, CO2 and water as products. The differences in chemical reactivity are discussed in light of possible structural terminations of the two surfaces. Recently nanocubes and nano-octahedra have been synthesized that display CeO2(100) and CeO2(111) faces, respectively. These nanoparticles enable us to correlate reactions on high surface area model catalysts at atmospheric pressure with model single crystal films in a UHV environment.

  10. Effect of cerium oxide nanoparticles on intestinal serotonin in zebrafish

    PubMed Central

    Özel, Rıfat Emrah; Hayat, Akhtar; Wallace, Kenneth N.; Andreescu, Silvana

    2013-01-01

    Cerium oxide nanoparticles or nanoceria are emerging as a new and promising class of nanoparticle technology for biomedical applications. The safe implementation of these particles in clinical applications requires evaluation of their redox properties and reactivity that might cause neurotoxic effects by interacting with redox components of the physiological environment. We report in vitro and in vivo studies to evaluate the impact of nanoceria exposure on serotonin (5-HT), an important neurotransmitter that plays a critical role in various physiological processes including motility and secretion in the digestive system. In vitro studies of 5-HT in the presence of nanoceria using spectroscopic, electrochemical and surface characterization methods demonstrate that nanoceria interacts with 5-HT and forms a surface adsorbed 5-HT-nanoceria complex. Further in vivo studies in live zebrafish embryos indicate depletion of the 5-HT level in the intestine for exposure periods longer than three days. Intestinal 5-HT was assessed quantitatively in live embryos using implantable carbon fiber microelectrodes and the results were compared to immunohistochemistry of the dissected intestine. 20 and 50 ppm nanoparticle exposure decreased the 5-HT level to 20.5 (±1.3) and 5.3 (±1.5) nM respectively as compared to 30.8 (±3.4) nM for unexposed control embryos. The results suggest that internalized nanoceria particles can concentrate 5-HT at the nanoparticle accumulation site depleting it from the surrounding tissue. This finding might have long term implications in the neurophysiology and functional development of organisms exposed to these particles through intended or unintended exposure. PMID:24015353

  11. Cerium oxide nanoparticle treatment ameliorates peritonitis-induced diaphragm dysfunction

    PubMed Central

    Asano, Shinichi; Arvapalli, Ravikumar; Manne, Nandini DPK; Maheshwari, Mani; Ma, Bing; Rice, Kevin M; Selvaraj, Vellaisamy; Blough, Eric R

    2015-01-01

    The severe inflammation observed during sepsis is thought to cause diaphragm dysfunction, which is associated with poor patient prognosis. Cerium oxide (CeO2) nanoparticles have been posited to exhibit anti-inflammatory and antioxidative activities suggesting that these particles may be of potential use for the treatment of inflammatory disorders. To investigate this possibility, Sprague Dawley rats were randomly assigned to the following groups: sham control, CeO2 nanoparticle treatment only (0.5 mg/kg iv), sepsis, and sepsis+CeO2 nanoparticles. Sepsis was induced by the introduction of cecal material (600 mg/kg) directly into the peritoneal cavity. Nanoparticle treatment decreased sepsis-associated impairments in diaphragmatic contractile (Po) function (sham: 25.6±1.6 N/cm2 vs CeO2: 23.4±0.8 N/cm2 vs Sep: 15.9±1.0 N/cm2 vs Sep+CeO2: 20.0±1.0 N/cm2, P<0.05). These improvements in diaphragm contractile function were accompanied by a normalization of protein translation signaling (Akt, FOXO-1, and 4EBP1), diminished proteolysis (caspase 8 and ubiquitin levels), and decreased inflammatory signaling (Stat3 and iNOS). Histological analysis suggested that nanoparticle treatment was associated with diminished sarcolemma damage and diminished inflammatory cell infiltration. These data indicate CeO2 nanoparticles may improve diaphragmatic function in the septic laboratory rat. PMID:26491293

  12. Effect of cerium oxide nanoparticles on intestinal serotonin in zebrafish.

    PubMed

    Ozel, Rıfat Emrah; Hayat, Akhtar; Wallace, Kenneth N; Andreescu, Silvana

    2013-09-21

    Cerium oxide nanoparticles or nanoceria are emerging as a new and promising class of nanoparticle technology for biomedical applications. The safe implementation of these particles in clinical applications requires evaluation of their redox properties and reactivity that might cause neurotoxic effects by interacting with redox components of the physiological environment. We report in vitro and in vivo studies to evaluate the impact of nanoceria exposure on serotonin (5-HT), an important neurotransmitter that plays a critical role in various physiological processes including motility and secretion in the digestive system. In vitro studies of 5-HT in the presence of nanoceria using spectroscopic, electrochemical and surface characterization methods demonstrate that nanoceria interacts with 5-HT and forms a surface adsorbed 5-HT-nanoceria complex. Further in vivo studies in live zebrafish embryos indicate depletion of the 5-HT level in the intestine for exposure periods longer than three days. Intestinal 5-HT was assessed quantitatively in live embryos using implantable carbon fiber microelectrodes and the results were compared to immunohistochemistry of the dissected intestine. 20 and 50 ppm nanoparticle exposure decreased the 5-HT level to 20.5 (±1.3) and 5.3 (±1.5) nM respectively as compared to 30.8 (±3.4) nM for unexposed control embryos. The results suggest that internalized nanoceria particles can concentrate 5-HT at the nanoparticle accumulation site depleting it from the surrounding tissue. This finding might have long term implications in the neurophysiology and functional development of organisms exposed to these particles through intended or unintended exposure. PMID:24015353

  13. Effects of Cerium Oxide Nanoparticles on Sorghum Plant Traits

    NASA Astrophysics Data System (ADS)

    Mu, L.; Chen, Y.; Darnault, C. J. G.; Rauh, B.; Kresovich, S.; Korte, C.

    2015-12-01

    Nanotechnology and nanomaterials are considered as the development of the modern science. However, besides with that wide application, nanoparticles arouse to the side effects on the environment and human health. As the catalyst of ceramics and fuel industry, Cerium (IV) oxide nanoparticles (CeO2 NPs) can be found in the environment following their use and life-cycle. Therefore, it is critical to assess the potential effects that CeO2 NPs found in soils may have on plants. In this study, CeO2 NPs were analyzed for the potential influence on the sorghum [Sorghum bicolor (L.) Moench] (Reg. no. 126) (PI 154844) growth and traits. The objectives of this research were to determine whether CeO2 NPs impact the sorghum germination and growth characteristics. The sorghum was grown in the greenhouse located at Biosystems Research Complex, Clemson University under different CeO2 NPs treatments (0mg; 100mg; 500mg; 1000mg CeO2 NPs/Kg soil) and harvested around each month. At the end of the each growing period, above ground vegetative tissue was air-dried, ground to 2mm particle size and compositional traits estimated using near-infrared spectroscopy. Also, the NPK value of the sorghum tissue was tested by Clemson Agriculture Center. After the first harvest, the result showed that the height of above ground biomass under the nanoparticles stress was higher than that of control group. This difference between the control and the nanoparticles treatments was significant (F>F0.05; LSD). Our results also indicated that some of the compositional traits were impacted by the different treatments, including the presence and/or concentrations of the nanoparticles.

  14. A Novel Chemical Nitrate Destruction Process

    SciTech Connect

    Dziewinski, J.; Marczak, S.

    1999-03-01

    Nitrates represent one of the most significant pollutant discharged to the Baltic Sea by the Sliiamae hydrometallurgical plant. This article contains a brief overview of the existing nitrate destruction technologies followed by the description of a new process developed by the authors. The new chemical process for nitrate destruction is cost effective and simple to operate. It converts the nitrate to nitrogen gas which goes to the atmosphere.

  15. 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.

  16. Nitrate reductase assay using sodium nitrate for rapid detection of multidrug resistant tuberculosis

    PubMed Central

    Macedo, Maíra Bidart; Groll, Andrea Von; Fissette, Krista; Palomino, Juan Carlos; da Silva, Pedro Eduardo Almeida; Martin, Anandi

    2012-01-01

    We validated the nitrate reductase assay (NRA) for the detection of multidrug-resistant Mycobacterium tuberculosis (MDR-TB) using sodium nitrate (NaNO3) in replacement of potassium nitrate (KNO3) as nitrate source. NaNO3 is cheaper than KNO3 and has no restriction on use which facilitates the implementation of NRA to detect MDR-TB. PMID:24031916

  17. 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...

  18. 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...

  19. 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...

  20. 49 CFR 176.410 - Division 1.5 materials, ammonium nitrate and ammonium nitrate mixtures.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 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...

  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...

  2. Nitration of Naphthol: A Laboratory Experiment.

    ERIC Educational Resources Information Center

    Mowery, Dwight F.

    1982-01-01

    Products of nitrations, upon distillation or steam distillation, may produce dermatitis in some students. A procedure for nitration of beta-naphthol producing a relatively non-volatile product not purified by steam distillation is described. Nitration of alpha-naphthol by the same procedure yields Martius Yellow dye which dyes wool yellow or…

  3. Modeling nitrate removal in a denitrification bed

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Denitrification beds are being promoted to reduce nitrate concentrations in agricultural drainage water to alleviate the adverse environmental effects associated with nitrate pollution in surface water. In this system, water flows through a trench filled with a carbon media where nitrate is transfor...

  4. Method of producing thin cellulose nitrate film

    DOEpatents

    Lupica, S.B.

    1975-12-23

    An improved method for forming a thin nitrocellulose film of reproducible thickness is described. The film is a cellulose nitrate film, 10 to 20 microns in thickness, cast from a solution of cellulose nitrate in tetrahydrofuran, said solution containing from 7 to 15 percent, by weight, of dioctyl phthalate, said cellulose nitrate having a nitrogen content of from 10 to 13 percent.

  5. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN... Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely used as a...

  6. Post-translational Regulation of Nitrate Reductase

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrate reductase (NR) catalyzes the reduction of nitrate to nitrite, which is the first step in the nitrate assimilation pathway, but can also reduce nitrite to nitric oxide (NO), an important signaling molecule that is thought to mediate a wide array of of developmental and physiological processes...

  7. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD... nitrate. The food additive potassium nitrate may be safely used as a curing agent in the processing of...

  8. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  9. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  10. Efflux Of Nitrate From Hydroponically Grown Wheat

    NASA Technical Reports Server (NTRS)

    Huffaker, R. C.; Aslam, M.; Ward, M. R.

    1992-01-01

    Report describes experiments to measure influx, and efflux of nitrate from hydroponically grown wheat seedlings. Ratio between efflux and influx greater in darkness than in light; increased with concentration of nitrate in nutrient solution. On basis of experiments, authors suggest nutrient solution optimized at lowest possible concentration of nitrate.

  11. 21 CFR 172.170 - Sodium nitrate.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium nitrate. 172.170 Section 172.170 Food and... PERMITTED FOR DIRECT ADDITION TO FOOD FOR HUMAN CONSUMPTION Food Preservatives § 172.170 Sodium nitrate. The food additive sodium nitrate may be safely used in or on specified foods in accordance with...

  12. 21 CFR 172.160 - Potassium nitrate.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Potassium nitrate. 172.160 Section 172.160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR... Food Preservatives § 172.160 Potassium nitrate. The food additive potassium nitrate may be safely...

  13. Protective effect of salivary nitrate and microbial nitrate reductase activity against caries.

    PubMed

    Doel, J J; Hector, M P; Amirtham, C V; Al-Anzan, L A; Benjamin, N; Allaker, R P

    2004-10-01

    To test the hypothesis that a combination of high salivary nitrate and high nitrate-reducing capacity are protective against dental caries, 209 children attending the Dental Institute, Barts and The London NHS Trust were examined. Salivary nitrate and nitrite levels, counts of Streptococcus mutans and Lactobacillus spp., and caries experience were recorded. Compared with control subjects, a significant reduction in caries experience was found in patients with high salivary nitrate and high nitrate-reducing ability. Production of nitrite from salivary nitrate by commensal nitrate-reducing bacteria may limit the growth of cariogenic bacteria as a result of the production of antimicrobial oxides of nitrogen, including nitric oxide. PMID:15458501

  14. Cerium Oxide Nanoparticles and Bulk Cerium Oxide Leading to Different Physiological and Biochemical Responses in Brassica rapa.

    PubMed

    Ma, Xingmao; Wang, Qiang; Rossi, Lorenzo; Zhang, Weilan

    2016-07-01

    Cerium oxide nanoparticles (CeO2NPs) have been incorporated into many commercial products, and their potential release into the environment through the use and disposal of these products has caused serious concerns. Despite the previous efforts and rapid progress on elucidating the environmental impact of CeO2NPs, the long-term impact of CeO2NPs to plants, a key component of the ecosystem, is still not well understood. The potentially different impact of CeO2NPs and their bulk counterparts to plants is also unclear. The main objectives of this study were (1) to investigate whether continued irrigation with solutions containing different concentrations of CeO2NPs (0, 10, and 100 mg/L) would induce physiological and biochemical adjustments in Brassica rapa in soil growing conditions and (2) to determine whether CeO2NPs and bulk CeO2 particles exert different impacts on plants. The results indicated that bulk CeO2 at 10 and 100 mg/L enhanced plant biomass by 28% and 35%, respectively, while CeO2NPs at equivalent concentrations did not. While the bulk CeO2 treatment resulted in significantly higher concentrations of hydrogen peroxide (H2O2) in plant tissues at the vegetative stage, CeO2NPs led to significantly higher H2O2 levels in plant tissues at the floral stage. The activity of superoxide dismutase (SOD) in Brassica rapa also displayed a growth-stage dependent response to different sizes of CeO2 while catalase (CAT) activity was not affected by either size of CeO2 throughout the life cycle of Brassica rapa. Altogether, the results demonstrated that plant responses to CeO2 exposure varied with the particle sizes and the growth stages of plants.

  15. Cerium Oxide Nanoparticles and Bulk Cerium Oxide Leading to Different Physiological and Biochemical Responses in Brassica rapa.

    PubMed

    Ma, Xingmao; Wang, Qiang; Rossi, Lorenzo; Zhang, Weilan

    2016-07-01

    Cerium oxide nanoparticles (CeO2NPs) have been incorporated into many commercial products, and their potential release into the environment through the use and disposal of these products has caused serious concerns. Despite the previous efforts and rapid progress on elucidating the environmental impact of CeO2NPs, the long-term impact of CeO2NPs to plants, a key component of the ecosystem, is still not well understood. The potentially different impact of CeO2NPs and their bulk counterparts to plants is also unclear. The main objectives of this study were (1) to investigate whether continued irrigation with solutions containing different concentrations of CeO2NPs (0, 10, and 100 mg/L) would induce physiological and biochemical adjustments in Brassica rapa in soil growing conditions and (2) to determine whether CeO2NPs and bulk CeO2 particles exert different impacts on plants. The results indicated that bulk CeO2 at 10 and 100 mg/L enhanced plant biomass by 28% and 35%, respectively, while CeO2NPs at equivalent concentrations did not. While the bulk CeO2 treatment resulted in significantly higher concentrations of hydrogen peroxide (H2O2) in plant tissues at the vegetative stage, CeO2NPs led to significantly higher H2O2 levels in plant tissues at the floral stage. The activity of superoxide dismutase (SOD) in Brassica rapa also displayed a growth-stage dependent response to different sizes of CeO2 while catalase (CAT) activity was not affected by either size of CeO2 throughout the life cycle of Brassica rapa. Altogether, the results demonstrated that plant responses to CeO2 exposure varied with the particle sizes and the growth stages of plants. PMID:26691446

  16. The effects of cerium doping on the size, morphology, and optical properties of α-hematite nanoparticles for ultraviolet filtration

    SciTech Connect

    Cardillo, Dean; Konstantinov, Konstantin; Devers, Thierry

    2013-11-15

    Highlights: • Possible application of cerium-doped α-hematite as ultraviolet filter. • Nanoparticles obtained through co-precipitation technique using various cerium doping levels followed by annealing. • Comprehensive materials characterisation utilizing XRD, DSC/TGA, STEM, UV–vis spectroscopy. • Increasing cerium content reduces particle sizing and alters morphology. • Solubility of cerium in hematite seen between 5 and 10% doping, 10% cerium doping greatly enhances attenuation in ultraviolet region and increases optical bandgap. - Abstract: Metal oxide nanoparticles have potential use in energy storage, electrode materials, as catalysts and in the emerging field of nanomedicine. Being able to accurately tailor the desirable properties of these nanoceramic materials, such as particle size, morphology and optical bandgap (E{sub g}) is integral in the feasibility of their use. In this study we investigate the altering of both the structure and physical properties through the doping of hematite (α-Fe{sub 2}O{sub 3}) nanocrystals with cerium at a range of concentrations, synthesised using a one-pot co-precipitation method. This extremely simple synthesis followed by thermal treatment results in stable Fe{sub 2−x}Ce{sub x}O{sub y} nanoceramics resulting from the burning of any unreacted precursors and transformation of goethite-cerium doped nanoparticle intermediate. The inclusion of Ce into the crystal lattice of these α-Fe{sub 2}O{sub 3} nanoparticles causes a significantly large reduction in mean crystalline size and alteration in particle morphology with increasing cerium content. Finally we report an increase optical semiconductor bandgap, along with a substantial increase in the ultraviolet attenuation found for a 10% Ce-doping concentration which shows the potential application of cerium-doped hematite nanocrystals to be used as a pigmented ultraviolet filter for cosmetic products.

  17. Continuous flow nitration in miniaturized devices

    PubMed Central

    2014-01-01

    Summary This review highlights the state of the art in the field of continuous flow nitration with miniaturized devices. Although nitration has been one of the oldest and most important unit reactions, the advent of miniaturized devices has paved the way for new opportunities to reconsider the conventional approach for exothermic and selectivity sensitive nitration reactions. Four different approaches to flow nitration with microreactors are presented herein and discussed in view of their advantages, limitations and applicability of the information towards scale-up. Selected recent patents that disclose scale-up methodologies for continuous flow nitration are also briefly reviewed. PMID:24605161

  18. Synthesis and characterization of linear cerium(IV) Schiff-base coordination polymers

    SciTech Connect

    Chen, H.; Cronin, J.A.; Archer, R.D. . Dept. of Chemistry)

    1994-04-11

    The first soluble linear Schiff-base rare earth coordination polymer, catena-poly[cerium-(4)-[mu]-N,N[prime],N[double prime],N[prime][double prime]-tetrasalicylidene (3,3[prime]-diaminobenzidinato)-O,N,N[prime],O[prime],O[double prime],N[double prime],N[prime][double prime],O[prime][double prime

  19. Cerium (IV) oxide nanotubes prepared by low temperature deposition at normal pressure.

    PubMed

    Boehme, M; Fu, G; Ionescu, E; Ensinger, W

    2011-02-11

    This paper reports the synthesis of cerium dioxide nanotubes (CeNTs) by electroless deposition using ion-track-etched polycarbonate templates. To achieve nanotubes with thin walls and small surface roughness the tubes were generated by a several-step-containing procedure under aqueous conditions. The approach reported below will process open end nanotubes with well-defined outer diameter and wall thickness.

  20. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-11-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol-1), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  1. Fabrication and characterization of cerium-doped barium titanate inverse opal by sol-gel method

    SciTech Connect

    Jin Yi; Zhu Yihua Yang Xiaoling; Li Chunzhong; Zhou Jinghong

    2007-01-15

    Cerium-doped barium titanate inverted opal was synthesized from barium acetate contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a polystyrene (PS) opal. This procedure involves infiltration of precursors into the interstices of the PS opal template followed by hydrolytic polycondensation of the precursors to amorphous barium titanate and removal of the PS opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). The pores were characterized by mercury intrusion porosimetry (MIP). X-ray photoelectron spectroscopy (XPS) investigation showed the doping structure of cerium, barium and titanium. And powder X-ray diffraction allows one to observe the influence of doping degree on the grain size. The lattice parameters, crystal size and lattice strain were calculated by the Rietveld refinement method. The synthesis of cerium-doped barium titanate inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices. - Graphical abstract: Cerium-doped barium titanate inverted opal was synthesized from barium acetate acid contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a PS opal, which involves infiltration of precursors into the interstices of the PS opal template and removal of the PS opal by calcination.

  2. Calculation of the volume effect at an electron phase transition in pure cerium and praseodymium

    NASA Astrophysics Data System (ADS)

    Ponomareva, S. A.; Koval', Yu. N.; Ponomarev, A. P.

    2014-03-01

    The experimental values of the volume effect at an electronic phase transition in several rare-earth metals are discussed. Specifically, volume changes at phase transitions in cerium and praseodymium are calculated using a semiphenomenological relationship derived in terms of the Falikov-Ramirez-Kimball model. A number of factors influencing the amount of the volume effect at electronic phase transitions are analyzed.

  3. Synthesis, electrical and dielectric characterization of cerium doped nano copper ferrites

    SciTech Connect

    Malana, Muhammad Aslam Qureshi, Raheela Beenish; Ashiq, Muhammad Naeem; Zafar, Zafar Iqbal

    2013-11-15

    Graphical abstract: Lattice constant (a) and activation energy (Ea) as a function of Ce (cerium) content. - Highlights: • The simple and economic method has been adopted for the synthesis of nanoferrites. • The electrical resistivity increases with cerium concentration. • DC electrical resistivity of these materials favours their use in microwave devices. • Dielectric measurements show semiconductor nature of the synthesized ferrites. - Abstract: The nanosized CuFe{sub 2−x}Ce{sub x}O{sub 4} (x = 0.0, 0.2, 0.4, 0.6, 0.8) ferrites doped with cerium are synthesized by chemical co-precipitation method. The synthesized materials are characterized by XRD, FTIR, TGA and SEM. XRD analysis of cerium substituted copper ferrites confirms the cubic spinel structure. The average crystallite size calculated by using Scherrer's formula ranges from 37 to 53 nm. The values of cell constant and cell volume vary with the dopant concentration. These variations can be explained in terms of their ionic radii. The DC electrical resistivity, measured by two point probe method, increases with increase in dopant concentration while it decreases with rise in temperature exhibiting semiconductor behaviour. Energy of activation of these ferrites is calculated by using Arrhenius type resistivity plots. Dielectric measurements of the synthesized compounds show exponential decrease in dielectric constant and dielectric loss factor with increase in frequency. This indicates the normal dielectric behaviour of ferrites.

  4. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants

    EPA Science Inventory

    The effects of exposure to two nanoparticles (NPs) -titanium dioxide (nano-titania) and cerium oxide (nano-ceria) at 500 mg NPs L-1 on gene expression and growth in Arabidopsis thaliana germinants were studied using microarrays and phenotype studies. After 12 days post treatment,...

  5. Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

    DOEpatents

    Bamberger, Carlos E.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

  6. Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

    DOEpatents

    Bamberger, C.E.

    A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

  7. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation.

    PubMed

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-01-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol(-1)), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  8. Cerium oxide coated anodes for aluminum electrowinning: Topical report, October 1, 1986-June 30, 1987

    SciTech Connect

    Walker, J. K.

    1987-12-01

    Because of the cost of building and maintaining a carbon anode plant and the energy penalties associated with the use of carbon anodes in the production of aluminum, the use of inert anodes has long been proposed. Various cermet anodes have been investigated. In this paper, tests on a material, cerium oxyfluoride (CEROX), deposited in situ as an anode, are reported. (JDH)

  9. Demonstration of enhanced K-edge angiography using a cerium target x-ray generator

    SciTech Connect

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ichimaru, Toshio; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2004-11-01

    The cerium target x-ray generator is useful in order to perform enhanced K-edge angiography using a cone beam because K-series characteristic x rays from the cerium target are absorbed effectively by iodine-based contrast mediums. The x-ray generator consists of a main controller, a unit with a Cockcroft-Walton circuit and a fixed anode x-ray tube, and a personal computer. The tube is a glass-enclosed diode with a cerium target and a 0.5-mm-thick beryllium window. The maximum tube voltage and current were 65 kV and 0.4 mA, respectively, and the focal-spot sizes were 1.0x1.3 mm. Cerium K{alpha} lines were left using a barium sulfate filter, and the x-ray intensity was 0.48 {mu}C/kg at 1.0 m from the source with a tube voltage of 60 kV, a current of 0.40 mA, and an exposure time of 1.0 s. Angiography was performed with a computed radiography system using iodine-based microspheres. In coronary angiography of nonliving animals, we observed fine blood vessels of approximately 100 {mu}m with high contrasts.

  10. Phosphate ester hydrolysis of biologically relevant molecules by cerium oxide nanoparticles.

    PubMed

    Kuchma, Melissa Hirsch; Komanski, Christopher B; Colon, Jimmie; Teblum, Andrew; Masunov, Artëm E; Alvarado, Beatrice; Babu, Suresh; Seal, Sudipta; Summy, Justin; Baker, Cheryl H

    2010-12-01

    In an effort to characterize the interaction of cerium oxide nanoparticles (CNPs) in biological systems, we explored the reactivity of CNPs with the phosphate ester bonds of p-nitrophenylphosphate (pNPP), ATP, o-phospho-l-tyrosine, and DNA. The activity of the bond cleavage for pNPP at pH 7 is calculated to be 0.860 ± 0.010 nmol p-nitrophenol/min/μg CNPs. Interestingly, when CNPs bind to plasmid DNA, no cleavage products are detected. While cerium(IV) complexes generally exhibit the ability to break phosphorus-oxygen bonds, the reactions we report appear to be dependent on the availability of cerium(III) sites, not cerium(IV) sites. We investigated the dephosphorylation mechanism from the first principles and find the reaction proceeds through inversion of the phosphate group similar to an S(N)2 mechanism. The ability of CNPs to interact with phosphate ester bonds of biologically relevant molecules has important implications for their use as potential therapeutics.

  11. Long range ordered alloys modified by addition of niobium and cerium

    DOEpatents

    Liu, C.T.

    1984-08-22

    Long range ordered alloys are described having the nominal composition (Fe,Ni,Co)/sub 3/ (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to dramatically enhance the creep properties of the resulting alloys.

  12. Long range ordered alloys modified by addition of niobium and cerium

    DOEpatents

    Liu, Chain T.

    1987-01-01

    Long range ordered alloys are described having the nominal composition (Fe,Ni,Co).sub.3 (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to drammatically enhance the creep properties of the resulting alloys.

  13. Resonant photoemission study of the 4f spectral function of cerium in Ce/Fe(100) interfaces

    SciTech Connect

    Witkowski, N.; Bertran, F.; Gourieux, T.; Kierren, B.; Malterre, D.; Panaccione, G. |

    1997-11-01

    In this paper, we present a resonant photoemission study of the cerium 4f spectral function in Ce/Fe(100) interfaces. By covering cerium ultrathin films with lanthanum, we completely suppress the surface contribution of the spectra. Then we show that the cerium atoms at the interface are in an intermediate valent state, whereas the f{sup 1} configuration is stabilized in the top layer. This method allows us to obtain the genuine 4f spectral function of the interface, and could be extended to a study of Ce-based compounds. {copyright} {ital 1997} {ital The American Physical Society}

  14. Phase diagram of ammonium nitrate

    NASA Astrophysics Data System (ADS)

    Dunuwille, M.; Yoo, C. S.

    2014-05-01

    Ammonium Nitrate (AN) has often subjected to uses in improvised explosive devices, due to its wide availability as a fertilizer and its capability of becoming explosive with slight additions of organic and inorganic compounds. Yet, the origin of enhanced energetic properties of impure AN (or AN mixtures) is neither chemically unique nor well understood -resulting in rather catastrophic disasters in the past1 and thereby a significant burden on safety in using ammonium nitrates even today. To remedy this situation, we have carried out an extensive study to investigate the phase stability of AN at high pressure and temperature, using diamond anvil cells and micro-Raman spectroscopy. The present results confirm the recently proposed phase IV-to-IV' transition above 17 GPa2 and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400 °C.

  15. Deconstructing nitrate isotope dynamics in aquifers

    NASA Astrophysics Data System (ADS)

    Granger, J.

    2012-12-01

    The natural abundance N and O stable isotope ratios of nitrate provide an invaluable tool to differentiate N sources to the environment, track their dispersal, and monitor their attenuation by biological transformations. The interpretation of patterns in isotope abundances relies on knowledge of the isotope ratios of the source end-members, as well as on constraints on the isotope discrimination imposed on nitrate by respective biological processes. Emergent observations from mono-culture experiments of denitrifying bacteria reveal nitrate fractionation trends that appear at odds with trends ascribed to denitrification in soils and aquifers. This discrepancy raises the possibility that additional biological N transformations may be acting in tandem with denitrification. Here, the N and O isotope enrichments associated with nitrate removal by denitrification in aquifers are posited to bear evidence of coincident biological nitrate production - from nitrification and/or from anammox. Simulations are presented from a simple time-dependent one-box model of a groundwater mass ageing that is subject to net nitrate loss by denitrification with coincident nitrate production by nitrification or anammox. Within boundary conditions characteristic of freshwater aquifers, the apparent slope of the parallel enrichments in nitrate N and O isotopes associated with net N loss to denitrification can vary in proportion to the nitrate added simultaneous by oxidative processes. Pertinent observations from nitrate plumes in suboxic to anoxic aquifers are examined to validate this premise. In this perspective, nitrate isotope distributions suggest that we may be missing important N fluxes inherent to most aquifers.

  16. Nitrate Utilization by the Diatom Skeletonema costatum

    PubMed Central

    Serra, Juan L.; Llama, Maria J.; Cadenas, Eduardo

    1978-01-01

    Nitrate uptake has been studied in nitrogen-deficient cells of the marine diatom Skeletonema costatum. When these cells are incubated in the presence of nitrate, this ion is quickly taken up from the medium, and nitrite is excreted by the cells. Nitrite is excreted following classical saturation kinetics, its rate being independent of nitrate concentration in the incubation medium for nitrate concentration values higher than 3 micromolar. Nitrate uptake shows mixed-transfer kinetics, which can be attributed to the simultaneous contributions of mediated and diffusion transfer. Cycloheximide and p-hydroxymercuribenzoate inhibit the carrier-mediated contribution to nitrate uptake, without affecting the diffusion component. When cells are preincubated with nitrate, the net nitrogen uptake is increased. PMID:16660652

  17. Pollution of drinking water with nitrate

    SciTech Connect

    Cabel, B.; Kozicki, R.; Lahl, U.; Podbielshi, A.; Stachel, B.; Struss, S.

    1982-01-01

    The main sources of nitrate in man are food and drinking water. The legislature in West Germany intends to lower the permitted level of nitrate in drinking water from the present 90 mg/l to 50 mg/l in 1982. The European Community has issued a directive that recommends a level of only 25 mg/l, and for babies 10 mg/l nitrate should not be exceeded. At present, nitrate cannot be removed from raw water at an acceptable cost. The problem of high nitrate content is mainly one of drinking water generation from ground water. Several analyses indicate rising concentrations of nitrate in ground water in different regions of West Germany, especially in the last few years. The following sources of nitrate-contamination of ground water aquifers in West are discussed: natural sources; over-manuring of agricultural areas with natural organic fertilizers; over-manuring of agricultural areas with synthetic fertilizers.

  18. High performance ammonium nitrate propellant

    NASA Technical Reports Server (NTRS)

    Anderson, F. A. (Inventor)

    1979-01-01

    A high performance propellant having greatly reduced hydrogen chloride emission is presented. It is comprised of: (1) a minor amount of hydrocarbon binder (10-15%), (2) at least 85% solids including ammonium nitrate as the primary oxidizer (about 40% to 70%), (3) a significant amount (5-25%) powdered metal fuel, such as aluminum, (4) a small amount (5-25%) of ammonium perchlorate as a supplementary oxidizer, and (5) optionally a small amount (0-20%) of a nitramine.

  19. 4d → 4f resonance in photoabsorption of cerium ion Ce3+ and endohedral cerium in fullerene complex {\\rm{Ce}}@{{{\\rm{C}}}_{82}}^{+}

    NASA Astrophysics Data System (ADS)

    Schrange-Kashenock, G.

    2016-09-01

    The theoretical investigation of the single-photoionization spectra in the 4d-resonance region (120-150 eV) for the ionic cerium Ce3+ and cerium in the endohedral complex {{Ce}}@{{{{C}}}82}+ (in practice, {{{Ce}}}3+@{{{{C}}}82}2-) is presented. The fullerene cage is modeled by ab initio spherical jellium shell with an accurate account for the real distribution of carbon electron density. The oscillator strengths are calculated within the multiconfiguration Dirac-Fock (MCDF) approach for phototransitions from the outermost shells of the ion Ce3+ with and without the influence of the potential generated by a fullerene cage. It is shown that the integrated oscillator strengths have the main contribution from the Ce3+ 4d → 4f (ten possible from the phototransitions {}2F{7/2,5/2}\\to {}2D{3/2,5/2},{}2F{5/2,7/2},{}2G{5/2,7/2}) resonance photoexcitations. The corresponding precise MCDF values for the oscillator strengths and the transition energies are presented for the first time. It is demonstrated that the resonance {f}4d\\to 4f oscillator strengths are slightly affected by the presence of the cage potential, despite the fact that the spectral levels structure is changed when the effect of this potential is included. The Auger 4d -1 decay from the cerium free ion Ce3+ and the encapsulated endohedral ion Ce3+@ are considered within the two-step model and the corresponding Lorentzian profiles are presented. This model clearly reveals the correspondence of the complex resonance profile in the Ce3+ photoabsorption to the fine structure of ion energy levels. The smoothing of the resonance profile in the photoabsorption of the endohedral system {{Ce}}@{{{{C}}}82}+ compared with the free ion Ce3+ is attributed to increasing the linewidths of the Auger transitions. This increase is estimated from the relevant experiment (Müller et al 2008 Phys. Rev. Lett. 101 133001) to be strong; as at least three times the value for an isolated ion. The presence of the confining fullerene

  20. 4d → 4f resonance in photoabsorption of cerium ion Ce3+ and endohedral cerium in fullerene complex {\\rm{Ce}}@{{{\\rm{C}}}_{82}}^{+}

    NASA Astrophysics Data System (ADS)

    Schrange-Kashenock, G.

    2016-09-01

    The theoretical investigation of the single-photoionization spectra in the 4d-resonance region (120–150 eV) for the ionic cerium Ce3+ and cerium in the endohedral complex {{Ce}}@{{{{C}}}82}+ (in practice, {{{Ce}}}3+@{{{{C}}}82}2-) is presented. The fullerene cage is modeled by ab initio spherical jellium shell with an accurate account for the real distribution of carbon electron density. The oscillator strengths are calculated within the multiconfiguration Dirac–Fock (MCDF) approach for phototransitions from the outermost shells of the ion Ce3+ with and without the influence of the potential generated by a fullerene cage. It is shown that the integrated oscillator strengths have the main contribution from the Ce3+ 4d → 4f (ten possible from the phototransitions {}2F{7/2,5/2}\\to {}2D{3/2,5/2},{}2F{5/2,7/2},{}2G{5/2,7/2}) resonance photoexcitations. The corresponding precise MCDF values for the oscillator strengths and the transition energies are presented for the first time. It is demonstrated that the resonance {f}4d\\to 4f oscillator strengths are slightly affected by the presence of the cage potential, despite the fact that the spectral levels structure is changed when the effect of this potential is included. The Auger 4d ‑1 decay from the cerium free ion Ce3+ and the encapsulated endohedral ion Ce3+@ are considered within the two-step model and the corresponding Lorentzian profiles are presented. This model clearly reveals the correspondence of the complex resonance profile in the Ce3+ photoabsorption to the fine structure of ion energy levels. The smoothing of the resonance profile in the photoabsorption of the endohedral system {{Ce}}@{{{{C}}}82}+ compared with the free ion Ce3+ is attributed to increasing the linewidths of the Auger transitions. This increase is estimated from the relevant experiment (Müller et al 2008 Phys. Rev. Lett. 101 133001) to be strong; as at least three times the value for an isolated ion. The presence of the confining

  1. Photochemical reduction of uranyl nitrate

    SciTech Connect

    Duerksen, W.K.

    1993-10-20

    The photochemical reduction of uranyl nitrate solutions to tetravalent uranium was investigated as a means of producing uranium dioxide feed for the saltless direct oxide reduction (SDOR) process. At high uranium concentrations, reoxidation of U{sup +4} occurs rapidly. The kinetics of the nitric oxidation of tetravalent uranium depend on the concentrations of hydrogen ion, nitrate ion, nitrous acid, and tetravalent uranium in the same manner as was reported elsewhere for the nitrate oxidation of PU{sup +3}. Reaction rate data were successfully correlated with a mechanism in which nitrogen dioxide is the reactive intermediate. Addition of a nitrous acid scavenger suppresses the reoxidation reaction. An immersion reactor employing a mercury vapor lamp gave reduction times fast enough for routine production usage. Precipitation techniques for conversion of aqueous U(NO{sub 3}){sub 4} to hydrous UO{sub 2} were evaluated. Prolonged dewatering times tended to make the process time consuming. Use of 3- to 4-M aqueous NaOH gave the best dewatering times observed. Reoxidation of the UO{sub 2} by water of hydration was encountered, which required the drying process to be carried out under a reducing atmosphere.

  2. Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form.

    SciTech Connect

    Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

    1999-09-03

    Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl{sub 3} forms UO{sub 2} and PuCl{sub 3} forms PuO{sub 2}. The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O{sub 2}.

  3. 49 CFR 176.415 - Permit requirements for Division 1.5, ammonium nitrates, and certain ammonium nitrate fertilizers.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 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...

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. Sensitivity of nitrate aerosols to ammonia emissions and to nitrate chemistry: implications for present and future nitrate optical depth

    NASA Astrophysics Data System (ADS)

    Paulot, F.; Ginoux, P.; Cooke, W. F.; Donner, L. J.; Fan, S.; Lin, M.-Y.; Mao, J.; Naik, V.; Horowitz, L. W.

    2016-02-01

    We update and evaluate the treatment of nitrate aerosols in the Geophysical Fluid Dynamics Laboratory (GFDL) atmospheric model (AM3). Accounting for the radiative effects of nitrate aerosols generally improves the simulated aerosol optical depth, although nitrate concentrations at the surface are biased high. This bias can be reduced by increasing the deposition of nitrate to account for the near-surface volatilization of ammonium nitrate or by neglecting the heterogeneous production of nitric acid to account for the inhibition of N2O5 reactive uptake at high nitrate concentrations. Globally, uncertainties in these processes can impact the simulated nitrate optical depth by up to 25 %, much more than the impact of uncertainties in the seasonality of ammonia emissions (6 %) or in the uptake of nitric acid on dust (13 %). Our best estimate for fine nitrate optical depth at 550 nm in 2010 is 0.006 (0.005-0.008). In wintertime, nitrate aerosols are simulated to account for over 30 % of the aerosol optical depth over western Europe and North America. Simulated nitrate optical depth increases by less than 30 % (0.0061-0.010) in response to projected changes in anthropogenic emissions from 2010 to 2050 (e.g., -40 % for SO2 and +38 % for ammonia). This increase is primarily driven by greater concentrations of nitrate in the free troposphere, while surface nitrate concentrations decrease in the midlatitudes following lower concentrations of nitric acid. With the projected increase of ammonia emissions, we show that better constraints on the vertical distribution of ammonia (e.g., convective transport and biomass burning injection) and on the sources and sinks of nitric acid (e.g., heterogeneous reaction on dust) are needed to improve estimates of future nitrate optical depth.

  9. Effect of nitrate on microbial perchlorate reduction

    NASA Astrophysics Data System (ADS)

    Sun, Y.; Coates, J. D.

    2007-12-01

    Over the last decade perchlorate has been recognized as an important emerging water contaminant that poses a significant public health threat. Because of its chemical stability, low ionic charge density, and significant water solubility microbial remediation has been identified as the most feasible method for its in situ attenuation. Our previous studies have demonstrated that dissimilatory perchlorate reducing bacteria (DPRB) capable of the respiratory reduction of perchlorate into innocuous chloride are ubiquitous in soil and sedimentary environments. As part of their metabolism these organisms reduce perchlorate to chlorite which is subsequently dismutated into chloride and molecular oxygen. These initial steps are mediated by the perchlorate reductase and chlorite dismutase enzymes respectively. Previously we found that the activity of these organisms is dependent on the presence of molybdenum and is inhibited by the presence of oxygen and to different extents nitrate. However, to date, there is little understanding of the mechanisms involved in the regulation of perchlorate reduction by oxygen and nitrate. As a continuation of our studies into the factors that control DPRB activity we investigated these regulatory mechanisms in more detail as a model organism, Dechloromonas aromatica strain RCB, transitions from aerobic metabolism through nitrate reduction to perchlorate reduction. In series of growth transition studies where both nitrate and perchlorate were present, preference for nitrate to perchlorate was observed regardless of the nitrate to perchlorate ratio. Even when the organism was pre-grown anaerobically in perchlorate, nitrate was reduced prior to perchlorate. Using non-growth washed cell suspension, perchlorate- grown D. aromatica was capable of reducing both perchlorate and nitrate concomitantly suggesting the preferentially utilization of nitrate was not a result of enzyme functionality. To elucidate the mechanism for preferential utilization of

  10. Nitrate deposition and impact on Adirondack streams

    SciTech Connect

    Simonin, H.A.; Kretser, W.A.

    1997-12-31

    Acidic deposition has a great impact on water chemistry and fish populations in the Adirondack region. Although the Clean Air Act Amendments of 1990 have resulted in some reductions of sulfate deposition, nitrate deposition has not yet been well controlled, and continues to impact aquatic resources. As part of the USEPA funded Episodic Response Project four Adirondack headwater streams were intensively monitored over an 18 month period. Atmospheric deposition was also monitored at a centrally located station. The quantity of nitrate being deposited on the study watersheds was calculated based on monthly net deposition data which ranged from 0.6 kg/ha/month to 3.6 kg/ha/month. These data were then compared to the monthly export of nitrate from the watershed in these streams. Nitrate concentrations were highest in the streamwater during the spring snowmelt period prior to the time when forest vegetation actively utilizes nitrate. On an annual basis the amount of nitrate which left the watershed via stream water exceeded the amount which fell as nitrate deposition. These data are important in documenting the impact of nitrate in the acidification of Adirondack streams during the spring, which coincides with brook trout hatching. Control programs for nitrous oxide emissions are presently aimed at reducing ozone levels during the May-September period. These emissions control programs need to be expanded to also reduce nitrate deposition in the sensitive Adirondack region during the winter and spring periods when nitrate deposition has its greatest impact on aquatic resources.

  11. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium.

  12. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium. PMID:14637345

  13. A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

    USGS Publications Warehouse

    Rose, H.J.; Murata, K.J.; Carron, M.K.

    1954-01-01

    In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80??0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5??0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error. ?? 1954.

  14. Nitrates

    MedlinePlus

    ... or interactions with other medicines and vitamin or herbal supplements. This information should not be used as medical ... your doctor about every medicine and vitamin or herbal supplement that you are taking, so he or she ...

  15. Membraneless, room-temperature, direct borohydride/cerium fuel cell with power density of over 0.25 W/cm2.

    PubMed

    Da Mota, Nicolas; Finkelstein, David A; Kirtland, Joseph D; Rodriguez, Claudia A; Stroock, Abraham D; Abruña, Héctor D

    2012-04-11

    The widespread adoption and deployment of fuel cells as an alternative energy technology have been hampered by a number of formidable technical challenges, including the cost and long-term stability of electrocatalyst and membrane materials. We present a microfluidic fuel cell that overcomes many of these obstacles while achieving power densities in excess of 250 mW/cm(2). The poisoning and sluggish reaction rate associated with CO-contaminated H(2) and methanol, respectively, are averted by employing the promising, high-energy density fuel borohydride. The high-overpotential reaction of oxygen gas at the cathode is supplanted by the high-voltage reduction of cerium ammonium nitrate. Expensive, ineffective membrane materials are replaced with laminar flow and a nonselective, porous convection barrier to separate the fuel and oxidant streams. The result is a Nafion-free, room-temperature fuel cell that has the highest power density per unit mass of Pt catalyst employed for a non-H(2) fuel cell, and exceeds the power density of a typical H(2) fuel cell by 50%.

  16. Trend Analyses of Nitrate in Danish Groundwater

    NASA Astrophysics Data System (ADS)

    Hansen, B.; Thorling, L.; Dalgaard, T.; Erlandsen, M.

    2012-04-01

    This presentation assesses the long-term development in the oxic groundwater nitrate concentration and nitrogen (N) loss due to intensive farming in Denmark. Firstly, up to 20-year time-series from the national groundwater monitoring network enable a statistically systematic analysis of distribution, trends and trend reversals in the groundwater nitrate concentration. Secondly, knowledge about the N surplus in Danish agriculture since 1950 is used as an indicator of the potential loss of N. Thirdly, groundwater recharge CFC (Chlorofluorocarbon) age determination allows linking of the first two dataset. The development in the nitrate concentration of oxic groundwater clearly mirrors the development in the national agricultural N surplus, and a corresponding trend reversal is found in groundwater. Regulation and technical improvements in the intensive farming in Denmark have succeeded in decreasing the N surplus by 40% since the mid 1980s while at the same time maintaining crop yields and increasing the animal production of especially pigs. Trend analyses prove that the youngest (0-15 years old) oxic groundwater shows more pronounced significant downward nitrate trends (44%) than the oldest (25-50 years old) oxic groundwater (9%). This amounts to clear evidence of the effect of reduced nitrate leaching on groundwater nitrate concentrations in Denmark. Are the Danish groundwater monitoring strategy obtimal for detection of nitrate trends? Will the nitrate concentrations in Danish groundwater continue to decrease or are the Danish nitrate concentration levels now appropriate according to the Water Framework Directive?

  17. Measurement of isoprene nitrates by GCMS

    NASA Astrophysics Data System (ADS)

    Mills, Graham P.; Hiatt-Gipson, Glyn D.; Bew, Sean P.; Reeves, Claire E.

    2016-09-01

    According to atmospheric chemistry models, isoprene nitrates play an important role in determining the ozone production efficiency of isoprene; however this is very poorly constrained through observations as isoprene nitrates have not been widely measured. Measurements have been severely restricted largely due to a limited ability to measure individual isoprene nitrate isomers. An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods are described for the speciated measurements of individual isoprene nitrate isomers. Five of the primary isoprene nitrates which formed in the presence of NOx by reaction of isoprene with the hydroxyl radical (OH) in the Master Chemical Mechanism are identified using known isomers on two column phases and are fully separated on the Rtx-200 column. Three primary isoprene nitrates from the reaction of isoprene with the nitrate radical (NO3) are identified after synthesis from the already identified analogous hydroxy nitrate. A Tenax adsorbent-based trapping system allows the analysis of the majority of the known hydroxy and carbonyl primary isoprene nitrates, although not the (1,2)-IN isomer, under field-like levels of humidity and showed no impact from typical ambient concentrations of NOx and ozone.

  18. Groundwater nitrate contamination: factors and indicators.

    PubMed

    Wick, Katharina; Heumesser, Christine; Schmid, Erwin

    2012-11-30

    Identifying significant determinants of groundwater nitrate contamination is critical in order to define sensible agri-environmental indicators that support the design, enforcement, and monitoring of regulatory policies. We use data from approximately 1200 Austrian municipalities to provide a detailed statistical analysis of (1) the factors influencing groundwater nitrate contamination and (2) the predictive capacity of the Gross Nitrogen Balance, one of the most commonly used agri-environmental indicators. We find that the percentage of cropland in a given region correlates positively with nitrate concentration in groundwater. Additionally, environmental characteristics such as temperature and precipitation are important co-factors. Higher average temperatures result in lower nitrate contamination of groundwater, possibly due to increased evapotranspiration. Higher average precipitation dilutes nitrates in the soil, further reducing groundwater nitrate concentration. Finally, we assess whether the Gross Nitrogen Balance is a valid predictor of groundwater nitrate contamination. Our regression analysis reveals that the Gross Nitrogen Balance is a statistically significant predictor for nitrate contamination. We also show that its predictive power can be improved if we account for average regional precipitation. The Gross Nitrogen Balance predicts nitrate contamination in groundwater more precisely in regions with higher average precipitation.

  19. Groundwater nitrate contamination: Factors and indicators

    PubMed Central

    Wick, Katharina; Heumesser, Christine; Schmid, Erwin

    2012-01-01

    Identifying significant determinants of groundwater nitrate contamination is critical in order to define sensible agri-environmental indicators that support the design, enforcement, and monitoring of regulatory policies. We use data from approximately 1200 Austrian municipalities to provide a detailed statistical analysis of (1) the factors influencing groundwater nitrate contamination and (2) the predictive capacity of the Gross Nitrogen Balance, one of the most commonly used agri-environmental indicators. We find that the percentage of cropland in a given region correlates positively with nitrate concentration in groundwater. Additionally, environmental characteristics such as temperature and precipitation are important co-factors. Higher average temperatures result in lower nitrate contamination of groundwater, possibly due to increased evapotranspiration. Higher average precipitation dilutes nitrates in the soil, further reducing groundwater nitrate concentration. Finally, we assess whether the Gross Nitrogen Balance is a valid predictor of groundwater nitrate contamination. Our regression analysis reveals that the Gross Nitrogen Balance is a statistically significant predictor for nitrate contamination. We also show that its predictive power can be improved if we account for average regional precipitation. The Gross Nitrogen Balance predicts nitrate contamination in groundwater more precisely in regions with higher average precipitation. PMID:22906701

  20. Phase Diagram of Ammonium Nitrate

    NASA Astrophysics Data System (ADS)

    Dunuwille, Mihindra; Yoo, Choong-Shik

    2013-06-01

    Ammonium Nitrate (AN) has often been subjected to uses in improvised explosive devices, due to its wide availability as a fertilizer and its capability of becoming explosive with slight additions of organic and inorganic compounds. Yet, the origin of enhanced energetic properties of impure AN (or AN mixtures) is neither chemically unique nor well understood - resulting in rather catastrophic disasters in the past1 and thereby a significant burden on safety, in using ammonium nitrates even today. To remedy this situation, we have carried out an extensive study to investigate the phase stability of AN, in different chemical environments, at high pressure and temperature, using diamond anvil cells and micro-Raman spectroscopy. The present results confirm the recently proposed phase IV-to-IV' transition above 15 GPa2 and provide new constraints for the melting and phase diagram of AN to 40 GPa and 673 K. The present study has been supported by the U.S. DHS under Award Number 2008-ST-061-ED0001.

  1. Peroxyacetyl nitrate and peroxypropionyl nitrate in Porto Alegre, Brazil

    NASA Astrophysics Data System (ADS)

    Grosjean, Eric; Grosjean, Daniel; Woodhouse, Luis F.; Yang, Yueh-Jiun

    For 41 days between 25 May 1996 and 27 March 1997, peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) have been measured by electron capture gas chromatography at Santa Rita near Porto Alegre, RS, Brazil, where light-duty vehicles used either ethanol or a gasoline-MTBE blend. Daily maximum concentrations ranged from 0.19 to 6.67 ppb for PAN and 0.06 to 0.72 ppb for PPN. Linear regression of maximum PPN vs. maximum PAN yielded a slope of 0.105±0.004 ( R2=0.974). Diurnal variations of ambient PAN often followed those of ozone with respect to time of day but not with respect to amplitude. This was reflected in the large relative standard deviations associated with the study-averaged PAN/ozone concentration ratio, 0.037±0.105 (ppb/ppb, n=789) and the maximum PAN/maximum ozone concentration ratio, 0.028±0.015 (ppb/ppb, range 0.005-0.078, n=41). On several days PAN accounted for large fractions of the total ambient NO x in the late morning and afternoon hours, e.g., PAN/NO x⩽0.58 and PAN/(NO x-NO) ⩽0.76 on 27 March 1997. The amount of PAN lost by thermal decomposition (TPAN) was comparable in magnitude to that present in ambient air. The ratios TPAN/(PAN+TPAN) were up to 0.53, 0.67 and 0.64 during the warm afternoons of 25, 26 and 27 March 1997, respectively. The highest calculated value of TPAN was 5.6 ppb on 27 March 1997. On that day the 24 h-averaged value of TPAN (1.01 ppb) was nearly the same as that of PAN (1.09 ppb). Using computer kinetic modeling (SAPRC 97 chemical mechanism) and sensitivity analysis of VOC incremental reactivity, we ranked VOC present in Porto Alegre ambient air for their importance as precursors to PAN and to PPN. Using as input data the averages of VOC concentrations measured in downtown Porto Alegre during the ca. 1 yr period March 1996-April 1997, we calculated that the most important precursors to PAN and PPN were the SAPRC 97 model species ARO2 (which includes the aromatics xylenes, trimethylbenzenes, ethyltoluenes, etc

  2. 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.

  3. 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

  4. 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 ...

  5. Removal of Nitrate from Groundwater by Cyanobacteria: Quantitative Assessment of Factors Influencing Nitrate Uptake

    PubMed Central

    Hu, Qiang; Westerhoff, Paul; Vermaas, Wim

    2000-01-01

    The feasibility of biologically removing nitrate from groundwater was tested by using cyanobacterial cultures in batch mode under laboratory conditions. Results demonstrated that nitrate-contaminated groundwater, when supplemented with phosphate and some trace elements, can be used as growth medium supporting vigorous growth of several strains of cyanobacteria. As cyanobacteria grew, nitrate was removed from the water. Of three species tested, Synechococcus sp. strain PCC 7942 displayed the highest nitrate uptake rate, but all species showed rapid removal of nitrate from groundwater. The nitrate uptake rate increased proportionally with increasing light intensity up to 100 μmol of photons m−2 s−1, which parallels photosynthetic activity. The nitrate uptake rate was affected by inoculum size (i.e., cell density), fixed-nitrogen level in the cells in the inoculum, and aeration rate, with vigorously aerated, nitrate-sufficient cells in mid-logarithmic phase having the highest long-term nitrate uptake rate. Average nitrate uptake rates up to 0.05 mM NO3− h−1 could be achieved at a culture optical density at 730 nm of 0.5 to 1.0 over a 2-day culture period. This result compares favorably with those reported for nitrate removal by other cyanobacteria and algae, and therefore effective nitrate removal from groundwater using this organism could be anticipated on large-scale operations. PMID:10618214

  6. Long-term testing of in-situ cerium oxide coated anodes for aluminum electrowinning

    SciTech Connect

    King, H.L.

    1989-10-01

    The ELTECH Anode Phase 2 Project (Contract Number AC07-86ID12655), as supported by the Department of Energy (DOE) from December 1988 through April 1989, focused on long-term testing of in-situ anodically deposited cerium oxide (CEROX) coatings on nickel ferrite/Cu cermets. The specific objective of this research was to determine the effectiveness of the CEROX coating in reducing the transfer of cermet components to the produced aluminum. A dosing regimen was first established for the minimum addition of cerium to the cell necessary to produce targeted CEROX coatings on the cermet anode and the periodic additions necessary to maintain coating thicknesses. The effects of the addition of CeF{sub 3} on CEROX coating formation was evaluated for targeted coating thicknesses at three different current densities. Analytical procedures were identified for determining alumina concentrations and the cryolite bath ratio for quasi-commercial baths.

  7. A DFT + U study of cerium solubility in La₂Zr₂O₇

    SciTech Connect

    Wang, X. J.; Xiao, Haiyan Y.; Zu, Xiaotao; Weber, William J.

    2012-02-17

    Density functional theory plus Hubbard U correction is employed to study the solubility of cerium in La₂Zr₂O₇. The results show that La₂Zr₂O₇ and Ce₂Zr₂O₇ form a solid solution over the whole range of cerium content. The solubility of Ce in La₂Zr₂O₇ can be partially attributed to the similar ionic radii of La³+ and Ce³+. Electronic structures of the La₂₋yCeyZr₂O₇ solid solution have been analyzed. The Ce 4ƒ states are found to be partially occupied, and Ce in the La₂₋yCeyZr₂O₇ solid solution exhibits a reduced charge state.

  8. Cerium Binding Activity of Pectins Isolated from the Seagrasses Zostera marina and Phyllospadix iwatensis

    PubMed Central

    Khotimchenko, Yuri; Khozhaenko, Elena; Kovalev, Valeri; Khotimchenko, Maxim

    2012-01-01

    Cerium binding activity of three different water soluble pectin compounds of different origin was studied in a batch sorption system. The Langmuir, Freundlich and BET sorption models were adopted to describe the binding reactions between metal ions and pectin molecules. The Langmuir model provided the best fit. Within the pH range from 4.0 to 6.0, the largest amount of the cerium ions was bound by pectin isolated from the seagrass Phylospadix iwatensis in comparison to pectin extracted from the seagrass Zostera marina and pectin obtained from citrus peel (commercial grade). The Langmuir constants were also highest for the pectin samples isolated from the seagrass P. iwatensis. The results obtained from this study suggest that pectin is a prospective source for the development of radioisotope-removing pharmaceuticals. PMID:22690146

  9. Measurement of the magnetic behaviour of 147Eu and 149Eu in cerium and platinum

    NASA Astrophysics Data System (ADS)

    Dietrich, M.; Zeitz, W.-D.; Weber, A.; Potzger, K.; Unterricker, S.; Schneider, F.; Samokhvalov, V.; Isolde Collaboration

    2005-07-01

    The local magnetism at europium in platinum and in cerium was studied using perturbed angular correlation (PAC) spectroscopy. In platinum, europium shows the electronic properties of the trivalent status, which has a non-magnetic ground state ( J=0). As a consequence, the Van Vleck contributions from the complete multiplet-level system predominantly determine the magnetic behaviour. In cerium, the measured data are close to the predictions for divalent europium. Here, only the electronic ground state, the pure spin state ( J=5/2), has to be taken into account. The measurements were done utilising the isomeric 11/2 - nuclear levels in 147Eu and 149Eu at 625 and 496 keV, respectively, after the precursors had been produced at the ion beam laboratory ISL Berlin or the on-line mass separator ISOLDE in Geneva.

  10. Luminescent Properties of Cerium Doped Potassium Iodide Single Crystals in Response to γ-irradiation.

    PubMed

    Bangaru, S; Saradha, K; Muralidharan, G

    2015-05-01

    Potassium iodide doped with cerium ions were prepared by Bridgemann Stockbarger technique and investigated by optical absorption, Photoluminescence(PL), Thermoluminescence(TL), Photostimulated Luminescence(PSL) and TL emission. The optical absorption measurement indicates that F and V centers are formed in the crystals during the γ-ray irradiation process. Optical absorption and Photoluminescence studies confirm the presence of cerium ions in the trivalent state. Spectral distribution under the Thermoluminescence Emission(TLE) and Optically Stimulated Luminescence(OSL) support the idea that the defect annihilation process to be due to thermal release of F-electron in KI:Ce(3+) crystals. Both Ce(3+) and Ce(2+) emissions were observed in the Thermoluminescence emission of the crystals. Thermoluminescence(TL) has been identified to be due to thermal release of electron produced during colouration process. PMID:25744528

  11. Variation of electronic transitions and reduction potentials of cerium(IV) complexes.

    PubMed

    Williams, Ursula J; Schneider, David; Dorfner, Walter L; Maichle-Mössmer, Cäcilia; Carroll, Patrick J; Anwander, Reiner; Schelter, Eric J

    2014-11-21

    The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(O(t)Bu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.

  12. Thermodynamics of the α -γ transition in cerium studied by an LDA + Gutzwiller method

    NASA Astrophysics Data System (ADS)

    Tian, Ming-Feng; Song, Hai-Feng; Liu, Hai-Feng; Wang, Cong; Fang, Zhong; Dai, Xi

    2015-03-01

    Utilizing the local-density approximation (LDA) + Gutzwiller method, we have studied the α -γ transition in cerium. Our results indicate that the volume collapse transition between α and γ phases is present at zero temperature with negative pressure. By further providing a newly finite temperature generalization of the LDA + Gutzwiller method (using the mean-field potential approach), the entropy contributed by both electronic quasiparticles and lattice vibration included, we obtain the Gibbs free energy at a given volume and temperature, from which we get the α -γ transition at finite temperature and pressure. Our results indicate that the electronic entropy and lattice vibrational entropy both play important roles in the α -γ transition. We also calculated the equation of state and phase diagram of cerium, finding good agreement with the experiments.

  13. A cerium-lead redox flow battery system employing supporting electrolyte of methanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Na, Zhaolin; Xu, Shengnan; Yin, Dongming; Wang, Limin

    2015-11-01

    A novel cerium-lead redox flow battery (RFB) employing Ce(IV)/Ce(III) and Pb(II)/Pb redox couples in the supporting electrolyte of methanesulfonic acid (MSA) is developed and preliminarily investigated. The RFB requires no additional catalyst and uses kinetically favorable reactions between low-cost reactants, and provides a desirable discharge voltage of approximately 1.7 V, with high average coulombic efficiency (CE) of 92% and energy efficiency (EE) of 86% over 800 cycles at 298 K. Stable cycling with an acceptable performance is achieved for a board operating temperature range of 253 K-313 K. The excellent performance obtained from the preliminary study suggests that the cerium-lead RFB promises to be applicable to large-scale energy storage for electricity grids.

  14. Improvement and analysis of the hydrogen-cerium redox flow cell

    NASA Astrophysics Data System (ADS)

    Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

    2016-09-01

    The H2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm-2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50 °C. The H2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.

  15. Safety in the Chemical Laboratory: Nitric Acid, Nitrates, and Nitro Compounds.

    ERIC Educational Resources Information Center

    Bretherick, Leslie

    1989-01-01

    Discussed are the potential hazards associated with nitric acid, inorganic and organic nitrate salts, alkyl nitrates, acyl nitrates, aliphatic nitro compounds, aromatic nitro compounds, and nitration reactions. (CW)

  16. Cerium Regulates Expression of Alternative Methanol Dehydrogenases in Methylosinus trichosporium OB3b

    PubMed Central

    Farhan Ul Haque, Muhammad; Kalidass, Bhagyalakshmi; Bandow, Nathan; Turpin, Erick A.; DiSpirito, Alan A.

    2015-01-01

    Methanotrophs have multiple methane monooxygenases that are well known to be regulated by copper, i.e., a “copper switch.” At low copper/biomass ratios the soluble methane monooxygenase (sMMO) is expressed while expression and activity of the particulate methane monooxygenase (pMMO) increases with increasing availability of copper. In many methanotrophs there are also multiple methanol dehydrogenases (MeDHs), one based on Mxa and another based on Xox. Mxa-MeDH is known to have calcium in its active site, while Xox-MeDHs have been shown to have rare earth elements in their active site. We show here that the expression levels of Mxa-MeDH and Xox-MeDH in Methylosinus trichosporium OB3b significantly decreased and increased, respectively, when grown in the presence of cerium but the absence of copper compared to the absence of both metals. Expression of sMMO and pMMO was not affected. In the presence of copper, the effect of cerium on gene expression was less significant, i.e., expression of Mxa-MeDH in the presence of copper and cerium was slightly lower than in the presence of copper alone, but Xox-MeDH was again found to increase significantly. As expected, the addition of copper caused sMMO and pMMO expression levels to significantly decrease and increase, respectively, but the simultaneous addition of cerium had no discernible effect on MMO expression. As a result, it appears Mxa-MeDH can be uncoupled from methane oxidation by sMMO in M. trichosporium OB3b but not from pMMO. PMID:26296730

  17. PURIFICATION OF PLUTONIUM USING A CERIUM PRECIPITATE AS A CARRIER FOR FISSION PRODUCTS

    DOEpatents

    Faris, B.F.; Olson, C.M.

    1961-07-01

    Bismuth phosphate carrier precipitation processes are described for the separation of plutonium from fission products wherein in at least one step bismuth phosphate is precipitated in the presence of hexavalent plutonium thereby carrying a portion of the fission products from soluble plu tonium values. In this step, a cerium phosphate precipitate is formed in conjunction with the bismuth phosphate precipitate, thereby increasing the amount of fission products removed from solution.

  18. Cerium regulates expression of alternative methanol dehydrogenases in Methylosinus trichosporium OB3b.

    PubMed

    Farhan Ul Haque, Muhammad; Kalidass, Bhagyalakshmi; Bandow, Nathan; Turpin, Erick A; DiSpirito, Alan A; Semrau, Jeremy D

    2015-11-01

    Methanotrophs have multiple methane monooxygenases that are well known to be regulated by copper, i.e., a "copper switch." At low copper/biomass ratios the soluble methane monooxygenase (sMMO) is expressed while expression and activity of the particulate methane monooxygenase (pMMO) increases with increasing availability of copper. In many methanotrophs there are also multiple methanol dehydrogenases (MeDHs), one based on Mxa and another based on Xox. Mxa-MeDH is known to have calcium in its active site, while Xox-MeDHs have been shown to have rare earth elements in their active site. We show here that the expression levels of Mxa-MeDH and Xox-MeDH in Methylosinus trichosporium OB3b significantly decreased and increased, respectively, when grown in the presence of cerium but the absence of copper compared to the absence of both metals. Expression of sMMO and pMMO was not affected. In the presence of copper, the effect of cerium on gene expression was less significant, i.e., expression of Mxa-MeDH in the presence of copper and cerium was slightly lower than in the presence of copper alone, but Xox-MeDH was again found to increase significantly. As expected, the addition of copper caused sMMO and pMMO expression levels to significantly decrease and increase, respectively, but the simultaneous addition of cerium had no discernible effect on MMO expression. As a result, it appears Mxa-MeDH can be uncoupled from methane oxidation by sMMO in M. trichosporium OB3b but not from pMMO. PMID:26296730

  19. Cerium Oxide Nanoparticles Reduce Microglial Activation and Neurodegenerative Events in Light Damaged Retina

    PubMed Central

    Fiorani, Lavinia; Passacantando, Maurizio; Santucci, Sandro; Di Marco, Stefano; Bisti, Silvia; Maccarone, Rita

    2015-01-01

    The first target of any therapy for retinal neurodegeneration is to slow down the progression of the disease and to maintain visual function. Cerium oxide or ceria nanoparticles reduce oxidative stress, which is known to play a pivotal role in neurodegeneration. Our aim was to investigate whether cerium oxide nanoparticles were able to mitigate neurodegeneration including microglial activation and related inflammatory processes induced by exposure to high intensity light. Cerium oxide nanoparticles were injected intravitreally or intraveinously in albino Sprague-Dawley rats three weeks before exposing them to light damage of 1000 lux for 24 h. Electroretinographic recordings were performed a week after light damage. The progression of retinal degeneration was evaluated by measuring outer nuclear layer thickness and TUNEL staining to quantify photoreceptors death. Immunohistochemical analysis was used to evaluate retinal stress, neuroinflammatory cytokines and microglial activation. Only intravitreally injected ceria nanoparticles were detected at the level of photoreceptor outer segments 3 weeks after the light damage and electoretinographic recordings showed that ceria nanoparticles maintained visual response. Moreover, this treatment reduced neuronal death and “hot spot” extension preserving the outer nuclear layer morphology. It is noteworthy that in this work we demonstrated, for the first time, the ability of ceria nanoparticles to reduce microglial activation and their migration toward outer nuclear layer. All these evidences support ceria nanoparticles as a powerful therapeutic agent in retinal neurodegenerative processes. PMID:26469804

  20. Cerium Biomagnification in a Terrestrial Food Chain: Influence of Particle Size and Growth Stage.

    PubMed

    Majumdar, Sanghamitra; Trujillo-Reyes, Jesica; Hernandez-Viezcas, Jose A; White, Jason C; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-07-01

    Mass-flow modeling of engineered nanomaterials (ENMs) indicates that a major fraction of released particles partition into soils and sediments. This has aggravated the risk of contaminating agricultural fields, potentially threatening associated food webs. To assess possible ENM trophic transfer, cerium accumulation from cerium oxide nanoparticles (nano-CeO2) and their bulk equivalent (bulk-CeO2) was investigated in producers and consumers from a terrestrial food chain. Kidney bean plants (Phaseolus vulgaris var. red hawk) grown in soil contaminated with 1000-2000 mg/kg nano-CeO2 or 1000 mg/kg bulk-CeO2 were presented to Mexican bean beetles (Epilachna varivestis), which were then consumed by spined soldier bugs (Podisus maculiventris). Cerium accumulation in plant and insects was independent of particle size. After 36 days of exposure to 1000 mg/kg nano- and bulk-CeO2, roots accumulated 26 and 19 μg/g Ce, respectively, and translocated 1.02 and 1.3 μg/g Ce, respectively, to shoots. The beetle larvae feeding on nano-CeO2 exposed leaves accumulated low levels of Ce since ∼98% of Ce was excreted in contrast to bulk-CeO2. However, in nano-CeO2 exposed adults, Ce in tissues was higher than Ce excreted. Additionally, Ce content in tissues was biomagnified by a factor of 5.3 from the plants to adult beetles and further to bugs.

  1. Application of Cerium (IV) as an Oxidimetric Agent for the Determination of Ethionamide in Pharmaceutical Formulations

    PubMed Central

    2016-01-01

    Two simple methods are described for the determination of ethionamide (ETM) in bulk drug and tablets using cerium (IV) sulphate as the oxidimetric agent. In both methods, the sample solution is treated with a measured excess of cerium (IV) solution in H2SO4 medium, and after a fixed standing time, the residual oxidant is determined either by back titration with standard iron (II) solution to a ferroin end point in titrimetry or by reacting with o-dianisidine followed by measurement of the absorbance of the orange-red coloured product at 470 nm in spectrophotometry. In titrimetry, the reaction proceeded with a stoichiometry of 1 : 2 (ETM : Ce (IV)) and the amount of cerium (IV) consumed by ETM was related to the latter's amount, and the method was applicable over 1.0–8.0 mg of drug. In spectrophotometry, Beer's law was obeyed over the concentration range of 0.5–5.0 μg/mL ETM with a molar absorptivity value of 2.66 × 104 L/(mol·cm). The limits of detection (LOD) and quantification (LOQ) calculated according to ICH guidelines were 0.013 and 0.043 μg/mL, respectively. The proposed titrimetric and spectrophotometric methods were found to yield reliable results when applied to bulk drug and tablets analysis, and hence they can be applied in quality control laboratories.

  2. Unveiling the mechanism of uptake and sub-cellular distribution of cerium oxide nanoparticles†

    PubMed Central

    Singh, Sanjay; Kumar, Amit; Karakoti, Ajay; Seal, Sudipta; Self, William T.

    2011-01-01

    Cerium oxide nanoparticles (CNPs) have been recently studied for their potent superoxide scavenging properties in both cell and animal model systems. Data from these model systems have shown that exposure of cells to CNPs results in the protection against reactive oxygen species (ROS). Despite these exciting findings, very little is known regarding the uptake or subcellular distribution of these nanomaterials inside cells. In this study we utilized fluorophore (carboxyfluorescein) conjugated cerium oxide NPs (CCNPs) to study the mechanism of uptake and to elucidate the subcellular localization of CNPs using a keratinocyte model system. We observed rapid uptake (within 3 h) of CCNPs that was governed by energy-dependent, clathrin-mediated and caveolae-mediated endocytic pathways. We found CCNPs co-localized with mitochondria, lysosomes and endoplasmic reticulum as well as being abundant in the cytoplasm and the nucleus. Given the radical scavenging properties of cerium oxide and the widespread cellular disposition we observed, CNPs likely act as cellular antioxidants in multiple compartments of the cell imparting protection against a variety of oxidant injuries. PMID:20697616

  3. The role of hydrogen peroxide in the deposition of cerium-based conversion coatings

    NASA Astrophysics Data System (ADS)

    Scholes, F. H.; Soste, C.; Hughes, A. E.; Hardin, S. G.; Curtis, P. R.

    2006-12-01

    Cerium-based conversion coatings are progressing as an effective alternative to hazardous chromate-based systems used in the treatment of metal surfaces. However, there is still considerable debate over the mechanism by which these coatings are formed. Here, titrations of cerium-based conversion coating solutions were carried out in order to model the reactions that occur at the metal-solution interface during coating, with a particular emphasis on investigating the role of hydrogen peroxide (H 2O 2). The titration curves obtained support the proposed formation of Ce(III) peroxo complexes such as Ce(H 2O 2) 3+ as an initial step, followed by deprotonation, oxidation and precipitation to form peroxo-containing Ce(IV) species such as Ce (IV)(O 2)(OH) 2. The precipitates resulting from titrations were characterised by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis, confirming the presence of peroxo bonds, and nano-sized CeO 2 crystallites that decreased in size with increasing H 2O 2 concentration. Characterisation of cerium conversion coatings on aluminium alloy surfaces confirmed the presence of peroxo species in the coatings, thereby supporting the titration model.

  4. Aqueous Co-precipitation of Pd-doped Cerium Oxide Nanoparticles: Chemistry Structure and Particle Growth

    SciTech Connect

    Liang H.; Zhang L.; Raitano J.M.; He G.; Akey A.J.; Herman I.P.; Chan S.-W.

    2012-01-01

    Nanoparticles of palladium-doped cerium oxide (Pd-CeO{sub 2}) have been prepared by aqueous co-precipitation resulting in a single phase cubic structure after calcination according to X-ray diffraction (XRD). Inhomogeneous strain, calculated using the Williamson-Hall method, was found to increase with palladium content, and the lattice contracts slightly, relative to nano-cerium oxide, as palladium content is increased. Moreover, high resolution transmission electron microscopy reveals some instances of defective microstructure. These factors combined imply that palladium is in solid solution with CeO{sub 2} in these nanoparticles, but palladium (II) oxide (PdO) peaks in the Raman spectra indicate that solid solution formation is partial and that highly dispersed PdO is present as well as the solid solution. Nevertheless, the addition of palladium to the CeO{sub 2} lattice inhibits the growth of the 6% Pd-CeO{sub 2} particles compared to pure CeO{sub 2} between 600 and 850 C. Activation energies for grain growth of 54 {+-} 7 and 79 {+-} 8 kJ/mol were determined for 6% Pd-CeO{sub 2} and pure CeO{sub 2}, respectively, along with pre-exponential Arrhenius factors of 10 for the doped sample and 600 for pure cerium oxide.

  5. Cerium, gallium and zinc containing mesoporous bioactive glass coating deposited on titanium alloy

    NASA Astrophysics Data System (ADS)

    Shruti, S.; Andreatta, F.; Furlani, E.; Marin, E.; Maschio, S.; Fedrizzi, L.

    2016-08-01

    Surface modification is one of the methods for improving the performance of medical implants in biological environment. In this study, cerium, gallium and zinc substituted 80%SiO2-15%CaO-5%P2O5 mesoporous bioactive glass (MBG) in combination with polycaprolactone (PCL) were coated over Ti6Al4 V substrates by dip-coating method in order to obtain an inorganic-organic hybrid coating (MBG-PCL). Structural characterization was performed using XRD, nitrogen adsorption, SEM-EDXS, FTIR. The MBG-PCL coating uniformly covered the substrate with the thickness found to be more than 1 μm. Glass and polymer phases were detected in the coating along with the presence of biologically potent elements cerium, gallium and zinc. In addition, in vitro bioactivity was investigated by soaking the coated samples in simulated body fluid (SBF) for up to 30 days at 37 °C. The apatite-like layer was monitored by FTIR, SEM-EDXS and ICP measurements and it formed in all the samples within 15 days except zinc samples. In this way, an attempt was made to develop a new biomaterial with improved in vitro bioactive response due to bioactive glass coating and good mechanical strength of Ti6Al4 V alloy along with inherent biological properties of cerium, gallium and zinc.

  6. Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework.

    PubMed

    Bogart, Justin A; Lippincott, Connor A; Carroll, Patrick J; Booth, Corwin H; Schelter, Eric J

    2015-12-01

    Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C6 H4 CH2 )3 N](3-) (TriNOx (3-) ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNOx )thf][BAr(F) 4 ], in which Ar(F) =3,5-(CF3 )2 -C6 H3 , and [Ce(TriNOx )py][OTf]. A rare complete Ce-halide series, Ce(TriNOx )X, in which X=F(-) , Cl(-) , Br(-) , I(-) , was also synthesized. The solution chemistry of these complexes was explored through detailed solution-phase electrochemistry and (1) H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X(-) group. DFT calculations on the series of calculations corroborated the experimental findings.

  7. Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

    NASA Astrophysics Data System (ADS)

    Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

    2016-07-01

    The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Sisbnd Osbnd Si and Sisbnd Osbnd M chemical bonds. The optimum corrosion resistance of the coating in the corrosive media is obtained by 25 ml L-1 BTESPT modification. This whole study implies that the cerium conversion coating modified with certain silane agent deserves cautiousness before its application for corrosion resistance.

  8. 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

  9. 76 FR 46907 - Ammonium Nitrate Security Program

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-03

    ... Federal Bureau of Investigation FR Federal Register HMR Hazardous Materials Regulations HMT Hazardous... ``Secure Handling of Ammonium Nitrate Program'' on October 29, 2008. See 73 FR 64280. The ANPRM solicited... interacting with state and local governments regarding ammonium nitrate security. ] See 73 FR 64280,...

  10. Dietary Nitrate, Nitric Oxide, and Cardiovascular Health.

    PubMed

    Bondonno, Catherine P; Croft, Kevin D; Hodgson, Jonathan M

    2016-09-01

    Emerging evidence strongly suggests that dietary nitrate, derived in the diet primarily from vegetables, could contribute to cardiovascular health via effects on nitric oxide (NO) status. NO plays an essential role in cardiovascular health. It is produced via the classical L-arginine-NO-synthase pathway and the recently discovered enterosalivary nitrate-nitrite-NO pathway. The discovery of this alternate pathway has highlighted dietary nitrate as a candidate for the cardioprotective effect of a diet rich in fruit and vegetables. Clinical trials with dietary nitrate have observed improvements in blood pressure, endothelial function, ischemia-reperfusion injury, arterial stiffness, platelet function, and exercise performance with a concomitant augmentation of markers of NO status. While these results are indicative of cardiovascular benefits with dietary nitrate intake, there is still a lingering concern about nitrate in relation to methemoglobinemia, cancer, and cardiovascular disease. It is the purpose of this review to present an overview of NO and its critical role in cardiovascular health; to detail the observed vascular benefits of dietary nitrate intake through effects on NO status as well as to discuss the controversy surrounding the possible toxic effects of nitrate.

  11. Intravesical silver nitrate for refractory hemorrhagic cystitis

    PubMed Central

    Montgomery, Brian D.; Boorjian, Stephen A.; Ziegelmann, Matthew J.; Joyce, Daniel D.; Linder, Brian J.

    2016-01-01

    Objective Hemorrhagic cystitis is a challenging clinical entity with limited evidence available to guide treatment. The use of intravesical silver nitrate has been reported, though supporting literature is sparse. Here, we sought to assess outcomes of patients treated with intravesical silver nitrate for refractory hemorrhagic cystitis. Material and methods We identified nine patients with refractory hemorrhagic cystitis treated at our institution with intravesical silver nitrate between 2000–2015. All patients had failed previous continuous bladder irrigation with normal saline and clot evacuation. Treatment success was defined as requiring no additional therapy beyond normal saline irrigation after silver nitrate instillation prior to hospital discharge. Results Median patient age was 80 years (IQR 73, 82). Radiation was the most common etiology for hemorrhagic cystitis 89% (8/9). Two patients underwent high dose (0.1%–0.4%) silver nitrate under anesthesia, while the remaining seven were treated with doses from 0.01% to 0.1% via continuous bladder irrigation for a median of 3 days (range 2–4). All nine patients (100%) had persistent hematuria despite intravesical silver nitrate therapy, requiring additional interventions and red blood cell transfusion during the hospitalization. There were no identified complications related to intravesical silver nitrate instillation. Conclusion Although well tolerated, we found that intravesical silver nitrate was ineffective for bleeding control, suggesting a limited role for this agent in the management of patients with hemorrhagic cystitis.

  12. COMPARTMENTAL MODEL OF NITRATE RETENTION IN STREAMS

    EPA Science Inventory

    A compartmental modeling approach is presented to route nitrate retention along a cascade of stream reach sections. A process transfer function is used for transient storage equations with first order reaction terms to represent nitrate uptake in the free stream, and denitrifica...

  13. Intravesical silver nitrate for refractory hemorrhagic cystitis

    PubMed Central

    Montgomery, Brian D.; Boorjian, Stephen A.; Ziegelmann, Matthew J.; Joyce, Daniel D.; Linder, Brian J.

    2016-01-01

    Objective Hemorrhagic cystitis is a challenging clinical entity with limited evidence available to guide treatment. The use of intravesical silver nitrate has been reported, though supporting literature is sparse. Here, we sought to assess outcomes of patients treated with intravesical silver nitrate for refractory hemorrhagic cystitis. Material and methods We identified nine patients with refractory hemorrhagic cystitis treated at our institution with intravesical silver nitrate between 2000–2015. All patients had failed previous continuous bladder irrigation with normal saline and clot evacuation. Treatment success was defined as requiring no additional therapy beyond normal saline irrigation after silver nitrate instillation prior to hospital discharge. Results Median patient age was 80 years (IQR 73, 82). Radiation was the most common etiology for hemorrhagic cystitis 89% (8/9). Two patients underwent high dose (0.1%–0.4%) silver nitrate under anesthesia, while the remaining seven were treated with doses from 0.01% to 0.1% via continuous bladder irrigation for a median of 3 days (range 2–4). All nine patients (100%) had persistent hematuria despite intravesical silver nitrate therapy, requiring additional interventions and red blood cell transfusion during the hospitalization. There were no identified complications related to intravesical silver nitrate instillation. Conclusion Although well tolerated, we found that intravesical silver nitrate was ineffective for bleeding control, suggesting a limited role for this agent in the management of patients with hemorrhagic cystitis. PMID:27635296

  14. NITRATE CONTAMINATION OF GROUND WATER (GW-761)

    EPA Science Inventory

    The occurrence of nitrate and related compounds in ground water is discussed from the perspectives of its natural as well as anthropogenic origins. A brief explanation of the nitrogen cycle touches on the production as well as utilization of ammonia, nitrite, nitrate, and nitrog...

  15. The contributions of nitrate uptake and efflux to isotope fractionation during algal nitrate assimilation

    NASA Astrophysics Data System (ADS)

    Karsh, K. L.; Trull, T. W.; Sigman, D. M.; Thompson, P. A.; Granger, J.

    2014-05-01

    In order to strengthen environmental application of nitrate N and O isotopes, we measured the N and O isotopic fractionation associated with cellular nitrate uptake and efflux in the nitrate-assimilating marine diatom Thalassiosira weissflogii. We isolated nitrate uptake and efflux from nitrate reduction by growing the cells in the presence of tungsten, which substitutes for molybdenum in assimilatory nitrate reductase, yielding an inactive enzyme. After growth on ammonium and then N starvation, cells were exposed to nitrate. Numerical models fit to the evolution of intracellular nitrate concentration and N and O isotopic composition yielded distinct N isotope effects (15ɛ) for nitrate uptake and nitrate efflux (2.0 ± 0.3‰ and 1.2 ± 0.4‰, respectively). The O isotope effects (18ɛ) for nitrate uptake and nitrate efflux were indistinguishable (2.8 ± 0.6‰), yielding a ratio of O to N isotopic fractionation for uptake of 1.4 ± 0.4 and for efflux of 2.3 ± 0.9. The 15ɛ for nitrate uptake can account for at most 40% of the organism-level N isotope effect (15ɛorg) measured in laboratory studies of T. weissflogii and in the open ocean (typically 5‰ or greater). This observation supports previous evidence that most isotope fractionation during nitrate assimilation is due to intracellular nitrate reduction, with nitrate efflux allowing the signal to be communicated to the environment. An O to N fractionation ratio (18ɛorg:15ɛorg) of ˜1 has been measured for nitrate assimilation in algal cultures and linked to the N and O isotope effects of nitrate reductase. Our results suggest that the ratios of O to N fractionation for both nitrate uptake and efflux may be distinct from a ratio of 1, to a degree that could cause the net 18ɛorg:15ɛorg to rise appreciably above 1 when 15ɛorg is low (e.g., yielding a ratio of 1.1 when 15ɛorg is 5‰). However, field and culture studies have consistently measured nearly equivalent fractionation of N and O isotopes in

  16. PREPARATION OF DIBASIC ALUMINUM NITRATE

    DOEpatents

    Gresky, A.T.; Nurmi, E.O.; Foster, D.L.; Wischow, R.P.; Savolainen, J.E.

    1960-04-01

    A method is given for the preparation and recovery of basic aluminum nltrates having an OH: Al ratio of at least two, comprising two steps. First, metallic aluminum is dissolved in aqueous Al(NO/sub 3/)/sub 3/, in the presence of a small quantity of elemental or ionic mercury, to increase its Al: NO/sub 3/ ratio into the range 1 to 1.2. The resulting aqueous solution is then added to an excess of a special organic solvent, typically a mixture of five parts methanol and six parts diethyl ether, whereupon the basic aluminum nitrate, e.g. Al/sub 6/(OH)/sub 13/-(NO/sub 3/)/sub 5/, recoverably precipitates.

  17. Phase diagram of ammonium nitrate.

    PubMed

    Dunuwille, Mihindra; Yoo, Choong-Shik

    2013-12-01

    Ammonium Nitrate (AN) is a fertilizer, yet becomes an explosive upon a small addition of chemical impurities. The origin of enhanced chemical sensitivity in impure AN (or AN mixtures) is not well understood, posing significant safety issues in using AN even today. To remedy the situation, we have carried out an extensive study to investigate the phase stability of AN and its mixtures with hexane (ANFO-AN mixed with fuel oil) and Aluminum (Ammonal) at high pressures and temperatures, using diamond anvil cells (DAC) and micro-Raman spectroscopy. The results indicate that pure AN decomposes to N2, N2O, and H2O at the onset of the melt, whereas the mixtures, ANFO and Ammonal, decompose at substantially lower temperatures. The present results also confirm the recently proposed phase IV-IV' transition above 17 GPa and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400°C.

  18. Phase diagram of ammonium nitrate

    NASA Astrophysics Data System (ADS)

    Dunuwille, Mihindra; Yoo, Choong-Shik

    2013-12-01

    Ammonium Nitrate (AN) is a fertilizer, yet becomes an explosive upon a small addition of chemical impurities. The origin of enhanced chemical sensitivity in impure AN (or AN mixtures) is not well understood, posing significant safety issues in using AN even today. To remedy the situation, we have carried out an extensive study to investigate the phase stability of AN and its mixtures with hexane (ANFO-AN mixed with fuel oil) and Aluminum (Ammonal) at high pressures and temperatures, using diamond anvil cells (DAC) and micro-Raman spectroscopy. The results indicate that pure AN decomposes to N2, N2O, and H2O at the onset of the melt, whereas the mixtures, ANFO and Ammonal, decompose at substantially lower temperatures. The present results also confirm the recently proposed phase IV-IV' transition above 17 GPa and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400°C.

  19. Nitrate removal from drinking water -- Review

    SciTech Connect

    Kapoor, A.; Viraraghavan, T.

    1997-04-01

    Nitrate concentrations in surface water and especially in ground water have increased in Canada, the US, Europe, and other areas of the world. This trend has raised concern because nitrates cause methemoglobiinemia in infants. Several treatment processes including ion exchange, biological denitrification, chemical denitrification, reverse osmosis, electrodialysis, and catalytic denitrification can remove nitrates from water with varying degrees of efficiency, cost, and ease of operation. Available technical data, experience, and economics indicate that ion exchange and biological denitrification are more acceptable for nitrate removal than reverse osmosis. Ion exchange is more viable for ground water while biological denitrification is the preferred alternative for surface water. This paper reviews the developments in the field of nitrate removal processes.

  20. Use of nitrates in ischemic heart disease.

    PubMed

    Giuseppe, Cocco; Paul, Jerie; Hans-Ulrich, Iselin

    2015-01-01

    Short-acting nitrates are beneficial in acute myocardial ischemia. However, many unresolved questions remain about the use of long-acting nitrates in stable ischemic heart disease. The use of long-acting nitrates is weakened by the development of endothelial dysfunction and tolerance. Also, we currently ignore whether lower doses of transdermal nitroglycerin would be better than those presently used. Multivariate analysis data from large nonrandomized studies suggested that long-acting nitrates increase the incidence of acute coronary syndromes, while data from another multivariate study indicate that they have positive effects. Because of methodological differences and open questions, the two studies cannot be compared. A study in Japanese patients with vasospastic angina has shown that, when compared with calcium antagonists, long-acting nitrates do not improve long-term prognosis and that the risk for cardiac adverse events increases with the combined therapy. We have many unanswered questions.

  1. Dietary nitrates, nitrites, and cardiovascular disease.

    PubMed

    Hord, Norman G

    2011-12-01

    Dietary nitrate (NO(3)), nitrite (NO(2)), and arginine can serve as sources for production of NO(x) (a diverse group of metabolites including nitric oxide, nitrosothiols, and nitroalkenes) via ultraviolet light exposure to skin, mammalian nitrate/nitrite reductases in tissues, and nitric oxide synthase enzymes, respectively. NO(x) are responsible for the hypotensive, antiplatelet, and cytoprotective effects of dietary nitrates and nitrites. Current regulatory limits on nitrate intakes, based on concerns regarding potential risk of carcinogenicity and methemoglobinemia, are exceeded by normal daily intakes of single foods, such as soya milk and spinach, as well as by some recommended dietary patterns such as the Dietary Approaches to Stop Hypertension diet. This review includes a call for regulatory bodies to consider all available data on the beneficial physiologic roles of nitrate and nitrite in order to derive rational bases for dietary recommendations.

  2. 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. PMID:27340495

  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. 70. INTERIOR VIEW OF AMMONIUM NITRATE HOUSE, LOOKING AT AMMONIUM ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    70. INTERIOR VIEW OF AMMONIUM NITRATE HOUSE, LOOKING AT AMMONIUM NITRATE IN STORAGE. APRIL 18, 1919. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  5. Nitrate Transport, Sensing, and Responses in Plants.

    PubMed

    O'Brien, José A; Vega, Andrea; Bouguyon, Eléonore; Krouk, Gabriel; Gojon, Alain; Coruzzi, Gloria; Gutiérrez, Rodrigo A

    2016-06-01

    Nitrogen (N) is an essential macronutrient that affects plant growth and development. N is an important component of chlorophyll, amino acids, nucleic acids, and secondary metabolites. Nitrate is one of the most abundant N sources in the soil. Because nitrate and other N nutrients are often limiting, plants have developed sophisticated mechanisms to ensure adequate supply of nutrients in a variable environment. Nitrate is absorbed in the root and mobilized to other organs by nitrate transporters. Nitrate sensing activates signaling pathways that impinge upon molecular, metabolic, physiological, and developmental responses locally and at the whole plant level. With the advent of genomics technologies and genetic tools, important advances in our understanding of nitrate and other N nutrient responses have been achieved in the past decade. Furthermore, techniques that take advantage of natural polymorphisms present in divergent individuals from a single species have been essential in uncovering new components. However, there are still gaps in our understanding of how nitrate signaling affects biological processes in plants. Moreover, we still lack an integrated view of how all the regulatory factors identified interact or crosstalk to orchestrate the myriad N responses plants typically exhibit. In this review, we provide an updated overview of mechanisms by which nitrate is sensed and transported throughout the plant. We discuss signaling components and how nitrate sensing crosstalks with hormonal pathways for developmental responses locally and globally in the plant. Understanding how nitrate impacts on plant metabolism, physiology, and growth and development in plants is key to improving crops for sustainable agriculture. PMID:27212387

  6. Nitrate Transport, Sensing, and Responses in Plants.

    PubMed

    O'Brien, José A; Vega, Andrea; Bouguyon, Eléonore; Krouk, Gabriel; Gojon, Alain; Coruzzi, Gloria; Gutiérrez, Rodrigo A

    2016-06-01

    Nitrogen (N) is an essential macronutrient that affects plant growth and development. N is an important component of chlorophyll, amino acids, nucleic acids, and secondary metabolites. Nitrate is one of the most abundant N sources in the soil. Because nitrate and other N nutrients are often limiting, plants have developed sophisticated mechanisms to ensure adequate supply of nutrients in a variable environment. Nitrate is absorbed in the root and mobilized to other organs by nitrate transporters. Nitrate sensing activates signaling pathways that impinge upon molecular, metabolic, physiological, and developmental responses locally and at the whole plant level. With the advent of genomics technologies and genetic tools, important advances in our understanding of nitrate and other N nutrient responses have been achieved in the past decade. Furthermore, techniques that take advantage of natural polymorphisms present in divergent individuals from a single species have been essential in uncovering new components. However, there are still gaps in our understanding of how nitrate signaling affects biological processes in plants. Moreover, we still lack an integrated view of how all the regulatory factors identified interact or crosstalk to orchestrate the myriad N responses plants typically exhibit. In this review, we provide an updated overview of mechanisms by which nitrate is sensed and transported throughout the plant. We discuss signaling components and how nitrate sensing crosstalks with hormonal pathways for developmental responses locally and globally in the plant. Understanding how nitrate impacts on plant metabolism, physiology, and growth and development in plants is key to improving crops for sustainable agriculture.

  7. Grain Growth Behavior, Tensile Impact Ductility, and Weldability of Cerium-Doped Iridium Alloys

    SciTech Connect

    McKamey, C.G.

    2002-05-28

    An iridium alloy doped with small amounts of cerium and thorium is being developed as a potential replacement for the iridium-based DOP-26 alloy (doped with thorium only) that is currently used by the National Aeronautics and Space Administration (NASA) for cladding and post-impact containment of the radioactive fuel in radioisotope thermoelectric generator (RTG) heat sources which provide electric power for interplanetary spacecraft. This report summarizes results of studies conducted to date under the Iridium Alloy Characterization and Development subtask of the Radioisotope Power System Materials Production and Technology Program to characterize the properties of the iridium-based alloy (designated as DOP-40) containing both cerium and thorium. Included within this report are data on grain growth of sheet material in vacuum and low-pressure oxygen environments, grain growth in vacuum of the clad vent set cup material, weldability, and the effect of grain size and test temperature on tensile properties. Where applicable, data for the DOP-26 alloy are included for comparison. Both grain size and grain-boundary cohesion affect the ductility of iridium alloys. In this study it was found that cerium and thorium, when added together, refine grain size more effectively than when thorium is added by itself (especially at high temperatures). In addition, the effect of cerium additions on grain-boundary cohesion is similar to that of thorium. Mechanical testing at both low ({approx} 10{sup -3}s{sup -1}) and high ({approx} 10{sup -3}s{sup -1}) strain rates showed that the Ce/Th-doped alloys have tensile ductilities that are as good or better than the DOP-26 alloy. The general conclusion from these studies is that cerium can be used to replace some of the radioactive thorium currently used in DOP-26 while maintaining or improving its metallurgical properties. The current DOP-26 alloy meets all requirements for cladding the radioactive fuel in the RTG heat source, but the

  8. Using cerium anomaly as an indicator of redox reactions in constructed wetland

    NASA Astrophysics Data System (ADS)

    Liang, R.

    2013-12-01

    dissolved oxygen (5 ppm) but the NH4 content is still high, which indicates a non-equilibrium condition. In this study, the cerium anomaly is alternatively utilized to evaluate the water redox state. The results demonstrate that the input water has the negative cerium anomaly of -0.16. Along the flow path, the cerium negative anomaly does not change in the first two cells and dramatically becomes -0.23 in cell 3. The trend of cerium anomaly is more close to the removal efficiency of NH4 rather than dissolve oxygen. Accordingly, cerium anomaly could become a better indicator of removal efficiency of constructed wetland.

  9. Self-poled transparent and flexible UV light-emitting cerium complex-PVDF composite: a high-performance nanogenerator.

    PubMed

    Garain, Samiran; Sinha, Tridib Kumar; Adhikary, Prakriti; Henkel, Karsten; Sen, Shrabanee; Ram, Shanker; Sinha, Chittaranjan; Schmeißer, Dieter; Mandal, Dipankar

    2015-01-21

    Cerium(III)-N,N-dimethylformamide-bisulfate [Ce(DMF)(HSO4)3] complex is doped into poly(vinylidene fluoride) (PVDF) to induce a higher yield (99%) of the electroactive phases (β- and γ-phases) of PVDF. A remarkable enhancement of the output voltage (∼32 V) of a nanogenerator (NG) based on a nonelectrically poled cerium(III) complex containing PVDF composite film is achieved by simple repeated human finger imparting, whereas neat PVDF does not show this kind of behavior. This high electrical output resembles the generation of self-poled electroactive β-phase in PVDF due to the electrostatic interactions between the fluoride of PVDF and the surface-active positive charge cloud of the cerium complex via H-bonding and/or bipolar interaction among the opposite poles of cerium complex and PVDF, respectively. The capacitor charging capability of the flexible NG promises its applicability as piezoelectric-based energy harvester. The cerium(III) complex doped PVDF composite film exhibit an intense photoluminescence in the UV region, which might be due to a participation of electron cloud from negative pole of bipolarized PVDF. This fact may open a new area for prospective development of high-performance energy-saving flexible solid-state UV light emitters. PMID:25523039

  10. Cyanex 923 as the extractant in a rare earth element impurity analysis of high-purity cerium oxide.

    PubMed

    Duan, Taicheng; Li, Hongfei; Kang, JianZhen; Chen, Hangting

    2004-06-01

    In this work, the feasibility of employing Cyanex 923 as an extractant into the non-cerium REE (rare earth elements) impurity analysis of high-purity cerium oxide was investigated. Through investigations on the choice of the extraction medium, the optimium extraction acidity, matrix Ce4+ effect on the non-cerium REE ion extraction, the optimium extractant concentration and suitable extracting time, and oscillation strengh, it was found that when the phase ratio was at 1:1 and the acicidity was about 2% H2SO4, by gently shaking by hand for about 2 min, 10 mL of 30% Cyanex 923 could not extract even for a 20 ng amount of non-cerium REE3+ ions. However, the extraction efficiency for Ce4+ of 100 mg total amount under the same conditions was about 96%, indicating that a 25-fold preconcentration factor could be achieved. Thus, it was concluded that Cyanex 923 could be used in a REE impurity analysis of 99.9999% or so pure cerium oxide for primary sepapation to elimilate matrix-induced interferences encountered in an ICP-MS (inductively coupled plasma mass spectroscopy) determination.

  11. Modeling nitrate removal in a denitrification bed.

    PubMed

    Ghane, Ehsan; Fausey, Norman R; Brown, Larry C

    2015-03-15

    Denitrification beds are promoted to reduce nitrate load in agricultural subsurface drainage water to alleviate the adverse environmental effects associated with nitrate pollution of surface water. In this system, drainage water flows through a trench filled with a carbon media where nitrate is transformed into nitrogen gas under anaerobic conditions. The main objectives of this study were to model a denitrification bed treating drainage water and evaluate its adverse greenhouse gas emissions. Field experiments were conducted at an existing denitrification bed. Evaluations showed very low greenhouse gas emissions (mean N2O emission of 0.12 μg N m(-2) min(-1)) from the denitrification bed surface. Field experiments indicated that nitrate removal rate was described by Michaelis-Menten kinetics with the Michaelis-Menten constant of 7.2 mg N L(-1). We developed a novel denitrification bed model based on the governing equations for water flow and nitrate removal kinetics. The model evaluation statistics showed satisfactory prediction of bed outflow nitrate concentration during subsurface drainage flow. The model can be used to design denitrification beds with efficient nitrate removal which in turn leads to enhanced drainage water quality. PMID:25638338

  12. Synthesis of Nitrate Reductase in Chlorella

    PubMed Central

    Funkhouser, Edward A.; Shen, Teh-Chien; Ackermann, Renate

    1980-01-01

    Synthesis of nitrate reductase (EC 1.6.6.1) in Chlorella vulgaris was studied under inducing conditions, i.e. with cells grown on ammonia and then transferred to nitrate medium. Cycloheximide (but not chloramphenicol) completely inhibited synthesis of the enzyme, but only if it was added at the start (i.e. at the time of nitrate addition) of the induction period. Cycloheximide inhibition became less effective as induction by nitrate proceeded. Enzyme from small quantities of culture (1 to 3 milliliters of packed cells) was purified to homogeneity with the aid of blue dextran-Sepharose chromatography. Incorporation of radioactivity from labeled arginine into nitrate reductase was measured in the presence and absence of cycloheximide. Conditions were found under which the inhibitor completely blocked the incorporation of labeled amino acid, but only slightly decreased the increase in nitrate reductase activity. The results indicate that synthesis of nitrate reductase from amino acids proceeds by way of a protein precursor which is inactive enzymically. PMID:16661310

  13. Microbial Uranium Immobilization Independent of Nitrate Reduction

    SciTech Connect

    Madden, Andrew; Smith, April; Balkwill, Dr. David; Fagan, Lisa Anne; Phelps, Tommy Joe

    2007-01-01

    At many uranium processing and handling facilities, including sites in the U.S. Department of Energy (DOE) complex, high levels of nitrate are present as co-contamination with uranium in groundwater. The daunting prospect of complete nitrate removal prior to the reduction of uranium provides a strong incentive to explore bioremediation strategies that allow for uranium bioreduction and stabilization in the presence of nitrate. Typical in-situ strategies involving the stimulation of metal-reducing bacteria are hindered by low pH environments at this study site and require that the persistent nitrate must first and continuously be removed or transformed prior to uranium being a preferred electron acceptor. This project investigates the possibility of stimulating nitrate-indifferent, pH-tolerant microorganisms to achieve bioreduction of U(VI) despite nitrate persistence. Successful enrichments from U-contaminated sediments demonstrated nearly complete reduction of uranium with very little loss of nitrate from pH 4.9-5.6 using methanol or glycerol as a carbon source. Higher pH enrichments also demonstrated similar U reduction capacity with 5-30% nitrate loss within one week. Bacterial 16S rRNA genes were amplified from uranium-reducing enrichments (pH 5.7-6.7) and sequenced. Phylogenetic analyses classified the clone sequences into four distinct clusters. Data from sequencing and T-RFLP profiles indicated that the majority of the microorganisms stimulated by these enrichment conditions consisted of low G+C Gram-positive bacteria most closely related to Clostridium and Clostridium-like organisms. This research demonstrates that the stimulation of a natural microbial community to immobilize U through bioreduction is possible without the removal of nitrate.

  14. Measurement and Chemistry of Atmospheric Organic Nitrates

    NASA Astrophysics Data System (ADS)

    Buhr, Martin Patrick

    1990-01-01

    Organic nitrates are important reservoir species for NO_{rm x} (NO + NO_2) in the atmosphere. Typically formed in and around urban areas, the organic nitrates sequester NO_{rm x} and allow it to be transported to rural and remote regions, wherein it may be released into the atmosphere and participate in catalytic cycles leading to the formation of ozone. The research described in this work focusses on two problems related to our understanding of the atmospheric chemistry of the organic nitrates, (1) measuring the organic nitrates contributions to total reactive nitrogen (NO_ {rm y}) in the atmosphere, and (2) determining the conditions under which the organic nitrates release NO_{rm x} into the atmosphere and thereby participate in ozone formation. The work performed included development of measurement methods for the organic nitrates, ambient measurements of several organic nitrates made under a variety of conditions, and data interpretation using a combination of bivariate and multivariate analysis. The instrument development that was performed centered around incorporation of capillary column technology in a gas chromatographic method. Use of a capillary column resulted in improved chromatographic resolution and instrument sensitivity. In addition to the work on the chromatographic separation of the organic nitrates, some work was done regarding the sensitivity of the electron capture detector (ECD) as a function of electrical mode of operation. Ambient measurements of several of the organic nitrates were made during three field experiments in conjunction with NOAA's Aeronomy laboratory, including PAN rm CH_3C(O)O_2NO_2), PPN rm (C_2H_5C(O)O_2NO _2), and the C_1-C _5 alkyl nitrates (RONO_2 ). The measurements were made in conjunction with a wide variety of other chemical and physical parameters. Data interpretation was performed using bivariate analysis in order to understand the diurnal variation of the concentrations of the organic nitrates and their

  15. Photodegradation of Paracetamol in Nitrate Solution

    SciTech Connect

    Meng Cui; Qu Ruijuan; Liang Jinyan; Yang Xi

    2010-11-24

    The photodegradation of paracetamol in nitrate solution under simulated solar irradiation has been investigated. The degradation rates were compared by varying environmental parameters including concentrations of nitrate ion, humic substance and pH values. The quantifications of paracetamol were conducted by HPLC method. The results demonstrate that the photodegradation of paracetamol followed first-order kinetics. The photoproducts and intermediates of paracetamol in the presence of nitrate ions were identified by extensive GC-MS method. The photodegradation pathways involving. OH radicals as reactive species were proposed.

  16. Phase diagram of ammonium nitrate

    SciTech Connect

    Dunuwille, Mihindra; Yoo, Choong-Shik

    2013-12-07

    Ammonium Nitrate (AN) is a fertilizer, yet becomes an explosive upon a small addition of chemical impurities. The origin of enhanced chemical sensitivity in impure AN (or AN mixtures) is not well understood, posing significant safety issues in using AN even today. To remedy the situation, we have carried out an extensive study to investigate the phase stability of AN and its mixtures with hexane (ANFO–AN mixed with fuel oil) and Aluminum (Ammonal) at high pressures and temperatures, using diamond anvil cells (DAC) and micro-Raman spectroscopy. The results indicate that pure AN decomposes to N{sub 2}, N{sub 2}O, and H{sub 2}O at the onset of the melt, whereas the mixtures, ANFO and Ammonal, decompose at substantially lower temperatures. The present results also confirm the recently proposed phase IV-IV{sup ′} transition above 17 GPa and provide new constraints for the melting and phase diagram of AN to 40 GPa and 400°C.

  17. Peroxyacetyl nitrate in eastern Scotland.

    PubMed

    McFadyen, G G; Cape, J N

    2005-01-20

    Peroxyacetyl nitrate (PAN) concentrations in air were sampled hourly from 1994 to 1998 at a rural site 15 km south-west of Edinburgh, in eastern Scotland. Annual average concentrations were between 0.1 and 0.15 nl l(-1), with episodes up to 3 nl l(-1) in long-range transported polluted air. PAN concentrations were approximately log-normally distributed. The concentrations measured are the result of a balance between photochemical production rates and removal by thermal decomposition and dry deposition. In general, there was a poor correlation between PAN and ozone concentrations at this rural site except during episodes of photochemical pollution, when the PAN/O(3) volume ratio exceeded 0.01. The PAN/NO(x) volume ratio had a median value of 0.015 but ranged up to 0.25. There was a pronounced seasonal maximum in PAN concentrations in late spring, and a strong diurnal cycle only in April-June, with a maximum at 1700 h. Individual episodes, with concentrations up to 3 nl l(-1), could be traced over distances of ca. 1000 km, with rapid changes in concentration as the prevailing winds advected polluted air masses across the site.

  18. Implementation of a complex multi-phase equation of state for cerium and its correlation with experiment

    SciTech Connect

    Cherne, Frank J; Jensen, Brian J; Elkin, Vyacheslav M

    2009-01-01

    The complexity of cerium combined with its interesting material properties makes it a desirable material to examine dynamically. Characteristics such as the softening of the material before the phase change, low pressure solid-solid phase change, predicted low pressure melt boundary, and the solid-solid critical point add complexity to the construction of its equation of state. Currently, we are incorporating a feedback loop between a theoretical understanding of the material and an experimental understanding. Using a model equation of state for cerium we compare calculated wave profiles with experimental wave profiles for a number of front surface impact (cerium impacting a plated window) experiments. Using the calculated release isentrope we predict the temperature of the observed rarefaction shock. These experiments showed that the release state occurs at different magnitudes, thus allowing us to infer where dynamic {gamma} - {alpha} phase boundary is.

  19. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    SciTech Connect

    Samin, Adib; Li, Xiang; Zhang, Jinsuo; Mariani, R. D.; Unal, Cetin

    2015-12-21

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10{sup −9} m{sup 2}/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  20. Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Niroumandrad, S.; Rostami, M.; Ramezanzadeh, B.

    2015-12-01

    The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce2O3 and CeO2 was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

  1. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    NASA Astrophysics Data System (ADS)

    Samin, Adib; Li, Xiang; Zhang, Jinsuo; Mariani, R. D.; Unal, Cetin

    2015-12-01

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10-9 m2/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  2. Production of CeO2 Nanoparticles by Method of Laser Ablation of Bulk Metallic Cerium Targets in Liquid

    NASA Astrophysics Data System (ADS)

    Svetlichnyi, V. A.; Lapin, I. N.

    2016-03-01

    The method of pulsed laser ablation in liquid was used to synthesize dispersions of cerium oxide nanoparticles when subjecting a metallic cerium target in water and alcohol to basic frequency radiation of the nanosecond Nd:YAG laser (1064 nm, 7 ns, 20 Hz). Researchers have studied the effect of laser radiation parameters, duration of impact, and optical scheme of experiment on the ablation process. The average rate of nanoparticle production was 50 mg/h in water and 25 mg/h in alcohol. Researchers have studied the size characteristics and crystalline structure of the nanoparticles produced. The particles have bimodal size distribution with 6 nm and 25 nm maximums. The average crystallite size is 17-19 nm. The crystalline structure of nanoparticles, namely cubic cerium oxide (fluorite structure), space group Fm-3m, is confirmed by the X-ray diffraction data, as well as optical absorption spectra and Raman spectroscopy.

  3. Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii.

    PubMed

    Röhder, Lena A; Brandt, Tanja; Sigg, Laura; Behra, Renata

    2014-07-01

    Cerium oxide nanoparticles (CeO2 NP) are increasingly used in industrial applications and may be released to the aquatic environment. The fate of CeO2 NP and effects on algae are largely unknown. In this study, the short term effects of CeO2 NP in two different agglomeration states on the green algae Chlamydomonas reinhardtii were examined. The role of dissolved cerium(III) on toxicity, its speciation and the dissolution of CeO2 NP were considered. The role of cell wall of C. reinhardtii as a barrier and its influence on the sensitivity to CeO2 NP and cerium(III) was evaluated by testing both, the wild type and the cell wall free mutant of C. reinhardtii. Characterization showed that CeO2 NP had a surface charge of ∼0mV at physiological pH and agglomerated in exposure media. Phosphate stabilized CeO2 NP at pH 7.5 over 24h. This effect was exploited to test CeO2 NP dispersed in phosphate with a mean size of 140nm and agglomerated in absence of phosphate with a mean size of 2000nm. The level of dissolved cerium(III) in CeO2 NP suspensions was very low and between 0.1 and 27nM in all tested media. Exposure of C. reinhardtii to Ce(NO3)3 decreased the photosynthetic yield in a concentration dependent manner with EC50 of 7.5±0.84μM for wild type and EC50 of 6.3±0.53μM for the cell wall free mutant. The intracellular level of reactive oxygen species (ROS) increased upon exposure to Ce(NO3)3 with effective concentrations similar to those inhibiting photosynthesis. The agglomerated CeO2 NP caused a slight decrease of photosynthetic yield at the highest concentrations (100μM), while no effect was observed for dispersed CeO2 NP. The low toxicity of agglomerated CeO2 NP was attributed quantitatively to Ce(3+) ions co-occurring in the nanoparticle suspension whereas for dispersed CeO2 NP, dissolved Ce(3+) was precipitated with phosphate and not bioavailable. Furthermore CeO2 NP did not affect the intracellular ROS level. The cell wall free mutant and wild type of C

  4. Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii.

    PubMed

    Röhder, Lena A; Brandt, Tanja; Sigg, Laura; Behra, Renata

    2014-07-01

    Cerium oxide nanoparticles (CeO2 NP) are increasingly used in industrial applications and may be released to the aquatic environment. The fate of CeO2 NP and effects on algae are largely unknown. In this study, the short term effects of CeO2 NP in two different agglomeration states on the green algae Chlamydomonas reinhardtii were examined. The role of dissolved cerium(III) on toxicity, its speciation and the dissolution of CeO2 NP were considered. The role of cell wall of C. reinhardtii as a barrier and its influence on the sensitivity to CeO2 NP and cerium(III) was evaluated by testing both, the wild type and the cell wall free mutant of C. reinhardtii. Characterization showed that CeO2 NP had a surface charge of ∼0mV at physiological pH and agglomerated in exposure media. Phosphate stabilized CeO2 NP at pH 7.5 over 24h. This effect was exploited to test CeO2 NP dispersed in phosphate with a mean size of 140nm and agglomerated in absence of phosphate with a mean size of 2000nm. The level of dissolved cerium(III) in CeO2 NP suspensions was very low and between 0.1 and 27nM in all tested media. Exposure of C. reinhardtii to Ce(NO3)3 decreased the photosynthetic yield in a concentration dependent manner with EC50 of 7.5±0.84μM for wild type and EC50 of 6.3±0.53μM for the cell wall free mutant. The intracellular level of reactive oxygen species (ROS) increased upon exposure to Ce(NO3)3 with effective concentrations similar to those inhibiting photosynthesis. The agglomerated CeO2 NP caused a slight decrease of photosynthetic yield at the highest concentrations (100μM), while no effect was observed for dispersed CeO2 NP. The low toxicity of agglomerated CeO2 NP was attributed quantitatively to Ce(3+) ions co-occurring in the nanoparticle suspension whereas for dispersed CeO2 NP, dissolved Ce(3+) was precipitated with phosphate and not bioavailable. Furthermore CeO2 NP did not affect the intracellular ROS level. The cell wall free mutant and wild type of C

  5. New methods of nitrate removal from water.

    PubMed

    Shrimali, M; Singh, K P

    2001-01-01

    Nitrate contamination in groundwater resources originates mainly from the excessive use of fertilisers and uncontrolled land discharges of treated wastewater. This can cause potential health hazards to infants and pregnant women, thus limiting the direct use of the groundwater resources for the human consumption in several parts of the world, including India. The conventional processes used to eliminate nitrate from water are ion exchange, reverse osmosis and electro-dialysis. The utility of these processes has been limited due to their expensive operation and subsequent disposal problem of the generated nitrate waste brine. This paper presents a comprehensive account of the methods/techniques used for the removal of nitrate ion from water during the last 10 years with special reference to the biological denitrification and fate of the metals in decontamination processes.

  6. Qualitative Determination of Nitrate with Triphenylbenzylphosphonium Chloride.

    ERIC Educational Resources Information Center

    Berry, Donna A.; Cole, Jerry J.

    1984-01-01

    Discusses two procedures for the identification of nitrate, the standard test ("Brown Ring" test) and a new procedure using triphenylbenzylphosphonium chloride (TPBPC). Effectiveness of both procedures is compared, with the TPBPC test proving to be more sensitive and accurate. (JM)

  7. Change of the cerium valence with temperature - Structure and chemical bonding of HT-CeRhGe

    NASA Astrophysics Data System (ADS)

    Svitlyk, Volodymyr; Hermes, Wilfried; Chevalier, Bernard; Matar, Samir F.; Gaudin, Etienne; Voßwinkel, Daniel; Chernyshov, Dmitry; Hoffmann, Rolf-Dieter; Pöttgen, Rainer

    2013-07-01

    Polycrystalline CeRhGe was prepared via arc-melting of the elements. Its TiNiSi-related structures (space groups Pnma) were studied by powder diffraction using synchrotron radiation over the temperature range of 315-770 K. CeRhGe shows a first-order structural phase transition at 520 K upon heating. Ab initio elelectronic structure calculations give evidence for the depletion of the cerium 4f band in HT-CeRhGe and in consequence a redistribution of the electron density from the cerium to the rhodium atoms. Purely trivalent cerium atoms in the low-temperature modification (LT) change to intermediate-valent cerium in the high-temperature modification (HT). The integrated crystal orbital Hamilton populations show an enhancement of the Ce-Rh bonding in HT-CeRhGe. The three-dimensional [RhGe] polyanionic network shows drastic puckering of the [Rh3Ge3] hexagons in LT-CeRhGe and a flattening in HT-CeRhGe. The cerium valence change is accompanied by a drastic jump in the lattice parameters: a = 7.42249(8), b = 4.46699(5) and c = 7.1276(1) Å at 315 K vs. a = 7.24579(6), b = 4.47506(4) and c = 7.43579(6) Å at 570 K. Large shifts occur for the x parameter of the rhodium and the z parameter of the cerium atomic positions (Wyckoff sites 4c (x 1/4 z)).

  8. Effect of ultrasound on the structural and textural properties of copper-impregnated cerium-modified zirconium-pillared bentonite

    NASA Astrophysics Data System (ADS)

    Tomul, Fatma

    2011-12-01

    In this study, the synthesis of zirconium-pillared bentonite modified with cerium was performed via two different methods by the application of conventional and ultrasonic treatments during the intercalation stage. To synthesise copper-impregnated pillared clays by wet impregnation, cerium-modified zirconium-pillared clays were used as supportive materials after being calcined at 300 °C. Ultrasonic treatment significantly decreased the required processing time compared with the conventional treatment of the synthesised pillared bentonites. Chemical analysis confirmed the incorporation of Zr 4+, Ce 4+ and Cu 2+ species into the pillared bentonites. X-ray diffraction (XRD) patterns of zirconium- and cerium/zirconium-pillared bentonites prepared by conventional treatment show that one large d-spacing above 3.5 nm corresponds to the mesoporous delaminated part, and another small d-spacing above 1.7 nm is indicative of the microporous pillared part. Zirconium- and cerium/zirconium-pillared bentonites prepared via ultrasonic treatment exhibited similar results, with the same high d-spacing but with a second low-intensity d-spacing above 1.9 nm. The delaminated structures of the pillared bentonites synthesised by both methods were conserved after copper impregnation. Nitrogen-adsorption isotherm analysis showed that the textural characteristics of products synthesised by ultrasonic treatment were comparable to those of products synthesised by conventional treatment. Fourier-transform infrared spectroscopy (FTIR) analyses showed the presence of Brønsted- and Lewis-acid sites, and zirconium-pillared clays synthesised by conventional treatment exhibited increased numbers of Brønsted- and Lewis-acid sites after cerium addition and copper impregnation. However, the products synthesised by ultrasonic treatment exhibited an increased number of Brønsted- and Lewis-acid sites after cerium addition, but a decreased number of acid sites after copper impregnation.

  9. Synthesis of a new energetic nitrate ester

    SciTech Connect

    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. 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.

  10. The UK Nitrate Time Bomb (Invited)

    NASA Astrophysics Data System (ADS)

    Ward, R.; Wang, L.; Stuart, M.; Bloomfield, J.; Gooddy, D.; Lewis, M.; McKenzie, A.

    2013-12-01

    The developed world has benefitted enormously from the intensification of agriculture and the increased availability and use of synthetic fertilizers during the last century. However there has also been unintended adverse impact on the natural environment (water and ecosystems) with nitrate the most significant cause of water pollution and ecosystem damage . Many countries have introduced controls on nitrate, e.g. the European Union's Water Framework and Nitrate Directives, but despite this are continuing to see a serious decline in water quality. The purpose of our research is to investigate and quantify the importance of the unsaturated (vadose) zone pathway and groundwater in contributing to the decline. Understanding nutrient behaviour in the sub-surface environment and, in particular, the time lag between action and improvement is critical to effective management and remediation of nutrient pollution. A readily-transferable process-based model has been used to predict temporal loading of nitrate at the water table across the UK. A time-varying nitrate input function has been developed based on nitrate usage since 1925. Depth to the water table has been calculated from groundwater levels based on regional-scale observations in-filled by interpolated river base levels and vertical unsaturated zone velocities estimated from hydrogeological properties and mapping. The model has been validated using the results of more than 300 unsaturated zone nitrate profiles. Results show that for about 60% of the Chalk - the principal aquifer in the UK - peak nitrate input has yet to reach the water table and concentrations will continue to rise over the next 60 years. The implications are hugely significant especially where environmental objectives must be achieved in much shorter timescales. Current environmental and regulatory management strategies rarely take lag times into account and as a result will be poorly informed, leading to inappropriate controls and conflicts

  11. A search for nitrates in Martian meteorites

    NASA Astrophysics Data System (ADS)

    Grady, Monica M.; Wright, I. P.; Pillinger, C. T.

    1995-03-01

    Martian atmospheric nitrogen is highly enriched in N-15; nitrates formed by interaction of the atmosphere with the Martian regolith should therefore also be characterized by an elevated delta N-15 value. A search has been made for nitrates in two Martian meteorites, in order to determine the extent of possible regolith-atmosphere interaction. Shock-produced glass from the Elephant Moraine (EET) A79001 shergottite (E1,149) and a water-soluble extract from Nakhla were analyzed by Fourier transform infrared (FTIR) spectroscopy and stepped combustion-stable isotope mass spectrometry. FTIR of both meteorites had features at 1375/cm and 1630/cm, consistent with nitrates. On account of their low thermal stability, nitrates break down at temperatures below 600 C; in this temperature range, E1,149 yeilded approximately 1250 ppb nitrogen with delta N-15 -8 +/- 5%. If this nitrogen is from a nitrate, then it cannot be distinquished from terrestial salts by its isotopic composition. The water-soluble extract from Nakhla also released nitrogen at low temperatures, approximately 17 ppb with delta N-15 approximately -11 +/- 4%. Since Nakhla is an observed 'fall', this is unlikely to be a terrestial weathering product. Nitrates apparently occur in E1,149 and Nakhla, but in very low abundance, and their origin is unclear. The isotopic composition of the salts, which is within the range of that proposed for Martian magmatic volatiles, is far removed from that of nitrogen in the present-day Martian atmosphere. If the nitrates are Martian in origin, they did not form in recent times from reactions involving atmospheric gases. Rather, the nitrates could be the result of an earlier episode of atmospheric interaction with the regolith, or with implantation of magmatic volatiles introduced during degassing.

  12. Microbial uranium immobilization independent of nitrate reduction.

    PubMed

    Madden, Andrew S; Smith, April C; Balkwill, David L; Fagan, Lisa A; Phelps, Tommy J

    2007-09-01

    At many uranium processing and handling facilities, including sites in the US Department of Energy (DOE) complex, high levels of nitrate are present as co-contamination with uranium in groundwater. The daunting prospect of complete nitrate removal prior to the reduction of uranium provides a strong incentive to explore bioremediation strategies that allow for uranium bioreduction and stabilization in the presence of nitrate. Typical in situ strategies involving the stimulation of metal-reducing bacteria are hindered by low-pH environments and require that the persistent nitrate must first and continuously be removed or transformed prior to uranium being a preferred electron acceptor. This work investigated the possibility of stimulating nitrate-indifferent, pH-tolerant microorganisms to achieve bioreduction of U(VI) despite nitrate persistence. Enrichments from U-contaminated sediments demonstrated nearly complete reduction of uranium with very little loss of nitrate from pH 5.7-6.2 using methanol or glycerol as a carbon source. Bacterial 16S rRNA genes were amplified from uranium-reducing enrichments (pH 5.7-6.2) and sequenced. Phylogenetic analyses classified the clone sequences into four distinct clusters. Data from sequencing and terminal-restriction fragment length polymorphism (T-RFLP) profiles indicated that the majority of the microorganisms stimulated by these enrichment conditions consisted of low G+C Gram-positive bacteria most closely related to Clostridium and Clostridium-like organisms. This research demonstrates that the stimulation of a natural microbial community to immobilize U through bioreduction is possible without the removal of nitrate.

  13. 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. PMID:26988767

  14. Preformed Nitrate in the Glacial North Atlantic

    NASA Astrophysics Data System (ADS)

    Homola, K.; Spivack, A. J.; D'Hondt, S.; Estes, E. R.; Insua, T. L.; McKinley, C. C.; Murray, R. W.; Pockalny, R. A.; Robinson, R. S.; Sauvage, J.

    2015-12-01

    Atmospheric CO2 abundances are highly correlated with global temperature variations over the past 800,000 years. Consequently, understanding the feedbacks between climate and CO2 is important for predictions of future climate. Leading hypotheses to explain this feedback invoke changes in ocean biology, circulation, chemistry, and/or gas exchange rates to trap CO2 in the deep ocean, thereby reducing the greenhouse effect of CO2 in the atmosphere. To test these hypotheses, we use sediment pore water profiles of dissolved nitrate and oxygen to reconstruct paleo-preformed nitrate concentrations at two deep-water sites in the western North Atlantic (23°N 57°W, 5557 m water depth; 30°N 58°W, 5367 m water depth). Preformed nitrate increases down-core to 22.7 μM (25.6 m core depth) at the northern site, and to 28.5 μM (27.8 m core depth) at the southern site. The large preformed nitrate gradient between these sites reveals a paleo-boundary between a southern water source high in preformed nitrate and a northern water source with lower concentrations, similar to today's ocean. However, the boundary between these water masses occurs north of where their modern counterparts meet, indicating that Antarctic Bottom Water (AABW) extended farther north during the Last Glacial Maximum (LGM). In addition, the southern source had a higher preformed nitrate concentration than today's AABW (25 μM), contradicting hypotheses that nutrient utilization was more efficient in the Southern Ocean deep-water formation regions during the LGM. Comparison to our previous Pacific data reveals that the average preformed nitrate concentration of the deep ocean was slightly higher during the LGM than today. This result implies that the CO2-climate feedback was not principally due to more efficient nitrate utilization.

  15. Nitrate inhibition of legume nodule growth and activity. II. Short term studies with high nitrate supply

    SciTech Connect

    Streeter, J.G.

    1985-02-01

    Soybean plants (Glycine max (L.) Merr) were grown in sand culture with 2 millimolar nitrate for 37 days and then supplied with 15 millimolar nitrate for 7 days. Control plants received 2 millimolar nitrate and 13 millimolar chloride and, after the 7-day treatment period, all plants were supplied with nil nitrate. The temporary treatment with high nitrate inhibited nitrogenase (acetylene reduction) activity by 80% whether or not Rhizobium japonicum bacteroids had nitrate reductase (NR) activity. The pattern of nitrite accumulation in nodules formed by NR/sup +/ rhizobia was inversely related to the decrease and recovery of nitrogenase activity. However, nitrite concentration in nodules formed by NR/sup -/ rhizobia appeared to be too low to explain the inhibition of nitrogenase. Nodules on plants treated with 15 millimolar nitrate contained higher concentrations of amino N and, especially, ureide N than control nodules and, after withdrawal of nitrate, reduced N content of treated and control nodules returned to similar levels. The accumulation of N/sub 2/ fixation products in nodules in response to high nitrate treatment was observed with three R. japonicum strains, two NR/sup +/ and one NR/sup -/.

  16. Approximate prediction of melting point of nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds.

    PubMed

    Keshavarz, Mohammad Hossein

    2006-12-01

    A simple new procedure is introduced to predict melting point of selected class of energetic compounds containing nitramines, nitrate esters, nitrate salts and nitroaliphatics energetic compounds. The number of nitrogen and oxygen as well as the number of nitramine group and the contribution of some specific functional groups would be needed in the new method. Energetic compounds should contain at least one of the functional groups including N-NO(2), C-ONO(2) or nonaromatic C-NO(2). Calculated melting point for 33 nitramines, nitrate esters, nitrate salt and nitroaliphatics are compared with experimental data. Predicted melting points have average deviation of 5.4% for these energetic compounds.

  17. The Arabidopsis ATNRT2.7 nitrate transporter controls nitrate content in seeds.

    PubMed

    Chopin, Franck; Orsel, Mathilde; Dorbe, Marie-France; Chardon, Fabien; Truong, Hoai-Nam; Miller, Anthony J; Krapp, Anne; Daniel-Vedele, Françoise

    2007-05-01

    In higher plants, nitrate is taken up by root cells where Arabidopsis thaliana NITRATE TRANSPORTER2.1 (ATNRT2.1) chiefly acts as the high-affinity nitrate uptake system. Nitrate taken up by the roots can then be translocated from the root to the leaves and the seeds. In this work, the function of the ATNRT2.7 gene, one of the seven members of the NRT2 family in Arabidopsis, was investigated. High expression of the gene was detected in reproductive organs and peaked in dry seeds. beta-Glucuronidase or green fluorescent protein reporter gene expression driven by the ATNRT2.7 promoter confirmed this organ specificity. We assessed the capacity of ATNRT2.7 to transport nitrate in Xenopus laevis oocytes or when it is expressed ectopically in mutant plants deficient in nitrate transport. We measured the impact of an ATNRT2.7 mutation and found no difference from the wild type during vegetative development. By contrast, seed nitrate content was affected by overexpression of ATNRT2.7 or a mutation in the gene. Finally, we showed that this nitrate transporter protein was localized to the vacuolar membrane. Our results demonstrate that ATNRT2.7 plays a specific role in nitrate accumulation in the seed.

  18. 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.

  19. Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

    PubMed Central

    Snow, Samantha J.; McGee, John; Miller, Desinia B.; Bass, Virginia; Schladweiler, Mette C.; Thomas, Ronald F.; Krantz, Todd; King, Charly; Ledbetter, Allen D.; Richards, Judy; Weinstein, Jason P.; Conner, Teri; Willis, Robert; Linak, William P.; Nash, David; Wood, Charles E.; Elmore, Susan A.; Morrison, James P.; Johnson, Crystal L.; Gilmour, Matthew Ian; Kodavanti, Urmila P.

    2014-01-01

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe. PMID:25239632

  20. High temperature stability of a 316 austenitic stainless steel coated with cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Mendoza Del Angel, Humberto

    Cerium oxide (CeO2-x) nanoparticles were used for coating protection on a 316 Austenitic Stainless Steel (Aust. SS) to enhance the thermal stability of the oxide films formed at high temperatures. Three simple coating methods were used, dipping, spraying and spinning in order to explore the coating film morphology, nanoparticle distribution and its effect on thermal stability of the steel substrates. Experimentally, the selected steel was exposed to 800°C/1000°C under dry air conditions. Weight changes (DeltaW/A) were monitored as a function of time and the results were compared with uncoated alloys tested under similar conditions. The cerium oxide nanoparticles used on the three methods were synthesized in the laboratory obtaining nanoparticles in the range of 3.5 to 6.2 nanometers. It was found that cerium oxide particle size is affected by temperature. In this case, the activation energy for particle growth was estimated to be around 21,1 kJ/mol. Characterization of the film morphologies before and after oxidation were carried out using Atomic Force Microscopy (AFM), Surface Profilometry, Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). A comparison of the three coating methods was carried out for the particular case of the 316 Aust. SS coupons. In addition, the oxidation kinetics was experimentally investigated for the coated samples. For this purpose thermal gravimetric determinations were made at 800°C, 900°C, and 1000°C and oxidation rate constants were calculated at each temperature.

  1. Inhaled diesel emissions generated with cerium oxide nanoparticle fuel additive induce adverse pulmonary and systemic effects.

    PubMed

    Snow, Samantha J; McGee, John; Miller, Desinia B; Bass, Virginia; Schladweiler, Mette C; Thomas, Ronald F; Krantz, Todd; King, Charly; Ledbetter, Allen D; Richards, Judy; Weinstein, Jason P; Conner, Teri; Willis, Robert; Linak, William P; Nash, David; Wood, Charles E; Elmore, Susan A; Morrison, James P; Johnson, Crystal L; Gilmour, Matthew Ian; Kodavanti, Urmila P

    2014-12-01

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe.

  2. Reactions of a cerium(iii) amide with heteroallenes: insertion, silyl-migration and de-insertion.

    PubMed

    Yin, Haolin; Carroll, Patrick J; Schelter, Eric J

    2016-07-28

    Reactions of Ce[N(SiMe3)Ph(F)]3 (-Ph(F) = pentafluorophenyl) toward small molecules of the type E1[double bond, length as m-dash]C[double bond, length as m-dash]E2 (E1, E2 = O, S, NR), including carbon disulfide, carbodiimide, carbon dioxide, isocyanate and isothiocyanate are reported, resulting in distinct products, including cerium(iii) dithiocarbamate, cerium(iii) guanidinate, isocyanates and unsymmetric carbodiimides. These reactions were rationalized as three consecutive stages of the same reaction pathway: insertion, silyl-migration and de-insertion. PMID:27416923

  3. Stimulating nitrate removal processes of restored wetlands.

    PubMed

    Ballantine, Kate A; Groffman, Peter M; Lehmann, Johannes; Schneider, Rebecca L

    2014-07-01

    The environmental and health effects caused by nitrate contamination of aquatic systems are a serious problem throughout the world. A strategy proposed to address nitrate pollution is the restoration of wetlands. However, although natural wetlands often remove nitrate via high rates of denitrification, wetlands restored for water quality functions often fall below expectations. This may be in part because key drivers for denitrification, in particular soil carbon, are slow to develop in restored wetlands. We added organic soil amendments that range along a gradient of carbon lability to four newly restored wetlands in western New York to investigate the effect of carbon additions on denitrification and other processes of the nitrogen cycle. Soil carbon increased by 12.67-63.30% with the use of soil amendments (p ≤ 0.0001). Soil nitrate, the carbon to nitrogen ratio, and microbial biomass nitrogen were the most significant predictors of denitrification potential. Denitrification potential, potential net nitrogen nitrification and mineralization, and soil nitrate and ammonium, were highest in topsoil-amended plots, with increases in denitrification potential of 161.27% over control plots. While amendment with topsoil more than doubled several key nitrogen cycling processes, more research is required to determine what type and level of amendment application are most effective for stimulating removal of exogenous nitrate and meeting functional goals within an acceptable time frame. PMID:24915604

  4. Denitrification inhibition by high nitrate wastes

    SciTech Connect

    Veydovec, W.; Silverstein, J.; Cook, N.E. Jr.; Figueroa, L.A.; Hund, R.; Lehmkuhl, G.D.

    1994-12-31

    The processing of radioactive metal products at nuclear weapons plants and research labs has produced wastewaters containing high concentrations of nitrate, often greater than 50,000 mg/l N. The adaptation of activated sludge and inhibition of denitrification at high nitrate concentrations was studied using pH controlled bench-scale sequencing batch reactors (SBRs), operated with 50% of the SBR volume recycled (recycle volume = influent volume). Denitrification of 1,350 and 2,700 mg/l NO{sub 3}{sup {minus}}-N was completed after approximately 5 hours and 15 hours, respectively. No denitrification of 5,400 mg/l NO{sub 3}{sup {minus}}-N was observed. These results suggest that there is a progressive inhibition of denitrification as nitrate concentrations increase from 1,350 to 5,400 mg/l NO{sub 3}{sup {minus}}-N. In a subsequent series of experiments at an initial reactor nitrate concentration of 1,350 mg/l N, a significant accumulation of nitrate was observed, resulting once in destabilization with loss of denitrification and once in successful adaptation of the activated sludge. At a nitrate concentration of 1,350 mg/l N, the adaptation of activated sludge appears to be unstable, resulting sometimes in stable denitrification and sometimes in biomass washout.

  5. Stimulating nitrate removal processes of restored wetlands.

    PubMed

    Ballantine, Kate A; Groffman, Peter M; Lehmann, Johannes; Schneider, Rebecca L

    2014-07-01

    The environmental and health effects caused by nitrate contamination of aquatic systems are a serious problem throughout the world. A strategy proposed to address nitrate pollution is the restoration of wetlands. However, although natural wetlands often remove nitrate via high rates of denitrification, wetlands restored for water quality functions often fall below expectations. This may be in part because key drivers for denitrification, in particular soil carbon, are slow to develop in restored wetlands. We added organic soil amendments that range along a gradient of carbon lability to four newly restored wetlands in western New York to investigate the effect of carbon additions on denitrification and other processes of the nitrogen cycle. Soil carbon increased by 12.67-63.30% with the use of soil amendments (p ≤ 0.0001). Soil nitrate, the carbon to nitrogen ratio, and microbial biomass nitrogen were the most significant predictors of denitrification potential. Denitrification potential, potential net nitrogen nitrification and mineralization, and soil nitrate and ammonium, were highest in topsoil-amended plots, with increases in denitrification potential of 161.27% over control plots. While amendment with topsoil more than doubled several key nitrogen cycling processes, more research is required to determine what type and level of amendment application are most effective for stimulating removal of exogenous nitrate and meeting functional goals within an acceptable time frame.

  6. Protein tyrosine nitration in the cell cycle

    SciTech Connect

    Jia, Min; Mateoiu, Claudia; Souchelnytskyi, Serhiy

    2011-09-23

    Highlights: {yields} Enrichment of 3-nitrotyrosine containing proteins from cells synchronized in different phases of the cell cycle. {yields} Identification of 76 tyrosine nitrated proteins that change expression during the cell cycle. {yields} Nineteen identified proteins were previously described as regulators of cell proliferation. -- Abstract: Nitration of tyrosine residues in proteins is associated with cell response to oxidative/nitrosative stress. Tyrosine nitration is relatively low abundant post-translational modification that may affect protein functions. Little is known about the extent of protein tyrosine nitration in cells during progression through the cell cycle. Here we report identification of proteins enriched for tyrosine nitration in cells synchronized in G0/G1, S or G2/M phases of the cell cycle. We identified 27 proteins in cells synchronized in G0/G1 phase, 37 proteins in S phase synchronized cells, and 12 proteins related to G2/M phase. Nineteen of the identified proteins were previously described as regulators of cell proliferation. Thus, our data indicate which tyrosine nitrated proteins may affect regulation of the cell cycle.

  7. Process for decomposing nitrates in aqueous solution

    DOEpatents

    Haas, Paul A.

    1980-01-01

    This invention is a process for decomposing ammonium nitrate and/or selected metal nitrates in an aqueous solution at an elevated temperature and pressure. Where the compound to be decomposed is a metal nitrate (e.g., a nuclear-fuel metal nitrate), a hydroxylated organic reducing agent therefor is provided in the solution. In accordance with the invention, an effective proportion of both nitromethane and nitric acid is incorporated in the solution to accelerate decomposition of the ammonium nitrate and/or selected metal nitrate. As a result, decomposition can be effected at significantly lower temperatures and pressures, permitting the use of system components composed of off-the-shelf materials, such as stainless steel, rather than more costly materials of construction. Preferably, the process is conducted on a continuous basis. Fluid can be automatically vented from the reaction zone as required to maintain the operating temperature at a moderate value--e.g., at a value in the range of from about 130.degree.-200.degree. C.

  8. Surface structures of cerium oxide nanocrystalline particles from the size dependence of the lattice parameters

    NASA Astrophysics Data System (ADS)

    Tsunekawa, S.; Ito, S.; Kawazoe, Y.

    2004-10-01

    Cerium oxide nanocrystalline particles are synthesized and monodispersed in the size range from 2 to 8nm in diameter. The dependence of the lattice parameters on particle size is obtained by x-ray and electron diffraction analyses. The size dependence well coincides with the estimation based on the assumption that the surface is composed of one layer of Ce2O3 and the inside consists of CeO2. The effect of particle size on lattice parameters is discussed from the differences in the fabrication method and the surface structure.

  9. Investigation of the elemental composition of lanthanum-cerium hexaboride crystals

    NASA Astrophysics Data System (ADS)

    Badalyan, Georgi; Kuzanyan, Armen; Petrosyan, Vahagn; Kuzanyan, Vazgen; Gulian, Armen

    2010-10-01

    Crystals of solid solutions of lanthanum-cerium hexaborides (La1-xCex)B6 possess unique thermoelectric properties in the temperature range of 0.3-9 K and they can be used in thermoelectric single-photon detectors as a sensor. One can observe a wide spread in thermoelectric measurement values reported in the literature, which is because of different qualities of studied crystals. The greatest influence on both the Seebeck coefficient and electrical resistivity of samples is exercised by the presence of uncontrolled impurities in crystals and the deviation from stoichiometry. In this work we have studied just the aforementioned parameters of the crystals obtained by three different methods.

  10. Silicate-free growth of high-quality ultrathin cerium oxide films on Si(111)

    SciTech Connect

    Flege, Jan Ingo; Kaemena, Bjoern; Wilkens, Torsten; Schmidt, Thomas; Falta, Jens; Gevers, Sebastian; Bruns, Daniel; Wollschlaeger, Joachim; Bertram, Florian; Baetjer, Jan

    2011-12-15

    Ultrathin Ce{sub 2}O{sub 3} layers have been grown on Si(111) by reactive metal deposition in an oxygen background and characterized by x-ray standing waves, x-ray diffraction, x-ray photoelectron spectroscopy, and low-energy electron diffraction to elucidate and quantify both atomic structure and chemical composition. It is demonstrated that highly ordered, mostly B-oriented, epitaxial ceria films can be achieved by preadsorption of a monolayer of atomic chlorine, effectively passivating the substrate and thereby suppressing cerium silicate and silicon oxide formation at the interface.

  11. β Coronae Bolealis: Lithium and Cerium Contribution to the Blend at 6708 Å

    NASA Astrophysics Data System (ADS)

    Drake, N. A.; Hubrig, S.; Polosukhina, N. S.; de La Reza, R.

    2006-06-01

    We analyze the Li I 6708 Å spectral region of the chemically peculiar Ap star βCrB using high resolution, high signal-to-noise spectra obtained at different rotation phases. Our study shows that the Ce II line at 6708.099 Å is a main contributor to the spectral feature at 6708 Å. This fact explains the observed red shift of the Li I doublet of about 0.2 Å found by Hack et al. (1997). We derive the values of lithium and cerium abundances for different rotation phases and show that βCrB has ``cosmic'' Li abundance.

  12. 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

  13. 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.

  14. Recovery of plutonium from HEPA filters by Ce(IV)-promoted dissolution of PuO/sub 2/ and recycle of the cerium promoter

    SciTech Connect

    Leuze, R. E.; Bond, W. D.; Scheitlin, F. M.

    1980-01-01

    The experimental studies carried out included (1) the electrolytic production of Ce(IV) from Ce(III), (2) the leaching of refractory PuO/sub 2/ from HEPA filter materials with maintenance of Ce(IV) concentrations by anodic oxidation during leaching, and (3) evaluation of methods for contacting the HEPA solids with the leaching solution and for separating the solid residue from the leaching liquor. Anodic oxidation of Ce(III) was accomplished with an electric current efficiency of about 85% at current densities of 0.04 to 0.4 A/dm/sup 2/ at a platinum anode. Refractory PuO/sub 2/ was dissolved by a 4.0 M HNO/sub 3/ - 0.1 M Ce(IV) solution in 1.5 h at 100/sup 0/C using stirred-contact leaching of the solids or by recirculating the leachant through a packed column of the solids. Cerium (IV) concentrations were maintained continuously by anodic oxidation throughout leaching. Dissolution times up to 10 h were required unless the HEPA media were oxidized initially in air at 300/sup 0/C to destroy carbonaceous species which consumed Ce(IV) more rapidly than it could be regenerated by anodic oxidation. Leaching solids in packed columns avoided the relatively difficult liquid-solids separation by centrifugation which was required after stirred-contact leaching; however, the solids handling difficulties associated with charging and discharging of the packed columns in a remote environment remain a significant design obstacle. A chemical flowsheet is proposed for the recovery of actinides from HEPA filters. A 4 M HNO/sub 3/ - 0.1 M Ce(IV) nitrate solution is used as the leachant and the Ce(III) is recycled to the leaching operation using bidentate solvent extraction.

  15. Nitrate in groundwater in the United States

    NASA Astrophysics Data System (ADS)

    Burow, K. R.; Nolan, B. T.; Rupert, M. G.; Dubrovsky, N. M.

    2009-12-01

    An assessment of nitrate concentrations in groundwater in the United States (US) indicates that concentrations are highest in shallow, oxic groundwater beneath areas with high nitrogen inputs. During 1991-2003, 5,101 wells were sampled in 51 study areas throughout the US as part of the USGS National Water-Quality Assessment program. Well locations for individual 30-well networks were selected for sampling using a computerized, stratified, random site-selection procedure to minimize spatial bias. These well networks reflect the existing used resource in major aquifers represented by domestic wells (major aquifer studies), and recently recharged groundwater beneath dominant land-surface activities (land-use studies). Nitrate concentrations in groundwater were compared with nationally-available variables such as nonpoint-source nitrogen inputs, soils, water chemistry, and other aquifer and well construction characteristics to predict the conditions most vulnerable to high nitrate concentrations. Nitrate was detected at concentrations above background of 1.0 mg/L (as N) in 50% of the wells sampled. Shallow groundwater beneath agricultural land had the highest median concentration of nitrate (3.1 mg/L). Median nitrate in shallow groundwater beneath urban land (1.4 mg/L) was lower than beneath agricultural land, but was higher than the median in major aquifers (0.56 mg/L). Although most wells sampled in the shallow land-use studies were not used for drinking water, concentrations exceeded the US EPA drinking-water standard (MCL) of 10 mg/L in 20% of wells in the agricultural land-use setting. Concentrations exceeded the MCL in only 3% of wells in the urban land-use setting, and 4% of wells in major aquifers. Classification and regression tree analysis was used to identify the relative importance of nitrogen inputs, water chemistry, and physical aquifer properties on nitrate concentrations in groundwater. Factors ranked by reduction in sum of squares indicate that

  16. Historical Tracking of Nitrate in Contrasting Vineyard Using Water Isotopes and Nitrate Depth Profiles

    NASA Astrophysics Data System (ADS)

    Sprenger, M.; Erhardt, M.; Riedel, M.; Weiler, M.

    2015-12-01

    The European Water Framework Directive (EWFD) aims to achieve a good chemical status for the groundwater bodies in Europe by the year 2015. Despite the effort to reduce the nitrate pollution from agriculture within the last two decades, there are still many groundwater aquifers that exceed nitrate concentrations above the EWFD threshold of 50 mg/l. Viticulture is seen as a major contributor of nitrate leaching and sowing of a green cover was shown to have a positive effect on lowering the nitrate loads in the upper 90 cm of the soil. However, the consequences for nitrate leaching into the subsoil were not yet tested. We analyzed the nitrate concentrations and pore water stable isotope composition to a depth of 380 cm in soil profiles under an old vineyard and a young vineyard with either soil tillage or permanent green cover in between the grapevines. The pore water stable isotopes were used to calibrate a soil physical model, which was then used to infer the age of the soil water at different depths. This way, we could relate elevated nitrate concentrations below an old vineyard to tillage processes that took place during the winter two years before the sampling. We further showed that the elevated nitrate concentration in the subsoil of a young vineyard can be related to the soil tillage prior to the planting of the new vineyard. If the soil is kept bare due to tillage, a nitrate concentration of 200 kg NO3--N/ha is found in 290 to 380 cm depth 2.5 years after the installation of the vineyard. The amount of nitrate leaching is considerably reduced due to a seeded green cover between the grapevines that takes up a high share of the mobilized nitrate reducing a potential contamination of the groundwater.

  17. Nitrate in aquifers beneath agricultural systems

    USGS Publications Warehouse

    Burkart, M.R.; Stoner, J.D.; ,

    2007-01-01

    Research from several regions of the world provides spatially anecdotal evidence to hypothesize which hydrologic and agricultural factors contribute to groundwater vulnerability to nitrate contamination. Analysis of nationally consistent measurements from the U.S. Geological Survey's NAWQA program confirms these hypotheses for a substantial range of agricultural systems. Shallow unconfined aquifers are most susceptible to nitrate contamination associated with agricultural systems. Alluvial and other unconsolidated aquifers are the most vulnerable and also shallow carbonate aquifers that provide a substantial but smaller contamination risk. Where any of these aquifers are overlain by permeable soils the risk of contamination is larger. Irrigated systems can compound this vulnerability by increasing leaching facilitated by additional recharge and additional nutrient applications. The system of corn, soybean, and hogs produced significantly larger concentrations of groundwater nitrate than all other agricultural systems because this system imports the largest amount of N-fertilizer per unit production area. Mean nitrate under dairy, poultry, horticulture, and cattle and grains systems were similar. If trends in the relation between increased fertilizer use and groundwater nitrate in the United States are repeated in other regions of the world, Asia may experience increasing problems because of recent increases in fertilizer use. Groundwater monitoring in Western and Eastern Europe as well as Russia over the next decade may provide data to determine if the trend in increased nitrate contamination can be reversed. If the concentrated livestock trend in the United States is global, it may be accompanied by increasing nitrogen contamination in groundwater. Concentrated livestock provide both point sources in the confinement area and intense non-point sources as fields close to facilities are used for manure disposal. Regions where irrigated cropland is expanding, such as

  18. Nitrate in aquifers beneath agricultural systems.

    PubMed

    Burkart, M R; Stoner, J D

    2007-01-01

    Research from several regions of the world provides spatially anecdotal evidence to hypothesize which hydrologic and agricultural factors contribute to groundwater vulnerability to nitrate contamination. Analysis of nationally consistent measurements from the U.S. Geological Survey's NAWQA program confirms these hypotheses for a substantial range of agricultural systems. Shallow unconfined aquifers are most susceptible to nitrate contamination associated with agricultural systems. Alluvial and other unconsolidated aquifers are the most vulnerable and also shallow carbonate aquifers that provide a substantial but smaller contamination risk. Where any of these aquifers are overlain by permeable soils the risk of contamination is larger. Irrigated systems can compound this vulnerability by increasing leaching facilitated by additional recharge and additional nutrient applications. The system of corn, soybean, and hogs produced significantly larger concentrations of groundwater nitrate than all other agricultural systems because this system imports the largest amount of N-fertilizer per unit production area. Mean nitrate under dairy, poultry, horticulture, and cattle and grains systems were similar. If trends in the relation between increased fertilizer use and groundwater nitrate in the United States are repeated in other regions of the world, Asia may experience increasing problems because of recent increases in fertilizer use. Groundwater monitoring in Western and Eastern Europe as well as Russia over the next decade may provide data to determine if the trend in increased nitrate contamination can be reversed. If the concentrated livestock trend in the United States is global, it may be accompanied by increasing nitrogen contamination in groundwater. Concentrated livestock provide both point sources in the confinement area and intense non-point sources as fields close to facilities are used for manure disposal. Regions where irrigated cropland is expanding, such as

  19. Nitrate removal from high strength nitrate-bearing wastes in granular sludge sequencing batch reactors.

    PubMed

    Krishna Mohan, Tulasi Venkata; Renu, Kadali; Nancharaiah, Yarlagadda Venkata; Satya Sai, Pedapati Murali; Venugopalan, Vayalam Purath

    2016-02-01

    A 6-L sequencing batch reactor (SBR) was operated for development of granular sludge capable of denitrification of high strength nitrates. Complete and stable denitrification of up to 5420 mg L(-1) nitrate-N (2710 mg L(-1) nitrate-N in reactor) was achieved by feeding simulated nitrate waste at a C/N ratio of 3. Compact and dense denitrifying granular sludge with relatively stable microbial community was developed during reactor operation. Accumulation of large amounts of nitrite due to incomplete denitrification occurred when the SBR was fed with 5420 mg L(-1) NO3-N at a C/N ratio of 2. Complete denitrification could not be achieved at this C/N ratio, even after one week of reactor operation as the nitrite levels continued to accumulate. In order to improve denitrification performance, the reactor was fed with nitrate concentrations of 1354 mg L(-1), while keeping C/N ratio at 2. Subsequently, nitrate concentration in the feed was increased in a step-wise manner to establish complete denitrification of 5420 mg L(-1) NO3-N at a C/N ratio of 2. The results show that substrate concentration plays an important role in denitrification of high strength nitrate by influencing nitrite accumulation. Complete denitrification of high strength nitrates can be achieved at lower substrate concentrations, by an appropriate acclimatization strategy.

  20. 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.

  1. Studies on luminescence from a cerium-doped strontium stannate phosphor.

    PubMed

    Karabulut, Yüksel; Ayvacikli, Mehmet; Canimoglu, Adil; Garcia Guinea, Javier; Can, Nurdogan

    2015-06-01

    The crystal structure and morphology of Ce(3+) -doped SrSnO3 materials prepared using the solid-state reaction method were extensively characterized using experimental techniques. X-Ray diffraction results show that the cerium substitution of strontium does not change the structure of the strontium stannate. Raman spectroscopy was used to investigate the microstructures and lattice vibrations. Environmental scanning electron microscopy images showed that phosphors aggregate and their particles form irregular shapes. SrSnO3 exhibits an intense green emission with a broad band originating from the 5d(1)  → 4f(1) transition of cerium. It was observed that, after exposure to beta-irradiation, the glow curve of this material has two broad thermoluminescence peaks, one centered at ~ 127°C and the other at ~ 245°C for a heating rate of 5 K/s. The kinetic parameters, which include the frequency factor and the activation energy of the material, were calculated using Chen's method, after beta-irradiation. The fading and reusability of the phosphor were also studied and it was found that the phosphor is suitable for radiation dosimetry.

  2. The role of cerium redox state in the SOD mimetic activity of nanoceria

    PubMed Central

    Heckert, Eric; Karakoti, Ajay; Seal, Sudipta; Self, William T.

    2008-01-01

    Cerium oxide nanoparticles (nanoceria) have recently been shown to protect cells against oxidative stress in both cell culture and animal models. Nanoceria has been shown to exhibit superoxide dismutase (SOD) activity using a ferricytochrome C assay, and it is this mimetic activity that has been postulated to be responsible for cellular protection by nanoceria. The nature of nanoceria’s antioxidant properties, specifically what physical characteristics make nanoceria effective at scavenging superoxide anion, is poorly understood. In this study electron paramagnetic resonance (EPR) analysis confirms the reactivity of nanoceria as an SOD mimetic. X-ray photoelectron spectroscopy (XPS) and UV-visible analysis of nanoceria treated with hydrogen peroxide demonstrate that a decrease in the Ce 3+/4+ ratio correlates directly with a loss of SOD mimetic activity. These results strongly suggest that the surface oxidation state of nanoceria plays an integral role in the SOD mimetic activity of nanoceria and that ability of nanoceria to scavenge superoxide is directly related to cerium (III) concentrations at the surface of the particle. PMID:18395249

  3. Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes.

    PubMed

    Janoš, Pavel; Henych, Jiří; Pelant, Ondřej; Pilařová, Věra; Vrtoch, Luboš; Kormunda, Martin; Mazanec, Karel; Štengl, Václav

    2016-03-01

    Four different synthetic routes were used to prepare active forms of cerium oxide that are capable of destroying toxic organophosphates: a sol-gel process (via a citrate precursor), homogeneous hydrolysis and a precipitation/calcination procedure (via carbonate and oxalate precursors). The samples prepared via homogeneous hydrolysis with urea and the samples prepared via precipitation with ammonium bicarbonate (with subsequent calcination at 500°C in both cases) exhibited the highest degradation efficiencies towards the extremely dangerous nerve agents soman (O-pinacolyl methylphosphonofluoridate) and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) and the organophosphate pesticide parathion methyl. These samples were able to destroy more than 90% of the toxic compounds in less than 10 min. The high degradation efficiency of cerium oxide is related to its complex surface chemistry (presence of surface OH groups and surface non-stoichiometry) and to its nanocrystalline nature, which promotes the formation of crystal defects on which the decomposition of organophosphates proceeds through a nucleophilic substitution mechanism that is not dissimilar to the mechanism of enzymatic hydrolysis of organic phosphates by phosphotriesterase. PMID:26561750

  4. Gene-Expression Changes in Cerium Chloride-Induced Injury of Mouse Hippocampus

    PubMed Central

    Sheng, Lei; Zhu, Liyuan; Guan, Ning; Gui, Suxin; Sang, Xuezi; Zhao, Xiaoyang; Sun, Qingqing; Wang, Ling; Cheng, Jie; Hu, Renping; Hong, Fashui

    2013-01-01

    Cerium is widely used in many aspects of modern society, including agriculture, industry and medicine. It has been demonstrated to enter the ecological environment, is then transferred to humans through food chains, and causes toxic actions in several organs including the brain of animals. However, the neurotoxic molecular mechanisms are not clearly understood. In this study, mice were exposed to 0.5, 1, and 2 mg/kg BW cerium chloride (CeCl3) for 90 consecutive days, and their learning and memory ability as well as hippocampal gene expression profile were investigated. Our findings suggested that exposure to CeCl3 led to hippocampal lesions, apoptosis, oxidative stress and impairment of spatial recognition memory. Furthermore, microarray data showed marked alterations in the expression of 154 genes involved in learning and memory, immunity and inflammation, signal transduction, apoptosis and response to stress in the 2 mg/kg CeCl3 exposed hippocampi. Specifically, the significant up-regulation of Axud1, Cdc37, and Ube2v1 caused severe apoptosis, and great suppression of Adcy8, Fos, and Slc5a7 expression led to impairment of mouse cognitive ability. Therefore, Axud1, Cdc37, Ube2v1, Adcy8, Fos, and Slc5a7 may be potential biomarkers of hippocampal toxicity caused by CeCl3 exposure. PMID:23573234

  5. Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes.

    PubMed

    Janoš, Pavel; Henych, Jiří; Pelant, Ondřej; Pilařová, Věra; Vrtoch, Luboš; Kormunda, Martin; Mazanec, Karel; Štengl, Václav

    2016-03-01

    Four different synthetic routes were used to prepare active forms of cerium oxide that are capable of destroying toxic organophosphates: a sol-gel process (via a citrate precursor), homogeneous hydrolysis and a precipitation/calcination procedure (via carbonate and oxalate precursors). The samples prepared via homogeneous hydrolysis with urea and the samples prepared via precipitation with ammonium bicarbonate (with subsequent calcination at 500°C in both cases) exhibited the highest degradation efficiencies towards the extremely dangerous nerve agents soman (O-pinacolyl methylphosphonofluoridate) and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) and the organophosphate pesticide parathion methyl. These samples were able to destroy more than 90% of the toxic compounds in less than 10 min. The high degradation efficiency of cerium oxide is related to its complex surface chemistry (presence of surface OH groups and surface non-stoichiometry) and to its nanocrystalline nature, which promotes the formation of crystal defects on which the decomposition of organophosphates proceeds through a nucleophilic substitution mechanism that is not dissimilar to the mechanism of enzymatic hydrolysis of organic phosphates by phosphotriesterase.

  6. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants.

    PubMed

    Tumburu, Laxminath; Andersen, Christian P; Rygiewicz, Paul T; Reichman, Jay R

    2015-01-01

    The effects of exposure to nanoparticles of titanium dioxide (nano-titanium) and cerium oxide (nano-cerium) on gene expression and growth in Arabidopsis thaliana germinants were studied by using microarrays and quantitative real-time polymerase chain reaction (qPCR), and by evaluating germinant phenotypic plasticity. Exposure to 12 d of either nano-titania or nano-ceria altered the regulation of 204 and 142 genes, respectively. Genes induced by the nanoparticles mainly include ontology groups annotated as stimuli responsive, including both abiotic (oxidative stress, salt stress, water transport) and biotic (respiratory burst as a defense against pathogens) stimuli. Further analysis of the differentially expressed genes indicates that both nanoparticles affected a range of metabolic processes (deoxyribonucleic acid [DNA] metabolism, hormone metabolism, tetrapyrrole synthesis, and photosynthesis). Individual exposures to the nanoparticles increased percentages of seeds with emergent radicles, early development of hypocotyls and cotyledons, and those with fully grown leaves. Although there were distinct differences between the nanoparticles in their affect on molecular mechanisms attributable to enhancing germinant growth, both particles altered similar suites of genes related to various pathways and processes related to enhanced growth.

  7. Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

    PubMed

    Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

    2015-10-14

    Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

  8. [XPS study on the influence of calcination conditions to cerium ion valence].

    PubMed

    Mei, Yan; Yan, Jian-ping; Nie, Zuo-ren

    2010-01-01

    For the system of Ce(NO3)2.6H2O and urea solution during homogeneous precipitation method, X-ray diffraction (XRD), infrared spectrum (IR) and especially X-ray photoelectron spectroscopy (XPS) were used to study and characterize the product structure, variety of cerium ion valence, compound surface character and kernel electronic configurations. The results of XRD and IR showed that calcination temperature had a great effect on the cerium ion valence. The products are orthorhombic Ce2 O(CO3)2.H2O with valence III by using homogeneous precipitation method directly. When heated from the temperature 200 degrees C to 250 degrees C, the product of CeO(CO3)2.H2O with valence VI was finally changed into stable CeO2 with valence IV. XPS was used to study the surface character and kernel electronic configurations of the three different compounds through fine scanning of O(1s), Ce(3d) and Ce(4d) apices, and the results approved that the compounds with different valences are caused by the different valence electronic configurations of the products.

  9. Neuroprotective mechanisms of cerium oxide nanoparticles in a mouse hippocampal brain slice model of ischemia.

    PubMed

    Estevez, A Y; Pritchard, S; Harper, K; Aston, J W; Lynch, A; Lucky, J J; Ludington, J S; Chatani, P; Mosenthal, W P; Leiter, J C; Andreescu, S; Erlichman, J S

    2011-09-15

    Cerium oxide nanoparticles (nanoceria) are widely used as catalysts in industrial applications because of their potent free radical-scavenging properties. Given that free radicals play a prominent role in the pathology of many neurological diseases, we explored the use of nanoceria as a potential therapeutic agent for stroke. Using a mouse hippocampal brain slice model of cerebral ischemia, we show here that ceria nanoparticles reduce ischemic cell death by approximately 50%. The neuroprotective effects of nanoceria were due to a modest reduction in reactive oxygen species, in general, and ~15% reductions in the concentrations of superoxide (O(2)(•-)) and nitric oxide, specifically. Moreover, treatment with nanoceria markedly decreased (~70% reduction) the levels of ischemia-induced 3-nitrotyrosine, a modification to tyrosine residues in proteins induced by the peroxynitrite radical. These findings suggest that scavenging of peroxynitrite may be an important mechanism by which cerium oxide nanoparticles mitigate ischemic brain injury. Peroxynitrite plays a pivotal role in the dissemination of oxidative injury in biological tissues. Therefore, nanoceria may be useful as a therapeutic intervention to reduce oxidative and nitrosative damage after a stroke. PMID:21704154

  10. Custom cerium oxide nanoparticles protect against a free radical mediated autoimmune degenerative disease in the brain.

    PubMed

    Heckman, Karin L; DeCoteau, William; Estevez, Ana; Reed, Kenneth J; Costanzo, Wendi; Sanford, David; Leiter, James C; Clauss, Jennifer; Knapp, Kylie; Gomez, Carlos; Mullen, Patrick; Rathbun, Elle; Prime, Kelly; Marini, Jessica; Patchefsky, Jamie; Patchefsky, Arthur S; Hailstone, Richard K; Erlichman, Joseph S

    2013-12-23

    Cerium oxide nanoparticles are potent antioxidants, based on their ability to either donate or receive electrons as they alternate between the +3 and +4 valence states. The dual oxidation state of ceria has made it an ideal catalyst in industrial applications, and more recently, nanoceria's efficacy in neutralizing biologically generated free radicals has been explored in biological applications. Here, we report the in vivo characteristics of custom-synthesized cerium oxide nanoparticles (CeNPs) in an animal model of immunological and free-radical mediated oxidative injury leading to neurodegenerative disease. The CeNPs are 2.9 nm in diameter, monodispersed and have a -23.5 mV zeta potential when stabilized with citrate/EDTA. This stabilizer coating resists being 'washed' off in physiological salt solutions, and the CeNPs remain monodispersed for long durations in high ionic strength saline. The plasma half-life of the CeNPs is ∼4.0 h, far longer than previously described, stabilized ceria nanoparticles. When administered intravenously to mice, the CeNPs were well tolerated and taken up by the liver and spleen much less than previous nanoceria formulations. The CeNPs were also able to penetrate the brain, reduce reactive oxygen species levels, and alleviate clinical symptoms and motor deficits in mice with a murine model of multiple sclerosis. Thus, CeNPs may be useful in mitigating tissue damage arising from free radical accumulation in biological systems.

  11. Mixed mode and sequential oscillations in the cerium-bromate-4-aminophenol photoreaction

    SciTech Connect

    Bell, Jeffrey G.; Wang Jichang

    2013-09-15

    Cerium was introduced to the bromate-aminophenol photochemical oscillator to implement coupled autocatalytic feedbacks. Mixed mode and sequential oscillations emerged in the studied system, making it one of the few chemical oscillators known to support consecutive bifurcations in a batch system. The complex reaction behavior showed a strong dependence on the intensity of illumination supplied to the system. Removal of illumination during an oscillatory window affected both the frequency and amplitude of the oscillation but did not fully extinguish them, indicating that the cerium-bromate-4-aminophenol oscillator was photosensitive rather than photo-controlled. A moderate light intensity allowed for a slow evolution of the system, which proved to be critical for the emergence of transient complex oscillations. Variation of individual reaction parameters was carried out, which indicated that the development of complex oscillations occur in a narrow region and a phase diagram in the 4-aminophenol and sulfuric acid plane demonstrated this. Simulations provide strong support that transient complex oscillations observed experimentally arise from the coupling of two autocatalytic cycles.

  12. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants.

    PubMed

    Tumburu, Laxminath; Andersen, Christian P; Rygiewicz, Paul T; Reichman, Jay R

    2015-01-01

    The effects of exposure to nanoparticles of titanium dioxide (nano-titanium) and cerium oxide (nano-cerium) on gene expression and growth in Arabidopsis thaliana germinants were studied by using microarrays and quantitative real-time polymerase chain reaction (qPCR), and by evaluating germinant phenotypic plasticity. Exposure to 12 d of either nano-titania or nano-ceria altered the regulation of 204 and 142 genes, respectively. Genes induced by the nanoparticles mainly include ontology groups annotated as stimuli responsive, including both abiotic (oxidative stress, salt stress, water transport) and biotic (respiratory burst as a defense against pathogens) stimuli. Further analysis of the differentially expressed genes indicates that both nanoparticles affected a range of metabolic processes (deoxyribonucleic acid [DNA] metabolism, hormone metabolism, tetrapyrrole synthesis, and photosynthesis). Individual exposures to the nanoparticles increased percentages of seeds with emergent radicles, early development of hypocotyls and cotyledons, and those with fully grown leaves. Although there were distinct differences between the nanoparticles in their affect on molecular mechanisms attributable to enhancing germinant growth, both particles altered similar suites of genes related to various pathways and processes related to enhanced growth. PMID:25242526

  13. Kinetics of Cerium(IV) Extraction from H(2)SO(4)-HF Medium with Cyanex 923.

    PubMed

    Liao, Wuping; Yu, Guihong; Yue, Shantang; Li, Deqian

    2002-03-11

    Studies of the extraction kinetics of cerium(IV) from H(2)SO(4)-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 kJ mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 kJ mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

  14. Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

    PubMed

    Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

    2015-10-14

    Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts. PMID:26355535

  15. Contribution of atmospheric nitrate deposition to nitrate loading in the Chesapeake Bay. Final report

    SciTech Connect

    Tyler, M.

    1988-12-01

    Recent studies have suggested that nitrate introduced into the Chesapeake Bay via atmospheric deposition may be a significant source of excess nutrients. In order to determine if concerns about atmospheric deposition are justified, modeled estimates of wetfall nitrate deposition over the Chesapeake Bay basin, based on monitoring data collected in 1984, were used to estimate basin-wide nitrate loading (1.38 x 10/sup 8/ kg) over the land area of the basin. Estimates of transfer coefficients and nitrate loadings to the Bay for various land-use categories were also calculated, using figures developed by the EPA Chesapeake Bay Program. The conservative nature of assumptions made in developing these figures suggests that the actual percentage contribution of atmospheric nitrate deposition may be lower than the estimated value.

  16. Structural and mechanistic insights on nitrate reductases.

    PubMed

    Coelho, Catarina; Romão, Maria João

    2015-12-01

    Nitrate reductases (NR) belong to the DMSO reductase family of Mo-containing enzymes and perform key roles in the metabolism of the nitrogen cycle, reducing nitrate to nitrite. Due to variable cell location, structure and function, they have been divided into periplasmic (Nap), cytoplasmic, and membrane-bound (Nar) nitrate reductases. The first crystal structure obtained for a NR was that of the monomeric NapA from Desulfovibrio desulfuricans in 1999. Since then several new crystal structures were solved providing novel insights that led to the revision of the commonly accepted reaction mechanism for periplasmic nitrate reductases. The two crystal structures available for the NarGHI protein are from the same organism (Escherichia coli) and the combination with electrochemical and spectroscopic studies also lead to the proposal of a reaction mechanism for this group of enzymes. Here we present an overview on the current advances in structural and functional aspects of bacterial nitrate reductases, focusing on the mechanistic implications drawn from the crystallographic data. PMID:26362109

  17. Exclusion of Nitrate from Frozen Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Marrocco, H. A.; Michelsen, R. R.

    2013-12-01

    Reactions occurring at the surface of ice, sea ice, and snow in Earth's cryosphere have an impact on the composition of the overlying atmosphere. In order to elucidate reaction mechanisms and model their contributions to atmospheric processes, the morphology of frozen aqueous surfaces and amounts of reactants contained therein must be determined. To this end, the exclusion of nitrate ions to the surface of frozen aqueous solutions has been studied by attenuated total reflection infrared spectroscopy (ATR-IR). In this technique the near-surface region of the frozen films are interrogated to a depth of a few hundred nanometers from the film-crystal interface. Aqueous solutions (0.001 to 0.01 M) of sodium nitrate (NaNO3), magnesium nitrate (Mg(NO3)2), and nitric acid (HNO3) were quickly frozen on the germanium ATR crystal and observed at a constant temperature of about -18°C. In addition to ice and the solutes, liquid water in varying amounts was observed in the spectra. The amount of nitrate in the surface liquid is three to four orders of magnitude higher than in the unfrozen solution. While all the nitrate salts exhibit exclusion to the unfrozen surface, the dynamics are different for different counter-ions. Results are compared to freezing point depression data and the predictions of equilibrium thermodynamics.

  18. Cutaneous candidiasis: treatment with miconazole nitrate.

    PubMed

    Cullin, S I

    1977-01-01

    In a well-controlled, double-blind, randomized study, 30 patients with cutaneous candidiasis were treated with a 2% miconazole nitrate lotion or its placebo control. By the 14th day, 13 of the 15 patients [87%] treated with miconazole nitrate achieved clinical and mycologic cures. Only a single patient treated with the placebo lotion would be classified as a therapeutic cure. In a second portion of the study those patients judged to be therapeutic failures were treated with the lotion containing 2% miconazole nitrate. By combining the results of both portions of the study we find that miconazole nitrate lotion produced both a clinical and mycologic cure in all patients receiving the active lotion. The miconazole lotion formula was well tolerated by all patients and no side effects were noted. The fact that miconazole nitrate acts rapidly in relieving symptoms, is well tolerated, and is highly effective against dermatophytes, yeasts and gram-positive bacteria, makes it a welcome addition to available topical therapy of skin infections.

  19. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities. PMID:26901167

  20. Measurement of Isoprene Nitrates by GCMS

    NASA Astrophysics Data System (ADS)

    Mills, Graham; Hiatt-Gipson, Glyn; Bew, Sean; Reeves, Claire

    2016-04-01

    We have, for the first time, synthesised and identified the majority of the primary isoprene nitrates (INs), formed by reaction of isoprene with the hydroxyl radical (OH) and nitrate radical (NO3) as described in the Master Chemical Mechanism (MCM). An instrument based on gas chromatography/mass spectrometry (GCMS) and the associated calibration methods is described for the speciated measurements of individual isoprene nitrate isomers. Seven of the primary isoprene nitrates formed by reaction of the OH with isoprene in the MCM and three primary isoprene nitrates from the reaction of the NO3 and isoprene are identified, including six newly synthesised INs. Simple photochemistry bag experiments were performed to demonstrate the capability to measure speciated INs in complex mixtures. Interestingly, the results showed isomeric distributions of INs that were quite different to those predicted by model calculations in earlier studies. In addition, we observed INs that we would expect from NO3 addition to isoprene despite the bag experiments being carried out in daylight conditions when we would expect OH to be the only isoprene oxidant.

  1. Ion Pairing in Alkali Nitrate Electrolyte Solutions.

    PubMed

    Xie, Wen Jun; Zhang, Zhen; Gao, Yi Qin

    2016-03-10

    In this study, we investigate the thermodynamics of alkali nitrate salt solutions, especially the formation of contact ion pairs between alkali cation and nitrate anion. The ion-pairing propensity shows an order of LiNO3 < NaNO3 < KNO3. Such results explain the salt activity coefficients and suggest that the empirical "law of matching water affinity" is followed by these alkali nitrate salt solutions. The spatial patterns of contact ion pairs are different in the three salt solutions studied here: Li(+) forms the contact ion pair with only one oxygen of the nitrate while Na(+) and K(+) can also be shared by two oxygens of the nitrate. In reproducing the salt activity coefficient using Kirkwood-Buff theory, we find that it is essential to include electronic polarization for Li(+) which has a high charge density. The electronic continuum correction for nonpolarizable force field significantly improves the agreement between the calculated activity coefficients and their experimental values. This approach also improves the performance of the force field on salt solubility. From these two aspects, this study suggests that electronic continuum correction can be a promising approach to force-field development for ions with high charge densities.

  2. 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).

  3. Near-road modeling and measurement of cerium-containing particles generated by nanoparticle diesel fuel additive use

    EPA Science Inventory

    Cerium oxide nanoparticles (nCe) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the exhaust particles are not well understood. To bridge the gap between emission measurements and ambient impac...

  4. A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

    NASA Astrophysics Data System (ADS)

    Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

    2015-01-01

    This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

  5. Predicting the Effects of Nano-Scale Cerium Additives in Diesel Fuel on Regional-Scale Air Quality

    EPA Science Inventory

    Diesel vehicles are a major source of air pollutant emissions. Fuel additives containing nanoparticulate cerium (nCe) are currently being used in some diesel vehicles to improve fuel efficiency. These fuel additives also reduce fine particulate matter (PM2.5) emissio...

  6. Germination and early plant development of ten plant species exposed to titanium dioxide and cerium oxide nanoparticles

    EPA Science Inventory

    Ten agronomic plant species were exposed to different concentrations of nano titanium dioxide (nTiO2) or nano cerium oxide (nCeO2) (0, 250, 500 and 1000 mg/L) to examine potential effects on germination and early seedling development. We modified a standard test protocol develop...

  7. Molecular Components of Nitrate and Nitrite Efflux in Yeast

    PubMed Central

    Cabrera, Elisa; González-Montelongo, Rafaela; Giraldez, Teresa; de la Rosa, Diego Alvarez

    2014-01-01

    Some eukaryotes, such as plant and fungi, are capable of utilizing nitrate as the sole nitrogen source. Once transported into the cell, nitrate is reduced to ammonium by the consecutive action of nitrate and nitrite reductase. How nitrate assimilation is balanced with nitrate and nitrite efflux is unknown, as are the proteins involved. The nitrate assimilatory yeast Hansenula polymorpha was used as a model to dissect these efflux systems. We identified the sulfite transporters Ssu1 and Ssu2 as effective nitrate exporters, Ssu2 being quantitatively more important, and we characterize the Nar1 protein as a nitrate/nitrite exporter. The use of strains lacking either SSU2 or NAR1 along with the nitrate reductase gene YNR1 showed that nitrate reductase activity is not required for net nitrate uptake. Growth test experiments indicated that Ssu2 and Nar1 exporters allow yeast to cope with nitrite toxicity. We also have shown that the well-known Saccharomyces cerevisiae sulfite efflux permease Ssu1 is also able to excrete nitrite and nitrate. These results characterize for the first time essential components of the nitrate/nitrite efflux system and their impact on net nitrate uptake and its regulation. PMID:24363367

  8. Ammonium and nitrate tolerance in lichens.

    PubMed

    Hauck, Markus

    2010-05-01

    Since lichens lack roots and take up water, solutes and gases over the entire thallus surface, these organisms respond more sensitively to changes in atmospheric purity than vascular plants. After centuries where effects of sulphur dioxide and acidity were in the focus of research on atmospheric chemistry and lichens, recently the globally increased levels of ammonia and nitrate increasingly affect lichen vegetation and gave rise to intense research on the tolerance of lichens to nitrogen pollution. The present paper discusses the main findings on the uptake of ammonia and nitrate in the lichen symbiosis and to the tolerance of lichens to eutrophication. Ammonia and nitrate are both efficiently taken up under ambient conditions. The tolerance to high nitrogen levels depends, among others, on the capability of the photobiont to provide sufficient amounts of carbon skeletons for ammonia assimilation. Lowly productive lichens are apparently predisposed to be sensitive to excess nitrogen.

  9. Organic nitrates: past, present and future.

    PubMed

    França-Silva, Maria S; Balarini, Camille M; Cruz, Josiane C; Khan, Barkat A; Rampelotto, Pabulo H; Braga, Valdir A

    2014-09-24

    Nitric oxide (NO) is one of the most important vasodilator molecules produced by the endothelium. It has already been established that NO/cGMP signaling pathway deficiencies are involved in the pathophysiological mechanisms of many cardiovascular diseases. In this context, the development of NO-releasing drugs for therapeutic use appears to be an effective alternative to replace the deficient endogenous NO and mimic the role of this molecule in the body. Organic nitrates represent the oldest class of NO donors that have been clinically used. Considering that tolerance can occur when these drugs are applied chronically, the search for new compounds of this class with lower tolerance potential is increasing. Here, we briefly discuss the mechanisms involved in nitrate tolerance and highlight some achievements from our group in the development of new organic nitrates and their preclinical application in cardiovascular disorders.

  10. Nitrate in aquifers beneath agricultural systems

    USGS Publications Warehouse

    Burkart, M.R.; Stoner, J.D.

    2002-01-01

    Research from several regions of the world provides spatially anecdotal evidence to hypothesize which hydrologic and agricultural factors contribute to groundwater vulnerability to nitrate contamination. Analysis of nationally consistent measurements from the U.S. Geological Survey's NAWOA program confirms these hypotheses for a substantial range of agricultural systems. Shallow unconfined aquifers are most susceptible to nitrate contamination associated with agricultural systems. Alluvial and other unconsolidated aquifers are the most vulnerable and shallow carbonate aquifers provide a substantial but smaller contamination risk. Where any of these aquifers are overlain by permeable soils the risk of contamination is larger. Irrigated systems can compound this vulnerability by increasing leaching facilitated by additional recharge and additional nutrient applications. The agricultural system of corn, soybeans, and hogs produced significantly larger concentrations of groundwater nitrate than all other agricultural systems, although mean nitrate concentrations in counties with dairy, poultry, cattle and grains, and horticulture systems were similar. If trends in the relation between increased fertilizer use and groundwater nitrate in the United States are repeated in other regions of the world, Asia may experience increasing problems because of recent increases in fertilizer use. Groundwater monitoring in Western and Eastern Europe as well as Russia over the next decade may provide data to determine if the trend in increased nitrate contamination can be reversed. If the concentrated livestock trend in the United States is global, it may be accompanied by increasing nitrogen contamination in groundwater. Concentrated livestock provide both point sources in the confinement area and intense non-point sources as fields close to facilities are used for manure disposal. Regions where irrigated cropland is expanding, such as in Asia, may experience the greatest impact of

  11. Halide Ion Enhancement of Nitrate Ion Photolysis

    NASA Astrophysics Data System (ADS)

    Richards, N. K.; Wingen, L. M.; Callahan, K. M.; Tobias, D. J.; Finlayson-Pitts, B. J.

    2009-12-01

    Nitrate ion photochemistry is an important source of NOx in the polar regions. It is uncertain whether coexisting ions such as halides play a role in nitrate photochemistry. The effect of halides on NO3 photolysis was investigated using photolysis experiments in 230 L Teflon chambers that contain deliquesced aerosols of NaBr:NaNO3, KBr:KNO3 and ternary mixtures of NaCl:NaBr:NaNO3. Gas phase NO2 and gaseous halogen products were measured as a function of photolysis time using long path FTIR, NOx chemiluminescence and API-MS (atmospheric pressure ionization mass spectrometry). Experiments were conducted with NO3- held at a constant 0.5 M and with the amount of total halide concentration varying from 0.25 M to 4 M. Studies on NaBr:NaNO3 mixtures suggest that as the bromide ion to nitrate ion ratio increases, there is an enhancement in the rate of production of NO2 in the nitrate-bromide mixtures over that formed in the photolysis of NaNO3. Molecular dynamic (MD) simulations provide molecular level insight into the ions near the air-water interface in the aqueous halide-nitrate mixtures. These studies suggest that the presence of sodium halides at the air-water interface may encourage some nitrate ions to approach the top layers of water, allowing for more efficient escape of photoproducts than is seen in the absence of halides. Experiments on mixtures of KBr:KNO3 are being conducted to determine potential cation effects. In addition, ternary mixtures of NaCl:NaBr:NaNO3 are being examined to determine the effects of mixtures of halides on production of NO2 and gaseous halogen products. The implications of this photochemistry for tropospheric chemistry will be discussed.

  12. Nitrate postdeposition processes in Svalbard surface snow

    NASA Astrophysics Data System (ADS)

    Björkman, Mats P.; Vega, Carmen P.; Kühnel, Rafael; Spataro, Francesca; Ianniello, Antonietta; Esposito, Giulio; Kaiser, Jan; Marca, Alina; Hodson, Andy; Isaksson, Elisabeth; Roberts, Tjarda J.

    2014-11-01

    The snowpack acts as a sink for atmospheric reactive nitrogen, but several postdeposition pathways have been reported to alter the concentration and isotopic composition of snow nitrate with implications for atmospheric boundary layer chemistry, ice core records, and terrestrial ecology following snow melt. Careful daily sampling of surface snow during winter (11-15 February 2010) and springtime (9 April to 5 May 2010) near Ny-Ålesund, Svalbard reveals a complex pattern of processes within the snowpack. Dry deposition was found to dominate over postdeposition losses, with a net nitrate deposition rate of (0.6 ± 0.2) µmol m-2 d-1 to homogeneous surface snow. At Ny-Ålesund, such surface dry deposition can either solely result from long-range atmospheric transport of oxidized nitrogen or include the redeposition of photolytic/bacterial emission originating from deeper snow layers. Our data further confirm that polar basin air masses bring 15N-depleted nitrate to Svalbard, while high nitrate δ(18O) values only occur in connection with ozone-depleted air, and show that these signatures are reflected in the deposited nitrate. Such ozone-depleted air is attributed to active halogen chemistry in the air masses advected to the site. However, here the Ny-Ålesund surface snow was shown to have an active role in the halogen dynamics for this region, as indicated by declining bromide concentrations and increasing nitrate δ(18O), during high BrO (low-ozone) events. The data also indicate that the snowpack BrO-NOx cycling continued in postevent periods, when ambient ozone and BrO levels recovered.

  13. Nitrate in aquifers beneath agricultural systems.

    PubMed

    Burkart, M R; Stoner, J D

    2002-01-01

    Research from several regions of the world provides spatially anecdotal evidence to hypothesize which hydrologic and agricultural factors contribute to groundwater vulnerability to nitrate contamination. Analysis of nationally consistent measurements from the U.S. Geological Survey's NAWOA program confirms these hypotheses for a substantial range of agricultural systems. Shallow unconfined aquifers are most susceptible to nitrate contamination associated with agricultural systems. Alluvial and other unconsolidated aquifers are the most vulnerable and shallow carbonate aquifers provide a substantial but smaller contamination risk. Where any of these aquifers are overlain by permeable soils the risk of contamination is larger. Irrigated systems can compound this vulnerability by increasing leaching facilitated by additional recharge and additional concentrations of groundwater nitrate than all other agricultural systems, although mean nitrate concentrations in counties with dairy, poultry, cattle and grains, and horticulture systems were similar. If trends in the relation between increased fertilizer use and groundwater nitrate in the United States are repeated in other regions of the world, Asia may experience increasing problems because of recent increases in fertilizer use. Groundwater monitoring in Western and Eastern Europe as well as Russia over the next decade may provide data to determine if the trend in increased nitrate contamination can be reversed. If the concentrated livestock trend in the United States is global, it may be accompanied by increasing nitrogen contamination in groundwater. Concentrated livestock provide both point sources in the confinement area and intense non-point sources as fields close to facilities are used for manure disposal. Regions where irrigated cropland is expanding, such as in Asia, may experience the greatest impact of this practice.

  14. Biodegradation of glycidol and glycidyl nitrate.

    PubMed

    Kaplan, D L; Cornell, J H; Kaplan, A M

    1982-01-01

    When calcium hydroxide is used to desensitize glycerol trinitrate (nitroglycerine)-containing waste streams, the epoxides glycidol and glycidyl nitrate are formed. The epoxide rings of both compounds are unstable to heat in aqueous solutions, and they open to form glycerol 1-mononitrate and presumably glycerol. These transformations were accelerated by microbial activity. Glycerol 1-mononitrate was slowly denitrated to form glycerol. Glycidol and glycidyl nitrate caused base-pair substitutions in the Ames test for mutagenicity, whereas glycerol 1-mononitrate tests were negative.

  15. Methylhydrazinium nitrate. [rocket plume deposit chemistry

    NASA Technical Reports Server (NTRS)

    Lawton, E. A.; Moran, C. M.

    1983-01-01

    Methylhydrazinium nitrate was synthesized by the reaction of dilute nitric acid with methylhydrazine in water and in methanol. The white needles formed are extremely hygroscopic and melt at 37.5-40.5 C. The IR spectrum differs from that reported elsewhere. The mass spectrum exhibited no parent peak at 109 m/z, and thermogravimetric analysis indicated that the compound decomposed slowly at 63-103 C to give ammonium and methylammonium nitrate. The density is near 1.55 g/cu cm.

  16. A Reservoir of Nitrate Beneath Desert Soils

    USGS Publications Warehouse

    Walvoord, M.A.; Phillips, F.M.; Stonestrom, D.A.; Evans, R.D.; Hartsough, P.C.; Newman, B.D.; Striegl, R.G.

    2003-01-01

    A large reservoir of bioavailable nitrogen (upto ???104 kilograms of nitrogen per hectare, as nitrate) has been previously overlooked in studies of global nitrogen distribution. The reservoir has been accumulating in subsoil zones of and regions throughout the Holocene. Consideration of the subsoil reservoir raises estimates of vadose-zone nitrogen inventories by 14 to 71% for warm deserts and arid shrublands worldwide and by 3 to 16% globally. Subsoil nitrate accumulation indicates long-term leaching from desert soils, impelling further evaluation of nutrient dynamics in xeric ecosystems. Evidence that subsoil accumulations are readily mobilized raises concern about groundwater contamination after land-use or climate change.

  17. A reservoir of nitrate beneath desert soils.

    PubMed

    Walvoord, Michelle A; Phillips, Fred M; Stonestrom, David A; Evans, R Dave; Hartsough, Peter C; Newman, Brent D; Striegl, Robert G

    2003-11-01

    A large reservoir of bioavailable nitrogen (up to approximately 10(4) kilograms of nitrogen per hectare, as nitrate) has been previously overlooked in studies of global nitrogen distribution. The reservoir has been accumulating in subsoil zones of arid regions throughout the Holocene. Consideration of the subsoil reservoir raises estimates of vadose-zone nitrogen inventories by 14 to 71% for warm deserts and arid shrublands worldwide and by 3 to 16% globally. Subsoil nitrate accumulation indicates long-term leaching from desert soils, impelling further evaluation of nutrient dynamics in xeric ecosystems. Evidence that subsoil accumulations are readily mobilized raises concern about groundwater contamination after land-use or climate change.

  18. Biodegradation of Glycidol and Glycidyl Nitrate

    PubMed Central

    Kaplan, David L.; Cornell, John H.; Kaplan, Arthur M.

    1982-01-01

    When calcium hydroxide is used to desensitize glycerol trinitrate (nitroglycerine)-containing waste streams, the epoxides glycidol and glycidyl nitrate are formed. The epoxide rings of both compounds are unstable to heat in aqueous solutions, and they open to form glycerol 1-mononitrate and presumably glycerol. These transformations were accelerated by microbial activity. Glycerol 1-mononitrate was slowly denitrated to form glycerol. Glycidol and glycidyl nitrate caused base-pair substitutions in the Ames test for mutagenicity, whereas glycerol 1-mononitrate tests were negative. PMID:16345917

  19. SEPARATION OF URANYL NITRATE BY EXTRACTION

    DOEpatents

    Stoughton, R.W.; Steahly, F.L.

    1958-08-26

    A process is presented for obtaining U/sup 233/ from solutions containing Pa/sup 233/. A carrier precipitate, such as MnO/sub 2/, is formed in such solutions and carries with it the Pa/sup 233/ present. This precipitate is then dissolved in nitric acid and the solution is aged to allow decay of the Pa/ sup 233/ into U/sup 233/. After a sufficient length of time the U/sup 233/ bearing solution is made 2.5 to 4.5 Molar in manganese nitrate by addition thereof, and the solution is then treated with ether to obtain uranyl nitrate by solvent extraction techniques.

  20. Techniques for Measurement of Nitrate Movement in Soils

    NASA Technical Reports Server (NTRS)

    Broadbent, F. E.

    1971-01-01

    Contamination of surface and ground waters with nitrate usually involves leaching through soil of nitrate produced by mineralization of soil organic matter, decomposition of animal wastes or plant residues, or derived from fertilizers. Nitrate concentrations in the soil solution may be measured by several chemical procedures or by the nitrate electrode. since nitrate is produced throughout the soil mass it is difficult to identify a source of nitrate contamination by conventional means. This problem can be solved by use of N-15-enriched or N-15-depleted materials as tracers. The latter is particularly attractive because of the negligible possibility of the tracer hazardous to health.

  1. Nitrate isotope fractionations during biological nitrate reduction: Insights from first principles theoretical modeling

    NASA Astrophysics Data System (ADS)

    Guo, W.; Granger, J.; Sigman, D. M.

    2010-12-01

    Coupled fractionations of N and O isotopes during biological nitrate reduction provide important constraints on the marine nitrogen cycle at present and in the geologic past. Recent laboratory experiments with mono-cultures of nitrate-assimilative algae and plankton, and denitrifying bacteria demonstrate that N and O isotopic compositions of the residual nitrate co-vary linearly with a constant ratio (i.e., Δδ18O: Δδ15N) of ~1 or ~0.6 [1]. These systematic variations have been inferred to derive from the kinetic isotope fractionations associated with nitrate reductases. The isotope fractionation mechanisms at the enzymatic level, however, remain elusive. Here we present models of isotope fractionations accompanying the nitrate reduction (NO3-→NO2-) by three functional types of nitrate reductases, using techniques from ab initio, transition state and statistical thermodynamic theory. We consider three types of nitrate reductases: eukNR (eukaryotic assimilatory nitrate reductase), NAR (prokaryotic respiratory nitrate reductase) and Nap (prokaryotic periplasmic nitrate reductase). All are penta- or hexa-coordinated molybdo-enzymes, but bear considerable differences in protein geometry among functional types. Our models, based on the simplified structures of their active sites, predict N and O isotope effects (15ɛ and 18ɛ) ranging from 32.7 to 36.6‰ and from 33.5 to 34.8‰, respectively, at 300K with 18ɛ:15ɛ ratios of 0.9-1.1. The predicted amplitudes of N and O isotope fractionations are in the range measured for eukNR in vitro (~27‰, Karsh et al. in prep), and also correspond to the upper amplitudes observed for denitrifiers in vivo (~25‰, [1]). Moreover, the computed 18ɛ:15ɛ ratios corroborate the consistent relationships of ~1 observed experimentally for eukNR and the respiratory NAR. These findings indicate the enzymatic reduction is likely the rate-limiting step in most biological nitrate reductions. In addition, the predicted similarity of 18

  2. Efficient syntheses of climate relevant isoprene nitrates and (1R,5S)-(−)-myrtenol nitrate

    PubMed Central

    Hiatt-Gipson, Glyn D; Mills, Graham P; Reeves, Claire E

    2016-01-01

    Summary 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. PMID:27340495

  3. 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.

  4. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    NASA Technical Reports Server (NTRS)

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.

    2004-01-01

    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  5. A model cerium oxide matrix composite reinforced with a homogeneous dispersion of silver particulate - prepared using the glycine-nitrate process

    SciTech Connect

    Weil, K. Scott; Hardy, John S.

    2005-01-31

    Recently a new method of ceramic brazing has been developed. Based on a two-phase liquid composed of silver and copper oxide, brazing is conducted directly in air without the need of an inert cover gas or the use of surface reactive fluxes. Because the braze displays excellent wetting characteristics on a number ceramic surfaces, including alumina, various perovskites, zirconia, and ceria, we were interested in investigating whether a metal-reinforced ceramic matrix composite (CMC) could be developed with this material. In the present study, two sets of homogeneously mixed silver/copper oxide/ceria powders were synthesized using a combustion synthesis technique. The powders were compacted and heat treated in air above the liquidus temperature for the chosen Ag-CuO composition. Metallographic analysis indicates that the resulting composite microstructures are extremely uniform with respect to both the size of the metallic reinforcement as well as its spatial distribution within the ceramic matrix. The size, morphology, and spacing of the metal particulate in the densified composite appears to be dependent on the original size and the structure of the starting combustion synthesized powders.

  6. COGEMA Experience in Uranous Nitrate Preparation

    SciTech Connect

    Tison, E.; Bretault, Ph.

    2006-07-01

    Separation and purification of plutonium by PUREX process is based on a sequence of extraction and back extraction which requires reducing plutonium Pu IV (extractable form) into Pu III (inextractable form) Different reducers can be used to reduce Pu IV into Pu III. Early plants such as that for Magnox fuel at Sellafield used ferrous sulfamate while UP 1 at Marcoule used uranous sulfamate. These reducers are efficient and easy to prepare but generates ferric and/or sulphate ions and so complicates management of the wastes from the plutonium purification cycle. Recent plants such as UP3 and UP2 800 at La Hague, THORP at Sellafield, and RRP at Rokkasho Mura (currently under tests) use uranous nitrate (U IV) stabilized by hydrazinium nitrate (N{sub 2}H{sub 5}NO{sub 3}) and hydroxyl ammonium nitrate (HAN). In the French plants, uranous nitrate is used in U-Pu separation and alpha barrier and HAN is used in Pu purification. Compared to sulfamate, U IV does not generate extraneous chemical species and uranyl nitrate (U VI) generated by reducing Pu IV follows the main uranium stream. More over uranous nitrate is prepared from reprocessed purified uranyl nitrate taken at the outlet of the reprocessing plant. Hydrazine and HAN offer the advantage to be salt-free reagents. Uranous nitrate can be generated either by electrolysis or by catalytic hydrogenation process. Electrolytic process has been implemented in early plant UP 1 at Marcoule (when changing reducer from uranous sulfamate to uranous nitrate) and was used again in UP2 plant at La Hague. However, the electrolytic process presented several disadvantages such as a low conversion rate and problems associated with the use of mercury. Electrolysis cells with no mercury were developed for the Eurochemic plant in Belgium and then implemented in the first Japanese reprocessing plant in Tokai-Mura. But finally, in 1975, the electrolytic process was abandoned in favor of the catalytic hydrogenation process developed at La

  7. Freshwater dispersion stability of PAA-stabilised cerium oxide nanoparticles and toxicity towards Pseudokirchneriella subcapitata.

    PubMed

    Booth, Andy; Størseth, Trond; Altin, Dag; Fornara, Andrea; Ahniyaz, Anwar; Jungnickel, Harald; Laux, Peter; Luch, Andreas; Sørensen, Lisbet

    2015-02-01

    An aqueous dispersion of poly (acrylic acid)-stabilised cerium oxide (CeO₂) nanoparticles (PAA-CeO₂) was evaluated for its stability in a range of freshwater ecotoxicity media (MHRW, TG 201 and M7), with and without natural organic matter (NOM). In a 15 day dispersion stability study, PAA-CeO₂ did not undergo significant aggregation in any media type. Zeta potential varied between media types and was influenced by PAA-CeO₂ concentration, but remained constant over 15 days. NOM had no influence on PAA-CeO₂ aggregation or zeta potential. The ecotoxicity of the PAA-CeO₂ dispersion was investigated in 72 h algal growth inhibition tests using the freshwater microalgae Pseudokirchneriella subcapitata. PAA-CeO₂ EC₅₀ values for growth inhibition (GI; 0.024 mg/L) were 2-3 orders of magnitude lower than pristine CeO₂ EC₅₀ values reported in the literature. The concentration of dissolved cerium (Ce(3+)/Ce(4+)) in PAA-CeO₂ exposure suspensions was very low, ranging between 0.5 and 5.6 μg/L. Free PAA concentration in the exposure solutions (0.0096-0.0384 mg/L) was significantly lower than the EC10 growth inhibition (47.7 mg/L) value of pure PAA, indicating that free PAA did not contribute to the observed toxicity. Elemental analysis indicated that up to 38% of the total Cerium becomes directly associated with the algal cells during the 72 h exposure. TOF-SIMS analysis of algal cell wall compounds indicated three different modes of action, including a significant oxidative stress response to PAA-CeO₂ exposure. In contrast to pristine CeO₂ nanoparticles, which rapidly aggregate in standard ecotoxicity media, PAA-stabilised CeO₂ nanoparticles remain dispersed and available to water column species. Interaction of PAA with cell wall components, which could be responsible for the observed biomarker alterations, could not be excluded. This study indicates that the increased dispersion stability of PAA-CeO₂ leads to an increase in toxicity compared to

  8. Adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface: dependence on the configuration of the cerium 4f electrons

    SciTech Connect

    Beste, Ariana; Mullins, David R; Overbury, Steven {Steve} H; Harrison, Robert J

    2008-01-01

    The adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface is studied using the PW91 functional as well as the PW91+U scheme. We investigate the influence of the detailed electronic structure of the Ce 4f band on the chemistry of methanol on the surface. For the partially reduced surface we obtain a spin delocalized, a ferromagnetic, and an anti-ferromagnetic solution. We find that the qualitative conclusions are independent of the surface type used. Methanol adsorption is exothermic on the fully oxidized as well as on the partially reduced surface. Also dissociation of methanol on the surface is exothermic but strongly enhanced by the presence of a vacancy. We localize an on-top methoxy species as a dissociation product on the fully oxidized surface and a triply bridged methoxy species on the partially reduced surface where the methoxy oxygen partly fills the oxygen vacancy in the surface. Adsorption energies are influenced by the introduction of the repulsive Hubbard (U) term. On the other hand, relative surface stabilities like dissociation energies are less sensitive.

  9. Assimilatory Nitrate Reduction in Hansenula polymorpha

    NASA Astrophysics Data System (ADS)

    Rossi, Beatrice; Berardi, Enrico

    In the last decade, the yeast Hansenula polymorpha (syn.: Pichia angusta) has become an excellent experimental model for genetic and molecular investigations of nitrate assimilation, a subject traditionally investigated in plants, filamentous fungi and bacteria. Among other advantages, H. polymorpha offers classical and molecular genetic tools, as well as the availability of genomic sequence data.

  10. Enzyme catalytic nitration of aromatic compounds.

    PubMed

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration. PMID:26002502

  11. Nitrates, Nitrites, and Health. Bulletin 750.

    ERIC Educational Resources Information Center

    Deeb, Barbara S.; Sloan, Kenneth W.

    This review is intended to assess available literature in order to define the range of nitrate/nitrite effects on animals. Though the literature deals primarily with livestock and experimental animals, much of the contemporary research is concerned with human nitrite intoxication. Thus, the effects on man are discussed where appropriate. Some of…

  12. Negative ion spectrometry for detecting nitrated explosives

    NASA Technical Reports Server (NTRS)

    Boettger, H. G.; Yinon, J.

    1975-01-01

    Ionization procedure is modified to produce mainly negative ions by electron capture. Peaks of negative ions are monitored conventionally. Nitrated organic materials could be identified directly from sample sniff inlet stream by suitably modified mass spectrometer because of unique electronegativity which nitro group imparts to organic material.

  13. Denitration of High Nitrate Salts Using Reductants

    SciTech Connect

    HD Smith; EO Jones; AJ Schmidt; AH Zacher; MD Brown; MR Elmore; SR Gano

    1999-05-03

    This report describes work conducted by Pacific Northwest National Laboratory (PNNL), in conjunction with Idaho National Engineering and Environmental Laboratory (INEEL), to remove nitrates in simulated low-activity waste (LAW). The major objective of this work was to provide data for identifying and demonstrating a technically viable and cost-effective approach to condition LAW for immobilization (grout).

  14. Nitrate Salt Surrogate Blending Scoping Test Plan

    SciTech Connect

    Anast, Kurt Roy

    2015-11-13

    Test blending equipment identified in the “Engineering Options Assessment Report: Nitrate Salt Waste Stream Processing”. Determine if the equipment will provide adequate mixing of zeolite and surrogate salt/Swheat stream; optimize equipment type and operational sequencing; impact of baffles and inserts on mixing performance; and means of validating mixing performance

  15. A toxicological study of gadolinium nitrate

    SciTech Connect

    London, J.E.

    1988-05-01

    The sensitization study in the guinea pig did not show gadolinium nitrate to have potential sensitizing properties. Skin application studies in the rabbit demonstrated that it was cutaneously a severe irritant. This material was considered an irritant in the rabbit eye application studies. 3 refs., 1 tab.

  16. 76 FR 70366 - Ammonium Nitrate Security Program

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-11-14

    ... Department previously announced a series of public meetings on the same topic on October 2, 2011 (see 76 FR... public comment on August 3, 2011. See 73 FR 64280 (advance notice of proposed rulemaking); 76 FR 46908... SECURITY Office of the Secretary 6 CFR Part 31 RIN 1601-AA52 Ammonium Nitrate Security Program...

  17. 76 FR 62311 - Ammonium Nitrate Security Program

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-07

    ... FR 64280 (advance notice of proposed rulemaking); 76 FR 46908 (notice of proposed rulemaking...; ] DEPARTMENT OF HOMELAND SECURITY Office of the Secretary 6 CFR Part 31 RIN 1601-AA52 Ammonium Nitrate Security.... SUMMARY: The National Protection and Programs Directorate of the Department of Homeland Security...

  18. Enzyme catalytic nitration of aromatic compounds.

    PubMed

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun

    2015-06-01

    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration.

  19. Background-like nitrate in desert air

    NASA Astrophysics Data System (ADS)

    Wu, Feng; Zhang, Daizhou; Cao, Junji; Zhang, Ting; An, Zhisheng

    2014-02-01

    The atmospheric nitrogen cycle is a key process driving the earth's environmental evolution. Current model studies require knowledge of NOx soil emissions from various land types, but desert emissions remain unquantified or are not addressed with high confidence. Our measurements at two observatories in Taklimakan desert during a dust episode showed an approximately stable and dust-independent nitrate in the air. Its concentration estimated from PM2.5, PM10 and TSP samples under non-dust, floating dust and dust storm conditions was 3.81 ± 1.24 μg m-3, 2.95 ± 0.69 μg m-3, 4.99 ± 1.71 μg m-3, respectively, despite the more-than-one-order difference of dust loading. This concentration was much larger than that in remote marine and tropical forest air. Comprehensive investigation revealed a similar presence of nitrate in other desert air. The nitrate was hypothesized to be the consequence of the conversion of NOx released from desert soils. These results indicate a background-like nitrate and active reactions of nitrogen compounds in desert air.

  20. 76 FR 47238 - Ammonium Nitrate From Russia

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-08-04

    ...)). Background The Commission instituted this review on March 1, 2011 (76 FR 11273) and determined on June 6, 2011 that it would conduct an expedited review (76 FR 34749, June 14, 2011). The Commission transmitted... COMMISSION Ammonium Nitrate From Russia Determination On the basis of the record \\1\\ developed in the...

  1. 76 FR 11273 - Ammonium Nitrate From Russia

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-03-01

    ... nitrate from Russia (71 FR 17080). The Commission is now conducting a second review to determine whether... recently amended at 74 FR 2847 (January 16, 2009). \\1\\ No response to this request for information is... (65 FR 37759, June 16, 2000). Following five-year reviews by Commerce and the Commission,...

  2. Silver nitrate masquerading as a radiopaque foreign body.

    PubMed

    Healy, Claragh; Canney, Mark; Murphy, Adrian; Regan, Padraic

    2007-04-01

    Silver nitrate is commonly used as a method of chemical cauterization to areas of hypergranulation. We report two cases wherein silver nitrate in the hand was misinterpreted radiologically as foreign bodies.

  3. Perchlorate and nitrate in situ bioremediation of ground water

    SciTech Connect

    Strietelmeier, E. A.; Nuttall, H. Eric; Hatzinger, Paul; Goltz, Mark

    2002-01-01

    Nitrate and perchlorate are growing worldwide problems as mobile anionic groundwater contaminants. Biological rduction of nitrate and perchlorate in groundwater is under development as a technology to address these problems.

  4. Cerium-based binary and ternary oxides in the transesterification of dimethylcarbonate with phenol.

    PubMed

    Dibenedetto, Angela; Angelini, Antonella; di Bitonto, Luigi; De Giglio, Elvira; Cometa, Stefania; Aresta, Michele

    2014-04-01

    Diphenyl carbonate (DPC) plays a key role in phosgene-free carbonylation processes. It can be produced by transesterification of dimethyl carbonate (DMC) with phenol in the presence of catalysts. Methyl phenyl carbonate (MPC) is first produced that is then converted into DPC by either disproportionation or further transesterification with phenol. Cerium-based bimetallic oxides (with the heterometal being niobium, iron, palladium, or aluminum) are used as catalysts in the transesterification of DMC to synthesize MPC. The catalytic activity is affected by the type and concentration of the heterometal. XPS, IR and elementary analyses are employed to characterize the new catalysts. Differently from pure oxides, the mixed oxides produce a significant increase of the conversion and selectivity towards MPC. PMID:24616260

  5. Stability and morphology of cerium oxide surfaces in an oxidizing environment: A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Fronzi, Marco; Soon, Aloysius; Delley, Bernard; Traversa, Enrico; Stampfl, Catherine

    2009-09-01

    We present density functional theory investigations of the bulk properties of cerium oxides (CeO2 and Ce2O3) and the three low index surfaces of CeO2, namely, (100), (110), and (111). For the surfaces, we consider various terminations including surface defects. Using the approach of "ab initio atomistic thermodynamics," we find that the most stable surface structure considered is the stoichiometric (111) surface under "oxygen-rich" conditions, while for a more reducing environment, the same (111) surface, but with subsurface oxygen vacancies, is found to be the most stable one, and for a highly reducing environment, the (111) Ce-terminated surface becomes energetically favored. Interestingly, this latter surface exhibits a significant reconstruction in that it becomes oxygen terminated and the upper layers resemble the Ce2O3(0001) surface. This structure could represent a precursor to the phase transition of CeO2 to Ce2O3.

  6. Cerium oxide-chitosan based nanobiocomposite for food borne mycotoxin detection

    NASA Astrophysics Data System (ADS)

    Kaushik, Ajeet; Solanki, Pratima R.; Pandey, M. K.; Ahmad, Sharif; Malhotra, Bansi D.

    2009-10-01

    Cerium oxide nanoparticles (NanoCeO2) and chitosan (CH) based nanobiocomposite film deposited onto indium-tin-oxide coated glass substrate has been used to coimmobilize rabbit immunoglobin (r-IgGs) and bovine serum albumin (BSA) for food borne mycotoxin [ochratoxin-A (OTA)] detection. Electrochemical studies reveal that presence of NanoCeO2 increases effective electro-active surface area of CH-NanoCeO2/indium tin oxide (ITO) nanobiocomposite resulting in high loading of r-IgGs. BSA/r-IgGs/CH-NanoCeO2/ITO immunoelectrode exhibits improved linearity (0.25-6.0 ng/dl), detection limit (0.25 ng/dl), response time (25 s), sensitivity (18 μA/ng dl-1 cm-2), and regression coefficient (r2˜0.997).

  7. Cerium-activated sol-gel silica glasses for radiation dosimetry in harsh environment

    NASA Astrophysics Data System (ADS)

    El Hamzaoui, Hicham; Capoen, Bruno; Helou, Nissrine Al; Bouwmans, Géraud; Ouerdane, Youcef; Boukenter, Aziz; Girard, Sylvain; Marcandella, Claude; Duhamel, Olivier; Chadeyron, Geneviève; Mahiou, Rachid; Bouazaoui, Mohamed

    2016-04-01

    Cerium-doped silica glass has been prepared for ionizing radiation dosimetry applications, using the sol-gel route and densification under different atmospheres. In comparison with the glass densified under air atmosphere, the one obtained after sintering the xerogel under helium gas presents improved optical properties, with an enhancement of the photoluminescence quantum yield up to 33%, which is attributed to a higher Ce3+ ions concentration. Such a glassy rod has been jacketed in a quartz tube and then drawn at high temperature to a cane, which has been used as active material in a fibered remote x-ray radiation dosimeter. The sample exhibited a reversible linear radioluminescence intensity response versus the dose rate up to 30 Gy s-1. These results confirm the potentialities of this material for in vivo or high rate dose remote dosimetry measurements.

  8. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process.

  9. The induction of angiogenesis by cerium oxide nanoparticles through the modulation of oxygen in intracellular environments

    PubMed Central

    Das, Soumen; Singh, Sanjay; Dowding, Janet M.; Oommen, Saji; Kumar, Amit; Sayle, Thi X. T.; Saraf, Shashank; Patra, Chitta Ranjan; Vlahakis, Nicholas E.; Sayle, Dean C.; Self, William T.; Seal, Sudipta

    2012-01-01

    Angiogenesis is the formation of new blood vessels from existing blood vessels and is critical for many physiological and pathophysiological processes. In this study we have shown the unique property of cerium oxide nanoparticle (CNPs) to induce angiogenesis, observed using both in vitro and in vivo model systems. In particular, CNPs trigger angiogenesis by modulating the intracellular oxygen environment and stabilizing hypoxia inducing factor 1α endogenously. Furthermore, correlations between angiogenesis induction and CNPs physicochemical properties including: surface Ce3+/Ce4+ ratio, surface charge, size, and shape were also explored. High surface area and increased Ce3+/Ce4+ ratio make CNPs more catalytically active towards regulating intracellular oxygen, which in turn led to more robust induction of angiogenesis. Atomistic simulation was also used, in partnership with in vitro and in vivo experimentation, to reveal that the surface reactivity of CNPs and facile oxygen transport promotes pro-angiogenesis. PMID:22858004

  10. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process. PMID:27433701

  11. Optical Evidence of Itinerant-Localized Crossover of 4f Electrons in Cerium Compounds

    NASA Astrophysics Data System (ADS)

    Kimura, Shin-ichi; Kwon, Yong Seung; Matsumoto, Yuji; Aoki, Haruyoshi; Sakai, Osamu

    2016-08-01

    Cerium (Ce)-based heavy-fermion materials have a characteristic double-peak structure (mid-IR peak) in the optical conductivity [σ(ω)] spectra originating from the strong conduction (c)-f electron hybridization. To clarify the behavior of the mid-IR peak at a low c-f hybridization strength, we compared the σ(ω) spectra of the isostructural antiferromagnetic and heavy-fermion Ce compounds with the calculated unoccupied density of states and the spectra obtained from the impurity Anderson model. With decreasing c-f hybridization intensity, the mid-IR peak shifts to the low-energy side owing to the renormalization of the unoccupied 4f state, but suddenly shifts to the high-energy side owing to the f-f on-site Coulomb interaction at a slight localized side from the quantum critical point (QCP). This finding gives us information on the change in the electronic structure across QCP.

  12. Impact of electrolyte composition on the performance of the zinc-cerium redox flow battery system

    NASA Astrophysics Data System (ADS)

    Nikiforidis, Georgios; Berlouis, Léonard; Hall, David; Hodgson, David

    2013-12-01

    The zinc-cerium redox flow battery has the highest open circuit cell voltage (Ecell = 2.4 V) of all the common redox flow battery (RFB) systems being investigated. In this paper, carbon polymer composite materials based on polyvinyl ester and polyvinylidene difluoride are investigated as the negative electrode for this RFB system. Electrolyte composition, particularly on the negative side, is found to play a key role in maintaining high (˜90%) coulombic efficiencies for the different charge durations, from 10 min to 4 h, examined. Energy efficiencies >60% are obtained for temperatures in the range 45 °C-55 °C when the zinc ion concentration in the methanesulfonic acid electrolyte is 2.5 mol dm-3. No dependence of the energy efficiency on the flow velocity is found, over the range 7.5 cm s-1-13.5 cm-1.

  13. Predicting Cerium + H2O Cluster Formation with Simulated and Experimental Spectroscopy

    NASA Astrophysics Data System (ADS)

    Topolski, Josey E.; Kafader, Jared O.; Ray, Manisha; Chick Jarrold, Caroline

    2016-06-01

    Ceria (CeO2) has been established as a good support in heterogeneous catalysts for the water gas shift reaction. This study looks into cerium's reactivity with water, a water gas shift reagent, and aims to build an understanding of the three reactions which can occur: direct oxidation, -OH abstraction, and H2O addition. Through the use of anion photoelectron spectroscopy and density functional theory calculations we have been able to determine that the reactivity is dependent on (1) the oxidation states of the metal centers, (2) the availability of 5d orbitals to form metal oxide bonds, and (3) the presence of electrons in the 6s* orbital. The results of this study can be used to inform design of catalytic materials for the water gas shift reaction.

  14. Transition Probabilities for Neutral Cerium from Boltzmann Analysis of Fourier Transform Spectra

    NASA Astrophysics Data System (ADS)

    Nitz, D. E.; Curry, J. J.; Buuck, M. J.; Mitchell, N. P.; Demann, A. D.; Shull, W. E.

    2012-06-01

    The recent availability of a large set of absolute transition probabilities for neutral cerium (Lawler et. al., J. Phys. B 43, 85701 (2010)) makes it possible to investigate the relative populations of the upper levels of these lines in radiometrically-calibrated spectra. In cases where these populations can be characterized by a single effective Boltzmann temperature, applying this temperature enables one to determine additional absolute transition probabilities for observable decay branches of nearby levels. While not as accurate as measurements based on branching fractions and lifetimes, the method can be applied to levels whose lifetimes are not known and does not require accounting for all of the branches. We are analyzing Fourier Transform spectra from NIST and from the National Solar Observatory data archive at Kitt Peak via this technique, seeking to increase the set of known transition probabilities for Ce I by a factor of 2-3. A summary of results obtained to date will be presented.

  15. Sensitization of Pancreatic Cancer Cells to Radiation by Cerium Oxide Nanoparticle-Induced ROS Production

    PubMed Central

    Wason, Melissa S.; Colon, Jimmie; Das, Soumen; Seal, Sudipta; Turkson, James; Zhao, Jihe; Baker, Cheryl H.

    2012-01-01

    Side effect of radiation therapy (RT) remains the most challenging issue for pancreatic cancer treatment. In this report we determined whether and how cerium oxide nanoparticles (CONPs) sensitize pancreatic cancer cells to RT. CONP pretreatment enhanced radiation-induced reactive oxygen species (ROS) production preferentially in acidic cell-free solutions as well as acidic human pancreatic cancer cells. In acidic environments, CONPs favor the scavenging of superoxide radical over the hydroxyl peroxide resulting in accumulation of the latter whereas in neutral pH CONPs scavenge both. CONP treatment prior to RT markedly potentiated the cancer cell apoptosis both in culture and in tumors and the inhibition of the pancreatic tumor growth without harming the normal tissues or host mice. Taken together, these results identify CONPs as a potentially novel RT-sensitizer as well as protectant for improving pancreatic cancer treatment. PMID:23178284

  16. Electrochemical nitrate biosensor based on poly(pyrrole-viologen) film-nitrate reductase-clay composite.

    PubMed

    Cosnier, S; Da Silva, S; Shan, D; Gorgy, K

    2008-11-01

    The immobilization of nitrate reductase (NR) was performed by entrapment in a laponite clay gel and cross-linking by glutaraldehyde. In presence of nitrate and methyl viologen, a catalytic current appeared at -0.60 V illustrating the enzymatic reduction of nitrate into nitrite via the reduced form of the freely diffusing methyl viologen. The electropolymerization of a water-soluble pyrrole viologen derivative within the interlamellar spaces and channels of the host clay matrix successfully carried out the electrical wiring of the entrapped NR. Rotating disk measurements led to the determination of kinetic constants, namely k(2)=10.7 s(-1) and K(M)=7 microM. These parameters reflect the efficiency of the electro-enzymatic reduction of nitrate and the substrate affinity for the immobilized enzyme.

  17. Evidence for a plasma-membrane-bound nitrate reductase involved in nitrate uptake of Chlorella sorokiniana

    NASA Technical Reports Server (NTRS)

    Tischner, R.; Ward, M. R.; Huffaker, R. C.

    1989-01-01

    Anti-nitrate-reductase (NR) immunoglobulin-G (IgG) fragments inhibited nitrate uptake into Chlorella cells but had no affect on nitrate uptake. Intact anti-NR serum and preimmune IgG fragments had no affect on nitrate uptake. Membrane-associated NR was detected in plasma-membrane (PM) fractions isolated by aqueous two-phase partitioning. The PM-associated NR was not removed by sonicating PM vesicles in 500 mM NaCl and 1 mM ethylenediaminetetraacetic acid and represented up to 0.8% of the total Chlorella NR activity. The PM NR was solubilized by Triton X-100 and inactivated by Chlorella NR antiserum. Plasma-membrane NR was present in ammonium-grown Chlorella cells that completely lacked soluble NR activity. The subunit sizes of the PM and soluble NRs were 60 and 95 kDa, respectively, as determined by sodium-dodecyl-sulfate electrophoresis and western blotting.

  18. Molten nitrate salt technology development status report

    SciTech Connect

    Carling, R.W.; Kramer, C.M.; Bradshaw, R.W.; Nissen, D.A.; Goods, S.H.; Mar, R.W.; Munford, J.W.; Karnowsky, M.M.; Biefeld, R.N.; Norem, N.J.

    1981-03-01

    Recognizing thermal energy storage as potentially critical to the successful commercialization of solar thermal power systems, the Department of Energy (DOE) has established a comprehensive and aggressive thermal energy storage technology development program. Of the fluids proposed for heat transfer and energy storage molten nitrate salts offer significant economic advantages. The nitrate salt of most interest is a binary mixture of NaNO/sub 3/ and KNO/sub 3/. Although nitrate/nitrite mixtures have been used for decades as heat transfer and heat treatment fluids the use has been at temperatures of about 450/sup 0/C and lower. In solar thermal power systems the salts will experience a temperature range of 350 to 600/sup 0/C. Because central receiver applications place more rigorous demands and higher temperatures on nitrate salts a comprehensive experimental program has been developed to examine what effects, if any, the new demands and temperatures have on the salts. The experiments include corrosion testing, environmental cracking of containment materials, and determinations of physical properties and decomposition mechanisms. This report details the work done at Sandia National Laboratories in each area listed. In addition, summaries of the experimental programs at Oak Ridge National Laboratory, the University of New York, EIC Laboratories, Inc., and the Norwegian Institute of Technology on molten nitrate salts are given. Also discussed is how the experimental programs will influence the near-term central receiver programs such as utility repowering/industrial retrofit and cogeneration. The report is designed to provide easy access to the latest information and data on molten NaNO/sub 3//KNO/sub 3/ for the designers and engineers of future central receiver projects.

  19. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI)

    PubMed Central

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-01-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators—via a degradable coating—and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4 Gy, 5 ng-g−1 of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2 nm sized NPs, with an initial concentration of 1 mg-g−1, we found that 2–10 days of diffusion is required to obtain desired concentrations of CONPs in regions 1–2 cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  20. Interactive effects of cerium oxide and diesel exhaust nanoparticles on inducing pulmonary fibrosis

    PubMed Central

    Ma, Jane Y.C.; Young, Shih-Houng; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Ma, Joseph K.; Castranova, Vincent

    2015-01-01

    Cerium compounds have been used as a fuel-borne catalyst to lower the generation of diesel exhaust particles (DEPs), but are emitted as cerium oxide nanoparticles (CeO2) along with DEP in the diesel exhaust. The present study investigates the effects of the combined exposure to DEP and CeO2 on the pulmonary system in a rat model. Specific pathogen-free male Sprague–Dawley rats were exposed to CeO2 and/or DEP via a single intratracheal instillation and were sacrificed at various time points post-exposure. This investigation demonstrated that CeO2 induces a sustained inflammatory response, whereas DEP elicits a switch of the pulmonary immune response from Th1 to Th2. Both CeO2 and DEP activated AM and lymphocyte secretion of the proinflammatory cytokines IL-12 and IFN-γ respectively. However, only DEP enhanced the anti-inflammatory cytokine IL-10 production in response to ex vivo LPS or Concanavalin A challenge that was not affected by the presence of CeO2, suggesting that DEP suppresses host defense capability by inducing the Th2 immunity. The micrographs of lymph nodes show that the particle clumps in DEP + CeO2 were significantly larger than CeO2 or DEP, exhibiting dense clumps continuous throughout the lymph nodes. Morphometric analysis demonstrates that the localization of collagen in the lung tissue after DEP + CeO2 reflects the combination of DEP-exposure plus CeO2-exposure. At 4 weeks post-exposure, the histological features demonstrated that CeO2 induced lung phospholipidosis and fibrosis. DEP induced lung granulomas that were not significantly affected by the presence of CeO2 in the combined exposure. Using CeO2 as diesel fuel catalyst may cause health concerns. PMID:24793434

  1. Air, aqueous and thermal stabilities of Ce3+ ions in cerium oxide nanoparticle layers with substrates.

    PubMed

    Naganuma, Tamaki; Traversa, Enrico

    2014-06-21

    Abundant oxygen vacancies coexisting with Ce(3+) ions in fluorite cerium oxide nanoparticles (CNPs) have the potential to enhance catalytic ability, but the ratio of unstable Ce(3+) ions in CNPs is typically low. Our recent work, however, demonstrated that the abundant Ce(3+) ions created in cerium oxide nanoparticle layers (CNPLs) by Ar ion irradiation were stable in air at room temperature. Ce valence states in CNPs correlate with the catalytic ability that involves redox reactions between Ce(3+) and Ce(4+) ions in given application environments (e.g. high temperature in carbon monoxide gas conversion and immersion conditions in biomedical applications). To better understand the mechanism by which Ce(3+) ions achieve stability in CNPLs, we examined (i) extra-long air-stability, (ii) thermal stability up to 500 °C, and (iii) aqueous stability of Ce(3+) ions in water, buffer solution and cell culture medium. It is noteworthy that air-stability of Ce(3+) ions in CNPLs persisted for more than 1 year. Thermal stability results showed that oxidation of Ce(3+) to Ce(4+) occurred at 350 °C in air. Highly concentrated Ce(3+) ions in ultra-thin CNPLs slowly oxidized in water within 1 day, but stability was improved in the cell culture medium. Ce(3+) stability of CNPLs immersed in the medium was associated with phosphorus adsorption on the Ce(3+) sites. This study also illuminates the potential interaction mechanisms of stable Ce(3+) ions in CNPLs. These findings could be utilized to understand catalytic mechanisms of CNPs with abundant oxygen vacancies in their application environments.

  2. Cerium stable isotope ratios in ferromanganese deposits and their potential as a paleo-redox proxy

    NASA Astrophysics Data System (ADS)

    Nakada, Ryoichi; Takahashi, Yoshio; Tanimizu, Masaharu

    2016-05-01

    The cerium (Ce) anomaly observed in rare earth element (REE) patterns has been used to estimate the redox state of paleo-marine environments. Cerium is unique because it forms tetravalent cations under oxic conditions, in contrast to the other REEs that occur in a trivalent state. This characteristic leads to anomalously high or low Ce concentrations relative to neighboring REEs. However, the use of Ce anomaly as a paleo-redox proxy is not well calibrated. This study shows that coupling of the Ce anomaly and Ce stable isotope ratio (δ142Ce) is more quantitative redox proxy to distinguish suboxic and oxic redox conditions. Our results revealed a progressive enrichment in heavy Ce isotopes in consecutive formations of iron (Fe) and manganese (Mn) precipitate from hot spring water without any associated change in REE patterns. The δ142Ce values of Mn precipitates were approximately 0.35‰ heavier than those of the Fe precipitates, which was consistent with experiment-based predictions. The δ142Ce values of marine ferromanganese deposits with three different formation processes were hydrogenetic (+0.25‰) > diagenetic (+0.10‰) ⩾ hydrothermal (+0.05‰), which also reflects redox conditions of their formation environment. These observations suggest that the Ce stable isotope ratios yield more quantitative information regarding redox state than REE patterns alone. We thus suggest that this novel proxy can be successfully utilized to reconstruct marine redox states, particularly from slightly oxic to highly oxic conditions such as the Great Oxidation Event (GOE).

  3. Interactive effects of cerium oxide and diesel exhaust nanoparticles on inducing pulmonary fibrosis.

    PubMed

    Ma, Jane Y C; Young, Shih-Houng; Mercer, Robert R; Barger, Mark; Schwegler-Berry, Diane; Ma, Joseph K; Castranova, Vincent

    2014-07-15

    Cerium compounds have been used as a fuel-borne catalyst to lower the generation of diesel exhaust particles (DEPs), but are emitted as cerium oxide nanoparticles (CeO2) along with DEP in the diesel exhaust. The present study investigates the effects of the combined exposure to DEP and CeO2 on the pulmonary system in a rat model. Specific pathogen-free male Sprague-Dawley rats were exposed to CeO2 and/or DEP via a single intratracheal instillation and were sacrificed at various time points post-exposure. This investigation demonstrated that CeO2 induces a sustained inflammatory response, whereas DEP elicits a switch of the pulmonary immune response from Th1 to Th2. Both CeO2 and DEP activated AM and lymphocyte secretion of the proinflammatory cytokines IL-12 and IFN-γ, respectively. However, only DEP enhanced the anti-inflammatory cytokine IL-10 production in response to ex vivo LPS or Concanavalin A challenge that was not affected by the presence of CeO2, suggesting that DEP suppresses host defense capability by inducing the Th2 immunity. The micrographs of lymph nodes show that the particle clumps in DEP+CeO2 were significantly larger than CeO2 or DEP, exhibiting dense clumps continuous throughout the lymph nodes. Morphometric analysis demonstrates that the localization of collagen in the lung tissue after DEP+CeO2 reflects the combination of DEP-exposure plus CeO2-exposure. At 4 weeks post-exposure, the histological features demonstrated that CeO2 induced lung phospholipidosis and fibrosis. DEP induced lung granulomas that were not significantly affected by the presence of CeO2 in the combined exposure. Using CeO2 as diesel fuel catalyst may cause health concerns.

  4. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI).

    PubMed

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-04-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators-via a degradable coating-and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4Gy, 5ng·g(-1) of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2nm sized NPs, with an initial concentration of 1mg·g(-1), we found that 2-10days of diffusion is required to obtain desired concentrations of CONPs in regions 1-2cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  5. Salivary nitrate, nitrite and nitrate reductase activity in relation to risk of oral cancer in Egypt.

    PubMed

    Badawi, A F; Hosny, G; el-Hadary, M; Mostafa, M H

    1998-10-01

    It has been suggested that nitrate and nitrite may play a role in the etiology of human oral cancer. We investigated whether salivary nitrate and nitrite and the activity of nitrate reductase (NRase) may affect the risk of oral cancer in Egypt, an area with high levels of environmental nitrosating agents. Levels of salivary nitrite (8.3 +/- 1.0 micrograms/ml) and nitrate (44 +/- 3.7 micrograms/ml) and activity of NRase (74 +/- 10 nmol/ml/min) were significantly (P < 0.05) higher in oral cancer patients (n = 42) compared to control Egyptian healthy individuals (n = 40, nitrite = 5.3 +/- 0.3 micrograms/ml, nitrate = 27 +/- 1.2 micrograms/ml, and NRase activity = 46 +/- 4 nmol/ml/min). The adjusted odds ratio (OR) and the 95% confidence intervals (C.I.) for risk of oral cancer, categorized by the levels of salivary nitrate and nitrite and NRase activity, showed a higher cancer risk associated with nitrite > 7.5 micrograms/ml (OR: 3.0, C.I.: 1.0-9.3), nitrite > 40 micrograms/ml (OR: 4.3, C.I.: 1.4-13.3) and NRase activity > 50 nmol/ml/min (OR: 2.9, C.I.: 1.1-7.4). Our findings suggest that increased consumption of dietary nitrate and nitrite is associated with elevated levels of salivary nitrite. Together with the increased activity of salivary NRase, these observations may explain, at least in part, the role of nitrate and nitrite in the development of oral cancer in individuals from an area with a high burden of N-nitroso precursors.

  6. Redox conditions in the Late Cretaceous Chalk Sea: the possible use of cerium anomalies as palaeoredox indicators in the Cenomanian and Turonian Chalk of England

    NASA Astrophysics Data System (ADS)

    Jeans, Christopher V.; Wray, David S.; Williams, C. Terry

    2015-09-01

    The cerium anomalies preserved in the Chalk have been investigated as possible palaeoredox indicators of the Late Cretaceous Sea and its sediment. This has been based upon over a hundred new rare earth element analyses of selected samples and grain size fractions from the Chalk. Particular attention has been given to the methodology of differentiating between the cerium anomalies preserved in the bioclastic calcite and those in carbonate-fluorapatite preserved in the acetic acid insoluble residues of chalks. Variations in the cerium anomaly of different particle size fractions of uncemented chalks suggest that fractionation of rare earth elements between the Chalk's seawater and the various organisms that contributed skeletal material to the bioclastic calcite of the Chalk may have occurred. Post-depositional processes of calcite cementation and late diagenetic sulphidisation have had no apparent effect on the cerium anomaly of the acetic acid insoluble residues. The cerium anomalies associated with the acetic acid insoluble residues from (1) an alternating sequence of chalks and marls from Ballard Cliff (Dorset, UK) typical of Milankovitch cyclicity show a marked diagenetic pattern, whereas those from (2) non-volcanic and volcanic marls display a pattern that is best explained by the variations in the availability of phosphorus and the timing of argillisation of volcanic glass during diagenesis. The general conclusion is drawn that the cerium anomalies preserved in the Chalk can provide an insight into the changing palaeoredox conditions in the Late Cretaceous Sea as well as in the pore fluids of its sediments.

  7. Extraction of nitric acid, uranyl nitrate, and bismuth nitrate from aqueous nitric acid solutions with CMPO

    SciTech Connect

    Spencer, B.B.

    1995-08-01

    DOE sponsored development of the transuranium extraction (TRUEX) process for removing actinides from radioactive wastes. The solvent is a mixture of CMPO and TBP. Since the extraction characteristics of CMPO are not as well understood as those of TBP, the extraction of nitric acid, uranyl nitrate, and bismuth nitrate with CMPO (dissolved in n-dodecane) were studied. Results indicate that CMPO extracts nitric acid with a 1:1 stoichiometry; equilibrium constant is 2. 660{plus_minus}0.092 at 25 C, and extraction enthalpy is -5. 46{plus_minus}0.46 kcal/mol. Slope analysis indicates that uranyl nitrate extracts with a mixed equilibria of 1:1 and 2:1 stoichiometries in nearly equal proportion. Equil. constant of the 2: 1 extraction was 1.213 {times} 10{sup 6}{plus_minus}3.56 {times} 10{sup 4} at 25 C; reaction enthalpy was -9.610{plus_minus}0.594 kcal/mol. Nitration complexation constant is 8.412{plus_minus}0.579, with an enthalpy of -10.72{plus_minus}1.87 kcal/mol. Bismuth nitrate also extracts with a mixed equilibria of (perhaps) 1:1 and 2:1 stoichiometries. A 2:1 extraction equilibrium and a nitrate complexation adequately model the data. Kinetics and enthalpies were also measured.

  8. Thermal Conductivity of Eutectic Nitrates and Nitrates/Expanded Graphite Composite as Phase Change Materials.

    PubMed

    Xiao, Xin; Zhang, Peng; Meng, Zhao-Nan; Li, Ming

    2015-04-01

    Nitrates and eutectic nitrate mixtures are considered as potential phase change materials (PCMs) for the middle-temperature-range solar energy storage applications. But the extensive utilization is restricted by the poor thermal conductivity and thermal stability. In the present study, sodium nitrate-potassium nitrate eutectic mixture was used as the base PCM, and expanded graphite (EG) was added to the mixture so as to improve the thermal conductivities. The elaboration method consists of a physically mixing of salt powders with or without EG, and the composite PCMs were cold-compressed to form shape-stabilized PCMs at room temperature. The thermal conductivities of the composite PCMs fabricated by cold-compression were investigated at different temperatures by the steady state method. The results showed that the addition of EG significantly enhanced the thermal conductivities. The thermal conductivities of pure nitrates and nitrates/EG composite PCMs in solid state showed the behavior of temperature dependant, and they slightly decreased with the increase of the temperature.

  9. 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)

  10. Disposable nitrate-selective optical sensor based on fluorescent dye

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A simple, disposable thin-film optical nitrate sensor was developed. The sensor was fabricated by applying a nitrate-selective polymer membrane on the surface of a thin polyester film. The membrane was composed of polyvinylchloride (PVC), plasticizer, fluorescent dye, and nitrate-selective ionophore...

  11. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  12. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  13. Nitrate to ammonia ceramic (NAC) bench scale stabilization study

    SciTech Connect

    Caime, W.J.; Hoeffner, S.L.

    1995-10-01

    Department of Energy (DOE) sites such as the Hanford site, Idaho National Engineering Laboratory (INEL), Savannah River site, Oak Ridge National Laboratory (ORNL) have large quantities of sodium-nitrate based liquid wastes. A process to reduce the nitrates to ammonia has been developed at ORNL. This technology creates a sludge lower in nitrates. This report describes stabilization possibilities of the sludge.

  14. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  15. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  16. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  17. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  18. 9 CFR 319.2 - Products and nitrates and nitrites.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 9 Animals and Animal Products 2 2014-01-01 2014-01-01 false Products and nitrates and nitrites... and nitrates and nitrites. Any product, such as frankfurters and corned beef, for which there is a standard in this part and to which nitrate or nitrite is permitted or required to be added, may be...

  19. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  20. 21 CFR 176.320 - Sodium nitrate-urea complex.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Sodium nitrate-urea complex. 176.320 Section 176... Substances for Use Only as Components of Paper and Paperboard § 176.320 Sodium nitrate-urea complex. Sodium nitrate-urea complex may be safely used as a component of articles intended for use in...

  1. 21 CFR 176.320 - Sodium nitrate-urea complex.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Sodium nitrate-urea complex. 176.320 Section 176... Substances for Use Only as Components of Paper and Paperboard § 176.320 Sodium nitrate-urea complex. Sodium nitrate-urea complex may be safely used as a component of articles intended for use in...

  2. 9 CFR 319.2 - Products and nitrates and nitrites.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 9 Animals and Animal Products 2 2012-01-01 2012-01-01 false Products and nitrates and nitrites... and nitrates and nitrites. Any product, such as frankfurters and corned beef, for which there is a standard in this part and to which nitrate or nitrite is permitted or required to be added, may be...

  3. 21 CFR 176.320 - Sodium nitrate-urea complex.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sodium nitrate-urea complex. 176.320 Section 176... Paperboard § 176.320 Sodium nitrate-urea complex. Sodium nitrate-urea complex may be safely used as a..., packaging, transporting, or holding food, subject to the provisions of this section. (a) Sodium...

  4. 46 CFR 148.220 - Ammonium nitrate-phosphate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Ammonium nitrate-phosphate fertilizers. 148.220 Section... § 148.220 Ammonium nitrate-phosphate fertilizers. (a) This section applies to the stowage and... nitrate and containing a maximum of 0.4 percent total added combustible material or containing a...

  5. 46 CFR 148.220 - Ammonium nitrate-phosphate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Ammonium nitrate-phosphate fertilizers. 148.220 Section... § 148.220 Ammonium nitrate-phosphate fertilizers. (a) This section applies to the stowage and... nitrate and containing a maximum of 0.4 percent total added combustible material or containing a...

  6. 46 CFR 148.227 - Calcium nitrate fertilizers.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Calcium nitrate fertilizers. 148.227 Section 148.227... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.227 Calcium nitrate fertilizers. This part does not apply to commercial grades of calcium nitrate fertilizers consisting mainly...

  7. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  8. 46 CFR 148.227 - Calcium nitrate fertilizers.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Calcium nitrate fertilizers. 148.227 Section 148.227... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.227 Calcium nitrate fertilizers. This part does not apply to commercial grades of calcium nitrate fertilizers consisting mainly...

  9. 46 CFR 148.220 - Ammonium nitrate-phosphate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Ammonium nitrate-phosphate fertilizers. 148.220 Section... § 148.220 Ammonium nitrate-phosphate fertilizers. (a) This section applies to the stowage and... nitrate and containing a maximum of 0.4 percent total added combustible material or containing a...

  10. 9 CFR 319.2 - Products and nitrates and nitrites.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 9 Animals and Animal Products 2 2011-01-01 2011-01-01 false Products and nitrates and nitrites... and nitrates and nitrites. Any product, such as frankfurters and corned beef, for which there is a standard in this part and to which nitrate or nitrite is permitted or required to be added, may be...

  11. 46 CFR 148.227 - Calcium nitrate fertilizers.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Calcium nitrate fertilizers. 148.227 Section 148.227... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.227 Calcium nitrate fertilizers. This part does not apply to commercial grades of calcium nitrate fertilizers consisting mainly...

  12. 9 CFR 319.2 - Products and nitrates and nitrites.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 9 Animals and Animal Products 2 2013-01-01 2013-01-01 false Products and nitrates and nitrites... and nitrates and nitrites. Any product, such as frankfurters and corned beef, for which there is a standard in this part and to which nitrate or nitrite is permitted or required to be added, may be...

  13. 21 CFR 176.320 - Sodium nitrate-urea complex.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Sodium nitrate-urea complex. 176.320 Section 176... Substances for Use Only as Components of Paper and Paperboard § 176.320 Sodium nitrate-urea complex. Sodium nitrate-urea complex may be safely used as a component of articles intended for use in...

  14. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  15. 46 CFR 148.227 - Calcium nitrate fertilizers.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Calcium nitrate fertilizers. 148.227 Section 148.227... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.227 Calcium nitrate fertilizers. This part does not apply to commercial grades of calcium nitrate fertilizers consisting mainly...

  16. 9 CFR 319.2 - Products and nitrates and nitrites.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Products and nitrates and nitrites... and nitrates and nitrites. Any product, such as frankfurters and corned beef, for which there is a standard in this part and to which nitrate or nitrite is permitted or required to be added, may be...

  17. 40 CFR 721.7500 - Nitrate polyether polyol (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Nitrate polyether polyol (generic name... Substances § 721.7500 Nitrate polyether polyol (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance nitrate polyether polyol (PMN P88-2540)...

  18. The nitrate time bomb: a numerical way to investigate nitrate storage and lag time in the unsaturated zone.

    PubMed

    Wang, L; Butcher, A S; Stuart, M E; Gooddy, D C; Bloomfield, J P

    2013-10-01

    Nitrate pollution in groundwater, which is mainly from agricultural activities, remains an international problem. It threatens the environment, economics and human health. There is a rising trend in nitrate concentrations in many UK groundwater bodies. Research has shown it can take decades for leached nitrate from the soil to discharge into groundwater and surface water due to the 'store' of nitrate and its potentially long travel time in the unsaturated and saturated zones. However, this time lag is rarely considered in current water nitrate management and policy development. The aim of this study was to develop a catchment-scale integrated numerical method to investigate the nitrate lag time in the groundwater system, and the Eden Valley, UK, was selected as a case study area. The method involves three models, namely the nitrate time bomb-a process-based model to simulate the nitrate transport in the unsaturated zone (USZ), GISGroundwater--a GISGroundwater flow model, and N-FM--a model to simulate the nitrate transport in the saturated zone. This study answers the scientific questions of when the nitrate currently in the groundwater was loaded into the unsaturated zones and eventually reached the water table; is the rising groundwater nitrate concentration in the study area caused by historic nitrate load; what caused the uneven distribution of groundwater nitrate concentration in the study area; and whether the historic peak nitrate loading has reached the water table in the area. The groundwater nitrate in the area was mainly from the 1980s to 2000s, whilst the groundwater nitrate in most of the source protection zones leached into the system during 1940s-1970s; the large and spatially variable thickness of the USZ is one of the major reasons for unevenly distributed groundwater nitrate concentrations in the study area; the peak nitrate loading around 1983 has affected most of the study area. For areas around the Bowscar, Beacon Edge, Low Plains, Nord Vue

  19. The nitrate time bomb: a numerical way to investigate nitrate storage and lag time in the unsaturated zone.

    PubMed

    Wang, L; Butcher, A S; Stuart, M E; Gooddy, D C; Bloomfield, J P

    2013-10-01

    Nitrate pollution in groundwater, which is mainly from agricultural activities, remains an international problem. It threatens the environment, economics and human health. There is a rising trend in nitrate concentrations in many UK groundwater bodies. Research has shown it can take decades for leached nitrate from the soil to discharge into groundwater and surface water due to the 'store' of nitrate and its potentially long travel time in the unsaturated and saturated zones. However, this time lag is rarely considered in current water nitrate management and policy development. The aim of this study was to develop a catchment-scale integrated numerical method to investigate the nitrate lag time in the groundwater system, and the Eden Valley, UK, was selected as a case study area. The method involves three models, namely the nitrate time bomb-a process-based model to simulate the nitrate transport in the unsaturated zone (USZ), GISGroundwater--a GISGroundwater flow model, and N-FM--a model to simulate the nitrate transport in the saturated zone. This study answers the scientific questions of when the nitrate currently in the groundwater was loaded into the unsaturated zones and eventually reached the water table; is the rising groundwater nitrate concentration in the study area caused by historic nitrate load; what caused the uneven distribution of groundwater nitrate concentration in the study area; and whether the historic peak nitrate loading has reached the water table in the area. The groundwater nitrate in the area was mainly from the 1980s to 2000s, whilst the groundwater nitrate in most of the source protection zones leached into the system during 1940s-1970s; the large and spatially variable thickness of the USZ is one of the major reasons for unevenly distributed groundwater nitrate concentrations in the study area; the peak nitrate loading around 1983 has affected most of the study area. For areas around the Bowscar, Beacon Edge, Low Plains, Nord Vue

  20. Genetic basis for nitrate resistance in Desulfovibrio strains

    PubMed Central

    Korte, Hannah L.; Fels, Samuel R.; Christensen, Geoff A.; Price, Morgan N.; Kuehl, Jennifer V.; Zane, Grant M.; Deutschbauer, Adam M.; Arkin, Adam P.; Wall, Judy D.

    2014-01-01

    Nitrate is an inhibitor of sulfate-reducing bacteria (SRB). In petroleum production sites, amendments of nitrate and nitrite are used to prevent SRB production of sulfide that causes souring of oil wells. A better understanding of nitrate stress responses in the model SRB, Desulfovibrio vulgaris Hildenborough and Desulfovibrio alaskensis G20, will strengthen predictions of environmental outcomes of nitrate application. Nitrate inhibition of SRB has historically been considered to result from the generation of small amounts of nitrite, to which SRB are quite sensitive. Here we explored the possibility that nitrate might inhibit SRB by a mechanism other than through nitrite inhibition. We found that nitrate-stressed D. vulgaris cultures grown in lactate-sulfate conditions eventually grew in the presence of high concentrations of nitrate, and their resistance continued through several subcultures. Nitrate consumption was not detected over the course of the experiment, suggesting adaptation to nitrate. With high-throughput genetic approaches employing TnLE-seq for D. vulgaris and a pooled mutant library of D. alaskensis, we determined the fitness of many transposon mutants of both organisms in nitrate stress conditions. We found that several mutants, including homologs present in both strains, had a greatly increased ability to grow in the presence of nitrate but not nitrite. The mutated genes conferring nitrate resistance included the gene encoding the putative Rex transcriptional regulator (DVU0916/Dde_2702), as well as a cluster of genes (DVU0251-DVU0245/Dde_0597-Dde_0605) that is poorly annotated. Follow-up studies with individual D. vulgaris transposon and deletion mutants confirmed high-throughput results. We conclude that, in D. vulgaris and D. alaskensis, nitrate resistance in wild-type cultures is likely conferred by spontaneous mutations. Furthermore, the mechanisms that confer nitrate resistance may be different from those that confer nitrite resistance