The measurement of neptunium in fast reactor fuel reprocessing

International Nuclear Information System (INIS)

Mair, M.A.; Savage, D.J.; Kyffin, T.W.

1986-02-01

Analytical techniques have been developed to measure neptunium in the feed, waste and product streams of a fast reactor fuel reprocessing plant. The estimated level of one microgram per milligram of plutonium in some solutions presented severe separation and measurement problems. An initial separation stage was essential, and both ion exchange and solvent extraction using thenoyltrifluoroacetone were studied. The redox chemistry of neptunium necessary to achieve good separation is considered. Spectrophotometry measurement of the stable neptunium/arsenazo III complex was selected for the final neptunium determination with additional analysis by radiometric methods. Incomplete recovery of neptunium during the separation stages necessitated yield measurements, using either neptunium-237 as an internal standard or the short lived gamma active neptunium-239 isotope as a tracer. The distribution of neptunium between the waste and product streams is discussed, in relation to the chemistry of neptunium in the reprocessing plant. (author)

Neptunium determination in PUREX process

International Nuclear Information System (INIS)

Rawat, Neetika; Kar, Aishwarya S.; Tomar, B.S.; Pandey, M.P.; Umadevi, K.

2016-10-01

237 Np is one of the most important minor actinides present in nuclear spent fuel both from environmental and application point of view. The routing of neptunium to the particular stream of PUREX process is necessary for its separation and purification as 237 Np is the target nuclide for production of 238 Pu. The routing of neptunium to a particular PUREX stream will also help in better nuclear waste management, which in turn, will impart less bearing on the environment considering its long half life, alpha emitting properties and mobile nature. In order to route Neptunium to a particular stream of PUREX process, it is imperative to understand the distribution of neptunium in various process streams. Owing to high dose of actual samples, the neptunium distribution was studied using 239 Np tracer by simulating actual column conditions of PUREX streams in lab scale. The present study deals with neptunium determination in actual PUREX streams samples also. (author)

Solubility product of tetravalent neptunium hydrous oxide and its ionic strength dependence

Energy Technology Data Exchange (ETDEWEB)

Fujiwara, K.; Mori, T. [Japan Nuclear Cycle Development Institute (JNC), 4-33, Muramatsu, Tokai-mura, Naka-gun, Ibaraki-ken, 319-1194 (Japan); Kohara, Y. [Inspection and Development Company, 4-33, Muramatsu, Tokaimura, Naka-gun, Ibaraki-ken, 319-1112 (Japan)

2005-07-01

Full text of publication follows: Solubility products (K{sub sp}) are key parameters in the context of reliable assessment of actinides migration in the repository conditions of high level radioactive waste. Neptunium (Np(IV)) is one of the most important actinide elements in the assessment, because of its inventory and the long half-life. A few previous data for Np(IV) solubility are varied widely due to experimental difficulties related to the extremely low solubility. We carried out batch-type experiments under nitrogen atmosphere using a glovebox. Np(V) was reduced to Np(III) by bubbling 0.5 ppm H{sub 2} / N{sub 2} gas through the solution for 30 days in the presence of platinum black as catalyst. After reducing treatment, the Np(III) converted to Np(IV) by auto-oxidation within approximately three days. The solubilities of the Np(IV) were measured in the pHc ranging from 2 to 4, at room temperature (23 {+-} 2 deg. C), in ionic strength(I) = 0.1, 0.5, 1.0 and 2.0 M NaClO{sub 4}. The equilibrium condition was confirmed by over-saturation and under-saturation method. After the equilibrium, the pH{sub c} and the E{sub h} value of the suspension were measured. The suspension was then filtered using a filter with a NMWL of 3000 (less than 2 nm{phi}). The Np radio activity in the filtrate was determined by alpha spectrometry and absorption spectra of Np(IV). The solubility decreased with increasing pHc and the hydrolysis species are predominantly formed. From the obtained results, the solubility products (K{sub sp}) of Np hydroxide, for the reaction, NpO{sub 2} . xH{sub 2}O {r_reversible} Np{sup 4+} + 4OH{sup -} + (x-2)H{sub 2}O, at I = 0.1, 0.5, 1.0 and 2.0 were determined by using formation constants ({beta}{sub n}(I)), which were determined for the reaction, Np{sup 4+} + nOH{sup -} {r_reversible} Np(OH){sub n}{sup (4-n)+}. By using the specific interaction theory (SIT), the solubility product of tetravalent Np hydrous oxide is calculated to be log K{sub sp}{sup 0

Sorption of americium and neptunium by deep-sea sediments

International Nuclear Information System (INIS)

Higgo, J.J.W.; Rees, L.V.C.; Cronan, D.S.

1983-01-01

The sorption and desorption of americium and neptunium by a wide range of deep-sea sediments from natural sea water at 4 0 C has been studied using a carefully controlled batch technique. All the sediments studied should form an excellent barrier to the migration of americium since distribution coefficients were uniformly greater than 10 5 and the sorption-desorption reaction may not be reversible. The sorption of neptunium was reversible and, except for one red clay, the distribution coefficients were greater than 10 3 for all the sediments investigated. Nevertheless the migration of neptunium should also be effectively retarded by most deep-sea sediments even under relatively oxidizing conditions. The neptunium in solution remained in the V oxidation state throughout the experiments. Under the experimental conditions used colloidal americium was trapped by the sediment and solubility did not seem to be the controlling factor in the desorption of americium. (Auth.)

Corrosion of type 304L stainless steel in boiling dilute neptunium nitrate solution

International Nuclear Information System (INIS)

Motooka, Takafumi; Kiuchi, Kiyoshi

2003-01-01

Corrosion of type 304L stainless steel in nitric acid solution containing neptunium was studied under immersion and heat-transfer condition. Corrosion rates of stainless steel were obtained by the weight loss measurement and the quantitative analysis of metallic ions dissolved in solution. The surface morphology was observed by scanning electron microscopy. The corrosion acceleration mechanism was investigated by polarization measurement and spectrophotometry. The corrosion rate in boiling 9M nitric acid was accelerated by addition of neptunium. The corrosion of stainless steel was promoted under heat-transfer condition compared to immersion condition. In polarization measurements, the cathodic current was increased by addition of neptunium. Spectrophotometric measurements showed the oxidization of neptunium in boiling nitric acid. It was suggested that the accelerated corrosion in nitric acid solution containing neptunium was caused by re-oxidation of neptunium. (author)

Redox reactions of neptunium in tributyl phosphate-dodecane mixtures

International Nuclear Information System (INIS)

Wehrey, F.

1989-01-01

In relation with the reprocessing of irradiated fuels, disproportionation and oxidation by nitric acid of pentavalent neptunium in tributyl phosphate-dodecane mixtures have been studied. The experimental part of this work is based on spectrophotometric measurements. The disproportionation of pentavalent neptunium in organic perchloric medium is a second order reaction with respect to neptunium V. The reaction rate is strongly influenced by the perchloric acid concentration and has a higher value than in an aqueous medium. The reverse reaction in nitric media is a first order with respect to tetravalent and hexavalent ions. The reaction rate is a function of the reverse of the square of the nitric acid concentration. The energy of activation is the same than in aqueous medium. The oxidation rate of pentavalent neptunium by nitric acid is increased by nitrous acid. When no nitrous acid is added to the mixture, the reaction revealed to be autocatalytic, possesses an induction period. When nitrous and nitric acids are in excess to neptunium the reaction is first order with respect to neptunium. The reaction rate depends on the concentration of nitric acid and is a linear function of the concentration of nitrous acid. In tributyl phosphate dodecane mixtures the reaction occurs spontaneously. It is not the case in aqueous media. The values of thermodynamical and kinetical constants determined in this work could be used in a modelization of the behavior of neptunium in the reprocessing of irradiated fuels, which has to eliminate this element among its tasks [fr

Two-stage precipitation of neptunium (IV) oxalate

International Nuclear Information System (INIS)

Luerkens, D.W.

1983-07-01

Neptunium (IV) oxalate was precipitated using a two-stage precipitation system. A series of precipitation experiments was used to identify the significant process variables affecting precipitate characteristics. Process variables tested were input concentrations, solubility conditions in the first stage precipitator, precipitation temperatures, and residence time in the first stage precipitator. A procedure has been demonstrated that produces neptunium (IV) oxalate particles that filter well and readily calcine to the oxide

Surface Complexation of Neptunium(V) with Goethite

International Nuclear Information System (INIS)

Jerden, James L.; Kropf, A. Jeremy

2007-01-01

Batch adsorption experiments in which neptunium-bearing solutions were reacted with goethite (alpha-FeOOH) have been performed to study uptake mechanisms in sodium chloride and calcium-bearing sodium silicate solutions. This paper presents results identifying and quantifying the mechanisms by which neptunium is adsorbed as a function of pH and reaction time (aging). Also presented are results from tests in which neptunium is reacted with goethite in the presence of other cations (uranyl and calcium) that may compete with neptunium for sorption sites. The desorption of neptunium from goethite has been studied by re-suspending the neptunium-loaded goethite samples in solutions containing no neptunium. Selected reacted sorbent samples were analyzed by x-ray absorption spectroscopy (XAS) to determine the oxidation state and molecular speciation of the adsorbed neptunium. Results have been used to establish the pH adsorption edge of neptunium on goethite in sodium chloride and calcium-bearing sodium silicate solutions. The results indicate that neptunium uptake on goethite reaches 95% at a pH of approximately 7 and begins to decrease at pH values greater than 8.5. Distribution coefficients for neptunium sorption range from less than 1000 (moles/kg) sorbed / (moles/kg) solution at pH less than 5.0 to greater than 10,000 (moles/kg) sorbed / (moles/kg) solution at pH greater than 7.0. Distribution coefficients as high as 100,000 (moles/kg) sorbed / (moles/kg) solution were recorded for the tests done in calcite equilibrated sodium silicate solutions. XAS results show that neptunium complexes with the goethite surface mainly as Np(V) (although Np(IV) is prevalent in some of the longer-duration sorption tests). The neptunium adsorbed to goethite shows Np-O bond length of approximately 1.8 angstroms which is representative of the Np-O axial bond in the neptunyl(V) complex. This neptunyl(V) ion is coordinated to 5 or 6 equatorial oxygens with Np-O bond lengths of 2

Method of neptunium recovery into the product stream of the Purex second codecontamination step for LWR fuel reprocessing

Energy Technology Data Exchange (ETDEWEB)

Tsuboya, T; Nemoto, S; Hoshino, T; Segawa, T [Power Reactor and Nuclear Fuel Development Corp., Tokyo (Japan)

1973-04-01

The neptunium behavior in the second codecontamination step in Purex process of Power Reactor and Nuclear Fuel Development Corporation was experimentally studied, and the conditions for discharging neptunium in product stream were examined. Improved nitrous acid method was applied to the second codecontamination step. Nitrous acid (NaNO/sub 2/) was supplied to the 1st stage of extraction section at feed rate of 7.5 mM/hr, and hydrazine (hydrazine nitrate) was supplied to some stages near feed point at feed rate of 1.6 mM/hr, by using laboratory scale mixer-settlers having 6 ml of mixing volume and 17 ml of settling volume. Neptunium extraction behavior was analyzed by the code NEPTUN-I simulating neptunium concentration profile and by the code NEPTUN-II for calculating Np (V) and Np (VI) concentration. Batch experiments were performed for explaining the reduction reaction of Np (VI) in organic phase. After shaking the aqueous solution containing Np (VI) in 3 M nitric acid with the various volume ratios of TBP, both phases were separated, and the neptunium concentration was determined. In conclusion, the improved nitrous acid method was effective for the neptunium discharge in product stream when the flow ratio of organic phase to aqueous phase was increased to about three times.

Process chemistry of neptunium. Part II

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, N.; Ramaniah, M. V.; Patil, S. K.; Ramakrishna, V. V.; Swarup, R.; Chadha, A.; Avadhany, G. V.N.

1974-07-01

The oxidation state analysis of neptunium in the aqueous feed solution from the Plutonium Plant at Trombay was carried out and it was found that neptunium existed mainly as Np(V) in the feed solution. Batch extraction data for Np(IV) and Np(VI) into 30% TBP/Shell Sol T at different aqueous nitric acid concentration and uranium saturation of the organic phase were obtained at 45 deg C and 60 deg C and the results are summarized. The distribution coefficients of Np(IV) and Np(VI) were obtained as a function of TBP concentration and the data are reported. The effect of nitrous acid on the extraction of neptunium, present in the aqueous phase as Np(IV) and Np(V), by 30% TBP was studied and the data obtained are given. The data on the rate of reduction of NP(VI) and Np(V) to Np(IV) by U(IV) were obtained for different U(IV) and nitric acid concentrations. Some redox reactions involving Np(IV), Pu(IV) and V(V) were investigated and their possible application in the purex process for neptunium recovery were explored. (auth)

Transuranium element chalcogenides. Crystallochemistry and Moessbauer spectrometry of neptunium 237 chalcogenides

International Nuclear Information System (INIS)

Thevenin, T.; Pages, M.; Damien, D.

1981-09-01

To study actinide compounds , neptunium 237 has been studied by Moessbauer resonance. The different oxidation degrees of neptunium (7, 6, 5, 4 and 3) have a very important effect on isomeric displacements. In the study of chalcogenides, the isomeric displacement value of NpS 3 confirms the valency 4+ of neptunium in this compound. Results obtained with Np 3 S 5 show two valency state +3 and +4 in this compound. There is a good agreement with the two crystalline sites determined by crystallography [fr

Investigation of Neptunium Precipitator Cleanout Options

International Nuclear Information System (INIS)

Hill, B.C.

2003-01-01

Oxalate precipitation followed by filtration is used to prepare plutonium oxalate. Historically, plutonium oxalate has tended to accumulate in the precipitation tanks. These solids are periodically removed by flushing with concentrated (64 percent) nitric acid. The same precipitation tanks will now be used in the processing of neptunium. Literature values indicate that neptunium oxalate may not be as soluble as plutonium oxalate in nitric acid. Although a wide variety of options is available to improve neptunium oxalate solubility for precipitator flushing, most of these options are not practical for use. Many of these options require the use of incompatible or difficult to handle chemicals. Other options would require expensive equipment modifications or are likely to lead to product contamination. Based on review of literature and experimental results, the two best options for flushing the precipitator are (1) 64 percent nitric acid and (2) addition of sodium permanganate follow ed by sodium nitrite. Nitric acid is the easiest option to implement. It is already used in the facility and will not lead to product contamination. Experimental results indicate that neptunium oxalate can be dissolved in concentrated nitric acid (64 percent) at 60 degree C to a concentration of 2.6 to 5.6 grams of Np/liter after at least three hours of heating. A lower concentration (1.1 grams of Np/liter) was measured at 60 degree C after less than two hours of heating. These concentrations are acceptable for flushing if precipitator holdup is low (approximately 100-250 grams), but a second method is required for effective flushing if precipitator holdup is high (approximately 2 kilograms). The most effective method for obtaining higher neptunium concentrations is the use of sodium permanganate followed by the addition of sodium nitrite. There is concern that residual manganese from these flushes could impact product purity. Gas generation during permanganate addition is also a concern

Comparison of neptunium sorption results using batch and column techniques

International Nuclear Information System (INIS)

Triay, I.R.; Furlano, A.C.; Weaver, S.C.; Chipera, S.J.; Bish, D.L.

1996-08-01

We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments under static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases

X-ray photoemission spectroscopy (XPS) study of uranium, neptunium and plutonium oxides in silicate-based glasses

International Nuclear Information System (INIS)

Lam, D.J.; Veal, B.W.; Paulikas, A.P.

1982-11-01

Using XPS as the principal investigative tool, we are in the process of examining the bonding properties of selected metal oxides added to silicate glass. In this paper, we present results of XPS studies of uranium, neptunium, and plutonium in binary and multicomponent silicate-based glasses. Models are proposed to account for the very diverse bonding properties of 6+ and 4+ actinide ions in the glasses

Metabolism and toxicity of neptunium

International Nuclear Information System (INIS)

Nenot, J.C.

1983-08-01

The biological behaviour and toxicity of neptunium were studied. Neptunium was administered either intravenously or intramuscularly in rats. In contrast to other transuranium elements the distribution patterns of neptunium in the case of intravenous injection is not dependent on the physico-chemical state. Urinary excretion is high. The distribution after intramuscular injection showed a rather fast migration from the injection site. 237 Neptonium in urine was approximately equal to bone deposit. Neptunium behaviour followed that of alkaline earths rather than that of transplutonium elements

Organometallic neptunium(III) complexes.

Science.gov (United States)

Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

Organometallic neptunium(III) complexes

Science.gov (United States)

Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

Separation of different valency states of neptunium from processing solutions

International Nuclear Information System (INIS)

Shabana, R.; EL-Naggar, H.A.

1990-01-01

The three main oxidation states of neptunium (Np(IV),Np(V) and Np(V I)) have been separated from each other by solvent extraction and extraction chromatographic techniques. The separation procedure is based on a systematic study of the extraction behaviour of each oxidation state using TBP as an extractant. The purity of separated species is identified using spectrophotometry

Fluorescent determination of neptunium in plutonium

International Nuclear Information System (INIS)

Alexandruk, V.M.; Babaev, A.S.; Dem'yanova, T.A.; Stepanov, A.V.

1991-01-01

This paper describes a new procedure for direct determination of Neptunium in Plutonium using laser induced time resolved fluorescence method. The procedure based on measurement of fluorescence intensity of Neptunium followed its concentration in effective layer of pellet of calcium fluoride. Detection limit of determination of Neptunium is 2 10 -12 g. At the level of Neptunium content in Plutonium more than 5 ppm relative standard deviation is equal 0.08-0.12. For carrying out of single measurement it is necessary neither more nor less 5 mkg Plutonium

Neptunium (IV) oxalate solubility

International Nuclear Information System (INIS)

Luerkens, D.W.

1983-07-01

The equilibrium solubility of neptunium (IV) oxalate in nitric/oxalic acid solutions was determined at 22 0 C, 45 0 C, and 60 0 C. The concentrations of nitric/oxalic acid solutions represented a wide range of free oxalate ion concentration. A mathematical solubility model was developed which is based on the formation of the known complexes of neptunium (IV) oxalate. the solubility model uses a simplified concentration parameter which is proportional to the free oxalate ion concentration. The solubility model can be used to estimate the equilibrium solubility of neptunium (IV) oxalate over a wide range of oxalic and nitric acid concentrations at each temperature

The metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

International Nuclear Information System (INIS)

Ralston, L.G.; Cohen, N.; Bhattacharyya, H.; Larsen, R.P.; Ayres, L.; Oldham, R.D.; Moretti, E.S.

1985-01-01

The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Neptunium-239, Np-237, and Pa-233 were prepared as either citrate-buffer, nitrate, or bicarbonate solutions with oxidation states of (V) and (VI). Samples of blood, urine, feces and autopsy tissues were measured by gamma spectrometry. Retention of neptunium and protactinium was determined in vivo using whole and partial body gamma-scintillation spectrometry with [NaI-CsI(T1)] detectors. Fed and fasted baboons were administered solutions of Np(VI) bicarbonate (10/sup -8/ to 10/sup -1/ mg/kg) and Pa(V) citrate-buffer (10/sup -9/ mg/kg) by gavage. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 + 2% was in liver, and 42 +- 0.1% was excreted in urine. The metabolism of neptunium followed oral and iv administrations was found to be similar. This observation was also true for baboons which had received oral and iv doses of protactinium. A method was developed to estimate GI absorption values for both nuclides in baboons, which were not sacrificed, by comparison of activities present in bioassay samples after injection and gavage. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. Further experiments are currently underway to evaluate this assay technique

Action of copper (3) in periodate complex on hexavalent neptunium and plutonium in alkaline medium

International Nuclear Information System (INIS)

Shatokhina, O.B.; Alekseeva, D.P.; Peretrukhin, B.F.; Krot, N.N.

1977-01-01

A complex of trivalent copper connected with periodate has been studied in order to determine its possible use for oxidizing hexavalent transuranium elements. Proceeding from the dependence of formal potentials of the pairs Cusup((3))-Cusup((2)), Npsup((7))-Npsup((6)), Pusup((7))-Pusup((6)) on alkali concentration, it has been established that beginning with concentration 1M the potential of the pair Cusup((3))-Cusup((2)) is higher than that of the pair Npsup((7))-Npsup((6)) by approximately 50 mV. This means that a rather complete oxidation of hexavalent neptunium to heptavalent is possible by the action of copper (3) excess on neptunium (6) when KOH concentration is 1M and higher. Oxidation close to quantitative is attained in 1M KOH when excess of copper(3) is used and the ratio Npsup((6)): Cusup((3)) is 1:4 and higher. When KOH concentration is more than 1M a sufficiently complete oxidation (96-97%) of neptunium (6) is attained at Npsup((6)):Cusup((3))=1:2 or 1:3. Optimum conditions for oxidizing plutonium are 11M KOH and 2-3-fold excess of copper (3) reagent. At 9M KOH and a ratio Pusup((6)):Cusup((3))=1:2 the yield of Pu (7) is 33 %

Biology of neptunium

International Nuclear Information System (INIS)

Wirth, R.E.

1985-11-01

This work contains detailed information about fractional absorption of neptunium through gastrointestinal tract in vivo as well as about organ and subcellular distribution in rats. Biochemical investigations have shown, that neptunium is bound to the iron transport protein transferrin in the blood serum. A long-term experiment resulted in osteosarkomincidences of 11% (0.2 mp Np-237/kg) and 36% (1 mg Np-237/kg); simultaneous the whole-body retention was measured during the natural lifespan of the animals of 2.5 years. (orig.) [de

Adsorption of neptunium and plutonium on metal phosphites

International Nuclear Information System (INIS)

Silver, G.L.

1979-01-01

The removal of neptunium and plutonium from water by adsorption on titanium, zirconium, bismuth, thorium, and uranium phosphites was investigated. These phosphites hydrolyze in neutral or alkaline solution producing the hydrous metal oxides that are more effective adsorbents than the original phosphite compounds. Ageing the plutonium-238 polymer changes its adsorption characteristics on commercial bone char. 37 figures, 7 tables

Determination of neptunium by redox titration

International Nuclear Information System (INIS)

Godbole, A.G.; Patil, S.K.

1979-01-01

A simple and quick method for the potentiometric determination of neptunium on the 2 to 5 mg scale has been developed. It consists of oxidation to Np(VI) by AgO or fuming with HClO 4 , destruction of excess of AgO by sulphamic acid, reduction of Np(VI) to Np(IV) with a slight excess of standard Fe(II) in 2M H 2 SO 4 and potentiometric titration of the excess of Fe(II) with standard Ce(IV). The precision is +- 0.5%. (author)

The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

International Nuclear Information System (INIS)

Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

2017-01-01

In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

Investigations into the sorption of neptunium by loose rock from the cap rock of the Gorleben salt dome under aerobic and anaerobic conditions

International Nuclear Information System (INIS)

Muehlenweg, U.

1988-01-01

In the experiments with the natural loose rock the sorption behaviour of neptunium was essentially determined by the chemical form in which the neptunium occurred in the ground waters. Under aerobic conditions with Eh values of 300 mV, neptunium in its oxidation state +5 occurred. At a pH of 2 + , and at pH > 8 as carbonato complex. The found neptunium species were relatively mobile, with sorption values from 1 ml/g to 20 ml/g. The sorption of neptunium is comparable to that of alkali and alkaline earth ions, such as Cs + or Sr 2+ . Cations attached to the rock surface are exchanged for NpO 2 + . Sorption in this case is reversible. (orig.) [de

Gastrointestinal absorption of neptunium in primates: effect of ingested mass, diet, and fasting

International Nuclear Information System (INIS)

Metivier, H.; Bourges, J.; Fritsch, P.; Nolibe, D.; Masse, R.

1986-01-01

Absorption and retention of neptunium were determined in baboons after intragastric administration of neptunium nitrate solutions at pH 1. The effects of mass, diet, and fasting on absorption were studied. At higher mass levels (400-800 micrograms Np/kg), absorption was about 1%; at lower mass intakes (0.0009-0.005 micrograms Np/kg), absorption was reduced by 10- to 20-fold. The addition of an oxidizing agent (Fe3+) increased gastrointestinal absorption and supported the hypothesis of a reduction of Np (V) when loss masses were ingested. Diets depleted of or enriched with hydroxy acids did not modify retention of neptunium but increased urinary excretion with increasing hydroxy acid content. The diet enriched with milk components reduced absorption by a factor of 5. Potatoes increased absorption and retention by a factor 5, not necessarily due to the effect of phytate. Fasting for 12 or 24 h increased retention and absorption by factors of about 3 and 10, respectively. Data obtained in baboons when low masses of neptunium were administered suggest that the f1 factor used by ICRP should be decreased. However, fasting as encountered in certain nutritional habits is a factor to be taken into consideration

Factors Controlling Redox Speciation of Plutonium and Neptunium in Extraction Separation Processes

Energy Technology Data Exchange (ETDEWEB)

Paulenova, Alena [Principal Investigator; Vandegrift, III, George F. [Collaborator

2013-09-24

The objective of the project was to examine the factors controlling redox speciation of plutonium and neptunium in UREX+ extraction in terms of redox potentials, redox mechanism, kinetics and thermodynamics. Researchers employed redox-speciation extractions schemes in parallel to the spectroscopic experiments. The resulting distribution of redox species w studied uring spectroscopic, electrochemical, and spectro-electrochemical methods. This work reulted in collection of data on redox stability and distribution of redox couples in the nitric acid/nitrate electrolyte and the development of redox buffers to stabilize the desired oxidation state of separated radionuclides. The effects of temperature and concentrations on the redox behavior of neptunium were evaluated.

Solvent extraction of irradiated neptunium targets. I. Valence stabilization

International Nuclear Information System (INIS)

Thompson, G.H.; Thompson, M.C.

1977-01-01

Solvent extraction of 237 Np and 238 Pu from irradiated neptunium is being investigated as a possible replacement for the currently used anion exchange process at the Savannah River Plant. Solvent extraction would reduce separations costs and waste volume and increase the production rate. The major difficulty in solvent extraction processing is maintaining neptunium and plutonium in the extractable IV or VI valence states during initial extraction. This study investigated the stability of these states. Results show that: The extractable M(IV) valence states of neptunium and plutonium are mutually unstable in plant dissolver solution (2 g/l 237 Np, 0.4 g/l 238 Pu, 1.2M Al 3+ , 4.6M NO 3 - , and 1M H + ). The reaction rates producing inextractable species from extractable M(IV) or M(VI) are fast enough that greater than or equal to 99.9 percent extractable species in 237 Np-- 238 Pu mixtures cannot be maintained for a practicable processing period

The use of neptunium-239 to assess neptunium distribution throughout a nuclear fuel reprocessing plant

International Nuclear Information System (INIS)

Mair, M.A.; Savage, D.J.; Prentice, P.C.

1989-08-01

A radiometric technique has been devised to use the gamma emission from the neptunium-239 daughter of americium-243 to estimate neptunium distribution in a plant reprocessing irradiated plutonium based fuels. Three trials were undertaken with samples from the Prototype Fast Reactor at Dounreay. The trials have confirmed the previous chemical measurements and the usefulness of this technique to highlight the effect of altered flowsheet conditions. (author)

Radiolytic oxidation

International Nuclear Information System (INIS)

Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

1991-01-01

Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

Preparation procedure and certification of uranous-uranic oxide and nitric acid solution of neptunium as standard specimens of plant

International Nuclear Information System (INIS)

Bulyanitsa, L.S.; Lipovskij, A.A.; Ryzhinskij, M.V.; Preobrazhensskaya, L.D.; Aleksandruk, V.M.; Alekseeva, N.A.; Gromova, E.A.; Solntseva, L.F.; Shereshevskaya, I.I.

1981-01-01

Two techniques of certification of standard specimens of plant (SSP) are considered. The first technique-comparison with initial SS-metallic uranium NBS-960 - is used for certification of uranium. protoxide-oxide. The mass part of the sum of analyzed impurities in prepared initial SS is (8.4+-0.8)x10 -3 %. For certification according to mass uranium part the method of gravimetric potentiometric titration with semiautomatic titrator is used; the mean quadratic deviation of the method is s=0.0002-0.0003, certified value of uranium mass part in SSP (taking account of the error of initial SS) is (84.80+-0.02)%. The second technigue - a simplified circular experiment - is used for certification of SSP-nitric acid solution of neptunium as to Np mass part. Coulometry at controlled potential and coulometry at controlled current and two variants of potentiometric titration are used as certification methods of analysis. Relative mean quadratic deviations of the methods are ssub(r)=0.0014-0.0023. When calculating total error of certified value of neptunium mass part constituents of both accidental and unremoved systematic errors of the methods were included. The final certification result of SSP is (5.707+-0.018)% [ru

The organometallic chemistry of neptunium

International Nuclear Information System (INIS)

Bohlander, R.

1986-09-01

Organometallic compounds of neptunium with carbocyclic ligands (C 5 H 5 - =cp, C 8 H 8 2- =cot) have been prepared and investigated. Starting from tetrakis(cyclopentadienyle)neptunium(IV) (cp 4 Np) and tris(cyclopentadienyle)neptunium(IV) chloride (cp 3 NpCl) a lot of other Np(IV)-compounds can be obtained by ligand-exchange reactions. These have the general formula cp 3 NpL with either inorganic ionic (L=Br - , I - , 1/2SO 4 2- , NCS - , AlCl 4 - ) or organic ligands (L=NC 4 H 4 - , N 2 C 3 H 3 - , C=CH - , 1/2C= 2- , CH 3 - , C 2 H 5 - , C 6 H 5 - ). Produced by reduction, tris(cyclopentadienyle)neptunium(III), cp 3 Np) gives similar structured 1:1-adduct complexes, cp 3 Np * B, with Lewis-bases like THF, diethylether, acetonitrile. Physico-chemical properties and changes in the molecular structure of the complexes have been studied using IR-, FTIR- and optical spectroscopy (in the NIR, VIS and UV region) as well as by magnetic and EPR measurements and Moessbauer spectrometry. The results are discussed as to their classification within the actinide complex chemistry and to the comparison with lanthanide complexes. (orig./RB) [de

Speciation and solubility of neptunium in underground environments by paper electrophoresis

International Nuclear Information System (INIS)

Nagasaki, S.; Tanaka, Satoru; Takahashi, Yoichi

1988-01-01

Speciation and solubility of neptunium were studied using paper electrophoresis, ion exchange and ultrafiltration. Among these methods, the paper electrophoresis was found to be suitable for measuring speciation and solubility of neptunium of low concentration, if chemical species had opposite charge to each other or dissolved species had a charge. Using paper electrophoresis, hydrolysis constants of NpO 2 OH 0 and NpO 2 - (OH) 2 - and solubility product of NpO 2 were obtained and ionic-strength dependence of speciation was observed. (author) 9 refs.; 3 figs.; 2 tabs

Neptunium: a bibliographic reference

International Nuclear Information System (INIS)

Mosley, R.E.

1979-06-01

A comprehensive bibliograhy of the literature on the element neptunium published prior to January 1976 is presented. A short abstract is given for each listed reference, with a few exceptions. The references are divided into sections categorized as General, Man-Made Sources (Reactors), Man-Made Sources (Fuel Reprocessing), Chemistry (Solubility), Chemistry (Compounds), Chemistry (Isotopes), Analyses (Instrumental), Analyses (Chemical), Chemical (Animal), Biological (Effects), Biological (Animal-Metabolism-Retention), Biological (Air Movement), Biological (Human Inhalation), Measurement, and Dosimetry. The bibliography contains author and keyword indexes and was compiled to serve as a quick reference source for neptunium-related work. 184 citations

Cyclopentadienyl uranium, neptunium and plutonium chemistry

International Nuclear Information System (INIS)

Plews, M.J.

1985-01-01

The thesis presents the preparation and characterisation of a number of mono, bis and tris(cyclopentadienyl) complexes of uranium(IV), neptunium(IV) and plutonium(IV). The work of previous studies on mono(cyclopentadienyl) thorium and uranium complexes has been extended, and a range of isostructural neptunium species isolated. Their mode of formation and stability in tetrahydrofuran and acetonitrile solutions was investigated. (author)

Study of neptunium hexafluoride formation and its adsorption on metallic fluorides

International Nuclear Information System (INIS)

Matcheret, Georges

1970-01-01

This report involves two parts. The first part deals with the action of elementary fluorine on neptunium compounds by a thermogravimetric method. The mechanism and the kinetics of this reaction vary according to the nature of the compound. 1 - With neptunium tetrafluoride the reaction, proceeds in a single step. The kinetics corresponds to a uniform attack of the entire surface of the sample and follows the kinetics law: (1-α) 1/3 1-k rel t . 2 - The reaction with neptunium dioxyde involves two steps, neptunium tetrafluoride being the intermediate compound. The kinetics of the first step corresponds to a diffusion process and follows the kinetic law: log (1-α) = kt 1/2 . The kinetics of the second step corresponds to an uniform attack of the entire sur face of the sample. The object of the second part is a study of the adsorption of uranium hexafluoride and neptunium hexafluoride on sodium, magnesium and barium fluorides by a volumetric method. The adsorption of UF 6 on MgF 2 has been investigated at 20 deg. C. The isothermal curve obtained is characteristic of a physical one layer monomolecular adsorption. In a way similar to the behaviour of UF 6 the adsorption of NpF 6 involves in addition a chemical reduction with formation of NpF 5 and release of fluorine. The reaction of NpF 6 with BaF 2 permitted to confirm the influence of the polarizing power of the Ba ++ ion on formation and stability of the product of addition. (author) [fr

The effect of carbonate on neptunium sorption by hydroxyapatite

International Nuclear Information System (INIS)

Moore, R.C.; Holt, K.

2005-01-01

Full text of publication follows: Hydroxyapatite, Ca 10 (PO 4 ) 6 (OH) 2 , is a common mineral, the main inorganic compound in bone and exhibits strong sorptive properties for many radionuclides. It has been widely studied and proposed as a backfill material for nuclear waste repositories. Neptunium is one the radionuclides sorbed by hydroxyapatite. Neptunium is of particular importance to nuclear waste repository performance because of its relatively high aqueous solubility, high mobility in the environment and long half-life. In this work, we report on the effects of carbonate on sorption of neptunium by hydroxyapatite. Batch sorption and desorption studies for neptunium were performed as a function of carbonate concentration in water using a synthetic hydroxyapatite. The results indicate even low concentrations of carbonate significantly reduce neptunium sorption and enhance desorption. The data were fit to several simple isotherm equations with the Langmuir equation giving the best results. The results of the work are discussed with respect to nuclear waste repository performance. (authors)

Sorption and direct speciation of neptunium(V) on aluminium oxide and montmorillonite

International Nuclear Information System (INIS)

Wendt, Sonja

2009-01-01

This study comprised batch experiments, direct speciation studies via EXAFS, and modelling with the 2SPNE SC/CE model to elucidate the mechanisms of Np(V) sorption on montmorillonite and, for reference, on γ-Al 2 O 3 . The sorption of pM 239 Np(V) and μM 237 Np(V) on montmorillonite (STx-1, 4 g/L) and γ-Al 2 O 3 (0.5 g/L) was studied at room temperature in the presence and absence of ambient CO 2 covering a pH-range from 2.5 (STx-1) or 5 (γ-Al 2 O 3 ) to 10.5 with 0.01 or 0.1M NaClO 4 as background electrolyte. The Np(V) uptake was determined by γ spectroscopy of the supernatants and calculated as percentage as well as distribution coefficient K d . Sorption starts from pH ∼6 and, under exclusion of CO 2 , increases continuously, while, in the presence of ambient air, it reaches a maximum at pH ∝8.5 (γ-Al 2 O 3 : logK d max ∼ 4 mL/g; STx-1: logK d max ∼ 2.7 mL/g). Beyond that it decreases again due to the formation of aqueous neptunium carbonate complexes. Furthermore, neptunium sorption on montmorillonite is influenced by ionic strength at pH <6 through ion exchange processes pointing towards the formation of outer-sphere surface complexes there. Isotherms measured at the sorption maximum showed the precipitation of presumably neptunium carbonate complexes above 3.10 -5 M under ambient air conditions. Additionally, they indicated progressive saturation of the sorption sites of γ-Al 2 O 3 . At selected pH (STx-1: 5.0, 7.0, 8.0, 8.5, 9.0, 9.5; γ-Al 2 O 3 : 8.5, 9.5) EXAFS samples were prepared as wet pastes with μM 237 Np and measured at room temperature in fluorescence mode at ANKA and ESRF. Several spectra were averaged and analysed with EXAFSPAK and FEFF 8.20 employing models of NaNpO 2 (CO 3 ) or soddyite, (UO 2 ) 2 SiO 4 .2(H 2 O). The shorter atomic distances of the neptunyl ion at pH 5 compared to the others hinted at the retention of the hydration shell and, thus, at outer-sphere sorption. On average the bond lengths for Np(V) sorbed on STx

Photochemical reactions of neptunium in nitric acid solution containing photocatalyst

International Nuclear Information System (INIS)

Fukasawa, Tetsuo; Kawamura, Fumio

1991-01-01

Photochemical oxidation and reduction behaviors of neptunium were preliminarily investigated in 3 mol/l nitric acid solution. Nitric acid of 3 mol/l simulated the high level waste solution from a spent fuel reprocessing process. Concentrations of Np(V), Np(VI) and nitrous acid were determined with a photospectrometer, and solution potential with an electrode. Without additives, Np(VI) was reduced to Np(V) by nitrous acid which was photolytically generated from nitric acid. With a scavenger for nitrous acid, Np(V) was oxidized to extractable Np(VI) by a photolytically generated oxidizing reagent which were predicted by the solution potential measurement. The reduction rate was higher than the oxidation rate because of the larger quantity and higher reactivity of nitrous acid than an oxidizing reagent. Photocatalyst was proved to be effective for the oxidation of Np(V) to Np(VI). (author)

Re-evaluating neptunium in uranyl phases derived from corroded spent fuel

International Nuclear Information System (INIS)

Fortner, J. A.; Finch, R. J.; Kropf, A. J.; Cunnane, J. C.; Chemical Engineering

2004-01-01

Interest in mechanisms that may control radioelement release from corroded commercial spent nuclear fuel (CSNF) has been heightened by the selection of the Yucca Mountain site in Nevada as the repository for high-level nuclear waste in the United States. Neptunium is an important radionuclide in repository models owing to its relatively long half-life and its high aqueous mobility as neptunyl [Np(V)O+2]. The possibility of neptunium sequestration into uranyl alteration phases produced by corroding CSNF would suggest-a process for lowering neptunium concentration and subsequent migration from a geologic repository. However, there remains little experimental evidence that uranyl compounds will, in fact, serve as long-term host phases for the retention of neptunium under conditions expected in a deep geologic repository. To directly explore this possibility, we examined specimens of uranyl alteration phases derived from humid-air-corroded CSNF by X-ray absorption spectroscopy to better determine neptunium uptake in these phases. Although neptunium fluorescence was readily observed from as-received CSNF, it was not observed from the uranyl alteration rind. We establish upper limits for neptunium incorporation into CSNF alteration phases that are significantly below previously reported concentrations obtained by using electron energy loss spectroscopy (EELS). We attribute the discrepancy to a plural-scattering event that creates a spurious EELS peak at the neptunium-MV energy

Determination of microamounts of neptunium by differential pulse polarography

International Nuclear Information System (INIS)

Cauchetier, Ph.

1979-01-01

Neptunium is produced in significant amounts in the ''light-water'' reactors and must be controlled at different steps of fuel reprocessing. For this purpose a method of differential pulse polarography has been developed. A tight cell containing 10 ml solution is set up in a Faraday cage. Adjustment to the tetravalent state, Np(IV), is carried out electrochemically on a mercury layer and the Np(IV) concentration is determined by differential pulse polarography, using a dropping mercury electrode. In 0.5M sulfuric acid medium, the redox potential of the reversible couple Np(IV)/Np(III) is -0.3 V/SCE. Concentrations as low as 5x10 -7 M neptunium can be measured and detection at the 2x10 -7 M level is still possible (0.5 μg in the polarographic cell). Precision is about 2% in the 10 -5 M and 10% in the 10 -6 M range. The method has been applied to aqueous and organic (TBP-dodecane) solutions. Neptunium can be determined without separation in the presence of plutonium or uranium at M/Np ratios of 10 3 and 5x10 4 , respectively. In the presence of fission products a separation is needed. (author)

Determination of microamounts of neptunium by differential pulse polarography

International Nuclear Information System (INIS)

Cauchetier, P.

1978-01-01

Neptunium is produced in significant amounts in the light water reactors and must be controlled at different steps of the fuel reprocessing. For this purpose, a method of differential pulse polarography was developed. A tight cell containing 10 ml of solution is set up in a Faraday's cage. Adjustment to the tetravalent state, Np (IV), is carried out electrochemically on a mercury layer and the Np (IV) concentration is determined by differential pulse polarography, using a dropping mercury electrode. In 0,5 M sulfuric acid medium, the redox potential of the reversible system Np (IV)/Np (III) is - 0,3 V/SCE. Concentrations as low as 5.10 -7 M of neptunium can be measured and detection at the 2.10 -7 M level is still possible (0,5 μg in the polarographic cell). Precision is about 2% in the 10 -5 M and 10% in 10 -6 M range. The method has been applied to the case of aqueous and organic (TBP dodecane) solutions. Neptunium can be determined without separation in the presence of plutonium or uranium in the M/Np ratios of 10 3 and 5.10 4 respectively. In the presence of fission products a separation is needed

Neptunium 237 behaviour in subcellular fractions of rat kidneys

International Nuclear Information System (INIS)

Kreslov, V.V.; Maksutova, A.Ya.; Mushkacheva, G.S.

1978-01-01

Subcellular distribution of intravenously injected (1 and 0.5 μCi/rat) neptunium nitrate (5- and 6-valent) in kidneys of rat males and females has been investigated. It has been shown that the radionuclide was unevenly distributed within the cell. As early as 24 hours after administration, about 50 per cent of neptunium were concentrated in the mitochondrial fraction. The data are presented on variations in neptunium behaviour within subcellular fractions of rat kidneys depending on the sex of animals, valency and dose of the isotope

Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

International Nuclear Information System (INIS)

Ken Czerwinski; Don Reed

2000-01-01

(B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R and D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

Chemical speciation of neptunium in spent fuel. Annual report for period 15 August 1999 to 15 August 2000

Energy Technology Data Exchange (ETDEWEB)

Ken Czerwinski; Don Reed

2000-09-01

(B204) This project will examine the chemical speciation of neptunium in spent nuclear fuel. The R&D fields covered by the project include waste host materials and actinide chemistry. Examination of neptunium is chosen since it was identified as a radionuclide of concern by the NERI workshop. Additionally, information on the chemical form of neptunium in spent fuel is lacking. The identification of the neptunium species in spent fuel would allow a greater scientific based understanding of its long-term fate and behavior in waste forms. Research to establish the application and development of X-ray synchrotrons radiation (XSR) techniques to determine the structure of aqueous, adsorbed, and solid actinide species of importance to nuclear considerations is being conducted at Argonne. These studies extend current efforts within the Chemical Technology Division at Argonne National Laboratory to investigate actinide speciation with more conventional spectroscopic and solids characterization (e.g. SEM, TEM, and XRD) methods. Our project will utilize all these techniques for determining neptunium speciation in spent fuel. We intend to determine the chemical species and oxidation state of neptunium in spent fuel and alteration phases. Different types of spent fuel will be examined. Once characterized, the chemical behavior of the identified neptunium species will be evaluated if it is not present in the literature. Special attention will be given to the behavior of the neptunium species under typical repository near-field conditions (elevated temperature, high pH, varying Eh). This will permit a timely inclusion of project results into near-field geochemical models. Additionally, project results and methodologies have applications to neptunium in the environment, or treatment of neptunium containing waste. Another important aspect of this project is the close cooperation between a university and a national laboratory. The PI has a transuranic laboratory at MIT where

Reduction and precipitation of neptunium(V) by sulfate-reducing bacteria

International Nuclear Information System (INIS)

Banaszak, J. E.; Rittmann, B. E.; Reed, D. T.

1999-01-01

Migration of neptunium, as NpO 2 + , has been identified as a potentially important pathway for actinide release at nuclear waste repositories and existing sites of subsurface contamination. Reduction of Np(V) to Np(IV) will likely reduce its volubility, resulting in lowered subsurface migration. The ability of sulfate-reducing bacteria (SRB) to utilize Np(V) as an electron acceptor was investigated, because these bacteria are active in many anaerobic aquifers and are known to facilitate the reduction of metals and radionuclides. Pure and mixed cultures of SRB were able to precipitate neptunium during utilization of pyruvate, lactate, and hydrogen as electron donors in the presence and absence of sulfate. The neptunium in the precipitate was identified as Np(IV) using X-ray absorption near edge spectroscopy (XANES) analysis. In mixed-culture studies, the addition of hydrogen to consortia grown by pyruvate fermentation stimulated neptunium reduction and precipitation. Experiments with pure cultures of Desulfovibrio vulgaris, growing by lactate fermentation in the absence of sulfate or by sulfate reduction, confirm that the organism is active in neptunium reduction and precipitation. Based on our results, the activity of SRB in the subsurface may have a significant, and potentially beneficial, impact on actinide mobility by reducing neptunium volubility

Sorption behavior of neptunium on bentonite -- Effect of calcium ion on the sorption

International Nuclear Information System (INIS)

Kozai, Naofumi; Ohnuki, Toshihiko; Muraoka, Susumu

1995-01-01

The sorption behavior of neptunium on bentonite was studied with batch type sorption and desorption experiments over a pH range of 2 to 8. A series of parallel studies using Na-smectite, Ca-smectite and admixtures of Na-smectite and calcite quantified the capacity of Ca 2+ (which occurs in bentonite as an exchangeable cation of smectite and as a component of calcite) to inhibit the sorption of neptunium. The distribution coefficient (K d ) of neptunium for bentonite was constant from pH 2 to 7, while for pure Na-smectite K d increased below pH 5 due to specific sorption of neptunium on Na-smectite. Specific sorption was defined as occurring when neptunium could be desorbed by a strong acid (1 M HCl) but was stable in the presence of 1 M KCl. It was found that the quantity of neptunium sorbed on Na-smectite was inversely proportional to the concentration of Ca 2+ in solution, an effect most pronounced at pH 2+ limits the specific sorption capacity of Na-smectite for neptunium. Similarly, in the mixture of Na-smectite and calcite, sufficient Ca 2+ was solubilized to depress neptunium sorption. This investigation demonstrates that Ca 2+ contained in bentonite as exchangeable cation and released from calcite reduces the specific sorption of neptunium

Precipitaion of neptunium(6) by urotropin from the heated solutions

International Nuclear Information System (INIS)

Logvis', A.I.; Krot, N.N.

1992-01-01

The composition of precipitate, formed in the course of neptunium(6) nitric acid solution heating with urotropin under different conditions was studied by the methods of X-ray phase analysis, gravimetry and spectrophotometry. The compound studied is determined as NpO 3 ·xH 2 O·yNH 3 , where x <= 2, y <= 0.28. It is shown that not less than 12 % of the initial amount of neptunium remain in solution in the form of neptunium(5)

Fate of neptunium in an anaerobic, methanogenic microcosm

International Nuclear Information System (INIS)

Banaszak, J.E.; Webb, S.M.; Rittmann, B.E.; Gaillard, J.F.; Reed, D.T.

1999-01-01

Neptunium is found predominantly as Np(IV) in reducing environments, but as Np(V) in aerobic environments. Currently, it is not known how the interplay between biotic and abiotic processes affects Np redox speciation in the environment. To evaluate the effect of anaerobic microbial activity on the fate of Np in natural systems, Np(V) was added to a microcosm inoculated with anaerobic sediments from a metal-contaminated freshwater lake. The consortium included metal-reducing, sulfate-reducing, and methanogenic microorganisms, and acetate was supplied as the only exogenous substrate. Addition of more than 10 -5 M Np did not inhibit methane production. Total Np solubility in the active microcosm, as well as in sterilized control samples, decreased by nearly two orders of magnitude. A combination of analytical techniques, including VIS-NIR absorption spectroscopy and XANES, identified Np(IV) as the oxidation state associated with the sediments. The similar results from the active microcosm and the abiotic controls suggest that microbially produced Mn(II/III) and Fe(II) may serve as electron donors for Np reduction

Electroanalytical studies of uranium, neptunium, and plutonium ions in solutions

International Nuclear Information System (INIS)

Yoshida, Zenko; Aoyagi, Hisao; Kihara, Sorin

1989-01-01

Redox behavior of uranium, neptunium, and plutonium ions, whose oxidation states in acid solutions are between (VI) and (III), were investigated by flow-coulometry with a column electrode of glassy carbon fibers as well as ordinary voltammetry with a rotating disc electrode. Based on current-potential curves the electrode processes were elucidated taking their disproportionation and/or complexation reactions into account. The flow-coulometry, which provides rapid and quantitative electrolysis, was applied to such analytical purposes as follows; the determination of uranium and plutonium in the solution or the solid with discerning their oxidation states, the preparation of species in a desired oxidation state, even in an unstable state which cannot be prepared by ordinary procedure, and the separation of trace amount of uranium in solutions by the electrodeposition of its hydroxide

Rapid and Automated Determination of Plutonium and Neptunium in Environmental Samples

DEFF Research Database (Denmark)

Qiao, Jixin

This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development...... and optimization for rapid determination of plutonium in environmental samples using SIextraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples...... for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including...

Neptunium separation in trace levels from uranium solutions by extraction chromatography

International Nuclear Information System (INIS)

Cotrim, M.B.; Matsuda, H.T.

1994-01-01

Neptunium and uranium behavior in extraction chromatograph system, aiming the separation of micro quantities of neptunium from uranyl solutions is described. Tri-n-octylamine (TOA), Tri-n-butylphosphate (TBP) as stationary phase, alumine, Voltalef UF-300 as support material were verified. The impregnation conditions as well as the best stationary phase/support material ratio were established. TBP/alumine, TBP/Voltalef and TOA/alumine system were selected to uranium and neptunium separation studies. (author) . 12 refs., 03 tabs., 03 figs

Metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

International Nuclear Information System (INIS)

Ralston, L.G.; Cohen, N.; Bhattacharyya, M.H.; Larsen, R.P.; Ayres, L.; Oldham, R.D.; Moretti, E.S.

1985-01-01

The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Immediately following intravenous injection (10 -1 to 10 -10 mg Np per kg body wt), neptunium cleared rapidly from blood, deposited primarily in the skeleton (54 +- 5%) and liver (3 +- 0.2%), and was excreted predominantly via urine (40 +- 3%). For the first year post injection, neptunium was retained with a biological half-time of approx.100 days in liver and 1.5 +- 0.2 yr in bone. In comparison, injected protactinium (10 -9 mg/kg) was retained in blood in higher concentrations and was initially eliminated in urine to a lesser extent (6 +- 3%). In vivo measurements indicated that protactinium was retained in bone (65 +- 0.3%) with a half-time of 3.5 +- 0.6 yr. Differences in the physicochemical states of the neptunium or protactinium solutions injected did not alter the metabolic behavior of these nuclides. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 +- 2% was in liver, and 42 +- 0.1% was excreted in urine. A method was developed to estimate GI absorption values for both nuclides in baboons which were not sacrificed. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. 14 refs., 3 figs., 4 tabs. (DT)

Metabolism and gastrointestinal absorption of neptunium and protactinium in adult baboons

Energy Technology Data Exchange (ETDEWEB)

Ralston, L.G.; Cohen, N.; Bhattacharyya, M.H.; Larsen, R.P.; Ayres, L.; Oldham, R.D.; Moretti, E.S.

1985-01-01

The metabolism of neptunium and protactinium was studied in adult female baboons following intravenous injection and intragastric intubation. Immediately following intravenous injection (10/sup -1/ to 10/sup -10/ mg Np per kg body wt), neptunium cleared rapidly from blood, deposited primarily in the skeleton (54 +- 5%) and liver (3 +- 0.2%), and was excreted predominantly via urine (40 +- 3%). For the first year post injection, neptunium was retained with a biological half-time of approx.100 days in liver and 1.5 +- 0.2 yr in bone. In comparison, injected protactinium (10/sup -9/ mg/kg) was retained in blood in higher concentrations and was initially eliminated in urine to a lesser extent (6 +- 3%). In vivo measurements indicated that protactinium was retained in bone (65 +- 0.3%) with a half-time of 3.5 +- 0.6 yr. Differences in the physicochemical states of the neptunium or protactinium solutions injected did not alter the metabolic behavior of these nuclides. The gastrointestinal absorption value for neptunium in two fasted baboons, sacrificed at 1 day post administration, was determined to be 0.92 +- 0.04%. Of the total amount of neptunium absorbed, 52 +- 3% was retained in bone, 6 +- 2% was in liver, and 42 +- 0.1% was excreted in urine. A method was developed to estimate GI absorption values for both nuclides in baboons which were not sacrificed. Absorption values calculated by this method for neptunium and protactinium in fasted baboons were 1.8 +- 0.8% and 0.65 +- 0.01%, respectively. Values for fed animals were 1 to 2 orders of magnitude less than those for fasted animals. 14 refs., 3 figs., 4 tabs. (DT)

Investigation of composition and properties of some neptunium (5) oxalate compounds

International Nuclear Information System (INIS)

Zubarev, V.G.; Krot, N.N.

1981-01-01

A simple way of neptunium (5) oxalate synthesis is described and its composition is determined: (NpO 2 ) 2 C 2 O 4 xH 2 O. The compound is precipitated from solution during pouring together stoichiometric quantities of neptunium (5) nitrate and ammonium, sodium or potassium oxalate at pH=4-5. An explanation to unusual effect of solubility change with time of neptunium (5) monooxalate complexes and alkali metal or ammonium ion is found taking into account the slow formation of precipitate and low solubility of the compound obtained (0.62 g/l as to metal). Thermal decomposition of the compound is studied. At 180 deg C a water molecule is split off and at 260 deg C decomposition of neptunium oxalate starts. IR spectra and interplane distances (dsub(hkl)) of the compound crystal lattice are determined. New data on the synthesis and properties of complex neptunium (5) oxalates and monovalent cation in second sphere with the ratio ligand: metal=2:1 and 3:1 are presented. On the basis of results of IR spectroscopy and X-ray phase analyses a supposition is made on the existence of such complex compounds [ru

Energy efficiency of neptunium redox battery in comparison with vanadium battery

International Nuclear Information System (INIS)

Yamamura, T.; Watanabe, N.; Shiokawa, Y.

2006-01-01

A neptunium ion possesses two isostructural and reversible redox couples (Np 3+ /Np 4+ and NpO 2 + /NpO 2 2+ ) and is therefore suitable as an active material for a redox-flow battery. Since the plastic formed carbon (PFC) is known to show the largest k values for Np(IV)/Np(III) and Np(V)/Np(VI) reactions among various carbon electrodes, a cell was constructed by using the PFC, with the circulation induced by bubbling gas through the electrolyte. In discharge experiments with a neptunium and a vanadium battery using the cell, the former showed a lower voltage loss which suggests a smaller reaction overvoltage. Because of the high radioactivity of the neptunium, it was difficult to obtain sufficient circulation required for the redox-flow battery, therefore a model for evaluating the energy efficiency of the redox-flow battery was developed. By using the known k values for neptunium and vanadium electrode reactions at PFC electrodes, the energy efficiency of the neptunium battery was calculated to be 99.1% at 70 mA cm -2 , which exceeds that of the vanadium battery by ca. 16%

Interaction of neptunium with humic acid and anaerobic bacteria

International Nuclear Information System (INIS)

Kubota, Takumi; Sasaki, Takayuki; Kudo, Akira

2002-01-01

Humic acid and bacteria play an important role in the migration of radionuclides in groundwaters. The interaction of neptunium with humic acid and anaerobic bacteria has been investigated by liquid/liquid and solid/liquid extraction systems. For liquid/liquid extraction, the apparent complex formation constant, β α was obtained from the distribution between two phases of neptunium. For solid/liquid extraction, the ratio of sorption to bacteria, K d , was measured. K d of humic acid can be evaluated from β α . The large value of β α and K d means strong interaction of neptunium with organisms. In order to examine the effect of the nature of organism on interaction, the interaction with humic acid was compared to that with non-sterilized or sterilized mixed anaerobic bacteria. The value of β α of humate depended on neptunium ion concentration as well as pH, which showed the effect of polyelectrolyte properties and heterogeneous composition of humic acid. The comparison of interaction with humic acid and bacteria indicated that the K d value of humic acid was larger than that of bacteria and more strongly depend on pH. (author)

Neptunium separation in trace levels from uranium solutions by extraction chromatography

International Nuclear Information System (INIS)

Figols, M.E.B.

1991-01-01

Neptunium and uranium behavior in extraction chromatography system, aiming the separation of microquantities of neptunium from uranyl nitrate solutions is described. Tri-n-octylamina (TOA), tri-n-butylphosphate (TBP), thenoyltrifluoroacetone (TTA) as stationary phase, alumina, Voltalef-UF-300, silica as support material were verified. The impregnation conditions as well as the best stationary phase/support material ratio were established. TBP/alumina, TBP/Voltalef and TOA/alumina system were selected to uranium and neptunium separation studies. In the system using TBP as extractant agent uranium and neptunium separation was reached by selective elution after the retention of both elements on the column. U-Np separation by selective retention of Np was possible with TOA system. The capacity of the column was the 66.6 mg U/mL and 191.6mg U/mL for the TBP/alumina and TBP/Voltalef systems, respectively. An application of extraction chromatography system in the final phase of irradiated uranium treatment process is proposed. (author)

Uranium/plutonium and uranium/neptunium separation by the Purex process using hydroxyurea

International Nuclear Information System (INIS)

Zhu Zhaowu; He Jianyu; Zhang Zefu; Zhang Yu; Zhu Jianmin; Zhen Weifang

2004-01-01

Hydroxyurea dissolved in nitric acid can strip plutonium and neptunium from tri-butyl phosphate efficiently and has little influence on the uranium distribution between the two phases. Simulating the 1B contactor of the Purex process by hydroxyurea with nitric acid solution as a stripping agent, the separation factors of uranium/plutonium and uranium/neptunium can reach values as high as 4.7 x 10 4 and 260, respectively. This indicates that hydroxyurea is a promising salt free agent for uranium/plutonium and uranium/neptunium separations. (author)

Selective localization of neptunium-237 in the nuclei of mammalian cells. Localisation selective du neptunium-237 au sein des noyaux des cellules de mammiferes

Energy Technology Data Exchange (ETDEWEB)

Galle, P.; Boulahdour, H. (Faculte de Medecine, 94 - Creteil (FR)); Metivier, H. (CEA Centre d' Etudes Nucleaires de Fontenay-aux-Roses, 92 (FR). Inst. de Protection et de Surete Nucleaire)

1992-01-01

After injection in the rat of soluble neptunium salt, the distribution of this element was studied at the subcellular level by electron microscopy and electron probe microanalysis. Abnormal structures have been observed by electron microscopy in the nuclei of hepatocytes, and the same structures have also been observed in the nuclei of the proximal tubules cells of the kidney. These structures are formed of clusters of very small and dense particles, several nanometers in diameter. The clusters are localized in the central part of the nuclei and they are separate from nucleoli and heterochromatin. Electron probe X-ray analysis of this cluster have shown that they contain neptunium associated with phosphorus. In the cell containing neptunium inclusions, other non specific lesions are also observed (nuclear pycnosis, mitochondrial depletion).

Rapid and automated determination of plutonium and neptunium in environmental samples

International Nuclear Information System (INIS)

Qiao, J.

2011-03-01

This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development in this work consists of 5 subjects stated as follows: 1) Development and optimization of an SI-anion exchange chromatographic method for rapid determination of plutonium in environmental samples in combination of inductively coupled plasma mass spectrometry detection (Paper II); (2) Methodology development and optimization for rapid determination of plutonium in environmental samples using SI-extraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples (Paper IV); (4) Investigation of the suitability and applicability of 242 Pu as a tracer for rapid neptunium determination using anion exchange chromatography in an SI-network coupled with inductively coupled plasma mass spectrometry (Paper V); (5) Exploration of macro-porous anion exchange chromatography for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including environmental risk monitoring and assessment, emergency preparedness and surveillance of contaminated areas. (Author)

Rapid and automated determination of plutonium and neptunium in environmental samples

Energy Technology Data Exchange (ETDEWEB)

Qiao, J.

2011-03-15

This thesis presents improved analytical methods for rapid and automated determination of plutonium and neptunium in environmental samples using sequential injection (SI) based chromatography and inductively coupled plasma mass spectrometry (ICP-MS). The progress of methodology development in this work consists of 5 subjects stated as follows: 1) Development and optimization of an SI-anion exchange chromatographic method for rapid determination of plutonium in environmental samples in combination of inductively coupled plasma mass spectrometry detection (Paper II); (2) Methodology development and optimization for rapid determination of plutonium in environmental samples using SI-extraction chromatography prior to inductively coupled plasma mass spectrometry (Paper III); (3) Development of an SI-chromatographic method for simultaneous determination of plutonium and neptunium in environmental samples (Paper IV); (4) Investigation of the suitability and applicability of 242Pu as a tracer for rapid neptunium determination using anion exchange chromatography in an SI-network coupled with inductively coupled plasma mass spectrometry (Paper V); (5) Exploration of macro-porous anion exchange chromatography for rapid and simultaneous determination of plutonium and neptunium within an SI system (Paper VI). The results demonstrate that the developed methods in this study are reliable and efficient for accurate assays of trace levels of plutonium and neptunium as demanded in different situations including environmental risk monitoring and assessment, emergency preparedness and surveillance of contaminated areas. (Author)

Application of Moessbauer spectroscopy to the study of neptunium adsorbed on deep-sea sediments

International Nuclear Information System (INIS)

Bennett, B.A.; Rees, L.V.C.

1987-03-01

A Neptunium Moessbauer spectrometer (the first in Great Britain) was constructed and the Moessbauer spectra of NpAl Laves phase alloy obtained. Neptunium was sorbed onto a calcareous deep-sea sediment from sea water, using a successive-loading technique. Sorption appeared to be by an equilibrium reaction, and because of the low solubility of neptunium in seawater, this meant that the maximum loading that could be achieved was 8mg 237 Np/g sediment. This proved to be an adequate concentration for Moessbauer measurements and a Moessbauer spectrum was obtained. This showed that most of the neptunium was in exchange sites and not present as precipitates of neptunium compounds. It was probably in the 4+ state indicating that reduction had occurred during sorption. This work has demonstrated that Moessbauer Spectroscopy has great potential as an aid to understanding the mechanism of actinide sorption in natural systems. (author)

Study of oxidation-reduction reactions of plutonium and neptunium in sulphuric-phosphoric acid media

International Nuclear Information System (INIS)

Moiseev, I.V.; Kuperman, A.Ya.; Borodina, N.N.; Galkina, V.N.; Vinokurov, V.A.

1976-01-01

Potentiostatic, coulometric, potentiometric, and amperometric methods have been used for determining the rate constants of disproportionation (ksub(d)) of plutonium(5) and neptunium (5) and normal real redox potentials (Esub(0)sup(p)) of the following ion pairs in sulphur-phosphoric-acid media: PuOsub(2)sup(2)sup(+) (PuO 2 + , Pu 4+ /Pu 3+ , NpO 2 2+ /NpO 2 + , NpO 2 2+ /Np 4+ , NpO 2 + /Np 4+ , and Fe 3+ /Fe 2+ . The regularities have been shown of changing ksub(d) and Esub(o)sup(p) as a function of H 2 SO 4 and H 3 PO 4 concentration. It has been established that for plutonium and neptunium a linear correlation is observed between lg ksub(d) and Esub(o)sup(p) of the ion pairs NpO 2 2+ /NpO 2 + , NpO 2 2 /Np 4+ , NpO 2 + /Np 4+ and PuO 2 2+ /PuO 2 + in a wide range of their values. The correlation coefficient is close to unity in all cases (no less than 0.96). The results of investigations have made it possible to recommend optimum compositions of background electrolytes for performing continuous amperostatic coulometric titration of Pusup((6)) and Npsup((6)) up to four valent state by electrogenerated ions of iron (2)

Counter-current extraction studies for the recovery of neptunium by the Purex process. Part II

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, N.; Nadkarni, M. N.; Kumar, S. V.; Kartha, P. K.S.; Sonavane, R. R.; Ramaniah, M. V.; Patil, S. K.

1974-07-01

Counter-extraction experiments were carried out under the conditions relevant to the partitioning column (IBX) in the purex process to know the path of neptunium present as Np (VI) the organic phase during the partitioning step. The results obtained show that when ferrous sulphamates is used as the reducing agent, most of the neptunium continues to remain with uranium in the organic stream while with hydrazine stabilized uranous nitrate as the reducing agent, a major fraction of neptunium follows the aqueous stream. Mixer-settler experiments were also carried out under the conditions relevant to the uranium purification cycle (2D) to establish the conditions for forcing neptunium to the aqueous raffinate or for partitioning it from uranium if both neptunium and uranium are co-extracted in this cycle and the results obtained are reported here. (auth)

Neptunium sorption and co-precipitation of strontium in simulated DWPF salt solution

International Nuclear Information System (INIS)

McIntyre, P.F.; Orebaugh, E.G.; King, C.M.

1988-01-01

Batch experiments performed using crushed slag saltstone (∼40 mesh) removed >80% of 237 Np from simulated Defense Waste Processing Facility (DWPF) salt solution. The concentration of 237 Np (110 pCi/ml) used was 1000x greater than levels in actual DWPF solutions. Neptunium-239 was used as a tracer and was formed by neutron activation of uranyl nitrate. Results showed that small amounts of crushed saltstone (as little as 0.05 grams), removed >80% of neptunium from 15 ml of simulated DWPF solution after several hours equilibration. The neptunium is sorbed on insoluble carbonates formed in and on the saltstone matrix. Further testing showed that addition of 0.01 and 0.10 ml of 1 molar Ca +2 (ie. Ca (NO 3 ) 2 , CaCl 2 ) into 15 ml of simulated DWPF solution yielded a white carbonate precipitate which also removed >80% of the neptunium after 1 hour equilibration. Further experiments were performed to determine the effectiveness of this procedure to co-precipitate strontium

Counter-current extraction studies for the recovery of neptunium by the Purex process. Part I

Energy Technology Data Exchange (ETDEWEB)

Srinivasan, N.; Nadkarni, M. N.; Kumar, S. V.; Kartha, P. K.S.; Sonavane, R. R.; Ramaniah, M. V.; Patil, S. K.

1974-07-01

It is proposed to recover neptunium-237, along with uranium and plutonium, during the fuel reprocessing in the PREFRE plant at Tarapur. Counter-current extraction studies, relevant to the code contamination (HA) and partitioning (IA) cycles of the purex process, were carried out to arrive at suitable chemical flowsheet conditions which would enable the co-extraction of neptunium along with uranium and plutonium. The results of the studies carried out using a laboratory mixer-settler unit and synthetic mixtures of neptunium and uranium are reported here. Based on these results, the chemical flowsheet conditions are proposed for the co-extraction of neptunium even if it exists as Np(V) in the aqueous feed solution. (auth)

Study on reduction reactions of neptunium(V) on magnetite surface

International Nuclear Information System (INIS)

Kitamura, Akira; Kamei, Gento; Nakata, Kotaro; Tanaka, Satoru; Tomura, Tsutomu

2004-01-01

Redox reactions between neptunium(V) (Np(V)) and magnetite (Fe(II) 1 Fe(III) 2 O 4 ) surface were investigated in N 2 gas atmosphere. A batch method was applied to the experiment. A magnetite sample and a 0.1 M NaCl solution were mixed in a polypropylene tube, and pH, redox potential and concentration of dissolved neptunium were measured as a function of shaking time, temperature and liquid/solid ratio. The concentration of dissolved neptunium was reduced rapidly within a day, due to the reducing reaction of Np(V) to Np(IV) and the precipitation of Np(IV). The rate constant of the redox reaction and the activation energy for the rate constant were preliminarily obtained. On the other hand, redox reactions between Np(V) and aqueous Fe(II) were hardly observed. Considering the number of transferred electrons, it was suggested that the redox reaction was promoted by not only Fe(II) on the magnetite surface, but also Fe(II) inside the magnetite. (author)

The effect of high ionic strength on neptunium (V) adsorption to a halophilic bacterium

Science.gov (United States)

Ams, David A.; Swanson, Juliet S.; Szymanowski, Jennifer E. S.; Fein, Jeremy B.; Richmann, Michael; Reed, Donald T.

2013-06-01

The mobility of neptunium (V) in subsurface high ionic strength aqueous systems may be strongly influenced by adsorption to the cell wall of the halophilic bacteria Chromohalobacter sp. This study is the first to evaluate the adsorption of neptunium (V) to the surface of a halophilic bacterium as a function of pH from approximately 2 to 10 and at ionic strengths of 2 and 4 M. This is also the first study to evaluate the effects of carbonate complexation with neptunium (V) on adsorption to whole bacterial cells under high pH conditions. A thermodynamically-based surface complexation model was adapted to describe experimental adsorption data under high ionic strength conditions where traditional corrections for aqueous ion activity are invalid. Adsorption of neptunium (V) was rapid and reversible under the conditions of the study. Adsorption was significant over the entire pH range evaluated for both ionic strength conditions and was shown to be dependent on the speciation of the sites on the bacterial surface and neptunium (V) in solution. Adsorption behavior was controlled by the relatively strong electrostatic attraction of the positively charged neptunyl ion to the negatively charged bacterial surface at pH below circum-neutral. At pH above circum-neutral, the adsorption behavior was controlled by the presence of negatively charged neptunium (V) carbonate complexes resulting in decreased adsorption, although adsorption was still significant due to the adsorption of negatively charged neptunyl-carbonate species. Adsorption in 4 M NaClO4 was enhanced relative to adsorption in 2 M NaClO4 over the majority of the pH range evaluated, likely due to the effect of increasing aqueous ion activity at high ionic strength. The protonation/deprotonation characteristics of the cell wall of Chromohalobacter sp. were evaluated by potentiometric titrations in 2 and 4 M NaClO4. Bacterial titration results indicated that Chromohalobacter sp. exhibits similar proton buffering

Coprecipitation of neptunium and plutonium with iron and zirconium dibutyl phosphates

International Nuclear Information System (INIS)

Sokhina, L.P.; Rovnyj, S.I.; Goncharuk, L.V.

1988-01-01

Neptunium and plutonium coprecipitation with precipitates of dibutyl phosphates of some elements significant for radiochemical technology is studied. By the ability to coprecipitation of actinides with precipitates of dibutyl phosphates the cations may be arranged in the series Fe > Al > La > ≥ Zr ≥ Th. The composition of neptunium and plutonium mixed precipitates on the basis of iron dibutyl phosphates corresponding to the formula (Me(NO 3 ) 2 Al 2 ) n x · FeA 3 , where Me-neptunium or plutonium, A-anion of dibutyl phosphoric acid, n=1-4, is determined. Solubility of mixed precipitations in nitric acid and carbonate solutions is studied. Mixed precipitations on the basis of iron dibutyl phosphates are found to have the least solubility, their solubility being lower than that of individual compounds of dibutyl phoshates. The mechanism of formation of mixed precipitates is suggested and discussed

Neptunium-the neglected actinide: a review of the biological and environmental literature

International Nuclear Information System (INIS)

Thompson, R.C.

1982-01-01

Data from 89 references relating to the biological and environmental behavior of neptunium are reviewed with particular attention to the potential risks from possible releases of neptunium isotopes by the nuclear industry. The behavior of neptunium differs in many significant respects from that of other transuranic elements. It is more mobile environmentally and more readily absorbed by man, although some of the higher reported values for gastrointestinal absorption appear to have been influenced by the very high mass levels of 237 Np required for experimental study. In studies with experimental animals its ratio of deposition in bone/liver is greater than that of other transuranic elements. Its long-term toxicity in experimental animals is similar to that of other transuranics

Geomicrobiological redox cycling of the transuranic element neptunium.

Science.gov (United States)

Law, Gareth T W; Geissler, Andrea; Lloyd, Jonathan R; Livens, Francis R; Boothman, Christopher; Begg, James D C; Denecke, Melissa A; Rothe, Jörg; Dardenne, Kathy; Burke, Ian T; Charnock, John M; Morris, Katherine

2010-12-01

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

A study of specific sorption of neptunium(V) on smectite in low pH solution

International Nuclear Information System (INIS)

Kozai, Naofumi; Ohnuki, Toshihiko; Matsumoto, Junko; Banba, Tsunetaka; Ito, Yoshimoto

1996-01-01

The 'specific sorption' of neptunium(V) on smectite, in other words, a strong sorption undesorbable by 1 M KCl, is studied with a combination of batch type sorption and desorption experiments over a pH range of 2 to 5. Six types of homoionic smectite (Li-, Na-, K-, Cs-, Mg-, and Ca-smectite) are used in this study. Distribution coefficients (K d ) of neptunium for smectite vary over a wide pH range; the maximum K d value of ∝300 cm 3 x g -1 at around pH 2 for Li- and Na-smectite and the minimum value of ∝2 cm 3 x g -1 for Cs-smectite. The specific sorption of neptunium depends on pH and on the affinity of the exchangeable cation for smectite; the lower the pH of solution or the affinity, the larger the specific sorption. The neptunium-smectite association varies with the elapse of contact time. Within the first day of the neptunium-smectite contact the neptunium sorbed on na-smectite at low pH is desorbable by 1 M KCl solution, and on the passage of time most of the neuptunium sorbed becomes undesorbable by KCl (the specific sorption). Hydronium ion in solution is sorbed on smectite at low pH and dissociates the exchangeable cation from smectite into solution, and the specific sorption of neuptunium increases with increasing the exchangeable cation that is dissociated from smectite. (orig.)

An assessment of the thermodynamic behaviour of neptunium in water and model groundwaters from 25 to 150 degrees C

International Nuclear Information System (INIS)

Lemire, R.J.

1984-03-01

Standard molal Gibbs energy of formation and entropy data for simple neptunium solids and aqueous neptunium complexes with OH - , Cl - , F - , CO 3 2- , PO 4 3- , SO-4 2- and Na + have been critically reviewed. Selected values are used with estimated heat capacity values to derive self-consistent analytical expressions for the temperature dependence of the standard molal Gibbs energies of formation of the species from 25 to 150 degrees C. The Gibbs energies have been used to evaluate the effect of different concentrations of ligands on the solubility of neptunium solids as a function of temperature. Potential-pH diagrams are given for neptunium in pure water and in two model groundwaters. Important deficiencies in the available thermodynamic data for neptunium species are discussed

Kinetics of the reaction between plutonium (4) and neptunium (4) in nitric acid solution

Energy Technology Data Exchange (ETDEWEB)

Koltunov, V S; Zhuravleva, G I; Marchenko, V I

1976-01-01

The kinetics of the oxidation of neptunium(IV) to neptunium(V) by tetravalent plutonium ions in solutions of HNO/sub 3/ + NaNO/sub 3/ at constant (..mu.. = 2) and variable (..mu.. = 0.7-2.0) ionic strengths of the solution was investigated by a spectrophotometric method. It was established that in the range of concentrations (Np(IV)) = (4.25-10.6) x 10/sup 13/; (Pu(IV)) = (2.6-3.9)x10/sup -3/ M; (H/sup +/) 0.37-1.91 M, a first order is observed with respect to the reagents, while the order of the reaction with respect to H/sup +/ ions is equal to -3. The average value of the true rate constant of the reaction is k = 27.9+-1.3 M/sup 2/xmin/sup -1/ at ..mu..=2 and 39/sup 0/C. It was shown that with increasing analytical concentration of HNO/sub 3/ and NO/sub 3//sup -/ ions (in a mixture of HNO/sub 3/ +HClO/sub 4/), the value of K decreases. On the basis of an invetigation of the dependence of the reaction rate on the temperature in the interval 31-44.8/sup 0/, we calculated the values of the energy (E = 34.6 kcal/mole), enthalpy (..delta..H* = 34 kcal/mole), free energy (..delta..F* = 19.6 kcal/mole, entropy (..delta..S* = 49 entropy units) of activation of the reaction and the formal ionic entropy of the activated complex (PuOOHNp/sup 5 +/)*, S* = -87 entropy units. A reaction mechanism including an interaction of hydrolyzed neptunium and plutonium ions as the rate-determining step was proposed and discusses. The results obtained are compared with data for this reaction in perchloric acid wolution and for other similar redox reactions.

Electrochemical determination of the oxidation potentials and the thermodynamic stability of the valence states of the transuranium elements in aqueous alkaline media

International Nuclear Information System (INIS)

Peretrukhin, V.F.; Spitsyn, V.I.

1982-01-01

The oxidation potentials of neptunium, plutonium, and americium in the valance states from (III) to (VII) have been determined experimentally in 0.1-15 M NaOH. Heptavalent plutonium and americium are thermodynamically able to oxidize water with the evolution of oxygen in 0.1-15 M NaOH, neptunium(VII) in 0.1-7 M NaOH. All valance states of plutonium resist disproportionation in alkaline solutions; in the case of neptunium and americium only one disproportionation reaction is possible; of the hexavalent state in to penta- and heptavalent states. The degree of completion of the reaction can be calculated accurately from the oxidation potentials determined

Assessment of the thermodynamic behavior of neptunium in water and model groundwaters from 25 to 150/sup 0/C

Energy Technology Data Exchange (ETDEWEB)

Lemire, R J

1984-03-15

Standard molal Gibbs energy of formation and entropy data for simple neptunium solids and aqueous neptunium complexes with OH/sup -/, Cl/sup -/, F/sup -/, CO/sub 3//sup 2 -/, PO/sub 4//sup 3 -/, SO/sub 4//sup 2 -/ and Na/sup +/ have been critically reviewed. Selected values are used with estimated heat capacity values to derive self-consistent analytical expressions for the temperature dependence of the standard molal Gibbs energies of formation of the species from 25 to 150/sup 0/C. The Gibbs energies have been used to evaluate the effect of different concentrations of ligands on the solubility of neptunium solids as a function of temperature. Potential-pH diagrams are given for neptunium in pure water and in two model groundwaters. Important deficiencies in the available thermodynamic data for neptunium species are discussed. 90 references, 12 figures, 6 tables.

Partitioning and recovery of neptunium from high level waste streams of PUREX origin using 30% TBP

International Nuclear Information System (INIS)

Mathur, J.N.; Murali, M.S.; Balarama Krishna, M.V.; Iyer, R.H.; Chitnis, R.R.; Wattal, P.K.; Theyyunni, T.K.; Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.

1995-01-01

237 Np is one of the longest-lived nuclides among the actinides present in the high level waste solutions of reprocessing origin. Its separation, recovery and transmutation can reduce the problem of long term storage of the vitrified waste to a great extent. With this objective, the present work was initiated to study the extraction of neptunium into TBP under the conditions relevant to high level waste, along with uranium and plutonium by oxidising it to hexavalent state using potassium dichromate and subsequently recovering it by selective stripping. Three types of simulated HLW solutions namely sulphate bearing (SB), with an acidity of ∼ 0.3 M and non-sulphate wastes originating from the reprocessing of fuels from pressurised heavy water reactor (PHWR) and fast breeder reactor (FBR) with acidities of 3.0 M HNO 3 were employed in these studies. The extraction of U(VI), Np(VI) and Pu(VI) was very high for PHWR- and FBR-HLW solutions, whereas for the SB-HLW solution, these values were less but reasonably high. Quantitative recovery of neptunium and plutonium was achieved using a stripping solution containing 0.1 M H 2 O 2 and 0.01 M ascorbic acid at an acidity of 2.0 M. Since, cerium present in the waste solutions is expected to undergo oxidation in presence of K 2 Cr 2 O 7 , its extraction behaviour was also studied under similar conditions. Based on the results, a scheme was formulated for the recovery of neptunium along with plutonium and was successfully applied to actual high level waste solution originating from the reprocessing of research reactor fuels. (author). 19 refs., 2 figs., 17 tabs

Radionuclide sorption in Yucca Mountain tuffs with J-13 well water: Neptunium, uranium, and plutonium. Yucca Mountain site characterization program milestone 3338

International Nuclear Information System (INIS)

Triay, I.R.; Cotter, C.R.; Kraus, S.M.; Huddleston, M.H.

1996-08-01

We studied the retardation of actinides (neptunium, uranium, and plutonium) by sorption as a function of radionuclide concentration in water from Well J-13 and of tuffs from Yucca Mountain. Three major tuff types were examined: devitrified, vitric, and zeolitic. To identify the sorbing minerals in the tuffs, we conducted batch sorption experiments with pure mineral separates. These experiments were performed with water from Well J-13 (a sodium bicarbonate groundwater) under oxidizing conditions in the pH range from 7 to 8.5. The results indicate that all actinides studied sorb strongly to synthetic hematite and also that Np(V) and U(VI) do not sorb appreciably to devitrified or vitric tuffs, albite, or quartz. The sorption of neptunium onto clinoptilolite-rich tuffs and pure clinoptilolite can be fitted with a sorption distribution coefficient in the concentration range from 1 X 10 -7 to 3 X 10 -5 M. The sorption of uranium onto clinoptilolite-rich tuffs and pure clinoptilolite is not linear in the concentration range from 8 X 10 -8 to 1 X 10 -4 M, and it can be fitted with nonlinear isotherm models (such as the Langmuir or the Freundlich Isotherms). The sorption of neptunium and uranium onto clinoptilolite in J-13 well water increases with decreasing pH in the range from 7 to 8.5. The sorption of plutonium (initially in the Pu(V) oxidation state) onto tuffs and pure mineral separates in J-13 well water at pH 7 is significant. Plutonium sorption decreases as a function of tuff type in the order: zeolitic > vitric > devitrified; and as a function of mineralogy in the order: hematite > clinoptilolite > albite > quartz

Magnetic and electronic properties of Neptunium chalcogenides from GGA + U + SOC and DFT investigations

Energy Technology Data Exchange (ETDEWEB)

Khan, Wilayat [New Technologies – Research Center, University of West Bohemia, Univerzitni 8, 306 14 Pilsen (Czech Republic); Goumri-Said, Souraya, E-mail: sosaid@alfaisal.edu [College of Science, Physics Department, Alfaisal University, Riyadh 11533 (Saudi Arabia)

2017-06-15

Highlights: • Electronic and magnetic properties of Neptunium chalcogenides were explored theoretically using DFT approach. • Spin orbit coupling and GGA + U approach described successfully the f–f coupling. • Np{sub 2}X{sub 5} ate metallic with high magnetic character due to the Neptunium. • Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. - Abstract: First-principles calculations techniques were employed to explore the structural, electronic and magnetic properties of Neptunium chalcogenides (Np{sub 2}X{sub 5}, X = S, Se and Te). No experimental or theoretical studies of their physical properties have been previously reported in the literature. The presence of highly localized f states has requested the employment of the spin orbit coupling and GGA + U approach in order to describe correctly the f–f coupling. Np{sub 2}X{sub 5} was found metallic with high magnetic character due to the Neptunium presence. Fermi surfaces of Np{sub 2}Te{sub 5} have shown a greater electrical conductivity compared to Np{sub 2}Se{sub 5} and Np{sub 2}S{sub 5}. The magnetic moment was found to be between 13.24 and 13.92μ{sub B}, principally induced by Np f and d-orbitals as well as the spin-polarization of the chalcogenes (Te, Se, S) induced by Np. Neptunium chalcogenides have shown interesting magnetic properties and should be manipulated with precaution due to their radioactive properties.

XAS and TRLIF spectroscopy of uranium and neptunium in seawater.

Science.gov (United States)

Maloubier, Melody; Solari, Pier Lorenzo; Moisy, Philippe; Monfort, Marguerite; Den Auwer, Christophe; Moulin, Christophe

2015-03-28

Seawater contains radionuclides at environmental levels; some are naturally present and others come from anthropogenic nuclear activity. In this report, the molecular speciation in seawater of uranium(VI) and neptunium(V) at a concentration of 5 × 10(-5) M has been investigated for the first time using a combination of two spectroscopic techniques: Time-resolved laser-induced fluorescence (TRLIF) for U and extended X-ray absorption fine structure (EXAFS) for U and Np at the LIII edge. In parallel, the theoretical speciation of uranium and neptunium in seawater at the same concentration is also discussed and compared to spectroscopic data. The uranium complex was identified as the neutral carbonato calcic complex UO2(CO3)3Ca2, which has been previously described in other natural systems. In the case of neptunium, the complex identified is mainly a carbonato complex whose exact stoichiometry is more difficult to assess. The knowledge of the actinide molecular speciation and reactivity in seawater is of fundamental interest in the particular case of uranium recovery and more generally regarding the actinide life cycle within the biosphere in the case of accidental release. This is the first report of actinide direct speciation in seawater medium that can complement inventory data.

OXIDATION OF TRANSURANIC ELEMENTS

Science.gov (United States)

Moore, R.L.

1959-02-17

A method is reported for oxidizing neptunium or plutonium in the presence of cerous values without also oxidizing the cerous values. The method consists in treating an aqueous 1N nitric acid solution, containing such cerous values together with the trivalent transuranic elements, with a quantity of hydrogen peroxide stoichiometrically sufficient to oxidize the transuranic values to the hexavalent state, and digesting the solution at room temperature.

Neptunium and manganese biocycling in nuclear legacy sediment systems

International Nuclear Information System (INIS)

Thorpe, Clare L.; Morris, Katherine; Lloyd, Jonathan R.; Denecke, Melissa A.; Law, Kathleen A.; Dardenne, Kathy; Boothman, Christopher; Bots, Pieter; Law, Gareth T.W.

2015-01-01

Understanding the behaviour of the highly radiotoxic, long half-life radionuclide neptunium in the environment is important for the management of radioactively contaminated land and the safe disposal of radioactive wastes. Recent studies have identified that microbial reduction can reduce the mobility of neptunium via reduction of soluble Np(V) to poorly soluble Np(IV), with coupling to both Mn- and Fe(III)- reduction implicated in neptunyl reduction. To further explore these processes Mn(IV) as δMnO 2 was added to sediment microcosms to create a sediment microcosm experiment “poised” under Mn-reducing conditions. Enhanced removal of Np(V) from solution occurred during Mn-reduction, and parallel X-ray absorption spectroscopy (XAS) studies confirmed Np(V) reduction to Np(IV) commensurate with microbially-mediated Mn-reduction. Molecular ecology analysis of the XAS systems, which contained up to 0.2 mM Np showed no significant impact of elevated Np concentrations on the microbial population. These results demonstrate the importance of Mn cycling on Np biogeochemistry, and clearly highlight new pathways to reductive immobilisation for this highly radiotoxic actinide. - Highlights: • Neptunium is a high radiotoxicity, alpha emitting actinide. • Biostimulation of Mn(IV)-enriched sediments leads to reductive removal of soluble Np(V) from groundwater onto sediments as Np(IV). • Np(V) reduction occurs under defined Mn-reducing conditions. • Under Mn-reducing conditions, enzymatic processes may be important for Np(V) reduction.

Quaternary ammonium based task specific ionic liquid for the efficient and selective extraction of neptunium

Energy Technology Data Exchange (ETDEWEB)

Gupta, Nishesh Kumar [National Institute of Technology, Odisha (India). Dept. of Chemistry; Sengupta, Arijit [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Biswas, Sujoy [Bhabha Atomic Research Centre, Mumbai (India). Uranium Extraction Div.

2017-07-01

Liquid-liquid extraction of neptunium from aqueous acidic solution using quaternary ammonium based task specific ionic liquid (TSIL) was investigated. The extraction of Np was predominated by the 'cation exchange' mechanism via [NpO{sub 2}.Hpth]{sup +} species for NpO{sub 2}{sup 2+}, while NpO{sub 2}{sup +} was extracted in ionic liquid as [NpO{sub 2}.H.Hpth]{sup +}. The extraction process was thermodynamically spontaneous while kinetically slower. Na{sub 2}CO{sub 3} as strippant showed quantitative back extraction of neptunium ions from TSIL. TSIL showed excellent radiolytic stability upto 500 kGy gamma exposure. Finally, the TSIL was employed for the processing of simulated high level waste solutions revealing high selectivity of TSIL towards neptunium.

Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

Science.gov (United States)

Ams, D.; Swanson, J. S.; Reed, D. T.

2010-12-01

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic

Neptunium(V) adsorption to bacteria at low and high ionic strength

International Nuclear Information System (INIS)

Ams, David A.; Swanson, Juliet S.; Reed, Donald T.; Fein, Jeremy B.

2010-01-01

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO 2 + aquo and associated complexed species, is readily soluble, weakly interacting with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface contaminant. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO 2 + ) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacterialNp mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight the key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. Similarities in adsorption behavior may be linked to similarities in the characteristics of the moieties between all bacterial cell walls. Differences in adsorption behavior may reflect differences in ionic strength effects, rather than differences in bacteria

Neptunium(V) adsorption to bacteria at low and high ionic strength

Energy Technology Data Exchange (ETDEWEB)

Ams, David A [Los Alamos National Laboratory; Swanson, Juliet S [Los Alamos National Laboratory; Reed, Donald T [Los Alamos National Laboratory; Fein, Jeremy B [UNIV OF NOTRE DAME

2010-12-08

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO{sub 2}{sup +} aquo and associated complexed species, is readily soluble, weakly interacting with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface contaminant. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO{sub 2}{sup +}) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacterialNp mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight the key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. Similarities in adsorption behavior may be linked to similarities in the characteristics of the moieties between all bacterial cell walls. Differences in adsorption behavior may reflect differences in ionic strength effects, rather than

Determination of neptunium in soil by ICP-MS

International Nuclear Information System (INIS)

Ayranov, M.; Kraehenbuehl, U.

2005-01-01

A fast and simple method for the determination of 237 Np in soil is presented. The borate fusion decreases the sample pre-treatment time and a TEVA extraction chromatography separates neptunium from uranium and the interfering matrix components. A comparison of the sensitivities of alpha spectrometry and sector field ICP-MS for determination of 237 Np is presented. (orig.)

Absorption, distribution, and fate of neptunium in plants

International Nuclear Information System (INIS)

Cataldo, D.A.; Garland, T.R.; Wildung, R.E.

1988-01-01

Soil-plant concentration ratios (CR) for neptunium (Np) in bushbean, measured over the range of 5.2 /times/ 10/sup /minus/7/ to 4.1 mg of Np/g of soil, are approximately 2 at soil concentrations below 4 /times/ 10/sup /minus/4/ mg/g and increase to 12 at higher soil levels. The CR values determined for soybean, bushbean, barley, and alfalfa range from 0.5 to 4 at a soil concentration of 2.6 /times/ 10/sup /minus/6/ mg/g. Root absorption by soybean seedlings of Np from solutions containing 7 /times/ 10/sup /minus/7/ to 473 mg of Np(V)/mL is generally proportional to concentration but exhibits some saturation in root absorption at higher concentrations. Seed concentrations in bushbean and wheat are a factor of 10 lower than vegetative tissues. Neptunium is transported within the plant in organic complexes containing one or more organic acid residues. Fractionation of plant tissues indicates that Np is substantially more soluble than plutonium, especially in seeds, with approximately 50% of the soluble Np in roots and leaves associated with plant ligands of less than 5000 molecular weight

Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

International Nuclear Information System (INIS)

Bonin, L.; Ansoborlo, E.; Moisy, Ph.

2005-01-01

Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np IV and Np V in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10 -4 mol/L), lactate (1.5 10 -3 mol/L), CO 3 2- (2.5 10 -2 mol/L), PO 4 3- (1.1 10 -3 mol/L), SO 4 2- (3.3 10 -4 mol/L) and Cl - (9 10 -2 mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np V with various acid-basic forms of the citrate anion was observed; regarding Np IV , two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np VI is probably similar to the behaviour of U VI , which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit 3- anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np VI was very quickly reduced to Np V by the citrate anions, whereas Np IV was stable. In the case of Np V , it was observed that, depending on the pH and the citrate

The XPS study of physical and chemical forms of neptunium group on the surface of minerals

Directory of Open Access Journals (Sweden)

Teterin Anton Yu.

2010-01-01

Full Text Available The sorption behavior and the physical and chemical forms of neptunium on the surface of minerals of the two chlorate samples, biotite and kaolin, with different contents of Fe(II was studied. The liquid-liquid extraction and the X-ray photoelectron spectroscopy were employed to identify the valence forms of neptunium. On the basis of the obtained data the quantitative elemental composition of the surface of the studied minerals, as well as the ionic composition of the formed neptunium complexes was determined. It was shown that the Np(IV and Np(VI containing compounds did not form, while the complexes Np(VO+ -hydroxyl did form on the surface. The oxygen ions bonded with iron and oxygen belonging to water and/or of carboxyl were suggested to be present in the equatorial plane of the neptunyl group NpO+.

Stabilization of neptunium valence states in nitric media for spent nuclear fuel reprocessing

International Nuclear Information System (INIS)

Feldhaus, P.

1996-12-01

A possibility of standarizing the extraction-behavior of Neptunium during the reprocessing of spent nuclear fuel corresponding to PUREX-Process was investigated. The aim of the work was a qualitative dirigation of the Transuraniumelement (TRUE) into the raffinat of the first extraction cycle by a complete redoxconversion of the Neptunium valence states to unextractable Np(V). In the beginning the theoretical and experimental research focussed on the redoxchemistry of the actinide during the fuel dissolution and the feed preparation. Thereby the nitrous acid, which is produced by a radiological, photochemical and reductive degradation of the nitric acid, revealed an ambivalent influence on the Neptunium valences. By a short-term increase in HNO 2 -concentration the Np(V)-fraction could be obviously risen. The use of some stabilizing reagents inhibited a later reoxidation to Np(VI) also catalyzed by nitrous acid. The urea used for this purpose also led to a further increase in the obtained conversion rates due to a Np(VI)-reduction. The analysis of the valence distribution was performed by an extraction method. This had been compared to chromatographic separation in some preliminary investigations and had turned out to be comparably reliable and easily manageable. (orig.) [de

Selective leaching studies of deep-sea sediments loaded with americium, neptunium and plutonium

International Nuclear Information System (INIS)

Cole, T.G.; Higgo, J.J.W.; Cronan, D.S.; Rees, L.V.C.

1984-07-01

A series of selective leaching experiments were undertaken to investigate the solid phase speciation and distribution of americium, neptunium and plutonium which had been experimentally loaded onto different marine sediment types. The chemical leaches employed showed rather poor selectivity but certain trends were evident. Adsorption was not by ion exchange. Americium showed a preferential affinity for carbonate and plutonium for organic matter. Neptunium appeared to have no preferential affinities. Americium was sorbed by acetic acid residues (CaCO 3 removed) and by unleached carbonate-rich sediments with equal efficiency. This indicates that it is able to diversify its solid phase affinity/distribution depending upon which solid phases are available. (author)

Concept and experimental studies on fuel and target for minor actinides and fission products transmutation

Energy Technology Data Exchange (ETDEWEB)

Prunier, C; Guerin, Y [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d` Etudes des Combustibles; Salvatores, M [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Direction des Reacteurs Nucleaires; Zaetta, A [CEA Centre d` Etudes de Cadarache, 13 - Saint-Paul-lez-Durance (France). Dept. d` Etudes des Reacteurs

1994-12-31

High activity long-lived radionuclides in nuclear wastes, namely minor actinides (americium and neptunium) are in large amount generated by current nuclear reactive. The destruction of these radionuclides is a part of the French SPIN (Partitioning and Burning) program consistent with the determination to send a minimum amount of harmful products for final storage. Transmutation concepts are defined for neptunium and americium taking into account fuel cycle strategies. Neptunium destruction does not pose any major problems. It`s a by-product of uranium consumption, as plutonium and in despite of a slight gamma activity due to the protactinium 233 it`s quite easy to handle. Diluting neptunium in the mixed oxide fuels (MOX) should not be an obstacle for fabrication, in-pile behaviour and reprocessing either. Consequently we make the proposal of homogeneous mode of neptunium in MOX which should be soon explored in the experimental OSIRIS reactor and in the Phenix and Superphenix reactors. The analysis is more complex for the multi isotope americium. Its destruction is difficult because of gamma radioactivity which complicates fabrication. Experiments in Phenix and calculation showed that Phenix reactor offers a good potential for americium incineration, but similar data do not exist for PWR. It will remain a well known difficulty for fabrication and reprocessing. In this case we have to put a real new face to the fabrication flow-sheet of americium compounds and we propose to develop the heterogeneous mode. Targets choice are defined in term of: -safety, considering fuel reaction with cladding and water sodium, -transmutation rate, limited by target behaviour, in FR`s (Phenix), PWR`s (OSIRIS) and HFR (Petten), -reprocessing, checking the solubility of such targets by Purex process. So, at the beginning of our program the account has been on improving fuel and targets properties related to safety and fuel cycle. (authors). 4 figs.

Neptunium immobilization and recovery using phase separated glasses

International Nuclear Information System (INIS)

Meaker, T.F.

1997-01-01

A phase separated (amorphous) glass has been developed which allows very efficient recovery of +4 valence actinides. The total amount of crystal formation in a heat treated vycor-type glass can be controlled with time, temperature and loading. Heat treatments at lower temperatures and for less time inhibit crystal formation while still allowing significant phase separation. If the Thorium loading exceeds 10 weight percent oxide, crystal formation during heat treatment may not be avoided. The total amount of crystal growth has a direct affect on thorium leachability. An increase in crystal formation limits the Th recovery significantly. High thorium loaded glasses (15 weight percent) with heat treatments (increased crystal formation) leach at approximately the same rate as non-heat treated glasses. A phase separated (amorphous) glass has been produced using thorium as a surrogate for neptunium. Two different homogeneous vycor compositions targeting 10 and 15 weight percent thorium oxide have been processed, heat treated and leached with concentrated nitric acid at 110 degrees C. Thorium recovery rates have been shown to be considerably better when the glass has been heat treated inducing phase separation that is relatively crystal free. Non-heat treated and crystalline (due to heat treatment) glasses have similar Th recovery rates with respect to surface area. Phase separated amorphous samples were found to have significantly higher thorium concentrations in the leachate compared to non-heat treated and crystalline glasses for all mesh sizes. All glasses had increased thorium concentration in the leachate as surface area increased

Transport of neptunium through Yucca Mountain tuffs

International Nuclear Information System (INIS)

Triay, I.R.; Robinson, B.A.; Mitchell, A.J.; Overly, C.M.; Lopez, R.M.

1993-01-01

Neptunium has a high solubility in groundwaters from Yucca Mountain [1]. Uranium in nuclear reactors produces 237 Np which has a half-life of 2.1 4 x 10 6 years. Consequently, the transport of 237 Np through tuffs is of major importance in assessing the performance of a high-level nuclear waste repository at Yucca Mountain. The objective of this work is to determine the amount of Np retardation that is provided by the minerals in Yucca Mountain tuffs as a function of groundwater chemistry

Simulation study of the chemical forms of neptunium and plutonium in groundwater from a borehole in the northwest region

International Nuclear Information System (INIS)

Ma Yingming; Jin Yuren; Wang Zhiqiang; Liu Dongxu; Liu Wei; Liu Yan

2009-01-01

According to physics-chymistry characteristic of groundwater from a borehole in the northwest region, we performed simulation study of the chemical forms of neptunium and plutonium by the geochemistry modeling program EQ3/6. The main conclusions are as follows: the main chemical form of neptunium in the groundwater is Np(V)'s NpO 2 + , subordination chemical forms are NpO 2 Cl, NpO 2 CO 3 - , NpO 2 OH, NpO 2 SO 4 - ; the main existing form of plutonium in the groundwater is Pu(IV)'s Pu(OH)5-and subordination chemical form is Pu(V)'s PuO 2 + . In addition,the temperature, pH and Eh also have different impacts on the chemical form of neptunium and plutonium. (authors)

Neptunium speciation (complexation and redox behaviour) in aqueous citrate medium

Energy Technology Data Exchange (ETDEWEB)

Bonin, L.; Ansoborlo, E.; Moisy, Ph. [CEA Marcoule (France)

2005-07-01

Full text of publication follows: In the framework of the French Environmental Nuclear Toxicology programme, additional experiments related to the decorporation of actinides are planned. The lack of information on the neptunium behaviour within blood and the inefficiency of therapeutic treatments, led us to study the complexation of this element with basic anions. Within this purpose, the in vitro behaviour of Np{sup IV} and Np{sup V} in simple media simulating biological media was studied: blood plasma is one of the media of interest and it can be simulated, from a chemical point of view, by an aqueous solution with pH 7.4, containing ions such as citrate (1.6 10{sup -4} mol/L), lactate (1.5 10{sup -3} mol/L), CO{sub 3}{sup 2-} (2.5 10{sup -2} mol/L), PO{sub 4}{sup 3-} (1.1 10{sup -3} mol/L), SO{sub 4}{sup 2-} (3.3 10{sup -4} mol/L) and Cl{sup -} (9 10{sup -2} mol/L). This study was more specifically focused on the behaviour of neptunium with citrate ion, which is also a basic ligand to consider when one wishes to study the migration of actinides in the environment, since it exists in significant amounts in the ground due to its production by the plants. In order to determine the speciation of this system, spectrophotometry was more particularly used. Concerning the complexation phenomenon, the existence of several complexes of Np{sup V} with various acid-basic forms of the citrate anion was observed; regarding Np{sup IV}, two complexes, with 1:1 and 1:2 stoichiometry, have been respectively observed. The reactivity of Np{sup VI} is probably similar to the behaviour of U{sup VI}, which is reported in literature to form a complex with a 1:1 stoichiometry with the Cit{sup 3-}anion From the quantitative study of these equilibria, it has been possible to determine the values of various equilibrium constants. Concerning the stability of neptunium towards oxido-reduction, it was confirmed that Np{sup VI} was very quickly reduced to Np{sup V} by the citrate anions

Fundamental studies of uranium and neptunium redox flow batteries (II)

International Nuclear Information System (INIS)

Shiokawa, Y.; Yamamura, T.; Watanabe, N.

2002-01-01

The atomic power generation entails production of so-called minor actinides and accumulation of depleted uranium. The theoretical and experimental investigations are underway to transmute minor actinides for minimizing the long-term radiotoxicity and reducing the radioactive waste. The utilization, however, would be alternative means. The actinide redox couples, An(VI)/An(V) and An(IV)/An(III), have excellent properties as battery active materials. Here j the uranium and neptunium redox flow batteries for the electric power storage are discussed from the electrochemical properties of U, Np, Pu and Am [1,2]. One of the required properties for the batteries for electric power storage is high energy efficiency, which is defined by the ratio of the discharge energy to the charge energy. These energies are dependent on the rapidness of kinetics in the electrode reactions, namely the standard rate constants and also the internal resistance of the battery

Influence of dissolved organic substances in groundwater on sorption behavior of americium and neptunium

International Nuclear Information System (INIS)

Boggs, S. Jr.; Seitz, M.G.

1984-01-01

Groundwaters typically contain dissolved organic carbon consisting largely of high molecular weight compounds of humic and fulvic acids. To evaluate whether these dissolved organic substances can enhance the tranport of radionuclides through the groundwater system, experiments were conducted to examine the sorption of americium and neptunium onto crushed basalt in the presence of dissolved humic- and fulvic-acid organic carbon introduced into synthetic groundwater. The partitioning experiments with synthetic groundwater show that increasing the concentration of either humic or fulvic acid in the water has a significant inhibiting effect on sorption of both americium and neptunium. At 22 0 C, adsorption of these radionuclides, as measured by distribution ratios (the ratio of nuclide sorbed onto the solid to nuclide in solution at the end of the experiment), decreased by 25% to 50% by addition of as little as 1 mg/L dissolved organic carbon and by one to two orders of magnitude by addition of 100 to 200 mg/L dissolved organic carbon. Distribution ratios measured in solutions reacted at 90 0 C similarly decreased with the addition of dissolved organic carbon but generally ranged from one to two orders of magnitude higher than those determined in the 22 0 C experiment. These results suggest that organic carbon dissolved in deep groundwaters may significantly enhance the mobility of radionuclides of americium and neptunium. 23 references, 5 figures, 11 tables

Influence of microorganisms on the oxidation state distribution of multivalent actinides under anoxic conditions

International Nuclear Information System (INIS)

Reed, Donald Timothy; Borkowski, Marian; Lucchini, Jean-Francois; Ams, David; Richmann, M.K.; Khaing, H.; Swanson, J.S.

2010-01-01

The fate and potential mobility of multivalent actinides in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium, uranium and neptunium are the near-surface multivalent contaminants of concern and are also key contaminants for the deep geologic disposal of nuclear waste. Their mobility is highly dependent on their redox distribution at their contamination source as well as along their potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. Under anoxic conditions, indirect and direct bioreduction mechanisms exist that promote the prevalence of lower-valent species for multivalent actinides. Oxidation-state-specific biosorption is also an important consideration for long-term migration and can influence oxidation state distribution. Results of ongoing studies to explore and establish the oxidation-state specific interactions of soil bacteria (metal reducers and sulfate reducers) as well as halo-tolerant bacteria and Archaea for uranium, neptunium and plutonium will be presented. Enzymatic reduction is a key process in the bioreduction of plutonium and uranium, but co-enzymatic processes predominate in neptunium systems. Strong sorptive interactions can occur for most actinide oxidation states but are likely a factor in the stabilization of lower-valent species when more than one oxidation state can persist under anaerobic microbiologically-active conditions. These results for microbiologically active systems are interpreted in the context of their overall importance in defining the potential migration of multivalent actinides in the subsurface.

Spectrophotometric study of neptunium (VI) complexation by nitrate ions; Etude par spectrophotometrie de la complexation du neptunium au degre d'oxydation (VI) par les ions nitrates

Energy Technology Data Exchange (ETDEWEB)

Pochon, P. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification (DRRV), 30 - Marcoule (France)]|[Conservatoire National des Arts et Metiers (CNAM), 75 - Paris (France)]|[Centre Regional Associe de Lyon, 69 (France)

2000-07-01

Neptunium(VI) complexation by nitrate ions was investigated by visible and near-infrared spectrophotometry, a technique suitable for observing the appearance and evolution of the species in solution. In the absence of reference spectra for Np(VI) nitrate- complexes, mathematical (factor analysis) tools were used to interpret the spectra. These chemo-metric techniques were first tested and validated on a simpler chemical system: Np(VI)complexation by the SiW{sub 11}O{sub 39}{sup 8-} anion. The test media used to investigate Np(VI) nitrate- complexes generally contain nitrate and perchlorate salts at high concentrations (high ionic strength). Media effects arising from the presence of cations, acidity or the perchlorate ion concentration are therefore significant, and no doubt account for the scattered values of the complexation constants published in the literature. The evolution of the neptunium spectra according to the parameters of the reaction medium illustrated these effects and allowed them to be quantified by a global 'perturbation constant'. In order to minimize the spectrum modifications due to media effects, the neptunium nitrate-complexes were studied at constant ionic strength in weak acidic media (2 mol.kg{sup -1}{sub H2O}) in the presence of sodium salts. The bulk formation constants and the spectrum of the NpO{sub 2}(NO{sub 3}){sup +} complex were determined for ionic strength values of 2.2, 4, 6 and 8 mol.kg{sup -1}{sub H2O}. The constants remained on the same order of magnitude regardless of the ionic strength; the thermodynamic constant {beta}{sub 1}{sup 0} determined from them according to specific interaction theory is thus probably of little significance. Conversely, the bulk constants can be corrected for the effects of the perchlorate ions by taking the global 'perturbation constant' into account. (author)

Gastrointestinal absorption and retention of neptunium by fasted and fed mice

International Nuclear Information System (INIS)

Larsen, R.P.; Bhattacharyya, M.H.; Oldham, R.D.; Moretti, E.S.

1982-01-01

The retention of neptunium in liver and bone subsequent to its gastrointestinal absorption has been determined in both fasted and fed mice. The values obtained for fractional retention were 3 x 10 - 3 and 1 x 10 - 4 , respectively, and are within a factor of two the same as those for plutonium in fasted and fed mice

Complexation of neptunium(V) by salicylate, phthalate and citrate ligands in a pH 7.5 phosphate buffered system

International Nuclear Information System (INIS)

Rees, T.F.; Daniel, S.R.

1984-01-01

Conditional stability constants, enthalpies and entropies of complexation at pH 7.5 and ionic strength 0.1 have been determined for neptunium(V) complexes of phosphate, salicylate, phthalate and citrate. Results are given and discussed. At pH 7.5 salicylate does not form a complex with neptunium(V) due to the low charge density of the NpO 2 + ion and incomplete ionization of the salicylate ion. In all cases, only 1:1 complexes were identified. (U.K.)

Computer modelling of the chemical speciation of caesium, uranium(VI) and neptunium(V) in human duodenal fluids under fasting conditions

International Nuclear Information System (INIS)

Jones, P.W.; Taylor, D.M.; Webb, L.M.; Williams, D.R.

2002-01-01

A model simulating the human duodenal contents under physiologically realistic, fasting conditions was developed using the joint expert speciation system (JESS) computer program and database and used to investigate the chemical speciation of caesium, uranium(VI) and neptunium(V). Over the pH range 5.0-9.0, and the concentration range 5x10 -15 -5x10 -5 mol dm -3 , caesium was predicted to occur predominantly as the absorbable free monovalent cation Cs + (∼95%) with species such as CsHPO 4 - and CsCl representing the remainder. The presence or absence of sulphate at 2.1x10 -3 mol dm -3 did not influence the predicted speciation. Uranium was predicted to be present entirely as a soluble, highly charged species, both in the absence and in the presence of sulphate. Between pH 5.0 and ∼6.5 the UO 2 H 2 (PO 4 ) 2 2- predominated, above this pH carbonate species, either UO 2 (CO 3 ) 4 6- or, possibly, UO 2 (CO 3 ) 5 8- . At pH 8.0, and in the presence of sulphate, neptunium(V) was predicted to exist solely as the tetrasulphate species, whilst in the absence of sulphate, an array of negatively charged soluble carbonate species predominated. Studies over the pH range 5.0-9.0 predicted the formation of a spectrum of negatively charged carbonate and phosphate species, ∼40% of the total neptunium was predicted to be present as the electrically net-neutral species NpO 2 HCO 3 at pH6.0, ∼20% at pH 7.0, ∼10% at pH 7.5 and ∼1% at pH 8.0. The observed speciation patterns of uranium and neptunium did not change over the concentration range 5x10 -15 -5x10 -5 mol dm -3 and no solid species were predicted to occur under the conditions simulated. Whether the predicted electrically net-neutral neptunium species or the uranium pentacarbonate species do actually occur under true physiological conditions remains to be established. The observed speciation patterns for caesium and uranium are consistent with the observed absorption of these elements by humans; however, the

Relationships among oxidation-reduction and acid-base properties of the actinides in high oxidation states

International Nuclear Information System (INIS)

Morss, L.R.

1992-01-01

The first chemical identification of plutonium, its subsequent isolation on the macroscopic scale, and more recent chemical separation schemes were achieved by taking advantage of the differences among the oxidation states of uranium, neptunium, and plutonium. Many acid-base properties modify the relative stabilities of oxidation states of the actinides. In the solid state, strongly basic compounds such as Cs 2 O yield complex oxides with oxidation states of Np(VII), Pu(VI), and Am(VI) whereas more acidic compounds such as CsF yield complex fluorides with lower oxidation states. In aqueous solution, high basicity and strongly covalent complexes favor high oxidation states. In nonaqueous solvent systems, high acidity generally favors low oxidation states. This paper elucidates and attempts to interpret the effects of these acid-base properties in a systematic fashion

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

International Nuclear Information System (INIS)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO 3 solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at [HNO 3 ]=1-6 mol/l as well as inhibiting effect at [HNO 3 ]=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined

Rapid and simultaneous determination of neptunium and plutonium isotopes in environmental samples by extraction chromatography using sequential injection analysis and ICP-MS

DEFF Research Database (Denmark)

Qiao, Jixin; Hou, Xiaolin; Roos, Per

2010-01-01

plutonium and neptunium in three reference materials were in agreement with the recommended or literature values at the 0.05 significance level. The developed method is suitable for the analysis of up to 10 g of soil and 20 g of seaweed samples. The extraction chromatographic separation within the SI system......This paper reports an automated analytical method for rapid and simultaneous determination of plutonium isotopes (239Pu and 240Pu) and neptunium (237Np) in environmental samples. An extraction chromatographic column packed with TrisKem TEVA® resin was incorporated in a sequential injection (SI...... for a single sample takes less than 1.5 h. As compared to batchwise procedures, the developed method significantly improves the analysis efficiency, reduces the labor intensity and expedites the simultaneous determination of plutonium and neptunium as demanded in emergency actions....

Technetium and neptunium reactions in basalt/groundwater systems

International Nuclear Information System (INIS)

Meyer, R.E.; Arnold, W.D.; Kelmers, A.D.; Kessler, J.H.; Clark, R.J.; Johnson, J.S. Jr.; Young, G.C.; Case, F.I.; Westmoreland, C.G.

1985-01-01

Sorption isotherms and apparent concentration limits for Tc(VII) and Np(V) for a variety of groundwater/basalt systems were determined using Grande Ronde basalt samples representative of the Hanford Site candidate high-level waste repository. Under oxic redox conditions (air present), little or no sorption of technetium was observed; neptunium exhibited low to moderate sorption ratios. Under anoxic redox conditions (oxygen-free), low to moderate sorption of technetium was often observed, but the extent of sorption was highly dependent upon the groundwater composition and the method of pretreatment (if any) of the basalt. Sorption isotherms for technetium under reducing redox conditions (hydrazine added) indicate an apparent concentration limit of approximately 10 -6 mol/l Tc. No apparent concentration limit was found for neptunium for concentrations in groundwater up to 10 -6 mol/l and 8 x 10 -7 mol/l under oxic and reducing (hydrazine added) redox conditions, respectively. Valence control and valence analysis experiments suggest that the sorption or precipitation of Tc and Np from groundwater in the presence of basalt may result from a heterogeneous reaction occurring on the surface of the basalt. One of the critical factors of this reduction reaction appears to be the accessibility of the reactive ferrous iron component of the basalt. The laboratory simulation of groundwater redox conditions representative of the repository environment through the use of solution phase redox reagents is of questionable validity, and information obtained by such experimental methods may not be defensible for site performance assessment calculations. Anoxic experiments conducted in an argon-filled glove box appear better suited for the laboratory simulation of in situ redox conditions. 15 references, 6 figures

Technetium and neptunium reactions in basalt/groundwater systems

International Nuclear Information System (INIS)

Meyer, R.E.; Arnold, W.D.; Kelmers, A.D.; Kessler, J.H.; Clark, R.J.; Johnson, J.S. Jr.; Young, G.C.; Case, F.I.; Westmoreland, C.G.; Florida State Univ., Tallahassee)

1984-01-01

Sorption isotherms and apparent concentration limits for Tc(VII) and Np(V) for a variety of groundwater/basalt systems were determined using Grande Ronde basalt samples representative of the Hanford Site candidate high-level waste repository. Under oxic redox conditions (air present), little or no sorption of technetium was observed; neptunium exhibited low to moderate sorption ratios. Under anoxic redox conditions (oxygen-free), low to moderate sorption of technetium was often observed, but the extent of sorption was highly dependent upon the groundwater composition and the method of pretreatment (if any) of the basalt. Sorption isotherms for technetium under reducing redox conditions (hydrazine added) indicate an apparent concentration limit of approximately 10 -6 mol/L Tc. No apparent concentration limit was found for neptunium for concentrations in groundwater up to approx. 10 -6 mol/L and 8 x 10 -7 mol/L under oxic and reducing (hydrazine added) redox conditions, respectively. Valence control and valence analysis experiments suggest that the sorption or precipitation of Tc and Np from groundwater in the presence of basalt may result from a heterogeneous reaction occurring on the surface of the basalt. One of the critical factors of this reduction reaction appears to be the accessibility of the reactive ferrous iron component of the basalt. The laboratory simulation of groundwater redox conditions representative of the repository environment through the use of solution phase redox reagents is of questionable validity, and information obtained by such experimental methods may not be defensible for site performance assessment calculations. Anoxic experiments conducted in an argon-filled glove box appear better suited for the laboratory simulation of in situ redox conditions. 15 refs., 6 tabs

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO/sub 3/ solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at (HNO/sub 3/)=1-6 mol/l as well as inhibiting effect at (HNO/sub 3/)=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined.

Neptunium detector using fiber-optic light guides

International Nuclear Information System (INIS)

Spencer, W.A.; Killeen, T.E.; Herold, T.R.

1981-01-01

A colorimeter has been constructed and installed to detect neptunium (IV) on-line as it elutes from an ion exchange column in a plant process stream. Because of the high radiation and corrosive atmosphere at the monitoring location, the instrument was designed using remote electronics and glass fiber optic cables. The five-foot cables transmit pulsed white light into a glass monitoring window in a containment box and return the transmitted portion to a photosensor. A simple spring clamp was designed to couple the cables to the monitoring window without modifying existing processes. Details of the design, installation, and operational problems are discussed. Other applications and modifications of the present colorimeter for other actinides, as well as preliminary results on a fiber optic spectrophotometer, are presented

Forefront of PUREX system engineering. Chemistry and engineering of ruthenium, technetium and neptunium

International Nuclear Information System (INIS)

2004-07-01

The paper reports the activity of the research committee organized by the Atomic Energy Society of Japan on 'Ruthenium and Technetium Chemistry in the PUREX System', with focusing on basic behaviors of ruthenium, technetium and neptunium in the PUREX process, the principles of plant design, and behaviors during the final waste treatment. The scope of the work includes the following major topics: (1) basic solution and solid-state chemistry; (2) basic solution and solid-state chemistry of minor actinides in particular, Np; (3) partitioning chemistry in the PUREX system and environmental behavior of the components; (4) processes of recovery, purification, and utilization of rare metal fission products; (5) field data on plant design, operation, decontamination, and decommissioning; (6) numerical process simulations and process control technologies; (7) compilation of a data base for process chemistry and plant engineering. (S. Ohno)

Development of analytical methods for the separation of plutonium, americium, curium and neptunium from environmental samples

Energy Technology Data Exchange (ETDEWEB)

Salminen, S.

2009-07-01

In this work, separation methods have been developed for the analysis of anthropogenic transuranium elements plutonium, americium, curium and neptunium from environmental samples contaminated by global nuclear weapons testing and the Chernobyl accident. The analytical methods utilized in this study are based on extraction chromatography. Highly varying atmospheric plutonium isotope concentrations and activity ratios were found at both Kurchatov (Kazakhstan), near the former Semipalatinsk test site, and Sodankylae (Finland). The origin of plutonium is almost impossible to identify at Kurchatov, since hundreds of nuclear tests were performed at the Semipalatinsk test site. In Sodankylae, plutonium in the surface air originated from nuclear weapons testing, conducted mostly by USSR and USA before the sampling year 1963. The variation in americium, curium and neptunium concentrations was great as well in peat samples collected in southern and central Finland in 1986 immediately after the Chernobyl accident. The main source of transuranium contamination in peats was from global nuclear test fallout, although there are wide regional differences in the fraction of Chernobyl-originated activity (of the total activity) for americium, curium and neptunium. The separation methods developed in this study yielded good chemical recovery for the elements investigated and adequately pure fractions for radiometric activity determination. The extraction chromatographic methods were faster compared to older methods based on ion exchange chromatography. In addition, extraction chromatography is a more environmentally friendly separation method than ion exchange, because less acidic waste solutions are produced during the analytical procedures. (orig.)

Nuclear forensics of a non-traditional sample: Neptunium

International Nuclear Information System (INIS)

Doyle, Jamie L.; Schwartz, Daniel; Tandon, Lav

2016-01-01

Recent nuclear forensics cases have focused primarily on plutonium (Pu) and uranium (U) materials. By definition however, nuclear forensics can apply to any diverted nuclear material. This includes neptunium (Np), an internationally safeguarded material like Pu and U, that could offer a nuclear security concern if significant quantities were found outside of regulatory control. This case study couples scanning electron microscopy (SEM) with quantitative analysis using newly developed specialized software, to evaluate a non-traditional nuclear forensic sample of Np. Here, the results of the morphological analyses were compared with another Np sample of known pedigree, as well as other traditional actinide materials in order to determine potential processing and point-of-origin

Neptunium(V) sorption on quartz and albite in aqueous suspension

International Nuclear Information System (INIS)

Kohler, M.; Leckie, J.O.

1991-10-01

The behavior of neptunium in the subsurface environment is of interest since neptunium isotopes are included in nuclear waste. Previous work investigated the sorption behavior of Np onto α-Fe 2 O 3 (hematite), an accessory mineral of the Yucca Mountain repository. The work reported herein involves the much more abundant silicate minerals quartz and albite, and is a logical continuation of the ongoing task. In previous work increased sorption was observed in systems containing hematite and EDTA, a ligand which acts as a surrogate for organic complexing agents. In addition, increased partial pressures of CO 2 are common in many ground waters and the effects of carbonate on sorption of radionuclides have to be studied as well. At concentration levels of 10 -7 M, Np(V) does not adsorb strongly on quartz and albite up to pH values of approximately 9 at solid/solution ratios of 30 to 40 g/l. Significant adsorption (> 20%) occurs on both minerals only at pH > 9. Pretreatment of albite affects the sorption behavior of this mineral at pH > 9, possibly due to the formation of secondary mineral phases at the albite surface. EDTA does not adsorb on quartz at concentrations of 10 -6 M. In the presence of 50 μM EDTA, Np(V) sorption seems to be restricted. EDTA at the 10 -6 M level adsorbs onto albite to an appreciable degree at pH values 3 - is the predominant solution species

Study of extraction chromatography methods of separation of neptunium and its radiometric determination

International Nuclear Information System (INIS)

Reich, M.

2009-04-01

In presented dissertation thesis the separation procedure for determination of neptunium in model solutions and also in soil samples was designed. 1. The sorbent was prepared on basis of hydrophobised silica gel with silica oil for hydrophobisation - Lukooil H. Extraction agent was anchored on this modified surface -quarternary ammonium salt Aliquat 336. In experiments was proved, that sorbent prepared like this is resist enough to the elution solutions using in separation procedures. It was found out that maximal concentration of deposited Aliquat 336 in benzene on hydrophobised silica gel selected granulate size is 40%. Sorbent prepared with silica gel lower granulate size and also with higher concentration of Aliquat 336 in benzene became sticky and unsuitable for using in separation columns. 2. The prepared sorbent is similar to commercial produced TEVA resin made by company Eichrom and for purpose of this project it was cheaper but the same effective alternative in comparing to mentioned commercial resin. 3. The separation procedure for isolation of 237 Np from radionuclides interfering during its radiometric determination with alpha spectrometry was designed -in scientific publications hasn't been described yet. The procedure consists of using formic acid for reduction of radionuclides interfering by alpha spectrometric determination of 237 Np and subsequent purification of neptunium on the next column by using ferrous sulphamate as reduction agent. This procedure was applied to the model solutions and also to the soil samples. The model solutions and soil samples for these experiments were contaminated with known amounts of 237 Np, 238 pU, 232 Th and mixture of 234 U/ 238 U. The effective separation of neptunium from described radionuclides was achieved with application of the described separation procedure. 4. The separation procedure for separation of 239 Np from its mother radionuclide 241 Am was designed with prepared sorbent. Different washing and

Application of extraction chromatography to the recovery of neptunium, plutonium and americium from an industrial waste

International Nuclear Information System (INIS)

Madic, C.; Kertesz, C.; Sontag, R.; Koehly, G.

1980-01-01

A pilot scale investigation was made to evaluate the possible application of the extraction chromatographic method (LLC) to the partitioning of alpha emitters from liquid wastes containing traces of transuranium elements. A secondary purpose was to obtain pure Am0 2 , which is used to produce alpha, gamma, and neutron sources. The process developed for alpha partitioning consists essentially of the extraction of macro amounts of uranium with 30% TBP in dodecane in mixer-settlers, then coextraction of Np-237, Pu-239, and Am-241 by LLC on a macro column filled with di-n-hexyl-octoxy-methyl-phosphine oxide (POX.11) adsorbed on an inert support. In each run about 200 liters of initial waste are decontaminated of alpha emitters. The loading step is followed by selective elution of americium, neptunium, and plutonium. The americium eluate is then subjected to the following operations: (1) separation of Am from Fe and Cd by LLC on a TBP column and (2) separation of Am from lanthanide traces by LLC on an HD(DiBM)P column after oxidation of Am(III) to Am(VI). The Am in the eluate is subsequently reduced to Am(III) and precipitated as oxalate with oxalic acid. The oxalate is then filtered and calcined to yield pure AmO 2

Investigation of separation factors of neptunium and plutonium in the process of mass transfer through liquid impregnated membranes with di-2-ethylhexylphosphoric acid

International Nuclear Information System (INIS)

Novikov, A.P.; Mikheeva, M.N.; Myasoedov, B.F.

1990-01-01

Kinetics of joint transfer of neptunium(6) and plutonium(4) through liquid membranes with di-2-ethylhexylphosphoric acid, depending on the concentration of the carrier, nature of reextracting agent and ratio of metal concentrations, was investigated. The optimal conditions for selective isolation of microimpurity of one of the elements from solutions of the other were determined. Solution of ammonium carbonate with carrier concentration of 0.1-0.2 mol/l can be expediently utilized as reextracting phase for neptunium impurity removal

Structural variability in neptunium(V) oxalate compounds: synthesis and structural characterization of Na2NpO2(C2O4)OH.H2O.

Science.gov (United States)

Bean, Amanda C; Garcia, Eduardo; Scott, Brian L; Runde, Wolfgang

2004-10-04

Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions.

Sorption and migration of neptunium in porous sedimentary materials

International Nuclear Information System (INIS)

Tanaka, Tadao; Mukai, Masayuki; Nakayama, Shinichi

2005-01-01

Column migration experiments of neptunium were conducted for porous sedimentary materials: coastal sand, tuffaceous sand, ando soil, reddish soil, yellowish soil and loess, and migration behavior, sorption mechanisms and chemical formation of Np were investigated. The migration behavior of Np in each material was much different each other, due to chemical formation in solution and/or sorption mechanism of Np. Mathematical models of different concepts were applied to the experimental results to interpret the sorption mechanism and the migration behavior. It can be concluded that both of instantaneous equilibrium sorption and sorption-desorption kinetics have to be considered to model the Np migration in sedimentary materials. (author)

Purification process of uranium hexafluoride containing traces of plutonium fluoride and/or neptunium fluoride

International Nuclear Information System (INIS)

Aubert, J.; Bethuel, L.; Carles, M.

1983-01-01

In this process impure uranium hexafluoride is contacted with a metallic fluoride chosen in the group containing lead fluoride PbF 2 , uranium fluorides UFsub(4+x) (0 3 at a temperature such as plutonium and/or neptunium are reduced and pure uranium hexafluoride is recovered. Application is made to uranium hexafluoride purification in spent fuel reprocessing [fr

Measurement of total alpha activity of neptunium, plutonium, and americium in highly radioactive Hanford waste by iron hydroxide precipitation and 2-heptanone solvent extraction

International Nuclear Information System (INIS)

Maiti, T.C.; Kaye, J.H.

1992-06-01

An improved method has been developed to concentrate the major alpha-emitting actinide elements neptunium, plutonium, and americium from samples with high salt content such as those resulting from efforts to characterize Hanford storage tank waste. Actinide elements are concentrated by coprecipitation of their hydroxides using iron carrier. The iron is removed by extraction from 8M HCI with 2-heptanone. The actinide elements remain in the aqueous phase free from salts, iron, and long-lived fission products. Recoveries averaged 98 percent

Hydrolysis constants of tetravalent neptunium by using solvent extraction method

International Nuclear Information System (INIS)

Fujiwara, K.; Kohara, Y.

2008-01-01

The hydrolysis constants of tetravalent neptunium (Np(IV)) were determined by solvent extraction method using thenoyltrifluoroacetone(TTA). In order to avoid colloid formation, a stock solution of carrier-free 239 Np(V) was from 243 Am milked. The valence of Np in the solution was then reduced to Np(IV) by using zinc amalgam. The hydrolysis constants (β m ) of the reactions, Np 4+ + mOH - = Np(OH) m (4-m)+ was evaluated by using distribution ratios at ionic strengths (I) = 0.1, 0.5 and 1.0. All experiments were performed in oxygen-free 0.5% H 2 -N 2 atmosphere (below 1.0 ppm of O 2 ) in a glove-box at room temperature (23 ± 2 C) to avoid oxidation of Np(IV). The β m values were extrapolated to the standard state (I = 0) by using the specific ion interaction theory (SIT), and the formation constants at I = 0 were determined to be log β 1 = 13.91 ± 0.23, log β 2 = 27.13 ± 0.15, log β 3 = 37.70 ± 0.30 and log β 4 = 46.16 ± 0.30. The ion interaction coefficients were also evaluated to be ε(NpOH 3+ , ClO 4 - ) = 0.49 ± 0.15, ε(Np(OH) 2 2+ , ClO 4 - ) = 0.35 ± 0.11, and ε(Np(OH) 3 + , ClO 4 - ) = 0.29 ± 0.15. (orig.)

Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

International Nuclear Information System (INIS)

Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gubina, M.Yu.

1988-01-01

Stability concetration constants K and solubility of neptunium and plutonium complexes with di- and monobuthylphosphoric acids (APC) and with orthophosphoric and di-2-ethylhexyl-phosphoric acids in 30% TBP solution-n-dodecane system are determined by spectrophotometric titration and radiometry methods. Posibility of forecasting radiation-chemical behaviour of actinids according to data on K and APC radiation-chemical yield values is demonstrated

Appraisal of available information on uptake by plants of transplutonium elements and neptunium

International Nuclear Information System (INIS)

Thomas, R.L.; Healy, J.W.

1976-07-01

A critical review was made of reported information from laboratory studies of plant uptake of transplutonic elements plus neptunium. The available data are meager but indicate that the uptake of Np is the greatest followed by Am and Cm. The data are not sufficient to provide recommended values for use in hazard calculations but they do indicate that the actinides other than plutonium will be accumulated in plants to a greater degree than plutonium

Investigation on neptunium behavior in electrolytic partitioning process of uranium and plutonium

International Nuclear Information System (INIS)

Zhang Qingxuan; Zhang Jiajun; Tian Baosheng; Jiang Dongliang; Li Zhaoyi; He Jianyu

1988-01-01

The electrolytic oxidation-raduction of Np(V, VI) in HNO 3 solution was studied. Experimental results showed that the electrode process of Np(V)-Np(VI) couple is reversible, and the half reaction time of the process mentioned above is about 1.5 minutes under given conditions. The overpotential of reduction of Np(V) is high, which makes it difficult to reduce Np(V) into Np(IV) directly at cathode. Owing to a large quantity of U(IV) produced through electrolysis, it is presaged that neptunium will be mainly in tetravalent state in the electrolytic M-S battery. A new type of electrolytic M-S battery was developed, in which anodes were installed in each settling chamber without any specific anode chamber in the battery. Owing to using of the mechanical stirrer driven by a wheel gear, stage efficiency is high. Demonstration campaign was carried out. It follows from the results that the yield of Pu is 99.90 ∼ 99.99%. Separation factor of U from Pu is 3900 ∼ 33000. Material balance of U and Pu is satisfactory. Heavy accumulation of Np in the battery was observed. Np in the battery is mainly in the tetravalent state. It is believed that it is difficult to recover Np quantitatively from single fluent (e.g. 1BP or 1BU) under normal conditions of partitioning step of the PUREX process

Hydrolysis constants of tetravalent neptunium by using solvent extraction method

Energy Technology Data Exchange (ETDEWEB)

Fujiwara, K. [Japan Atomic Energy Agency (JAEA), Naka-gun, Ibaraki-ken (Japan); Kohara, Y. [Inspection and Development Co., Naka-gun, Ibaraki-ken (Japan)

2008-07-01

The hydrolysis constants of tetravalent neptunium (Np(IV)) were determined by solvent extraction method using thenoyltrifluoroacetone(TTA). In order to avoid colloid formation, a stock solution of carrier-free {sup 239}Np(V) was from {sup 243}Am milked. The valence of Np in the solution was then reduced to Np(IV) by using zinc amalgam. The hydrolysis constants ({beta}{sub m}) of the reactions, Np{sup 4+} + mOH{sup -} = Np(OH){sub m}{sup (4-m)+} was evaluated by using distribution ratios at ionic strengths (I) = 0.1, 0.5 and 1.0. All experiments were performed in oxygen-free 0.5% H{sub 2}-N{sub 2} atmosphere (below 1.0 ppm of O{sub 2}) in a glove-box at room temperature (23 {+-} 2 C) to avoid oxidation of Np(IV). The {beta}{sub m} values were extrapolated to the standard state (I = 0) by using the specific ion interaction theory (SIT), and the formation constants at I = 0 were determined to be log {beta}{sub 1} = 13.91 {+-} 0.23, log {beta}{sub 2} = 27.13 {+-} 0.15, log {beta}{sub 3} = 37.70 {+-} 0.30 and log {beta}{sub 4} = 46.16 {+-} 0.30. The ion interaction coefficients were also evaluated to be {epsilon}(NpOH{sup 3+}, ClO{sub 4}{sup -}) = 0.49 {+-} 0.15, {epsilon}(Np(OH){sub 2}{sup 2+}, ClO{sub 4}{sup -}) = 0.35 {+-} 0.11, and {epsilon}(Np(OH){sub 3}{sup +}, ClO{sub 4}{sup -}) = 0.29 {+-} 0.15. (orig.)

Stability constants and solubility of neptunium and plutonium complexes with alkylphosphoric acids in TBP

International Nuclear Information System (INIS)

Fedoseev, D.A.; Romanovskaya, I.A.; Artemova, L.A.; Gibina, M.Yu.

1989-01-01

The concentration stability constants (K s ) and solubility of neptunium and plutonium complexes with di- and monobutylphosphoric acids (APA), as well as with orthophosphoric acid in the system composed of 30% TBP + n-dodecane, have been determined by spectrophotometric titration and radiometry. The feasibility of predicting the radiative chemical behavior of actinides based on their K s values and the radiative chemical yield of APA has been demonstrated

Separation of neptunium from uranium and plutonium in the Purex process

International Nuclear Information System (INIS)

Kolarik, Z.; Schuler, R.

1984-01-01

The possibility of removing neptunium from the Purex process in the first extraction cycle was investigated. Butyraldehyde was found to reduce Np(VI) to Np(V), but not Pu(IV) to Pu(III). Up to 99.7% Np can be separated from uranium and plutonium in the 1A extractor or, much more favourably, in an additional partitioning extractor. Hydroxylamine nitrate can be used for reducing Np(VI) to Np(V) in a uranium purification cycle at a high U concentration in the feed solution. Here the decontamination factor for Np can be as high as 2300 and is lowered if iron is present in the feed. (author)

Speciation of neptunium during migration in clay rock; Speziation von Neptunium bei der Migration in Tongestein

Energy Technology Data Exchange (ETDEWEB)

Froehlich, Daniel

2011-12-15

The present work was performed within a fellowship of the interdisciplinary research training group 826 ''trace analysis of elemental species: method development and application'' funded by the German Research Foundation (DFG) and the federal state Rheinland-Pfalz. Aim of this work was to gain new knowledge of the interaction between neptunium and natural clay rock with respect to the disposal of high-level nuclear waste in deep geological formations. The isotope {sup 237}Np with its long half-life of more than two million years will be one of main contributors to the radiotoxicity of the radioactive waste material after storage times of more than 1000 years. In aqueous solution under environmental relevant conditions Np can exist in the oxidation states +IV and +V. Due to its high solubility and higher mobility Np(V) is the much more hazardous species compared to Np(IV). Opalinus Clay (OPA) from Mont Terri, Switzerland, was used as a natural reference material in the migration studies. The focus of this work was on speciation of Np on the mineral surface by synchrotron based X-ray absorption spectroscopy (EXAFS/XANES). The interaction between Np(V) and OPA was studied in batch sorption and diffusion experiments in dependence of various experimental parameters (e.g. pH, temperature, background electrolyte, effect of humic acid, concurrence with U(VI), aerobic/anaerobic conditions). The investigation of Np speciation was performed on two types of samples. Powder samples from batch experiments were prepared under aerobic and anaerobic conditions and measured by EXAFS spectroscopy. Diffusion samples and OPA thin sections contacted with Np(V) were analyzed by locally resolved μ-XANES measurements on enrichments of Np. A combination with μ-XRF (X-ray fluorescence) mapping and μ-XRD (X-ray diffraction) measurements provided further information about the spatial distribution of Np and other elements contained in OPA as well as crystalline mineral

Mechanisms of sorption of neptunium and technetium on argillaceous materials

International Nuclear Information System (INIS)

Hooker, P.J.; West, J.M.; Noy, D.J.

1986-01-01

It is of pressing concern to understand the behaviour of radionuclides in the environment and in particular long-lived ones (e.g. Np-237 and Te-99) in argillaceous rocks. Clay formations have been chosen as likely candidates for holding low level radioactive waste repositories and in the event of leakage of radionuclides into the geosphere some knowledge of their fate is required in a far-field safety assessment study. The objectives of this present work were to examine the properties of neptunium and technetium in ground-waters associated with clay-rich materials and to ascertain the variations in sorption of these radionuclides under different environmental conditions and to use the information in a forecast of transport through a clay layer

Solvent-extraction purification of neptunium

International Nuclear Information System (INIS)

Kyser, E.A.; Hudlow, S.L.

2008-01-01

The Savannah River Site (SRS) has recovered 237 Np from reactor fuel that is currently being processed into NpO 2 for future production of 238 Pu. Several purification flowsheets have been utilized. An oxidizing solvent-extraction (SX) flowsheet was used to remove Fe, sulfate ion, and Th while simultaneously 237 Np, 238 Pu, u, and nonradioactive Ce(IV) was extracted into the tributyl phosphate (TBP) based organic solvent. A reducing SX flowsheet (second pass) removed the Ce and Pu and recovered both Np and U. The oxidizing flowsheet was necessary for solutions that contained excessive amounts of sulfate ion. Anion exchange was used to perform final purification of Np from Pu, U, and various non-actinide impurities. The Np(IV) in the purified solution was then oxalate-precipitated and calcined to an oxide for shipment to other facilities for storage and future target fabrication. Performance details of the SX purification and process difficulties are discussed. (authors)

Source-driven noise analysis measurements with neptunium metal reflected by high enriched uranium

International Nuclear Information System (INIS)

Valentine, Timothy E.; Mattingly, John K.

2003-01-01

Subcritical noise analysis measurements have been performed with neptunium ( 237 Np) sphere reflected by highly enriched uranium. These measurements were performed at the Los Alamos Critical Experiment Facility in December 2002 to provide an estimate of the subcriticality of 237 Np reflected by various amounts of high-enriched uranium. This paper provides a description of the measurements and presents some preliminary results of the analysis of the measurements. The measured and calculated spectral ratios differ by 15% whereas the 'interpreted' and calculated k eff values differ by approximately 1%. (author)

Mathematical modeling of the radiation-chemical behavior of neptunium in HNO3. Equilibrium states

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

A mathematical model of the radiation-chemical behavior of neptunium is presented for a wide range of α-and γ-irradiation doses. Equations determining the equilibrium concentrations of NP(IV), Np(V), and Np(VI) are derived for various concentrations of HNO 3 and dose rates of the ionizing irradiation. The rate constants of the reactions NP(IV) + OH, Np(IV) + NO 3 , Np(V) + NO 2 , Np(V) + H, Np(IV), and Np(V) + Np(V) are obtained by the mathematical modeling

On the use of thermal NF3 as the fluorination and oxidation agent in treatment of used nuclear fuels

Science.gov (United States)

Scheele, Randall; McNamara, Bruce; Casella, Andrew M.; Kozelisky, Anne

2012-05-01

This paper presents results of our investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. Our thermodynamic calculations show that nitrogen trifluoride has the potential to produce volatile fission product and actinide fluorides from oxides and metals that can form volatile fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of lanthanum, cerium, rhodium, and plutonium are fluorinated but do not form volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550 °C. However, depending on temperature, volatile fluorides or oxyfluorides can form from nitrogen trifluoride treatment of the oxides of niobium, molybdenum, ruthenium, tellurium, uranium, and neptunium. Thermoanalytical studies demonstrate near-quantitative separation of uranium from plutonium in a mixed 80% uranium and 20% plutonium oxide. Our studies of neat oxides and metals suggest that the reactivity of nitrogen trifluoride may be adjusted by temperature to selectively separate the major volatile fuel constituent uranium from minor volatile constituents, such as Mo, Tc, Ru and from the non-volatile fuel constituents based on differences in their reaction temperatures and kinetic behaviors. This reactivity is novel with respect to that reported for other fluorinating reagents F2, BrF5, ClF3.

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

Science.gov (United States)

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

1976-01-01

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

Production of oceanic nitrous oxide by ammonia-oxidizing archaea

Directory of Open Access Journals (Sweden)

C. R. Löscher

2012-07-01

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

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

Diffusion of water, cesium and neptunium in pores of rocks

International Nuclear Information System (INIS)

Puukko, E.; Heikkinen, T.; Hakanen, M.

1993-10-01

Teollisuuden Voima Oy (TVO) is investigating the feasibility to dispose of spent nuclear fuel within Finland. The present plan calls for the repository to be located in crystalline rock at a depth of several hundred meters. The safety assessment of the repository includes calculations of migration of waste nuclides. The flow of waste elements in groundwater will be retarded through sorption interaction with minerals and through diffusion into rock. Diffusion is the only mechanism retarding the migration of non-sorbing species and, it is expected to be the dominating retardation mechanism of many of the sorbing elements. In the investigation the simultaneous diffusion of tritiated water (HTO), cesium and neptunium in rocks of TVO investigation sites at Kivetty, Olkiluoto and Romuvaara were studied. (11 refs., 33 figs., 9 tabs.)

Nitrous Oxide Production by Abundant Benthic Macrofauna

DEFF Research Database (Denmark)

Stief, Peter; Schramm, Andreas

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

Criticality of a 237Np sphere

International Nuclear Information System (INIS)

Sanchez, Rene; Loaiza, David; Kimpland, Robert; Hayes, David; Cappiello, Charlene; Chadwick, Mark

2006-01-01

For the past five years, scientists at Los Alamos National Laboratory have mounted an unprecedented effort to get a better estimate of the critical mass of 237 Np. To accomplish this task, a 6-kg neptunium sphere was recently cast at the Chemical and Metallurgy Research (CMR) facility, which is part of the Los Alamos National Laboratory. The neptunium sphere was clad with tungsten and nickel to reduce the dose rates from the 310 keV gamma rays from the first daughter of neptunium, namely, 233 Pa. 237 Np is a byproduct of power production in nuclear reactors. It is primarily produced by successive neutron captures in 235 U or through the (n,2n) reaction in 238 U. These nuclear reactions lead to the production of 237 U, which decays by beta emission into 237 Np, namely, 235 U(n,γ) 236 U, 236 U(n,γ) 237 U→β→ 237 Np, 238 U (n,2n) 237 U→β→ 237 Np. It is estimated that a typical 1000 MW(e) produces on the order of 12 to 13 kg of neptunium in a year. Some of this neptunium in irradiated fuel elements has been separated and is presently stored in containers in a liquid form. This method of storage is quite adequate because the fission cross section for 237 Np at thermal energies is quite low and any moderation of the neutron population by diluting the configurations with water would increase the critical mass to infinity. However, for long term storage, the neptunium liquid solutions must be converted into oxides and metals because these form are less movable and less likely to leak out of containers. Metals and oxides made out of neptunium have finite critical masses but there is a great uncertainty about these values because of the lack of experimental criticality data. Knowing precisely the critical mass of neptunium not only will help to validate mass storage limits or optimize storage configurations for safe disposition of these materials, but will also save thousands of dollars in transportation and disposition costs. The experimental results presented in

An evaluation of safeguards approaches for neptunium

International Nuclear Information System (INIS)

Burr, Tom; Stanbro, William D.; Charlton, William

2001-01-01

The International Atomic Energy Agency has recently drawn attention to the fact that neptunium (Np), a byproduct of the nuclear power industry, can be used to make nuclear weapons. Current monitoring approaches for Np do not rely on material balance accounting as is used for uranium and plutonium. In the future this may change. Although full material balance accounting is not anticipated for Np, it is informative to evaluate the impact and benefit of full material balance accounting when considering other options. Therefore, this paper will apply systems analysis to evaluate ways to convert the current system to full materials balance accounting that will minimize the intrusiveness of the verification system and minimize costs to both the facility operator and the inspection agency. We then compare full material balance accounting to partial material balance accounting and to a ratio-monitoring technique referred to as flow sheet verification. We conclude that sampling approximately 25% of the batches is likely to be adequate and that Pu (or perhaps 137 Cs) will be the most effective surrogate for estimating the Np in the input accountability tank. (author)

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

Science.gov (United States)

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

2014-04-01

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

Comparison of sample preparation methods for reliable plutonium and neptunium urinalysis using automatic extraction chromatography

DEFF Research Database (Denmark)

Qiao, Jixin; Xu, Yihong; Hou, Xiaolin

2014-01-01

This paper describes improvement and comparison of analytical methods for simultaneous determination of trace-level plutonium and neptunium in urine samples by inductively coupled plasma mass spectrometry (ICP-MS). Four sample pre-concentration techniques, including calcium phosphate, iron......), it endows urinalysis methods with better reliability and repeatability compared with co-precipitation techniques. In view of the applicability of different pre-concentration techniques proposed previously in the literature, the main challenge behind relevant method development is pointed to be the release...

Method for the recovery of actinide elements from nuclear reactor waste

International Nuclear Information System (INIS)

Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

1979-01-01

A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid

Transparent conducting oxides and production thereof

Science.gov (United States)

Gessert, Timothy A.; Yoshida, Yuki; Coutts, Timothy J.

2014-06-10

Transparent conducting oxides and production thereof are disclosed. An exemplary method of producing a transparent conducting oxide (TCO) material may comprise: providing a TCO target doped with either a high-permittivity oxide or a low-permittivity oxide in a process chamber. The method may also comprise depositing a metal oxide on the target in the process chamber to form a thin film having enhanced optical properties without substantially decreasing electrical quality.

Sorption of cesium, radium, protactinium, uranium, neptunium and plutonium on rapakivi granite

International Nuclear Information System (INIS)

Huitti, T.; Hakanen, M.

1996-12-01

The aim of the study is to determine the sorption of cesium, radium, protactinium, uranium, neptunium and plutonium on rapakivi granite in the brackish groundwater of Haestholmen (site of the Loviisa-1, Loviisa-2 reactors). The studies were carried out under aerobic (Cs, Ra, Pa, U, Np, Pu) and anaerobic (Np, Pa, Pu, Tc) laboratory conditions. The cation exchange capasity was determined for the rock and the diffusion of tritiated water in the rocks of different degree of alteration. The sorption and diffusion properties of the rocks are briefly compared with those of host rocks at other sites under investigation by the Finnish company Posiva Oy for the final disposal of spent fuel. (29 refs.)

Recent advances in Phytosterol Oxidation Products.

Science.gov (United States)

O'Callaghan, Yvonne; McCarthy, Florence O; O'Brien, Nora M

2014-04-11

Phytosterols and their oxidation products have become increasingly investigated in recent years with respect to their roles in diet and nutrition. We present a comprehensive review of recent literature on Phytosterol Oxidation Products (POP) identifying critical areas for future investigation. It is evident that POP are formed on food storage/preparation; are absorbed and found in human serum; do not directly affect cholesterol absorption; have evidence of atherogenicity and inflammation; have distinct levels of cytotoxicity; are implicated with high levels of oxidative stress, glutathione depletion, mitochondrial dysfunction and elevated caspase activity. Copyright © 2014 Elsevier Inc. All rights reserved.

Gamma radiolysis of alkaline aqueous solutions of neptunium and plutonium ions

International Nuclear Information System (INIS)

Pikaev, A.K.; Gogolev, A.V.; Shilov, V.P.

1998-01-01

Full text: The paper is a brief review of data obtained by the authors from the study on redox reactions of neptunium and plutonium ions upon γ radiolysis of their aerated alkaline aqueous solutions. It includes the information on radiolytic reduction of Np(V), Np(VI) and Pu(VI) ions under various experimental conditions. It was found that the values of Np(VI) and Pu(VI) reduction yields do not depend on alkali concentration. The values considerably increase in the presence of some organic compounds (EDTA and formate were investigated). The formation of the Np(V) peroxo complex was observed in the γ radiolysis of alkaline aqueous solutions of Np(VI) and Np(V) in the presence of nitrate. The mechanism of radiolytic redox reactions of the ions is discussed in some detail

The incorporation of neptunium and plutonium in thorutite (ThTi{sub 2}O{sub 6})

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Lumpkin, Gregory R.; Begg, Bruce D.; Jovanovic, Miodrag

2013-12-25

Highlights: •The incorporation of neptunium (Np) and plutonium (Pu) in thorutite (ThTi{sub 2}O{sub 6}) has been studied. •The effect of Np/Pu doping on the unit cell parameter changes has been discussed from the structure point of view. •The effect of Y as charge compensator to encourage the formation of higher valences of Np and Pu has been explored. •The resulting Np/Pu doped thorutite samples have been characterised by using XRD, SEM and DRS. -- Abstract: The incorporation of neptunium (Np) and plutonium (Pu) into the brannerite structured lattice was studied using thorutite (ThTi{sub 2}O{sub 6}) as host lattice and sintering in air. The uncompensated Np and Pu doped samples and the low Y-charge compensated Np and Pu doped samples showed main phases as designed together with trace amounts of rutile. Those samples with larger amounts of Y produced yttrium pyrochlores as an additional minor phase. XRD analyses reveal anisotropic changes of the cell parameters; the a-parameter contracts while b- and c-parameters expand with mean cationic radius. This is in reasonable agreement with previous experimental data on ThTi{sub 2}O{sub 6} and Ce{sub 0.975}Ti{sub 2}O{sub 5.95}. Attempts to form Np or Pu valences >4+ by adding Y as a charge compensator were unsuccessful, suggesting that tetravalent Np and Pu ions are favoured in air-fired thorutite.

Radiation-chemical oxidation of neptunium in perchloric acid solutions

International Nuclear Information System (INIS)

Shilov, V.P.; Gusev, Yu.K.; Pikaev, A.K.; Stepanova, E.S.; Krot, N.N.

1979-01-01

The γ-radiation effect (at a dose rate of 5x10 16 eV/mlxs) on 1x10 -3 Np(6) and Np(5) perchloric acid solutions is studied. The output of Np(6) loss in aerated 0.001-0.005M HClO 4 solutions was 2.4 ions/100 eV. The output of Np(5) loss in solutions saturated with nitrous oxide was 2.1 ions/100 eV at pH-4. In aerated 0.1-1.0 M HClO 4 solutions in presence of XeO 4 the output of Np(5) loss grows from 6.6 to 13.5 ions/100 eV as (XeO 3 ) 0 increases from 1x10 -3 to 2x10 -2 M. Possible process mechanisms have been proposed

Pressure effects on magnetism in the uranium and neptunium monopnictides

International Nuclear Information System (INIS)

Braithwaite, D.; Demuer, A.; Ichas, V.; Rebizant, J.; Spirlet, J.C.; Zwirner, S.; Vogt, O.

1998-01-01

The magnetic properties of the cubic NaCl uranium and neptunium monopnictides (UX, NpX; X=N, P, As, Sb, Bi) have been widely studied at ambient pressure. Properties ranging from itinerant to localized magnetism, and a variety of ordered magnetic structures have been observed. In particular the profusion of non-collinear double-k or triple-k structures is a consequence of strongly anisotropic exchange interactions. The application of pressure is a clean way of continuously varying the lattice parameter, and the exchange interactions, from one compound to another. A number of studies have been performed using different high pressure techniques. Some of the effects of pressure can be understood in a simple picture of a continuous variation of the lattice parameter, but some highly anomalous effects are also found which are discussed in relation to the possible nature of the magnetic interactions. (orig.)

Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

International Nuclear Information System (INIS)

Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L.

1996-06-01

Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed

Investigation on the co-precipitation of transuranium elements from alkaline solutions by the method of appearing reagents

Energy Technology Data Exchange (ETDEWEB)

Krot, N.; Shilov, V.; Bessonov, A.; Budantseva, N.; Charushnikova, I.; Perminov, V.; Astafurova, L. [Russian Academy of Science (Russian Federation). Inst. of Physical Chemistry

1996-06-06

Highly alkaline radioactive waste solutions originating from production of plutonium for military purposes are stored in underground tanks at the U.S. Department of Energy Hanford Site. The purification of alkaline solutions from neptunium and plutonium is important in the treatment and disposal of these wastes. This report describes scoping tests with sodium hydroxide solutions, where precipitation techniques were investigated to perform the separation. Hydroxides of iron (III), manganese (II), cobalt (II, III), and chromium (III); manganese (IV) oxide, and sodium uranate were investigated as carriers. The report describes the optimum conditions that were identified to precipitate these carriers homogeneously throughout the solution by reductive, hydrolytic, or catalytic decomposition of alkali-soluble precursor compounds by a technique called the Method of Appearing Reagents. The coprecipitation of pentavalent and hexavalent neptunium and plutonium was investigated for the candidate agents under optimum conditions and is described in this report along with the following results. Plutonium coprecipitated well with all tested materials except manganese (IV) oxide. Neptunium only coprecipitated well with uranate. The report presents a hypothesis to explain these behaviors. Further tests with more complex solution matrices must be performed.

Direct complexonometric determination of thorium (IV), uranium (IV), neptunium (IV), plutonium (IV) by titration of diethylenetriaminepentaacetic acid with xylenol orange as indicator

International Nuclear Information System (INIS)

Rykov, A.G.; Piskunov, E.M.; Timofeev, G.A.

1975-01-01

The purpose of the present work was to develop a method of determining Th(IV), U(IV), Np(N) and Pu(IV) in acid solutions by titration with diethylenetriamine pentacetic acid, the indicator being xylenol orange. It has been established that Th, U, Np and Pu can be determined to within 0.5-1.5%. Th and U in quantities of tens of milligrams can be determined with greater accuracy, attaining hundredths of one per cent. During titration the determination is not hindered by singly- and doubly-charged metal ions, trivalent lanthanides and actinides, except plutonium. The proposed method can be used to determine U(IV) in the presence of considerable quantities of U(VI) and Np(IV) in the presence of Np(V). Total concentrations of uranium or neptunium are determined by reducing uranium (VI) or neptunium (V) by a standard method (for example, using metallic lead, cadmium or zinc amalgam) to the tetravalent state and applying the method described in the paper. (E.P.)

The redox chemistry of neptunium in gamma-irradiated aqueous nitric acid in the presence of an organic phase

Czech Academy of Sciences Publication Activity Database

Mincher, B.J.; Přeček, Martin; Paulenova, A.

2016-01-01

Roč. 308, č. 3 (2016), s. 1005-1009 ISSN 0236-5731 R&D Projects: GA MŠk EE2.3.30.0057 Grant - others:OP VK 4 POSTDOK(XE) CZ.1.07/2.3.00/30.0057 Institutional support: RVO:68378271 Keywords : neptunium * redox chemistry * radiation chemistry * solvent extraction Subject RIV: CH - Nuclear ; Quantum Chemistry OBOR OECD: Inorganic and nuclear chemistry Impact factor: 1.282, year: 2016

Methods for forming complex oxidation reaction products including superconducting articles

International Nuclear Information System (INIS)

Rapp, R.A.; Urquhart, A.W.; Nagelberg, A.S.; Newkirk, M.S.

1992-01-01

This patent describes a method for producing a superconducting complex oxidation reaction product of two or more metals in an oxidized state. It comprises positioning at least one parent metal source comprising one of the metals adjacent to a permeable mass comprising at least one metal-containing compound capable of reaction to form the complex oxidation reaction product in step below, the metal component of the at least one metal-containing compound comprising at least a second of the two or more metals, and orienting the parent metal source and the permeable mass relative to each other so that formation of the complex oxidation reaction product will occur in a direction towards and into the permeable mass; and heating the parent metal source in the presence of an oxidant to a temperature region above its melting point to form a body of molten parent metal to permit infiltration and reaction of the molten parent metal into the permeable mass and with the oxidant and the at least one metal-containing compound to form the complex oxidation reaction product, and progressively drawing the molten parent metal source through the complex oxidation reaction product towards the oxidant and towards and into the adjacent permeable mass so that fresh complex oxidation reaction product continues to form within the permeable mass; and recovering the resulting complex oxidation reaction product

Training Course of Experimental Chemistry in the Nuclear Fuel Cycle: Solid State and Solution Chemistry

Energy Technology Data Exchange (ETDEWEB)

Lee, Ju hyeong; Park, Kwangheon; Kim, Tae hoon; Park, Hyoung gyu; Kim, Jisu [Kyunghee University, Yongin (Korea, Republic of); Song, Hyuk jin [Dongguk University, Gyeongju (Korea, Republic of); Lee, Chan ki; Kang, Do kyu; Jeong, Hyeon jun [UNIST, Ulsan (Korea, Republic of)

2016-10-15

In this experimental study program in Tohoku University, basic experiments were done by the participants. First one is the hydrogen reduction experiment of the mixture of UO{sub 2} and ZrO{sub 2}. Second one is to observe microscopic structure of solid solution of UO{sub 2} and ZrO{sub 2} using SEM/EDX and XRD system, simulated fuel debris. Third one is milking process of {sup 239}Np from {sup 243}Am by solvent extraction using Tri-n-Octylamine (TOA). Last one is solvent extraction in PUREX by the simulated mixed aqueous solution of U, {sup 85}Sr and {sup 239}Np which is represented minor actinide elements included in the spent nuclear fuel. Uranium is separated from aqueous phase to organic phase during solvent extraction procedure using TBP and dodecane. Also, neptunium can be extracted to organic phase as nitric acid concentration change. The extraction behavior of neptunium is different by oxidation state in aqueous phase. The behavior of neptunium is represented as a combined form of these oxidation states in experiment. Therefore, because the oxidation states of neptunium can be controlled by controlling the concentration of nitric acid, the extractability of neptunium can be controlled.

Osteosarcoma induction by plutonium-239, americium-241 and neptunium-237 : the problem of deriving risk estimates for man

International Nuclear Information System (INIS)

Taylor, D.M.

1988-01-01

Spontaneous bone cancer (osteosarcoma) represents only about 0.3% of all human cancers, but is well known to be inducible in humans by internal contamination with radium-226 and radium-224. plutonium-239, americium-241 and neptunium-237 form, or will form, the principal long-lived alpha particle emitting components of high activity waste and burnt-up nuclear fuel elements. These three nuclides deposit extensively in human bone and although, fortunately, no case of a human osteosarcoma induced by any of these nuclides is known, evidence from animal studies suggests that all three are more effective than radium-226 in inducing osteosarcoma. The assumption that the ratio of the risk factors, the number of osteosarcoma expected per 10000 person/animal Gy, for radium-226 and any other bone-seeking alpha-emitter will be independent of animal species has formed the basis of all the important studies of the radiotoxicity of actinide nuclides in experimental animals. The aim of this communication is to review the risk factors which may be calculated from the various animal studies carried out over the last thirty years with plutonium-237, americium-241 and neptunium-237 and to consider the problems which may arise in extrapolating these risk factors to homo sapiens

Potential for radionuclide immobilization in the EBS/NFE: solubility limiting phases for neptunium, plutonium, and uranium

Energy Technology Data Exchange (ETDEWEB)

Rard, J. A., LLNL

1997-10-01

Retardation and dispersion in the far field of radionuclides released from the engineered barrier system/near field environment (EBS/NFE) may not be sufficient to prevent regulatory limits being exceeded at the accessible environment. Hence, a greater emphasis must be placed on retardation and/or immobilization of radionuclides in the EBS/NFE. The present document represents a survey of radionuclide-bearing solid phases that could potentially form in the EBS/NFE and immobilize radionuclides released from the waste package and significantly reduce the source term. A detailed literature search was undertaken for experimental solubilities of the oxides, hydroxides, and various salts of neptunium, plutonium, and uranium in aqueous solutions as functions of pH, temperature, and the concentrations of added electrolytes. Numerous solubility studies and reviews were identified and copies of most of the articles were acquired. However, this project was only two months in duration, and copies of some the identified solubility studies could not be obtained at short notice. The results of this survey are intended to be used to assess whether a more detailed study of identified low- solubility phase(s) is warranted, and not as a data base suitable for predicting radionuclide solubility. The results of this survey may also prove useful in a preliminary evaluation of the efficacy of incorporating chemical additives to the EBS/NFE that will enhance radionuclide immobilization.

Method for the recovery of actinide elements from nuclear reactor waste

Science.gov (United States)

Horwitz, E. Philip; Delphin, Walter H.; Mason, George W.

1979-01-01

A process for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid.

Recovery actinide values

International Nuclear Information System (INIS)

Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

1979-01-01

A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of di-hexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid. (author)

Sequential injection approach for simultaneous determination of ultratrace plutonium and neptunium in urine with accelerator mass spectrometry

DEFF Research Database (Denmark)

Qiao, Jixin; Hou, Xiaolin; Roos, Per

2013-01-01

An analytical method was developed for simultaneous determination of ultratrace level plutonium (Pu) and neptunium (Np) using iron hydroxide coprecipitation in combination with automated sequential injection extraction chromatography separation and accelerator mass spectrometry (AMS) measurement...... show that preboiling and aging are important for obtaining high chemical yields for both Pu and Np, which is possibly related to the aggregation and adsorption behavior of organic substances contained in urine. Although the optimal condition for Np and Pu simultaneous determination requires 5-day aging...

Investigation on leaching of actinide oxides into supercritical fluids

International Nuclear Information System (INIS)

Shafikov, D.N.; Kamachev, V.A.; Babain, V.A.; Murzin, A.A.; Shadrin, A.Yu.; Podojnitsin, S.V.

2006-01-01

The extraction of actinide oxides into solutions of the TBP-HNO 3 complex in supercritical (SC) CO 2 was investigated. Experiments on the extraction of the TBP-HNO 3 complex into SC CO 2 were first conducted. It was found that a constant concentration of TBP in SC CO 2 of 13.5-14.8 % vol. can be attained using a constant molar ratio of [HNO 3 ]:[TBP] about 2.5 : 1. Joint leaching of uranium, plutonium and neptunium from mixtures of actinide oxides with solutions of TBP-HNO 3 in SC CO 2 was found feasible. If the leaching of uranium is about 95 %, its purification coefficients from major gamma-emitting radionuclides (Cs and Sr) exceed 100, while the purification coefficients of uranium from rare earth elements are 10-20

Hydrogen sulfide oxidation without oxygen - oxidation products and pathways

International Nuclear Information System (INIS)

Fossing, H.

1992-01-01

Hydrogen sulfide oxidation was studied in anoxic marine sediments-both in undisturbed sediment cores and in sediment slurries. The turn over of hydrogen sulfide was followed using 35 S-radiolabeled hydrogen sulfide which was injected into the sediment. However, isotope exchange reactions between the reduced sulfur compounds, in particular between elemental sulfur and hydrogen sulfide, influenced on the specific radioactivity of these pools. It was, therefore, not possible to measure the turn over rates of the reduced sulfur pools by the radiotracer technique but merely to use the radioisotope to demonstrate some of the oxidation products. Thiosulfate was one important intermediate in the anoxic oxidation of hydrogen sulfide and was continuously turned over by reduction, oxidation and disproportionation. The author discusses the importance of isotope exchange and also presents the results from experiments in which both 35 S-radiolabeled elemental sulfur, radiolabeled hydrogen sulfide and radiolabeled thiosulfate were used to study the intermediates in the oxidative pathways of the sulfur cycle

Method for Determination of Neptunium in Large-Sized Urine Samples Using Manganese Dioxide Coprecipitation and ²⁴²Pu as Yield Tracer

DEFF Research Database (Denmark)

Qiao, Jixin; Hou, Xiaolin; Roos, Per

2013-01-01

A novel method for bioassay of large volumes of human urine samples using manganese dioxide coprecipitation for preconcentration was developed for rapid determination of 237Np. 242Pu was utilized as a nonisotopic tracer to monitor the chemical yield of 237Np. A sequential injection extraction chr...... and rapid analysis of neptunium contamination level for emergency preparedness....

Comparison of extraction chromatography and a procedure based on the molecular recognition method as separation methods in the determination of neptunium and plutonium radionuclides

International Nuclear Information System (INIS)

Strisovska, Jana; Galanda, Dusan; Drabova, Veronika; Kuruc, Jozef

2012-01-01

The potential of various types of sorbents for separation of radionuclides of plutonium and neptunium were examined. Extraction chromatography and a procedure based on the molecular recognition method were used for the separation. The suitability of the various sorbent types and brands for this purpose was determined. (orig.)

Effect of time dependence of neutron flux on the plutonium 238 production

International Nuclear Information System (INIS)

Rudik, A.P.

1975-01-01

An analytical treatment is given of the dependence of a plutonium-238 yield when irradiating neptunium-237 on the time variation of the neutron flux. This dependence is governed by the two physical factors: the competition between the beta decay and the neptunium-238 depletion, and the differences in the depletion rate of neptunium-237, neptunium-238 and plutonium-238 with thermal and resonance neutrons. The role of the neptunium-238 nonprompt decay has been studied and the order of the effect determined, and it has been established that it is advantageous to irradiate neptunium-237 in the lowest central neutron flux possible for thermal and resonance neutron reactors. A perturbation theory has been developed to determine the role of the time variation of the thermal neutron flux and it has been established that, the integral neutron flux being the same, it is advantageous to irradiate the material in a drooping rather than a constant flux of neutrons. The simplest example of great time variations of a neutron flux has been considered and it has been established that in this particular case the conclusions made in the framework of the perturbation theory find a qualitative support. Convenient formulas are given for determining the number of neutrons used to produce plutonium-238

A contribution to the study of thorium and neptunium (IV) complexes in acidic phosphoric media; Contribution a l`etude des complexes de thorium et de neptunium (IV) en milieux phosphoriques acides

Energy Technology Data Exchange (ETDEWEB)

Ghafar, M

1995-11-30

The thorium and neptunium (IV) phosphate complexes formation in acidic media has been investigated, essentially at the indicator`s level with {sup 227} Th, {sup 234} Th, {sup 235} Np and {sup 239} Np. Solvent extraction, a commonly used method for determining stability constants in solutions, was used with HDEHP in toluene. In order to get a better understanding of inorganic transparent gels formation in phosphoric aqueous solutions, the effect of the thorium concentration is also studied. Specific experimental conditions have been chosen in order to avoid the formation of chelate and hydrolysis in the aqueous solution. The equilibrium constants and stability constants are calculated, and the results are compared with literature. The results show that increasing the thorium concentration does not lead to polymer forms. refs., 42 figs., 19 tabs.

The aqueous solubility and speciation analysis for uranium, neptunium and selenium by the geochemical code(EQ3/6)

International Nuclear Information System (INIS)

Takeda, Seiji; Shima, Shigeki; Kimura, Hideo; Matsuzuru, Hideo

1995-11-01

The geochemical condition of a geologic disposal system of HLW controls the solubility and physicochemical forms of dominant aqueous species for elements, which are one of essential information required for safety assessment. Based on the measured compositions of groundwater, the compositions of groundwater in the disposal system were calculated. The solubility and speciation analyses for the polyvalent elements, uranium, neptunium, and selenium, were performed by the geochemical code EQ3/6. The results obtained were compared with the data appeared in the literatures on the solubilities and speciations. The geochemical behaviors of the elements with respect to the solubility and speciation could quantitatively be elucidated for the compositions of the interstitial waters in an engineered barrier and ground water in a natural barrier. In the pH range of neutral to alkali, the solubilities of U and Np tend to increase with an increase of the carbonate concentration in groundwater. This carbonate concentration dependence of the solubility was also estimated. In the engineered barrier the predominant aqueous species were specified, and in the natural barrier the change of aqueous species was also predicted while the chemical compositions changed from the reducing to oxidizing conditions. The dominant aqueous species for the elements, which migrate in and through the disposal system, were determined by the speciation analysis. (author)

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

International Nuclear Information System (INIS)

Feng, Xi; Ahn, Dong Uk

2016-01-01

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

Oxidation kinetics of reaction products formed in uranium metal corrosion.

Energy Technology Data Exchange (ETDEWEB)

Totemeier, T. C.

1998-04-22

The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O{sub 2} and Ar-20%O{sub 2} were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates.

Oxidation kinetics of reaction products formed in uranium metal corrosion

International Nuclear Information System (INIS)

Totemeier, T. C.

1998-01-01

The oxidation behavior of uranium metal ZPPR fuel corrosion products in environments of Ar-4%O 2 and Ar-20%O 2 were studied using thermo-gravimetric analysis (TGA). These tests were performed to extend earlier work in this area specifically, to assess plate-to-plate variations in corrosion product properties and the effect of oxygen concentration on oxidation behavior. The corrosion products from two relatively severely corroded plates were similar, while the products from a relatively intact plate were not reactive. Oxygen concentration strongly affected the burning rate of reactive products, but had little effect on low-temperature oxidation rates

Atlas of Atomic Spectral Lines of Neptunium Emitted by Inductively Coupled Plasma

Energy Technology Data Exchange (ETDEWEB)

DeKalb, E.L. and Edelson, M. C.

1987-08-01

Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlas of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred [1] and Haaland [2]. Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.

40 CFR 415.50 - Applicability; description of the calcium oxide production subcategory.

Science.gov (United States)

2010-07-01

... calcium oxide production subcategory. 415.50 Section 415.50 Protection of Environment ENVIRONMENTAL... SOURCE CATEGORY Calcium Oxide Production Subcategory § 415.50 Applicability; description of the calcium... the production of calcium oxide. ...

Effect of mass of neptunium V in intestinal absorption in the monkey and the rat

International Nuclear Information System (INIS)

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

1983-01-01

The coefficient of gastrointestinal transfer of neptunium as pentavalent neptunyl nitrate was studied in rats and monkeys as a function of the ingested mass. In both species, the transfer coefficient ranged between 1.10 - 3 - 1.10 - 2 when the administered mass varied from 0.3 ng to 2 mg per kg. At low concentrations, the values obtained in the monkey are about twice as low as thoses obtained in the rat. Considering the strong urinary excretion, the amounts retained at the organ levels represent about 0.1% in the rat and 0.04% in the monkey for low concentrations. The values obtained are usually in good agreement with the few data published on the rat [fr

The reduction of plutonium (IV) and neptunium (VI) ions by N,N-ethyl (hydroxyethyl) hydroxylamine in nitric acid

International Nuclear Information System (INIS)

Koltunov, V.S.; Baranov, S.M.; Mezhov, E.A.; Taylor, R.J.; May, I.

1999-01-01

The kinetics of the reduction of neptunium (VI) and plutonium (IV) ions in nitric acid solution by a new rapid salt free reductant, N,N-ethyl (hydroxyethyl) hydroxylamine, have been studied and rate equations determined. Under equivalent conditions, both Np(VI) and Pu(IV) are reduced faster than by the related reagent, N,N-diethyl hydroxylamine, and it is suggested that this is due to the introduction of the hydroxy group into the reductant molecule. Possible reaction mechanisms have been suggested to account for the observed reaction stoichiometry. (orig.)

Distribution behavior of uranium, neptunium, rare-earth elements (Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiCl-KCl eutectic salt and liquid cadmium or bismuth

International Nuclear Information System (INIS)

Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

1995-01-01

Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCl eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system. (orig.)

Method of manufacturing gadolinium oxide-incorporated nuclear fuel sintering products

International Nuclear Information System (INIS)

Komono, Akira; Seki, Makoto; Omori, Sadayuki.

1987-01-01

Purpose: To manufacture nuclear fuel sintering products excellent in burning property and mechanical property. Constitution: In the manufacturing step for nuclear fuel sintering products, specific metal oxides are added for promoting the growth of crystal grains in the sintering. Those metal oxides melted at a temperature lower than the sintering temperature of a mixture of nuclear fuel oxide powder and oxide power, or those metal oxides causing eutectic reaction are used as the metal oxide. Particularly, those compounds having oxygen atom - metal atom ratio (O/M) of not less than 2 are preferably used. As such metal oxides usable herein transition metal oxides, e.g., Nb 2 O 5 , TiO 2 , MoO 3 and WO 3 are preferred, with Nb 2 O 3 and TiO 2 being preferred particularly. (Seki, T.)

Study of the oxidation-reduction kinetics involved in the Np(V) + Fe(II) in equilibrium Np(IV) + Fe(III) system in nitric acid solutions

International Nuclear Information System (INIS)

Jao, Y.

1975-08-01

Ferrous nitrate-hydrazine is one of the more attractive alternate reactants to the currently used reagent, ferrous sulfamate, for partitioning plutonium from neptunium and uranium. An understanding of the kinetics of the reduction of Np(VI) to Np(IV) by ferrous nitrate-hydrazine is needed before a satisfactory evaluation of the feasibility of this reductant in actinide element separations can be made. The purpose of this work was to study the kinetics and mechanisms of the reduction of Np(V) by Fe(II) and the oxidation of Np(IV) by Fe(III) in 1-2 M nitric acid solutions. The acid concentration range was chosen to include that typically used in the separation of plutonium from neptunium and uranium by solvent extraction with tributylphosphate. The forward and reverse rate constants, hydrogen ion dependence, temperature dependence, ionic strength effects and nitrate ion influence were determined. The proposed reaction mechanisms involve protonation of the NpO 2 + ions and hydroxyoxygenation of Np 4 + ions. (LK)

Microscopic Examination of a Corrosion Front in Spent Nuclear Fuel

International Nuclear Information System (INIS)

J.A. Fortner; A.J. Kropf; R.J. Finch; J.C. Cunnane

2006-01-01

Spent uranium oxide nuclear fuel hosts a variety of trace chemical constituents, many of which must be sequestered from the biosphere during fuel storage and disposal. In this paper we present synchrotron x-ray absorption spectroscopy and microscopy findings that illuminate the resultant local chemistry of neptunium and plutonium within spent uranium oxide nuclear fuel before and after corrosive alteration in an air-saturated aqueous environment. We find the plutonium and neptunium in unaltered spent fuel to have a +4 oxidation state and an environment consistent with solid-solution in the UO 2 matrix. During corrosion in an air-saturated aqueous environment, the uranium matrix is converted to uranyl U(VI)O 2 2+ mineral assemblage that is depleted in plutonium and neptunium relative to the parent fuel. At the corrosion front interface between intact fuel and the uranyl-mineral corrosion layer, we find evidence of a thin (∼20 micrometer) layer that is enriched in plutonium and neptunium within a predominantly U 4+ environment. Available data for the standard reduction potentials for NpO 2+ /Np 4+ and UO 2 2+ /U 4+ couples indicate that Np(IV) may not be effectively oxidized to Np(V) at the corrosion potentials of uranium dioxide spent nuclear fuel in air-saturated aqueous solutions. Neptunium is an important radionuclide in dose contribution according to performance assessment models of the proposed U. S. repository at Yucca Mountain, Nevada. A scientific understanding of how the UO 2 matrix of spent nuclear fuel impacts the oxidative dissolution and reductive precipitation of neptunium is needed to predict its behavior at the fuel surface during aqueous corrosion. Neptunium would most likely be transported as aqueous Np(V) species, but for this to occur it must first be oxidized from the Np(IV) state found within the parent spent nuclear fuel [1]. In the immediate vicinity of the spent fuel's surface the redox and nucleation behavior is likely to promote

Production of biogenic manganese oxides coupled with methane oxidation in a bioreactor for removing metals from wastewater.

Science.gov (United States)

Matsushita, Shuji; Komizo, Daisuke; Cao, Linh Thi Thuy; Aoi, Yoshiteru; Kindaichi, Tomonori; Ozaki, Noriatsu; Imachi, Hiroyuki; Ohashi, Akiyoshi

2018-03-01

Biogenic manganese oxide (BioMnO x ) can efficiently adsorb various minor metals. The production of BioMnO x in reactors to remove metals during wastewater treatment processes is a promising biotechnological method. However, it is difficult to preferentially enrich manganese-oxidizing bacteria (MnOB) to produce BioMnO x during wastewater treatment processes. A unique method of cultivating MnOB using methane-oxidizing bacteria (MOB) to produce soluble microbial products is proposed here. MnOB were successfully enriched in a methane-fed reactor containing MOB. BioMnO x production during the wastewater treatment process was confirmed. Long-term continual operation of the reactor allowed simultaneous removal of Mn(II), Co(II), and Ni(II). The Co(II)/Mn(II) and Ni(II)/Mn(II) removal ratios were 53% and 19%, respectively. The degree to which Mn(II) was removed indicated that the enriched MnOB used utilization-associated products and/or biomass-associated products. Microbial community analysis revealed that methanol-oxidizing bacteria belonging to the Hyphomicrobiaceae family played important roles in the oxidation of Mn(II) by using utilization-associated products. Methane-oxidizing bacteria were found to be inhibited by MnO 2 , but the maximum Mn(II) removal rate was 0.49 kg m -3  d -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Production and characterization of quality gadolinium oxide nanoparticles

International Nuclear Information System (INIS)

Hazarika, Samiran; Mohanta, Dambarudhar

2013-01-01

Rare earth system Gadolinium (Gd), in either pure form or oxide form, is highly stable against environmental attack. It has immense potential as a contrast agent in magnetic resonance imaging (MRI) devices. Being mechanically and thermally stable it is always difficult to obtain Gd 2 O 3 nanopowders directly from its bulk counterpart using conventional top-down approach. Recently, we have reported production of Gd 2 O 3 nanopowders by first converting bulk Gd 2 O 3 into a nitrate compound and subsequently reduced into a hydroxide product and finally to the oxide product (nanopowder form)

Redox stability of neptunium(V) in the presence of humic substances of varying functionality

Energy Technology Data Exchange (ETDEWEB)

Schmeide, K.; Geipel, G.; Bernhard, G. [Forschungszentrum Rossendorf e.V., Institute of Radiochemistry, P.O. Box 510 119, D-01314 Dresden (Germany)

2005-07-01

be stabilized in lower oxidation states, e.g. in complexation and sorption studies. [1] Sachs, S., Schmeide, K., Brendler, V., Krepelova, A., Mibus, J., Geipel, G., Heise, K.H., Bernhard, G.: Investigation of the Complexation and the Migration of Actinides and Nonradioactive Substances with Humic Acids under Geo-genic Conditions. Complexation of Humic Acids with Actinides in the Oxidation State IV Th, U, Np. FZR-399, Wissenschaftlich- Technische Berichte, Forschungszentrum Rossendorf, Dresden 2004. [2] Schmeide, K., Geipel, G., Bernhard, G.: Study of the Neptunium(V) Reduction by Various Natural and Synthetic Humic Substances. In: FZKA 7070, Wissenschaftliche Berichte (G. Buckau, ed.). Forschungszentrum Karlsruhe, Karlsruhe 2005, in press. (authors)

Neptunium(V) sorption onto kaolinite in the absence and presence of CO2

International Nuclear Information System (INIS)

Amayri, S.; Reich, Ta.; Reich, T.

2005-01-01

Full text of publication follows: The adsorption of heavy metals on clay minerals such as kaolinite is an important process that affects the migration and retardation of neptunium and other actinides in the geosphere. The sorption of Np(V) onto the reference clay mineral kaolinite KGa-1b was investigated both by batch experiments and EXAFS measurements. The aim of our study was to combine macroscopic studies (batch experiments) with microscopic techniques (EXAFS) to study the Np(V) speciation at the kaolinite surface. The batch experiments were done under relevant environmental conditions with Np(V) concentrations of 10 -11 and 10 -12 mol/L. Sorption samples were prepared in 0.1 mol/L NaClO 4 , 4 g/L kaolinite, pH 6.0 to 10.5, presence and absence of ambient CO 2 , and 60-h equilibration. The sorption curves for 10 -11 and 10 -12 mol/L Np(V) obtained in the presence and absence of CO 2 , respectively, show that the adsorption edge occurs at pH 8.5. The uptake of Np(V) by kaolinite strongly increased above pH 7.0 and reached its sorption maximum (70 %) at pH 9.0. Above pH 9.0, the amount of Np(V) sorbed onto kaolinite decreased and reached ca. 30 % at pH 10.5 due to the formation of Np(V) carbonato species in the aqueous solution. In the CO 2 -free system, the sorption of Np(V) increased continuously with pH until the sorption maximum of 100 % was reached at pH 10.5. The same sorption behavior was found in batch experiments in the CO 2 equilibrated system with Np concentrations ranging from 1 μmol/L to 10 μmol/L. EXAFS experiments on some of these batch samples indicated the formation of Np(V) carbonato species at the kaolinite surface at pH 9.0 where the uptake of Np(V) by kaolinite reaches its maximum [1]. [1] T. Reich, S. Amayri, Ta. Reich, J. Drebert, A. Jermolajev, P. Thoerle, N. Trautmann, C. Hennig, S. Sachs, Feasibility of EXAFS experiments at the Np L-edge to investigate neptunium sorption on kaolinite, Institut fuer Kernchemie, Universitaet Mainz, Annual

Atlas of Atomic Spectral Lines of Neptunium Emitted by an Inductively Coupled Plasma

International Nuclear Information System (INIS)

DeKalb, E.L.; Edelson, M.C.

1987-01-01

Optical emission spectra from high-purity Np-237 were generated with a glovebox-enclosed inductively coupled plasma (ICP) source. Spectra covering the 230-700 nm wavelength range are presented along with general commentary on the methodology used in collecting the data. The Ames Laboratory Nuclear Safeguards and Security Program has been charged with the task of developing optical spectroscopic methods to analyze the composition of spent nuclear fuels. Such materials are highly radioactive even after prolonged 'cooling' and are chemically complex. Neptunium (Np) is a highly toxic by-product of nuclear power generation and is found, in low abundance, in spent nuclear fuels. This atlas of the optical emission spectrum of Np, as produced by an inductively coupled plasma (ICP) spectroscopic source, is part of a general survey of the ICP emission spectra of the actinide elements. The ICP emission spectrum of the actinides originates almost exclusively from the electronic relaxation of excited, singly ionized species. Spectral data on the Np ion emission spectrum (i.e., the Np II spectrum) have been reported by Tomkins and Fred (1) and Haaland (2). Tomkins and Fred excited the Np II spectrum with a Cu spark discharge and identified 114 Np lines in the 265.5 - 436.3 nm spectral range. Haaland, who corrected some spectral line misidentifications in the work of Tomkins and Fred, utilized an enclosed Au spark discharge to excite the Np II spectrum and reported 203 Np lines within the 265.4 - 461.0 nm wavelength range.

The effect of temperature on the sorption of technetium, uranium, neptunium and curium on bentonite, tuff and granodiorite

International Nuclear Information System (INIS)

Baston, G.M.N.; Berry, J.A.; Brownsword, M.; Heath, T.G.; Ilett, D.J.; Tweed, C.J.; Yui, M.

1997-01-01

A study of the sorption of the radioelements technetium; uranium; neptunium; and curium onto geological materials has been carried out as part of the PNC program to increase confidence in the performance assessment for a high-level radioactive waste repository in Japan. Batch sorption experiments have been performed in order to study the sorption of the radioelements onto bentonite, tuff and granodiorite from equilibrated de-ionized water under strongly-reducing conditions at both room temperature and at 60 C. Mathematical modelling using the geochemical speciation program HARPHRQ in conjunction with the HATCHES database has been undertaken in order to interpret the experimental results

{open_quotes}Transmutation efficiency calculation in the blanket on melted salts with central neptunium target{close_quotes}

Energy Technology Data Exchange (ETDEWEB)

Kolesov, V.F.; Shtarev, S.K.; Khoruzhiy, V.K. [Russia Federal Nuclear Center, Arzamas (Russian Federation)] [and others

1995-10-01

In the limits of ABC project version of two-sectional reactor system in the form of combination of subcritical blanket on melted salts and multiplying target from threshold fissile material {sup 237}Np is considered. This research is the development of the VNIIEF`s earlier work`s (Russia) investigating of usage possibilities in ABC project the conception of multisectional blankets with single-sided neutron coupling between sections. With the help of Monte-Carlo program the calculations results of system mentioned are given. The possibility of accelerator`s considerable power reduction at the account of thorium target substitution with neptunium-237 multiplying target is shown.

The sorption of uranium(VI) and neptunium(V) onto surfaces of selected metal oxides and alumosilicates studied by in situ vibrational spectroscopy

International Nuclear Information System (INIS)

Mueller, Katharina

2010-05-01

The migration behavior of actinides and other radioactive contaminants in the environment is controlled by prominent molecular phenomena such as hydrolysis and complexation reactions in aqueous solutions as well as the diffusion and sorption onto minerals present along groundwater flow paths. These reactions significantly influence the mobility and bioavailability of the metal ions in the environment, in particular at liquid-solid interfaces. Hence, for the assessment of migration processes the knowledge of the mechanisms occurring at interfaces is crucial. The required structural information can be obtained using various spectroscopic techniques. In the present study, the speciation of uranium(VI) and neptunium(V) at environmentally relevant mineral-water interfaces of oxides of titania, alumina, silica, zinc, and alumosilicates has been investigated by the application of attenuated total reflection Fouriertransform infrared (ATR FT-IR) spectroscopy. Moreover, the distribution of the hydrolysis products in micromolar aqueous solutions of U(VI) and Np(V/VI) at ambient atmosphere has been characterized for the first time, by a combination of ATR FT-IR spectroscopy, near infrared (NIR) absorption spectroscopy, and speciation modeling applying updated thermodynamic databases. From the infrared spectra, a significant change of the U(VI) speciation is derived upon lowering the U(VI) concentration from the milli- to the micromolar range, strongly suggesting the dominance of monomeric U(VI) hydrolysis products in the micromolar solutions. In contradiction to the predicted speciation, monomeric hydroxo species are already present at pH ≥ 2.5 and become dominant at pH 3. At higher pH levels (> 6), a complex speciation is evidenced including carbonate containing complexes. For the first time, spectroscopic results of Np(VI) hydrolysis reactions are provided in the submillimolar concentration range and at pH values up to 5.3, and they are comparatively discussed with U

Hydrogen Production via Steam Reforming of Ethyl Alcohol over Palladium/Indium Oxide Catalyst

Directory of Open Access Journals (Sweden)

Tetsuo Umegaki

2009-01-01

Full Text Available We report the synergetic effect between palladium and indium oxide on hydrogen production in the steam reforming reaction of ethyl alcohol. The palladium/indium oxide catalyst shows higher hydrogen production rate than indium oxide and palladium. Palladium/indium oxide affords ketonization of ethyl alcohol with negligible by-product carbon monoxide, while indium oxide mainly affords dehydration of ethyl alcohol, and palladium affords decomposition of ethyl alcohol with large amount of by-product carbon monoxide. The catalytic feature of palladium/indium oxide can be ascribed to the formation of palladium-indium intermetallic component during the reaction as confirmed by X-ray diffraction and X-ray photoelectron spectroscopic measurements.

Electrodeposition of Actinide and Lanthanide Elements

International Nuclear Information System (INIS)

Baerring, N.E.

1966-02-01

Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given

Electrodeposition of Actinide and Lanthanide Elements

Energy Technology Data Exchange (ETDEWEB)

Baerring, N E

1966-02-15

Some deposition parameters for the quantitative electrodeposition of hydrolysis products of plutonium were qualitatively studied at trace concentrations of plutonium. The hydrogen ion concentration, the current and the electrolysis time proved to be the determining factors in the quantitative electrolytic precipitation of plutonium, while other factors such as cathode material, the pretreatment of the cathode surface, the nature of the electrolytic anion, and the oxidation state of plutonium in the starting solution were found to be of less importance. The conditions selected for quantitative electrodeposition of plutonium from slightly acid nitrate solutions on a stainless steel cathode were successfully tried also with uranium, neptunium, americium, cerium and thulium. Details of a procedure used for plating mg amounts of plutonium and neptunium on small stainless steel cylinders are also given.

Cathode recovery products of oxidation of oils

Directory of Open Access Journals (Sweden)

М.М. Захарчук

2009-01-01

Full Text Available  The article provides the review of electrochemical reduction of carbonic compounds – those that are among main oxidation of oils  hydrocarbons products. The principal possibility of ketons to alcohols  reduction is proved in practice based on the experimental data . The methodical algoritm of quantative control of the catod reduction is developed, which uses the reduction-oxidizing potentiometric titration method.

Analysis of 137Cs in fission based neutron dosimetry

International Nuclear Information System (INIS)

Peltonen, T.

1995-11-01

137 Cs analysis is based on dissolving an irradiated fission dosimeter and chemically separating the cesium from the rest of the fission material. The samples consisted of uranium and neptunium in the form of metal or oxide. The uranium samples were dissolved in nitric acid and the neptunium samples in a mixture of nitric acid and chloric acid with addition of hydrogen peroxide. Cs was precipitated into a mixture of ammonium molyndophoshate and cellulose powder. A preparate for measurement was made from the precipitate and covered with polyethen plastic. Since other fission products than cesium were precipitated as well from the more recently irradiated samples, the activity measurements could not be carried out with a NaI(Tl) cavity crystal, but had to be made with a less efficient but more selective germanium semiconductor crystal. The method is well suited for 137 Cs determination, especially for older dosimeters where the more short-lived fission products have decayed. (orig.) (6 refs., 7 figs., 7 tabs.)

Low nitrous oxide production in intermittent-feed high performance nitritating reactors

DEFF Research Database (Denmark)

Su, Qingxian; Jensen, Malene M.; Smets, Barth F.

Nitrous oxide (N2O) production from autotrophic nitrogen removal processes, especially nitritating systems, is of growing concern. N2O dynamics were characterized and N2O production factors were quantified in two lab-scale intermittent-feed nitritating SBRs. 93 ± 14% of the oxidized ammonium...... was converted to nitrite, with the average total net N2O production of 2.1 ± 0.7% of the ammonium oxidized. Operation with intermittent feeding appears an effective optimization approach to mitigate N2O emissions from nitritating systems. Net N2O production rates transiently increased with a rise in pH after...

Influence of the redox state on the neptunium sorption under alkaline conditions. Batch sorption studies on titanium dioxide and calcium silicate hydrates

International Nuclear Information System (INIS)

Tits, Jan; Laube, Andreas; Wieland, Erich; Gaona, Xavier

2014-01-01

Wet chemistry experiments were carried out to investigate the effect of the redox state and aqueous speciation on the uptake of neptunium by titanium dioxide (TiO 2 ) and by calcium silicate hydrates (C-S-H) under alkaline conditions. TiO 2 was chosen as a reference sorbent to determine the surface complexation behaviour of neptunium under alkaline conditions. C-S-H phases are important constituents of cement and concrete. They may contribute significantly to radionuclide retention due to their high recrystallization rates making incorporation the dominating sorption mechanism for many radionuclides (e.g. the actinides) on these materials. The sorption of neptunium on both solids was found to depend strongly on the degree of hydrolysis. On TiO 2 R d values for Np(IV), Np(V) and Np(VI) are identical at pH = 10 and decrease with progressing hydrolysis in case of Np(V) and Np(VI). On C-S-H phases, R d values for the three redox states are also identical at pH = 10. While the R d values for Np(VI) sorption on C-S-H phases decrease with progressing hydrolysis, the R d values for Np(IV) and Np(V) sorption are not affected by the pH. In addition to the effect of hydrolysis, the presence of Ca is found to promote Np(V) and Np(VI) sorption on TiO 2 whereas on C-S-H phases, the present wet chemistry data do not give unambiguous evidence. Thus, the aqueous speciation appears to have a similar influence on the sorption of the actinides on both types of solids despite the different sorption mechanism. The similar R d values for Np(IV,V,VI) sorption at pH = 10 can be explained qualitatively by invoking inter-ligand electrostatic repulsion between OH groups in the coordination sphere of Np(V) and Np(VI). This mechanism was proposed earlier in the literature for the prediction of actinide complexation constants with inorganic ligands. A limiting coordination number for each Np redox state, resulting from the inter-ligand electrostatic repulsion, allows the weaker sorption of the

Bio-reduction of plutonyl and neptunyl by Shewanella alga

International Nuclear Information System (INIS)

Reed, D.T.; Lucchini, J.F; Rittmann, B.E.; Songkasiri, W.

2005-01-01

Full text of publication follows: The results of a concurrent experimental and modeling study to investigate the bio-reduction of higher-valent plutonium and neptunium by Shewanella alga strain BrY are presented. S. Alga, as a facultative metal reducer, is representative of bacteria that will be important in defining the mobility of plutonium and neptunium species as they migrate from oxic to anoxic zones. This is also an important consideration in defining the long-term stability of bio-precipitated 'immobilized' plutonium phases under changing redox conditions in biologically active systems and subsequently the effectiveness of remediation/containment approaches used for bio-remediation. Neptunium (VI) is readily reduced in groundwaters by many organics. In biologically active systems, it is unlikely, for this reason, that this oxidation state of neptunium will be important. Under all conditions investigated, neptunium (V) was reduced to neptunium (IV) when anaerobic conditions were established for a wide variety of electron donors. This was evidences by 3-4 orders of magnitude reduction in solution concentration and confirmed by XANES analysis. This led to high bio-association and/or precipitation of the neptunium. Plutonium (VI), as was the case with neptunium (VI) was reduced by the organics typically present in biologically active systems. Analogous bio-reduction experiments with plutonium (V) and plutonium (VI) are in progress and are expected to show that bio-reduction will predominate under anaerobic conditions, as was the case with neptunium. These results for neptunium and plutonium show S. Alga to be an effective microbe for the bio-reduction, and consequently the immobilization, of these important actinide contaminants. (authors)

Computational Study on Mössbauer Isomer Shifts of Some Organic-neptunium (IV Complexes

Directory of Open Access Journals (Sweden)

Masashi Kaneko

2015-12-01

Full Text Available Relativistic DFT calculations are applied to some organo-neptunium (IV complexes, Cp3NpIVX (Cp = η5-C5H5; X = BH4, Cl, OtBu, Ph, nBu, in order to understand their bonding properties between Np and the ligands. We employ scalar-relativistic ZORA Hamiltonian with all-electron basis set (SARC. The calculated electron densities at Np nucleus position in the complexes at B2PLYP / SARC theory strongly correlate to the experimental Mössbauer isomer shifts of 237Np system. The result of bond overlap population analysis indicates that the bonding strength decreases in order of X = BH4, Cl, OtBu, Ph and nBu. The tendency depends on the degree of the covalent interaction between Np 5f-electron and X ligand. It is suggested that it is important to estimate the bonding contribution of 5f-orbital to understand the electronic state for organo-actinide complexes.

Fact and Fiction of Nitrous Oxide Production By Nitrification

Science.gov (United States)

Stein, L. Y.; Kozlowski, J.; Stieglmeier, M.; Klotz, M. G.; Schleper, C.

2014-12-01

An accepted dogma in nitrification research is that ammonia-oxidizing bacteria (AOB) produce a modicum of nitrous oxide (N2O) during nitritation via incomplete oxidation of hydroxylamine, and substantially more at low oxygen concentrations via nitrifier denitrification.The nitrifier denitrification pathway involves the reduction of nitrite to N2O via nitric oxide and was thought to require activities of a copper-containing nitrite reductase (NirK) and nitric oxide reductase (NorB); inventory encoded in most, but not all AOB genome sequences. The discovery of nirK genes in ammonia-oxidizing Thaumarchaeota (AOA) resulted in a slew of publications stating that AOA must also perform nitrifier denitrification and, due to their high abundance, must control the majority of nitrification-linked N2O emissions. Prior to a publication by Stieglmeier et al. (2014), which definitively showed a lack of nitrifier denitrification by two axenic AOA cultures, other researchers relied on enrichment cultures, negative data, and heavy inferencing without direct demonstration of either a functional pathway or involvement of specific genes or enzymes. AOA genomes lack recognizable nitric oxide reductases and thermophilic AOA also lack nirK genes. Physiological and microrespirometry experiments with axenic AOB and AOA cultures allowed us to demonstrate that: 1) AOB produce N2O via nitrifier denitrification even though some lack annotated nirK and/or norB genes; 2) nitrifier denitrification by AOB is reliant on nitric oxide but ammonia oxidation is not; 3) ammonia oxidation by AOA is reliant on production of nitric oxide; 4) AOA are incapable of generating N2O via nitrifier denitrification; 5) N2O production by AOA is from chemical interactions between NO and media components, most likely not by enzyme activity. Our results reveal operation of different N oxide transformation pathways in AOB and AOA governed by different environmental controls and involving different mechanisms of N2O

Hydrogen production by ethanol partial oxidation over nano-iron oxide catalysts produced by chemical vapour synthesis

Energy Technology Data Exchange (ETDEWEB)

Ahmed, Wael Ahmed Abou Taleb Sayed

2011-01-13

This work presents the experimental results of the synthesis of unsupported and supported SiC iron oxide nanoparticles and their catalytic activity towards ethanol partial oxidation. For comparison, further unsupported iron oxide phases were investigated towards the ethanol partial oxidation. These {gamma}-Fe{sub 2}O{sub 3} and {alpha}/{gamma}-Fe{sub 2}O{sub 3} phase catalysts were prepared by the CVS method using Fe(CO){sub 5} as precursor, supplied by another author. The {alpha}-Fe{sub 2}O{sub 3} and SiC nanoparticles were prepared by the CVS method using a home made hot wall reactor technique at atmospheric pressure. Ferrocene and tetramethylsilane were used as precursor for the production process. Process parameters of precursor evaporation temperature, precursor concentration, gas mixture velocity and gas mixture dilution were investigated and optimised to produce particle sizes in a range of 10 nm. For Fe{sub 2}O{sub 3}/SiC catalyst series production, a new hot wall reactor setup was used. The particles were produced by simultaneous thermal decomposition of ferrocene and tetramethylsilane in one reactor from both sides. The production parameters of inlet tube distance inside the reactor, precursor evaporation temperature and carrier gas flow were investigated to produce a series of samples with different iron oxide content. The prepared catalysts composition, physical and chemical properties were characterized by XRD, EDX, SEM, BET surface area, FTIR, XPS and dynamic light scattering (DLS) techniques. The catalytic activity for the ethanol gas-phase oxidation was investigated in a temperature range from 260 C to 290 C. The product distributions obtained over all catalysts were analysed with mass spectrometry analysis tool. The activity of bulk Fe{sub 2}O{sub 3} and SiC nanoparticles was compared with prepared nano-iron oxide phase catalysts. The reaction parameters, such as reaction temperature and O{sub 2}/ethanol ratio were investigated. The catalysts

An investigation of oxidation products and SOA yields from OH + pesticide reactions

Science.gov (United States)

Murschell, T.; Friedman, B.; Link, M.; Farmer, D.

2016-12-01

Pesticides are used globally in agricultural and residential areas. After application and/or volatilization from a surface, these compounds can be transported over long distances in the atmosphere. However, their chemical fate, including oxidation and gas-particle partitioning in the atmosphere, is not well understood. We present gas and particle measurements of oxidation products from pesticide + OH reactions using a dynamic solution injection system coupled to an Oxidative Flow Reactor. Products were detected with a High Resolution Time of Flight Iodide Chemical Mass Spectrometer (HR-ToF-CIMS) and a Size Mobility Particle Scanner (SMPS). The OFR allows pesticides to react with variable OH radical exposures, ranging from the equivalent of one day to a full week of atmospheric oxidative aging. In this work, we explore pesticide oxidation products from reaction with OH and ozone, and compare those products to photolysis reactions. Pesticides of similar chemical structures were explored, including acetochlor / metolachlor and permethrin / cypermethrin, to explore mechanistic differences. We present chemical parameters including average product oxidation state, average oxygen to carbon ratio, and potential secondary organic aerosol formation for each of these compounds.

Study of the influence of radiolysis on the stability of plutonium III. Application to a heterogeneous medium formed by a nitric solution of ferrous ions and an organic solution of trilauryl-ammonium nitrate

International Nuclear Information System (INIS)

Fourmaux, J.M.

1980-01-01

The objective of this research thesis is to study the behaviour of plutonium 238 in media which are commonly used to isolate it from other elements such as neptunium and fission products created during the neutron irradiation of the neptunium 237 isotope. As plutonium 238 purification processes are all based on redox reaction, it is essential to know the influence of radiolysis on the redox behaviour, and on the distribution coefficients of this isotope in solutions used during its separation from the neptunium 237 isotope. Therefore, it is necessary to study the influence of radiolysis on the stability of plutonium with an oxidation III level. As this extraction is performed by an organic solvent (trilauryl-ammonium nitrate), this study addresses the behaviour of plutonium in an emulsion formed by this solvent and the nitric aqueous solution previously adjusted in terms of Fe 2+ ions. After a brief recall of bibliographical generalities related to radiolysis, the author presents and comments the Nernst law in the case of a two-phase system (emulsion), and reports the use of this law to obtain the plutonium potential-distribution coefficient relationship. The last part reports experimental data

Neptunium(V) sorption on kaolinite

Energy Technology Data Exchange (ETDEWEB)

Amayri, S.; Jermolajev, A.; Reich, T. [Mainz Univ. (Germany). Inst. of Nuclear Chemistry

2011-07-01

The sorption behavior of neptunium(V) onto the clay mineral kaolinite was studied in batch experiments under different experimental conditions: [Np(V)] = 7 x 10{sup -12}-8 x 10{sup -6} M, solid-to-liquid ratio 2-20 g L{sup -1}, I = 0.1 and 0.01 M NaClO{sub 4}, pH = 6-10, ambient air and Ar atmosphere. The short-lived isotope {sup 239}Np (T{sub 1/2} = 2.36 d) was used instead of {sup 237}Np (T{sub 1/2} = 2.14 x 10{sup 6} a) to study the sorption behavior of Np(V) at environmentally-relevant concentrations, i.e., 7 x 10{sup -12} M Np. In addition, {sup 239}Np(V) served as tracer to measure sorption isotherms over six orders of magnitude in Np concentration (4.8 x 10{sup -12}-1.0 x 10{sup -4} M). The results show that Np(V) sorption on kaolinite is strongly influenced by pH, CO{sub 2}, and ionic strength. The sorption of 8 x 10{sup -6} M Np(V) at pH 9.0, and ionic strength of 0.1 M NaClO{sub 4} was proportional to the solid-to-liquid ratio of kaolinite in the range of 2-10 g L{sup -1}. In the absence of CO{sub 2}, the Np(V) uptake increased continuously with increasing pH value up to 97% at pH 10. Under ambient CO{sub 2}, the sorption of Np decreased above pH 8 up to zero at pH 10. An increase of Np(V) concentration from 7 x 10{sup -12} to 8 x 10{sup -6} M resulted in a shift of the sorption pH edge by up to one pH unit to higher pH values. The ionic strength influenced the Np(V) sorption onto kaolinite only in the presence of ambient CO{sub 2}. Under Ar atmosphere the sorption of Np(V) was independent from ionic strength, indicating the formation of inner-sphere complexes of Np(V) with kaolinite. Time-dependent batch experiments at pH 9.0 under ambient CO{sub 2} showed that the sorption of Np(V) on kaolinite is fast and fully reversible over six orders in Np(V) concentration. (orig.)

Oxide production program monthly report - December 2014

Energy Technology Data Exchange (ETDEWEB)

Kelley, Evelyn A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Whitworth, Julia [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lloyd, Jane Alexandria [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Hampton, David Earl [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Benavidez, Amelia A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-01-15

A summary of the major activities, accomplishments, milestones, financial summary, project performance and issues facing the ARIES Oxide Production Program for the month of December 2014 is presented in this Executive Summary.

Graphene oxide and H2 production from bioelectrochemical graphite oxidation.

Science.gov (United States)

Lu, Lu; Zeng, Cuiping; Wang, Luda; Yin, Xiaobo; Jin, Song; Lu, Anhuai; Jason Ren, Zhiyong

2015-11-17

Graphene oxide (GO) is an emerging material for energy and environmental applications, but it has been primarily produced using chemical processes involving high energy consumption and hazardous chemicals. In this study, we reported a new bioelectrochemical method to produce GO from graphite under ambient conditions without chemical amendments, value-added organic compounds and high rate H2 were also produced. Compared with abiotic electrochemical electrolysis control, the microbial assisted graphite oxidation produced high rate of graphite oxide and graphene oxide (BEGO) sheets, CO2, and current at lower applied voltage. The resultant electrons are transferred to a biocathode, where H2 and organic compounds are produced by microbial reduction of protons and CO2, respectively, a process known as microbial electrosynthesis (MES). Pseudomonas is the dominant population on the anode, while abundant anaerobic solvent-producing bacteria Clostridium carboxidivorans is likely responsible for electrosynthesis on the cathode. Oxygen production through water electrolysis was not detected on the anode due to the presence of facultative and aerobic bacteria as O2 sinkers. This new method provides a sustainable route for producing graphene materials and renewable H2 at low cost, and it may stimulate a new area of research in MES.

Bee products prevent agrichemical-induced oxidative damage in fish.

Directory of Open Access Journals (Sweden)

Daiane Ferreira

Full Text Available In southern South America and other parts of the world, aquaculture is an activity that complements agriculture. Small amounts of agrichemicals can reach aquaculture ponds, which results in numerous problems caused by oxidative stress in non-target organisms. Substances that can prevent or reverse agrichemical-induced oxidative damage may be used to combat these effects. This study includes four experiments. In each experiment, 96 mixed-sex, 6-month-old Rhamdia quelen (118±15 g were distributed into eight experimental groups: a control group that was not exposed to contaminated water, three groups that were exposed to various concentrations of bee products, three groups that were exposed to various concentrations of bee products plus tebuconazole (TEB; Folicur 200 CE™ and a group that was exposed to 0.88 mg L(-1 of TEB alone (corresponding to 16.6% of the 96-h LC50. We show that waterborne bee products, including royal jelly (RJ, honey (H, bee pollen (BP and propolis (P, reversed the oxidative damage caused by exposure to TEB. These effects were likely caused by the high polyphenol contents of these bee-derived compounds. The most likely mechanism of action for the protective effects of bee products against tissue oxidation and the resultant damage is that the enzymatic activities of superoxide dismutase (SOD, catalase (CAT and glutathione-S-transferase (GST are increased.

Bee products prevent agrichemical-induced oxidative damage in fish.

Science.gov (United States)

Ferreira, Daiane; Rocha, Helio Carlos; Kreutz, Luiz Carlos; Loro, Vania Lucia; Marqueze, Alessandra; Koakoski, Gessi; da Rosa, João Gabriel Santos; Gusso, Darlan; Oliveira, Thiago Acosta; de Abreu, Murilo Sander; Barcellos, Leonardo José Gil

2013-01-01

In southern South America and other parts of the world, aquaculture is an activity that complements agriculture. Small amounts of agrichemicals can reach aquaculture ponds, which results in numerous problems caused by oxidative stress in non-target organisms. Substances that can prevent or reverse agrichemical-induced oxidative damage may be used to combat these effects. This study includes four experiments. In each experiment, 96 mixed-sex, 6-month-old Rhamdia quelen (118±15 g) were distributed into eight experimental groups: a control group that was not exposed to contaminated water, three groups that were exposed to various concentrations of bee products, three groups that were exposed to various concentrations of bee products plus tebuconazole (TEB; Folicur 200 CE™) and a group that was exposed to 0.88 mg L(-1) of TEB alone (corresponding to 16.6% of the 96-h LC50). We show that waterborne bee products, including royal jelly (RJ), honey (H), bee pollen (BP) and propolis (P), reversed the oxidative damage caused by exposure to TEB. These effects were likely caused by the high polyphenol contents of these bee-derived compounds. The most likely mechanism of action for the protective effects of bee products against tissue oxidation and the resultant damage is that the enzymatic activities of superoxide dismutase (SOD), catalase (CAT) and glutathione-S-transferase (GST) are increased.

Solubility of neptunium and technetium dioxides in a Yucca Mountain simulated groundwaters

International Nuclear Information System (INIS)

Kulyako, Yu.; Perevalov, S.; Malikov, D.; Myasoedov, B.; Atkins-Duffin, Cynthia E.

2005-01-01

Full text of publication follows: Solubility of NpO 2 and TcO 2 in the Yucca Mountain simulated ground waters J-13 and UE-25p-1 were studied. It is shown that contents of the dissolved neptunium and technetium in simulated groundwater (SGW) depend on solid/liquid phase ratio in these systems under ambient conditions. Average values of NpO 2 solubility in the suspensions of J-13 SGW are equal to (1.1±0.2) x 10 -6 M, (4.7±0.5) x 10 -6 M and (1.3±0.2) x 10 -5 M at solid/liquid ratios (mg/mL) of 0.4, 2.5 and 9.8 respectively. Average solubility values of NpO 2 in the suspensions of UE-25p-1 SGW are equal to (1.6±0.2) x 10 -7 M, (4.3±0.7) x 10 -7 M and (4.2±1.2) x 10 -6 M for solid/liquid ratios (mg/mL) of 1.2, 3.7 and 18.6, respectively. At equal solid/liquid ratios the solubility of NpO 2 in J-13 SGW is higher than that in UE-25p-1 SGW. At equal contents of solid phase in the suspensions solubility of TcO 2 in J-13 SGW are close to those in UE-25p-1 SGW and they are approximately proportional to the solid/liquid ratio. Average values of TcO 2 solubility in the suspensions of J-13 SGW are equal to (3.0±0.2) x 10 -5 M, (1.7±0.2) x 10 -4 , (6.2±0.2) x 10 -4 M at solid/liquid ratios (mg/mL) of 0.6, 4.8 and 15.5 respectively. Average values of TcO 2 solubility in the suspensions of UE-25p-1 SGW are equal to (5.8±0.3) x 10 -5 M, (2.2±0.1) x 10 -4 M and (3.8±0.2) x 10 -4 M at solid/liquid ratios 1.6, 7.0 and 13.6 (mg/mL) respectively. The dependence of solubility of NpO 2 and TcO 2 on solid/liquid ratio may be explained by the fact that transition of the neptunium and technetium from solid phase into the liquid one occurs on phase interface owing to the dissolving of Np(V) and Tc(VII) compounds being formed under ambient conditions. (authors)

Uranium, neptunium and plutonium kinetics of extraction by tributylphosphate and trilaurylamine in a centrifugal contactor

International Nuclear Information System (INIS)

Bergeonneau, P.; Jaouen, C.; Germain, M.; Bathellier, A.

1977-01-01

Uranium, plutonium and neptunium kinetics of transfer between various aqueous nitric solutions and solvents have been measured at the laboratory scale, using a centrifugal contactor especially developed in the laboratory. The transfer kinetics of nitric acid, hexavalent U, tetravalent U, Np and Pu from nitric acid solutions into 30% TBP in r-dodecane and 10% trilaurylamine in r-dodecane have been studied. The effects of rotation speed, temperature, initial nitric acid concentration, metal concentration on extraction and stripping kinetics have been investigated. The results obtained show that TBP extraction and stripping are more rapid than trilaurylamine ones. The low activation energies of transfer reactions with TBP suggest that both in extraction and stripping, the transfer rate is limited by the diffusion of the species in the aqueous and organic phases. For trilaurylamine, the transfer mechanism appears more complex

Catalytic abatement of nitrous oxide from nitric and production

NARCIS (Netherlands)

Oonk, J.

1998-01-01

Nitric acid production is identified as a main source of nitrous oxide. Options for emission reduction however are not available. TNO and Hydro Agri studied the technological and economic feasibility of catalytic decomposition of nitrous oxide in nitric acid tail-gases. Although in literature

Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

Science.gov (United States)

Cavazos, A. R.; Taillefert, M.; Glass, J. B.

2016-12-01

The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-01-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. The efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness, and as a monitor of system corrosion effects. The discussion is based mostly on the results and observations from Ontario Hydro plants, and their comparisons with PWRs. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of lay-up and various start-up conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on corrosion-product transport on the primary side of steam generators are also discussed. (author)

Bilirubin and its oxidation products damage brain white matter

Science.gov (United States)

Lakovic, Katarina; Ai, Jinglu; D'Abbondanza, Josephine; Tariq, Asma; Sabri, Mohammed; Alarfaj, Abdullah K; Vasdev, Punarjot; Macdonald, Robert Loch

2014-01-01

Brain injury after intracerebral hemorrhage (ICH) occurs in cortex and white matter and may be mediated by blood breakdown products, including hemoglobin and heme. Effects of blood breakdown products, bilirubin and bilirubin oxidation products, have not been widely investigated in adult brain. Here, we first determined the effect of bilirubin and its oxidation products on the structure and function of white matter in vitro using brain slices. Subsequently, we determined whether these compounds have an effect on the structure and function of white matter in vivo. In all, 0.5 mmol/L bilirubin treatment significantly damaged both the function and the structure of myelinated axons but not the unmyelinated axons in brain slices. Toxicity of bilirubin in vitro was prevented by dimethyl sulfoxide. Bilirubin oxidation products (BOXes) may be responsible for the toxicity of bilirubin. In in vivo experiments, unmyelinated axons were found more susceptible to damage from bilirubin injection. These results suggest that unmyelinated axons may have a major role in white-matter damage in vivo. Since bilirubin and BOXes appear in a delayed manner after ICH, preventing their toxic effects may be worth investigating therapeutically. Dimethyl sulfoxide or its structurally related derivatives may have a potential therapeutic value at antagonizing axonal damage after hemorrhagic stroke. PMID:25160671

The Evonik-Uhde HPPO process for proplene oxide production

Energy Technology Data Exchange (ETDEWEB)

Jaeger, B.; Baerz, M. [Evonik Industries, Hanau (Germany); Schemel, J.; Kolbe, B. [Uhde GmbH, Dortmund/Bad Soden (Germany)

2011-07-01

In 2008 the HPPO technology has shown up as an economically and environmentally friendly alternative for manufacturing of propylene oxide. The HPPO technology offers the advantage of an on purpose process for manufacturing of propylene oxide without dependency on disposal or marketing of coupling products. (orig.)

Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

Science.gov (United States)

Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

2018-03-01

In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

Science.gov (United States)

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Creation of a simplified benchmark model for the neptunium sphere experiment

International Nuclear Information System (INIS)

Mosteller, Russell D.; Loaiza, David J.; Sanchez, Rene G.

2004-01-01

Although neptunium is produced in significant amounts by nuclear power reactors, its critical mass is not well known. In addition, sizeable uncertainties exist for its cross sections. As an important step toward resolution of these issues, a critical experiment was conducted in 2002 at the Los Alamos Critical Experiments Facility. In the experiment, a 6-kg sphere of 237 Np was surrounded by nested hemispherical shells of highly enriched uranium. The shells were required in order to reach a critical condition. Subsequently, a detailed model of the experiment was developed. This model faithfully reproduces the components of the experiment, but it is geometrically complex. Furthermore, the isotopics analysis upon which that model is based omits nearly 1 % of the mass of the sphere. A simplified benchmark model has been constructed that retains all of the neutronically important aspects of the detailed model and substantially reduces the computer resources required for the calculation. The reactivity impact, of each of the simplifications is quantified, including the effect of the missing mass. A complete set of specifications for the benchmark is included in the full paper. Both the detailed and simplified benchmark models underpredict k eff by more than 1% Δk. This discrepancy supports the suspicion that better cross sections are needed for 237 Np.

Oxidation of trimethoprim by ferrate(VI): kinetics, products, and antibacterial activity.

Science.gov (United States)

Anquandah, George A K; Sharma, Virender K; Knight, D Andrew; Batchu, Sudha Rani; Gardinali, Piero R

2011-12-15

Kinetics, stoichiometry, and products of the oxidation of trimethoprim (TMP), one of the most commonly detected antibacterial agents in surface waters and municipal wastewaters, by ferrate(VI) (Fe(VI)) were determined. The pH dependent second-order rate constants of the reactions of Fe(VI) with TMP were examined using acid-base properties of Fe(VI) and TMP. The kinetics of reactions of diaminopyrimidine (DAP) and trimethoxytoluene (TMT) with Fe(VI) were also determined to understand the reactivity of Fe(VI) with TMP. Oxidation products of the reactions of Fe(VI) with TMP and DAP were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Reaction pathways of oxidation of TMP by Fe(VI) are proposed to demonstrate the cleavage of the TMP molecule to ultimately result in 3,4,5,-trimethoxybenzaldehyde and 2,4-dinitropyrimidine as among the final identified products. The oxidized products mixture exhibited no antibacterial activity against E. coli after complete consumption of TMP. Removal of TMP in the secondary effluent by Fe(VI) was achieved.

Alpha self-irradiation effects in ternary oxides of actinides elements: The zircon-like phases AmIIIVO4 and AIINpIV(VO4)2 (A=Sr, Pb)

International Nuclear Information System (INIS)

Goubard, F.; Griesmar, P.; Tabuteau, A.

2005-01-01

We report the experimental studies of irradiation damage from alpha decay in neptunium and americium vanadates versus cumulative dose. The isotopes used were the transuranium α-emitter 237 Np and the α,γ-emitter 241 Am. Neptunium and americium vanadates self-irradiation was studied by X-ray diffraction method (XRD). The comparison of the powder diffraction patterns reveal that the irradiation has no apparent effect on the neptunium phases while the americium vanadate swells and becomes metamict as a function of cumulative dose

Production of superconducting ceramic oxides by coprecipitation

International Nuclear Information System (INIS)

Bizaio, L.R.; Lima, M.A.F. de; Figueiredo Jardim, R.de; Pinheiro, E.A.; Galembeck, F.

1988-01-01

An alternative method for production of ceramic oxides is described. The method consist in the coprecipitation reaction of metallic ions with oxalic acid. The obtainment samples present additional phases characterized by X-rays and optical microscopy. (C.G.C.) [pt

Corrosion-product transport, oxidation state and remedial measures

International Nuclear Information System (INIS)

Sawicki, J.A.; Brett, M.E.; Tapping, R.L.

1998-10-01

The issues associated with monitoring and controlling corrosion-product transport (CPT) in the balance-of-plant (BOP) and steam generators (SG) of CANDU stations are briefly reviewed. Efforts are focused on minimizing corrosion of carbon steel, which is used extensively in the CANDU primary and secondary systems. Emphasis is placed on the corrosion-product oxidation state as a monitor of water chemistry effectiveness and as a monitor of system corrosion effects. The discussion is based mostly on the results of observations from Ontario Hydro plants, and their comparisons with pressurized-water reactors. The effects of low oxygen and elevated hydrazine chemistry are reviewed, as well as the effects of layup and various startup conditions. Progress in monitoring electrochemical potential (ECP) at Ontario Hydro plants and its relationship to the oxidation state of corrosion products is reviewed. Observations on CPT on the primary side of SGs are also discussed. (author)

Hydrodeoxygenation of oxidized distilled bio-oil for the production of gasoline fuel type

International Nuclear Information System (INIS)

Luo, Yan; Guda, Vamshi Krishna; Hassan, El Barbary; Steele, Philip H.; Mitchell, Brian; Yu, Fei

2016-01-01

Highlights: • Oxidation had more influence on the yield of total hydrocarbons than distillation. • The highest total hydrocarbon yield was obtained from oxidized distilled bio-oil. • The 2nd-stage hydrocarbons were in the range of gasoline fuel boiling points. • The main products for upgrading of oxidized bio-oil were aliphatic hydrocarbons. • The main products for upgrading of non-oxidized bio-oil were aromatic hydrocarbons. - Abstract: Distilled and oxidized distilled bio-oils were subjected to 1st-stage mild hydrodeoxygenation and 2nd-stage full hydrodeoxygenation using nickel/silica–alumina catalyst as a means to enhance hydrocarbon yield. Raw bio-oil was treated for hydrodeoxygenation as a control to which to compare study treatments. Following two-stage hydrodeoxygenation, four types of hydrocarbons were mainly comprised of gasoline and had water contents, oxygen contents and total acid numbers of nearly zero and higher heating values of 44–45 MJ/kg. Total hydrocarbon yields for raw bio-oil, oxidized raw bio-oil, distilled bio-oil and oxidized distilled bio-oil were 11.6, 16.2, 12.9 and 20.5 wt.%, respectively. The results indicated that oxidation had the most influence on increasing the yield of gasoline fuel type followed by distillation. Gas chromatography/mass spectrometry characterization showed that 66.0–76.6% of aliphatic hydrocarbons and 19.5–31.6% of aromatic hydrocarbons were the main products for oxidized bio-oils while 35.5–38.7% of aliphatic hydrocarbons and 58.2–63.1% of aromatic hydrocarbons were the main products for non-oxidized bio-oils. Both aliphatic and aromatic hydrocarbons are important components for liquid transportation fuels and chemical products.

Nitrous oxide production by lithotrophic ammonia-oxidizing bacteria and implications for engineered nitrogen-removal systems.

Science.gov (United States)

Chandran, Kartik; Stein, Lisa Y; Klotz, Martin G; van Loosdrecht, Mark C M

2011-12-01

Chemolithoautotrophic AOB (ammonia-oxidizing bacteria) form a crucial component in microbial nitrogen cycling in both natural and engineered systems. Under specific conditions, including transitions from anoxic to oxic conditions and/or excessive ammonia loading, and the presence of high nitrite (NO₂⁻) concentrations, these bacteria are also documented to produce nitric oxide (NO) and nitrous oxide (N₂O) gases. Essentially, ammonia oxidation in the presence of non-limiting substrate concentrations (ammonia and O₂) is associated with N₂O production. An exceptional scenario that leads to such conditions is the periodical switch between anoxic and oxic conditions, which is rather common in engineered nitrogen-removal systems. In particular, the recovery from, rather than imposition of, anoxic conditions has been demonstrated to result in N₂O production. However, applied engineering perspectives, so far, have largely ignored the contribution of nitrification to N₂O emissions in greenhouse gas inventories from wastewater-treatment plants. Recent field-scale measurements have revealed that nitrification-related N₂O emissions are generally far higher than emissions assigned to heterotrophic denitrification. In the present paper, the metabolic pathways, which could potentially contribute to NO and N₂O production by AOB have been conceptually reconstructed under conditions especially relevant to engineered nitrogen-removal systems. Taken together, the reconstructed pathways, field- and laboratory-scale results suggest that engineering designs that achieve low effluent aqueous nitrogen concentrations also minimize gaseous nitrogen emissions.

STIMULATION OF OXIDANT PRODUCTION IN ALVEOLAR MACROPHAGES BY POLLUTANT AND LATEX PARTICLES

Science.gov (United States)

Air pollutant dusts as well as chemically defined particles were examined for their activating effect on oxidant production (O2- and H2O2) in guinea pig alveolar macrophages (AM). Oxidant production was measured as chemiluminescence of albumin-bound luminol. All particles examine...

Processing of irradiated, enriched uranium fuels at the Savannah River Plant

Energy Technology Data Exchange (ETDEWEB)

Hyder, M L; Perkins, W C; Thompson, M C; Burney, G A; Russell, E R; Holcomb, H P; Landon, L F

1979-04-01

Uranium fuels containing /sup 235/U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction with dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of /sup 238/Pu is high enough to make its recovery desirable. Most of the /sup 238/Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, /sup 239/Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse.

Processing of irradiated, enriched uranium fuels at the Savannah River Plant

International Nuclear Information System (INIS)

Hyder, M.L.; Perkins, W.C.; Thompson, M.C.; Burney, G.A.; Russell, E.R.; Holcomb, H.P.; Landon, L.F.

1979-04-01

Uranium fuels containing 235 U at enrichments from 1.1% to 94% are processed and recovered, along with neptunium and plutonium byproducts. The fuels to be processed are dissolved in nitric acid. Aluminum-clad fuels are disssolved using a mercury catalyst to give a solution rich in aluminum. Fuels clad in more resistant materials are dissolved in an electrolytic dissolver. The resulting solutions are subjected to head-end treatment, including clarification and adjustment of acid and uranium concentration before being fed to solvent extraction. Uranium, neptunium, and plutonium are separated from fission products and from one another by multistage countercurrent solvent extraction with dilute tri-n-butyl phosphate in kerosene. Nitric acid is used as the salting agent in addition to aluminum or other metal nitrates present in the feed solution. Nuclear safety is maintained through conservative process design and the use of monitoring devices as secondary controls. The enriched uranium is recovered as a dilute solution and shipped off-site for further processing. Neptunium is concentrated and sent to HB-Line for recovery from solution. The relatively small quantities of plutonium present are normally discarded in aqueous waste, unless the content of 238 Pu is high enough to make its recovery desirable. Most of the 238 Pu can be recovered by batch extraction of the waste solution, purified by counter-current solvent extraction, and converted to oxide in HB-Line. By modifying the flowsheet, 239 Pu can be recovered from low-enriched uranium in the extraction cycle; neptunium is then not recovered. The solvent is subjected to an alkaline wash before reuse to remove degraded solvent and fission products. The aqueous waste is concentrated and partially deacidified by evaporation before being neutralized and sent to the waste tanks; nitric acid from the overheads is recovered for reuse

Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

Science.gov (United States)

David, Dennis D.; Dee, Louis A.; Beeson, Harold D.

1997-01-01

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

Secondary organic aerosol production from pinanediol, a semi-volatile surrogate for first-generation oxidation products of monoterpenes

Science.gov (United States)

Ye, Penglin; Zhao, Yunliang; Chuang, Wayne K.; Robinson, Allen L.; Donahue, Neil M.

2018-05-01

We have investigated the production of secondary organic aerosol (SOA) from pinanediol (PD), a precursor chosen as a semi-volatile surrogate for first-generation oxidation products of monoterpenes. Observations at the CLOUD facility at CERN have shown that oxidation of organic compounds such as PD can be an important contributor to new-particle formation. Here we focus on SOA mass yields and chemical composition from PD photo-oxidation in the CMU smog chamber. To determine the SOA mass yields from this semi-volatile precursor, we had to address partitioning of both the PD and its oxidation products to the chamber walls. After correcting for these losses, we found OA loading dependent SOA mass yields from PD oxidation that ranged between 0.1 and 0.9 for SOA concentrations between 0.02 and 20 µg m-3, these mass yields are 2-3 times larger than typical of much more volatile monoterpenes. The average carbon oxidation state measured with an aerosol mass spectrometer was around -0.7. We modeled the chamber data using a dynamical two-dimensional volatility basis set and found that a significant fraction of the SOA comprises low-volatility organic compounds that could drive new-particle formation and growth, which is consistent with the CLOUD observations.

Production of Oxygen from Lunar Regolith by Molten Oxide Electrolysis

Science.gov (United States)

Curreri, Peter A.

2009-01-01

This paper describes the use of the molten oxide electrolysis (MOE) process for the extraction of oxygen for life support and propellant, and silicon and metallic elements for use in fabrication on the Moon. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis is ideal for extraction, since the electron is the only practical reducing agent. MOE has several advantages over other extraction methods. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. Alternatively, MOE requires no import of consumable reagents (e.g. fluorine and carbon) as other processes do, and does not rely on interfacing multiple processes to obtain refined products. Electrolytic processing has the advantage of selectivity of reaction in the presence of a multi-component feed. Products from lunar regolith can be extracted in sequence according to the stabilities of their oxides as expressed by the values of the free energy of oxide formation (e.g. chromium, manganese, Fe, Si, Ti, Al, magnesium, and calcium). Previous work has demonstrated the viability of producing Fe and oxygen from oxide mixtures similar in composition to lunar regolith by molten oxide electrolysis (electrowinning), also called magma electrolysis having shown electrolytic extraction of Si from regolith simulant. This paper describes recent advances in demonstrating the MOE process by a joint project with participation by NASA KSC and

Dispersion strengthening of aluminium-aluminium-oxide products

DEFF Research Database (Denmark)

Hansen, Niels

1970-01-01

The true stress-true strain curves at room temperature and at 400°C were determined for various types of aluminium-aluminium-oxide products containing from 0.2 to 4.7 weight per cent of aluminium oxide. The effect of particles on the initial flow stress and the flow stress for 0.2% offset at room...... temperature and at 400°C is in agreement with Orowan's theory. The increase in flow stress at room temperature for strain values below 3 per cent was related to the plastic strain by the equation σ-σoy=k1ε 1/2, where σoy is the initial flow stress and where k1 increases for increasing volume fraction...... and decreasing particle size of the dispersed particles. A general expression for k1 was derived for the relationship between the dislocation density and the strain in dispersion-strengthened products...

Production of beryllium oxide of nuclear purity from beryl

Energy Technology Data Exchange (ETDEWEB)

Copat, A; Sood, S P

1984-01-01

Production of beryllium oxide from beryl by the fluoride process was optimized in this study. Optimum results were obtained using a mixture of sodium hexafluorsilicate and sodium hexafluorferrate as flux and calcinating at 740/sup 0/C for 2 hours. The beryllium concentrate produced was further purified by crystallization as beryllium sulfate to obtain nuclear grade beryllium oxide

Production of beryllium oxide of nuclear purity from beryl

International Nuclear Information System (INIS)

Copat, A.; Sood, S.P.

1983-01-01

Production of beryllium oxide from beryl by the fluoride process was optimized in this study. Optimum results were obtained using a mixture of sodium hexafluorsilicate and sodium hexafluorferrate as flux and calcinating at 740 0 C for 2 hours. The beryllium concentrate produced was further purified by crystallization as beryllium sulfate to obtain nuclear grade beryllium oxide (Author) [pt

Photoelectrochemical and electrocatalytic properties of thermally oxidized copper oxide for efficient solar fuel production

KAUST Repository

Garcia Esparza, Angel T.; Limkrailassiri, Kevin; Leroy, Fré dé ric; Rasul, Shahid; Yu, Weili; Lin, Liwei; Takanabe, Kazuhiro

2014-01-01

We report the use of a facile and highly scalable synthesis process to control growth products of earth-abundant Cu-based oxides and their application in relevant photoelectrochemical and electrochemical solar fuel generation systems. Characterization of the synthesized Cu(I)/Cu(II) oxides indicates that their surface morphology and chemical composition can be simply tuned by varying two synthesis parameters (time and temperature). UV-Vis spectroscopy and impedance spectroscopy studies are performed to estimate the band structures and electronic properties of these p-type semiconductor materials. Photoelectrodes made of Cu oxides possess favorable energy band structures for production of hydrogen from water; the position of their conduction band is ≈1 V more negative than the water-reduction potential. High acceptor concentrations on the order of 1018-1019 cm-3 are obtained, producing large electric fields at the semiconductor-electrolyte interface and thereby enhancing charge separation. The highly crystalline pristine samples used as photocathodes in photoelectrochemical cells exhibit high photocurrents under AM 1.5G simulated illumination. When the samples are electrochemically reduced under galvanostatic conditions, the co-existence of the oxide with metallic Cu on the surface seems to function as an effective catalyst for the selective electrochemical reduction of CO2. © the Partner Organisations 2014.

Analysis of microbial populations, denitrification, and nitrous oxide production in riparian buffers

Science.gov (United States)

Riparian buffers are used extensively to protect water bodies from nonpoint source nitrogen pollution. However there is relatively little information on the impact of these buffers on production of nitrous oxide (N2O). In this study, we assessed nitrous oxide production in riparian buffers of the so...

Thermal Oxidation of Tail Gases from the Production of Oil-furnace Carbon Black

Directory of Open Access Journals (Sweden)

Bosak, Z.

2009-01-01

Full Text Available This paper describes the production technology of oil-furnace carbon black, as well as the selected solution for preventing the emissions of this process from contaminating the environment.The products of industrial oil-furnace carbon black production are different grades of carbon black and process tail gases. The qualitative composition of these tail gases during the production of oil-furnace carbon black are: carbon(IV oxide, carbon(II oxide, hydrogen, methane, hydrogen sulfide, nitrogen, oxygen, and water vapor.The quantitative composition and lower caloric value of process tail gases change depending on the type of feedstock used in the production, as well as the type of process. The lower caloric value of process tail gases is relatively small with values ranging between 1500 and 2300 kJ m–3.In the conventional production of oil-furnace carbon black, process tail gases purified from carbon black dust are freely released into the atmosphere untreated. In this manner, the process tail gases pollute the air in the town of Kutina, because their quantitative values are much higher than the prescribed emissions limits for hydrogen sulfide and carbon(II oxide. A logical solution for the prevention of such air pollution is combustion of the process tail gases, i. e. their thermal oxidation. For this purpose, a specially designed flare system has been developed. Consuming minimum amounts of natural gas needed for oxidation, the flare system is designed to combust low caloric process tail gases with 99 % efficiency. Thus, the toxic and flammable components of the tail gases (hydrogen sulfide, hydrogen, carbon(II oxide, methane and other trace hydrocarbons would be transformed into environmentally acceptable components (sulfur(IV oxide, water, carbon(IV oxide and nitrogen(IV oxide, which are in compliance with the emissions limit values prescribed by law.Proper operation of this flare system in the production of oil-furnace carbon black would solve

Biodiesel production using calcium manganese oxide as catalyst and different raw materials

International Nuclear Information System (INIS)

Dias, Joana Maia; Conceição Machado Alvim-Ferraz, Maria; Fonseca Almeida, Manuel; Méndez Díaz, José Diego; Sánchez Polo, Manuel; Rivera Utrilla, José

2013-01-01

Highlights: ► Biodiesel production using a calcium manganese oxide catalyst was studied. ► The active specie was Ca 0.9 Mn 0.1 O and its deactivation occurred by hydration. ► The studied catalyst presented lower activation temperature than CaO. ► Biodiesel production and quality using different raw materials is reported. ► Compared to the conventional process, biodiesel water content improved. - Abstract: The use of heterogeneous catalysts for biodiesel production aims to simplify the production process as well as to reduce purification costs and related environmental impacts. Calcium manganese oxide was recently identified by the authors as an interesting heterogeneous catalyst for biodiesel production from animal fat; however, the difference between this and other catalysts, the catalyst activation/deactivation mechanisms, its behaviour in the synthesis using different raw materials as well as the impacts of its use on product quality remained unclear. Therefore, the present work: (i) compared biodiesel production using calcium manganese oxide and other catalysts (CaO and NaOH); (ii) studied the reasons leading to activation/deactivation of the heterogeneous catalyst; (iii) analysed biodiesel heterogeneous synthesis using calcium manganese oxide and different raw materials (lard, waste frying oil and a mixture); and (iv) evaluated raw material and catalyst impact on the product quality. Considering the use of different catalysts, the results showed that, after 8 h of reaction, product purity was similar using the different catalysts, being 92.5 wt.% using both NaOH and calcium manganese oxide and 93.8 wt.% using CaO. The active species of the heterogeneous catalysts were CaO, in the case of calcinated calcium carbonate, and Ca 0.9 Mn 0.1 O, in the case of calcinated calcium manganese oxide. Because the deactivating species were different for both catalysts, the calcium manganese oxide required lower activation temperature, which should be an advantage

Nitroxyl-mediated oxidation of lignin and polycarboxylated products

Energy Technology Data Exchange (ETDEWEB)

Stahl, Shannon S.; Rafiee, Mohammad

2018-02-27

Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on .beta.-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric .beta.-hydroxy acid. The polymeric .beta.-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The .beta.-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.

New Synthetic Methods and Structure-Property Relationships in Neptunium, Plutonium, and Americium Borates. Final report

Energy Technology Data Exchange (ETDEWEB)

Albrecht-Schmitt, Thomas Edward

2013-09-14

The past three years of support by the Heavy Elements Chemistry Program have been highly productive in terms of advanced degrees awarded, currently supported graduate students, peer-reviewed publications, and presentations made at universities, national laboratories, and at international conferences. Ph.D. degrees were granted to Shuao Wang and Juan Diwu, who both went on to post-doctoral appointments at the Glenn T. Seaborg Center at Lawrence Berkeley National Laboratory with Jeff Long and Ken Raymond, respectively. Pius Adelani completed his Ph.D. with me and is now a post-doc with Peter C. Burns. Andrea Alsobrook finished her Ph.D. and is now a post-doc at Savannah River with Dave Hobbs. Anna Nelson completed her Ph.D. and is now a post-doc with Rod Ewing at the University of Michigan. As can be gleaned from this list, students supported by the Heavy Elements Chemistry grant have remained interested in actinide science after leaving my program. This follows in line with previous graduates in this program such as Richard E. Sykora, who did his post-doctoral work at Oak Ridge National Laboratory with R. G. Haire, and Amanda C. Bean, who is a staff scientist at Los Alamos National Laboratory, and Philip M. Almond and Thomas C. Shehee, who are both staff scientists at Savannah River National Laboratory, Gengbang Jin who is a staff scientist at Argonne National Lab, and Travis Bray who has been a post-doc at both LBNL and ANL. Clearly this program is serving as a pipe-line for students to enter into careers in the national laboratories. About half of my students depart the DOE complex for academia or industry. My undergraduate researchers also remain active in actinide chemistry after leaving my group. Dan Wells was a productive undergraduate of mine, and went on to pursue a Ph.D. on uranium and neptunium chalcogenides with Jim Ibers at Northwestern. After earning his Ph.D., he went directly into the nuclear industry.

New Synthetic Methods and Structure-Property Relationships in Neptunium, Plutonium, and Americium Borates. Final report

International Nuclear Information System (INIS)

Albrecht-Schmitt, Thomas Edward

2013-01-01

The past three years of support by the Heavy Elements Chemistry Program have been highly productive in terms of advanced degrees awarded, currently supported graduate students, peer-reviewed publications, and presentations made at universities, national laboratories, and at international conferences. Ph.D. degrees were granted to Shuao Wang and Juan Diwu, who both went on to post-doctoral appointments at the Glenn T. Seaborg Center at Lawrence Berkeley National Laboratory with Jeff Long and Ken Raymond, respectively. Pius Adelani completed his Ph.D. with me and is now a post-doc with Peter C. Burns. Andrea Alsobrook finished her Ph.D. and is now a post-doc at Savannah River with Dave Hobbs. Anna Nelson completed her Ph.D. and is now a post-doc with Rod Ewing at the University of Michigan. As can be gleaned from this list, students supported by the Heavy Elements Chemistry grant have remained interested in actinide science after leaving my program. This follows in line with previous graduates in this program such as Richard E. Sykora, who did his post-doctoral work at Oak Ridge National Laboratory with R. G. Haire, and Amanda C. Bean, who is a staff scientist at Los Alamos National Laboratory, and Philip M. Almond and Thomas C. Shehee, who are both staff scientists at Savannah River National Laboratory, Gengbang Jin who is a staff scientist at Argonne National Lab, and Travis Bray who has been a post-doc at both LBNL and ANL. Clearly this program is serving as a pipe-line for students to enter into careers in the national laboratories. About half of my students depart the DOE complex for academia or industry. My undergraduate researchers also remain active in actinide chemistry after leaving my group. Dan Wells was a productive undergraduate of mine, and went on to pursue a Ph.D. on uranium and neptunium chalcogenides with Jim Ibers at Northwestern. After earning his Ph.D., he went directly into the nuclear industry

Methods to assess secondary volatile lipid oxidation products in complex food matrices

DEFF Research Database (Denmark)

Jacobsen, Charlotte; Yesiltas, Betül

A range of different methods are available to determine secondary volatile lipid oxidation products. These methods include e.g. spectrophotometric determination of anisidine values and TBARS as well as GC based methods for determination of specific volatile oxidation products such as pentanal...... headspace methods on the same food matrices will be presented....

Oxidation of Benzene by Persulfate in the Presence of Fe(III)- and Mn(IV)-Containing Oxides: Stoichiometric Efficiency and Transformation Products.

Science.gov (United States)

Liu, Haizhou; Bruton, Thomas A; Li, Wei; Buren, Jean Van; Prasse, Carsten; Doyle, Fiona M; Sedlak, David L

2016-01-19

Sulfate radical (SO4(•-)) is a strong, short-lived oxidant that is produced when persulfate (S2O8(2-)) reacts with transition metal oxides during in situ chemical oxidation (ISCO) of contaminated groundwater. Although engineers are aware of the ability of transition metal oxides to activate persulfate, the operation of ISCO remediation systems is hampered by an inadequate understanding of the factors that control SO4(•-) production and the overall efficiency of the process. To address these shortcomings, we assessed the stoichiometric efficiency and products of transition metal-catalyzed persulfate oxidation of benzene with pure iron- and manganese-containing minerals, clays, and aquifer solids. For most metal-containing solids, the stoichiometric efficiency, as determined by the loss of benzene relative to the loss of persulfate, approached the theoretical maximum. Rates of production of SO4(•-) or hydroxyl radical (HO(•)) generated from radical chain reactions were affected by the concentration of benzene, with rates of S2O8(2-) decomposition increasing as the benzene concentration increased. Under conditions selected to minimize the loss of initial transformation products through reaction with radicals, the production of phenol only accounted for 30%-60% of the benzene lost in the presence of O2. The remaining products included a ring-cleavage product that appeared to contain an α,β-unsaturated aldehyde functional group. In the absence of O2, the concentration of the ring-cleavage product increased relative to phenol. The formation of the ring-cleavage product warrants further studies of its toxicity and persistence in the subsurface.

Large-scale Modeling of Nitrous Oxide Production: Issues of Representing Spatial Heterogeneity

Science.gov (United States)

Morris, C. K.; Knighton, J.

2017-12-01

Nitrous oxide is produced from the biological processes of nitrification and denitrification in terrestrial environments and contributes to the greenhouse effect that warms Earth's climate. Large scale modeling can be used to determine how global rate of nitrous oxide production and consumption will shift under future climates. However, accurate modeling of nitrification and denitrification is made difficult by highly parameterized, nonlinear equations. Here we show that the representation of spatial heterogeneity in inputs, specifically soil moisture, causes inaccuracies in estimating the average nitrous oxide production in soils. We demonstrate that when soil moisture is averaged from a spatially heterogeneous surface, net nitrous oxide production is under predicted. We apply this general result in a test of a widely-used global land surface model, the Community Land Model v4.5. The challenges presented by nonlinear controls on nitrous oxide are highlighted here to provide a wider context to the problem of extraordinary denitrification losses in CLM. We hope that these findings will inform future researchers on the possibilities for model improvement of the global nitrogen cycle.

Oxidation kinetics of hydride-bearing uranium metal corrosion products

International Nuclear Information System (INIS)

Totemeier, T.C.; Pahl, R.G.; Frank, S.M.

1998-01-01

The oxidation behavior of hydride-bearing uranium metal corrosion products from zero power physics reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2 , Ar-9%O 2 , and Ar-20%O 2 . Ignition of corrosion product samples from two moderately corroded plates was observed between 125 C and 150 C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride. (orig.)

Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products

Science.gov (United States)

Janechek, Nathan J.; Hansen, Kaj M.; Stanier, Charles O.

2017-07-01

Cyclic volatile methyl siloxanes (cVMSs) are important components in personal care products that transport and react in the atmosphere. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and their gas-phase oxidation products have been incorporated into the Community Multiscale Air Quality (CMAQ) model. Gas-phase oxidation products, as the precursor to secondary organic aerosol from this compound class, were included to quantify the maximum potential for aerosol formation from gas-phase reactions with OH. Four 1-month periods were modeled to quantify typical concentrations, seasonal variability, spatial patterns, and vertical profiles. Typical model concentrations showed parent compounds were highly dependent on population density as cities had monthly averaged peak D5 concentrations up to 432 ng m-3. Peak oxidized D5 concentrations were significantly less, up to 9 ng m-3, and were located downwind of major urban areas. Model results were compared to available measurements and previous simulation results. Seasonal variation was analyzed and differences in seasonal influences were observed between urban and rural locations. Parent compound concentrations in urban and peri-urban locations were sensitive to transport factors, while parent compounds in rural areas and oxidized product concentrations were influenced by large-scale seasonal variability in OH.

Aerobic nitrous oxide production through N-nitrosating hybrid formation in ammonia-oxidizing archaea.

Science.gov (United States)

Stieglmeier, Michaela; Mooshammer, Maria; Kitzler, Barbara; Wanek, Wolfgang; Zechmeister-Boltenstern, Sophie; Richter, Andreas; Schleper, Christa

2014-05-01

Soil emissions are largely responsible for the increase of the potent greenhouse gas nitrous oxide (N2O) in the atmosphere and are generally attributed to the activity of nitrifying and denitrifying bacteria. However, the contribution of the recently discovered ammonia-oxidizing archaea (AOA) to N2O production from soil is unclear as is the mechanism by which they produce it. Here we investigate the potential of Nitrososphaera viennensis, the first pure culture of AOA from soil, to produce N2O and compare its activity with that of a marine AOA and an ammonia-oxidizing bacterium (AOB) from soil. N. viennensis produced N2O at a maximum yield of 0.09% N2O per molecule of nitrite under oxic growth conditions. N2O production rates of 4.6±0.6 amol N2O cell(-1) h(-1) and nitrification rates of 2.6±0.5 fmol NO2(-) cell(-1) h(-1) were in the same range as those of the AOB Nitrosospira multiformis and the marine AOA Nitrosopumilus maritimus grown under comparable conditions. In contrast to AOB, however, N2O production of the two archaeal strains did not increase when the oxygen concentration was reduced, suggesting that they are not capable of denitrification. In (15)N-labeling experiments we provide evidence that both ammonium and nitrite contribute equally via hybrid N2O formation to the N2O produced by N. viennensis under all conditions tested. Our results suggest that archaea may contribute to N2O production in terrestrial ecosystems, however, they are not capable of nitrifier-denitrification and thus do not produce increasing amounts of the greenhouse gas when oxygen becomes limiting.

Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

Directory of Open Access Journals (Sweden)

Madi Abilev

2015-03-01

Full Text Available Oxidation of unsymmetrical dimethylhydrazine (UDMH during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of chemical oxidants in respect to main metabolites of UDMH – 1-formyl-2,2-dimethylhydrazine, dimethylaminoacetontrile, N-nitrosodimethylamine and 1-methyl-1H-1,2,4-triazole. Experiments on chemical oxidation by Fenton's reagent, potassium permanganate and sodium nitrite were conducted. Quantitative determination was performed by HPLC. Oxidation products were identified by gas chromatography-mass spectrometry in combination with solid-phase microextraction. 1-Formyl-2,2-dimethylhydrazine was completely oxidized by Fenton's reagent with formation of formaldehyde N-formyl-N-methyl-hydrazone, 1,4-dihydro-1,4-dimethyl-5H-tetrazol-5-one by the action of potassium permanganate and N-methyl-N-nitro-methanamine in the presence of sodium nitrite. Oxidation of 1-formyl-2,2-dimethylhydrazine also resulted in formation of N-nitrosodimethylamine. Oxidation of dimethylaminoacetontrile proceeded with formation of hydroxyacetonitrile, dimethylformamide and 1,2,5-trimethylpyrrole. After 30 days, dimethylaminoacetontrile was not detected in the presence of Fenton’s reagent and potassium permanganate, but it’s concentration in samples with sodium nitrite was 77.3 mg/L. In the presence of Fenton’s reagent, potassium permanganate and sodium nitrite after 30 days, N-nitrosodimethylamine concentration decreased by 85, 80 and 50%, respectively. In control sample, N-nitrosodimethylamine concentration decreased by 50%, indicating that sodium nitrite has no effect of on N-nitrosodimethylamine concentration. Only Fenton's reagent allowed to reduce the concentration of 1-methyl-1H-1,2,4-triazole to 50% in 30 days. In the presence of other oxidants, 1-methyl-1H-1,2,4-triazole

Complex formation between neptunium(V) and various thiosemicarbazide derivatives in aqueous solution

International Nuclear Information System (INIS)

Chuguryan, D.G.; Dzyubenko, V.I.; Gerbeleu, N.V.

1987-01-01

Complex formation between neptunium(V) and various thiosemicarbazide derivatives in solution has been studied spectrophotometrically in the pH range 4-10. Stepwise formation of three types of complexes, with composition NpO 2 HA, NpO 2 A - , and NpOHA 2- , has been demonstrated with salicylaldehyde thiosemicarbazone (H 2 L) and salicylaldehyde S-methyl-isothiosemicarbazone (H 2 Q) at t = 25 +/- 1 0 C and μ = 0.05. The logarithmic stability constants of the first two complexes are 5.14 +/- 0.06, 11.85 +/- 0.04 and 8.42 +/- 0.09, 13.33 +/- 0.015 for H 2 L and H 2 Q, respectively; equilibrium constants for the formation of hydroxo complexes of the form NpO 2 OHL 2- and NpO 2 OHQ 2- were also determined, and found to be equal to (2.23 +/-0.37) x 10 -5 and (5.02 +/- 0.9) x 10 -5 , respectively. In the case of S-methyl-N 1 ,N 4 -bis(salicylidene)isothiosemicarbazide (H 2 Z), only one type of complex is formed under these experimental conditions, namely, NpO 2 Z - , with a logarithmic stability constant of 4.78 +/- 0.03. Dissociation constants for H 2 Q and H 2 Z were also determined

Improving technology and setting-up a production line for high quality zinc oxide (99.5%) with a capacity of 150 ton/year by evaporation-oxidation process

International Nuclear Information System (INIS)

Phan Dinh Thinh; Pham Minh Tuan; Luong Manh Hung; Tran Ngoc Vuong

2015-01-01

This report presents the technology improvement and a production line to produce high quality zinc oxide of purity upper than 99.5% ZnO by evaporation-oxidation method. Secondary zinc metal recovered from galvanizing industrial will undergo a pre-treatment to meet all requirements of standardized feed material for evaporation-oxidation process. Zinc metal is melted at a temperature of about 650"oC, some impurities and metallic oxides are separated preliminary, then zinc metal is converted into liquid in evaporation pot. Here the temperature is maintained around 1050"oC, zinc liquid is evaporated, zinc vapor is oxidized by air in the oxidation chamber naturally by oxygen in the air and then zinc vapor is converted to zinc oxide. Zinc oxide is passed through a product classification systems and then go to a product collection of filtering bag design. The whole process of melting, evaporation, oxidation, particles classification and product collection is a continuous process. The efficiency of the transformation of zinc metal into zinc oxide can reach the value of 1.1 to 1.2. ZnO product quality is higher than 99.5%. (author)

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

International Nuclear Information System (INIS)

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

2016-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2016-12-15

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

TiO2 assisted photo-oxidative pretreatment of wheat straw for biogas production

DEFF Research Database (Denmark)

Awais, Muhammad; Alvarado-Morales, Merlin; Tsapekos, Panagiotis

Photo-catalytic oxidation is an advanced oxidation process in which a catalyst is used to absorb light energy and oxidize the target substrates such as organic polymers. A number of metal oxides and metal ions can efficiently increase substrate’s depolymerisation during the process of photo...... to be markedly higher in the pretreated samples that were exposed for 180min with 1.5 wt% and 2 wt% of TiO2 compared to the untreated wheat straw. Moreover, it was concluded that the products of lignin oxidation and also, the presence of TiO2 did not inhibit the AD process. Finally, UV treatment or TiO2 alone......-catalytic oxidation. Titanium oxide (TiO2) is a photo-catalyst that in its rutile and anatase forms presents the property to enhance the photo-oxidation of lignin-containing substrates. Due to lignin is one of the major obstacles in methane production from lignocellulosic biomass, its destruction is a necessary step...

Model-based evaluation of the role of Anammox on nitric oxide and nitrous oxide productions in membrane aerated biofilm reactor

DEFF Research Database (Denmark)

Ni, Bing-Jie; Smets, Barth F.; Yuan, Zhiguo

2013-01-01

A multispecies one-dimensional biofilm model considering nitric oxide (NO) and nitrous oxide (N2O) productions for membrane aerated biofilm reactor (MABR) that remove nitrogen autotrophically through aerobic ammonia oxidation followed by Anammox is used to study the role of Anammox activity...... on the total nitrogen (TN) removal and the productions of NO and N2O. The model is applied to evaluate how periodic aeration as a control parameter reduces NO and N2O production but maintains high TN removal in MABR. The simulation results show over 3.5% of the removed TN could be attributed to NO and N2O...... production in MABR under the operational conditions optimal for TN removal (72%). An analysis of factors governing the Anammox activity in MABR shows that enhancing Anammox activity not only helps to achieve a high level of nitrogen removal but also reduces NO and N2O productions. Comparison of aeration...

Nitrous oxide emissions of energy production

International Nuclear Information System (INIS)

Kinnunen, L.

1998-01-01

The share of energy production of the world-wide total N 2 O emissions is about 10 %. In 1991 the N 2 O emissions estimated to be up to 30 %. The previous estimates based on incorrect measurements. The measurement methods have been improved during the past few years. The present measurements have shown that the share of the combustion of fossil fuels is about 2.0 % and the share biomass combustion about 5.0 % of the total. The uncertainty of the values can be few percentage units. According to the present measurements the share of natural emissions and the fertilizers of the total N 2 O emissions is up to 60 %. The formation of nitrous oxide has been studied widely in various countries in the world. In Finland nitrous oxide has been studied in the national LIEKKI research programme. As a result of the research carried out in the programme it has been possible to reduce the formation of N 2 O by using appropriate catalysts and combustion technologies. Nitrous oxide is formed e.g. in fluidized-bed combustion of nitrogen containing fuels. The combustion temperature of other combustion methods is so high that the gas disintegrates in the furnace. By the new methods the nitrous oxide emissions of the fluidized-bed combustion has been possible to reduce from 100-200 ppm to the level less than 50 ppm of the flue gas volume. The Japanese research has shown that the nitrous oxide emissions of bubbling beds vary in between 58 - 103 ppm, but when combusting paper the emissions are 6 - 29 ppm. The corresponding value of circulating fluidized beds is 40 - 153 ppm

Biodegradation of photo-oxidized lignite and characterization of the products

Science.gov (United States)

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

2018-01-01

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

ARIES Oxide Production Program Annual Report - FY14

Energy Technology Data Exchange (ETDEWEB)

Kelley, Evelyn A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Dinehart, Steven Mark [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2015-02-01

A summary of the major accomplishments (September), milestones, financial summary, project performance and issues facing the ARIES Oxide Production Program at the close of FY14 is presented in this Executive Summary. Annual accomplishments are summarized in the body of the report.

The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters

Science.gov (United States)

2016-01-04

AFRL-AFOSR-VA-TR-2016-0075 The Oxidation Products of Aluminum Hydride and Boron Aluminum Hydride Clusters KIT BOWEN JOHNS HOPKINS UNIV BALTIMORE MD...2. REPORT TYPE Final Performance 3. DATES COVERED (From - To) 30-09-2014 to 29-09-2015 4. TITLE AND SUBTITLE The Oxidation Products of Aluminum ...Hydride and Boron Aluminum Hydride Clusters 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-14-1-0324 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S) KIT

Oxidation kinetics of hydride-bearing uranium metal corrosion products

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Totemeier, Terry C.; Pahl, Robert G.; Frank, Steven M.

The oxidation behavior of hydride-bearing uranium metal corrosion products from Zero Power Physics Reactor (ZPPR) fuel plates was studied using thermo-gravimetric analysis (TGA) in environments of Ar-4%O 2, Ar-9%O 2, and Ar-20%O 2. Ignition of corrosion product samples from two moderately corroded plates was observed between 125°C and 150°C in all environments. The rate of oxidation above the ignition temperature was found to be dependent only on the net flow rate of oxygen in the reacting gas. Due to the higher net oxygen flow rate, burning rates increased with increasing oxygen concentration. Oxidation rates below the ignition temperature were much slower and decreased with increasing test time. The hydride contents of the TGA samples from the two moderately corroded plates, determined from the total weight gain achieved during burning, were 47-61 wt% and 29-39 wt%. Samples from a lightly corroded plate were not reactive; X-ray diffraction (XRD) confirmed that they contained little hydride.

Glufosinate ammonium stimulates nitric oxide production through N-methyl D-aspartate receptors in rat cerebellum.

Science.gov (United States)

Nakaki, T; Mishima, A; Suzuki, E; Shintani, F; Fujii, T

2000-09-01

Glufosinate ammonium, a structural analogue of glutamate, is an active herbicidal ingredient. The neuronal activities of this compound were investigated by use of a microdialysis system that allowed us to measure nitric oxide production in the rat cerebellum in vivo. Kainate (0.3-30 nmol/10 microliter), N-methyl-D-aspartate (NMDA) (3-300 nmol/10 microliter) and glufosinate ammonium (30-3000 nmol/10 microliter), which were administered through the microdialysis probe at a rate of 1 microliter/min for 10 min, stimulated nitric oxide production. The glufosinate ammonium-elicited increase in nitric oxide production was suppressed by an inhibitor of nitric oxide synthase and was antagonized by NMDA receptor antagonists, but not by a kainate/(+/-)-alphaamino-3-hydroxy-5-methylisoxazole-4-propionic acid receptor antagonist. These results suggest that glufosinate ammonium stimulates nitric oxide production through NMDA receptors.

The production of iron oxide during peridotite serpentinization: Influence of pyroxene

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Ruifang Huang

2017-11-01

Full Text Available Serpentinization produces molecular hydrogen (H2 that can support communities of microorganisms in hydrothermal fields; H2 results from the oxidation of ferrous iron in olivine and pyroxene into ferric iron, and consequently iron oxide (magnetite or hematite forms. However, the mechanisms that control H2 and iron oxide formation are poorly constrained. In this study, we performed serpentinization experiments at 311 °C and 3.0 kbar on olivine (with <5% pyroxene, orthopyroxene, and peridotite. The results show that serpentine and iron oxide formed when olivine and orthopyroxene individually reacted with a saline starting solution. Olivine-derived serpentine had a significantly lower FeO content (6.57 ± 1.30 wt.% than primary olivine (9.86 wt.%, whereas orthopyroxene-derived serpentine had a comparable FeO content (6.26 ± 0.58 wt.% to that of primary orthopyroxene (6.24 wt.%. In experiments on peridotite, olivine was replaced by serpentine and iron oxide. However, pyroxene transformed solely to serpentine. After 20 days, olivine-derived serpentine had a FeO content of 8.18 ± 1.56 wt.%, which was significantly higher than that of serpentine produced in olivine-only experiments. By contrast, serpentine after orthopyroxene had a slightly higher FeO content (6.53 ± 1.01 wt.% than primary orthopyroxene. Clinopyroxene-derived serpentine contained a significantly higher FeO content than its parent mineral. After 120 days, the FeO content of olivine-derived serpentine decreased significantly (5.71 ± 0.35 wt.%, whereas the FeO content of orthopyroxene-derived serpentine increased (6.85 ± 0.63 wt.% over the same period. This suggests that iron oxide preferentially formed after olivine serpentinization. Pyroxene in peridotite gained some Fe from olivine during the serpentinization process, which may have led to a decrease in iron oxide production. The correlation between FeO content and SiO2 or Al2O3 content in olivine- and

Influence of corium oxidation on fission product release from molten pool

International Nuclear Information System (INIS)

Bechta, S.V.; Krushinov, E.V.; Vitol, S.A.

2009-01-01

Release of low-volatile fission products and core materials from molten oxidic corium was investigated in the EVAN project under the auspices of ISTC. The experiments carried out in cold crucible with induction heating and RASPLAV test facility are described. The results are discussed in terms of reactor application; in particular, pool configuration, melt oxidation kinetics, critical influence of melt surface temperature and oxidation index on the fission product release rate and aerosol particle composition. The relevance of measured high release of Sr from the molten pool for the reactor application is highlighted. Comparisons of the experimental data with those from the COLIMA CA-U3 test and the VERCORS tests, as well as with predictions from IVTANTHERMO and GEMINI/NUCLEA are set. (author)

Methods to Collect, Compile, and Analyze Observed Short-lived Fission Product Gamma Data

Energy Technology Data Exchange (ETDEWEB)

Finn, Erin C.; Metz, Lori A.; Payne, Rosara F.; Friese, Judah I.; Greenwood, Lawrence R.; Kephart, Jeremy D.; Pierson, Bruce D.; Ellis, Tere A.

2011-09-29

A unique set of fission product gamma spectra was collected at short times (4 minutes to 1 week) on various fissionable materials. Gamma spectra were collected from the neutron-induced fission of uranium, neptunium, and plutonium isotopes at thermal, epithermal, fission spectrum, and 14-MeV neutron energies. This report describes the experimental methods used to produce and collect the gamma data, defines the experimental parameters for each method, and demonstrates the consistency of the measurements.

Use of radioanalytical methods for determination of uranium, neptunium, plutonium, americium and curium isotopes in radioactive wastes

International Nuclear Information System (INIS)

Geraldo, Bianca

2012-01-01

Activated charcoal is a common type of radioactive waste that contains high concentrations of fission and activation products. The management of this waste includes its characterization aiming the determination and quantification of the specific radionuclides including those known as Difficult-to-Measure Radionuclides (RDM). The analysis of the RDM's generally involves complex radiochemical analysis for purification and separation of the radionuclides, which are expensive and time-consuming. The objective of this work was to define a methodology for sequential analysis of the isotopes of uranium, neptunium, plutonium, americium and curium present in a type of radioactive waste, evaluating chemical yield, analysis of time spent, amount of secondary waste generated and cost. Three methodologies were compared and validated that employ ion exchange (TI + EC), extraction chromatography (EC) and extraction with polymers (ECP). The waste chosen was the activated charcoal from the purification system of primary circuit water cooling the reactor IEA-R1. The charcoal samples were dissolved by acid digestion followed by purification and separation of isotopes with ion exchange resins, extraction and chromatographic extraction polymers. Isotopes were analyzed on an alpha spectrometer, equipped with surface barrier detectors. The chemical yields were satisfactory for the methods TI + EC and EC. ECP method was comparable with those methods only for uranium. Statistical analysis as well the analysis of time spent, amount of secondary waste generated and cost revealed that EC method is the most effective for identifying and quantifying U, Np, Pu, Am and Cm present in charcoal. (author)

The recycling of the actinides neptunium, americium and curium in a fast power reactor to reduce the long term activity in a final store

International Nuclear Information System (INIS)

Beims, H.D.

1986-01-01

The starting point for the considerations and calculations given in this dissertation is the inevitable production of radioactive materials in the use of nuclear energy, which creates a considerable potential danger in a final store for a very long period. As one possibility of alleviating this problem, a concept for recycling the waste actinides neptunium, americium and curium was proposed. The waste actinides are separated in the reprocessing of burnt-up fuel elements and reach a further irradiation circuit. There they pass through the stages 'manufacture of irradiation elements', 'use in a fast power reactor' and reprocessing of irradiation elements' several times. In each irradiation and subsequent storage, about 17% of the waste actinides are removed by fission or by conversion into nuclides which can be reused as fuel, so that during the life of 40 years of the fast recycling reacor, the waste actinides can be reduced in mass by one half. In order to determine this mass reduction effect, a model calculation was developed, which includes the representation of the neutron physics and thermal properties of the reactor core and the storage and reprocessing of the irradiation elements. (orig./RB) [de

Retention of redox sensitive waste elements in compacted bentonite

International Nuclear Information System (INIS)

Torstenfelt, B.; Allard, B.

1984-01-01

The diffusion of technetium, iodine, uranium and neptunium in compacted bentonite has been studied. The possible reduction of the transport rate of these elements (i.e. redoxsensitive elements) by mixing the clay with metallic iron (for technetium, uranium and neptunium) or by adding a chemisorbent (for iodine) to the clay is reported. Technetium has an apparent diffusivity about 5 times higher in the heptavalent state (TcO 4 - ) than in the tetravalent state (TcO(OH) 2 or TcO 2 ), uranium and neptunium in their higher oxidation state (VI and V) have apparent diffusivities about 6 and 50 times higher, respectively, than in the tetravalent state. Iodine, as I - (or IO 3 - ), has a transport rate more than one order of magnitude lower than TcO 4 - . 10 references, 5 figures, 3 tables

Detection of HOCl-mediated protein oxidation products in the extracellular matrix of human atherosclerotic plaques

DEFF Research Database (Denmark)

Woods, Alan A; Linton, Stuart M; Davies, Michael Jonathan

2003-01-01

Oxidation is believed to play a role in atherosclerosis. Oxidized lipids, sterols and proteins have been detected in early, intermediate and advanced human lesions at elevated levels. The spectrum of oxidized side-chain products detected on proteins from homogenates of advanced human lesions has...... been interpreted in terms of the occurrence of two oxidative mechanisms, one involving oxygen-derived radicals catalysed by trace transition metal ions, and a second involving chlorinating species (HOCl or Cl2), generated by the haem enzyme myeloperoxidase (MPO). As MPO is released extracellularly...... for 83-96% of the total oxidized protein side-chain products detected in these plaques. Oxidation of matrix components extracted from healthy artery tissue, and model proteins, with reagent HOCl is shown to give rise to a similar pattern of products to those detected in advanced human lesions...

Oxidative stress and production of bioactive monoterpene indole alkaloids: biotechnological implications.

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Matsuura, Hélio Nitta; Rau, Mariana Ritter; Fett-Neto, Arthur Germano

2014-02-01

Monoterpene indole alkaloids (MIAs) encompass plant natural products with important pharmacological relevance. They include the anti-tumoral MIAs found in Catharanthus roseus and Camptotheca acuminata. The often low yields of bioactive alkaloids in plants has prompted research to identify the factors regulating MIA production. Oxidative stress is a general response associated with biotic and abiotic stresses leading to several secondary responses, including elicitation of MIA production. These changes in secondary metabolism may take place directly or via second messengers, such as Ca(2+) and reactive oxygen species (ROS). H2O2 is the main ROS that participates in MIA biosynthesis. This review analyzes the links between oxidative stress, elicitation of bioactive MIA production and their potential roles in antioxidant defense, as well as exploring the implications to developing biotechnological strategies relevant for alkaloid supply.

Low nitrous oxide production through nitrifier-denitrification in intermittent-feed high-rate nitritation reactors

DEFF Research Database (Denmark)

Su, Qingxian; Ma, Chun; Domingo-Felez, Carlos

2017-01-01

Nitrous oxide (N2O) production from autotrophic nitrogen conversion processes, especially nitritation systems, can be significant, requires understanding and calls for mitigation. In this study, the rates and pathways of N2O production were quantified in two lab-scale sequencing batch reactors...... to maintain high nitritation efficiency and high nitritation rates at 20-26 °C over a period of ∼300 days. Even at the high nitritation efficiencies, net N2O production was low (∼2% of the oxidized ammonium). Net N2O production rates transiently increased with a rise in pH after each feeding, suggesting...... operated with intermittent feeding and demonstrating long-term and high-rate nitritation. The resulting reactor biomass was highly enriched in ammonia-oxidizing bacteria, and converted ∼93 ± 14% of the oxidized ammonium to nitrite. The low DO set-point combined with intermittent feeding was sufficient...

Advanced oxidation protein products — biological marker of oxidative stress = Zaawansowane produkty utleniania białek – biologiczne markery stresu oksydacyjnego

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Anna Cwynar

2016-09-01

  ABSTRACT Advanced oxidation protein products (AOPPs are mostly derivatives of oxidatively modified albumin. The results of many experimental studies confirm intensification of oxidative modifications of proteins and an increase in concentration of advanced oxidation protein products (AOPPs in different pathological conditions, particularly those with well documented involvement of oxidative stress in their etiopathogenesis, but also those where its role is not yet well understood. Currently intensive research is carried out on the possibility of using AOPPs as useful indicators for diagnosing, prognosis and monitoring of diseases.   Keywords: advanced oxidation protein products, autoimmune disease, oxidative stress   STRESZCZENIE Zaawansowane produkty utleniania białek (AOPPs, to najczęściej pochodne zmodyfikowanej oksydacyjnie albuminy. Wyniki licznych badań doświadczalnych potwierdzają nasilenie oksydacyjnych modyfikacji białek i wzrost stężenia zaawansowanych produktów utleniania białek (AOPPs w różnych stanach patologicznych, szczególnie tych o dobrze udokumentowanym udziale stresu oksydacyjnego w ich etiopatogenezie, ale także takich, w których jego rola nie jest jeszcze dobrze poznana.. Obecnie trwają intensywne badania nad możliwością wykorzystania AOPPs, jako użytecznych wskaźników do diagnozowania, prognozowania oraz monitorowania chorób.   Słowa kluczowe: zaawansowane produkty utleniania białek, choroby autoimmunologiczne, stres oksydacyjny

Mn(II) oxidation by an ascomycete fungus is linked to superoxide production during asexual reproduction.

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Hansel, Colleen M; Zeiner, Carolyn A; Santelli, Cara M; Webb, Samuel M

2012-07-31

Manganese (Mn) oxides are among the most reactive minerals within the environment, where they control the bioavailability of carbon, nutrients, and numerous metals. Although the ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides is scattered throughout the bacterial and fungal domains of life, the mechanism and physiological basis for Mn(II) oxidation remains an enigma. Here, we use a combination of compound-specific chemical assays, microspectroscopy, and electron microscopy to show that a common Ascomycete filamentous fungus, Stilbella aciculosa, oxidizes Mn(II) to Mn oxides by producing extracellular superoxide during cell differentiation. The reactive Mn oxide phase birnessite and the reactive oxygen species superoxide and hydrogen peroxide are colocalized at the base of asexual reproductive structures. Mn oxide formation is not observed in the presence of superoxide scavengers (e.g., Cu) and inhibitors of NADPH oxidases (e.g., diphenylene iodonium chloride), enzymes responsible for superoxide production and cell differentiation in fungi. Considering the recent identification of Mn(II) oxidation by NADH oxidase-based superoxide production by a common marine bacterium (Roseobacter sp.), these results introduce a surprising homology between some prokaryotic and eukaryotic organisms in the mechanisms responsible for Mn(II) oxidation, where oxidation appears to be a side reaction of extracellular superoxide production. Given the versatility of superoxide as a redox reactant and the widespread ability of fungi to produce superoxide, this microbial extracellular superoxide production may play a central role in the cycling and bioavailability of metals (e.g., Hg, Fe, Mn) and carbon in natural systems.

Neptunium redox behavior and sorption onto goethite and hematite in the presence of humic acids with different hydroquinone content

International Nuclear Information System (INIS)

Khasanova, A.B.; Kalmykov, St.N.; Perminova, I.V.; Clark, S.B.

2007-01-01

The effect of humic acids (HA) on neptunium redox behavior and sorption onto hematite, α-Fe 2 O 3 , and goethite, α-FeOOH, colloids was established in batch sorption experiments that were carried out in broad pH interval. The sorption isotherms were provided for two samples of HA: commercial sample of leonardite humic acid and its hydroquinone-enriched derivative obtained using formaldehyde copolycondensation. The distribution of Np fitted the distribution of hydroquinone-enriched HA at low pH values in case of both solids while the influence of parent HA on Np sorption was negligible. This is due to Np(V) reduction upon interaction with hydroquinone-enriched derivative having higher reducing capacity compared to the parent HA. The order of components addition was found to be significant for Np retention

Does increased Nitric Oxide production and oxidative stress due to high fat diet affect cardiac function after myocardial infarction?

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Marjan Aghajani

2017-01-01

Full Text Available Background &Objectives: High fat (HF diet by affecting the oxidative stress and nitric oxide (NO production may lead to different effects on function of the heart after myocardial infarction (MI. In the present study we aimed to address the hypothesis that high release of NO by activated macrophages affects LV function after MI.Methods: The animals were randomly divided into four groups comprising each of 10 rats: 1 Sham; 2 MI; 3 Sham+ HF diet; 4 MI+ HF diet. Animals fed with HF diet 30 days before sham and MI surgery. MI was induced by permanent ligation of left anterior descending coronary artery (LAD. Nitric oxide (NO production of peritoneal macrophages, the concentrations of MDA in the heart and the infarct size were measured.Results: Our study indicated that HF has adverse effects on myocardium and it may increase NO production as well as oxidative stress, resulting in augmentation of infarct size.Conclusion: Our results add to our knowledge that HF diet was associated with overproduction of NO by peritoneal macrophages and ROS that lead to development of infarct size and adverse remodeling.

Two-Step Electrochemical Intercalation and Oxidation of Graphite for the Mass Production of Graphene Oxide.

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Cao, Jianyun; He, Pei; Mohammed, Mahdi A; Zhao, Xin; Young, Robert J; Derby, Brian; Kinloch, Ian A; Dryfe, Robert A W

2017-12-06

Conventional chemical oxidation routes for the production of graphene oxide (GO), such as the Hummers' method, suffer from environmental and safety issues due to their use of hazardous and explosive chemicals. These issues are addressed by electrochemical oxidation methods, but such approaches typically have a low yield due to inhomogeneous oxidation. Herein we report a two-step electrochemical intercalation and oxidation approach to produce GO on the large laboratory scale (tens of grams) comprising (1) forming a stage 1 graphite intercalation compound (GIC) in concentrated sulfuric acid and (2) oxidizing and exfoliating the stage 1 GIC in an aqueous solution of 0.1 M ammonium sulfate. This two-step approach leads to GO with a high yield (>70 wt %), good quality (>90%, monolayer), and reasonable oxygen content (17.7 at. %). Moreover, the as-produced GO can be subsequently deeply reduced (3.2 at. % oxygen; C/O ratio 30.2) to yield highly conductive (54 600 S m -1 ) reduced GO. Electrochemical capacitors based on the reduced GO showed an ultrahigh rate capability of up to 10 V s -1 due to this high conductivity.

Frequency analysis of pulmonary tumors occurrence at the rat after exposure to actinide oxide aerosols. Risk factors identification by comparing NpO2 and PuO2

International Nuclear Information System (INIS)

Dudoignon, N.

2001-07-01

Inhalation of actinide oxide particles is potentially one route of contamination of workers, which might induce pulmonary tumours due to aerosol generation during nuclear fuel fabrication process. Dose-effect relationships for lung tumour induction have been well established from epidemiological and experimental studies. However, they do not take into account specific parameters of exposure. The aim of this study was to compare cancer incidence among groups of rats exposed either to NpO 2 or to PuO 2 , two actinide oxides with different specific activity, but with similar aerosol granulometry. During the rat life-span, lung tumour development could occur and the individual follow-up allowed the determination of lung dose at death. Although aerosol particle sizes were similar, the mean number of particles per unit of activity was 2400 times higher for NpO 2 as compared to PuO 2 . This range of variation appeared higher than the variation of specific activity (450). Initial distribution of aerosol was then much more homogeneous for neptunium. In the range of initial lung deposits studied, the only physiological changes observed concerned lung clearance and rat life- span after exposure to the highest levels of Np activity. Pathological examination performed at death showed that carcinogenic power of neptunium was 2 to 3 times higher than that of plutonium. Dose-effect relationships appeared linear and when compared to previous studies, showed an increase of lung cancer risk as the specific activity of the inhaled actinide oxide decreases. The range of risk variation can reach a factor of 10, revealing that the consideration of lung dose at death solely might not be sufficient for an accurate estimate of risk and that specific parameters of exposure, such as nature and granulometry of aerosols, should also be taken into account. (author)

Electrochemistry of actinide on electrochemically reduced graphene oxide: Electrocatalysis of Np(VI)O22+/Np(V)O2+ in nitric acid solution

International Nuclear Information System (INIS)

Ambolikar, Arvind S.; Guin, Saurav K.; Kasar, U.M.; Kamat, J.V.

2015-01-01

Highlights: • First report of aqueous electrochemistry of neptunium on electrochemically reduced graphene oxide (ERGNO). • First report on the electrochemical impedance spectroscopy of Np (VI) O 2 2+ /Np (V) O 2 + . • The electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple improves on ERGNO compared to GC. • ERGNO shows higher sensitivity for the determination of Np compared to bare GC electrode. • The efficiency of detection of Np by ERGNO is improved by virtue of the electrocatalysis. - Abstract: Driven by the academic interest, we have studied the aqueous electrochemistry of neptunium (Np) in 1 M nitric acid solution on the electrochemically reduced graphene oxide (ERGNO) modified glassy carbon (GC) electrode. Similar to our previous experiences on the electrocatalytic action of ERGNO on the electrochemistry of uranium(VI)/uranium(IV) and plutonium(IV)/plutonium(III) redox couples, the present study confirms the robust electrocatalytic ability of ERGNO for the redox reaction of Np (VI) O 2 2+ /Np (V) O 2 + in acidic solution even at high anodic working potentials. The extent of the electrochemical reversibility of Np (VI) O 2 2+ /Np (V) O 2 + redox couple increases on ERGNO compared to the bare GC electrode. For the first time, the electron transfer reaction of Np (VI) O 2 2+ /Np (V) O 2 + redox couple is investigated by electrochemical impedance spectroscopy. The improved sensitivity as well as the lower limit of detection of Np by anodic square wave voltammetry on ERGNO compared to bare GC opens up the application of ERGNO in the nuclear science and technology.

Evaluating four mathematical models for nitrous oxide production by autotrophic ammonia-oxidizing bacteria.

Science.gov (United States)

Ni, Bing-Jie; Yuan, Zhiguo; Chandran, Kartik; Vanrolleghem, Peter A; Murthy, Sudhir

2013-01-01

There is increasing evidence showing that ammonia-oxidizing bacteria (AOB) are major contributors to N(2)O emissions from wastewater treatment plants (WWTPs). Although the fundamental metabolic pathways for N(2)O production by AOB are now coming to light, the mechanisms responsible for N(2)O production by AOB in WWTP are not fully understood. Mathematical modeling provides a means for testing hypotheses related to mechanisms and triggers for N(2)O emissions in WWTP, and can then also become a tool to support the development of mitigation strategies. This study examined the ability of four mathematical model structures to describe two distinct mechanisms of N(2)O production by AOB. The production mechanisms evaluated are (1) N(2)O as the final product of nitrifier denitrification with NO(2)- as the terminal electron acceptor and (2) N(2)O as a byproduct of incomplete oxidation of hydroxylamine (NH(2)OH) to NO(2)-. The four models were compared based on their ability to predict N(2)O dynamics observed in three mixed culture studies. Short-term batch experimental data were employed to examine model assumptions related to the effects of (1) NH4+ concentration variations, (2) dissolved oxygen (DO) variations, (3) NO(2)- accumulations and (4) NH(2OH as an externally provided substrate. The modeling results demonstrate that all these models can generally describe the NH4+, NO(2)-, and NO(3)- data. However, none of these models were able to reproduce all measured N(2)O data. The results suggest that both the denitrification and NH(2)OH pathways may be involved in N(2)O production and could be kinetically linked by a competition for intracellular reducing equivalents. A unified model capturing both mechanisms and their potential interactions needs to be developed with consideration of physiological complexity. Copyright © 2012 Wiley Periodicals, Inc.

Catalytic cracking of vegetable oil with metal oxides for biofuel production

International Nuclear Information System (INIS)

Yigezu, Zerihun Demrew; Muthukumar, Karuppan

2014-01-01

Highlights: • Biofuel was synthesized from vegetable oil by catalytic cracking. • Performance of six different metal catalysts was studied. • Influence of temperature and reaction time on the process was evaluated. • Methyl and ethyl esters are the major components of the biofuel synthesized. - Abstract: This study presents the utilization of metal oxides for the biofuel production from vegetable oil. The physical and chemical properties of the diesel-like products obtained, and the influence of reaction variables on the product distribution were investigated. Six different metal oxides (Co 3 O 4 , KOH, MoO 3 , NiO, V 2 O 5 , and ZnO) were employed as catalysts and the results indicated that the metal oxides are suitable for catalyzing the conversion of oil into organic liquid products (OLPs). The maximum conversion (87.6%) was obtained with V 2 O 5 at 320 °C in 40 min whereas a minimum conversion (55.1%) was obtained with MoO 3 at 390 °C in 30 min. The physical characteristics of the product obtained (density, specific gravity, higher heat value, flash point and kinematic viscosity), were in line with ASTM D6751 (B100) standards. The hydrocarbons majorly present in the product were found to be methyl and ethyl esters. Furthermore, OLPs obtained were distilled and separated into four components. The amount of light hydrocarbons, gasoline, kerosene and heavy oil like components obtained were 18.73%, 33.62%, 24.91% and 90.93%, respectively

Mo-V-Te-Nb oxides as catalysts for ethene production by oxidative dehydrogenation of ethane

Energy Technology Data Exchange (ETDEWEB)

Hartmann, D. [Technische Universitaet Muenchen, Garching (Germany). Dept. of Chemistry and Catalysis Research Center; Meiswinkel, A.; Thaller, C.; Bock, M.; Alvarado, L. [Linde AG, Pullach (Germany)

2013-11-01

The availability of ethane in shale gas, as well as the interest in valorising previously underutilized carbon feedstocks, makes the oxidative dehydrogenation (ODH) of ethane an attractive alternative to the industrially established processes for production of ethylene. Mo-V-Te-Nb mixed oxide has been chosen as catalyst for the ODH reaction in view of its outstanding ability to activate alkane molecules. Catalytic test results showed that this type of catalyst can selectively oxidize ethane to ethene at moderate temperatures (350-400 C) with minor production of CO{sub x}. The catalytic performance of Mo-V-Te-Nb mixed-oxide is mainly attributable to the crystalline phase 'M1'. Rietveld analysis of the X-Ray diffractograms allowed us to quantify the amount of MoVTeNb oxide that has crystallized as M1. In this way, it was possible to find a linear correlation of the reaction rate with the abundance of M1 in the solid. Therefore, it is clear that for improving the efficiency of MoVTeNb oxide in ODH, the amount of M1 in the catalyst should be maximized. With this purpose, several MoVTeNb oxides were subject to different thermal treatments prior to the catalytic test. Structural changes in the catalyst were monitored by in-situ XRD technique. Under oxidative atmosphere, it was observed a recrystallization of M2 and possibly, amorphous oxide, into M1 phase, leading to correspondingly more active and selective catalysts (selectivities above 95 % for ethane conversions up to 40 % under industrially relevant conditions). The active site of M1 involves V species, likely with redox properties enhanced by the proximity of Mo and Te species, while the function of the crystalline structure itself is to provide the spatial configuration that allows interaction between these species. However, ethene formation rate was observed to be independent of the V content of the samples. The vanadium species exposed at the surface were studied by LEIS and by IR spectroscopy of CO

Oxidized lipids enhance RANKL production by T lymphocytes: implications for lipid-induced bone loss.

Science.gov (United States)

Graham, Lucia S; Parhami, Farhad; Tintut, Yin; Kitchen, Christina M R; Demer, Linda L; Effros, Rita B

2009-11-01

Osteoporosis is a systemic disease that is associated with increased morbidity, mortality and health care costs. Whereas osteoclasts and osteoblasts are the main regulators of bone homeostasis, recent studies underscore a key role for the immune system, particularly via activation-induced T lymphocyte production of receptor activator of NFkappaB ligand (RANKL). Well-documented as a mediator of T lymphocyte/dendritic cell interactions, RANKL also stimulates the maturation and activation of bone-resorbing osteoclasts. Given that lipid oxidation products mediate inflammatory and metabolic disorders such as osteoporosis and atherosclerosis, and since oxidized lipids affect several T lymphocyte functions, we hypothesized that RANKL production might also be subject to modulation by oxidized lipids. Here, we show that short term exposure of both unstimulated and activated human T lymphocytes to minimally oxidized low density lipoprotein (LDL), but not native LDL, significantly enhances RANKL production and promotes expression of the lectin-like oxidized LDL receptor-1 (LOX-1). The effect, which is also observed with 8-iso-Prostaglandin E2, an inflammatory isoprostane produced by lipid peroxidation, is mediated via the NFkappaB pathway, and involves increased RANKL mRNA expression. The link between oxidized lipids and T lymphocytes is further reinforced by analysis of hyperlipidemic mice, in which bone loss is associated with increased RANKL mRNA in T lymphocytes and elevated RANKL serum levels. Our results suggest a novel pathway by which T lymphocytes contribute to bone changes, namely, via oxidized lipid enhancement of RANKL production. These findings may help elucidate clinical associations between cardiovascular disease and decreased bone mass, and may also lead to new immune-based approaches to osteoporosis.

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

Directory of Open Access Journals (Sweden)

Dong Chang

2013-01-01

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

Requirement of argininosuccinate lyase for systemic nitric oxide production.

Science.gov (United States)

Erez, Ayelet; Nagamani, Sandesh C S; Shchelochkov, Oleg A; Premkumar, Muralidhar H; Campeau, Philippe M; Chen, Yuqing; Garg, Harsha K; Li, Li; Mian, Asad; Bertin, Terry K; Black, Jennifer O; Zeng, Heng; Tang, Yaoping; Reddy, Anilkumar K; Summar, Marshall; O'Brien, William E; Harrison, David G; Mitch, William E; Marini, Juan C; Aschner, Judy L; Bryan, Nathan S; Lee, Brendan

2011-11-13

Nitric oxide (NO) is crucial in diverse physiological and pathological processes. We show that a hypomorphic mouse model of argininosuccinate lyase (encoded by Asl) deficiency has a distinct phenotype of multiorgan dysfunction and NO deficiency. Loss of Asl in both humans and mice leads to reduced NO synthesis, owing to both decreased endogenous arginine synthesis and an impaired ability to use extracellular arginine for NO production. Administration of nitrite, which can be converted into NO in vivo, rescued the manifestations of NO deficiency in hypomorphic Asl mice, and a nitric oxide synthase (NOS)-independent NO donor restored NO-dependent vascular reactivity in humans with ASL deficiency. Mechanistic studies showed that ASL has a structural function in addition to its catalytic activity, by which it contributes to the formation of a multiprotein complex required for NO production. Our data demonstrate a previously unappreciated role for ASL in NOS function and NO homeostasis. Hence, ASL may serve as a target for manipulating NO production in experimental models, as well as for the treatment of NO-related diseases.

Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

NARCIS (Netherlands)

Abilev, M.; Kenessov, B.N.; Batyrbekova, S.; Grotenhuis, J.T.C.

2015-01-01

Oxidation of unsymmetrical dimethylhydrazine (UDMH) during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of

The Geochemical Behaviour of Tc, Np, and Pu in Spent Nuclear Fuel in an Oxidizing Environment

Energy Technology Data Exchange (ETDEWEB)

Buck, Edgar C.; Hanson, Brady D.; McNamara, Bruce K.; R. Giere and P. Stille

2004-10-01

Studies at the Nopal and Shinkolowbwe uranium deposits show that the primary uraninite (UO2) altered to a suite of secondary uranyl minerals similar to those observed in corrosion tests with uranium oxide . Although the Nopal I deposit tells us something about the possible fate of uranium, it tells us little about the likely fate of the important long-lived radionuclides; iodine (129I), cesium (135Cs), technetium (99Tc), neptunium (237Np), and plutonium (239Pu). Most performance assessment (PA) models, assume conservatively, that as the UO2 matrix corrodes, the key radionuclides (129I, 99Tc, 237Np, and 239Pu) will be released congruently. In so doing, these PA models force increased reliance on human engineered barriers.

The Geochemical Behavior of Tc, Np, and Pu in Spent Nuclear Fuel in an Oxidizing Environment

International Nuclear Information System (INIS)

Buck, Edgar C.; Hanson, Brady D.; McNamara, Bruce K.; R. Giere; P. Stille

2004-01-01

Studies at the Nopal and Shinkolowbwe uranium deposits show that the primary uraninite (UO2) altered to a suite of secondary uranyl minerals similar to those observed in corrosion tests with uranium oxide . Although the Nopal I deposit tells us something about the possible fate of uranium, it tells us little about the likely fate of the important long-lived radionuclides; iodine (129I), cesium (135Cs), technetium (99Tc), neptunium (237Np), and plutonium (239Pu). Most performance assessment (PA) models, assume conservatively, that as the UO2 matrix corrodes, the key radionuclides (129I, 99Tc, 237Np, and 239Pu) will be released congruently. In so doing, these PA models force increased reliance on human engineered barriers

Microarc Oxidation of Product Surfaces without Using a Bath

Directory of Open Access Journals (Sweden)

V. K. Shatalov

2015-01-01

Full Text Available While using an electrochemical method to cover the large-sized work-pieces, units, and products up to 6 м3 by protective coating, there is a certain difficulty to apply traditional anodizing techniques in a plating vat, and it is necessary to find various processing techniques.To use the existing micro-arc oxide coating (MOC methods for work-pieces of various forms and sizes in a plating vat is complicated in case it is required to provide oxide layers in separate places rather than over entire surface of a work-piece. The challenge is to treat flat surfaces in various directions, external and internal surfaces of rotation bodies, profiled surfaces, intersections, closed and through holes, pipes, as well as spline and thread openings for ensuring anti-seize properties in individual or small-scale production to meet technical requirements and operational properties of products.A design of tools to provide MOC-process of all possible surfaces of various engineering box-type products depends on many factors and can be considerably different even when processing the surfaces of the same forms. An attachment to be used is fixed directly on a large-sized design (a work-piece, a product or fastened in the special tool. The features of technological process, design shape, and arrangement of the processed surfaces define a fastening method of the attachment. Therefore it is necessary to pay much attention to a choice of the processing pattern and a design of tools.The Kaluga-branch of Bauman Moscow State Technical University is an original proposer of methods to form MOC-coatings on the separate surfaces of large-sized work-pieces using the moved and stationary electrodes to solve the above listed tasks.The following results of work will have an impact on development of the offered processing methods and their early implementation in real production:1. To provide oxide coatings on the surfaces of large-sized products or assemblies in a single or small

Production and consumption of nitric oxide by three methanotrophic bacteria.

Science.gov (United States)

Ren, T; Roy, R; Knowles, R

2000-09-01

We studied nitrogen oxide production and consumption by methanotrophs Methylobacter luteus (group I), Methylosinus trichosporium OB3b (group II), and an isolate from a hardwood swamp soil, here identified by 16S ribosomal DNA sequencing as Methylobacter sp. strain T20 (group I). All could consume nitric oxide (nitrogen monoxide, NO), and produce small amounts of nitrous oxide (N(2)O). Only Methylobacter strain T20 produced large amounts of NO (>250 parts per million by volume [ppmv] in the headspace) at specific activities of up to 2.0 x 10(-17) mol of NO cell(-1) day(-1), mostly after a culture became O(2) limited. Production of NO by strain T20 occurred mostly in nitrate-containing medium under anaerobic or nearly anaerobic conditions, was inhibited by chlorate, tungstate, and O(2), and required CH(4). Denitrification (methanol-supported N(2)O production from nitrate in the presence of acetylene) could not be detected and thus did not appear to be involved in the production of NO. Furthermore, cd(1) and Cu nitrite reductases, NO reductase, and N(2)O reductase could not be detected by PCR amplification of the nirS, nirK, norB, and nosZ genes, respectively. M. luteus and M. trichosporium produced some NO in ammonium-containing medium under aerobic conditions, likely as a result of methanotrophic nitrification and chemical decomposition of nitrite. For Methylobacter strain T20, arginine did not stimulate NO production under aerobiosis, suggesting that NO synthase was not involved. We conclude that strain T20 causes assimilatory reduction of nitrate to nitrite, which then decomposes chemically to NO. The production of NO by methanotrophs such as Methylobacter strain T20 could be of ecological significance in habitats near aerobic-anaerobic interfaces where fluctuating O(2) and nitrate availability occur.

Denitrification: an important pathway for nitrous oxide production in tropical mangrove sediments (Goa, India).

Science.gov (United States)

Fernandes, Sheryl Oliveira; Bharathi, P A Loka; Bonin, Patricia C; Michotey, Valérie D

2010-01-01

Net nitrous oxide production and denitrification activity were measured in two mangrove ecosystems of Goa, India. The relatively pristine site Tuvem was compared to Divar, which is prone to high nutrient input. Stratified sampling at 2-cm intervals within the 0- to 10-cm depth range showed that N2O production at both the locations decreased with depth. Elevated denitrification activity at Divar resulted in maximum production of up to 1.95 nmol N2O-N g(-1) h(-1) at 2 to 4 cm, which was three times higher than at Tuvem. Detailed investigations to understand the major pathway contributing to N2O production performed at Tuvem showed that incomplete denitrification was responsible for up to 43 to 93% of N2O production. Nitrous oxide production rates closely correlated to nitrite concentration (n = 15; r = -0.47; p production. Nitrous oxide production through nitrification was below detection, affirming that denitrification is the major pathway responsible for production of the greenhouse gas. Net N2O production in these mangrove systems are comparatively higher than those reported from other natural estuarine sediments and therefore warrant mitigation measures.

Low nitrous oxide production through nitrifier-denitrification in intermittent-feed high-rate nitritation reactors.

Science.gov (United States)

Su, Qingxian; Ma, Chun; Domingo-Félez, Carlos; Kiil, Anne Sofie; Thamdrup, Bo; Jensen, Marlene Mark; Smets, Barth F

2017-10-15

Nitrous oxide (N 2 O) production from autotrophic nitrogen conversion processes, especially nitritation systems, can be significant, requires understanding and calls for mitigation. In this study, the rates and pathways of N 2 O production were quantified in two lab-scale sequencing batch reactors operated with intermittent feeding and demonstrating long-term and high-rate nitritation. The resulting reactor biomass was highly enriched in ammonia-oxidizing bacteria, and converted ∼93 ± 14% of the oxidized ammonium to nitrite. The low DO set-point combined with intermittent feeding was sufficient to maintain high nitritation efficiency and high nitritation rates at 20-26 °C over a period of ∼300 days. Even at the high nitritation efficiencies, net N 2 O production was low (∼2% of the oxidized ammonium). Net N 2 O production rates transiently increased with a rise in pH after each feeding, suggesting a potential effect of pH on N 2 O production. In situ application of 15 N labeled substrates revealed nitrifier denitrification as the dominant pathway of N 2 O production. Our study highlights operational conditions that minimize N 2 O emission from two-stage autotrophic nitrogen removal systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Oxidation products are increased in patients affected by non-segmental generalized vitiligo.

Science.gov (United States)

Vaccaro, Mario; Bagnato, Gianluca; Cristani, Mariateresa; Borgia, Francesco; Spatari, Giovanna; Tigano, Valeria; Saja, Antonina; Guarneri, Fabrizio; Cannavò, Serafinella P; Gangemi, Sebastiano

2017-08-01

Several lines of evidence support the relevance of reactive oxygen species (ROS) in vitiligo, but the exact role of glycation and oxidation of macromolecules needs to be better addressed. To investigate the involvement of advanced oxidation protein products (AOPPs) and advanced glycation end-products (AGEs), we performed a case-control association study by spectrofluorimetry and spectrophotometry, in 47 patients with non-segmental generalized vitiligo and 47 age- and sex-matched controls. Significantly higher levels of both AOPPs (p vitiligo patients compared to healthy controls. In vitiligo patients, AGEs and AOPPs serum levels were directly associated with extension, duration of vitiligo, and disease activity. ROS, and in particular AGEs and AOPPs, could represent one of the main biomarkers to assess the onset and progression of vitiligo, due to the potential role as direct inducers of cell damage and also as autoimmunity triggers. Further longitudinal studies involving larger cohorts of patients are required to elucidate the role of oxidation products in the pathogenesis of vitiligo.

Nitrous Oxide Production in a Granule-based Partial Nitritation Reactor: A Model-based Evaluation.

Science.gov (United States)

Peng, Lai; Sun, Jing; Liu, Yiwen; Dai, Xiaohu; Ni, Bing-Jie

2017-04-03

Sustainable wastewater treatment has been attracting increasing attentions over the past decades. However, the production of nitrous oxide (N 2 O), a potent GHG, from the energy-efficient granule-based autotrophic nitrogen removal is largely unknown. This study applied a previously established N 2 O model, which incorporated two N 2 O production pathways by ammonia-oxidizing bacteria (AOB) (AOB denitrification and the hydroxylamine (NH 2 OH) oxidation). The two-pathway model was used to describe N 2 O production from a granule-based partial nitritation (PN) reactor and provide insights into the N 2 O distribution inside granules. The model was evaluated by comparing simulation results with N 2 O monitoring profiles as well as isotopic measurement data from the PN reactor. The model demonstrated its good predictive ability against N 2 O dynamics and provided useful information about the shift of N 2 O production pathways inside granules for the first time. The simulation results indicated that the increase of oxygen concentration and granule size would significantly enhance N 2 O production. The results further revealed a linear relationship between N 2 O production and ammonia oxidation rate (AOR) (R 2  = 0.99) under the conditions of varying oxygen levels and granule diameters, suggesting that bulk oxygen and granule size may exert an indirect effect on N 2 O production by causing a change in AOR.

Simple proxies for estimating the concentrations of monoterpenes and their oxidation products at a boreal forest site

Directory of Open Access Journals (Sweden)

J. Kontkanen

2016-10-01

Full Text Available The oxidation products of monoterpenes likely have a crucial role in the formation and growth of aerosol particles in boreal forests. However, the continuous measurements of monoterpene concentrations are usually not available on decadal timescales, and the direct measurements of the concentrations of monoterpene oxidation product have so far been scarce. In this study we developed proxies for the concentrations of monoterpenes and their oxidation products at a boreal forest site in Hyytiälä, southern Finland. For deriving the proxies we used the monoterpene concentration measured with a proton transfer reaction mass spectrometer (PTR-MS during 2006–2013. Our proxies for the monoterpene concentration take into account the temperature-controlled emissions from the forest ecosystem, the dilution caused by the mixing within the boundary layer and different oxidation processes. All the versions of our proxies captured the seasonal variation of the monoterpene concentration, the typical proxy-to-measurements ratios being between 0.8 and 1.3 in summer and between 0.6 and 2.6 in winter. In addition, the proxies were able to describe the diurnal variation of the monoterpene concentration rather well, especially in summer months. By utilizing one of the proxies, we calculated the concentration of oxidation products of monoterpenes by considering their production in the oxidation and their loss due to condensation on aerosol particles. The concentration of oxidation products was found to have a clear seasonal cycle, with a maximum in summer and a minimum in winter. The concentration of oxidation products was lowest in the morning or around noon and highest in the evening. In the future, our proxies for the monoterpene concentration and their oxidation products can be used, for example, in the analysis of new particle formation and growth in boreal environments.

Radionuclide sorption kinetics and column sorption studies with Columbia River basalts

International Nuclear Information System (INIS)

Barney, G.S.

1983-09-01

The kinetics of radionuclide sorption and desorption reactions in basalt-groundwater systems were evaluated at 60 degrees C using a batch equilibration method. It was found that many sorption reactions on surfaces of fresh (unaltered) basalt from the Umtanum and Cohassett flows are slow. Some reactions require more than 50 days to reach a steady state. Sorption of neptunium and uranium in oxidizing (air saturated) groundwater appears to be controlled by slow reduction of these elements by the basalt surfaces. The resulting lower oxidation states are more strongly sorbed. Technetium and selenium, which are anionic under oxidizing conditions, are not measurably sorbed on fresh basalt surfaces, but are slightly sorbed on the altered surfaces of flow top basalt. Under reducing conditions, where the groundwater contains dilute hydrazine, sorption is faster for neptunium, uranium, technetium, selenium, and lead. Plutonium sorption rates were not affected by the groundwater Eh. It was shown that radium was precipitated rather than sorbed under the conditions of these experiments. Umtanum flow top material sorbed radionuclides much faster than fresh basalt surfaces due to its greater surface area and cation exchange capacity. Desorption rates for plutonium, uranium, neptunium, technetium, and selenium were generally much less than sorption rates (especially for reducing conditions). These radionuclides are irreversibly sorbed on the basalts. 25 refs., 20 figs., 19 tabs

Aqueous-phase oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Product identification from methyl jasmonate and methyl salicylate oxidation

Science.gov (United States)

Hansel, Amie K.; Ehrenhauser, Franz S.; Richards-Henderson, Nicole K.; Anastasio, Cort; Valsaraj, Kalliat T.

2015-02-01

Green leaf volatiles (GLVs) are a group of biogenic volatile organic compounds (BVOCs) released into the atmosphere by vegetation. BVOCs produce secondary organic aerosol (SOA) via gas-phase reactions, but little is known of their aqueous-phase oxidation as a source of SOA. GLVs can partition into atmospheric water phases, e.g., fog, mist, dew or rain, and be oxidized by hydroxyl radicals (˙OH). These reactions in the liquid phase also lead to products that have higher molecular weights, increased polarity, and lower vapor pressures, ultimately forming SOA after evaporation of the droplet. To examine this process, we investigated the aqueous, ˙OH-mediated oxidation of methyl jasmonate (MeJa) and methyl salicylate (MeSa), two GLVs that produce aqueous-phase SOA. High performance liquid chromatography/electrospray ionization mass spectrometry (HPLC-ESI-MS) was used to monitor product formation. The oxidation products identified exhibit higher molecular mass than their parent GLV due to either dimerization or the addition of oxygen and hydroxyl functional groups. The proposed structures of potential products are based on mechanistic considerations combined with the HPLC/ESI-MS data. Based on the structures, the vapor pressure and the Henry's law constant were estimated with multiple methods (SPARC, SIMPOL, MPBPVP, Bond and Group Estimations). The estimated vapor pressures of the products identified are significantly (up to 7 orders of magnitude) lower than those of the associated parent compounds, and therefore, the GLV oxidation products may remain as SOA after evaporation of the water droplet. The contribution of the identified oxidation products to SOA formation is estimated based on measured HPLC-ESI/MS responses relative to previous aqueous SOA mass yield measurements.

Experimental and simulation analysis of hydrogen production by partial oxidation of methanol

Energy Technology Data Exchange (ETDEWEB)

Sikander, U. [National Univ. of Science and Technology, Islamabad (Pakistan)

2014-10-15

Partial oxidation of methanol is the only self-sustaining process for onboard production of hydrogen. For this a fixed bed catalytic reactor is designed, based on heterogeneous catalytic reaction. To develop an optimized process, simulation is carried out using ASPEN HYSYS v 7.1. Reaction kinetics is developed on the basis of Langmuir Hinshel wood model. 45:55:5 of CuO: ZnO: Al/sub 2/O/sub 3/ is used as a catalyst. Simulation results are studied in detail to understand the phenomenon of partial oxidation of methanol inside the reactor. An experimental rig is developed for hydrogen production through partial oxidation of methanol. Results obtained from process simulation and experimental work; are compared with each other. (author)

Improving Technology And Setting-Up A Production Line For High Quality Zinc Oxide (99.5%) With A Capacity Of 150 Ton/Year By Reduction-Oxidation Process

International Nuclear Information System (INIS)

Pham Minh Tuan; Tran The Dinh; Tran Ngoc Vuong; Tuong Duy Nhan; Tran Trung Son; Le Huu Thiep; Nguyen Trung Dung; Le Thi Hong; Luong Manh Hung; Bui Huy Cuong

2014-01-01

Zinc oxide is used not only for the rubber industry, but also in many other industries such as pigments, ceramics, cosmetics etc. On the basis of references on international scientific researches and practical activities for the production of zinc oxide in our country, we have carried out additional research and testing to establish a zinc oxide production line for preparation of high quality (99.5%) product by treating the industrial zinc containing waste to obtain required composition materials [Zn] >50%; [Pb] < 0.3%; [Cl]/[PbO] < 0.2 for reduction-oxidation processes using reverberatory furnace. (author)

Influence of corium oxidation on fission product release from molten pool

Energy Technology Data Exchange (ETDEWEB)

Bechta, S.V., E-mail: bechta@sbor.spb.s [Alexandrov Scientific-Research Institute of Technology (NITI), Sosnovy Bor (Russian Federation); Krushinov, E.V.; Vitol, S.A.; Khabensky, V.B.; Kotova, S.Yu.; Sulatsky, A.A. [Alexandrov Scientific-Research Institute of Technology (NITI), Sosnovy Bor (Russian Federation); Gusarov, V.V.; Almyashev, V.I. [Grebenschikov Institute of Silicate Chemistry of the Russian Academy of Sciences (ISC RAS), St. Petersburg (Russian Federation); Ducros, G.; Journeau, C. [CEA, DEN, Cadarache, F-13108 St. Paul lez Durance (France); Bottomley, D. [Joint Research Centre Institut fuer Transurane (ITU), Karlsruhe (Germany); Clement, B. [Institut de Radioprotection et Surete Nucleaire (IRSN), St. Paul lez Durance (France); Herranz, L. [CIEMAT, Madrid (Spain); Guentay, S. [PSI, Wuerenlingen (Switzerland); Trambauer, K. [GRS, Muenchen (Germany); Auvinen, A. [VTT, Espoo (Finland); Bezlepkin, V.V. [SPbAEP, St. Petersburg (Russian Federation)

2010-05-15

Qualitative and quantitative determination of the release of low-volatile fission products and core materials from molten oxidic corium was investigated in the EVAN project under the auspices of ISTC. The experiments carried out in a cold crucible with induction heating and RASPLAV test facility are described. The results are discussed in terms of reactor application; in particular, pool configuration, melt oxidation kinetics, critical influence of melt surface temperature and oxidation index on the fission product release rate, aerosol particle composition and size distribution. The relevance of measured high release of Sr from the molten pool for the reactor application is highlighted. Comparisons of the experimental data with those from the COLIMA CA-U3 test and the VERCORS tests, as well as with predictions from IVTANTHERMO and GEMINI/NUCLEA codes are made. Recommendations for further investigations are proposed following the major observations and discussions.

A model for the release of low-volatility fission products in oxidizing conditions

International Nuclear Information System (INIS)

Cox, D.S.; Hunt, C.E.L.; Liu, Z.; Keller, N.A.; Barrand, R.D.; O'Connor, R.F.

1991-07-01

A thermodynamic and kinetic model has been developed for calculating low-volatility fission-product releases from UO 2 at high temperatures in oxidizing conditions. Volatilization of the UO 2 matrix is assumed to be the rate controlling process. Oxidation kinetics of the UO 2 are modelled by either interfacial rate control, gas phase oxidant transport control, or solid-state diffusion of oxygen. The vapour pressure of UO 3 in equilibrium with the oxidizing fuel is calculated from thermodynamic data, and volatilization rates are determined using a model for forced convective mass transport. Low-volatility fission-product releases are calculated from the volume of vapourized fuel. Model calculations are conservative compared to experimental data for Zr, La, Ce and Nb fission-product releases from irradiated UO 2 exposed to air at 1973-2350 K. The implications of this conservatism are discussed in terms of possible rate control by processes other than convective mass transport of UO 3 . Coefficients for effective surface area (based on experimental data) and for heterogeneous rate controlling reaction kinetics are introduced to facilitate agreement between calculations and the experimental data.

Amorphous semiconducting and conducting transparent metal oxide thin films and production thereof

Science.gov (United States)

Perkins, John; Van Hest, Marinus Franciscus Antonius Maria; Ginley, David; Taylor, Matthew; Neuman, George A.; Luten, Henry A.; Forgette, Jeffrey A.; Anderson, John S.

2010-07-13

Metal oxide thin films and production thereof are disclosed. An exemplary method of producing a metal oxide thin film may comprise introducing at least two metallic elements and oxygen into a process chamber to form a metal oxide. The method may also comprise depositing the metal oxide on a substrate in the process chamber. The method may also comprise simultaneously controlling a ratio of the at least two metallic elements and a stoichiometry of the oxygen during deposition. Exemplary amorphous metal oxide thin films produced according to the methods herein may exhibit highly transparent properties, highly conductive properties, and/or other opto-electronic properties.

Production of aromas and fragrances through microbial oxidation of monoterpenes

Directory of Open Access Journals (Sweden)

H. F. Rozenbaum

2006-09-01

Full Text Available Aromas and fragrances can be obtained through the microbial oxidation of monoterpenes. Many microorganisms can be used to carry out extremely specific conversions using substrates of low commercial value. However, for many species, these substrates are highly toxic, consequently inhibiting their metabolism. In this work, the conversion ability of Aspergillus niger IOC-3913 for terpenic compounds was examined. This species was preselected because of its high resistance to toxic monoterpenic substrates. Though it has been grown in media containing R-limonene (one of the cheapest monoterpenic hydrocarbons, which is widely available on the market, the species has not shown the ability to metabolize it, since biotransformation products were not detected in high resolution gas chromatography analyses. For this reason, other monoterpenes (alpha-pinene, beta-pinene and camphor were used as substrates. These compounds were shown to be metabolized by the selected strain, producing oxidized compounds. Four reaction systems were used: a biotransformation in a liquid medium with cells in growth b with pre-grown cultures c with cells immobilized in a synthetic polymer network and d in a solid medium to which the substrate was added via the gas phase. The main biotransformation products were found in all the reaction systems, although the adoption of previously cultivated cells seemed to favor biotransformation. Cell immobilization seemed to be a feasible strategy for alleviating the toxic effect of the substrate. Through mass spectrometry it was possible to identify verbenone and alpha-terpineol as the biotransformation products of alpha-pinene and beta-pinene, respectively. The structures of the other oxidation products are described.

Controlling nitrous oxide emissions from grassland livestock production systems

NARCIS (Netherlands)

Oenema, O.; Gebauer, G.; Rodriguez, M.; Sapek, A.; Jarvis, S.C.; Corré, W.J.; Yamulki, S.

1998-01-01

There is growing awareness that grassland livestock production systems are major sources of nitrous oxide (N2O). Controlling these emissions requires a thorough understanding of all sources and controlling factors at the farm level. This paper examines the various controlling factors and proposes

Size characterization of metal oxide nanoparticles in commercial sunscreen products

Science.gov (United States)

Bairi, Venu Gopal; Lim, Jin-Hee; Fong, Andrew; Linder, Sean W.

2017-07-01

There is an increase in the usage of engineered metal oxide (TiO2 and ZnO) nanoparticles in commercial sunscreens due to their pleasing esthetics and greater sun protection efficiency. A number of studies have been done concerning the safety of nanoparticles in sunscreen products. In order to do the safety assessment, it is pertinent to develop novel analytical techniques to analyze these nanoparticles in commercial sunscreens. This study is focused on developing analytical techniques that can efficiently determine particle size of metal oxides present in the commercial sunscreens. To isolate the mineral UV filters from the organic matrices, specific procedures such as solvent extraction were identified. In addition, several solvents (hexane, chloroform, dichloromethane, and tetrahydrofuran) have been investigated. The solvent extraction using tetrahydrofuran worked well for all the samples investigated. The isolated nanoparticles were characterized by using several different techniques such as transmission electron microscopy, scanning electron microscopy, dynamic light scattering, differential centrifugal sedimentation, and x-ray diffraction. Elemental analysis mapping studies were performed to obtain individual chemical and morphological identities of the nanoparticles. Results from the electron microscopy techniques were compared against the bulk particle sizing techniques. All of the sunscreen products tested in this study were found to contain nanosized (≤100 nm) metal oxide particles with varied shapes and aspect ratios, and four among the 11 products were showed to have anatase TiO2.

Enhanced 15-HPETE production during oxidant stress induces apoptosis of endothelial cells.

Science.gov (United States)

Sordillo, Lorraine M; Weaver, James A; Cao, Yu-Zhang; Corl, Chris; Sylte, Matt J; Mullarky, Isis K

2005-05-01

Oxidant stress plays an important role in the etiology of vascular diseases by increasing rates of endothelial cell apoptosis, but few data exist on the mechanisms involved. Using a unique model of oxidative stress based on selenium deficiency (-Se), the effects of altered eicosanoid production on bovine aortic endothelial cells (BAEC) apoptosis was evaluated. Oxidant stress significantly increased the immediate oxygenation product of arachidonic acid metabolized by the 15-lipoxygenase pathway, 15-hydroxyperoxyeicosatetraenoic acid (15-HPETE). Treatment of -Se BAEC with TNFalpha/cyclohexamide (CHX) exhibited elevated levels of apoptosis, which was significantly reduced by the addition of a specific 15-lipoxygenase inhibitor PD146176. Furthermore, the addition of 15-HPETE to PD146176-treated BAEC, partially restored TNF/CHX-induced apoptosis. Increased exposure to 15-HPETE induced apoptosis, as determined by internucleosomal DNA fragmentation, chromatin condensation, caspase-3 activation, and caspase-9 activation, which suggests mitochondrial dysfunction. The expression of Bcl-2 protein also was decreased in -Se BAEC. Addition of a caspase-9 inhibitor (LEHD-fmk) completely blocked 15-HPETE-induced chromatin condensation in -Se BAEC, suggesting that 15-HPETE-induced apoptosis is caspase-9 dependent. Increased apoptosis of BAEC as a result of oxidant stress and subsequent production of 15-HPETE may play a critical role in a variety of inflammatory based diseases.

Electrochemistry-High Resolution Mass Spectrometry to Study Oxidation Products of Trimethoprim

Directory of Open Access Journals (Sweden)

Marc-André Lecours

2018-01-01

Full Text Available The study of the fate of emerging organic contaminants (EOCs, especially the identification of transformation products, after water treatment or in the aquatic environment, is a topic of growing interest. In recent years, electrochemistry coupled to mass spectrometry has attracted a lot of attention as an alternative technique to investigate oxidation metabolites of organic compounds. The present study used different electrochemical approaches, such as cyclic voltammetry, electrolysis, electro-assisted Fenton reaction coupled offline to high resolution mass spectrometry and thin-layer flow cell coupled online to high resolution mass spectrometry, to study oxidation products of the anti-infective trimethoprim, a contaminant of emerging concern frequently reported in wastewaters and surface waters. Results showed that mono- and di-hydroxylated derivatives of trimethoprim were generated in electrochemically and possibly tri-hydroxylated derivatives as well. Those compounds have been previously reported as mammalian and bacterial metabolites as well as transformation products of advance oxidation processes applied to waters containing trimethoprim. Therefore, this study confirmed that electrochemical techniques are relevant not only to mimic specific biotransformation reactions of organic contaminants, as it has been suggested previously, but also to study the oxidation reactions of organic contaminants of interest in water treatment. The key role that redox reactions play in the environment make electrochemistry-high resolution mass spectrometry a sensitive and simple technique to improve our understanding of the fate of organic contaminants in the environment.

Global oceanic production of nitrous oxide

Science.gov (United States)

Freing, Alina; Wallace, Douglas W. R.; Bange, Hermann W.

2012-01-01

We use transient time distributions calculated from tracer data together with in situ measurements of nitrous oxide (N2O) to estimate the concentration of biologically produced N2O and N2O production rates in the ocean on a global scale. Our approach to estimate the N2O production rates integrates the effects of potentially varying production and decomposition mechanisms along the transport path of a water mass. We estimate that the oceanic N2O production is dominated by nitrification with a contribution of only approximately 7 per cent by denitrification. This indicates that previously used approaches have overestimated the contribution by denitrification. Shelf areas may account for only a negligible fraction of the global production; however, estuarine sources and coastal upwelling of N2O are not taken into account in our study. The largest amount of subsurface N2O is produced in the upper 500 m of the water column. The estimated global annual subsurface N2O production ranges from 3.1 ± 0.9 to 3.4 ± 0.9 Tg N yr−1. This is in agreement with estimates of the global N2O emissions to the atmosphere and indicates that a N2O source in the mixed layer is unlikely. The potential future development of the oceanic N2O source in view of the ongoing changes of the ocean environment (deoxygenation, warming, eutrophication and acidification) is discussed. PMID:22451110

Global oceanic production of nitrous oxide.

Science.gov (United States)

Freing, Alina; Wallace, Douglas W R; Bange, Hermann W

2012-05-05

We use transient time distributions calculated from tracer data together with in situ measurements of nitrous oxide (N(2)O) to estimate the concentration of biologically produced N(2)O and N(2)O production rates in the ocean on a global scale. Our approach to estimate the N(2)O production rates integrates the effects of potentially varying production and decomposition mechanisms along the transport path of a water mass. We estimate that the oceanic N(2)O production is dominated by nitrification with a contribution of only approximately 7 per cent by denitrification. This indicates that previously used approaches have overestimated the contribution by denitrification. Shelf areas may account for only a negligible fraction of the global production; however, estuarine sources and coastal upwelling of N(2)O are not taken into account in our study. The largest amount of subsurface N(2)O is produced in the upper 500 m of the water column. The estimated global annual subsurface N(2)O production ranges from 3.1 ± 0.9 to 3.4 ± 0.9 Tg N yr(-1). This is in agreement with estimates of the global N(2)O emissions to the atmosphere and indicates that a N(2)O source in the mixed layer is unlikely. The potential future development of the oceanic N(2)O source in view of the ongoing changes of the ocean environment (deoxygenation, warming, eutrophication and acidification) is discussed.

Experimental study on neptunium migration under in situ geochemical conditions

Science.gov (United States)

Kumata, M.; Vandergraaf, T. T.

1998-12-01

Results are reported for migration experiments performed with Np under in situ geochemical conditions over a range of groundwater flow rates in columns of crushed rock in a specially designed facility at the 240-level of the Underground Research Laboratory (URL) near Pinawa, Manitoba, Canada. This laboratory is situated in an intrusive granitic rock formation, the Lac du Bonnet batholith. Highly altered granitic rock and groundwater were obtained from a major subhorizontal fracture zone at a depth of 250 m in the URL. The granite was wet-crushed and wet-sieved with groundwater from this fracture zone. The 180-850-μm size fraction was selected and packed in 20-cm long, 2.54-cm in diameter Teflon™-lined stainless steel columns. Approximately 30-ml vols of groundwater containing 3HHO and 237Np were injected into the columns at flow rates of 0.3, 1, and 3 ml/h, followed by elution with groundwater, obtained from the subhorizontal fracture, at the same flow rates, for a period of 95 days. Elution profiles for 3HHO were obtained, but no 237Np was detected in the eluted groundwater. After terminating the migration experiments, the columns were frozen, the column material was removed and cut into twenty 1-cm thick sections and each section was analyzed by gamma spectrometry. Profiles of 237Np were obtained for the three columns. A one-dimensional transport model was fitted to the 3HHO breakthrough curves to obtain flow parameters for this experiment. These flow parameters were in turn applied to the 237Np concentration profiles in the columns to produce sorption and dispersion coefficients for Np. The results show a strong dependence of retardation factors ( Rf) on flow rate. The decrease in the retarded velocity of the neptunium ( Vn) varied over one order of magnitude under the geochemical conditions for these experiments.

Determination of uranium in plutonium--238 metal and oxide by differential pulse polarography

International Nuclear Information System (INIS)

Fawcett, N.C.

1976-01-01

A differential pulse polarographic method was developed for the determination of total uranium in 238 Pu metal and oxides. A supporting electrolyte of 0.5 M ascorbic acid in 0.15 N H 2 SO 4 was found satisfactory for the determination of 500 ppM or more of uranium in 10 mg or less of plutonium. A relative standard deviation of 0.27 to 4.3 percent was obtained in the analysis of samples ranging in uranium content from 0.65 to 2.79 percent. The limit of detection was 0.18 μg ml -1 . Peak current was a linear function of uranium concentration up to at least 100 μg ml -1 . Amounts of neptunium equal to the uranium content were tolerated. The possible interference of a number of other cations and anions were investigated

Impact of residual elements on zinc quality in the production of zinc oxide

Czech Academy of Sciences Publication Activity Database

Luptáková, Natália; Dymáček, Petr; Pešlová, F.; Jurkovič, Z.; Barborák, O.; Stodola, J.

2016-01-01

Roč. 55, č. 3 (2016), s. 407-410 ISSN 0543-5846 Institutional support: RVO:68081723 Keywords : zinc * metallography * microstructure of zinc * zinc oxide * production of zinc oxide Subject RIV: JG - Metallurgy Impact factor: 0.959, year: 2014

Arginase expression modulates nitric oxide production in Leishmania (Leishmania) amazonensis.

Science.gov (United States)

Acuña, Stephanie Maia; Aoki, Juliana Ide; Laranjeira-Silva, Maria Fernanda; Zampieri, Ricardo Andrade; Fernandes, Juliane Cristina Ribeiro; Muxel, Sandra Marcia; Floeter-Winter, Lucile Maria

2017-01-01

Arginase is an enzyme that converts L-arginine to urea and L-ornithine, an essential substrate for the polyamine pathway supporting Leishmania (Leishmania) amazonensis replication and its survival in the mammalian host. L-arginine is also the substrate of macrophage nitric oxide synthase 2 (NOS2) to produce nitric oxide (NO) that kills the parasite. This competition can define the fate of Leishmania infection. The transcriptomic profiling identified a family of oxidoreductases in L. (L.) amazonensis wild-type (La-WT) and L. (L.) amazonensis arginase knockout (La-arg-) promastigotes and axenic amastigotes. We highlighted the identification of an oxidoreductase that could act as nitric oxide synthase-like (NOS-like), due to the following evidences: conserved domain composition, the participation of NO production during the time course of promastigotes growth and during the axenic amastigotes differentiation, regulation dependence on arginase activity, as well as reduction of NO amount through the NOS activity inhibition. NO quantification was measured by DAF-FM labeling analysis in a flow cytometry. We described an arginase-dependent NOS-like activity in L. (L.) amazonensis and its role in the parasite growth. The increased detection of NO production in the mid-stationary and late-stationary growth phases of La-WT promastigotes could suggest that this production is an important factor to metacyclogenesis triggering. On the other hand, La-arg- showed an earlier increase in NO production compared to La-WT, suggesting that NO production can be arginase-dependent. Interestingly, La-WT and La-arg- axenic amastigotes produced higher levels of NO than those observed in promastigotes. As a conclusion, our work suggested that NOS-like is expressed in Leishmania in the stationary growth phase promastigotes and amastigotes, and could be correlated to metacyclogenesis and amastigotes growth in a dependent way to the internal pool of L-arginine and arginase activity.

Continuous operation of a pilot plant for the production of beryllium oxide

International Nuclear Information System (INIS)

Costa, T.C.; Amaral, S.; Silveira, C.M.S.; Oliveira, A.P. de

1975-01-01

A method of obtaining beryllium oxide with a purity of 99,2% was developed in a pilot plant with a capacity of 7 tons per month destined to operate continuously. The operation market prospects and control of production with the objective of obtaining internacional technical grade beryllium oxide are discussed [pt

Continuous operation of a pilot plant for the production of beryllium oxide

Energy Technology Data Exchange (ETDEWEB)

Costa, T C; Amaral, S; Silveira, C M.S.; de Oliveira, A P [Instituto de Tecnologia, Governador Valadares (Brazil)

1975-12-01

A method of obtaining beryllium oxide with a purity of 99,2% was developed in a pilot plant with a capacity of 7 tons per month destined to operate continuously. The operation market prospects and control of production with the objective of obtaining internacional technical grade beryllium oxide are discussed.

Modification of Casein by the Lipid Oxidation Product Malondialdehyde

NARCIS (Netherlands)

Adams, A.; Kimpe, de N.; Boekel, van T.

2008-01-01

The reaction of malondialdehyde with casein was studied in aqueous solution to evaluate the impact of this lipid oxidation product on food protein modification. By using multiresponse modeling, a kinetic model was developed for this reaction. The influence of temperature and pH on protein browning

Field study of nitrous oxide production with in situ aeration in a closed landfill site.

Science.gov (United States)

Nag, Mitali; Shimaoka, Takayuki; Nakayama, Hirofumi; Komiya, Teppei; Xiaoli, Chai

2016-03-01

Nitrous oxide (N(2)O) has gained considerable attention as a contributor to global warming and depilation of stratospheric ozone layer. Landfill is one of the high emitters of greenhouse gas such as methane and N(2)O during the biodegradation of solid waste. Landfill aeration has been attracted increasing attention worldwide for fast, controlled and sustainable conversion of landfills into a biological stabilized condition, however landfill aeration impel N(2)O emission with ammonia removal. N(2)O originates from the biodegradation, or the combustion of nitrogen-containing solid waste during the microbial process of nitrification and denitrification. During these two processes, formation of N(2)O as a by-product from nitrification, or as an intermediate product of denitrification. In this study, air was injected into a closed landfill site and investigated the major N(2)O production factors and correlations established between them. The in-situ aeration experiment was carried out by three sets of gas collection pipes along with temperature probes were installed at three different distances of one, two and three meter away from the aeration point; named points A-C, respectively. Each set of pipes consisted of three different pipes at three different depths of 0.0, 0.75 and 1.5 m from the bottom of the cover soil. Landfill gases composition was monitored weekly and gas samples were collected for analysis of nitrous oxide concentrations. It was evaluated that temperatures within the range of 30-40°C with high oxygen content led to higher generation of nitrous oxide with high aeration rate. Lower O(2) content can infuse N(2)O production during nitrification and high O(2) inhibit denitrification which would affect N(2)O production. The findings provide insights concerning the production potentials of N(2)O in an aerated landfill that may help to minimize with appropriate control of the operational parameters and biological reactions of N turnover. Investigation of

Enhancing lipid productivity of Chlorella vulgaris using oxidative stress by TiO2 nanoparticles

International Nuclear Information System (INIS)

Kang, Nam Kyu; Lee, Bongsoo; Choi, Gang-Guk; Moon, Myounghoon; Park, Min S.; Yang, Ji-Won; Lim, JitKang

2014-01-01

Ability to increase the lipid production in microalgae is one of the heavily sought-after ideas to improve the economic feasibility of microalgae-derived transportation fuels for commercial applications. We used the oxidative stress by TiO 2 nanoparticles, a well-known photocatalyst, to induce lipid production in microalgae. Chlorella vulgaris UTEX 265 was cultivated under various concentrations of TiO 2 ranging from 0.1 to 5 g/L under UV-A illumination. Maximum specific growth rate was affected in responding to TiO 2 concentrations. In the presence of UV-A, chlorophyll concentration was decreased at the highest concentration of TiO 2 (5 g/L TiO 2 ) by oxidative stress. The fatty acid methyl ester (FAME) composition analysis suggested that oxidative stress causes the accumulation and decomposition of lipids. The highest FAME productivity was 18.2 g/L/d under low concentrations of TiO 2 (0.1 g/L) and a short induction time (two days). The controlled condition of TiO 2 /UV-A inducing oxidative stress (0.1 g/L TiO 2 and two days induction) could be used to increase the lipid productivity of C. vulgaris UTEX 265. Our results show the possibility of modulating the lipid induction process through oxidative stress with TiO 2 /UV-A

Enhancing Biodiesel Production Using Green Glycerol-Enriched Calcium Oxide Catalyst : An Optimization Study

NARCIS (Netherlands)

Avhad, Mangesh R.; Gangurde, L.S.; Sánchez, Marcos; Bouaid, Abderrahim; Aracil, José; Martínez, Mercedes; Marchetti, Jorge M.

2018-01-01

The present article demonstrates a superior catalytic performance of glycerol-enriched calcium oxide for biodiesel production than other calcium-based counterparts. The proficiency of glycerol-enriched calcium oxide in catalyzing the methanolysis of crude Jatropha curcas oil containing high free

Lunar Metal Oxide Electrolysis with Oxygen and Photovoltaic Array Production Applications

Science.gov (United States)

Curreri, P. A.; Ethridge, E.; Hudson, S.; Sen, S.

2006-01-01

This paper presents the results of a Marshall Space Flight Center funded effort to conduct an experimental demonstration of the processing of simulated lunar resources by the molten oxide electrolysis (MOE) process to produce oxygen and metal from lunar resources to support human exploration of space. Oxygen extracted from lunar materials can be used for life support and propellant, and silicon and metallic elements produced can be used for in situ fabrication of thin-film solar cells for power production. The Moon is rich in mineral resources, but it is almost devoid of chemical reducing agents, therefore, molten oxide electrolysis, MOE, is chosen for extraction, since the electron is the most practical reducing agent. MOE was also chosen for following reasons. First, electrolytic processing offers uncommon versatility in its insensitivity to feedstock composition. Secondly, oxide melts boast the twin key attributes of highest solubilizing capacity for regolith and lowest volatility of any candidate electrolytes. The former is critical in ensuring high productivity since cell current is limited by reactant solubility, while the latter simplifies cell design by obviating the need for a gas-tight reactor to contain evaporation losses as would be the case with a gas or liquid phase fluoride reagent operating at such high temperatures. In the experiments reported here, melts containing iron oxide were electrolyzed in a low temperature supporting oxide electrolyte (developed by D. Sadoway, MIT). The production of oxygen and reduced iron were observed. Electrolysis was also performed on the supporting electrolyte with JSC-1 Lunar Simulant. The cell current for the supporting electrolyte alone is negligible while the current for the electrolyte with JSC-1 shows significant current and a peak at about -0.6 V indicating reductive reaction in the simulant.

Study of cryoprotectors effect on oxidation processes at storage of frozen halffinished products

Directory of Open Access Journals (Sweden)

O. Glushkov

2016-12-01

Full Text Available The publication presents data on the effect of polysaccharides as cryoprotectants on changes of the lipid fraction of quick-frozen semi-finished products during storage. Since the structure of minced systems is formed as a result of the destruction of the native structure of the meat and the formation of a new secondary structure, it is important to establish the effect of cryoprotectants on the key functional and technological properties of meat systems after freezing, and in the process of storage. Based on studies of the kinetics of the oxidation of fat and accumulation data on the accumulation of the primary and secondary products of oxidation inhibition of oxidative processes has been found.

Formaldehyde production from isoprene oxidation across NOx regimes

Directory of Open Access Journals (Sweden)

G. M. Wolfe

2016-03-01

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

Lipid and cholesterol oxidation, color changes, and volatile compounds production in irradiated raw pork batters with different fat content

International Nuclear Information System (INIS)

Jo, Cheo Run; Byun, Myung Woo

2000-01-01

An emulsion-type product was prepared to determine the effect of irradiation on lipid and cholesterol oxidation, color change, and volatile production in raw pork with different fat content. Lipid oxidation increased with an increase in fat content or irradiation dose. Irradiated batters had higher cholesterol oxides than did non-irradiated batters, and the major cholesterol oxides formed in irradiated pork batters were 7α- and 7β- hydroxycholesterol. Hunter color a- and b-values of raw pork batters were decreased by irradiation regardless of fat content. Irradiation significantly increased the amount of volatile compounds. Although lipid oxidation of high fat products (10 and 15% fat) was higher than that of low fat products (4%), high fat products did not always produce greater amount of volatile compounds in raw pork batters. In summary, irradiation increased lipid and cholesterol oxidation, and volatile compounds production, and had detrimental effects on the color of raw pork batter under aerobic conditions

Study on coordination characteristics of neptunium and uranium ions in calcium nitrate hydrate melt by Raman spectrometry and UV/Vis/NIR spectrometry

International Nuclear Information System (INIS)

Fujii, T; Okude, G; Uehara, A; Yamana, H

2010-01-01

Extraction behavior of neptunium (Np) by tri-n-butyl phosphate from calcium nitrate hydrate melt was investigated. Distribution ratio of Np was found to increase with the decrease of water content. Adding nitric acid into the system resulted in an increase of the distribution ratio. In order to understand the extraction trends, Np species in the hydrate melt were analyzed by Raman spectrometry and UV/Vis/NIR spectrometry. Major fraction was assigned to be NpO 2 2+ of Np(VI) and small fraction to be NpO 2 + of Np(V). A shift of the v 1 symmetric vibrational frequency of NpO 2 2+ in nitrate media was found in Raman spectra. This suggests a coordination circumstance change of NpO 2 2+ .

Epiphytes modulate Posidonia oceanica photosynthetic production, energetic balance, antioxidant mechanisms and oxidative damage

Directory of Open Access Journals (Sweden)

Monya Mendes Costa

2015-12-01

Full Text Available Epiphytes impose physical barriers to light penetration into seagrass leaves causing shading, which may decrease the production of oxygen reactive species (ROS, but also constitute a physical aggression that may trigger the production of ROS, leading to oxidative damage. Here we investigate the effects of epiphytes on Posidonia oceanica under both interactive perspectives, light attenuation and oxidative stress. Specifically the role of epiphytes in net photosynthesis, chlorophyll a and b, photoprotection (Violaxanthin+Anteraxanthin+Zeaxanthin cycle, soluble sugar and starch contents, enzymatic (ascorbate peroxidase (APX and dehydroascorbate reductase (DHAR and global (trolox equivalent antioxidant capacity (TEAC and oxygen radical antioxidant capacity (ORAC antioxidant responses, phenolics and oxidative damage (malondialdehyde are tested. Leaves with epiphytes showed higher chlorophyll b and lower content in VAZ cycle carotenoids. Epiphyte shading was the probable reason for the lower VAZ de-epoxidation-ratio of leaves with epiphytes. In spite of being shaded, leaves with epiphytes showed higher antioxidant levels, indicating that epiphytes trigger the production of ROS. Both ORAC and TEAC and also APX and DHAR activities were higher in leaves with epiphytes, indicating that this response was related with its presence. Malondialdehyde concentrations also suggest oxidative damage caused by epiphytes. We conclude that the epiphyte load causes oxidative stress in P. oceanica and the mechanisms to scavenge ROS were not completely effective to avoid cell damage.

Mathematical modeling of nitrous oxide production in an anaerobic/oxic/anoxic process.

Science.gov (United States)

Ding, Xiaoqian; Zhao, Jianqiang; Hu, Bo; Chen, Ying; Ge, Guanghuan; Li, Xiaoling; Wang, Sha; Gao, Kun; Tian, Xiaolei

2016-12-01

This study incorporates three currently known nitrous oxide (N 2 O) production pathways: ammonium-oxidizing bacteria (AOB) denitrification, incomplete hydroxylamine (NH 2 OH) oxidation, and heterotrophic denitrification on intracellular polymers, into a mathematical model to describe N 2 O production in an anaerobic/oxic/anoxic (AOA) process for the first time. The developed model was calibrated and validated by four experimental cases, then evaluated by two independent anaerobic/aerobic (AO) studies from literature. The modeling results displayed good agreement with the measured data. N 2 O was primarily generated in the aerobic stage by AOB denitrification (67.84-81.64%) in the AOA system. Smaller amounts of N 2 O were produced via incomplete NH 2 OH oxidation (15.61-32.17%) and heterotrophic denitrification on intracellular polymers (0-12.47%). The high nitrite inhibition on N 2 O reductase led to the increased N 2 O accumulation in heterotrophic denitrification on intracellular polymers. The new model was capable of modeling nitrification-denitrification dynamics and heterotrophic denitrification on intracellular polymers in the AOA system. Copyright © 2016 Elsevier Ltd. All rights reserved.

High production volume chemical Amine Oxide [C8-C20] category environmental risk assessment

DEFF Research Database (Denmark)

Sanderson, Hans; Tibazarwa, Caritas; Greggs, William

2009-01-01

and personal care products. Given the lack of persistence or bioaccumulation, and the low likelihood of these chemicals partitioning to soil, the focus of the environmental assessment is on the aquatic environment. In the United States, the E-FAST model is used to estimate effluent concentrations in the United......An environmental assessment of amine oxides has been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Amine Oxides Consortium. Amine oxides are primarily used in conjunction with surfactants in cleaning...... States from manufacturing facilities and from municipal facilities resulting from consumer product uses. Reasonable worst-case ratios of predicted environmental concentration (PEC) to predicted no effect concentration (PNEC) range from 0.04 to 0.003, demonstrating that these chemicals are a low risk...

Fission product release by fuel oxidation after water ingress

International Nuclear Information System (INIS)

Schreiber.

1990-01-01

On the basis of data obtained by a literature search, a computer code has been established for the calculation of the degree of oxidation of the fuel in the damaged fuel particles, and hence of the fission product release as a function of the time period of steam ingress. (orig.) [de

Ultrasensitive determination of DNA oxidation products by gas chromatography-tandem mass spectrometry and the role of antioxidants in the prevention of oxidative damage.

Science.gov (United States)

Dawbaa, Sam; Aybastıer, Önder; Demir, Cevdet

2017-04-15

Oxidative stress is considered as one of the significant causes of DNA damage which in turn contributes to cell death through a series of intermediate processes such as cancer formation, mutation, and aging. Natural sources such as plant and fruit products have provided us with interesting substances of antioxidant activity that could be recruited in protecting the genetic materials of the cells. This study is an effort to discover some of those antioxidants effects in their standard and natural forms by performing an ultrasensitive determination of the products of DNA oxidation using GC-MS/MS. Experiments were used to determine the direct antioxidant activity of the substances contained in the tendrils of Vitis vinifera (var. alphonse) by extracting them and achieving Folin-Ciocalteau and CHROMAC analyses to determine the total phenolic content (TPC) and the antioxidant capacity of the extract, respectively; results revealed a phenolic content of 11.39±0.30mg Gallic Acid Equivalent (GAE)/g of the plant's fresh weight (FW) by Folin-Ciocalteau and 8.17±0.49mg Trolox Equivalent (TE)/g FW by CHROMAC assays. The qualitative analysis of the plant extract by HPLC-DAD technique revealed that two flavonoid glycosides namely rutin and isoquercitrin in addition to chlorogenic acid were contained in the extract. The determination of the DNA oxidation products was performed after putting DNA, rutin and isoquercitrin standard samples with different concentration, and the extract's sample under oxidative stress. Eighteen DNA oxidation products were traced using GC-MS/MS with ultra-sensitivity and the experiments proved a significant decrease in the concentration of the DNA oxidation products when the extract was used as a protectant against the oxidative stress. It is believed by conclusion that the extract of V. vinifera's (var. alphonse) tendrils has a good antioxidant activity; hence it is recommended to be used as a part of the daily healthy food list if possible

Ethanol generation, oxidation and energy production in a cooperative bioelectrochemical system.

Science.gov (United States)

Pagnoncelli, Kamila C; Pereira, Andressa R; Sedenho, Graziela C; Bertaglia, Thiago; Crespilho, Frank N

2018-08-01

Integrating in situ biofuel production and energy conversion into a single system ensures the production of more robust networks as well as more renewable technologies. For this purpose, identifying and developing new biocatalysts is crucial. Herein, is reported a bioelectrochemical system consisting of alcohol dehydrogenase (ADH) and Saccharomyces cerevisiae, wherein both function cooperatively for ethanol production and its bioelectrochemical oxidation. Here, it is shown that it is possible to produce ethanol and use it as a biofuel in a tandem manner. The strategy is to employ flexible carbon fibres (FCF) electrode that could adsorb both the enzyme and the yeast cells. Glucose is used as a substrate for the yeast for the production of ethanol, while the enzyme is used to catalyse the oxidation of ethanol to acetaldehyde. Regarding the generation of reliable electricity based on electrochemical systems, the biosystem proposed in this study operates at a low temperature and ethanol production is proportional to the generated current. With further optimisation of electrode design, we envision the use of the cooperative biofuel cell for energy conversion and management of organic compounds. Copyright © 2018 Elsevier B.V. All rights reserved.

Technology for recovery of by-products

International Nuclear Information System (INIS)

Van Tuy, H.H.

1983-01-01

Products of conventional nuclear fuel processing plants are uranium and plutonium, and any other recovered material is considered to be a by-product. Some by-products have been recovered from past nuclear fuel processing operations, either as a normal mode of operation or by special campaigns. Routing recovery over an extended period has been limited to neptunium, but extended campaigns were used at Hanford to recover strontium for radioisotope thermoelectric generators. Krypton is recovered at Idaho Chemical Processing Plant on a campaign basis, and isotope separation of krypton is done at Oak Ridge National Laboratory. Past campaigns at Hanford PUREX have recovered cesium, promethium, amercium, cerium, and technetium. Past by-product recovery efforts were usually severely constrained by the status of flowsheet development and availability of existing facilities at the time decisions wee made to recover the by-products. Additional processes were developed to accommodate other unit operations and in response to changes in waste management objectives or user requirements. Now an impressive variety of recovery technology is available for most potential by-products, with varying degrees of demonstration under conditions which satisfy today's environmental protection and waste management constraints

Nitrous oxide production in grassland soils: assessing the contribution of nitrifier denitrification

NARCIS (Netherlands)

Wrage, N.; Velthof, G.L.; Laanbroek, H.J.; Oenema, O.

2004-01-01

Nitrifier denitrification is the reduction of NO2- to N2 by nitrifiers. It leads to the production of the greenhouse gas nitrous oxide (N2O) as an intermediate and possible end product. It is not known how important nitrifier denitrification is for the production of N2O in soils. We explored N2O

Effects of solid fission products forming dissolved oxide (Nd) and metallic precipitate (Ru) on the thermal conductivity of uranium base oxide fuel

International Nuclear Information System (INIS)

Kim, Dong-Joo; Yang, Jae-Ho; Kim, Jong-Hun; Rhee, Young-Woo; Kang, Ki-Won; Kim, Keon-Sik; Song, Kun-Woo

2007-01-01

The effects of solid fission products on the thermal conductivity of uranium base oxide nuclear fuel were experimentally investigated. Neodymium (Nd) and ruthenium (Ru) were added to represent the physical states of solid fission products such as 'dissolved oxide' and 'metallic precipitate', respectively. Thermal conductivity was determined on the basis of the thermal diffusivity, density and specific heat values. The effects of the additives on the thermal conductivity were quantified in the form of the thermal resistivity equation - the reciprocal of the phonon conduction equation - which was determined from the measured data. It is concluded that the thermal conductivity of the irradiated nuclear fuel is affected by both the 'dissolved oxide' and the 'metallic precipitate', however, the effects are in the opposite direction and the 'dissolved oxide' influences the thermal conductivity more significantly than that of the 'metallic precipitate'

Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols

DEFF Research Database (Denmark)

Kristensen, Kasper; Enggrob, Kirsten L.; King, S. M.

2013-01-01

products cis-pinic and terpenylic acids, but similar to the second-generation oxidation products 3-methyl-1,2,3-butane tricarboxylic acid (MBTCA) and diaterpenylic acid acetate (DTAA). Dimer esters were observed within the first 30 min, indicating rapid production simultaneous to their structural...

Application of simplified desorption method to sorption study. (2) Sorption of neptunium (V) on montmorillonite-based mixtures

International Nuclear Information System (INIS)

Kozai, Naofumi; Ohnuki, Toshihiko

2013-01-01

To elucidate the sorption behaviors of radionuclides in multi-mineral systems and the mutual effects of minerals on the sorption, this paper carried out the sorption and desorption experiments of neptunium(V) on montmorillonite-based two-mineral mixtures. The Np sorbed on montmorillonite at pH from 4 to 8 was desorbed with 1M KCl solutions, indicating that the sorption was cation exchange. The Np sorbed on apatite and calcite was nondesorbable with 1M KCl solutions, which is in harmony with the knowledge that Np forms strong complexes with the phosphate groups of apatite and the carbonate groups of calcite. This study utilized these clear distinguishes of the desorption behaviors for examining the two-mineral systems. In montmorillonite-apatite mixtures, the sorption on the montmorillonite was decreased and Np was accumulated on the apatite. In montmorillonite-calcite mixtures, the sorption on the montmorillonite was decreased due to the interference by the calcium and carbonate ions dissolved from calcite while no accumulation of Np to calcite was observed. (author)

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

Science.gov (United States)

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

2015-10-14

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

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

OpenAIRE

Natália Luptáková; Evgeniy Anisimov; Františka Pešlová

2014-01-01

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

Investigation of neptunium(V) reduction to neptunium(IV) by semiconductor photocatalysis

International Nuclear Information System (INIS)

Takahashi, M.; Nakamura, T.; Ikeda, T.; Karasawa, H.

1990-01-01

Np(V) is the dominant Np oxidation state in high level liquid waste from reprocessing plants. Since low extractability of Np(V) makes its separation from other nuclei difficult, valence control is required. When a 1mM Np(V) solution of 3M nitric acid was irradiated by a Xe-lamp, using n-SiC (5g/dm 3 ) as photocatalyst and hydrazine (0.1M) as donor, 100% of the Np(V) was reduced to Np(IV) within 30 min at room temperature. Electrochemical investigations suggested that Np(V) is reduced by the atomic hydrogen adsorbed on the photocatalyst surface. According to this mechanism, platinum group metals can act as reducing catalysts for No(V) reduction due to their low hydrogen overvoltage. The proposed mechanism was experimentally confirmed using platinum black (5g/dm 3 ) as catalyst and hydroxylammonium nitrate (0.9M) as reducing agent

Tandem Oxidative Derivatization of Nitrene Insertion Products for the Highly Diastereoselective Synthesis of 1,3-aminoalcohols.

Science.gov (United States)

Alderson, Juliet M; Schomaker, Jennifer M

2017-06-27

Transition-metal-catalyzed nitrene insertion into tertiary C-H bonds located at stereogenic carbons often results in mixtures of diastereomeric products, especially if the reaction proceeds through a concerted pathway. In this communication, we report a solution to this problem that invokes a one-pot, silver-catalyzed C-H nitrene transfer reaction. Nitrene insertion is followed by facile oxidation of the amine to an imine and nucleophilic addition to furnish α-tertiary amine 1,3-aminoalcohol products in high diastereoselectivities. The silver catalyst, PhIO oxidant, and TEMPO additive are crucial to success in this unusual oxidation, which is proposed to occur via hydrogen-atom abstraction from pre-activation of the initial nitrene insertion product by additional oxidant. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The impact of respiration and oxidative stress response on recombinant α-amylase production by Saccharomyces cerevisiae.

Science.gov (United States)

Martínez, José L; Meza, Eugenio; Petranovic, Dina; Nielsen, Jens

2016-12-01

Studying protein production is important for fundamental research on cell biology and applied research for biotechnology. Yeast Saccharomyces cerevisiae is an attractive workhorse for production of recombinant proteins as it does not secrete many endogenous proteins and it is therefore easy to purify a secreted product. However, recombinant production at high rates represents a significant metabolic burden for the yeast cells, which results in oxidative stress and ultimately affects the protein production capacity. Here we describe a method to reduce the overall oxidative stress by overexpressing the endogenous HAP1 gene in a S. cerevisiae strain overproducing recombinant α-amylase. We demonstrate how Hap1p can activate a set of oxidative stress response genes and meanwhile contribute to increase the metabolic rate of the yeast strains, therefore mitigating the negative effect of the ROS accumulation associated to protein folding and hence increasing the production capacity during batch fermentations.

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

Czech Academy of Sciences Publication Activity Database

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

2014-01-01

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

Effect of nanoparticles binding ß-amyloid peptide on nitric oxide production by cultured endothelial cells and macrophages

Directory of Open Access Journals (Sweden)

Orlando A

2013-04-01

Full Text Available Antonina Orlando,1 Francesca Re,1 Silvia Sesana,1 Ilaria Rivolta,1 Alice Panariti,1 Davide Brambilla,2 Julien Nicolas,2 Patrick Couvreur,2 Karine Andrieux,2 Massimo Masserini,1 Emanuela Cazzaniga1 1Department of Health Sciences, University of Milano-Bicocca, Monza, Italy; 2Institut Galien Paris Sud, University Paris-Sud, Châtenay-Malabry, France Background: As part of a project designing nanoparticles for the treatment of Alzheimer’s disease, we have synthesized and characterized a small library of nanoparticles binding with high affinity to the β-amyloid peptide and showing features of biocompatibility in vitro, which are important properties for administration in vivo. In this study, we focused on biocompatibility issues, evaluating production of nitric oxide by cultured human umbilical vein endothelial cells and macrophages, used as models of cells which would be exposed to nanoparticles after systemic administration. Methods: The nanoparticles tested were liposomes and solid lipid nanoparticles carrying phosphatidic acid or cardiolipin, and PEGylated poly(alkyl cyanoacrylate nanoparticles (PEG-PACA. We measured nitric oxide production using the Griess method as well as phosphorylation of endothelial nitric oxide synthase and intracellular free calcium, which are biochemically related to nitric oxide production. MTT viability tests and caspase-3 detection were also undertaken. Results: Exposure to liposomes did not affect the viability of endothelial cells at any concentration tested. Increased production of nitric oxide was detected only with liposomes carrying phosphatidic acid or cardiolipin at the highest concentration (120 µg/mL, together with increased synthase phosphorylation and intracellular calcium levels. Macrophages exposed to liposomes showed a slightly dose-dependent decrease in viability, with no increase in production of nitric oxide. Exposure to solid lipid nanoparticles carrying phosphatidic acid decreased viability in

Oxidant production and SOD1 protein expression in single skeletal myofibers from Down syndrome mice

Directory of Open Access Journals (Sweden)

Patrick M. Cowley

2017-10-01

Full Text Available Down syndrome (DS is a genetic condition caused by the triplication of chromosome 21. Persons with DS exhibit pronounced muscle weakness, which also occurs in the Ts65Dn mouse model of DS. Oxidative stress is thought to be an underlying factor in the development of DS-related pathologies including muscle dysfunction. High-levels of oxidative stress have been attributed to triplication and elevated expression of superoxide dismutase 1 (SOD1; a gene located on chromosome 21. The elevated expression of SOD1 is postulated to increase production of hydrogen peroxide and cause oxidative injury and cell death. However, it is unknown whether SOD1 protein expression is associated with greater oxidant production in skeletal muscle from Ts65Dn mice. Thus, our objective was to assess levels of SOD1 expression and oxidant production in skeletal myofibers from the flexor digitorum brevis obtained from Ts65Dn and control mice. Measurements of oxidant production were obtained from myofibers loaded with 2′,7′-dichlorodihydrofluorescein diacetate (DCFH2-DA in the basal state and following 15 min of stimulated unloaded contraction. Ts65Dn myofibers exhibited a significant decrease in basal DCF emissions (p 0.05. Myofibers from Ts65Dn mice tended to be smaller and myonuclear domain was lower (p < 0.05. In summary, myofibers from Ts65Dn mice exhibited decreased basal DCF emissions that were coupled with elevated protein expression of SOD1. Stimulated contraction in isolated myofibers did not affect DCF emissions in either group. These findings suggest the skeletal muscle dysfunction in the adult Ts65Dn mouse is not associated with skeletal muscle oxidative stress.

Cholesterol oxidation in meat products and its regulation by supplementation of sodium nitrite and apple polyphenol before processing.

Science.gov (United States)

Osada, K; Hoshina, S; Nakamura, S; Sugano, M

2000-09-01

The levels of cholesterol oxidation derivatives (OxChol) in eight commercial species of meat products were examined. These products contained more than 1 mg/100 g of OxChol, and 7beta-hydroxycholesterol + 5beta-epoxycholesterol (111-1092 microg/100 g), 5alpha-epoxycholesterol (80-712 microg/100 g), cholestanetriol (0-368 microg/100 g), and 7-ketocholesterol (708-1204 microg/100 g) were detected. To know the interaction of sodium nitrite supplementation against cholesterol oxidation in meat products, sausage was produced with or without varying levels of sodium nitrite and stored in the refrigerator for 15 days. As a result, cholesterol oxidation in sausage was inhibited by addition of sodium nitrite in a dose-dependent manner. This observation may be associated with inactivation of O(2)(-) radical and stabilization of polyunsaturated fatty acids (PUFAs). In fact, the levels of OxChol in sausage increased, accompanying the decrease of coexisting linoleic acid when sodium nitrite was not added to sausage meat. Thus, cholesterol oxidation in meat products seems to be considarably promoted by the oxidation of coexisting PUFAs. On the other hand, additive apple polyphenol also inhibited linoleic acid oxidation in sausage and then suppressed cholesterol oxidation through its radical scavenging effects. Therefore, apple polyphenol, having a large amount of an oligomer of catechin, may interfere with cholesterol oxidation in meat processing or storage of meat products through its antioxidative action and be useful as a new antioxitant for meat products when it is added to the original meat before processing.

Short exposure to acetylene to distinguish between nitrifier and denitrifier nitrous oxide production in soil and sediment samples

OpenAIRE

Kester, R.A.; Boer, W. de; Laanbroek, H.J.

1996-01-01

The contribution of nitrifiers and denitrifiers to the nitrous oxide production in slurries of calcareous silt loam and river bank sediment at different oxygen concentrations was determined using acetylene as nitrification inhibitor. The addition of 10 Pa acetylene resulted in inhibition of nitrous oxide production at oxic conditions, but strongly enhanced the nitrous oxide production at oxygen-poor and anoxic conditions. Inhibition of nitrification by short exposure (1 to 24 h) to high conce...

The effect of lipid peroxidation products on reactive oxygen species formation and nitric oxide production in lipopolysaccharide-stimulated RAW 264.7 macrophages.

Science.gov (United States)

Ambrozova, Gabriela; Pekarova, Michaela; Lojek, Antonin

2011-02-01

Lipid peroxidation induced by oxidants leads to the formation of highly reactive metabolites. These can affect various immune functions, including reactive oxygen species (ROS) and nitric oxide (NO) production. The aim of the present study was to investigate the effects of lipid peroxidation products (LPPs) - acrolein, 4-hydroxynonenal, and malondialdehyde - on ROS and NO production in RAW 264.7 macrophages and to compare these effects with the cytotoxic properties of LPPs. Macrophages were stimulated with lipopolysaccharide (0.1 μg/ml) and treated with selected LPPs (concentration range: 0.1-100 μM). ATP test, luminol-enhanced chemiluminescence, Griess reaction, Western blotting analysis, amperometric and total peroxyl radical-trapping antioxidant parameter assay were used for determining the LPPs cytotoxicity, ROS and NO production, inducible nitric oxide synthase expression, NO scavenging, and antioxidant properties of LPPs, respectively. Our study shows that the cytotoxic action of acrolein and 4-hydroxynonenal works in a dose- and time-dependent manner. Further, our results imply that acrolein, 4-hydroxynonenal, and malondialdehyde can inhibit, to a different degree, ROS and NO production in stimulated macrophages, partially independently of their toxic effect. Also, changes in enzymatic pathways (especially NADPH-oxidase and nitric oxide synthase inhibition) and NO scavenging properties are included in the downregulation of reactive species formation. Copyright © 2010 Elsevier Ltd. All rights reserved.

Measurement of the initial conversion ratio in AQUILON and EDF 2 reactors

International Nuclear Information System (INIS)

Bergeron, J.; Le Baud, P.; Sautiez, B.

1968-01-01

In natural uranium fuelled reactors, it is important to know the initial conversion ratio, i.e. the ratio of uranium 238 absorption to uranium 235 destruction. The separation of absorption products from fission products is a difficult feature in the measurement of the conversion ratio. A physical method was chosen, the γγ coincidence technique which uses the properties of the decay scheme of neptunium 239 and allows the neptunium activity to be separated from the fission product activity, with some corrections. Detectors of natural uranium are used. The accuracy obtained in the measurements is of the order of 2%. (authors) [fr

Enhancing lipid productivity of Chlorella vulgaris using oxidative stress by TiO{sub 2} nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Kang, Nam Kyu; Lee, Bongsoo; Choi, Gang-Guk; Moon, Myounghoon; Park, Min S.; Yang, Ji-Won [Daejeon, Daejeon (Korea, Republic of); Lim, JitKang [Universiti Sains Malaysia, Penang (Malaysia)

2014-05-15

Ability to increase the lipid production in microalgae is one of the heavily sought-after ideas to improve the economic feasibility of microalgae-derived transportation fuels for commercial applications. We used the oxidative stress by TiO{sub 2} nanoparticles, a well-known photocatalyst, to induce lipid production in microalgae. Chlorella vulgaris UTEX 265 was cultivated under various concentrations of TiO{sub 2} ranging from 0.1 to 5 g/L under UV-A illumination. Maximum specific growth rate was affected in responding to TiO{sub 2} concentrations. In the presence of UV-A, chlorophyll concentration was decreased at the highest concentration of TiO{sub 2} (5 g/L TiO{sub 2}) by oxidative stress. The fatty acid methyl ester (FAME) composition analysis suggested that oxidative stress causes the accumulation and decomposition of lipids. The highest FAME productivity was 18.2 g/L/d under low concentrations of TiO{sub 2} (0.1 g/L) and a short induction time (two days). The controlled condition of TiO{sub 2}/UV-A inducing oxidative stress (0.1 g/L TiO{sub 2} and two days induction) could be used to increase the lipid productivity of C. vulgaris UTEX 265. Our results show the possibility of modulating the lipid induction process through oxidative stress with TiO{sub 2}/UV-A.

Electrochemical characterisation of solid oxide cell electrodes for hydrogen production

DEFF Research Database (Denmark)

Bernuy-Lopez, Carlos; Knibbe, Ruth; He, Zeming

2011-01-01

Oxygen electrodes and steam electrodes are designed and tested to develop improved solid oxide electrolysis cells for H2 production with the cell support on the oxygen electrode. The electrode performance is evaluated by impedance spectroscopy testing of symmetric cells at open circuit voltage (OCV...

Piper sarmentosum increases nitric oxide production in oxidative stress: a study on human umbilical vein endothelial cells.

Science.gov (United States)

Ugusman, Azizah; Zakaria, Zaiton; Hui, Chua Kien; Nordin, Nor Anita Megat Mohd

2010-07-01

Nitric oxide produced by endothelial nitric oxide synthase (eNOS) possesses multiple anti-atherosclerotic properties. Hence, enhanced expression of eNOS and increased Nitric oxide levels may protect against the development of atherosclerosis. Piper sarmentosum is a tropical plant with antioxidant and anti-inflammatory activities. This study aimed to investigate the effects of Piper sarmentosum on the eNOS and Nitric oxide pathway in cultured human umbilical vein endothelial cells (HUVECs). HUVECS WERE DIVIDED INTO FOUR GROUPS: control, treatment with 180 microM hydrogen peroxide (H(2)O(2)), treatment with 150 microg/mL aqueous extract of Piper sarmentosum, and concomitant treatment with aqueous extract of PS and H(2)O(2) for 24 hours. Subsequently, HUVECs were harvested and eNOS mRNA expression was determined using qPCR. The eNOS protein level was measured using ELISA, and the eNOS activity and Nitric oxide level were determined by the Griess reaction. Human umbilical vein endothelial cells treated with aqueous extract of Piper sarmentosum showed a marked induction of Nitric oxide. Treatment with PS also resulted in increased eNOS mRNA expression, eNOS protein level and eNOS activity in HUVECs. Aqueous extract of Piper sarmentosum may improve endothelial function by promoting NO production in HUVECs.

Products of BVOC oxidation: ozone and organic aerosols

Science.gov (United States)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to

JAEA thermodynamic database for performance assessment of geological disposal of high-level and TRU wastes. Refinement of thermodynamic data for tetravalent thorium, uranium, neptunium and plutonium

International Nuclear Information System (INIS)

Fujiwara, Kenso; Kitamura, Akira; Yui, Mikazu

2010-03-01

Within the scope of the JAEA thermodynamic database project for performance assessment of geological disposal of high-level and TRU radioactive wastes, the refinement of the thermodynamic data for the inorganic compounds and complexes of Thorium(IV), Uranium(IV), Neptunium(IV) and Plutonium(IV) was carried out. Refinement of thermodynamic data for the element was performed on a basis of the thermodynamic database for actinide published by the Nuclear Energy Agency in the Organisation for Economic Co-operation and Development (OECD/NEA). Additionally, the latest data after publication of thermodynamic data by OECD/NEA were reevaluated to determine whether the data should be included in the JAEA-TDB. (author)

Understanding the behaviour of the actinides under disposal conditions: A comparison between calculated and experimental solubilities

International Nuclear Information System (INIS)

Pryke, D.C.; Rees, J.H.

1986-01-01

The solubilities of plutonium, americium and neptunium measured in simulated near-field waters have compared with those predicted using the simple thermodynamic model NearSol. The dependence of solubility on pH and redox potential is examined in an effort to understand the behaviour of actinides in disposal. The agreement was variable. Differences could be appreciable, in particular for neptunium under oxidizing conditions; conversly, the model successfully predicted the behaviour of neptunium under reducing conditions. Such comparisons pinpointed deficiences in the thermodynamic data base and showed the sensitivity of solubilities to certain experimental parameters such as Eh and the concentration of carbonate ions. A comparison between NearSol and the reaction pathway program PHREEQE gave generally good agreement. NearSol was quicker and easier to use, requiring only limited preselection of participating species; however it did not account for the behaviour of bulk inactive species in solution; like feature will be built into an updated version. (orig.)

Complementary sample preparation strategies for analysis of cereal β-glucan oxidation products by UPLC-MS/MS

Science.gov (United States)

Boulos, Samy; Nyström, Laura

2017-11-01

The oxidation of cereal (1→3,1→4)-β-D-glucan can influence the health promoting and technological properties of this linear, soluble homopolysaccharide by introduction of new functional groups or chain scission. Apart from deliberate oxidative modifications, oxidation of β-glucan can already occur during processing and storage, which is mediated by hydroxyl radicals (HO•) formed by the Fenton reaction. We present four complementary sample preparation strategies to investigate oat and barley β-glucan oxidation products by hydrophilic interaction ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), employing selective enzymatic digestion, graphitized carbon solid phase extraction (SPE), and functional group labeling techniques. The combination of these methods allows for detection of both lytic (C1, C3/4, C5) and non-lytic (C2, C4/3, C6) oxidation products resulting from HO•-attack at different glucose-carbons. By treating oxidized β-glucan with lichenase and β-glucosidase, only oxidized parts of the polymer remained in oligomeric form, which could be separated by SPE from the vast majority of non-oxidized glucose units. This allowed for the detection of oligomers with mid-chain glucuronic acids (C6) and carbonyls, as well as carbonyls at the non-reducing end from lytic C3/C4 oxidation. Neutral reducing ends were detected by reductive amination with anthranilic acid/amide as labeled glucose and cross-ring cleaved units (arabinose, erythrose) after enzyme treatment and SPE. New acidic chain termini were observed by carbodiimide-mediated amidation of carboxylic acids as anilides of gluconic, arabinonic, and erythronic acids. Hence, a full characterization of all types of oxidation products was possible by combining complementary sample preparation strategies. Differences in fine structure depending on source (oat vs. barley) translates to the ratio of observed oxidized oligomers, with in-depth analysis corroborating a random HO�

Extracellular Polysaccharide Production in a Scytonemin-Deficient Mutant of Nostoc punctiforme Under UVA and Oxidative Stress.

Science.gov (United States)

Soule, Tanya; Shipe, Dexter; Lothamer, Justin

2016-10-01

Some cyanobacteria can protect themselves from ultraviolet radiation by producing sunscreen pigments. In particular, the sheath pigment scytonemin protects cells against long-wavelength UVA radiation and is only found in cyanobacteria which are capable of extracellular polysaccharide (EPS) production. The presence of a putative glycosyltransferase encoded within the scytonemin gene cluster, along with the localization of scytonemin and EPS to the extracellular sheath, prompted us to investigate the relationship between scytonemin and EPS production under UVA stress. In this study, it was hypothesized that there would be a relationship between the biosynthesis of scytonemin and EPS under both UVA and oxidative stress, since the latter is a by-product of UVA radiation. EPS production was measured following exposure of wild-type Nostoc punctiforme and the non-scytonemin-producing strain SCY59 to UVA and oxidative stress. Under UVA, SCY59 produced significantly more EPS than the unstressed controls and the wild type, while both strains produced more EPS under oxidative stress compared to the controls. The results suggest that EPS secretion occurs in response to the oxidative stress by-product of UVA rather than as a direct response to UVA radiation.

Sorption of neptunium(V) on opalinus clay under aerobic/anaerobic conditions

International Nuclear Information System (INIS)

Froehlich, D.R.; Amayri, S.; Drebert, J.; Reich, T.

2011-01-01

The interaction between neptunium(V) and a natural argillaceous rock (Opalinus Clay (OPA), Mont Terri, Switzerland) has been investigated in batch sorption experiments by varying pH (6-10), Np(V) concentration (10 -12 -10 -4 M), solid-to-liquid ratio (2-20 g/L), and partial pressure of CO 2 (10 -3.5 and 10 -2.3 atm) under aerobic/anaerobic conditions in saturated calcite solution. All batch experiments were carried out using well characterized aerobic and anaerobic dry powders of OPA. The results show a great influence of pH on Np(V) sorption. Under aerobic conditions sorption increases with increasing pH until maximum sorption is reached between pH 8-9. At pH > 9 sorption decreases due to the formation of negatively charged Np(V)-carbonate complexes. By increasing p CO 2 from 10 -3.5 to 10 -2.3 atm, the sorption edge is shifted ∼ 0.5 units to lower pH values. Under anaerobic conditions stronger sorption of 8 x 10 -6 M Np(V) was found, possibly due to partial reduction of Np(V) to Np(IV). The sorption of 8 x 10 -6 M Np(V) under aerobic conditions at pH 8.2 in saturated calcite solution increases continuously with increasing solid-to-liquid ratio of OPA in the range of 2-20 g/L with a constant K d value of 126 ± 13 L/kg. The sorption isotherm was measured over seven orders of magnitude in Np(V) concentration using 239 Np as tracer. The sorption isotherm could be divided in a part of linear sorption behaviour between 10 -13 -10 -9 M Np(V) and non-linear behaviour in the range of 10 -9 -10 -4 M Np(V). (orig.)

Plutonium and neptunium absorption from the gastrointestinal tract of neonatal baboons

International Nuclear Information System (INIS)

Lataillade, Ghislaine; Duserre, Claude; Rateau, Gerard; Verry, Monique; Fritsch, Paul; Metivier, Henri

1992-06-01

Nineteen baboons aged 1 to 310 days were given oral doses of 238 Pu citrate or 239 Np nitrate. Gastrointestinal (GI) absorption of Pu and Np were higher than those observed in adults. The values of Pu GI absorption were 0.22% at 1 d, 0.17% at 17 d then about 0.10% until 177 d of age. From 195 d onwards, GI absorption was about 0.02% vs adult values (0.008%). GI absorption of neptunium decreased rapidly with age from 1.71% at 4 d to 0.14% at 6 d and remained at this value until 26 d. From 77 d onwards Np GI absorption was decreased to adult value (0.042%). Gastrointestinal retention associated with GI absorption was small, below 0.4% for Pu and 0.2% for Np. Np and Pu was mainly retained in the small intestine. Pu was retained in the ileum wall till 66 d, and afterwards in the duodenum wall. Histological study of Pu retention showed that it was confined to the macrophages under the ileum villi epithelial cells. Np did not seem to have a well-defined retention compartment. Retention occurred first in the ileum wall up to 6 d, afterwards it was divided between the ileum and duodenum walls up to 77 d and finally, between the duodenum and jejunum walls from 132 days of age onwards. The study shows a difference between Np and Pu GI absorption in neonatal baboons. Np GI absorption decreased to adult value in less than 3 months whereas Pu GI absorption decreased to adult value within 195 days. Our Pu results demonstrated that, the tenfold increase of actinides gastrointestinal transfer proposed by ICRP up to 12 months of age in newborn humans seems acceptable. (authors) [fr

Production of nitrous oxide in the auroral D and E regions

Science.gov (United States)

Zipf, E. C.; Prasad, S. S.

1980-01-01

A study of nitrous oxide formation mechanisms indicates that N2O concentrations greater than 10 to the 9th per cu cm could be produced in IBC III aurora or by lower-level activity lasting for many hours, and, in favorable conditions, the N2O concentration could exceed the local nitric oxide density. An upper limit on the globally averaged N2O production rate from auroral activity is estimated at 2 x 10 to the 27th per second.

Molecular basis for arsenic-Induced alteration in nitric oxide production and oxidative stress: implication of endothelial dysfunction

International Nuclear Information System (INIS)

Kumagai, Yoshito; Pi Jingbo

2004-01-01

Accumulated epidemiological studies have suggested that prolonged exposure of humans to arsenic in drinking water is associated with vascular diseases. The exact mechanism of how this occurs currently unknown. Nitric oxide (NO), formed by endothelial NO synthase (eNOS), plays a crucial role in the vascular system. Decreased availability of biologically active NO in the endothelium is implicated in the pathophysiology of several vascular diseases and inhibition of eNOS by arsenic is one of the proposed mechanism s for arsenic-induced vascular diseases. In addition, during exposure to arsenic, overproduction of reactive oxygen species (ROS) can occur, resulting in oxidative stress, which is another major risk factor for vascular dysfunction. The molecular basis for decreased NO levels and increased oxidative stress during arsenic exposure is poorly understood. In this article, evidence for arsenic-mediated alteration in NO production and oxidative stress is reviewed. The results of a cross-sectional study in an endemic area of chronic arsenic poisoning and experimental animal studies to elucidate a potential mechanism for the impairment of NO formation and oxidative stress caused by prolonged exposure to arsenate in the drinking water are also reviewed

Oxidative Stability and Sensory Attributes of Fermented Milk Product Fortified with Fish Oil and Marine Phospholipids

DEFF Research Database (Denmark)

Lu, Henna Fung Sieng; Thomsen, Birgitte Raagaard; Hyldig, Grethe

2013-01-01

Marine phospholipids (PL) are potential ingredients for food fortification due to its numerous advantages. The main objective of this study was to investigate whether a fermented milk product fortified with a mixture of marine PL and fish oil had better oxidative stability than a fermented milk...... product fortified with fish oil alone. Fortification of a fermented milk product with marine PL was performed by incorporating 1 % w/w lipids, either in the form of neat oil or in the form of a pre-emulsion. Lipid oxidation was investigated in the neat emulsions and fortified products by the measurements...... of primary, secondary volatile oxidation products and tocopherol content upon 32 days storage at 2 °C and 28 days storage at 5 °C, respectively. Analyses of particle size distribution, viscosity and microbial growth were also performed. In addition, sensory attributes such as sour, fishy and rancid flavor...

Hybrid Nitrous Oxide Production from a Partial Nitrifying Bioreactor: Hydroxylamine Interactions with Nitrite.

Science.gov (United States)

Terada, Akihiko; Sugawara, Sho; Hojo, Keisuke; Takeuchi, Yuki; Riya, Shohei; Harper, Willie F; Yamamoto, Tomoko; Kuroiwa, Megumi; Isobe, Kazuo; Katsuyama, Chie; Suwa, Yuichi; Koba, Keisuke; Hosomi, Masaaki

2017-03-07

The goal of this study was to elucidate the mechanisms of nitrous oxide (N 2 O) production from a bioreactor for partial nitrification (PN). Ammonia-oxidizing bacteria (AOB) enriched from a sequencing batch reactor (SBR) were subjected to N 2 O production pathway tests. The N 2 O pathway test was initiated by supplying an inorganic medium to ensure an initial NH 4 + -N concentration of 160 mg-N/L, followed by 15 NO 2 - (20 mg-N/L) and dual 15 NH 2 OH (each 17 mg-N/L) spikings to quantify isotopologs of gaseous N 2 O ( 44 N 2 O, 45 N 2 O, and 46 N 2 O). N 2 O production was boosted by 15 NH 2 OH spiking, causing exponential increases in mRNA transcription levels of AOB functional genes encoding hydroxylamine oxidoreductase (haoA), nitrite reductase (nirK), and nitric oxide reductase (norB) genes. Predominant production of 45 N 2 O among N 2 O isotopologs (46% of total produced N 2 O) indicated that coupling of 15 NH 2 OH with 14 NO 2 - produced N 2 O via N-nitrosation hybrid reaction as a predominant pathway. Abiotic hybrid N 2 O production was also observed in the absence of the AOB-enriched biomass, indicating multiple pathways for N 2 O production in a PN bioreactor. The additional N 2 O pathway test, where 15 NH 4 + was spiked into 400 mg-N/L of NO 2 - concentration, confirmed that the hybrid N 2 O production was a dominant pathway, accounting for approximately 51% of the total N 2 O production.

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

Science.gov (United States)

Tuominen, Anu; Sundman, Terhi

2013-01-01

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

Shelf-life modeling of bakery products by using oxidation indices.

Science.gov (United States)

Calligaris, Sonia; Manzocco, Lara; Kravina, Giuditta; Nicoli, Maria Cristina

2007-03-07

The aim of this work was to develop a shelf-life prediction model of lipid-containing bakery products. To this purpose (i) the temperature dependence of the oxidation rate of bakery products was modeled, taking into account the changes in lipid physical state; (ii) the acceptance limits were assessed by sensory analysis; and (iii) the relationship between chemical oxidation index and acceptance limit was evaluated. Results highlight that the peroxide number, the changes of which are linearly related to consumer acceptability, is a representative index of the quality depletion of biscuits during their shelf life. In addition, the evolution of peroxides can be predicted by a modified Arrhenius equation accounting for the changes in the physical state of biscuit fat. Knowledge of the relationship between peroxides and sensory acceptability together with the temperature dependence of peroxide formation allows a mathematical model to be set up to simply and quickly calculate the shelf life of biscuits.

Biodiesel Production from Castor Oil by Using Calcium Oxide Derived from Mud Clam Shell

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S. Ismail

2016-01-01

Full Text Available The catalytic potential of calcium oxide synthesized from mud clam shell as a heterogeneous catalyst for biodiesel production was studied. The mud clam shell calcium oxide was characterized using particle size analyzer, Fourier transform infrared spectroscopy, scanning electron microscopy, and BET gas sorption analyzer. The catalyst performance of mud clam shell calcium oxide was studied in the transesterification of castor oil as biodiesel. Catalyst characterization and transesterification study results of synthesized catalyst proved the efficiency of the natural derived catalyst for biodiesel production. A highest biodiesel yield of 96.7% was obtained at optimal parameters such as 1 : 14 oil-to-methanol molar ratio, 3% w/w catalyst concentration, 60°C reaction temperature, and 2-hour reaction time. Catalyst reusability test shows that the synthesized calcium oxide from mud clam shell is reusable up to 5 times.

Potential for the use of hydrochloric acid in fission reactor fuel recycle

International Nuclear Information System (INIS)

Mailen, J.C.; Bell, J.T.

1985-01-01

The chemistry and the effects of the use of hydrochloric acid as the aqueous phase in fuel recycle are surveyed. Available data are sufficient to suggest that separations of actinides and fission products can be at least as good in an HCl-trialkyl amine system as in Purex. Advantages of the HCl system are simpler operations of the off-gas system, better separation of neptunium from uranium and plutonium, better control of oxidation states of the dissolved species, and simpler recycle of the acid. A possible advantage is the more complete dissolution of the fission products, leaving very little insoluble residue. Disadvantages include lack of development of methods for dissolution of oxide fuel in hydrochloric acid, the requirement for processing equipment constructed of titanium, possible complications in the waste-handling system, and the dissolution of much of the cladding in the case of stainless-steel clad fuel

Parabanic acid is the singlet oxygen specific oxidation product of uric acid.

Science.gov (United States)

Iida, Sayaka; Ohkubo, Yuki; Yamamoto, Yorihiro; Fujisawa, Akio

2017-11-01

Uric acid quenches singlet oxygen physically or reacts with it, but the oxidation product has not been previously characterized. The present study determined that the product is parabanic acid, which was confirmed by LC/TOFMS analysis. Parabanic acid was stable at acidic pH (acid at neutral or alkaline pH. The total yields of parabanic acid and oxaluric acid based on consumed uric acid were ~100% in clean singlet oxygen production systems such as UVA irradiation of Rose Bengal and thermal decomposition of 3-(1,4-dihydro-1,4-epidioxy-4-methyl-1-naphthyl)propionic acid. However, the ratio of the amount of uric acid consumed to the total amount of singlet oxygen generated was less than 1/180, indicating that most of the singlet oxygen was physically quenched. The total yields of parabanic acid and oxaluric acid were high in the uric acid oxidation systems with hydrogen peroxide plus hypochlorite or peroxynitrite. They became less than a few percent in peroxyl radical-, hypochlorite- or peroxynitrite-induced oxidation of uric acid. These results suggest that parabanic acid could be an in vivo probe of singlet oxygen formation because of the wide distribution of uric acid in human tissues and extracellular spaces. In fact, sunlight exposure significantly increased human skin levels of parabanic acid.

Production of Nitrous Oxide from Nitrite in Stable Type II Methanotrophic Enrichments.

Science.gov (United States)

Myung, Jaewook; Wang, Zhiyue; Yuan, Tong; Zhang, Ping; Van Nostrand, Joy D; Zhou, Jizhong; Criddle, Craig S

2015-09-15

The coupled aerobic-anoxic nitrous decomposition operation is a new process for wastewater treatment that removes nitrogen from wastewater and recovers energy from the nitrogen in three steps: (1) NH4(+) oxidation to NO2(-), (2) NO2(-) reduction to N2O, and (3) N2O conversion to N2 with energy production. Here, we demonstrate that type II methanotrophic enrichments can mediate step two by coupling oxidation of poly(3-hydroxybutyrate) (P3HB) to NO2(-) reduction. Enrichments grown with NH4(+) and NO2(-) were subject to alternating 48-h aerobic and anoxic periods, in which CH4 and NO2(-) were added together in a "coupled" mode of operation or separately in a "decoupled mode". Community structure was stable in both modes and dominated by Methylocystis. In the coupled mode, production of P3HB and N2O was low. In the decoupled mode, significant P3HB was produced, and oxidation of P3HB drove reduction of NO2(-) to N2O with ∼ 70% conversion for >30 cycles (120 d). In batch tests of wasted cells from the decoupled mode, N2O production rates increased at low O2 or high NO2(-) levels. The results are significant for the development of engineered processes that remove nitrogen from wastewater and for understanding of conditions that favor environmental production of N2O.

Biodiesel Production from Castor Oil by Using Calcium Oxide Derived from Mud Clam Shell

OpenAIRE

Ismail, S.; Ahmed, A. S.; Anr, Reddy; Hamdan, S.

2016-01-01

The catalytic potential of calcium oxide synthesized from mud clam shell as a heterogeneous catalyst for biodiesel production was studied. The mud clam shell calcium oxide was characterized using particle size analyzer, Fourier transform infrared spectroscopy, scanning electron microscopy, and BET gas sorption analyzer. The catalyst performance of mud clam shell calcium oxide was studied in the transesterification of castor oil as biodiesel. Catalyst characterization and transesterification s...

Oxidative stress induced inflammation initiates functional decline of tear production.

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Yuichi Uchino

Full Text Available Oxidative damage and inflammation are proposed to be involved in an age-related functional decline of exocrine glands. However, the molecular mechanism of how oxidative stress affects the secretory function of exocrine glands is unclear. We developed a novel mev-1 conditional transgenic mouse model (Tet-mev-1 using a modified tetracycline system (Tet-On/Off system. This mouse model demonstrated decreased tear production with morphological changes including leukocytic infiltration and fibrosis. We found that the mev-1 gene encodes Cyt-1, which is the cytochrome b(560 large subunit of succinate-ubiquinone oxidoreductase in complex II of mitochondria (homologous to succinate dehydrogenase C subunit (SDHC in humans. The mev-1 gene induced excessive oxidative stress associated with ocular surface epithelial damage and a decrease in protein and aqueous secretory function. This new model provides evidence that mitochondrial oxidative damage in the lacrimal gland induces lacrimal dysfunction resulting in dry eye disease. Tear volume in Tet-mev-1 mice was lower than in wild type mice and histopathological analyses showed the hallmarks of lacrimal gland inflammation by intense mononuclear leukocytic infiltration and fibrosis in the lacrimal gland of Tet-mev-1 mice. These findings strongly suggest that oxidative stress can be a causative factor for the development of dry eye disease.

Comprehensive Analysis of the Gas- and Particle-Phase Products of VOC Oxidation

Science.gov (United States)

Bakker-Arkema, J.; Ziemann, P. J.

2017-12-01

Controlled environmental chamber studies are important for determining atmospheric reaction mechanisms and gas and aerosol products formed in the oxidation of volatile organic compounds (VOCs). Such information is necessary for developing detailed chemical models for use in predicting the atmospheric fate of VOCs and also secondary organic aerosol (SOA) formation. However, complete characterization of atmospheric oxidation reactions, including gas- and particle-phase product yields, and reaction branching ratios, are difficult to achieve. In this work, we investigated the reactions of terminal and internal alkenes with OH radicals in the presence of NOx in an attempt to fully characterize the chemistry of these systems while minimizing and accounting for the inherent uncertainties associated with environmental chamber experiments. Gas-phase products (aldehydes formed by alkoxy radical decomposition) and particle-phase products (alkyl nitrates, β-hydroxynitrates, dihydroxynitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls) formed through pathways involving addition of OH to the C=C double bond as well as H-atom abstraction were identified and quantified using a suite of analytical techniques. Particle-phase products were analyzed in real time with a thermal desorption particle beam mass spectrometer; and off-line by collection onto filters, extraction, and subsequent analysis of functional groups by derivatization-spectrophotometric methods developed in our lab. Derivatized products were also separated by liquid chromatography for molecular quantitation by UV absorbance and identification using chemical ionization-ion trap mass spectrometry. Gas phase aldehydes were analyzed off-line by collection onto Tenax and a 5-channel denuder with subsequent analysis by gas chromatography, or by collection onto DNPH-coated cartridges and subsequent analysis by liquid chromatography. The full product identification and quantitation, with careful

Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds

Directory of Open Access Journals (Sweden)

R. Holzinger

2005-01-01

Full Text Available Vertical gradients of mixing ratios of volatile organic compounds have been measured in a Ponderosa pine forest in Central California (38.90° N, 120.63° W, 1315m. These measurements reveal large quantities of previously unreported oxidation products of short lived biogenic precursors. The emission of biogenic precursors must be in the range of 13-66µmol m-2h-1 to produce the observed oxidation products. That is 6-30 times the emissions of total monoterpenes observed above the forest canopy on a molar basis. These reactive precursors constitute a large fraction of biogenic emissions at this site, and are not included in current emission inventories. When oxidized by ozone they should efficiently produce secondary aerosol and hydroxyl radicals.

Piper sarmentosum increases nitric oxide production in oxidative stress: a study on human umbilical vein endothelial cells

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Azizah Ugusman

2010-01-01

Full Text Available OBJECTIVE: Nitric oxide produced by endothelial nitric oxide synthase (eNOS possesses multiple anti-atherosclerotic properties. Hence, enhanced expression of eNOS and increased Nitric oxide levels may protect against the development of atherosclerosis. Piper sarmentosum is a tropical plant with antioxidant and anti-inflammatory activities. This study aimed to investigate the effects of Piper sarmentosum on the eNOS and Nitric oxide pathway in cultured human umbilical vein endothelial cells (HUVECs. METHODS: HUVECs were divided into four groups: control, treatment with 180 μM hydrogen peroxide (H2O2, treatment with 150 μg/mL aqueous extract of Piper sarmentosum, and concomitant treatment with aqueous extract of PS and H2O2 for 24 hours. Subsequently, HUVECs were harvested and eNOS mRNA expression was determined using qPCR. The eNOS protein level was measured using ELISA, and the eNOS activity and Nitric oxide level were determined by the Griess reaction. RESULTS: Human umbilical vein endothelial cells treated with aqueous extract of Piper sarmentosum showed a marked induction of Nitric oxide. Treatment with PS also resulted in increased eNOS mRNA expression, eNOS protein level and eNOS activity in HUVECs. CONCLUSION: Aqueous extract of Piper sarmentosum may improve endothelial function by promoting NO production in HUVECs.

Intensity of lipid oxidation and formation of cholesterol oxidation products during frozen storage of raw and cooked chicken

OpenAIRE

Conchillo, A. (Ana); Ansorena, D. (Diana); Astiasarán, I. (Iciar)

2004-01-01

Raw and cooked chicken breasts were stored at −18 °C for 3 months under aerobic and vacuum conditions, and the intensity of lipid oxidation and the formation of COP (cholesterol oxidation products) were studied. Raw samples showed low COP levels (4.60–7.40 µg g−1 fat), TBARS (thiobarbituric acid reactive substances) levels (0.01–0.03 mg kg−1) and peroxide values (not detected) under both aerobic and vacuum conditions. Cooked samples (grilled and roasted) showed TBARS levels of 0.36–0.99 mg kg...

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

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XINZHUANG ZHANG

2016-03-01

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

Shell biofilm-associated nitrous oxide production in marine molluscs

DEFF Research Database (Denmark)

Heisterkamp, I.M.; Schramm, Andreas; Larsen, Lone Heimann

2013-01-01

Emission of the greenhouse gas nitrous oxide (N2O) from freshwater and terrestrial invertebrates has exclusively been ascribed to N2O production by ingested denitrifying bacteria in the anoxic gut of the animals. Our study of marine molluscs now shows that also microbial biofilms on shell surfaces...... are important sites of N2O production. The shell biofilms of Mytilus edulis, Littorina littorea and Hinia reticulata contributed 18-94% to the total animal-associated N2O emission. Nitrification and denitrification were equally important sources of N2O in shell biofilms as revealed by 15N-stable isotope...... mollusc species. Ammonium excretion by the animals was found to be sufficient to sustain N2O production in the shell biofilm. Apparently, the animals provide a nutrient-enriched microenvironment that stimulates growth and N2O production of the shell biofilm. This animal-induced stimulation...

Oxidative Stress in Shiga Toxin Production by Enterohemorrhagic Escherichia coli

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Katarzyna Licznerska

2016-01-01

Full Text Available Virulence of enterohemorrhagic Escherichia coli (EHEC strains depends on production of Shiga toxins. These toxins are encoded in genomes of lambdoid bacteriophages (Shiga toxin-converting phages, present in EHEC cells as prophages. The genes coding for Shiga toxins are silent in lysogenic bacteria, and prophage induction is necessary for their efficient expression and toxin production. Under laboratory conditions, treatment with UV light or antibiotics interfering with DNA replication are commonly used to induce lambdoid prophages. Since such conditions are unlikely to occur in human intestine, various research groups searched for other factors or agents that might induce Shiga toxin-converting prophages. Among other conditions, it was reported that treatment with H2O2 caused induction of these prophages, though with efficiency significantly lower relative to UV-irradiation or mitomycin C treatment. A molecular mechanism of this phenomenon has been proposed. It appears that the oxidative stress represents natural conditions provoking induction of Shiga toxin-converting prophages as a consequence of H2O2 excretion by either neutrophils in infected humans or protist predators outside human body. Finally, the recently proposed biological role of Shiga toxin production is described in this paper, and the “bacterial altruism” and “Trojan Horse” hypotheses, which are connected to the oxidative stress, are discussed.

Investigation into formation of nanoparticles of tetravalent neptunium in slightly alkaline aqueous solution

International Nuclear Information System (INIS)

Husar, Richard

2015-01-01

Considering the worldwide growing discharge of minor actinides and the current need for geological disposal facilities for radioactive waste, this work provides a contribution to the safety case concerning Np transport if it would be released from deep repository sites and moving from alkaline cement conditions (near-field) to more neutral environmental conditions (far-field). The reducing conditions in a nuclear waste repository render neptunium tetravalent, which is assumed to be immobile in aqueous environment due to the low solubility solution of Np(IV). For tetravalent actinide nuclides, the most significant transport should occur via colloidal particles. This work demonstrates the formation of intrinsic neptunium dioxide nanocrystals and amorphous Np(IV) silica colloids under environmentally relevant conditions. The dissociation of the initial soluble Np(IV) complex (i.e. [Np(IV)(CO 3 ) 5 ] 6- ) induces the intrinsic formation of nanocrystalline NpO 2 in the solution phase. The resulting irregularly shaped nanocrystals with an average size of 4 nm exhibit a face-centered cubic (fcc), fluorite-type structure (space group Fm anti 3m). The NCs tend to agglomerate under ambient conditions due to the weakly charged hydrodynamic surface at neutral pH (zetapotential ζ ∝0 mV). The formation of micron-sized agglomerates, composed of nanocrystals of 2-5 nm in size, and the subsequent precipitation cause immobilization of the major amount of Np(IV) in the Np carbonate system. Agglomeration of NpO 2 nanocrystals in dependence on time was indicated by PCS and UV-vis absorption spectroscopy with the changes of baseline characteristics and absorption maximum at 742 nm. Hitherto, unknown polynuclear species as intermediate species of NpO 2 nanocrystal formation were isolated from solution and observed by HR-TEM. These polynuclear Np species appear as dimers, trimers and hexanuclear compounds in analogy with those reported for other actinides. Intrinsic formation of NpO 2

Agglomerates, smoke oxide particles, and carbon inclusions in condensed combustion products of an aluminized GAP-based propellant

Science.gov (United States)

Ao, Wen; Liu, Peijin; Yang, Wenjing

2016-12-01

In solid propellants, aluminum is widely used to improve the performance, however the condensed combustion products especially the large agglomerates generated from aluminum combustion significantly affect the combustion and internal flow inside the solid rocket motor. To clarify the properties of the condensed combustion products of aluminized propellants, a constant-pressure quench vessel was adopted to collect the combustion products. The morphology and chemical compositions of the collected products, were then studied by using scanning electron microscopy coupled with energy dispersive (SEM-EDS) method. Various structures have been observed in the condensed combustion products. Apart from the typical agglomerates or smoke oxide particles observed before, new structures including the smoke oxide clusters, irregular agglomerates and carbon-inclusions are discovered and investigated. Smoke oxide particles have the highest amount in the products. The highly dispersed oxide particle is spherical with very smooth surface and is on the order of 1-2 μm, but due to the high temperature and long residence time, these small particles will aggregate into smoke oxide clusters which are much larger than the initial particles. Three types of spherical agglomerates have been found. As the ambient gas temperature is much higher than the boiling point of Al2O3, the condensation layer inside which the aluminum drop is burning would evaporate quickly, which result in the fact that few "hollow agglomerates" has been found compared to "cap agglomerates" and "solid agglomerates". Irregular agglomerates usually larger than spherical agglomerates. The formation of irregular agglomerates likely happens by three stages: deformation of spherical aluminum drops; combination of particles with various shape; finally production of irregular agglomerates. EDS results show the ratio of O to Al on the surface of agglomerates is lower in comparison to smoke oxide particles. C and O account for

Quantitative and qualitative sensing techniques for biogenic volatile organic compounds and their oxidation products.

Science.gov (United States)

Kim, Saewung; Guenther, Alex; Apel, Eric

2013-07-01

The physiological production mechanisms of some of the organics in plants, commonly known as biogenic volatile organic compounds (BVOCs), have been known for more than a century. Some BVOCs are emitted to the atmosphere and play a significant role in tropospheric photochemistry especially in ozone and secondary organic aerosol (SOA) productions as a result of interplays between BVOCs and atmospheric radicals such as hydroxyl radical (OH), ozone (O3) and NOX (NO + NO2). These findings have been drawn from comprehensive analysis of numerous field and laboratory studies that have characterized the ambient distribution of BVOCs and their oxidation products, and reaction kinetics between BVOCs and atmospheric oxidants. These investigations are limited by the capacity for identifying and quantifying these compounds. This review highlights the major analytical techniques that have been used to observe BVOCs and their oxidation products such as gas chromatography, mass spectrometry with hard and soft ionization methods, and optical techniques from laser induced fluorescence (LIF) to remote sensing. In addition, we discuss how new analytical techniques can advance our understanding of BVOC photochemical processes. The principles, advantages, and drawbacks of the analytical techniques are discussed along with specific examples of how the techniques were applied in field and laboratory measurements. Since a number of thorough review papers for each specific analytical technique are available, readers are referred to these publications rather than providing thorough descriptions of each technique. Therefore, the aim of this review is for readers to grasp the advantages and disadvantages of various sensing techniques for BVOCs and their oxidation products and to provide guidance for choosing the optimal technique for a specific research task.

Ultrasound-assisted oxidative process for sulfur removal from petroleum product feedstock.

Science.gov (United States)

Mello, Paola de A; Duarte, Fábio A; Nunes, Matheus A G; Alencar, Mauricio S; Moreira, Elizabeth M; Korn, Mauro; Dressler, Valderi L; Flores, Erico M M

2009-08-01

A procedure using ultrasonic irradiation is proposed for sulfur removal of a petroleum product feedstock. The procedure involves the combination of a peroxyacid and ultrasound-assisted treatment in order to comply with the required sulfur content recommended by the current regulations for fuels. The ultrasound-assisted oxidative desulfurization (UAOD) process was applied to a petroleum product feedstock using dibenzothiophene as a model sulfur compound. The influence of ultrasonic irradiation time, oxidizing reagents amount, kind of solvent for the extraction step and kind of organic acid were investigated. The use of ultrasonic irradiation allowed higher efficiency for sulfur removal in comparison to experiments performed without its application, under the same reactional conditions. Using the optimized conditions for UAOD, the sulfur removal was about 95% after 9min of ultrasonic irradiation (20kHz, 750W, run at 40%), using hydrogen peroxide and acetic acid, followed by extraction with methanol.

Effects of silver nanoparticles on nitrification and associated nitrous oxide production in aquatic environments.

Science.gov (United States)

Zheng, Yanling; Hou, Lijun; Liu, Min; Newell, Silvia E; Yin, Guoyu; Yu, Chendi; Zhang, Hongli; Li, Xiaofei; Gao, Dengzhou; Gao, Juan; Wang, Rong; Liu, Cheng

2017-08-01

Silver nanoparticles (AgNPs) are the most common materials in nanotechnology-based consumer products globally. Because of the wide application of AgNPs, their potential environmental impact is currently a highly topical focus of concern. Nitrification is one of the processes in the nitrogen cycle most susceptible to AgNPs but the specific effects of AgNPs on nitrification in aquatic environments are not well understood. We report the influence of AgNPs on nitrification and associated nitrous oxide (N 2 O) production in estuarine sediments. AgNPs inhibited nitrification rates, which decreased exponentially with increasing AgNP concentrations. The response of nitrifier N 2 O production to AgNPs exhibited low-dose stimulation (production could be enhanced by >100% at low doses of AgNPs. This result was confirmed by metatranscriptome studies showing up-regulation of nitric oxide reductase (norQ) gene expression in the low-dose treatment. Isotopomer analysis revealed that hydroxylamine oxidation was the main N 2 O production pathway, and its contribution to N 2 O emission was enhanced when exposed to low-dose AgNPs. This study highlights the molecular underpinnings of the effects of AgNPs on nitrification activity and demonstrates that the release of AgNPs into the environment should be controlled because they interfere with nitrifying communities and stimulate N 2 O emission.

Study of Nitric Oxide production by murine peritoneal macrophages induced by Brucella Lipopolysaccharide

Directory of Open Access Journals (Sweden)

Kavoosi G

2001-07-01

Full Text Available Brueclla is a gram negative bacteria that causes Brucellosis. Lipopolysaccharide (LPS ", the pathogenic agent of Brucella is composed of O-chain, core oligosaccharide and lipid A. in addition, the structural and biological properties of different LPS extracted from different strains are not identical. The first defense system against LPS is nonspecific immunity that causes macrophage activation. Activated macrophages produce oxygen and nitrogen radicals that enhance the protection against intracellular pathogens.In this experiment LPS was extracted by hot phenol- water procedure and the effect of various LPSs on nitric oxide prodution by peritoneal mouse macrophages was examined.Our results demonstrated that the effect of LPS on nitric oxide production is concentration-dependent we observed the maximum response in concentration of 10-20 microgram per milliliter. Also our results demonstrate that LPS extracted from vaccine Brucella abortus (S 19 had a highe effect on nitric oxide production than the LPS from other strains

Yucca Mountain project : FY 2006 annual report for waste form testingactivities.

Energy Technology Data Exchange (ETDEWEB)

Ebert, W. L.; Fortner, J. A.; Guelis, A. V.; Cunnane, J. C.

2006-11-01

This report describes the experimental work performed at Argonne National Laboratory (Argonne) during fiscal year (FY 2006) under the Bechtel SAIC Company, LLC (BSC) Memorandum Purchase Order (MPO) contract number B004210CM3X. Because this experimental work is focused on the dissolution and precipitation behavior of neptunium, the report also includes, or incorporates by reference, earlier results that are relevant to presenting a more complete understanding of the likely behavior of neptunium under experimental conditions relevant to the Yucca Mountain repository. Important results relevant to the technical bases, validations, and conservatisms in current source term models are summarized. The CSNF samples were observed to corrode following the general contour of the surface rather than via (for instance) grain boundary attack. This supports the current approach of estimating the effective surface area of corroding CSNF based on the geometric surface area of fuel pellet fragments. It was observed that the neptunium and plutonium concentrations in corroded CSNF samples were somewhat higher at and near the corrosion front (i.e., at the interface between the alteration product ''rind'' layer and the underlying fuel) than in the bulk fuel. The neptunium and plutonium at the corrosion front and in the uranyl alteration layer were found to be in the quadravalent (4+) oxidation state. The uranyl phases that constitute most of the alteration rind were depleted in neptunium relative to the bulk fuel: neptunium concentrations in the uranyl alteration rind were less than 20% of that in the parent fuel. Homogeneous precipitation tests have shown that solids precipitate from a 1 x 10{sup -4} M Np(V) solution over the temperature range of 200-280 C, but no evidence was found that any solids precipitated from the same solution at 150 C through 289 days. The solids formed in the homogeneous precipitation tests were predominantly a Np(IV)-bearing phase

Plasmon-enhanced Solar Fuel Production with Gold-metal Oxide Hybrid Nanomaterials

DEFF Research Database (Denmark)

Engelbrekt, Christian; Law, Matt; Zhang, Jingdong

, provide new catalytic routes and expands the scope of solar photocatalysis. We prepare metal oxide SNPs, gold PNPs and their hybrids through mild aqueous syntheses to develop efficient photocatalyst for solar fuel production. Focus is placed on the synergetic interplay between SNPs and PNPs, understanding...

Primary oxidation and reduction products in x-irradiated aspartic acid

International Nuclear Information System (INIS)

Adams, S.M.; Budzinski, E.E.; Box, H.C.

1976-01-01

The primary reduction products identified by ESR--ENDOR spectroscopy in single crystals of DL-aspartic acid hydrochloride irradiated at 4.2degreeK are anions formed by addition of an electron to the carbonyl oxygen atoms of the carboxylic acid groups. The main consequence of the oxidation process is to produce a hole centered mainly on atomic chlorine

The production of nitric oxide in EL4 lymphoma cells overexpressing growth hormone.

Science.gov (United States)

Arnold, Robyn E; Weigent, Douglas A

2003-01-01

Growth hormone (GH) is produced by immunocompetent cells and has been implicated in the regulation of a multiplicity of functions in the immune system involved in growth and activation. However, the actions of endogenous or lymphocyte GH and its contribution to immune reactivity when compared with those of serum or exogenous GH are still unclear. In the present study, we overexpressed lymphocyte GH in EL4 lymphoma cells, which lack the GH receptor (GHR), to determine the role of endogenous GH in nitric oxide (NO) production and response to genotoxic stress. Western blot analysis demonstrated that the levels of GH increased approximately 40% in cells overexpressing GH (GHo) when compared with cells with vector alone. The results also show a substantial increase in NO production in cells overexpressing GH that could be blocked by N(G)-monomethyl-L-arginine (L-NMMA), an L-arginine analogue that competitively inhibits all three isoforms of nitric oxide synthase (NOS). No evidence was obtained to support an increase in peroxynitrite in cells overexpressing GH. Overexpression of GH increased NOS activity, inducible nitric oxide synthase (iNOS) promoter activity, and iNOS protein expression, whereas endothelial nitric oxide synthase and neuronal nitric oxide synthase protein levels were essentially unchanged. In addition, cells overexpressing GH showed increased arginine transport ability and intracellular arginase activity when compared with control cells. GH overexpression appeared to protect cells from the toxic effects of the DNA alkylating agent methyl methanesulfonate. This possibility was suggested by maintenance of the mitochondrial transmembrane potential in cells overexpressing GH when compared with control cells that could be blocked by L-NMMA. Taken together, the data support the notion that lymphocyte GH, independently of the GH receptor, may play a key role in the survival of lymphocytes exposed to stressful stimuli via the production of NO.

Dissimilatory reduction of nitrate and nitrite in the bovine rumen: nitrous oxide production and effect of acetylene.

Science.gov (United States)

Kaspar, H F; Tiedje, J M

1981-03-01

15N tracer methods and gas chromatography coupled to an electron capture detector were used to investigate dissimilatory reduction of nitrate and nitrite by the rumen microbiota of a fistulated cow. Ammonium was the only 15N-labeled end product of quantitative significance. Only traces of nitrous oxide were detected as a product of nitrate reduction; but in experiments with nitrite, up to 0.3% of the added nitrogen accumulated as nitrous oxide, but it was not further reduced. Furthermore, when 13NO3- was incubated with rumen microbiota virtually no [13N]N2 was produced. Acetylene partially inhibited the reduction of nitrite to ammonium as well as the formation of nitrous oxide. It is suggested that in the rumen ecosystem nitrous oxide is a byproduct of dissimilatory nitrite reduction to ammonium rather than a product of denitrification and that the latter process is absent from the rumen habitat.

Determination of polycyclic aromatic hydrocarbons and their oxy-, nitro-, and hydroxy-oxidation products

International Nuclear Information System (INIS)

Cochran, R.E.; Dongari, N.; Jeong, H.; Beránek, J.; Haddadi, S.; Shipp, J.; Kubátová, A.

2012-01-01

Highlights: ► We describe a method for determining PAHs and their oxidation products. ► Solid-phase extraction was used to fractionate PAHs and their oxidation products. ► Gas chromatography–mass spectrometry methods were optimized. ► The developed method was applied to two particulate matter (PM) samples. - Abstract: A sensitive method has been developed for the trace analysis of PAHs and their oxidation products (i.e., nitro-, oxy-, and hydroxy-PAHs) in air particulate matter (PM). Following PM extraction, PAHs, nitro-, oxy-, and hydroxy-PAHs were fractionated using solid phase extraction (SPE) based on their polarities. Gas chromatography–mass spectrometry (GC–MS) conditions were optimized, addressing injection (i.e., splitless time), negative-ion chemical ionization (NICI) parameters, i.e., source temperature and methane flow rate, and MS scanning conditions. Each class of PAH oxidation products was then analyzed using the sample preparation and appropriate ionization conditions (e.g., nitro-PAHs exhibited the greatest sensitivity when analyzed with NICI–MS while hydroxy-PAHs required chemical derivatization prior to GC–MS analysis). The analyses were performed in selected-ion-total-ion (SITI) mode, combining the increased sensitivity of selected-ion monitoring (SIM) with the identification advantages of total-ion current (TIC). The instrumental LODs determined were 6–34 pg for PAHs, 5–36 pg for oxy-PAHs, and 1–21 pg for derivatized hydroxy-PAHs using electron ionization (GC-EI-MS). NICI–MS was found to be a useful tool for confirming the tentative identification of oxy-PAHs. For nitro-PAHs, LODs were 1–10 pg using negative-ion chemical ionization (GC-NICI-MS). The developed method was successfully applied to two types of real-world PM samples, diesel exhaust standard reference material (SRM 2975) and wood smoke PM.

Influence of Catalyst Acid/Base Properties in Acrolein Production by Oxidative Coupling of Ethanol and Methanol.

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Lilić, Aleksandra; Bennici, Simona; Devaux, Jean-François; Dubois, Jean-Luc; Auroux, Aline

2017-05-09

Oxidative coupling of methanol and ethanol represents a new route to produce acrolein. In this work, the overall reaction was decoupled in two steps, the oxidation and the aldolization, by using two consecutive reactors to investigate the role of the acid/base properties of silica-supported oxide catalysts. The oxidation of a mixture of methanol and ethanol to formaldehyde and acetaldehyde was performed over a FeMoO x catalyst, and then the product mixture was transferred without intermediate separation to a second reactor, in which the aldol condensation and dehydration to acrolein were performed over the supported oxides. The impact of the acid/base properties on the selectivity towards acrolein was investigated under oxidizing conditions for the first time. The acid/base properties of the catalysts were investigated by NH 3 -, SO 2 -, and methanol-adsorption microcalorimetry. A MgO/SiO 2 catalyst was the most active in acrolein production owing to an appropriate ratio of basic to acidic sites. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Progesterone modulates the LPS-induced nitric oxide production by a progesterone-receptor independent mechanism.

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Wolfson, Manuel Luis; Schander, Julieta Aylen; Bariani, María Victoria; Correa, Fernando; Franchi, Ana María

2015-12-15

Genital tract infections caused by Gram-negative bacteria induce miscarriage and are one of the most common complications of human pregnancy. LPS administration to 7-day pregnant mice induces embryo resorption after 24h, with nitric oxide playing a fundamental role in this process. We have previously shown that progesterone exerts protective effects on the embryo by modulating the inflammatory reaction triggered by LPS. Here we sought to investigate whether the in vivo administration of progesterone modulated the LPS-induced nitric oxide production from peripheral blood mononuclear cells from pregnant and non-pregnant mice. We found that progesterone downregulated LPS-induced nitric oxide production by a progesterone receptor-independent mechanism. Moreover, our results suggest a possible participation of glucocorticoid receptors in at least some of the anti-inflammatory effects of progesterone. Copyright © 2015 Elsevier B.V. All rights reserved.

Iron oxides alter methanogenic pathways of acetate in production water of high-temperature petroleum reservoir.

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Pan, Pan; Hong, Bo; Mbadinga, Serge Maurice; Wang, Li-Ying; Liu, Jin-Feng; Yang, Shi-Zhong; Gu, Ji-Dong; Mu, Bo-Zhong

2017-09-01

Acetate is a key intermediate in anaerobic crude oil biodegradation and also a precursor for methanogenesis in petroleum reservoirs. The impact of iron oxides, viz. β-FeOOH (akaganéite) and magnetite (Fe 3 O 4 ), on the methanogenic acetate metabolism in production water of a high-temperature petroleum reservoir was investigated. Methane production was observed in all the treatments amended with acetate. In the microcosms amended with acetate solely about 30% of the acetate utilized was converted to methane, whereas methane production was stimulated in the presence of magnetite (Fe 3 O 4 ) resulting in a 48.34% conversion to methane. Methane production in acetate-amended, β-FeOOH (akaganéite)-supplemented microcosms was much faster and acetate consumption was greatly improved compared to the other conditions in which the stoichiometric expected amounts of methane were not produced. Microbial community analysis showed that Thermacetogenium spp. (known syntrophic acetate oxidizers) and hydrogenotrophic methanogens closely related to Methanothermobacter spp. were enriched in acetate and acetate/magnetite (Fe 3 O 4 ) microcosms suggesting that methanogenic acetate metabolism was through hydrogenotrophic methanogenesis fueled by syntrophic acetate oxidizers. The acetate/β-FeOOH (akaganéite) microcosms, however, differed by the dominance of archaea closely related to the acetoclastic Methanosaeta thermophila. These observations suggest that supplementation of β-FeOOH (akaganéite) accelerated the production of methane further, driven the alteration of the methanogenic community, and changed the pathway of acetate methanogenesis from hydrogenotrophic methanogenesis fueled by syntrophic acetate oxidizers to acetoclastic.

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

Science.gov (United States)

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

2014-01-01

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

Identification of the Products of Oxidation of Quercetin by Air Oxygenat Ambient Temperature

Directory of Open Access Journals (Sweden)

Viktor A Utsal

2007-03-01

Full Text Available Oxidation of quercetin by air oxygen takes place in water and aqueous ethanol solutions under mild conditions, namely in moderately-basic media (pH ∼ 8-10 at ambient temperature and in the absence of any radical initiators, without enzymatic catalysis or irradiation of the reaction media by light. The principal reaction products are typical of other oxidative degradation processes of quercetin, namely 3,4-dihydroxy-benzoic (proto-catechuic and 2,4,6-trihydroxybenzoic (phloroglucinic acids, as well as the decarboxylation product of the latter – 1,3,5-trihydroxybenzene (phloroglucinol. In accordance with the literature data, this process involves the cleavage of the γ-pyrone fragment (ring C of the quercetin molecule by oxygen, with primary formation of 4,6-dihydroxy-2-(3,4-dihydroxybenzoyloxybenzoic acid (depside. However under such mild conditions the accepted mechanism of this reaction (oxidative decarbonylation with formation of carbon monoxide, CO should be reconsidered as preferably an oxidative decarboxylation with formation of carbon dioxide, CO2. Direct head-space analysis of the gaseous components formed during quercetin oxidation in aqueous solution at ambient temperature indicates that the ratio of carbon dioxide/carbon monoxide in the gas phase after acidification of the reaction media is ca. 96:4 %. Oxidation under these mild conditions is typical for other flavonols having OH groups at C3 (e.g., kaempferol, but it is completely suppressed if this hydroxyl group is substituted by a glycoside fragment (as in rutin, or a methyl substituent. An alternative oxidation mechanism involving the direct cleavage of the C2-C3 bond in the diketo-tautomer of quercetin is proposed.

Determination of lipid oxidation products in vegetable oils and marine omega-3 supplements.

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Halvorsen, Bente Lise; Blomhoff, Rune

2011-01-01

There is convincing evidence that replacing dietary saturated fats with polyunsaturated fats (PUFA) decreases risk of cardiovascular diseases. Therefore, PUFA rich foods such as vegetable oils, fatty fish, and marine omega-3 supplements are recommended. However, PUFA are easily oxidizable and there is concern about possible negative health effects from intake of oxidized lipids. Little is known about the degree of lipid oxidation in such products. To assess the content of lipid oxidation products in a large selection of vegetable oils and marine omega-3 supplements available in Norway. Both fresh and heated vegetable oils were studied. A large selection of commercially available vegetable oils and marine omega-3 supplements was purchased from grocery stores, pharmacies, and health food stores in Norway. The content of lipid oxidation products were measured as peroxide value and alkenal concentration. Twelve different vegetable oils were heated for a temperature (225°C) and time (25 minutes) resembling conditions typically used during cooking. The peroxide values were in the range 1.04-10.38 meq/kg for omega-3 supplements and in the range 0.60-5.33 meq/kg for fresh vegetable oils. The concentration range of alkenals was 158.23-932.19 nmol/mL for omega-3 supplements and 33.24-119.04 nmol/mL for vegetable oils. After heating, a 2.9-11.2 fold increase in alkenal concentration was observed for vegetable oils. The contents of hydroperoxides and alkenals in omega-3 supplements are higher than in vegetable oils. After heating vegetable oils, a large increase in alkenal concentration was observed.

Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

International Nuclear Information System (INIS)

Chitnis, R.R.; Dhami, P.S.; Gopalkrishnan, V.; Wattal, P.K.; Ramanujam, A.; Murali, M.S.; Mathur, J.N.; Bauri, A.K.; Chattopadhyay, S.

2000-10-01

A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

Insight into nitrous oxide production processes in the western North Pacific based on a marine ecosystem isotopomer model

Science.gov (United States)

Yoshikawa, C.; Sasai, Y.; Wakita, M.; Honda, M. C.; Fujiki, T.; Harada, N.; Makabe, A.; Matsushima, S.; Toyoda, S.; Yoshida, N.; Ogawa, N. O.; Suga, H.; Ohkouchi, N.

2016-02-01

Based on the observed inverse relationship between the dissolved oxygen and N2O concentrations in the ocean, previous models have indirectly predicted marine N2O emissions from the apparent oxygen utilization (AOU), In this study, a marine ecosystem model that incorporates nitrous oxide (N2O) production processes (i.e., ammonium oxidation during nitrification and nitrite reduction during nitrifier denitrification) was newly developed to estimate the sea-air N2O flux and to quantify N2O production processes. Site preference of 15N (SP) in N2O isotopomers (14N15N16O and 15N14N16O) and the average nitrogen isotope ratio (δ15N) were added to the model because they are useful tracers to distinguish between ammonium oxidation and nitrite reduction. This model was applied to two contrasting time series sites, a subarctic station (K2) and a subtropical station (S1) in the western North Pacific. The model was validated with observed nitrogen concentration and nitrogen isotopomer datasets, and successfully simulated the higher N2O concentrations, higher δ15N values, and higher site preference values for N2O at K2 compared with S1. The annual mean N2O emissions were estimated to be 34 mg N m-2 yr-1 at K2 and 2 mg N m-2 yr-1 at S1. Using this model, we conducted three case studies: 1) estimating the ratio of in-situ biological N2O production to nitrate (NO3-) production during nitrification, 2) estimating the ratio of N2O production by ammonium oxidation to that by nitrite reduction, and 3) estimating the ratio of AOA ammonium oxidation to AOB ammonium oxidation. The results of case studies estimated the ratios of in situ biological N2O production to nitrate production during nitrification to be 0.22% at K2 and 0.06% at S1. It is also suggested that N2O was mainly produced via ammonium oxidation at K2 but was produced via both ammonium oxidation and nitrite reduction at S1. It is also revealed that 80% of the ammonium oxidation at K2 was caused by archaea in the subsurface

Oxidative metabolism of 5-o-caffeoylquinic acid (chlorogenic acid), a bioactive natural product, by metalloporphyrin and rat liver mitochondria.

Science.gov (United States)

dos Santos, Michel D; Martins, Patrícia R; dos Santos, Pierre A; Bortocan, Renato; Iamamoto, Y; Lopes, Norberto P

2005-09-01

Synthetic metalloporphyrins, in the presence of monooxygen donors, are known to mimic the various reactions of cytochrome P450 enzymes systems in the oxidation and oxygenation of various drugs and biologically active compounds. This paper reports an HPLC-MS-MS investigation of chlorogenic acid (CGA) oxidation by iodosylbenzene using iron(III) tetraphenylporphyrin chloride as catalyst. The oxidation products have been detected by sequential MS analyses. In addition, CGA was submitted to an in vitro metabolism assay employing isolated rat liver mitochondria. The single oxidized product obtained from mitochondrial metabolism corresponds to the major product formed by the metalloporphyrin-catalyzed reaction. These results indicate that biomimetic oxidation reactions, in addition to in vitro metabolism assays employing isolated organs/organelles, could replace some in vivo metabolism studies, thus minimizing the problems related to the use of a large number of living animals in experimental research.

Production of SmCo5 alloy by calciothermic reduction of samarium oxide

International Nuclear Information System (INIS)

Krishnan, T.S.; Gupta, C.K.

1988-01-01

Among the established permanent magnets, SmCo 5 magnet occupies the foremost position as it offers a unique combination of high energy product, coercivity and curie temperature. The SmCo 5 magnets are thus extensively used for high field applications. These are also best suited for use in environments where high demagnetizing field and high temperature are operative. Also, for applications where high performance and miniaturization are the over-riding considerations, the choice again falls on SmCo 5 magnets. The main deterrent to the widespread use of SmCo 5 magnet is its high cost. Both samarium and cobalt metals are high priced, and the magnets prepared from their directly melted alloy are thus naturally very expensive. An alternate process involving calcium reduction of their oxide intermediates has, therefore, been studied and the alloy prepared by this process has been evaluated and found satisfactory for magnet production. The process essentially involves compaction of the charge mix containing samarium oxide, cobalt oxide (or metal) and calcium metal and reduction of the charge compact at 1000-1300 degrees C in hydrogen atmosphere, followed by water and acid leaching, drying and classification

Identification of key nitrous oxide production pathways in aerobic partial nitrifying granules.

Science.gov (United States)

Ishii, Satoshi; Song, Yanjun; Rathnayake, Lashitha; Tumendelger, Azzaya; Satoh, Hisashi; Toyoda, Sakae; Yoshida, Naohiro; Okabe, Satoshi

2014-10-01

The identification of the key nitrous oxide (N2O) production pathways is important to establish a strategy to mitigate N2O emission. In this study, we combined real-time gas-monitoring analysis, (15)N stable isotope analysis, denitrification functional gene transcriptome analysis and microscale N2O concentration measurements to identify the main N2O producers in a partial nitrification (PN) aerobic granule reactor, which was fed with ammonium and acetate. Our results suggest that heterotrophic denitrification was the main contributor to N2O production in our PN aerobic granule reactor. The heterotrophic denitrifiers were probably related to Rhodocyclales bacteria, although different types of bacteria were active in the initial and latter stages of the PN reaction cycles, most likely in response to the presence of acetate. Hydroxylamine oxidation and nitrifier denitrification occurred, but their contribution to N2O emission was relatively small (20-30%) compared with heterotrophic denitrification. Our approach can be useful to quantitatively examine the relative contributions of the three pathways (hydroxylamine oxidation, nitrifier denitrification and heterotrophic denitrification) to N2O emission in mixed microbial populations. © 2014 Society for Applied Microbiology and John Wiley & Sons Ltd.

Inherent health and environmental risk assessment of nanostructured metal oxide production processes.

Science.gov (United States)

Torabifard, Mina; Arjmandi, Reza; Rashidi, Alimorad; Nouri, Jafar; Mohammadfam, Iraj

2018-01-10

The health and environmental effects of chemical processes can be assessed during the initial stage of their production. In this paper, the Chemical Screening Tool for Exposure and Environmental Release (ChemSTEER) software was used to compare the health and environmental risks of spray pyrolysis and wet chemical techniques for the fabrication of nanostructured metal oxide on a semi-industrial scale with a capacity of 300 kg/day in Iran. The pollution sources identified in each production process were pairwise compared in Expert Choice software using indicators including respiratory damage, skin damage, and environmental damages including air, water, and soil pollution. The synthesis of nanostructured zinc oxide using the wet chemical technique (with 0.523 wt%) leads to lower health and environmental risks compared to when spray pyrolysis is used (with 0.477 wt%). The health and environmental risk assessment of nanomaterial production processes can help select safer processes, modify the operation conditions, and select or modify raw materials that can help eliminate the risks.

Wet oxidation pretreatment of rape straw for ethanol production

International Nuclear Information System (INIS)

Arvaniti, Efthalia; Bjerre, Anne Belinda; Schmidt, Jens Ejbye

2012-01-01

Rape straw can be used for production of second generation bioethanol. In this paper we optimized the pretreatment of rape straw for this purpose using Wet oxidation (WO). The effect of reaction temperature, reaction time, and oxygen gas pressure was investigated for maximum ethanol yield via Simultaneous Saccharification and Fermentation (SSF). To reduce the water use and increase the energy efficiency in WO pretreatment features like recycling liquid (filtrate), presoaking of rape straw in water or recycled filtrate before WO, skip washing pretreated solids (filter cake) after WO, or use of whole slurry (Filter cake + filtrate) in SSF were also tested. Except ethanol yields, pretreatment methods were evaluated based on achieved glucose yields, amount of water used, recovery of cellulose, hemicellulose, and lignin. The highest ethanol yield obtained was 67% after fermenting the whole slurry produced by WO at 205 °C for 3 min with 12 bar of oxygen gas pressure and featured with presoaking in water. At these conditions after pre-treatment, cellulose and hemicellulose was recovered quantitatively (100%) together with 86% of the lignin. WO treatments of 2–3 min at 205–210 °C with 12 bar of oxygen gas produced higher ethanol yields and cellulose, hemicelluloses, and lignin recoveries, than 15 min WO treatment at 195 °C. Also, recycling filtrate and use of higher oxygen gas pressure reduced recovery of materials. The use of filtrate could be inhibitory for the yeast, but also reduced lactic acid formation in SSF. -- Highlights: ► Wet Oxidation pretreatment on rape straw for sugar and ethanol production. ► Variables were reaction time, temperature, and oxygen gas pressure. ► Also, other configurations for increase of water and energy efficiency. ► Short Wet oxidation pretreatment (2–3 min) produced highest ethanol yield. ► After these pretreatment conditions recovery of lignin in solids was 86%.

Spectroscopic Analyses of the Biofuels-Critical Phytochemical Coniferyl Alcohol and Its Enzyme-Catalyzed Oxidation Products

Energy Technology Data Exchange (ETDEWEB)

Achyuthan, Komandoor; Adams, Paul; Simmons, Blake; Singh, Anup

2011-07-13

Lignin composition (monolignol types of coniferyl, sinapyl or p-coumaryl alcohol) is causally related to biomass recalcitrance. We describe multiwavelength (220, 228, 240, 250, 260, 290, 295, 300, 310 or 320 nm) absorption spectroscopy of coniferyl alcohol and its laccase- or peroxidase-catalyzed products during real time kinetic, pseudo-kinetic and endpoint analyses, in optical turn on or turn off modes, under acidic or basic conditions. Reactions in microwell plates and 100 mu L volumes demonstrated assay miniaturization and high throughput screening capabilities. Bathochromic and hypsochromic shifts along with hyperchromicity or hypochromicity accompanied enzymatic oxidations by laccase or peroxidase. The limits of detection and quantitation of coniferyl alcohol averaged 2.4 and 7.1 mu M respectively, with linear trend lines over 3 to 4 orders of magnitude. Coniferyl alcohol oxidation was evident within 10 minutes or with 0.01 mu g/mL laccase and 2 minutes or 0.001 mu g/mL peroxidase. Detection limit improved to 1.0 mu M coniferyl alcohol with Km of 978.7 +/- 150.7 mu M when examined at 260 nm following 30 minutes oxidation with 1.0 mu g/mL laccase. Our assays utilized the intrinsic spectroscopic properties of coniferyl alcohol or its oxidation products for enabling detection, without requiring chemical synthesis or modification of the substrate or product(s). These studies facilitate lignin compositional analyses and augment pretreatment strategies for reducing biomass recalcitrance.

Temperature controls oxidative phosphorylation and reactive oxygen species production through uncoupling in rat skeletal muscle mitochondria.

Science.gov (United States)

Jarmuszkiewicz, Wieslawa; Woyda-Ploszczyca, Andrzej; Koziel, Agnieszka; Majerczak, Joanna; Zoladz, Jerzy A

2015-06-01

Mitochondrial respiratory and phosphorylation activities, mitochondrial uncoupling, and hydrogen peroxide formation were studied in isolated rat skeletal muscle mitochondria during experimentally induced hypothermia (25 °C) and hyperthermia (42 °C) compared to the physiological temperature of resting muscle (35 °C). For nonphosphorylating mitochondria, increasing the temperature from 25 to 42 °C led to a decrease in membrane potential, hydrogen peroxide production, and quinone reduction levels. For phosphorylating mitochondria, no temperature-dependent changes in these mitochondrial functions were observed. However, the efficiency of oxidative phosphorylation decreased, whereas the oxidation and phosphorylation rates and oxidative capacities of the mitochondria increased, with increasing assay temperature. An increase in proton leak, including uncoupling protein-mediated proton leak, was observed with increasing assay temperature, which could explain the reduced oxidative phosphorylation efficiency and reactive oxygen species production. Copyright © 2015 Elsevier Inc. All rights reserved.

Anti-nitric oxide production, anti-proliferation and antioxidant effects of the aqueous extract from Tithonia diversifolia

Directory of Open Access Journals (Sweden)

Poonsit Hiransai

2016-11-01

Conclusions: Our study demonstrated the immunomodulation caused by the aqueous leaf extract of T. diversifolia, resulting from the inhibition of phytohemagglutinin-M-induced PBMCs proliferation and LPS-induced nitric oxide production in RAW264.7 macrophages. Although the anti-oxidative activity was presented in the chemical-based anti-oxidant assay, the extract cannot protect cell death from stress conditions.

Quantification of nitrous oxide (N2O) emissions and soluble microbial product (SMP) production by a modified AOB-NOB-N2O-SMP model.

Science.gov (United States)

Kim, MinJeong; Wu, Guangxue; Yoo, ChangKyoo

2017-03-01

A modified AOB-NOB-N 2 O-SMP model able to quantify nitrous oxide (N 2 O) emissions and soluble microbial product (SMP) production during wastewater treatment is proposed. The modified AOB-NOB-N 2 O-SMP model takes into account: (1) two-step nitrification by ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), (2) N 2 O production by AOB denitrification under oxygen-limited conditions and (3) SMP production by microbial growth and endogenous respiration. Validity of the modified model is demonstrated by comparing the simulation results with experimental data from lab-scale sequencing batch reactors (SBRs). To reliably implement the modified model, a model calibration that adjusts model parameters to fit the model outputs to the experimental data is conducted. The results of this study showed that the modeling accuracy of the modified AOB-NOB-N 2 O-SMP model increases by 19.7% (NH 4 ), 51.0% (NO 2 ), 57.8% (N 2 O) and 16.7% (SMP) compared to the conventional model which does not consider the two-step nitrification and SMP production by microbial endogenous respiration. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transport of radionuclides by bentonite and silica colloids in a GR-3 synthetic groundwater-interim report

International Nuclear Information System (INIS)

Ames, L.L.; McGarrah, J.E.; Walker, B.A.

1983-08-01

Radionuclide distributions in groundwater-colloid-basalt systems were measured using GR-3 groundwater and crushed Umtanum basalt at 60 degree C. The objective was to estimate the potential for radionuclide transport from a nuclear waste repository in basalt by colloids suspended in groundwater. Three colloids were studied -- a bentonite colloid representing a potential component of packing or backfill materials in the repository, and two hydrated silica colloids which might represent those generated from a glass waste form. The radioelements studied included isotopes of neptunium, uranium, selenium, technetium, and radium. Measurements of radionuclide distributions in experiments with the bentonite colloid showed that uranium was sorbed strongly on the colloid (under both oxidizing and reducing conditions) but was readily transferred to basalt when it was added to the system. Sorption of neptunium, technetium, and selenium on the colloid was greatly enhanced by using reducing conditions. Only small amounts of neptunium and technetium were transferred to the basalt under reducing conditions, but most of the selenium was readily transferred under these conditions

Photoelectrocatalytic Glucose Oxidation to Promote Hydrogen Production over Periodically Ordered TiO2 Nanotube Arrays Assembled of Pd Quantum Dots

International Nuclear Information System (INIS)

Zhang, Yajun; Zhao, Guohua; Shi, Huijie; Zhang, Ya-nan; Huang, Wenna; Huang, Xiaofeng; Wu, Zhongyi

2015-01-01

Highlights: • Solar-driven PEC glucose oxidation to promote hydrogen production was presented. • The excellent PEC activity of Pd QDs@TNTAs was investigated. • The rate of hydrogen production from glucose was about 15 times than water. • A low-cost and efficient method in renewables-to-hydrogen conversion was put forward. - Abstract: The development of highly efficient and low-cost approaches for catalytic hydrogen production from renewable energy is of tremendous importance for a truly sustainable hydrogen-based energy carrier in future life. Herein, the probability of utilizing solar light to product hydrogen from biomass derivative, glucose, was systematically demonstrated by using the periodically ordered TiO 2 nanotube arrays (TNTAs) assembled of Palladium quantum dots (Pd QDs), i.e. Pd QDs@ TNTAs as photoanode. The results showed that remarkably increased photocurrent density was obtained in the glucose solution compared to the pure KOH electrolyte over as-prepared photoelectrode, which indicated that the glucose could be faster oxidized than water oxidation, and thus could promote the hydrogen production on Pt cathode. The yield of hydrogen production from glucose oxidation reached as high as 164.8 μmol cm −1 over Pd QDs@TNTAs photoanode and Pt cathode system (denoted as Pd QDs@TNTAs/Pt) under the solar light irradiation for 6 h, which was about 15 times higher than that from pure water splitting. The superior hydrogen production performance could be attributed to the less endergonic process of the glucose oxidation than water, as well as the efficient synergistic photoelectrocatalytic (PEC) glucose oxidation over Pd QDs@TNTAs photoanode which possesses excellent photoelectrochemical performance and structure characteristics. Moreover, a probable mechanism for the PEC hydrogen production from biomass derivatives oxidation was proposed and discussed

SEPARATION OF TRANSURANIC ELEMENTS FROM RARE EARTH COMPOUNDS

Science.gov (United States)

Kohman, T.P.

1961-11-21

A process of separating neptunium and plutonium values from rare earths and alkaline earth fission products present on a solid mixed actinide carrier (Th or U(IV) oxalate or fluoride) --fission product carrier (LaF/sub 3/, CeF/sub 3/, SrF/sub 2/, CaF/sub 2/, YF/sub 3/, La oxalate, cerous oxalate, Sr oxalate, Ca oxalate or Y oxalate) by extraction of the actinides at elevated temperature with a solution of ammonium fluoride and/or ammonium oxalate is described. Separation of the fission-product-containing carriers from the actinide solution formed and precipitation of the neptunium and plutonium from the solution with mineral acid are also accomplished. (AEC)

The Effect of Buckwheat Hull Extract on Lipid Oxidation in Frozen-Stored Meat Products.

Science.gov (United States)

Hęś, Marzanna; Szwengiel, Artur; Dziedzic, Krzysztof; Le Thanh-Blicharz, Joanna; Kmiecik, Dominik; Górecka, Danuta

2017-04-01

This study investigated the effect of antioxidants on lipid stability of frozen-stored meat products. Buckwheat hull extract was used to enrich fried meatballs made from ground pork. During 180-d storage of meat products, lipid oxidation (peroxide and 2-thiobarbituric acid reactive substances [TBARS] value) was periodically monitored. The results were compared with butylated hydroxytoluene (BHT). The addition of antioxidants decreased lipid oxidation in stored meatballs. The highest ability to control peroxide and TBARS values was demonstrated for buckwheat hull extract. Moreover, buckwheat hull extract showed a higher 2,2-diphenyl-1-picrylhydrazyl free radical scavenging activity as well as higher Fe(II) ion chelating ability, as compared with BHT. The total content of phenolic compounds are highly correlated to the individual polyphenols in extract of buckwheat hull, among which the following were assayed: 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, gallic acid, isovanillic acid and p-coumaric acid, and flavonoids: isoorientin, quercetin, quercetin 3-d-glucoside, rutin, and vitexin. These results indicate that plant extracts can be used to prolong shelf life of products by protecting them against lipid oxidation and deterioration of their nutritional quality. © 2017 Institute of Food Technologists®.

AMMONIA REMOVAL AND NITROUS OXIDE PRODUCTION IN GAS-PHASE COMPOST BIOFILTERS

Science.gov (United States)

Biofiltration technology is widely utilized for treating ammonia gas (NH3), with one of its potential detrimental by-products being nitrous oxide (N2O), a greenhouse gas approximately 300 times more reactive to infrared than CO2. The present work intends to provide the relation between NH3 removal d...

Uranium oxidation: characterization of oxides formed by reaction with water

International Nuclear Information System (INIS)

Fuller, E.L. Jr.; Smyrl, N.R.; Condon, J.B.; Eager, M.H.

1983-01-01

Three different uranium oxide samples have been characterized with respect to the different preparation techniques. Results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. 27 figures

Impact of green tea extract addition on oxidative changes in the lipid fraction of pastry products.

Science.gov (United States)

Żbikowska, Anna; Kowalska, Małgorzata; Rutkowska, Jarosława; Kozłowska, Mariola; Onacik-Gür, Sylwia

2017-01-01

Alongside flour, fat is the key ingredient of sponge cakes, including those with long shelf lives. It is an unstable food component, whose quality and nutritional safety depend on the composition and pres- ence of oxidation products. Consumption of fat oxidation products adversely affects the human body and contributes to the incidence of a number of medical conditions. Qualitative changes in fats extracted from thermostat sponge cakes with and without antioxidant additions were determined in this study. In the study, two types of antioxidant were used: natural - green tea extract in three doses (0.02%; 0.2% and 1.0%) and synthetic BHA (0.02%) and 100%, solid bakery shortening. Sponge-cakes were thermostatted at temperatures 63°C after twenty-eight days. In this study, the quality of the lipid fraction was analyzed. The amount of primary (PV) and secondary (AnV) oxidation products was determined, and   a Rancimat test was performed. Adding antioxidants to fats varied in the degree to which oxidation processes of lipids fractions were inhibited. The peroxide value after twenty-eight days of thermostatting ranged from 3.57 meq O/kg (BHA) and 11.14 O meq/kg (extract content - 1%) to 62.85 meq O/kg (control sample). In turn, the value of AnV after the storage period ranged from 4.84 (BHA) and 6.71 (extract content - 1%) to 16.83 (control sample). The best protective effects in the process of oxidation was achieved by BHA. The longest in- duction time and the lowest peroxide value and anisidine value were obtained for this antioxidant. It was achieved after twenty-eight days of fat thermostatting. Nonetheless, the results demonstrated it is possible to use the commercially available green tea extract to slow the adverse process of fat oxidation in sponge cake products.

Study of the production of zirconium tetrachloride by chlorination of its oxide

International Nuclear Information System (INIS)

Seo, E.S.M.

1983-01-01

The studies carried out on the production of zirconium tetrachloride by chlorination of pure zirconium oxide with carbon tetrachloride and chlorine in the presence of carbon. In the process of chlorination with carbon tetrachloride, the chlorination efficiency increases with the rise in temperature at intervals between 450 and 750 0 C. The flow of the carbon tetrachloride vapour was 1.50l/min. Higher temperatures of 700 to 850 0 C were used for the zirconium oxide chlorination in the presence of carbon, and the flowrate of the chlorine gas used in the process was 0.50 l/min. Pure zirconium oxide chlorination as well as zirconium oxide - carbon misture chlorination have been studied in connection with the time of reaction at different temperatures and the apparent rate constant, the activation energies, the order of reaction in relation to the concentration of the gases (CCl 4 and Cl 2 ) and the content of carbon in the pellet have all been determined. (Author) [pt

Release of fission products during and after oxidation of trace-irradiated uranium dioxide at 300-900 deg. C

Energy Technology Data Exchange (ETDEWEB)

Wood, P; Bannister, G H [Central Electricity Generating Board, Berkeley Nuclear Laboratories (United Kingdom)

1985-07-01

Should defected UO{sub 2} fuel pins come into contact with air then oxidation of the fuel may occur, the rate and consequences of which are dependent upon temperature and oxygen partial pressure. At CEGB-BNL an experimental programme is underway investigating the kinetics, and extent, of release of fission products during and after oxidation of trace-irradiated UO{sub 2} to U{sub 3}O{sub 8}, and reduction of U{sub 3}O{sub 8} to UO{sub 2}. This paper presents preliminary results and analysis of experiments performed at 300-900 deg. C. Dense sintered UO{sub 2} has been oxidised at 300-500 deg. C using a thermo balance with simultaneous counting of released {sup 85}Kr. The kinetics of the {sup 85}Kr release are shown to correlate with the kinetics of oxidation, and the extent of release has been determined as 3-8% of that in the UO{sub 2} converted to U{sub 3}O{sub 8}. The release of {sup 106}Ru and {sup 137}Cs during this oxidation has been estimated by {gamma}-counting of the fuel sample, before and after oxidation, and of glassware in the vicinity of the sample. This indicates slight release of ruthenium and caesium. Greater fission product release is caused by oxidation at higher temperatures or by heating of the oxidation product. U{sub 3}O{sub 8} produced at 400 deg. C has been heated at 800 and 900 deg. C in air for 20 hours. This results in near total release of {sup 85}Kr and {sup 106}Ru, but still only slight release of {sup 137}Cs. The kinetics of the {sup 85}Kr release have been analysed and found to follow the Booth diffusion equation at 900 deg. C, but not at 800 deg. C. The fuel burn-up level may also have an effect. Some results of fission product release during reduction of the oxidation product U{sub 3}O{sub 8} are presented, and the influence of chemical effects upon the release of individual fission products is discussed. The future programme is outlined. (author)

Determination of lipid oxidation products in vegetable oils and marine omega-3 supplements

Directory of Open Access Journals (Sweden)

Rune Blomhoff

2011-06-01

Full Text Available Background : There is convincing evidence that replacing dietary saturated fats with polyunsaturated fats (PUFA decreases risk of cardiovascular diseases. Therefore, PUFA rich foods such as vegetable oils, fatty fish, and marine omega-3 supplements are recommended. However, PUFA are easily oxidizable and there is concern about possible negative health effects from intake of oxidized lipids. Little is known about the degree of lipid oxidation in such products. Objective : To assess the content of lipid oxidation products in a large selection of vegetable oils and marine omega-3 supplements available in Norway. Both fresh and heated vegetable oils were studied. Design : A large selection of commercially available vegetable oils and marine omega-3 supplements was purchased from grocery stores, pharmacies, and health food stores in Norway. The content of lipid oxidation products were measured as peroxide value and alkenal concentration. Twelve different vegetable oils were heated for a temperature (225°C and time (25 minutes resembling conditions typically used during cooking. Results : The peroxide values were in the range 1.04–10.38 meq/kg for omega-3 supplements and in the range 0.60–5.33 meq/kg for fresh vegetable oils. The concentration range of alkenals was 158.23–932.19 nmol/mL for omega-3 supplements and 33.24–119.04 nmol/mL for vegetable oils. After heating, a 2.9–11.2 fold increase in alkenal concentration was observed for vegetable oils. Conclusions : The contents of hydroperoxides and alkenals in omega-3 supplements are higher than in vegetable oils. After heating vegetable oils, a large increase in alkenal concentration was observed.

Yttrium bismuth titanate pyrochlore mixed oxides for photocatalytic hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Merka, Oliver

2012-10-18

In this work, the sol-gel synthesis of new non-stoichiometric pyrochlore titanates and their application in photocatalytic hydrogen production is reported. Visible light response is achieved by introducing bismuth on the A site or by doping the B site by transition metal cations featuring partially filled d orbitals. This work clearly focusses on atomic scale structural changes induced by the systematical introduction of non-stoichiometry in pyrochlore mixed oxides and the resulting influence on the activity in photocatalytic hydrogen production. The materials were characterized in detail regarding their optical properties and their atomic structure. The pyrochlore structure tolerates tremendous stoichiometry variations. The non-stoichiometry in A{sub 2}O{sub 3} rich compositions is compensated by distortions in the cationic sub-lattice for the smaller Y{sup 3+} cation and by evolution of a secondary phase for the larger Bi{sup 3+} cation on the A site. For TiO{sub 2} rich compositions, the non-stoichiometry leads to a special vacancy formation in the A and optionally O' sites. It is shown that pyrochlore mixed oxides in the yttrium bismuth titanate system represent very active and promising materials for photocatalytic hydrogen production, if precisely and carefully tuned. Whereas Y{sub 2}Ti{sub 2}O{sub 7} yields stable hydrogen production rates over time, the bismuth richer compounds of YBiTi{sub 2}O{sub 7} and Bi{sub 2}Ti{sub 2}O{sub 7} are found to be not stable under irradiation. This drawback is overcome by applying a special co-catalyst system consisting of a precious metal core and a Cr{sub 2}O{sub 3} shell on the photocatalysts.

Low Temperature Selective Catalytic Reduction of Nitrogen Oxides in Production of Nitric Acid by the Use of Liquid

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Kabljanac, Ž.

2011-11-01

Full Text Available This paper presents the application of low-temperature selective catalytic reduction of nitrous oxides in the tail gas of the dual-pressure process of nitric acid production. The process of selective catalytic reduction is carried out using the TiO2/WO3 heterogeneous catalyst applied on a ceramic honeycomb structure with a high geometric surface area per volume. The process design parameters for nitric acid production by the dual-pressure procedure in a capacity range from 75 to 100 % in comparison with designed capacity for one production line is shown in the Table 1. Shown is the effectiveness of selective catalytic reduction in the temperature range of the tail gas from 180 to 230 °C with direct application of liquid ammonia, without prior evaporation to gaseous state. The results of inlet and outlet concentrations of nitrous oxides in the tail gas of the nitric acid production process are shown in Figures 1 and 2. Figure 3 shows the temperature dependence of the selective catalytic reduction of nitrous oxides expressed as NO2in the tail gas of nitric acid production with the application of a constant mass flow of liquid ammonia of 13,0 kg h-1 and average inlet mass concentration of the nitrous oxides expressed as NO2of 800,0 mgm-3 during 100 % production capacity. The specially designed liquid-ammonia direct-dosing system along with the effective homogenization of the tail gas resulted in emission levels of nitrous oxides expressed as NO2 in tail gas ranging from 100,0 to 185,0 mg m-3. The applied low-temperature selective catalytic reduction of the nitrous oxides in the tail gases by direct use of liquid ammonia is shown in Figure 4. It is shown that low-temperature selective catalytic reduction with direct application of liquid ammonia opens a new opportunity in the reduction of nitrous oxide emissions during nitric acid production without the risk of dangerous ammonium nitrate occurring in the process of subsequent energy utilization of

Production and analysis of ultradispersed uranium oxide powders

Science.gov (United States)

Zajogin, A. P.; Komyak, A. I.; Umreiko, D. S.; Umreiko, S. D.

2010-05-01

Spectroscopic studies are made of the laser plasma formed near the surface of a porous body containing nanoquantities of uranium compounds which is irradiated by two successive laser pulses. The feasibility of using laser chemical methods for obtaining nanoclusters of uranium oxide particles in the volume of a porous body and the simultaneous possibility of determining the uranium content with good sensitivity are demonstrated. The thermochemical and spectral characteristics of the analogs of their compounds with chlorine are determined and studied. The possibility of producing uranium dioxides under ordinary conditions and their analysis in the reaction products is demonstrated.

UVA Light-excited Kynurenines Oxidize Ascorbate and Modify Lens Proteins through the Formation of Advanced Glycation End Products

Science.gov (United States)

Linetsky, Mikhail; Raghavan, Cibin T.; Johar, Kaid; Fan, Xingjun; Monnier, Vincent M.; Vasavada, Abhay R.; Nagaraj, Ram H.

2014-01-01

Advanced glycation end products (AGEs) contribute to lens protein pigmentation and cross-linking during aging and cataract formation. In vitro experiments have shown that ascorbate (ASC) oxidation products can form AGEs in proteins. However, the mechanisms of ASC oxidation and AGE formation in the human lens are poorly understood. Kynurenines are tryptophan oxidation products produced from the indoleamine 2,3-dioxygenase (IDO)-mediated kynurenine pathway and are present in the human lens. This study investigated the ability of UVA light-excited kynurenines to photooxidize ASC and to form AGEs in lens proteins. UVA light-excited kynurenines in both free and protein-bound forms rapidly oxidized ASC, and such oxidation occurred even in the absence of oxygen. High levels of GSH inhibited but did not completely block ASC oxidation. Upon UVA irradiation, pigmented proteins from human cataractous lenses also oxidized ASC. When exposed to UVA light (320–400 nm, 100 milliwatts/cm2, 45 min to 2 h), young human lenses (20–36 years), which contain high levels of free kynurenines, lost a significant portion of their ASC content and accumulated AGEs. A similar formation of AGEs was observed in UVA-irradiated lenses from human IDO/human sodium-dependent vitamin C transporter-2 mice, which contain high levels of kynurenines and ASC. Our data suggest that kynurenine-mediated ASC oxidation followed by AGE formation may be an important mechanism for lens aging and the development of senile cataracts in humans. PMID:24798334

Nitrous oxide production kinetics during nitrate reduction in river sediments.

Science.gov (United States)

Laverman, Anniet M; Garnier, Josette A; Mounier, Emmanuelle M; Roose-Amsaleg, Céline L

2010-03-01

A significant amount of nitrogen entering river basins is denitrified in riparian zones. The aim of this study was to evaluate the influence of nitrate and carbon concentrations on the kinetic parameters of nitrate reduction as well as nitrous oxide emissions in river sediments in a tributary of the Marne (the Seine basin, France). In order to determine these rates, we used flow-through reactors (FTRs) and slurry incubations; flow-through reactors allow determination of rates on intact sediment slices under controlled conditions compared to sediment homogenization in the often used slurry technique. Maximum nitrate reduction rates (R(m)) ranged between 3.0 and 7.1microg Ng(-1)h(-1), and affinity constant (K(m)) ranged from 7.4 to 30.7mg N-NO(3)(-)L(-1). These values were higher in slurry incubations with an R(m) of 37.9microg Ng(-1)h(-1) and a K(m) of 104mg N-NO(3)(-)L(-1). Nitrous oxide production rates did not follow Michaelis-Menten kinetics, and we deduced a rate constant with an average of 0.7 and 5.4ng Ng(-1)h(-1) for FTR and slurry experiments respectively. The addition of carbon (as acetate) showed that carbon was not limiting nitrate reduction rates in these sediments. Similar rates were obtained for FTR and slurries with carbon addition, confirming the hypothesis that homogenization increases rates due to release of and increasing access to carbon in slurries. Nitrous oxide production rates in FTR with carbon additions were low and represented less than 0.01% of the nitrate reduction rates and were even negligible in slurries. Maximum nitrate reduction rates revealed seasonality with high potential rates in fall and winter and low rates in late spring and summer. Under optimal conditions (anoxia, non-limiting nitrate and carbon), nitrous oxide emission rates were low, but significant (0.01% of the nitrate reduction rates). Copyright 2009 Elsevier Ltd. All rights reserved.

Production and release of acylcarnitines by primary myotubes reflect the differences in fasting fat oxidation of the donors.

Science.gov (United States)

Wolf, Magnus; Chen, Shili; Zhao, Xinjie; Scheler, Mika; Irmler, Martin; Staiger, Harald; Beckers, Johannes; de Angelis, Martin Hrabé; Fritsche, Andreas; Häring, Hans-Ulrich; Schleicher, Erwin D; Xu, Guowang; Lehmann, Rainer; Weigert, Cora

2013-06-01

Acylcarnitines are biomarkers of incomplete β-oxidation and mitochondrial lipid overload but indicate also high rates of mitochondrial fatty acid oxidation. It is unknown whether the production of acylcarnitines in primary human myotubes obtained from lean, metabolically healthy subjects reflects the fat oxidation in vivo. Our objective was to quantify the acylcarnitine production in myotubes obtained from subjects with low and high fasting respiratory quotient (RQ). Fasting RQ was determined by indirect calorimetry. Muscle biopsies from the vastus lateralis muscle were taken from 6 subjects with low fasting RQ (mean 0.79 ± 0.03) and 6 with high fasting RQ (0.90 ± 0.03), and satellite cells were isolated, cultured, and differentiated to myotubes. Myotubes were cultivated with 125 μM (13)C-labeled palmitate for 30 minutes and 4 and 24 hours. Quantitative profiling of 42 intracellular and 31 extracellular acylcarnitines was performed by stable isotope dilution-based metabolomics analysis by liquid chromatography coupled to mass spectrometry. Myotubes from donors with high fasting RQ produced and released significant higher amounts of medium-chain acylcarnitines. High (13)C8 and (13)C10 acylcarnitine levels in the extracellular compartment correlated with high fasting RQ. The decreased expression of medium-chain acyl-coenzyme A dehydrogenase (MCAD) in these myotubes can explain the higher rate of incomplete fatty acid oxidation. A lower intracellular [(13)C]acetylcarnitine to carnitine and lower intracellular (13)C16/(13)C18 acylcarnitine to carnitine ratio indicate reduced fatty acid oxidation capacity in these myotubes. Mitochondrial DNA content was not different. Acylcarnitine production and release from primary human myotubes of donors with high fasting RQ indicate a reduced fatty acid oxidation capacity and a higher rate of incomplete fatty acid oxidation. Thus, quantitative profiling of acylcarnitine production in human myotubes can be a suitable tool to

Formation of electrophilic oxidation products from mitochondrial cardiolipin in vitro and in vivo in the context of apoptosis and atherosclerosis

Directory of Open Access Journals (Sweden)

Huiqin Zhong

2014-01-01

Full Text Available Emerging evidence indicates that mitochondrial cardiolipins (CL are prone to free radical oxidation and this process appears to be intimately associated with multiple biological functions of mitochondria. Our previous work demonstrated that a significant amount of potent lipid electrophiles including 4-hydroxy-nonenal (4-HNE was generated from CL oxidation through a novel chemical mechanism. Here we provide further evidence that a characteristic class of CL oxidation products, epoxyalcohol-aldehyde-CL (EAA-CL, is formed through this novel mechanism in isolated mice liver mitochondria when treated with the pro-apoptotic protein t-Bid to induce cyt c release. Generation of these oxidation products are dose-dependently attenuated by a peroxidase inhibitor acetaminophen (ApAP. Using a mouse model of atherosclerosis, we detected significant amount of these CL oxidation products in liver tissue of low density lipoprotein receptor knockout (LDLR −/− mice after Western diet feeding. Our studies highlight the importance of lipid electrophiles formation from CL oxidation in the settings of apoptosis and atherosclerosis as inhibition of CL oxidation and lipid electrophiles formation may have potential therapeutic value in diseases linked to oxidant stress and mitochondrial dysfunctions.

Effect of oxidation on the chemical nature and distribution of low-temperature pyrolysis products from bituminous coal

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.; MacPhee, J.A.; Vancea, L.; Ciavaglia, L.A.; Nandi, B.N.

1983-04-01

Two bituminous coals, a high volatile Eastern Canadian and a medium volatile Western Canadian, were used to investigate the effect of oxidation on yields and chemical composition of gases, liquids and chars produced during coal pyrolysis. Pyrolysis experiments were performed at 500 C using the Fischer assay method. Mild oxidation of coals resulted in a decrease of liquid hydrocarbon yields. Further coal oxidation increased the proportion of aromatic carbon in liquid products as determined by N.M.R. and also increased the content of oxygen in liquid products. The content of oxygen in chars was markedly lower than in corresponding coals. An attempt is made to explain reactions occurring during oxidation and subsequent pyrolysis of coal on the basis of differences in chemical composition of gases, liquids and chars. (19 refs.)